NC State
BioResources
Zhang, X., Huang, M., Long, Y., Li, Q., Zhou, W., Xiao, N., and Cai, J. (2026). "Research progress in the application of advanced oxidation pretreatment for biomass energy production," BioResources 21(3), Page numbers to be added.

Abstract

Graphic Summary: Research Progress in the Application of Advanced Oxidation Pretreatment for Biomass Energy Production

Lignocellulosic biomass is an abundant renewable energy resource whose total energy content far exceeds current global demand. Its polysaccharides, cellulose, and hemicelluloses are primary targets for valorization; however, the recalcitrant structure of plant cell walls necessitates effective pretreatment. Among physical, physicochemical, chemical, and biological methods, advanced oxidation processes (AOPs) have emerged as an efficient and environmentally compatible chemical strategy. This review systematically evaluates nine major AOPs for lignocellulosic biomass pretreatment: Fenton and Fenton-like processes, alkaline H₂O₂, peracetic acid, persulfate, ozone, photocatalysis, electrochemical oxidation, wet air oxidation, and cavitation-assisted methods. For each, reaction mechanisms, advantages and limitations, recent advances, economic considerations, and scale-up challenges are discussed. Persulfate-based systems, wet air oxidation, and hybrid strategies (e.g., photo-Fenton, alkaline H₂O₂–cavitation, electrochemical–ozone–H₂O₂) are identified as particularly promising. Future research should prioritize novel catalyst development, reactor optimization, multi-mechanism integration, and rigorous techno-economic and life-cycle assessments. Coupling AOPs with renewable energy sources will be critical to improving energy efficiency and enabling cost-effective large-scale application.


Download PDF

Full Article

Research Progress in the Application of Advanced Oxidation Pretreatment for Biomass Energy Production

Xueshuai Zhang,a Mengtian Huang,b,c,# Yao Long,b,c Qihang Li,b,c Yao Cao,b,c Wenbing Zhou,b,c,* Naidong Xiao,b,c and Jianbo Cai b,c

Lignocellulosic biomass is an abundant renewable energy resource whose total energy content far exceeds current global demand. Its polysaccharides, cellulose, and hemicelluloses are primary targets for valorization; however, the recalcitrant structure of plant cell walls necessitates effective pretreatment. Among physical, physicochemical, chemical, and biological methods, advanced oxidation processes (AOPs) have emerged as an efficient and environmentally compatible chemical strategy. This review systematically evaluates nine major AOPs for lignocellulosic biomass pretreatment: Fenton and Fenton-like processes, alkaline H₂O₂, peracetic acid, persulfate, ozone, photocatalysis, electrochemical oxidation, wet air oxidation, and cavitation-assisted methods. For each, reaction mechanisms, advantages and limitations, recent advances, economic considerations, and scale-up challenges are discussed. Persulfate-based systems, wet air oxidation, and hybrid strategies (e.g., photo-Fenton, alkaline H₂O₂–cavitation, electrochemical–ozone–H₂O₂) are identified as particularly promising. Future research should prioritize novel catalyst development, reactor optimization, multi-mechanism integration, and rigorous techno-economic and life-cycle assessments. Coupling AOPs with renewable energy sources will be critical to improving energy efficiency and enabling cost-effective large-scale application.

DOI: 10.15376/biores.21.3.Zhang2

Keywords: Lignocellulose; Biomass energy; Pretreatment; Advanced oxidation processes (AOPs)

Contact information: a: Xinjiang Biomass Solid Waste Resources Technology and Engineering Center, Kashi University, Kashi 844000, China; b: Frontiers Science Center for Animal Breeding and Sustainable Production, Wuhan 430070, China; c: Lab of Ecological and Environmental Engineering, College of Resources and Environment, Huazhong Agricultural University, Wuhan 430070, China; #: Co-first author; * Corresponding author: zhouwb@mail.hzau.edu.cn

Graphical Abstract

Graphic Summary: Research Progress in the Application of Advanced Oxidation Pretreatment for Biomass Energy Production

INTRODUCTION

Lignocellulosic biomass, as the most abundant renewable carbon source, is not only vast in reserves but also low in cost, making it an ideal raw material for large-scale biofuel and bio-based chemical production (Ashokkumar et al. 2022; IEA 2024). However, the complex structure and cross-linking properties of lignin hinder the efficient degradation of lignocellulosic biomass, representing a significant barrier in the biomass conversion process (Ashokkumar et al. 2022). In lignocellulosic bioconversion, pretreatment modifies the structural and chemical features of biomass to facilitate subsequent enzymatic hydrolysis and fermentation. After pretreatment, enzymatic saccharification releases fermentable sugars, which are then converted into biofuels or other production through microbial fermentation and product recovery (Bansod et al. 2024). Because the efficiency of these downstream processes strongly depends on substrate accessibility and structural disruption, pretreatment plays a decisive role in determining overall conversion performance. Effective pretreatment strategies aim to reduce lignin-associated recalcitrance and enhance cellulose accessibility to improve bioconversion efficiency (Alvira et al. 2010; Rezania et al. 2020). Advanced oxidation processes (AOPs), characterized by the in situ generation of highly reactive radical species such as ·OH and SO4·−, have recently emerged as promising alternatives for lignocellulosic pretreatment (Prado et al. 2022). Rather than relying solely on bulk chemical dissolution or harsh physical disruption, AOPs introduce controlled oxidative reactions capable of modifying lignin-rich domains and altering interpolymer linkages within the biomass matrix. In this context, it can be hypothesized that an appropriately regulated advanced oxidation process will be able to partially disrupt lignin barriers and weaken structural constraints without extensive degradation of fermentable polysaccharides, thereby rendering biomass more accessible to cellulases, fermentative microorganisms, and other bioconversion factors. Among these, persulfate-based technologies, particularly peroxymonosulfate (PMS), Fenton-like processes, and wet air oxidation are gaining attention because of their superior oxidative performance. Such approaches are being increasingly used to improve the saccharification rate of lignocellulose. Therefore, this article provides a comprehensive review of recent advances in advanced oxidation-based pretreatment strategies for lignocellulosic biomass, with particular emphasis on their mechanisms, performance, and challenges.

LIGNOCELLULOSIC PRETREATMENT

Lignocellulosic biomass primarily consists of three types of biopolymers: cellulose, hemicellulose, and lignin (Jiang et al. 2017). Cellulose forms highly ordered crystalline microfibrils stabilized by extensive intra- and intermolecular hydrogen bonding. Hemicellulose acts as a branched, amorphous polysaccharide that associates with cellulose surfaces, while lignin forms a three-dimensional aromatic polymer that embeds the carbohydrate fraction (Ashokkumar et al. 2022). The recalcitrance of lignocellulose arises from several structural factors: (i) cellulose crystallinity, which limits enzymatic accessibility; (ii) the physical shielding effect of lignin; (iii) lignin-carbohydrate complexes (LCCs) that chemically link polysaccharides and lignin; and (iv) restricted pore structure and low surface area. Among these, lignin plays a central role by limiting enzyme adsorption and, in some cases, promoting non-productive enzyme binding. Therefore, effective pretreatment strategies often aim to disrupt lignin structure, increase porosity, and enhance enzyme-substrate interactions while preserving fermentable carbohydrates (Hassan et al. 2018; Liu et al. 2018).

Pretreatment methods are generally classified into physical, biological, chemical, and physicochemical combined treatments (Putro et al. 2016; Sun et al. 2016). Physical methods enhance enzymatic hydrolysis by disrupting the cell wall structure and increasing the surface area. While simple to operate, they have high energy consumption and are noted for limited lignin removal, so that they are typically used as supplementary methods. Biological methods, which use enzymes secreted by microorganisms to degrade lignin, are energy-efficient and operate under mild conditions, but they require long processing times and high microbial activity (Rouches et al. 2016). Chemical methods break the chemical bonds in lignocellulose using acids, bases, or solvents, lowering crystallinity and accelerating degradation. These methods offer good degradation efficiency, but they often require strong acids or bases, leading to high equipment requirements and costs (Taherzadeh and Karimi 2008). Additionally, chemical pretreatment includes the use of ionic liquids, low eutectic solvents, and, more recently, advanced oxidation methods (Behera et al. 2014). Advanced oxidation processes (AOPs), by generating highly oxidative free radicals, significantly improve the degradability of lignocellulose and offer advantages such as high efficiency, environmental friendliness, and mild operating conditions (Joshi and Manjare 2024).

AOP PRETREATMENT OF BIOMASS AND ITS APPLICATIONS

The Principle of AOP Pretreatment of Lignocellulose

Advanced oxidation processes (AOPs) are chemical pretreatment methods that generate strong oxidizing free radicals, such as ·OH, SO4·−, O2·−. These can effectively break down the lignocellulosic structure. The mechanism of AOP pretreatment of lignocellulosic substrates for energy production is illustrated in Fig. 1. The AOPs have been widely applied in wastewater treatment and soil remediation (Zhou et al. 2019; Liu et al. 2021a). Recent studies highlight their potential in enhancing cellulose accessibility and promoting the production of biogas, bioethanol, biodiesel, and biohydrogen. The primary mechanisms involve the disruption of lignin barriers, improving cellulose accessibility, and enhancing hydrolysis, and fermentation performance (Dong et al. 2018; Zhang et al. 2019a; Göncü et al. 2021).

Schematics of AOPs pretreatment for lignocellulosic biomass

Fig. 1. Schematics of AOPs pretreatment for lignocellulosic biomass

Various AOP Pretreatment Methods

Fenton and Fenton-like pretreatment

Fenton technology is a commonly used method within AOPs. It is widely applied and studied due to its high efficiency and simplicity in operation, particularly in reducing the chemical oxygen demand (COD) content of domestic sewage (Liu et al. 2021b). In recent years, Fenton technology has also been used for the pretreatment of lignocellulosic biomass (Zhang and Zhu 2016; Wu et al. 2018). The essence of the Fenton technique is the reaction of H2Owith Fe2+ under acidic conditions to generate the ·OH radical (Wu et al. 2020). The ·OH radical can abstract protons from the substrate, forming organic free radicals, which can then react with other substrates. The reaction mechanism is shown in Eqs. 1-3 (Wang and Tang 2021):

Studies have shown that Fenton pretreatment effectively disrupts the lignin structure and increases cellulose accessibility, thereby enhancing enzymatic hydrolysis and fermentation efficiency. Research has demonstrated that Fenton pretreatment is effective for various biomass substrates such as crop straw, sugarcane bagasse, and corn stover, with sugar yields increasing by 1.5 to 3 times, and improved conversion efficiencies for ethanol and biogas (Zhang and Zhu 2016; Koo et al. 2017; Wu et al. 2018; Huang et al. 2019). However, this method has some limitations. Traditional Fenton reactions generally require acidic conditions (pH ≈ 3) (Clarizia et al. 2017), which leads to high consumption of acid during pretreatment, and often requires the pH to be adjusted to neutral after pretreatment, resulting in higher reaction costs. Additionally, large amounts of iron-containing wastewater are generated, causing secondary pollution or additional cost enhancement for treatment (Fernandez et al. 1999; Andreozzi et al. 2002).

To address the limitations of traditional Fenton treatments, research has gradually shifted toward Fenton-like systems. The core mechanism of Fenton-like processes lies in the metal redox cycling on the catalyst surface (e.g., Fe3⁺/Fe2⁺ or other transition metal pairs), which can continuously activate oxidants to generate reactive species such as ·OH radicals without relying on excess soluble Fe²⁺. This alleviates the problems of iron ion leaching and iron sludge accumulation. This mechanism allows the reaction to be no longer limited to the instantaneous release of free radicals. As a consequence, it usually exhibits more sustained oxidative activity and broadening the applicable pH range, while improving the catalyst’s stability and recyclability (Lin and Gurol 1998). Catalysts such as BiFeO3, FeVO4, carbon-based composite catalysts, iron oxides, and Fe-Mn composite oxides have been shown to be effective for lignocellulosic biomass pretreatment (Koo et al. 2017; Zhang et al. 2019b; Liang et al. 2024). These Fenton-like catalysts generally exhibit better lignin removal and saccharification efficiency than traditional Fenton in lignocellulosic biomass pretreatment. For example, Fe3O4 has bridged the gap from homogeneous to heterogeneous catalysis (Fernandez et al. 1999; Koo et al. 2017); BiFeO3 generates higher concentrations and longer-lived ·OH in rice straw and sugarcane bagasse treatments, improving saccharification rates more than twice compared to traditional Fenton (Zhang et al. 2019b). The FeVO4 catalyst, with Fe3⁺ and V5⁺ metal ions both catalyzing H2O2, exhibited superior sugar conversion capability compared to ɑ-Fe2O3, Fe3O4, ɑ-FeOOH, and FeS2 (Liang et al. 2024).

Furthermore, the combination of Fenton technology with other pretreatment methods has become a recent research focus, such as the synergy of Fenton with photochemical processes (Mahy et al. 2023), cavitation (Lee and Han 2021; Li et al. 2024; Askarniya et al. 2025), and deep eutectic solvents (Gong et al. 2024). Photo-Fenton accelerates the generation of free radicals under weak acidic conditions by promoting the photoreduction of Fe3⁺ and the photodegradation of H2O2 (Mahy et al. 2023); sonochemical Fenton utilizes the high temperatures, pressures, and intense shear forces generated by ultrasonic cavitation to promote the cleavage of H2O2 and water molecules, producing ·OH and enhancing the structural disruption of lignocellulose (Li et al. 2024; Askarniya et al. 2025). These studies show that the coupling of Fenton with other pretreatment methods offers synergistic benefits, significantly outperforming traditional Fenton in terms of lignin removal and saccharification efficiency.

In summary, Fenton and Fenton-like technologies have broad application prospects in lignocellulose pretreatment, especially Fenton-like methods, which overcome the reliance on acidic conditions and iron sludge issues in traditional Fenton processes, thereby enabling catalyst recyclability. However, some Fenton-like catalysts still face issues such as complex synthesis processes, high preparation costs, and low recycling efficiency. Additionally, combinations of Fenton with light, deep eutectic solvents, and cavitation methods show synergistic advantages in efficiency, economics, and environmental friendliness, providing new insights for enhancing pretreatment efficiency.

Alkaline hydrogen peroxide pretreatment

Hydrogen peroxide (H2O2) is an environmentally friendly chemical oxidant with strong oxidative capabilities. Alkaline hydrogen peroxide (AHP) technology is a selective oxidation method for lignin removal, typically performed under mild conditions (at ambient pressure and temperatures ranging from 25 to 100 °C), offering low energy consumption and good environmental adaptability (Mun and Mun 2024). The AHP can effectively generate ·OH and O2·− under alkaline conditions (at a pH of approximately 11.5) (Gould 1984), with ·OH capable of cleaving ether bonds (such as β-O-4 ) and side chains in lignin. This initiates a series of reactions, such as ring opening of aromatic structures and the introduction of carboxyl groups, thus facilitating lignin removal and cellulose exposure (Li et al. 2012; Maziero et al. 2012). Concurrently, the alkaline conditions promote the saponification of ester bonds between lignin and hemicellulose, partially dissolving the hemicellulose and thereby enhancing cellulose accessibility for subsequent enzymatic hydrolysis (Whistler 1993). After AHP treatment, the biomass structure typically exhibits fiber disintegration, increased porosity, expanded specific surface area, and improved crystallinity, significantly enhancing enzymatic hydrolysis efficiency (Cui and Bai 2025). For instance, a critical saturation point (CSP) for lignin removal in bamboo was identified, with a significant increase in removal as H2O2 concentration rose from 0% to 2%, but no further improvement beyond 2% (Huang et al. 2022). Furthermore, the AHP can be coupled with other methods for enhanced results (Devadasu et al. 2020; Askarniya et al. 2025; Li et al. 2025).

Despite its excellent performance at the experimental level, the industrial application of AHP faces several critical challenges regarding safety and economics. First, the safety issues associated with AHP mixtures must be strictly addressed. High concentrations of hydrogen peroxide in strongly alkaline solutions can undergo rapid, exothermic decomposition, leading to rapid gas evolution and potential explosion hazards (Hart and Rudie 2007). Second, practical applications face economic limitations, such as the high cost of H2O2, significant alkaline solution consumption, and longer reaction times. Therefore, rigorous control of H2O2 concentrations, precise temperature regulation, and appropriate pressure-relief reactor designs are critical prerequisites for safe operations. Process optimization is urgently needed to reduce the H2O2 dosage or combine AHP with other physical/chemical methods to improve pretreatment efficiency, ensure safety, and control costs, thereby facilitating its industrial scale-up in lignocellulosic biorefining.

Peracetic acid pretreatment

Peracetic acid (PAA) is an organic peracid with strong oxidizing properties, bactericidal activity, and the ability to selectively remove lignin. Its chemical structure consists of a peroxide group (-OOH) bonded to an acetyl group (CH3CO-), with a high oxidation potential of 1.748 V (Shi et al. 2022). The molecular structure of PAA contains an active peroxide bond (-O-O-), which has a lower bond energy compared to hydrogen peroxide, allowing for efficient lignin degradation under mild conditions. The PAA is typically synthesized by the reaction of hydrogen peroxide and acetic acid under sulfuric acid catalysis (Zhao et al. 2007; Kundu et al. 2021). Alternatively, it can be generated in situ by perhydrolase enzymes, reducing costs and transportation risks (Hu et al. 2022). Its action mechanism involves electrophilic attack on electron-rich sites in the lignin molecule by hydrogen ion (H⁺) generated under acidic conditions, initiating a series of oxidative degradation reactions. This can oxidize the hydroxyl groups in lignin side chains to carbonyl groups, cleave the β-O-4 bond in lignin, reduce the molecular weight, and introduce hydrophilic groups (Yin et al. 2011; Shi et al. 2022). As a result, the depolymerized lignin fragments dissolve in water, effectively removing lignin from lignocellulosic biomass (Teixeira et al. 2000).

PAA pretreatment is typically performed under mild conditions below 80 °C to avoid excessive cellulose degradation and PAA decomposition (Yin et al. 2011; Hu et al. 2022). Numerous studies have demonstrated that PAA pretreatment exhibits good lignin removal efficiency for a variety of biomass types (Darus et al. 2022). PAA can also be coupled with other methods to optimize pretreatment effectiveness (Meng et al. 2022). Compared to Fenton pretreatment, the PAA pretreatment has been shown to be effective for plant biomass with higher lignin content and crystallinity index (CrI) (Xiao et al. 2017).

However, this method has some limitations. On the one hand, the selective lignin removal capability of PAA is lost under more severe conditions (high PAA concentration, high temperature, and metal ions involved), leading to degradation of cellulose and hemicellulose. On the other hand, the chemical synthesis of PAA presents high costs and explosion risks, limiting its large-scale application (Hu et al. 2022). Additionally, cost issues continue to hinder the industrialization of this technology. Therefore, current research focuses on improving the efficiency of PAA pretreatment and exploring its coupling with other processes such as alkali treatment, acid treatment, or steam explosion to enhance pretreatment effectiveness and reduce costs.

Persulfate pretreatment

Advanced oxidation technologies can be divided into sulfate radical-based advanced oxidation processes (SR-AOPs) and hydroxyl radical-based advanced oxidation processes (HR-AOPs), based on the type of free radical generated. Studies have shown that both ·OH and SO4·− possess strong oxidizing abilities (Qiu et al. 2020). Compared to ·OH, SO4·− have a longer half-life (30-40 μs), broader pH applicability, and higher stability (Wang et al. 2020; Liu et al. 2023), which has led to increasing research interest in recent years.

SR-AOP involves the activation of peroxymonosulfate (PMS) and peroxydisulfate (PDS), breaking the O-O bond to generate strong oxidizing free radicals, such as ·OH, SO4·−, and O2·−. For example, in the case of PDS, the activation mechanism involves two typical reactions: one is the O-O bond cleavage of PDS under high temperature, light, or ultrasound, producing two SO4·−, as shown in Eq. 4; the other is the electron transfer from transition metals, carbon-based materials, or other electron donors to generate a single SO4·−, as shown in Eq. 5. The SO4·− can further react to produce ·OH (Eq. 6):

The reactive ·OH and SO4·− radicals can attack lignin, breaking it down, as well as targeting internal bonds in hemicellulose and glycosidic bonds in cellulose and hemicellulose, thereby improving the pretreatment efficiency of lignocellulose and yielding other derivative products. In recent years, numerous studies have validated the feasibility of PMS/PDS pretreatment (Ahmed et al. 2016; Zhang et al. 2024c). In particular, the potassium peroxymonosulfate (PPMS) system has shown excellent performance in pretreating sugarcane bagasse, achieving a lignin removal of 87.5% and a sugar conversion efficiency of 90.3%, while maximizing cellulose retention. This system also generates more free radicals (·OH and SO4·−) than the PDS system, exhibiting higher selectivity for lignin degradation (Li et al. 2023).

Persulfate (PS) can be activated via several methods, including energy activation (e.g., UV, ultrasound, heat), catalyst activation (e.g., transition metals, non-metals such as carbon-based materials), alkaline activation (e.g., NaOH), and electrochemical activation (e.g., using boron-doped diamond electrodes) (Peng et al. 2021). Each activation method has certain drawbacks. Thermal activation is effective but requires high energy consumption and harsh reaction conditions; ultrasonic activation requires complex instrumentation and has low efficiency when used alone, thus often needing to be coupled with other methods (Fagan et al. 2020; Moradnia et al. 2022). While homogeneous transition metal ions exhibit high initial reactivity for PS activation, they are prone to rapid oxidation into higher valence states during the process (e.g., the rapid conversion of Fe²⁺ to Fe³⁺). This restricts the continuous activation of PS and typically results in the generation of metal sludge (Wang and Wang 2018). Alkaline activation of PS is effective for lignocellulosic biomass treatment, but it requires a strong alkaline environment, which may lead to environmental pollution (Song et al. 2023); UV activation is renewable, eco-friendly, and considered a promising activation method, though solar activation of PS is less efficient, making the development of effective photocatalysts a key issue (Yang et al. 2021; Li et al. 2022); heterogeneous metal activation and carbon-based carriers must consider economic and recyclability issues (Mei et al. 2021). Carbon-based catalysts such as carbon nanotubes, graphene, and biochar have been used to activate PS, but their catalytic processes involve non-radical activation pathways, and the activation mechanism requires further study (Wu et al. 2022). Despite these challenges, recent studies have reported the development of a range of advanced PS activation strategies that exhibit strong activation performance in lignocellulose conversion. For example, a composite material of nano zero-valent iron and biochar was developed to activate persulfate, demonstrating excellent activation efficiency (Qu et al. 2024; Guo et al. 2025).

It is important to note that during the reaction process, persulfate oxidation systems generate sulfate ion as a by-product. If not handled properly, this may lead to the accumulation of salts in wastewater, thereby increasing the burden of subsequent treatment and posing potential environmental risks (Liu et al. 2023). Therefore, related research needs to focus on improving pretreatment efficiency while managing by-product control and waste liquid management. In terms of economics, HR-AOPs have lower unit costs compared to SR-AOPs (Crincoli and Huling 2020), but PS has a lower O-O bond dissociation energy (140 kJ/mol vs. 213 kJ/mol for H2O2). A smaller oxidant dosage is typically required to achieve effective activation, partially offsetting the higher unit price. The SR-AOPs have a broader pH adaptability, and under certain activation methods such as transition metal activation, the cost of SR-AOP pretreatment can be lower than that of HR-AOP. For example, PDS pretreatment required only 0.2 g/g of oxidant to achieve the same enzymatic hydrolysis efficiency as the Fenton process (0.85 g/g), which resulted in approximately six times lower costs when reagent unit prices were considered (Ahmed et al. 2016).

In summary, SR-AOP can activate persulfate through various methods to generate SO4·−, exhibiting excellent lignin removal and saccharification capabilities enhancement in lignocellulosic pretreatment. However, challenges such as energy consumption, by-product control, and catalyst costs remain key obstacles. Future research needs to focus on improving free radical generation efficiency while ensuring environmental and economic feasibility to promote the practical application of SR-AOP in the clean conversion of lignocellulose.

Ozone pretreatment

Ozone is a highly reactive gas with strong oxidizing properties, possessing a high redox potential (+2.07 V). It can react with C-C, C-N, and their double or triple bonds, and has been widely used for environmental applications such as dye degradation and water purification (M’Arimi et al. 2020). Similar to most dye molecules, lignocellulose is rich in aromatic structures and unsaturated bonds, which makes ozone not only an ideal oxidant for water treatment but also a unique agent for the selective degradation of lignin.

Ozone degradation of lignin can proceed through two pathways: direct oxidation and indirect oxidation (Hoigné and Bader 1983). Direct oxidation involves ozone molecules acting as electrophilic reagents, directly attacking electron-rich groups in lignin. This process occurs under mild conditions and can be performed at ambient temperature and pressure. It exhibits high selectivity and preferentially degrades lignin (which contains many unsaturated bonds) while retaining over 90% of the cellulose and hemicellulose in lignocellulose pretreatment by ozone (Travaini et al. 2013). However, the reaction rate is relatively slow and limited by the diffusion efficiency of ozone molecules, with the lignin degradation being only about one-third that of indirect oxidation. Indirect oxidation is dominant under alkaline conditions, where ozone decomposes to generate ·OH. The oxidation potential of ·OH radical (2.80 V) is higher than that of O3, making it more efficient for lignin degradation, with a higher radical transfer rate and better penetration into biomass pores. However, indirect oxidation has lower selectivity and requires precise control of pH and reaction time, making industrial control more challenging. Ozone can also cooperate with H2O2 to generate more ·OH radical, enhancing the overall oxidation capacity (Staehelin and Hoigne 1982; Glaze and Kang 1989; Adams et al. 1994). Relevant reaction processes include reactions in Eqs. 7- 9:

The effectiveness of ozone pretreatment is significantly affected by reaction time, ozone concentration, and moisture content. Moderate moisture can facilitate ozone diffusion, but excessive water films reduce gas-solid mass transfer efficiency, and prolonged reaction times can lead to cellulose degradation (Zhang et al. 2024a). Studies have shown that ozone not only effectively removes lignin but also disrupts the crystalline structure of cellulose, increasing its accessibility for enzymatic hydrolysis (Zhang et al. 2024a). Ozone has been shown to have good pretreatment effects on various lignocellulosic biomasses (Travaini et al. 2013; Andersen et al. 2019; Shamjuddin et al. 2021). In addition to its standalone effect, ozone can also be combined with other methods to further improve sugar yield (Perrone et al. 2016; Orduña Ortega et al. 2020; Li et al. 2021). For example, research has used an ozone-alkali-ultrasound combined system to treat straw, achieving a sugar conversion rate of up to 85% (Perrone et al. 2016).

Although ozone pretreatment has significant advantages in selectivity and environmental friendliness, the generation of ozone requires a substantial amount of energy (36 MJ kg⁻¹ of ozone), and the required dosage in pretreatment is also high, leading to relatively high operational costs (Osuna-Laveaga et al. 2020). Therefore, reducing ozone energy consumption and improving ozone utilization efficiency are key to achieving industrial-scale application. Future research directions include the development of low-energy ozone generation devices (Shamjuddin et al. 2021), optimization of reactors (Orduña Ortega et al. 2020), use of catalyst-assisted systems, and synergies with other methods, along with economic and life cycle analysis to promote large-scale application.

Photocatalytic pretreatment

Photocatalysis refers to the use of ultraviolet (UV) or visible light as energy to degrade lignin. However, ultraviolet irradiation alone requires prolonged exposure, which limits the overall photocatalytic efficiency. To overcome this limitation, photocatalysts are commonly introduced to enhance lignocellulose degradation. These photocatalysts are generally classified as homogeneous or heterogeneous systems. Homogeneous photocatalysis typically relies on ·OH generated from traditional Fenton reactions to drive oxidative degradation. Under light irradiation, the traditional Fenton system can synergistically promote the generation of ·OH with Fe2⁺ (Eq. 10), and studies have shown that light can reduce the cost of the traditional Fenton system and improve lignin removal (Yang et al. 2018). However, this system has limitations such as iron ion loss, the need for acidic conditions, and potential secondary pollution, which restrict its application.

The heterogeneous photocatalytic process mainly utilizes semiconductor photocatalytic materials (such as TiO2, Bi2O3, Fe2O3, etc.) for photocatalysis. Taking TiO2, a widely used photocatalyst, as an example, when the energy irradiated on the photocatalyst exceeds its bandgap, electron-hole pairs (TiO2(h+)) and free electrons (e⁻) are generated within the semiconductor (Lee et al. 2016; Yang and Wang 2018), as shown in reaction (11):

The electron-hole pairs (TiO2(h+)) react with H2O and OH⁻ on the surface of the material, generating ·OH (Eqs. 12 and 13) (Yang and Wang 2018). The (TiO2(h+)) can also directly react with the substrate (RH), as shown in reaction (14).

The e⁻ reacts with O2 on the surface of the material, generating O2·− and the e⁻ further oxidizes O2·− to generate H2O2, as shown in reactions (15) and (16). The interactions among e⁻, O2·−, and H2O2 further generate ·OH (reactions (17) and (18)) (Lee et al. 2016). The ·OH produced in reactions (12), (13), (17), and (18) react with the substrate, thus degrading lignin and hemicellulose.

Among many semiconductor-based photocatalytic materials, TiO2 is widely studied due to its non-toxicity, stability, corrosion resistance, and absence of secondary pollution. It has been shown to effectively degrade lignin and improve enzymatic sugar yields (Alvarado-Morales et al. 2017; Lee et al. 2019; Sabeeh et al. 2020). However, its application still faces challenges, such as activation only under UV light, easy recombination of photogenerated charge carriers, and difficulty in recovering powdered catalysts. To address these shortcomings, researchers have proposed modification strategies such as ion doping, noble metal deposition, semiconductor composites, and carbon-based material loading to expand the visible light response range and improve the electron-hole separation efficiency (Park et al. 2013; Elleuch et al. 2020; Zhang et al. 2021; Xu et al. 2023). In addition to TiO2, photocatalyst materials such as Bi2O3, Fe2O3, ZnO, and ZnIn2S4 have also shown various advantages in terms of visible light response, stability, and selectivity (Zewde et al. 2019; Awais et al. 2020; Kumar et al. 2021; Cao et al. 2024).

In recent years, photocatalytic pretreatment has also gradually been combined with other processes to overcome the limitations of single methods (Yang et al. 2018; Jia et al. 2022). For example, the TiO2/UV/H2O2 synergetic system has significantly removed lignin and improved enzymatic sugar yield during the treatment of straw and sisal waste (Yang et al. 2018). Overall, photocatalytic pretreatment offers significant advantages such as mild conditions, green processes, and controllability. However, its industrial application is still limited by insufficient photon utilization, difficulties in reactor scaling, and high energy consumption costs. Future research should focus on designing highly efficient visible-light-responsive catalysts, optimizing light fields and reactor structures, and coupling photocatalysis with other pretreatment methods to achieve efficient hierarchical conversion of lignocellulose and promote the greening of biorefining processes.

Electrochemical pretreatment

Electrochemical pretreatment technology is a synergistic method that combines electrolysis with chemical reactions. It offers advantages such as being environmentally friendly, producing minimal by-products, strong controllability, and requiring no external chemical oxidants (Stiefel et al. 2016; Garedew et al. 2021). In recent years, it has gradually been applied to the pretreatment of lignocellulosic biomass (Du et al. 2020). This method applies a direct current electric field to generate highly active free radicals (such as ·OH) in the reaction system, which initiate the depolymerization of lignin (Wang et al. 2015; Panigrahi and Dubey 2019). It also utilizes effects such as electrophoresis, electroosmosis, and ohmic heating to promote structural disruption and component dissolution (Shao et al. 2014; Panigrahi and Dubey 2019). Common electrode materials include PbO2, IrO2, Ti/Sb, Ti/PbO2, Ni, and graphite (Di Marino et al. 2016; Cai et al. 2018; Di Fidio et al. 2021). For instance, the use of Pb/PbO2 anodes and Cu/Ni-Mo-Co cathodes in alkaline solutions was shown to effectively treat corn stover, achieving lignin degradation with the simultaneous production of hydrogen. After 6 cycles of electro-catalysis, the lignin product conversion efficiency reached 96.8% (Cai et al. 2018). Furthermore, saponification reactions can occur under high pH conditions, further altering the lignin structure and enhancing biomass digestibility (Di Marino et al. 2016).

Although electrochemical methods show unique advantages in improving lignocellulose degradability and achieving high-value utilization of lignin (Wijaya et al. 2020), their practical application is still limited by issues such as electrode passivation and corrosion, increased energy consumption at high current densities, and the generation of inhibitory by-products (Shao et al. 2014). Current research mostly remains at the laboratory stage, with a lack of overall system integration and energy efficiency assessments for continuous and large-scale operations. To address these bottlenecks, research is gradually shifting towards material and process optimization, such as developing low-cost, highly active, and corrosion-resistant novel electrode materials, or designing compact and efficient reactor structures (Liu et al. 2012; Bawareth et al. 2019; Zhu et al. 2020). Additionally, synergistic strategies are receiving increasing attention, such as the electro-Fenton system (Liu et al. 2012), the combination of electrochemical and photocatalysis (Fernandes et al. 2021), the combination of electrochemistry and peracetic acid (Yuan et al. 2021), or integration with deep eutectic solvents or ionic liquids (Fernandes et al. 2021). These studies indicate that synergistic applications provide possibilities for overcoming the current limitations of electrochemical methods and enhancing their role in the efficient conversion of lignocellulose.

Wet air oxidation pretreatment

Wet air oxidation (WAO) is one of the most commonly used lignocellulosic pretreatment methods, typically carried out at 125 to 250 °C and 3 bar to 35 bar pressure conditions to dissolve lignin and hemicellulose (McGinnis et al. 1983). The WAO process generates free radicals (such as ⋅OH, ⋅HO2, ROO·) through the interaction of oxygen with the C-H bonds in organic compounds, initiating chain reactions that disrupt the lignocellulosic structure and produce low-molecular-weight products such as organic acids (Tembhekar et al. 2015; Demesa et al. 2020). The reaction mechanism is as follows:

Oxygen oxidizes the C-H bonds in organic compounds under high temperature and high pressure, generating organic free radicals (R⋅) and HO2⋅ (reaction (19)). These R⋅ react with molecular oxygen to form organic peroxyl radicals (ROO⋅) (reaction (20)).

The rapid decomposition of hydrogen peroxide generates ⋅OH (reaction 21).

HO2⋅ and ·OH oxidize organic compounds, generating more R⋅ (reactions 22 and 23).

ROO⋅ can extract a hydrogen atom from other organic compounds (reaction (24)), leading to the formation of organic peroxides, or ROO⋅ can react with each other (reaction (25)) to generate stable products.

The WAO process is an exothermic reaction, so once the reaction is initiated, some of the energy can be self-supplied, reducing the need for external energy input (Gout et al. 2022). Additionally, this method does not require large amounts of expensive chemical reagents, and the by-products are mainly organic acids and soluble sugars, making the overall process relatively low in operating costs (Szijártó et al. 2009; Poveda-Giraldo and Cardona Alzate 2025). In recent years, the introduction of transition metal oxides (Cu, Co, Mn, Fe, Zn) and noble metals (Ru, Rh, Pt, Ir, Pd) as catalysts has further reduced the dependence on high temperature and high pressure (Tekin et al. 2022). Furthermore, alkaline WAO, alkaline peroxidized WAO, and catalytic WAO technologies have been developed. These methods exhibit higher cellulose degradation rates and lignin removal efficiencies compared to uncatalyzed WAO (Castro and Agblevor 2022). For example, wheat bran was pretreated by WAO at 170 °C and 12 bar, followed by forward osmosis (FO) membrane concentration, which yielded a xylose concentration of 13.75 g/L (Bhavana et al. 2023). Efficient depolymerization of alkaline lignin was achieved under WAO pretreatment at 150 °C and 1000 psi, leading to the generation of vanillic acid (Irmak et al. 2020). Similarly, the use of CuSO4/Fe2O3 catalysts during WAO treatment of bamboo at 195 °C and 6 bar yielded 14.9 wt% bio-oil, with vanillin identified as the primary product (McCallum et al. 2021).

The main factors affecting WAO efficiency include the nature of the treated material, reaction temperature, reaction time, reaction pressure, solution pH, and the addition of catalysts. Longer residence times favor lignin removal and enhance cellulose recovery. At temperatures exceeding 100 °C, the rising temperature increases dissolved oxygen concentration due to elevated saturated vapor pressure, thereby promoting lignin oxidation, although the solubility of hemicellulose decreases. Moderate pressurization can further facilitate lignin degradation by increasing dissolved oxygen levels. However, the effect of pressure on cellulose recovery is relatively limited, and excessively high pressures significantly increase equipment costs; therefore, practical applications should balance energy consumption and treatment efficiency to determine an appropriate operating pressure (Morone et al. 2018b). Overall, WAO demonstrates good pretreatment effects and has high application potential, but issues related to equipment corrosion and energy consumption have yet to be adequately addressed. Future developments should focus on coupling with other pretreatment methods, optimizing catalysts and reactors, and achieving efficient component separation and high-value utilization while reducing energy consumption and operational costs.

Cavitation-based advanced oxidation processes

Cavitation-based advanced oxidation processes (Cavitation-AOPs) have recently been considered one of the most promising technologies for lignocellulose pretreatment. The core mechanism involves the formation, growth, and violent collapse of bubbles in the liquid (Madison et al. 2017). During bubble collapse, extreme conditions are created locally, with instantaneous temperatures reaching 10,000 K and pressures exceeding 500 atm, accompanied by intense shear forces, turbulence, and microjets, which generate strong oxidative species such as ·OH, ⋅H and O2·− (Badve et al. 2014; Madison et al. 2017; Devadasu et al. 2020). These physical-chemical effects can effectively break down the dense structure of lignocellulose, promote lignin dissolution, and enhance enzymatic hydrolysis accessibility. Based on the energy input method, cavitation can be divided into two types: ultrasonic cavitation and hydrodynamic cavitation.

Ultrasonic cavitation (UC) refers to the generation, and collapse of bubbles induced by alternating compression and rarefaction in the liquid phase within the sonic frequency range of 20 kHz to 2 MHz. This process simultaneously generates free radicals and strong physical disruption (Passos et al. 2014; Costa et al. 2020). In lignocellulosic pretreatment, ultrasound can break the lignin-carbohydrate bonds, disrupt the crystalline structure of cellulose, and enhance solvent permeability, showing high lignin removal efficiency (Singh et al. 2014). Studies have shown that ultrasonic-assisted hydrogen peroxide pretreatment of sawdust increased lignin removal by 2 to 3 times (Devadasu et al. 2020). In the treatment of sisal waste, ultrasound combined with a UV/TiO2/H2O2 system achieved over 70% lignin removal and significantly improved enzymatic sugar yields (Yang et al. 2018). After pretreating rice straw for fermentation to produce lactic acid, combinations of ultrasound with acid, alkali, or H₂O₂ increased lactic acid yields by 100%, 104%, and 109%, respectively (Askarniya et al. 2025). Ultrasonic cavitation has significant advantages in lignin removal and structural disruption, and it can synergize with various chemical methods; however, its application is limited by high energy consumption, high equipment costs, and difficulty in large-scale promotion.

Hydrodynamic cavitation (HC) involves the generation of local pressure drops in the liquid, induced by devices such as venturi tubes, orifices, or valves, which reduce fluid pressure below the saturated vapor pressure, leading to bubble formation and collapse. Its mechanism is similar to that of UC, generating high local temperatures and pressures, as well as free radicals, which disrupt the biomass structure through high-speed microjets and shock waves (Gogate and Pandit 2005; Madison et al. 2017). Alkali-assisted HC has shown excellent lignin removal effects in the pretreatment of various lignocellulosic materials such as sugarcane bagasse, reed, and miscanthus (Kim et al. 2015; Terán Hilares et al. 2017; Bimestre et al. 2020; Lee and Han 2021; Tsalagkas et al. 2021). Compared to ultrasound, the advantages of HC lie in its simple equipment structure, requiring only pumps and pipes, low energy consumption, and ease of scaling up to industrial levels. However, its cavitation intensity and free radical production rates are typically lower than those of ultrasound, which may limit its effectiveness in standalone applications.

Overall, cavitation-based AOPs provide an important green pretreatment pathway for lignocellulose. Future research should focus on improving reactor design to enhance energy conversion and cavitation uniformity; combining cavitation with other oxidants (such as H2O2, ozone, persulfates) to enhance treatment effectiveness; and conducting techno-economic and life cycle assessments to verify its feasibility in the industrialization of biorefining.

Potential Impacts of Residual Metals and Oxidation By-products on Downstream Bioconversion

Advanced oxidation pretreatment frequently involves transition metals (e.g., Fe, Co, Mn) and strong oxidants, raising concerns about the potential influence of residual metal species and oxidation by-products on subsequent enzymatic hydrolysis and fermentation. In iron-based systems such as Fenton and Fenton-like processes, soluble Fe²⁺/Fe³⁺ species may remain associated with the solid or liquid fractions after pretreatment. Although iron is an essential micronutrient for many microorganisms, excessive metal concentrations can interfere with enzyme activity through nonspecific binding, alteration of redox conditions, or promotion of secondary oxidative reactions. It is important, however, to distinguish between transient radical species and stable residues (Di Fraia et al. 2024). Reactive radicals such as ·OH and SO4·− exhibit extremely short lifetimes (typically in the nanosecond to microsecond range) and therefore they do not persist into downstream hydrolysis or fermentation stages (Zhang et al. 2024b). Observed inhibitory effects are more likely related to excessive metal accumulation or to soluble lignin-derived oxidation products generated under severe conditions. Partial oxidation of lignin can produce low-molecular-weight phenolics, quinone-type intermediates, organic acids, or aldehydes, some of which are known to affect cellulase activity or microbial metabolism when present at high concentrations (Liu et al. 2021b) Nevertheless, under controlled oxidant dosage and optimized reaction conditions, many studies report enhanced enzymatic digestibility without significant inhibition, indicating that selective modification of lignin-rich domains can improve accessibility while maintaining downstream compatibility (Toghiani et al. 2024; Zhang et al. 2024c). In practice, washing, neutralization, solid-liquid separation, or catalyst recovery steps are typically employed to minimize residual metal and soluble inhibitor levels prior to enzymatic processing (Zhang et al. 2024c). Despite these mitigation strategies, systematic evaluation of residual metal thresholds and inhibitor tolerance in integrated bioconversion systems remains limited, highlighting the need for standardized reporting and coupled enzymatic performance assessments in future studies.

Comparison of the Advantages, Disadvantages, and Application Effects of Different AOP Pretreatments

The various AOP pretreatment methods of lignocellulosic biomass are compared in Table 1, which outlines their advantages and disadvantages and analyzes their application status. Overall, the Fenton system has been widely studied and applied due to its ability to efficiently degrade lignin and hemicellulose by rapidly generating ·OH under mild conditions. However, its dependence on acidic conditions and the issue of iron salt residue limit its industrial potential. The Fenton-like methods, by introducing heterogeneous catalysts, have expanded the pH range, and improved catalyst recyclability, though there is still room for improvement in stability and cost reduction.

Alkaline hydrogen peroxide (AHP) offers the advantages of being environmentally friendly and operating under mild conditions, effectively breaking down lignin structures and promoting cellulose accessibility. However, it requires a large amount of oxidants and has long reaction times and is still primarily at the laboratory and pilot study stages. Peracetic acid (PAA) has gained attention due to its higher oxidation potential and selective lignin removal, working efficiently at lower temperatures. Its lack of stability and high synthesis cost limit its widespread application. Persulfates (PDS/PMS) generate SO4·−, which have a longer lifetime and higher stability than ·OH, showing excellent lignin removal ability and a broad pH applicability range. However, activation methods and system economics still need optimization. Ozone is highly selective for the degradation of aromatic structures and can remove lignin while retaining carbohydrates, but its high energy consumption and complex equipment requirements limit its feasibility. Photocatalysis and electrochemical methods are notable for their environmental friendliness and controllability. The former relies on light to generate ·OH, while the latter uses electrode reactions for oxidative decomposition. Both avoid the introduction of large amounts of external chemicals, but photon utilization, electrode material stability, and energy efficiency issues remain challenges for large-scale applications. Wet air oxidation (WAO) can efficiently degrade lignin structures in a short time and offers potential for high-value utilization of by-products under certain conditions, though it requires harsh operating conditions and high equipment requirements. Cavitation oxidation (including UC and HC) generates high temperatures, pressures, and free radicals through bubble collapse, significantly improving substrate structure, and can synergize with acids, alkalis, or peroxides. However, its high energy consumption and limited cavitation intensity in hydrodynamic cavitation still require further verification for industrial applications.

In general, different AOP methods have distinct characteristics in terms of efficiency, selectivity, and application potential. Fenton, AHP, and PAA can achieve efficient lignin removal under mild conditions; ozone offers high selectivity for aromatic structure degradation and can remove lignin while retaining carbohydrates; WAO demonstrates rapid lignin degradation and potential for by-product valorization under high temperature and high pressure. Photocatalysis, electrochemical methods, and cavitation processes have been widely studied for their green, sustainable, and controllable properties. Persulfate oxidation, which produces SO4·− with long half-lives, high stability, and strong oxidative capacity, has seen rapid development in recent years, particularly in photocatalytic activation, transition metal activation, and carbon-based catalyst activation. It may become one of the most promising AOPs in the future.

Table 2 presents typical case studies of AOP pretreatment of lignocellulosic biomass and their application effects. From Table 2, it is evident that different AOP methods exhibit varying pretreatment effects under different raw materials and operating conditions.

Fenton, Fenton-like, alkaline hydrogen peroxide, peracetic acid, and persulfate have particularly outstanding pretreatment effects. Photocatalysis and electrochemical methods show milder effects but still effectively improve enzymatic hydrolysis rates. In addition, ozone, wet air oxidation, and cavitation methods also show good potential in lignin removal and enhancing enzymatic hydrolysis efficiency. The differences in application effects reflect the potential influence of multiple factors such as raw materials, pretreatment conditions, and catalysts, with further optimization of operating conditions enhancing the overall pretreatment effect.

Table 1. Comparison of the Advantages, Disadvantages, and Application Status of Different AOP Pretreatments

Comparison of the Advantages, Disadvantages, and Application Status of Different AOP Pretreatments

Comparison of the Advantages, Disadvantages, and Application Status of Different AOP Pretreatments

Table 2. Application Cases of Various AOP Pretreatment Methods

Application Cases of Various AOP Pretreatment Methods

PROSPECTS FOR AOP PRETREATMENT

Advanced oxidation processes (AOPs) can generate highly oxidative free radicals such as ·OH, SO4·−, and O2·−, offering high efficiency, environmental friendliness, and non-toxicity in lignocellulose pretreatment. Compared to traditional acid-base and physical methods, AOPs have certain advantages in terms of environmental impact and energy consumption. Currently, research on AOP pretreatment of lignocellulose is mainly at the laboratory or pilot stage, with no large-scale industrial application, primarily due to economic feasibility issues. On the one hand, most AOP systems rely on high-cost oxidants, catalysts, or reaction equipment, leading to high operating costs. On the other hand, there is a lack of comprehensive techno-economic analysis (TEA) of AOPs, making it difficult to evaluate the investment cost versus the economic or environmental benefits generated. To promote the industrialization of AOPs in the future, several approaches can be considered: (1) Conducting techno-economic analysis (TEA) and life cycle assessments (LCA) to determine whether a process has investment benefits or needs further optimization for large-scale industrial application; (2) Focusing on high-value utilization of pretreatment products to directly increase the process’s profitability; (3) Further understanding the radical reaction mechanisms and by-product generation pathways to achieve more precise process control and optimize process parameters (such as temperature, pressure, and the ratio of raw materials to oxidants); (4) Developing new low-cost, high-efficiency, recyclable catalysts, optimizing reactor design, or developing dual/multi-mechanism synergistic technologies to improve reaction efficiency; (5) Promoting the coupling of AOPs with green energy sources (such as solar energy, bioelectricity) and downstream product upgrading systems to improve overall energy efficiency.

Overall, although AOP pretreatment currently faces economic and technical barriers for large-scale application, it offers significant advantages in selective oxidation, reaction activity, environmental sustainability, and the diversity of system activation methods and synergistic effects. The potential for process optimization is vast, and AOPs are considered to have a strategic position in future biorefining systems. With continued technological innovation and system integration, advanced oxidation technologies are expected to become key pillar technologies in the production of second- and third-generation green biofuels.

CONCLUDING STATEMENTS

This review has provided a comprehensive analysis of nine major advanced oxidation processes (AOPs) for lignocellulosic biomass pretreatment, including Fenton and Fenton-like, alkaline hydrogen peroxide, peracetic acid, persulfate, ozonolysis, photocatalytic, electrochemical, wet air oxidation, and cavitation. These methods show significant potential for enhancing lignin removal and enzymatic efficiency, particularly under mild conditions. Among these, persulfate, wet air oxidation, and combinations of multiple pretreatment technologies (such as light-Fenton, alkaline H2O2-cavitation, and electrochemical-ozone-H2O2) offer the most promising prospects for future applications. To achieve large-scale industrial implementation, future research should focus on developing novel catalysts, optimizing reactor design, and integrating multiple pretreatment techniques to reduce costs and improve efficiency, ultimately advancing the sustainable utilization of lignocellulosic biomass.

ACKNOWLEDGEMENTS

This work was supported by Open project of Xinjiang Biomass Solid Waste Resources Technology and Engineering Center (KSUGCZX202408); Fundamental Research Funds for the Central Universities (No. 2662023DKPY003), China.

Author Contribution

Zhang Xueshuai: Writing – original draft, writing – review and editing; Huang Mengtian: Writing – original draft, writing – review and editing, Methodology; Long Yao: Writing – original draft, visualization; Li Qihang: Methodology; Cao Yao: Methodology; Zhou Wenbing: Conceptualization, Writing – review and editing, Methodology and Supervision; Xiao Naidong: Methodology; Cai Jianbo: Methodology.

Funding

This work was financially supported by Xinjiang Biomass Solid Waste Resources Technology and Engineering Center (KSUGCZX202408) and Fundamental Research Funds for the Central Universities (No. 2662023DKPY003), China.

Declarations

The authors declare no competing interests.

REFERENCES CITED

Adams, C. D., Scanlan, P. A. and Secrist, N. D. (1994). “Oxidation and biodegradability enhancement of 1,4-dioxane using hydrogen peroxide and ozone,” Environmental Science & Technology 28(11), 1812-1818. https://doi.org/10.1021/es00060a010

Ahmed, M. A., Seo, Y. H., Terán-Hilares, R., Rehman, M. S. U. R. and Han, J.-I. (2016). “Persulfate based pretreatment to enhance the enzymatic digestibility of rice straw,” Bioresource Technology 222(1), 523-526. https://doi.org/10.1016/j.biortech.2016.09.122

Alvarado-Morales, M., Tsapekos, P., Awais, M., Gulfraz, M. and Angelidaki, I. (2017). “TiO2/UV based photocatalytic pretreatment of wheat straw for biogas production,” Anaerobe 46(SI), 155-161. https://doi.org/10.1016/j.anaerobe.2016.11.002

Alvira, P., Tomás-Pejó, E., Ballesteros, M. and Negro, M. J. (2010). “Pretreatment technologies for an efficient bioethanol production process based on enzymatic hydrolysis: A review,” Bioresource Technology 101(13), 4851-4861. https://doi.org/10.1016/j.biortech.2009.11.093

Andersen, S. L. F., Castoldi, R., Garcia, J. A. A., Bracht, A., Peralta, R. A., de Lima, E. A., Helm, C. V., Moreira, R. d. F. P. M. and Peralta, R. M. (2019). “Improving enzymatic saccharification of Eucalyptus grandis branches by ozone pretreatment,” Wood Science and Technology 53(1), 49-69. https://doi.org/10.1007/s00226-018-1061-7

Andreozzi, R., D’Apuzzo, A. and Marotta, R. (2002). “Oxidation of aromatic substrates in water/goethite slurry by means of hydrogen peroxide,” Water Research 36(19), 4691-4698. https://doi.org/10.1016/S0043-1354(02)00204-X

Ashokkumar, V., Venkatkarthick, R., Jayashree, S., Chuetor, S., Dharmaraj, S., Kumar, G., Chen, W.-H. and Ngamcharussrivichai, C. (2022). “Recent advances in lignocellulosic biomass for biofuels and value-added bioproducts – A critical review,” Bioresource Technology 344(3), 126195. https://doi.org/10.1016/j.biortech.2021.126195

Askarniya, Z., Khanzada, A. K., Ciesielski, S., Wei, Z., Mąkinia, J. and Boczkaj, G. (2025). “Influence of acoustic cavitation and its combination with H2O2, acid, and alkali as a pre-treatment technique on lactic acid production from rice as a model food waste,” Ultrasonics Sonochemistry 120(9), 107422. https://doi.org/10.1016/j.ultsonch.2025.107422

Awais, M., Mustafa, M. S., Rasheed, M. A. and Jamil, F. (2020). “Metal oxides and ultraviolet light-based photocatalytic pretreatment of biomass for biogas production and lignin oxidation,” BioResources 15(1), 1747-1762. https://doi.org/10.15376/biores.15.1.1747-1762

Badve, M. P., Gogate, P. R., Pandit, A. B. and Csoka, L. (2014). “Hydrodynamic cavitation as a novel approach for delignification of wheat straw for paper manufacturing,” Ultrasonics Sonochemistry 21(1), 162-168. https://doi.org/10.1016/j.ultsonch.2013.07.006

Bansod, S. P., Makwana, K., Sarangi, P. K. and Parikh, J. K. (2024). “Advanced pretreatment processes for lignocellulosic biomass to biofuels production: Path towards circular bioeconomy,” Sustainable Chemistry and Pharmacy 39(3), 101514. https://doi.org/10.1016/j.scp.2024.101514

Bawareth, B., Di Marino, D., Nijhuis, T. A., Jestel, T. and Wessling, M. (2019). “Electrochemical membrane reactor modeling for lignin depolymerization,” ACS Sustainable Chemistry & Engineering 7(2), 2091-2099. https://doi.org/10.1021/acssuschemeng.8b04670

Behera, S., Arora, R., Nandhagopal, N. and Kumar, S. (2014). “Importance of chemical pretreatment for bioconversion of lignocellulosic biomass,” Renewable and Sustainable Energy Reviews 36(8), 91-106. https://doi.org/10.1016/j.rser.2014.04.047

Bhavana, B. K., Mudliar, S. N. and Debnath, S. (2023). “Life cycle assessment of fermentative xylitol production from wheat bran: A comparative evaluation of sulphuric acid and chemical-free wet air oxidation-based pretreatment,” Journal of Cleaner Production 423(42), 138666. https://doi.org/10.1016/j.jclepro.2023.138666

Bimestre, T. A., Júnior, J. A. M., Botura, C. A., Canettieri, E. and Tuna, C. E. (2020). “Theoretical modeling and experimental validation of hydrodynamic cavitation reactor with a Venturi tube for sugarcane bagasse pretreatment,” Bioresource Technology 311(17), 123540. https://doi.org/10.1016/j.biortech.2020.123540

Cai, P., Fan, H., Cao, S., Qi, J., Zhang, S. and Li, G. (2018). “Electrochemical conversion of corn stover lignin to biomass-based chemicals between Cu/NiMoCo cathode and Pb/PbO2 anode in alkali solution,” Electrochimica Acta 264(6), 128-139. https://doi.org/10.1016/j.electacta.2018.01.111

Cao, Z., Zhao, T., Yang, X., Jiang, W., Nie, K., Xia, W., Wang, X., Wang, L., Zhou, C., Zhang, Y., Han, G. and Ben, H. (2024). “Synergistic action of photocatalytic oxidation and alkaline degumming of hemp fibres under simulated sunlight,” Industrial Crops and Products 209(4), 118068. https://doi.org/10.1016/j.indcrop.2024.118068

Castro, Y. A. and Agblevor, F. A. (2022). “Effect of wet air oxidation on the composition and biomethanation of water hyacinth,” Biomass Conversion and Biorefinery 12(7), 2737-2748. https://doi.org/10.1007/s13399-020-00825-8

Clarizia, L., Russo, D., Di Somma, I., Marotta, R. and Andreozzi, R. (2017). “Homogeneous photo-Fenton processes at near neutral pH: A review,” Applied Catalysis B: Environment and Energy 209(10), 358-371. https://doi.org/10.1016/j.apcatb.2017.03.011

Costa, J. A. V., Freitas, B. C. B., Moraes, L., Zaparoli, M. and Morais, M. G. (2020). “Progress in the physicochemical treatment of microalgae biomass for value-added product recovery,” Bioresource Technology 301(7), 122727. https://doi.org/10.1016/j.biortech.2019.122727

Crincoli, K. R. and Huling, S. G. (2020). “Contrasting hydrogen peroxide- and persulfate-driven oxidation systems: Impact of radical scavenging on treatment efficiency and cost,” Chemical Engineering Journal 404(2), 126404. https://doi.org/10.1016/j.cej.2020.126404

Cui, M.-J. and Bai, G.-M. (2025). “Promoting enzymatic hydrolysis of corncob through alkaline hydrogen peroxide pretreatment and addition of additives,” Biomass Conversion and Biorefinery 15(8), 12753-12761. https://doi.org/10.1007/s13399-024-06067-2

Darus, L., Susana, S., Sihombing, H., Utami, A. R. I. and Mel, M. (2022). “Enzymatic hydrolysis enhancement of oil palm empty fruit bunch by Peracetic-Sulfuric acid pretreatment,” Chemical Engineering Journal 429(3), 132452. https://doi.org/10.1016/j.cej.2021.132452

Demesa, A. G., Laari, A. and Sillanpää, M. (2020). “Chapter 6 – Value-added chemicals and materials from lignocellulosic biomass: Carboxylic acids and cellulose nanocrystals,” in: Advanced Water Treatment, SILLANPää, M., ed., Elsevier, 367-436.

Devadasu, S., Joshi, S. M., Gogate, P. R., Sonawane, S. H. and Suranani, S. (2020). “Intensification of delignification of Tectona grandis saw dust as sustainable biomass using acoustic cavitational devices,” Ultrasonics Sonochemistry 63(4), 104914. https://doi.org/10.1016/j.ultsonch.2019.104914

Di Fidio, N., Timmermans, J. W., Antonetti, C., Raspolli Galletti, A. M., Gosselink, R. J. A., Bisselink, R. J. M. and Slaghek, T. M. (2021). “Electro-oxidative depolymerisation of technical lignin in water using platinum, nickel oxide hydroxide and graphite electrodes,” New Journal of Chemistry 45(21), 9647-9657. https://doi.org/10.1039/D1NJ01037A

Di Fraia, A., Di Fraia, S., Sharmila, V. G., Banu, J. R. and Massarotti, N. (2024). “Role of advanced oxidation processes in lignocellulose pretreatment towards biorefinery applications: a review on emerging trends and economic considerations,” Green Chemistry 26(15), 8461-8496. https://doi.org/10.1039/d3gc05108k

Di Marino, D., Stöckmann, D., Kriescher, S., Stiefel, S. and Wessling, M. (2016). “Electrochemical depolymerisation of lignin in a deep eutectic solvent,” Green Chemistry 18(22), 6021-6028. https://doi.org/10.1039/C6GC01353H

Dong, L., Cao, G., Zhao, L., Liu, B. and Ren, N. (2018). “Alkali/urea pretreatment of rice straw at low temperature for enhanced biological hydrogen production,” Bioresource Technology 267(22), 71-76. https://doi.org/10.1016/j.biortech.2018.05.055

Du, X., Zhang, H., Sullivan, K. P., Gogoi, P. and Deng, Y. (2020). “Electrochemical Lignin Conversion,” ChemSusChem 13(17), 4318-4343. https://doi.org/10.1002/cssc.202001187

Elleuch, L., Messaoud, M., Djebali, K., Attafi, M., Cherni, Y., Kasmi, M., Elaoud, A., Trabelsi, I. and Chatti, A. (2020). “A new insight into highly contaminated landfill leachate treatment using Kefir grains pre-treatment combined with Ag-doped TiO2 photocatalytic process,” Journal of Hazardous Materials 382(2), 121119. https://doi.org/10.1016/j.jhazmat.2019.121119

Fagan, W. P., Zhao, J., Villamena, F. A., Zweier, J. L. and Weavers, L. K. (2020). “Synergistic, aqueous PAH degradation by ultrasonically-activated persulfate depends on bulk temperature and physicochemical parameters,” Ultrasonics Sonochemistry 67(8), 105172. https://doi.org/10.1016/j.ultsonch.2020.105172

Fang, H., Liu, Y. H., Qiu, P. X., Rajasekar, A., Song, H. L., Wang, C. Q. and Zhang, S. (2022). “Application of a molybdenum carbide electrode enhanced the biodegradability of wheat straw,” Journal of Electronic Materials 51(1), 163-171. https://doi.org/10.1007/s11664-021-09243-6

Fernandes, C. H. M., Silva, B. F. and Aquino, J. M. (2021). “On the performance of distinct electrochemical and solar-based advanced oxidation processes to mineralize the insecticide imidacloprid,” Chemosphere 275(15), 130010. https://doi.org/10.1016/j.chemosphere.2021.130010

Fernandez, J., Bandara, J., Lopez, A., Buffat, P. and Kiwi, J. (1999). “Photoassisted Fenton degradation of nonbiodegradable Azo Dye (Orange II) in Fe-free solutions mediated by cation transfer membranes,” Langmuir 15(1), 185-192. https://doi.org/10.1021/la980382a

García-Cubero, M. T., González-Benito, G., Indacoechea, I., Coca, M. and Bolado, S. (2009). “Effect of ozonolysis pretreatment on enzymatic digestibility of wheat and rye straw,” Bioresource Technology 100(4), 1608-1613. https://doi.org/10.1016/j.biortech.2008.09.012

Garedew, M., Lam, C. H., Petitjean, L., Huang, S., Song, B., Lin, F., Jackson, J. E., Saffron, C. M. and Anastas, P. T. (2021). “Electrochemical upgrading of depolymerized lignin: A review of model compound studies,” Green Chemistry 23(8), 2868-2899. https://doi.org/10.1039/D0GC04127K

Glaze, W. H. and Kang, J. W. (1989). “Advanced oxidation processes. Description of a kinetic model for the oxidation of hazardous materials in aqueous media with ozone and hydrogen peroxide in a semibatch reactor,” Industrial & Engineering Chemistry Research 28(11), 1573-1580. https://doi.org/10.1021/ie00095a001

Gogate, P. R. and Pandit, A. B. (2005). “A review and assessment of hydrodynamic cavitation as a technology for the future,” Ultrasonics Sonochemistry 12(1), 21-27. https://doi.org/10.1016/j.ultsonch.2004.03.007

Göncü, B., Gülşen, H. and Hoşgün, E. Z. (2021). “Bioethanol production from pistachio (Pistacia vera L.) shells applying ozone pretreatment and subsequent enzymatic hydrolysis,” Environmental Technology 42(15), 2438-2446. https://doi.org/10.1080/09593330.2021.1903565

Gong, L., Wu, X., Wang, Y., Zhu, J., Wang, S., Xiu, Y., Dong, J., Xu, G. and Ni, Y. (2024). “A novel deep eutectic solvent–mediated Fenton-like system for pretreatment of water hyacinth and biobutanol production,” Biomass Conversion and Biorefinery 14(7), 8341-8351. https://doi.org/10.1007/s13399-022-02940-0

Gould, J. M. (1984). “Alkaline peroxide delignification of agricultural residues to enhance enzymatic saccharification,” Biotechnology and Bioengineering 26(1), 46-52. https://doi.org/10.1002/bit.260260110

Gout, E., Monnot, M., Boutin, O., Vanloot, P., Claeys-Bruno, M. and Moulin, P. (2022). “Assessment and optimization of wet air oxidation for treatment of landfill leachate concentrated with reverse osmosis,” Process Safety and Environmental Protection 162(6), 765-774. https://doi.org/10.1016/j.psep.2022.04.046

Guo, Y., Cheng, M., Wang, Z., Zhang, G., Wang, G., Liu, H., Chen, A., Shi, Q., Kang, H. and Yuan, Z. (2025). “Carbon-based single-atom catalysts from biomass for persulfate-advanced oxidation processes: Perspectives on synthesis, application, modulation, and sustainability,” Chemical Engineering Journal 520(18), 166119. https://doi.org/10.1016/j.cej.2025.166119

Hart, P. W. and Rudie, A. (2007). “Published. Hydrogen peroxide—An environmentally friendly but dangerous bleaching chemical “. TAPPI Press 2007 Engineering, Pulping & Environmental Conference, (https://www.fs.usda.gov/treesearch/pubs/34782).

Hassan, S. S., Williams, G. A. and Jaiswal, A. K. (2018). “Emerging technologies for the pretreatment of lignocellulosic biomass,” Bioresource Technology 262(17), 310-318. https://doi.org/10.1016/j.biortech.2018.04.099

Hoigné, J. and Bader, H. (1983). “Rate constants of reactions of ozone with organic and inorganic compounds in water—I: Non-dissociating organic compounds,” Water Research 17(2), 173-183. https://doi.org/10.1016/0043-1354(83)90098-2

Hu, M., Chen, J., Yu, Y. and Liu, Y. (2022). “Peroxyacetic acid pretreatment: A potentially promising strategy towards lignocellulose biorefinery,” Molecules 27(19), 6359. https://doi.org/10.3390/molecules27196359

Huang, C., Zhan, Y., Cheng, J., Wang, J., Meng, X., Fang, G. and Ragauskas, A. J. (2022). “The bamboo delignification saturation point in alkaline hydrogen peroxide pretreatment and its association with enzymatic hydrolysis,” Bioresource Technology 359(18), 127462. https://doi.org/10.1016/j.biortech.2022.127462

Huang, D., Li, T., Xu, P., Zeng, G., Chen, M., Lai, C., Cheng, M., Guo, X., Chen, S. and Li, Z. (2019). “Deciphering the Fenton-reaction-aid lignocellulose degradation pattern by Phanerochaete chrysosporium with ferroferric oxide nanomaterials: Enzyme secretion, straw humification and structural alteration,” Bioresource Technology 276(6), 335-342. https://doi.org/10.1016/j.biortech.2019.01.013

IEA. (2024). World Energy Outlook 2024, International Energy Agency, (https://www.iea.org/reports/world-energy-outlook-2024).

Irmak, S., Kang, J. and Wilkins, M. (2020). “Depolymerization of lignin by wet air oxidation,” Bioresource Technology Reports 9(1), 100377. https://doi.org/10.1016/j.biteb.2019.100377

Jia, Z., Sun, Y., Wang, S., Fan, X., Yu, H., Wang, H., Li, L., Jiang, E., Wu, C. and Xu, X. (2022). “Hydrothermal and photocatalytic synergistic pretreatment to improve the full utilization of corn stalk,” Bioresource Technology 363(22), 127989. https://doi.org/10.1016/j.biortech.2022.127989

Jiang, Y., Zeng, X., Luque, R., Tang, X., Sun, Y., Lei, T., Liu, S. and Lin, L. (2017). “Cooking with active oxygen and solid alkali: A promising alternative approach for lignocellulosic biorefineries,” ChemSusChem 10(20), 3982-3993. https://doi.org/10.1002/cssc.201700906

Joshi, M. and Manjare, S. (2024). “Chemical approaches for the biomass valorisation: a comprehensive review of pretreatment strategies,” Environmental Science and Pollution Research 31(36), 48928-48954. https://doi.org/10.1007/s11356-024-34473-6

Kato, D. M., Elía, N., Flythe, M. and Lynn, B. C. (2014). “Pretreatment of lignocellulosic biomass using Fenton chemistry,” Bioresource Technology 162(12), 273-278. https://doi.org/10.1016/j.biortech.2014.03.151

Kim, I., Lee, I., Jeon, S. H., Hwang, T. and Han, J.-I. (2015). “Hydrodynamic cavitation as a novel pretreatment approach for bioethanol production from reed,” Bioresource Technology 192(18), 335-339. https://doi.org/10.1016/j.biortech.2015.05.038

Koo, H., Salunke, B. K., Iskandarani, B., Oh, W.-G. and Kim, B. S. (2017). “Improved degradation of lignocellulosic biomass pretreated by Fenton-like reaction using Fe3O4 magnetic nanoparticles,” Biotechnology and Bioprocess Engineering 22(5), 597-603. https://doi.org/10.1007/s12257-017-0225-x

Kumar, N., Yadav, S., Mittal, A. and Kumari, K. (2021). “15 – Photocatalysis by zinc oxide-based nanomaterials,” in: Nanostructured Zinc Oxide, AWASTHI, K., ed., Elsevier, 393-457.

Kundu, C., Samudrala, S. P., Kibria, M. A. and Bhattacharya, S. (2021). “One-step peracetic acid pretreatment of hardwood and softwood biomass for platform chemicals production,” Scientific Reports 11(1), 11183. https://doi.org/10.1038/s41598-021-90667-9

Lee, I. and Han, J.-I. (2021). “Development of a pretreatment method based on Fenton-like reaction combined with hydrodynamic cavitation for lipid extraction from wet microalgae,” Renewable Energy 175(13), 415-421. https://doi.org/10.1016/j.renene.2021.04.130

Lee, K., Yoon, H., Ahn, C., Park, J. and Jeon, S. (2019). “Strategies to improve the photocatalytic activity of TiO2: 3D nanostructuring and heterostructuring with graphitic carbon nanomaterials,” Nanoscale 11(15), 7025-7040. https://doi.org/10.1039/C9NR01260E

Lee, K. M., Lai, C. W., Ngai, K. S. and Juan, J. C. (2016). “Recent developments of zinc oxide based photocatalyst in water treatment technology: A review,” Water research 88(1), 428-448. https://doi.org/10.1016/j.watres.2015.09.045

Li, C., Wang, L., Chen, Z., Li, Y., Luo, X. and Zhao, F. (2021). “Ozonolysis of wheat bran in subcritical water for enzymatic saccharification and polysaccharide recovery,” The Journal of Supercritical Fluids 168(2), 105092. https://doi.org/10.1016/j.supflu.2020.105092

Li, J., Han, Y., Shi, S., Xiao, W. and Han, L. (2025). “The synergetic effect of ultrafine grinding and alkaline hydrogen peroxide pretreatment for the enzymatic saccharification of corn stover,” Industrial Crops and Products 223(1), 120186. https://doi.org/10.1016/j.indcrop.2024.120186

Li, L., Yuan, X., Zhou, Z., Tang, R., Deng, Y., Huang, Y., Xiong, S., Su, L., Zhao, J. and Gong, D. (2022). “Research progress of photocatalytic activated persulfate removal of environmental organic pollutants by metal and nonmetal based photocatalysts,” Journal of Cleaner Production 372(43), 133420. https://doi.org/10.1016/j.jclepro.2022.133420

Li, M., Foster, C., Kelkar, S., Pu, Y., Holmes, D., Ragauskas, A., Saffron, C. M. and Hodge, D. B. (2012). “Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes,” Biotechnology for Biofuels 5(1), 38. https://doi.org/10.1186/1754-6834-5-38

Li, Q., Guo, Z., Long, Y., Zhou, W., Xiao, N. and Cai, J. (2023). “Effects of various persulfate oxidation pretreatments on enzymatic saccharification efficiency of sugarcane bagasse biomass and the related mechanism,” Industrial Crops and Products 202(14), 116956. https://doi.org/10.1016/j.indcrop.2023.116956

Li, W.-B., Lei, J., Qu Mo, M.-M., Li, J., Wei, J., Liu, Y., Wang, S., Hu, Y.-C., Zou, L. and Wu, D.-T. (2024). “Impacts of ultrasound-assisted Fenton degradation and alkaline de-esterification on structural properties and biological effects of pectic polysaccharides from Tartary buckwheat leaves,” Ultrasonics Sonochemistry 106(5), 106895. https://doi.org/10.1016/j.ultsonch.2024.106895

Liang, J., Zeng, H., Zhang, Y., Zhou, W. and Xiao, N. (2024). “Higher efficiency of vanadate iron in heterogeneous Fenton-like systems to pretreat sugarcane bagasse and its enzymatic saccharification,” Biotechnology and Bioengineering 121(9), 2780-2792. https://doi.org/10.1002/bit.28733

Lin, S.-S. and Gurol, M. D. (1998). “Catalytic decomposition of hydrogen peroxide on iron oxide:  Kinetics, mechanism, and implications,” Environmental Science & Technology 32(10), 1417-1423. https://doi.org/10.1021/es970648k

Liu, L., Ren, J., Zhang, Y., Liu, X. and Ouyang, J. (2018). “Simultaneously separation of xylo-oligosaccharide and lignosulfonate from wheat straw magnesium bisulfite pretreatment spent liquor using ion exchange resin,” Bioresource Technology 249(4), 189-195. https://doi.org/10.1016/j.biortech.2017.09.207

Liu, W., Ai, Z. and Zhang, L. (2012). “Design of a neutral three-dimensional electro-Fenton system with foam nickel as particle electrodes for wastewater treatment,” Journal of Hazardous Materials 243(23), 257-264. https://doi.org/10.1016/j.jhazmat.2012.10.024

Liu, Y., Zhao, Y. and Wang, J. (2021a). “Fenton/Fenton-like processes with in-situ production of hydrogen peroxide/hydroxyl radical for degradation of emerging contaminants: Advances and prospects,” Journal of Hazardous Materials 404(4), 124191. https://doi.org/10.1016/j.jhazmat.2020.124191

Liu, Z., Demeestere, K. and Hulle, S. V. (2021b). “Comparison and performance assessment of ozone-based AOPs in view of trace organic contaminants abatement in water and wastewater: A review,” Journal of Environmental Chemical Engineering 9(4), 105599. https://doi.org/10.1016/j.jece.2021.105599

Liu, Z., Ren, X., Duan, X., Sarmah, A. K. and Zhao, X. (2023). “Remediation of environmentally persistent organic pollutants (POPs) by persulfates oxidation system (PS): A review,” Science of The Total Environment 863(16), 160818. https://doi.org/10.1016/j.scitotenv.2022.160818

Lyu, Q., Chen, X., Zhang, Y., Yu, H., Han, L. and Xiao, W. (2021). “One-pot fractionation of corn stover with peracetic acid and maleic acid,” Bioresource Technology 320(2), 124306. https://doi.org/10.1016/j.biortech.2020.124306

M’Arimi, M. M., Mecha, C. A., Kiprop, A. K. and Ramkat, R. (2020). “Recent trends in applications of advanced oxidation processes (AOPs) in bioenergy production: Review,” Renewable & Sustainable Energy Reviews 121(5), 109669. https://doi.org/10.1016/j.rser.2019.109669

Madison, M. J., Coward-Kelly, G., Liang, C., Karim, M. N., Falls, M. and Holtzapple, M. T. (2017). “Mechanical pretreatment of biomass – Part I: Acoustic and hydrodynamic cavitation,” Biomass and Bioenergy 98(3), 135-141. https://doi.org/10.1016/j.biombioe.2017.01.007

Mahy, J. G., Kiendrebeogo, M., Farcy, A. and Drogui, P. (2023). “Enhanced decomposition of H2O2 using metallic silver nanoparticles under UV/visible light for the removal of p-Nitrophenol from water,” Catalysts 13(5), 842. https://doi.org/10.3390/catal13050842

Maziero, P., Neto, M. d. O., Machado, D., Batista, T., Cavalheiro, C. C. S., Neumann, M. G., Craievich, A. F., Rocha, G. J. d. M., Polikarpov, I. and Gonçalves, A. R. (2012). “Structural features of lignin obtained at different alkaline oxidation conditions from sugarcane bagasse,” Industrial Crops and Products 35(1), 61-69. https://doi.org/10.1016/j.indcrop.2011.06.008

McCallum, C. S., Wang, W., Doran, W. J., Forsythe, W. G., Garrett, M. D., Hardacre, C., Leahy, J. J., Morgan, K., Shin, D.-S. and Sheldrake, G. N. (2021). “Life cycle thinking case study for catalytic wet air oxidation of lignin in bamboo biomass for vanillin production,” Green Chemistry 23(4), 1847-1860. https://doi.org/10.1039/D0GC03685D

McGinnis, G. D., Wilson, W. W. and Mullen, C. E. (1983). “Biomass pretreatment with water and high-pressure oxygen. The wet-oxidation process,” Industrial & Engineering Chemistry Product Research and Development 22(2), 352-357. https://doi.org/10.1021/i300010a036

Mei, H., Wang, Q., Liu, G., Zhu, X., Zhang, M., Huang, K. and Lin, K. (2021). “Nanoscale zero-valent iron supported on carbon nitride as a peroxymonosulfate activator for the efficient degradation of paraxylene,” Catalysis Letters 151(12), 3532-3542. https://doi.org/10.1007/s10562-021-03596-7

Meng, F., Li, N., Yang, H., Shi, Z., Zhao, P. and Yang, J. (2022). “Investigation of hydrogen peroxide-acetic acid pretreatment to enhance the enzymatic digestibility of bamboo residues,” Bioresource Technology 344(2), 126162. https://doi.org/10.1016/j.biortech.2021.126162

Moradnia, M., Noorisepehr, M., Salari, M. and Darvishmotevalli, M. (2022). “Optimization of 2-chlorophenol removal using ultrasound/persulfate: Prediction by RSM method, biodegradability improvement of petrochemical refinery wastewater,” Arabian Journal for Science and Engineering 47(6), 6931-6939. https://doi.org/10.1007/s13369-021-06084-7

Morone, A., Chakrabarti, T. and Pandey, R. A. (2018a). “Effect of chemical input during wet air oxidation pretreatment of rice straw in reducing biomass recalcitrance and enhancing cellulose accessibility,” Korean Journal of Chemical Engineering 35(12), 2403-2412. https://doi.org/10.1007/s11814-018-0129-2

Morone, A., Sharma, G., Sharma, A., Chakrabarti, T. and Pandey, R. A. (2018b). “Evaluation, applicability and optimization of advanced oxidation process for pretreatment of rice straw and its effect on cellulose digestibility,” Renewable Energy 120(7), 88-97. https://doi.org/10.1016/j.renene.2017.12.074

Mun, J. S. and Mun, S. P. (2024). “Alkaline hydrogen peroxide delignification of three lignocellulosic biomass under atmospheric pressure,” BIORESOURCES 19(1), 998-1009. https://doi.org/10.15376/biores.19.1.998-1009

Niu, K., Chen, P., Zhang, X. and Tan, W.-S. (2009). “Enhanced enzymatic hydrolysis of rice straw pretreated by alkali assisted with photocatalysis technology,” Journal of Chemical Technology & Biotechnology 84(8), 1240-1245. https://doi.org/10.1002/jctb.2185

Orduña Ortega, J., Mora Vargas, J. A., Perrone, O. M., Metzker, G., Gomes, E., da Silva, R. and Boscolo, M. (2020). “Soaking and ozonolysis pretreatment of sugarcane straw for the production of fermentable sugars,” Industrial Crops and Products 145(3), 111959. https://doi.org/10.1016/j.indcrop.2019.111959

Osuna-Laveaga, D. R., García-Depraect, O., Vallejo-Rodríguez, R., López-López, A. and León-Becerril, E. (2020). “Integrated ozonation-enzymatic hydrolysis pretreatment of sugarcane bagasse: Enhancement of sugars released to expended ozone ratio,” Processes 8(10), 1274. https://doi.org/10.3390/pr8101274

Panigrahi, S. and Dubey, B. K. (2019). “Electrochemical pretreatment of yard waste to improve biogas production: Understanding the mechanism of delignification, and energy balance,” Bioresource Technology 292(22), 121958. https://doi.org/10.1016/j.biortech.2019.121958

Park, H., Park, Y., Kim, W. and Choi, W. (2013). “Surface modification of TiO2 photocatalyst for environmental applications,” Journal of Photochemistry and Photobiology C: Photochemistry Reviews 15(2), 1-20. https://doi.org/10.1016/j.jphotochemrev.2012.10.001

Passos, F., Uggetti, E., Carrère, H. and Ferrer, I. (2014). “Pretreatment of microalgae to improve biogas production: A review,” Bioresource Technology 172(22), 403-412. https://doi.org/10.1016/j.biortech.2014.08.114

Peng, W., Dong, Y., Fu, Y., Wang, L. and Wang, Z. (2021). “Non-radical reactions in persulfate-based homogeneous degradation processes: A review,” Chemical Engineering Journal 421(22), 127818. https://doi.org/10.1016/j.cej.2020.127818

Perrone, O. M., Colombari, F. M., Rossi, J. S., Moretti, M. M. S., Bordignon, S. E., Nunes, C. d. C. C., Gomes, E., Boscolo, M. and Da-Silva, R. (2016). “Ozonolysis combined with ultrasound as a pretreatment of sugarcane bagasse: Effect on the enzymatic saccharification and the physical and chemical characteristics of the substrate,” Bioresource Technology 218(20), 69-76. https://doi.org/10.1016/j.biortech.2016.06.072

Poveda-Giraldo, J. A. and Cardona Alzate, C. A. (2025). “Valorization of lignocellulosic platform products based on biorefinery schemes through sequential pretreatments,” Biomass Conversion and Biorefinery 15(1), 637-651. https://doi.org/10.1007/s13399-023-05140-6

Prado, C. A., Antunes, F. A. F., Rocha, T. M., Sánchez-Muñoz, S., Barbosa, F. G., Terán-Hilares, R., Cruz-Santos, M. M., Arruda, G. L., da Silva, S. S. and Santos, J. C. (2022). “A review on recent developments in hydrodynamic cavitation and advanced oxidative processes for pretreatment of lignocellulosic materials,” Bioresource Technology 345(4), 126458. https://doi.org/10.1016/j.biortech.2021.126458

Putro, J. N., Soetaredjo, F. E., Lin, S.-Y., Ju, Y.-H. and Ismadji, S. (2016). “Pretreatment and conversion of lignocellulose biomass into valuable chemicals,” RSC Advances 6(52), 46834-46852. https://doi.org/10.1039/c6ra09851g

Qiu, Q., Li, G., Dai, Y., Xu, Y. and Bao, P. (2020). “Removal of antibiotic resistant microbes by Fe(II)-activated persulfate oxidation,” Journal of Hazardous Materials 396(16), 122733. https://doi.org/10.1016/j.jhazmat.2020.122733

Qu, J., Xue, J., Sun, M., Li, K., Wang, J., Zhang, G., Wang, L., Jiang, Z. and Zhang, Y. (2024). “Superefficient non-radical degradation of benzo[a]pyrene in soil by Fe-biochar composites activating persulfate,” Chemical Engineering Journal 481(3), 148585. https://doi.org/10.1016/j.cej.2024.148585

Rezania, S., Oryani, B., Cho, J., Talaiekhozani, A., Sabbagh, F., Hashemi, B., Rupani, P. F. and Mohammadi, A. A. (2020). “Different pretreatment technologies of lignocellulosic biomass for bioethanol production: An overview,” Energy 199(10), 117457. https://doi.org/10.1016/j.energy.2020.117457

Rouches, E., Herpoël-Gimbert, I., Steyer, J. P. and Carrere, H. (2016). “Improvement of anaerobic degradation by white-rot fungi pretreatment of lignocellulosic biomass: A review,” Renewable and Sustainable Energy Reviews 59(7), 179-198. https://doi.org/10.1016/j.rser.2015.12.317

Sabeeh, M., Zeshan, Liaquat, R. and Maryam, A. (2020). “Effect of alkaline and alkaline-photocatalytic pretreatment on characteristics and biogas production of rice straw,” Bioresource Technology 309(15), 123449. https://doi.org/10.1016/j.biortech.2020.123449

Shamjuddin, A., Ab Rasid, N. S., Michele Raissa, M. M., Abu Zarin, M. A., Wan Omar, W. N. N., Syahrom, A., Mohd Szali Januddi, M. A. F. and Saidina Amin, N. A. (2021). “Kinetic and dynamic analysis of ozonolysis pre-treatment of empty fruit bunch in a well-mixed reactor for sugar production,” Energy Conversion and Management 244(18), 114526. https://doi.org/10.1016/j.enconman.2021.114526

Shao, D., Liang, J., Cui, X., Xu, H. and Yan, W. (2014). “Electrochemical oxidation of lignin by two typical electrodes: Ti/SbSnO2 and Ti/PbO2,” Chemical Engineering Journal 244(10), 288-295. https://doi.org/10.1016/j.cej.2014.01.074

Shi, C., Li, C., Wang, Y., Guo, J., Barry, S., Zhang, Y. and Marmier, N. (2022). “Review of advanced oxidation processes based on peracetic acid for organic pollutants,” Water 14(15), 2309. https://doi.org/10.3390/w14152309

Singh, S., Bharadwaja, S. T. P., Yadav, P. K., Moholkar, V. S. and Goyal, A. (2014). “Mechanistic investigation in ultrasound-assisted (alkaline) delignification of parthenium hysterophorus biomass,” Industrial & Engineering Chemistry Research 53(37), 14241-14252. https://doi.org/10.1021/ie502339q

Song, T., Kang, X., Guo, C., He, Z. and Ge, M. (2023). “Recent advances in persulfate activation by magnetic ferrite-carbon composites for organic contaminants degradation: Role of carbon materials and environmental application,” Journal of Environmental Chemical Engineering 11(1), 109087. https://doi.org/10.1016/j.jece.2022.109087

Staehelin, J. and Hoigne, J. (1982). “Decomposition of ozone in water: Rate of initiation by hydroxide ions and hydrogen peroxide,” Environmental Science & Technology 16(10), 676-681. https://doi.org/10.1021/es00104a009

Stiefel, S., Schmitz, A., Peters, J., Di Marino, D. and Wessling, M. (2016). “An integrated electrochemical process to convert lignin to value-added products under mild conditions,” Green Chemistry 18(18), 4999-5007. https://doi.org/10.1039/C6GC00878J

Sun, S., Sun, S., Cao, X. and Sun, R. (2016). “The role of pretreatment in improving the enzymatic hydrolysis of lignocellulosic materials,” Bioresource Technology 199(1), 49-58. https://doi.org/10.1016/j.biortech.2015.08.061

Szijártó, N., Kádár, Z., Varga, E., Thomsen, A. B., Costa-Ferreira, M. and Réczey, K. (2009). “Pretreatment of reed by wet oxidation and subsequent utilization of the pretreated fibers for ethanol production,” Applied Biochemistry and Biotechnology 155(1), 83-93. https://doi.org/10.1007/s12010-009-8549-4

Taherzadeh, M. J. and Karimi, K. (2008). “Pretreatment of lignocellulosic wastes to improve ethanol and biogas production: A review,” International Journal of Molecular Sciences 9(9), 1621-1651. https://doi.org/10.3390/ijms9091621

Teixeira, L. C., Linden, J. C. and Schroeder, H. A. (2000). “Simultaneous saccharification and cofermentation of peracetic acid-pretreated biomass,” Applied Biochemistry and Biotechnology 84(6), 111-127. https://doi.org/10.1385/ABAB:84-86:1-9:111

Tekin, G., Ersöz, G. and Atalay, S. (2022). “Valorization of biomass as co-catalyst for simultaneous remediation and hydrogen production from sugar industry wastewater by catalytic wet air oxidation,” Journal of Cleaner Production 330(1), 129728. https://doi.org/10.1016/j.jclepro.2021.129728

Tembhekar, P. D., Padoley, K. V., Mudliar, S. L. and Mudliar, S. N. (2015). “Kinetics of wet air oxidation pretreatment and biodegradability enhancement of a complex industrial wastewater,” Journal of Environmental Chemical Engineering 3(1), 339-348. https://doi.org/10.1016/j.jece.2014.02.009

Terán Hilares, R., Ienny, J. V., Marcelino, P. F., Ahmed, M. A., Antunes, F. A. F., da Silva, S. S. and Santos, J. C. d. (2017). “Ethanol production in a simultaneous saccharification and fermentation process with interconnected reactors employing hydrodynamic cavitation-pretreated sugarcane bagasse as raw material,” Bioresource Technology 243(21), 652-659. https://doi.org/10.1016/j.biortech.2017.06.159

Toghiani, J., Malekzadeh, S., Jamali, N., Afsham, N., Fallah, N., Mahboubi, A., Nasernejad, B., Taherzadeh, M. J. and Oladzad, S. (2024). “Novel advanced oxidation processes (AOPs) as lignocellulosic biomass pretreatment approaches and their sustainability assessment: A review,” Current Pollution Reports 10(2), 207-246. https://doi.org/10.1007/s40726-024-00295-w

Travaini, R., Otero, M. D. M., Coca, M., Da-Silva, R. and Bolado, S. (2013). “Sugarcane bagasse ozonolysis pretreatment: Effect on enzymatic digestibility and inhibitory compound formation,” Bioresource Technology 133(7), 332-339. https://doi.org/10.1016/j.biortech.2013.01.133

Tsalagkas, D., Börcsök, Z., Pásztory, Z., Gogate, P. and Csóka, L. (2021). “Assessment of the papermaking potential of processed Miscanthus giganteus stalks using alkaline pre-treatment and hydrodynamic cavitation for delignification,” Ultrasonics Sonochemistry 72(3), 105462. https://doi.org/10.1016/j.ultsonch.2021.105462

Wang, J., Cui, H., Xie, G., Liu, B., Cao, G. and Xing, D. (2020). “Co-treatment of potassium ferrate and peroxymonosulfate enhances the decomposition of the cotton straw and cow manure mixture,” Science of The Total Environment 724(27), 138321. https://doi.org/10.1016/j.scitotenv.2020.138321

Wang, J. and Tang, J. (2021). “Fe-based Fenton-like catalysts for water treatment: Catalytic mechanisms and applications,” Journal of Molecular Liquids 332(12), 115755. https://doi.org/10.1016/j.molliq.2021.115755

Wang, J. and Wang, S. (2018). “Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants,” Chemical Engineering Journal 3341502-1517. https://doi.org/10.1016/j.cej.2017.11.059

Wang, Y.-s., Yang, F., Liu, Z.-h., Yuan, L. and Li, G. (2015). “Electrocatalytic degradation of aspen lignin over Pb/PbO2 electrode in alkali solution,” Catalysis Communications 67(10), 49-53. https://doi.org/10.1016/j.catcom.2015.03.033

Wang, Z., Huang, Y., Zhang, F., Xie, H., Jiang, G., Lv, D., Zhang, H., Lam, S. S. and Song, A. (2022). “Improving enzymatic saccharification of corn stover via thioglycolic acid-mediated Fenton pretreatment,” Journal of Cleaner Production 365(36), 132804. https://doi.org/10.1016/j.jclepro.2022.132804

Whistler, R. L. (1993). “HEMICELLULOSES,” in: Industrial Gums,3rd edn, WHISTLER, R. L. and BEMILLER, J. N., ed., Academic Press, London, 295-308.

Wijaya, Y. P., Smith, K. J., Kim, C. S. and Gyenge, E. L. (2020). “Electrocatalytic hydrogenation and depolymerization pathways for lignin valorization: Toward mild synthesis of chemicals and fuels from biomass,” Green Chemistry 22(21), 7233-7264. https://doi.org/10.1039/D0GC02782K

Wu, K., Wu, H., Zhang, H., Zhang, B., Wen, C., Hu, C., Liu, C. and Liu, Q. (2020). “Enhancing levoglucosan production from waste biomass pyrolysis by Fenton pretreatment,” Waste Management 108(8), 70-77. https://doi.org/10.1016/j.wasman.2020.04.023

Wu, K., Ying, W., Shi, Z., Yang, H., Zheng, Z., Zhang, J. and Yang, J. (2018). “Fenton reaction-oxidized bamboo lignin surface and structural modification to reduce nonproductive cellulase binding and improve enzyme digestion of cellulose,” ACS Sustainable Chemistry & Engineering 6(3), 3853-3861. https://doi.org/10.1021/acssuschemeng.7b04191

Wu, L., Wu, T., Liu, Z., Tang, W., Xiao, S., Shao, B., Liang, Q., He, Q., Pan, Y., Zhao, C., Liu, Y. and Tong, S. (2022). “Carbon nanotube-based materials for persulfate activation to degrade organic contaminants: Properties, mechanisms and modification insights,” Journal of Hazardous Materials 431(15), 128536. https://doi.org/10.1016/j.jhazmat.2022.128536

Xiao, K., Yuan, Y., Xiao, N., Zhou, W., Yang, Q., Feng, W. and Zhu, D. (2017). “Enzymatic saccharification responses of Eichhornia crassipes, sugarcane bagasse and Metasequoia glyptostroboides to two oxidation pretreatments for biofuel production,” Industrial Crops and Products 107(13), 22-29. https://doi.org/10.1016/j.indcrop.2017.05.017

Xu, J., Zhang, X., Long, J. and Ge, C. (2023). “Photocatalytic breaking of C-C bonds in lignin models by combining N-doped carbon nitride and persulfate in micellar aqueous medium,” Journal of Environmental Chemical Engineering 11(5), 110854. https://doi.org/10.1016/j.jece.2023.110854

Yang, L., Hao, X., Yu, D., Zhou, P., Peng, Y., Jia, Y., Zhao, C., He, J., Zhan, C. and Lai, B. (2021). “High visible-light catalytic activity of Bis-PDI-T@TiO2 for activating persulfate toward efficient degradation of carbamazepine,” Separation and Purification Technology 263(11), 118384. https://doi.org/10.1016/j.seppur.2021.118384

Yang, X. and Wang, D. (2018). “Photocatalysis: From fundamental principles to materials and applications,” ACS Applied Energy Materials 1(12), 6657-6693. https://doi.org/10.1021/acsaem.8b01345

Yang, Y., Yang, J., Cao, J. and Wang, Z. (2018). “Pretreatment with concurrent UV photocatalysis and alkaline H2O2 enhanced the enzymatic hydrolysis of sisal waste,” Bioresource Technology 267(22), 517-523. https://doi.org/10.1016/j.biortech.2018.07.038

Yin, D., Jing, Q., AlDajani, W. W., Duncan, S., Tschirner, U., Schilling, J. and Kazlauskas, R. J. (2011). “Improved pretreatment of lignocellulosic biomass using enzymatically-generated peracetic acid,” Bioresource Technology 102(8), 5183-5192. https://doi.org/10.1016/j.biortech.2011.01.079

Yuan, D., Yang, K., Pan, S., Xiang, Y., Tang, S., Huang, L., Sun, M., Zhang, X., Jiao, T., Zhang, Q. and Li, B. (2021). “Peracetic acid enhanced electrochemical advanced oxidation for organic pollutant elimination,” Separation and Purification Technology 276(24), 119317. https://doi.org/10.1016/j.seppur.2021.119317

Zewde, A. A., Zhang, L., Li, Z. and Odey, E. A. (2019). “A review of the application of sonophotocatalytic process based on advanced oxidation process for degrading organic dye,” Reviews on Environmental Health 34(4), 365-375. https://doi.org/10.1515/reveh-2019-0024

Zhang, K., Xu, R., Abomohra, A. E.-F., Xie, S., Yu, Z., Guo, Q., Liu, P., Peng, L. and Li, X. (2019a). “A sustainable approach for efficient conversion of lignin into biodiesel accompanied by biological pretreatment of corn straw,” Energy Conversion and Management 199(21), 111928. https://doi.org/10.1016/j.enconman.2019.111928

Zhang, L.-Y., Yang, J.-J. and You, Y.-H. (2021). “Construction and photocatalytic performance of fluorinated ZnO–TiO2 heterostructure composites,” RSC Advances 11(61), 38654-38666. https://doi.org/10.1039/D1RA07757K

Zhang, L., Fu, J., Gao, W., Li, Y. and Fan, X. (2024a). “Revealing the structural variation and degradation mechanism of cellulose during ozone oxidation treatment,” Industrial Crops and Products 219(14), 119101. https://doi.org/10.1016/j.indcrop.2024.119101

Zhang, Q., Zheng, D., Bai, B., Ma, Z. and Zong, S. (2024b). “Insight into antibiotic removal by advanced oxidation processes (AOPs): Performance, mechanism, degradation pathways, and ecotoxicity assessment,” Chemical Engineering Journal 500(22), 157134. https://doi.org/10.1016/j.cej.2024.157134

Zhang, T. and Zhu, M.-J. (2016). “Enhancing enzymolysis and fermentation efficiency of sugarcane bagasse by synergistic pretreatment of Fenton reaction and sodium hydroxide extraction,” Bioresource Technology 214(16), 769-777. https://doi.org/10.1016/j.biortech.2016.05.032

Zhang, Y., Liang, J., Zhou, W. and Xiao, N. (2019b). “Comparison of Fenton and bismuth ferrite Fenton-like pretreatments of sugarcane bagasse to enhance enzymatic saccharification,” Bioresource Technology 285(15), 121343. https://doi.org/10.1016/j.biortech.2019.121343

Zhang, Z., Rao, Y., Ye, M., Zou, D., Liu, R. and Liu, Y. (2024c). “Reduction of inhibitory effect of lignin via degradation and improvement of anaerobic digestion performance of maize straw by oxidative pretreatment with Fe2+-activated persulfate,” Renewable Energy 231(12), 120795. https://doi.org/10.1016/j.renene.2024.120795

Zhao, X., Zhang, T., Zhou, Y. and Liu, D. (2007). “Preparation of peracetic acid from hydrogen peroxide: Part I: Kinetics for peracetic acid synthesis and hydrolysis,” Journal of Molecular Catalysis A: Chemical 271(1), 246-252. https://doi.org/10.1016/j.molcata.2007.03.012

Zhou, Z., Liu, X., Sun, K., Lin, C., Ma, J., He, M. and Ouyang, W. (2019). “Persulfate-based advanced oxidation processes (AOPs) for organic-contaminated soil remediation: A review,” Chemical Engineering Journal 372(18), 836-851. https://doi.org/10.1016/j.cej.2019.04.213

Zhu, Y., Qiu, S., Deng, F., Ma, F., Li, G. and Zheng, Y. (2020). “Three-dimensional nickel foam electrode for efficient electro-Fenton in a novel reactor,” Environmental Technology 41(6), 730-740. https://doi.org/10.1080/09593330.2018.1509890

Article submitted: January 31, 2026; Peer review completed: February 21, 2026; Revised version received and accepted: May 26, 2026; Published: June 11, 2026.

DOI: 10.15376/biores.21.3.Zhang2