Frontiers of Chemical Science and Engineering

ISSN 2095-0179

ISSN 2095-0187(Online)

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Direct pyrolysis to convert biomass to versatile 3D carbon nanotubes/mesoporous carbon architecture: conversion mechanism and electrochemical performance
Chenxi Xu, Shunli Li, Zhaohui Hou, Liming Yang, Wenbin Fu, Fujia Wang, Yafei Kuang, Haihui Zhou, Liang Chen
Front. Chem. Sci. Eng.    2023, 17 (6): 679-690.   https://doi.org/10.1007/s11705-022-2266-8
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The massive conversion of resourceful biomass to carbon nanomaterials not only opens a new avenue to effective and economical disposal of biomass, but provides a possibility to produce highly valued functionalized carbon-based electrodes for energy storage and conversion systems. In this work, biomass is applied to a facile and scalable one-step pyrolysis method to prepare three-dimensional (3D) carbon nanotubes/mesoporous carbon architecture, which uses transition metal inorganic salts and melamine as initial precursors. The role of each employed component is investigated, and the electrochemical performance of the attained product is explored. Each component and precise regulation of their dosage is proven to be the key to successful conversion of biomass to the desired carbon nanomaterials. Owing to the unique 3D architecture and integration of individual merits of carbon nanotubes and mesoporous carbon, the as-synthesized carbon nanotubes/mesoporous carbon hybrid exhibits versatile application toward lithium-ion batteries and Zn-air batteries. Apparently, a significant guidance on effective conversion of biomass to functionalized carbon nanomaterials can be shown by this work.

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Lignin-derived dual-function red light carbon dots for hypochlorite detection and anti-counterfeiting
Yixuan Chang, Fanwei Kong, Zihao Zhu, Ziai Wang, Chunxia Chen, Xiaobai Li, Hongwei Ma
Front. Chem. Sci. Eng.    2023, 17 (7): 966-975.   https://doi.org/10.1007/s11705-022-2244-1
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The efficient utilization of natural lignin, which is the main by-product of the cellulose industry, is crucial for enhancing its economic value, alleviating the environmental burden, and improving ecological security. By taking advantage of the large sp2 hybrid domain of lignin and introducing amino functional groups, new lignin-derived carbon dots (SPN-CDs) with red fluorescence were successfully synthesized. Compared with green and blue fluorescent materials, red SPN-CDs have desirable anti-interference properties of short-wave background and exhibit superior luminescence stability. The SPN-CDs obtained exhibited sensitive and distinctive visible color with fluorescence-dual responses toward hypochlorite. Considering this feature, a portable, low-cost, and sensitive fluorescence sensing paper with a low limit of detection of 0.249 μmol∙L–1 was fabricated using the SPN-CDs for hypochlorite detection. Furthermore, a new type of visible-light and fluorescence dual-channel information encryption platform was constructed. Low-concentration hypochlorite can be employed as an accessible and efficient information encryption/decryption stimulus, as well as an information “eraser”, facilitating a safe and diversified transmission and convenient decryption of information. This work opens new avenues for high-value-added applications of lignin-based fluorescent materials.

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Facile strategy for carbon foam fabrication with lignin as sole feedstock and its applications
Linghong Yin, Zizhu Zhao, Meng Han, Wangda Qu
Front. Chem. Sci. Eng.    2023, 17 (8): 1051-1064.   https://doi.org/10.1007/s11705-022-2248-x
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This research is a follow-up to our recent discovery of a facile strategy for directly converting lignin powder into carbon foam. In this work, we report that the thermal pretreatment parameters in air can remarkably influence the formation and properties of the derived carbon foam. Thermal pretreatment parameters (heating rate, temperature, and residence time) were systematically investigated and a conversion mechanism into carbon foam was proposed. During the thermal pretreatment, relatively low temperatures, low heating rates, and short residence time hindered the formation of smooth and well-connected structures in the carbon foam. The overall product yields were similar regardless of the thermal pretreatment conditions. The densities of the different carbon foams ranged 0.27–0.83 g∙cm−3. The carbon foams with the highest compressive strengths (> 10 MPa) were KLPC280-2-5, KLPC300-0-5, and KLPC300-2-2.5. KLPC280-2-5 exhibited a high iodine sorption value (182 mg∙g−1). KLPC300-2-5 exhibited a specific capacitance of 158 F∙g−1 at a current density of 0.05 A∙g−1. The maximum evaporation rates in the solar vapor generation experiments were 1.05 and 1.38 kg∙m−2∙h−1 under 100 and 150 mW∙cm−2 irradiation, respectively. The good performances are attributed to the robust, porous, and continuous structure.

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Triboelectric nanogenerators: the beginning of blue dream
Wanli Wang, Dongfang Yang, Xiaoran Yan, Licheng Wang, Han Hu, Kai Wang
Front. Chem. Sci. Eng.    2023, 17 (6): 635-678.   https://doi.org/10.1007/s11705-022-2271-y
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Wave energy is inexhaustible renewable energy. Making full use of the huge ocean wave energy resources is the dream of mankind for hundreds of years. Nowadays, the utilization of water wave energy is mainly absorbed and transformed by electromagnetic generators (EMGs) in the form of mechanical energy. However, waves usually have low frequency and uncertainty, which means low power generation efficiency for EMGs. Fortunately, in this slow current and random direction wave case, the triboelectric nanogenerator (TENG) has a relatively stable output power, which is suitable for collecting blue energy. This article summarizes the main research results of TENG in harvesting blue energy. Firstly, based on Maxwell’s displacement current, the basic principle of the nanogenerator is expounded. Then, four working modes and three applications of TENG are introduced, especially the application of TENG in blue energy. TENG currently used in blue energy harvesting is divided into four categories and discussed in detail. After TENG harvests water wave energy, it is meaningless if it cannot be used. Therefore, the modular storage of TENG energy is discussed. The output power of a single TENG unit is relatively low, which cannot meet the demand for high power. Thus, the networking strategy of large-scale TENG is further introduced. TENG’s energy comes from water waves, and each TENG’s output has great randomness, which is very unfavorable for the energy storage after large-scale TENG integration. On this basis, this paper discusses the power management methods of TENG. In addition, in order to further prove its economic and environmental advantages, the economic benefits of TENG are also evaluated. Finally, the development potential of TENG in the field of blue energy and some problems that need to be solved urgently are briefly summarized.

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Enhancing the aromatic selectivity of cyclohexane aromatization by CO2 coupling
Xiangxiang Ren, Zhong-Pan Hu, Jingfeng Han, Yingxu Wei, Zhongmin Liu
Front. Chem. Sci. Eng.    2023, 17 (11): 1801-1808.   https://doi.org/10.1007/s11705-023-2325-9
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Improving the aromatic selectivity in the alkane aromatization process is of great importance for its practical utilization but challenge to make because the high H/C ratio of alkanes would lead to a serious hydrogen transfer process and a large amount of light alkanes. Herein, CO2 is introduced into the cyclohexane conversion process on the HZSM-5 zeolite, which can improve the aromatic selectivity. By optimizing the reaction conditions, an improved aromatic (benzene, toluene, xylene, and C9+) selectivity of 48.2% can be obtained at the conditions of 2.7 MPa (CO2), 450 °C, and 1.7 h−1, which is better than that without CO2 (aromatic selectivity = 43.2%). In situ transmission Fourier transform infrared spectroscopy spectra illustrate that many oxygenated chemical intermediates (e.g., carboxylic acid, anhydride, unsaturated aldehydes/ketones or ketene) would be formed during the cyclohexane conversion process in the presence of CO2. 13C isotope labeling experimental results demonstrate that CO2 can enter into the aromatics through the formation of oxygenated chemical intermediates and thereby improve the aromatic selectivity. This study may open a green, economic, and promising way to improve the aromatic selectivity for alkane aromatization process.

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Catalytic conversion of biomass-derived compounds to various amino acids: status and perspectives
Benjing Xu, Jinhang Dai, Ziting Du, Fukun Li, Huan Liu, Xingxing Gu, Xingmin Wang, Ning Li, Jun Zhao
Front. Chem. Sci. Eng.    2023, 17 (7): 817-829.   https://doi.org/10.1007/s11705-022-2254-z
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Amino acids are important nitrogen-containing chemicals that have a variety of applications. Currently, fermentation is the widely employed method to produce amino acids; however, the products are mostly limited to natural amino acids in the L-configuration. Catalytic synthesis is an alternative approach for the synthesis of amino acids with different types and configurations, where the use of renewable biomass-based feedstocks is highly attractive. To date, several lignocellulose and triacylglycerol-derived intermediates, typically α-keto acids and α-hydroxyl acids, have been transformed into amino acids via the amination reaction in the presence of additional nitrogen sources (i.e., NH3·H2O). Making full use of inherent nitrogen in biomass (i.e., chitin and protein) to produce amino acids avoids the use of extra nitrogen sources and meets the requirements of green chemistry, which is attracting increasing attention. In this review, we summarize different chemical-catalytic systems for the transformation of biomass to amino acids. An outlook on the challenges and opportunities for more effective production of amino acids from biomass by catalytic methods is provided.

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Anthocyanins/chitosan films doped by nano zinc oxide for active and intelligent packaging: comparison of anthocyanins source from purple tomato or black wolfberry
Yana Li, Zenghui Li, Yuwen Wang, Liangbo Sun, Houchang Pei
Front. Chem. Sci. Eng.    2023, 17 (6): 704-715.   https://doi.org/10.1007/s11705-022-2270-z
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The multifunctional films was prepared by blending chitosan and nano-ZnO with purple tomato anthocyanins or black wolfberry anthocyanins. The properties of films functioned by anthocyanins source and nano-ZnO content were studied. It was found purple tomato anthocyanins showed more significant color change against pH than black wolfberry anthocyanins. The nano-ZnO were widely dispersed in matrix and enhanced the compatibility of anthocyanins with chitosan. However, the anthocyanins source influenced the properties of the films more slightly than nano-ZnO addition. The tensile strength, antioxidant and antibacterial effects of the chitosan films dramatically increased after cooperated by nano-ZnO and anthocyanins, which also enhanced with increase of nano-ZnO content, whereas the elongation at break of the composite films decreased. Especially, the anthocyanin and nano-ZnO promoted the antibacterial activity of films synergistically. Composite films made from black wolfberry anthocyanins exhibited higher mechanical performance than those made from purple tomato anthocyanins but weaker antibacterial effects. The purple tomato anthocyanins/chitosan and nano-ZnO/purple tomato anthocyanins/chitosan films effectively reflected pork spoilage, changing their colors from dark green to brown, indicating the potential for applications in active and intelligent food packaging.

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Improving hole transfer of boron nitride quantum dots modified PDI for efficient photodegradation
Shiqing Ma, Chundong Peng, Zeyu Jia, Yanmei Feng, Kai Chen, Hao Ding, Daimei Chen, Zhong-Yong Yuan
Front. Chem. Sci. Eng.    2023, 17 (11): 1718-1727.   https://doi.org/10.1007/s11705-023-2319-7
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In recent years, organic photocatalyst under visible-light absorption has shown significant potential for solving environmental problems. However, it is still a great challenge for constructing a highly active organic photocatalyst due to the low separation efficiency of photogenerated carriers. Herein, an effective and robust photocatalyst perylene-3,4,9,10-tetracarboxylic diamide/boron nitride quantum dots (PDI/BNQDs), consisting of self-assemble PDI with π–π stacking structure and BNQDs, has been constructed and researched under visible light irradiation. The PDI/BNQDs composite gradually increases organic pollutant photodegradation with the loading amount of BNQDs. With 10 mL of BNQDs solution added (PDI/BNQDs-10), the organic pollutant photodegradation performance reaches a maximum, about 6.16 times higher with methylene blue and 1.68 times higher with ciprofloxacin than that of pure PDI supramolecular. The enhancement is attributed to improved separation of photogenerated carriers from self-assembled PDI by BNQDs due to their preeminent ability to extract holes. This work is significant for the supplement of PDI supramolecular composite materials. We believe that this photocatalytic design is capable of expanding organic semiconductors’ potential for their applications in photocatalysis.

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Power-to-chemicals: sustainable liquefaction of food waste with plasma-electrolysis
Wenquan Xie, Xianhui Zhang, Dengke Xi, Rusen Zhou, Size Yang, Patrick Cullen, Renwu Zhou
Front. Chem. Sci. Eng.    2023, 17 (5): 594-605.   https://doi.org/10.1007/s11705-022-2255-y
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The increasing amount of food waste from various industrial, agricultural, and household sources is an environmental burden if managed inappropriately. Numerous waste management approaches have been developed for the disposal of food waste, but still suffer from either high cost, production of toxic by-products, or secondary environmental pollutions. Herein, we report a new and sustainable plasma electrolysis biorefinery route for the rapid and efficient liquefaction of food waste. During the plasma electrolysis process, only the solvent is added to liquefy the waste, and anions in the waste can contribute to catalyzing the biowaste conversion. While liquefying the waste, the highly reactive species produced in the plasma electrolysis process can efficiently reduce the content of O, N, and Cl in the liquefied products and oxidize most of the metals into solid residues. Especially, the removal rate of Na and K elements was greater than 81%, which is significantly higher than using the traditional oil bath liquefaction, resulting in a relatively high-quality biocrude oil with a high heating value of 25.86 MJ·kg–1. Overall, this proposed strategy may provide a new sustainable and eco-friendly avenue for the power-to-chemicals valorization of food waste under benign conditions.

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Catalytic combustion of volatile organic compounds using perovskite oxides catalysts—a review
Shan Wang, Ping Xiao, Jie Yang, Sónia A.C. Carabineiro, Marek Wiśniewski, Junjiang Zhu, Xinying Liu
Front. Chem. Sci. Eng.    2023, 17 (11): 1649-1676.   https://doi.org/10.1007/s11705-023-2324-x
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With the rapid development of industry, volatile organic compounds (VOCs) are gaining attention as a class of pollutants that need to be eliminated due to their adverse effects on the environment and human health. Catalytic combustion is the most popular technology used for the removal of VOCs as it can be adapted to different organic emissions under mild conditions. This review first introduces the hazards of VOCs, their treatment technologies, and summarizes the treatment mechanism issues. Next, the characteristics and catalytic performance of perovskite oxides as catalysts for VOC removal are expounded, with a special focus on lattice distortions and surface defects caused by metal doping and surface modifications, and on the treatment of different VOCs. The challenges and the prospects regarding the design of perovskite oxides catalysts for the catalytic combustion of VOCs are also discussed. This review provides a reference base for improving the performance of perovskite catalysts to treat VOCs.

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A review on co-pyrolysis of agriculture biomass and disposable medical face mask waste for green fuel production: recent advances and thermo-kinetic models
Melvin X. J. Wee, Bridgid L. F. Chin, Agus Saptoro, Chung L. Yiin, Jiuan J. Chew, Jaka Sunarso, Suzana Yusup, Abhishek Sharma
Front. Chem. Sci. Eng.    2023, 17 (9): 1141-1161.   https://doi.org/10.1007/s11705-022-2230-7
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The Association of Southeast Asian Nations is blessed with agricultural resources, and with the growing population, it will continue to prosper, which follows the abundance of agricultural biomass. Lignocellulosic biomass attracted researchers’ interest in extracting bio-oil from these wastes. However, the resulting bio-oil has low heating values and undesirable physical properties. Hence, co-pyrolysis with plastic or polymer wastes is adopted to improve the yield and quality of the bio-oil. Furthermore, with the spread of the novel coronavirus, the surge of single-use plastic waste such as disposable medical face mask, can potentially set back the previous plastic waste reduction measures. Therefore, studies of existing technologies and techniques are referred in exploring the potential of disposable medical face mask waste as a candidate for co-pyrolysis with biomass. Process parameters, utilisation of catalysts and technologies are key factors in improving and optimising the process to achieve commercial standard of liquid fuel. Catalytic co-pyrolysis involves a series of complex mechanisms, which cannot be explained using simple iso-conversional models. Hence, advanced conversional models are introduced, followed by the evolutionary models and predictive models, which can solve the non-linear catalytic co-pyrolysis reaction kinetics. The outlook and challenges for the topic are discussed in detail.

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Size-controllable synthesis of monodispersed nitrogen-doped carbon nanospheres from polydopamine for high-rate supercapacitors
Ning Zhang, Fu-Cheng Gao, Hong Liu, Feng-Yun Wang, Ru-Liang Zhang, Qing Yu, Lei Liu
Front. Chem. Sci. Eng.    2023, 17 (11): 1788-1800.   https://doi.org/10.1007/s11705-023-2326-8
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Monodispersed nitrogen-doped carbon nanospheres with tunable particle size (100–230 nm) were synthesized via self-polymerization of biochemical dopamine in the presence of hexamethylenetetramine as a buffer and F127 as a size controlling agent. Hexamethylenetetramine can mildly release NH3, which in turn initiates the polymerization reaction of dopamine. The carbon nanospheres obtained exhibited a significant energy storage capability of 265 F·g–1 at 0.5 A·g–1 and high-rate performance of 82% in 6 mol·L–1 KOH (20 A·g–1), which could be attributed to the presence of abundant micro-mesoporous structure, doped nitrogen functional groups and the small particle size. Moreover, the fabricated symmetric supercapacitor device displayed a high stability of 94% after 5000 cycles, revealing the considerable potential of carbon nanospheres as electrode materials for energy storage.

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Insights into influence of aging processes on zero-valent iron modified biochar in copper(II) immobilization: from batch solution to pilot-scale investigation
Huabin Wang, Dingxiang Chen, Yi Wen, Ting Cui, Ying Liu, Yong Zhang, Rui Xu
Front. Chem. Sci. Eng.    2023, 17 (7): 880-892.   https://doi.org/10.1007/s11705-022-2282-8
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The zero-valent iron modified biochar materials are widely employed for heavy metals immobilization. However, these materials would be inevitably aged by natural forces after entering into the environment, while there are seldom studies reported the aging effects of zero-valent iron modified biochar. In this work, the hydrogen peroxide and hydrochloric acid solution were applied to simulate aging conditions of zero-valent iron modified biochar. According to the results, the adsorption capacity of copper(II) contaminants on biochar, zero-valent iron modified biochar-1, and zero-valent iron modified biochar-2 after aging was decreased by 15.36%, 22.65% and 23.26%, respectively. The surface interactions were assigned with chemisorption occurred on multi-molecular layers, which were proved by the pseudo-second-order and Langmuir models. After aging, the decreasing of capacity could be mainly attributed to the inhibition of ion-exchange and zero-valent iron oxidation. Moreover, the plant growth and soil leaching experiments also proved the effects of aging treatment, the zero-valent iron modified biochar reduced the inhibition of copper(II) bioavailability and increased the mobility of copper(II) after aging. All these results bridged the gaps between bio-adsorbents customization and their environmental behaviors during practical agro-industrial application.

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Lignin-based polymer with high phenolic hydroxyl group content prepared by the alkyl chain bridging method and applied as a dopant of PEDOT
Nanlong Hong, Jiahui Wang, Jinhua You
Front. Chem. Sci. Eng.    2023, 17 (8): 1075-1084.   https://doi.org/10.1007/s11705-022-2272-x
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Inspired by the importance of the phenolic group to the electron transporting property of hole transport materials, phenolic hydroxyl groups were introduced in lignosulfonate (LS) via the alkyl chain bridging method to prepare phenolated-lignosulfonate (PLS). The results showed that the phenolic group was boosted from 0.81 mmol∙g–1 of LS to 1.19 mmol∙g–1 of PLS. The electrochemical property results showed two oxidation peaks in the cyclic voltammogram (CV) curve of PLS, and the oxidation potential of the PLS-modified electrode decreased by 0.5 eV compared with that of LS. This result indicates that PLS is more easily oxidized than LS. Based on the excellent electron transporting property of PLS, PLS was applied as a dopant in poly(3,4-ethylenedioxythiophene) (PEDOT, called PEDOT:PLSs). PLS showed excellent dispersion properties for PEDOT. Moreover, the transmittance measurement results showed that the transmittance of PEDOT:PLSs exceeded 85% in the range of 300–800 nm. The CV results showed that the energy levels of PEDOT:PLSs could be flexibly adjusted by PLS amounts. The results indicate that the phenolic hydroxyl group of lignin can be easily boosted by the alkyl chain bridging method, and phenolated lignin-based polymers may have promising potential as dopants of PEDOT to produce hole transporting materials for different organic photovoltaic devices.

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Insights into carbon-based materials for catalytic dehydrogenation of low-carbon alkanes and ethylbenzene
Sijia Xing, Sixiang Zhai, Lei Chen, Huabin Yang, Zhong-Yong Yuan
Front. Chem. Sci. Eng.    2023, 17 (11): 1623-1648.   https://doi.org/10.1007/s11705-023-2328-6
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Direct dehydrogenation with high selectivity and oxidative dehydrogenation with low thermal limit has been regarded as promising methods to solve the increasing demands of light olefins and styrene. Metal-based catalysts have shown remarkable performance for these reactions, such as Pt, CrOx, Co, ZrOx, Zn and V. Compared with metal-based catalysts, carbon materials with stable structure, rich pore texture and large surface area, are ideal platforms as the catalysts and the supports for dehydrogenation reactions. In this review, carbon materials applied in direct dehydrogenation and oxidative dehydrogenation reactions including ordered mesoporous carbon, carbon nanodiamond, carbon nanotubes, graphene and activated carbon, are summarized. A general introduction to the dehydrogenation mechanism and active sites of carbon catalysts is briefly presented to provide a deep understanding of the carbon-based materials used in dehydrogenation reactions. The unique structure of each carbon material is presented, and the diversified synthesis methods of carbon catalysts are clarified. The approaches for promoting the catalytic activity of carbon catalysts are elaborated with respect to preparation method optimization, suitable structure design and heteroatom doping. The regeneration mechanism of carbon-based catalysts is discussed for providing guidance on catalytic performance enhancement. In addition, carbon materials as the support of metal-based catalysts contribute to exploiting the excellent catalytic performance of catalysts due to superior structural characteristics. In the end, the challenges in current research and strategies for future improvements are proposed.

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Sustainable conversion regenerated cellulose into cellulose oleate by sonochemistry
De-Fa Hou, Pan-Pan Yuan, Zi-Wei Feng, Meng An, Pei-Yao Li, Can Liu, Ming-Bo Yang
Front. Chem. Sci. Eng.    2023, 17 (8): 1096-1108.   https://doi.org/10.1007/s11705-023-2317-9
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Derivatization has great potential for the high-value utilization of cellulose by enhancing its processability and functionality. However, due to the low reactivity of natural cellulose, it remains challenging to rapidly prepare cellulose derivatives with high degrees of substitution. The “cavitation effect” of ultrasound can reduce the particle size and crystalline index of cellulose, which provides a possible method for preparing cellulose derivatives. Herein, a feasible method was proposed for efficiently converting regenerated cellulose to cellulose oleate with the assistance of ultrasonic treatment. By adjusting the reaction conditions including ultrasonic intensity, feeding ratios of oleic acid, reaction time, and reaction solvent, a series of cellulose oleates with degrees of substitution ranging from 0.37 to 1.71 were synthesized. Additionally, the effects of different reaction conditions on the chemical structures, crystalline structures, and thermal behaviors were investigated thoroughly. Cellulose oleates with degrees of substitution exceeding 1.23 exhibited amorphous structures and thermoplasticity with glass transition temperatures at 159.8 to 172.6 °C. This study presented a sustainable and practicable method for effectively derivatizing cellulose.

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Surface modification techniques of membranes to improve their antifouling characteristics: recent advancements and developments
Muhammad Tawalbeh, Haya Aljaghoub, Muhammad Qasim, Amani Al-Othman
Front. Chem. Sci. Eng.    2023, 17 (12): 1837-1865.   https://doi.org/10.1007/s11705-023-2347-3
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Extensive research efforts are currently devoted to developing and improving conventional technologies for water treatment. Membrane-based water treatment technologies are among the most preferred options due to their commercial success, simple operation, low energy and space requirements, and high separation efficiency. Despite the advances made in membrane-based technologies, fouling remains a critical challenge. Fouling occurs upon the accumulation of unwanted impurities on the membrane surface and within the membrane pores which results in a significant decline in the membrane permeate flux. To alleviate the operational challenges from fouling, surface modification to develop antifouling membranes appears to be an effective technique. A comprehensive review of the surface modification techniques for the development of antifouling membranes is provided in this paper. Chemical surface modification techniques (grafting and plasma treatment), physical modification techniques (blending, coating, adsorption, and thermal treatment), and combined physical and chemical modification techniques have been discussed. Moreover, the challenges related to surface modification and the future research directions are addressed.

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Rosin side chain type catalyst-free vitrimers with high cross-link density, mechanical strength, and thermal stability
Yunpeng Shen, Weishan Tang, Jinyang Li, Zhijun Ke, Lirong Liao, Peng Yang, Yuntao Lu, Xiaoping Rao
Front. Chem. Sci. Eng.    2023, 17 (9): 1267-1279.   https://doi.org/10.1007/s11705-022-2291-7
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The emergence of vitrimer, a new class of polymer materials can address the problem of recyclability, reprocess ability and recyclability of thermosetting plastics. Rosin, a natural product, is an ideal raw material for the preparation of polymers in a more sustainable way. Nevertheless, due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure, the cross-link density of materials is frequently lowered. In this study, hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids, which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers. It was completely characterized by differential scanning calorimetry test, thermogravimetric analysis, shape memory test and self-healing test. The prepared vitrimers exhibited good self-healing properties, excellent heat resistance (Td = 352 °C) as well as high mechanical properties (tensile strength of 46.75 MPa). The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton. Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy. Moreover, our work expanded the application field of rosin, increased the added value of rosin, and provided a novel method for preparing rosin-based vitrimers with ideal properties.

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Sulfur-deficient CoNi2S4 nanoparticles-anchored porous carbon nanofibers as bifunctional electrocatalyst for overall water splitting
Gaohui Du, Yi Fan, Lina Jia, Yunting Wang, Yawen Hao, Wenqi Zhao, Qingmei Su, Bingshe Xu
Front. Chem. Sci. Eng.    2023, 17 (11): 1707-1717.   https://doi.org/10.1007/s11705-023-2308-x
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Water electrolysis technology is considered to be one of the most promising means to produce hydrogen. Herein, aiming at the problems of high overpotential and slow kinetics in water splitting, N-doped porous carbon nanofibers-coupled CoNi2S4 nanoparticles are prepared as bifunctional electrocatalyst. In the strategy, NaCl is used as the template to prepare porous carbon nanofibers with a large surface area, and sulfur vacancies are created to modulate the electronic structure of CoNi2S4. Electron spin resonance confirms the formation of abundant sulfur vacancies, which largely reduce the bandgap of CoNi2S4 from 1.68 to 0.52 eV. The narrowed bandgap is conducive to the migration of valence electrons and decreases the charge transfer resistance for electrocatalytic reaction. Moreover, the uniform distribution of CoNi2S4 nanoparticles on carbon nanofibers can prevent the aggregation and facilitate the exposure of electrochemical active sites. Therefore, the composite catalyst exhibits low overpotentials of 340 mV@100 mA·cm–2 for oxygen evolution reaction and 380 mV@100 mA·cm–2 for hydrogen evolution reaction. The assembled electrolyzer requires 1.64 V to achieve 10 mA·cm–2 for overall water-splitting with good long-term stability. The excellent performance results from the synergistic effect of porous structures, sulfur deficiency, nitrogen doping, and the well-dispersed active component.

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NiFeRuOx nanosheets on Ni foam as an electrocatalyst for efficient overall alkaline seawater splitting
Yu Liu, Lin Chen, Yong Wang, Yuan Dong, Liang Zhou, Susana I. Córdoba de Torresi, Kenneth I. Ozoemena, Xiao-Yu Yang
Front. Chem. Sci. Eng.    2023, 17 (11): 1698-1706.   https://doi.org/10.1007/s11705-023-2334-8
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The electrocatalyst NiFeRuOx/NF, comprised of NiFeRuOx nanosheets grown on Ni foam, was synthesized using a hydrothermal process followed by thermal annealing. NiFeRuOx/NF displays high electrocatalytic activity and stability for overall alkaline seawater splitting: 98 mV@ 10 mA∙cm−2 in hydrogen evolution reaction, 318 mV@ 50 mA∙cm−2 in oxygen evolution reaction, and a cell voltage of 1.53 V@ 10 mA∙cm−2, as well as 20 h of durability. A solar-driven system containing such a bifunctional NiFeRuOx/NF has an almost 100% Faradaic efficiency. The NiFeRuOx coating around Ni foam is an anti-corrosion layer and also a critical factor for enhancement of bifunctional performances.

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Construction of NiCo2O4 nanoflake arrays on cellulose-derived carbon nanofibers as a freestanding electrode for high-performance supercapacitors
Xuepeng Ni, Kunming Li, Changlei Li, Qianqian Wu, Chenglin Liu, Huifang Chen, Qilin Wu, Anqi Ju
Front. Chem. Sci. Eng.    2023, 17 (6): 691-703.   https://doi.org/10.1007/s11705-022-2268-6
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Cellulose has a wide range of applications in many fields due to their naturally degradable and low-cost characteristics, but few studies can achieve cellulose-nanofibers by conventional electrospinning. Herein, we demonstrate that the freestanding cellulose-based carbon nanofibers are successfully obtained by a special design of electrospinning firstly, pre-oxidation and high-temperature carbonization (1600 °C), which display a superior electrical conductivity of 31.2 S·cm–1 and larger specific surface area of 35.61 m2·g–1 than that of the polyacrylonitrile-based carbon nanofibers (electrical conductivity of 18.5 S·cm–1, specific surface area of 12 m2·g–1). The NiCo2O4 nanoflake arrays are grown uniformly on the cellulose-based carbon nanofibers successfully by a facile one-step solvothermal and calcination method. The as-prepared cellulose-based carbon nanofibers/NiCo2O4 nanoflake arrays are directly used as electrodes to achieve a high specific capacitance of 1010 F·g–1 at 1 A·g–1 and a good cycling stability with 90.84% capacitance retention after 3000 times at 10 A·g–1. Furthermore, the all-solid-state symmetric supercapacitors assembled from the cellulose-based carbon nanofibers/NiCo2O4 deliver a high energy density of 62 W·h·kg–1 at a power density of 1200 W·kg–1. Six all-solid-state symmetric supercapacitors in series can also power a ‘DHU’ logo consisted of 36 light emitting diodes, confirming that the cellulose-based carbon nanofiber is a promising carbon matrix material for energy storage devices.

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Encapsulation of polyethylene glycol in cellulose-based porous capsules for latent heat storage and light-to-thermal conversion
Jiangwei Li, Lina Meng, Jiaxuan Chen, Xu Chen, Yonggui Wang, Zefang Xiao, Haigang Wang, Daxin Liang, Yanjun Xie
Front. Chem. Sci. Eng.    2023, 17 (8): 1038-1050.   https://doi.org/10.1007/s11705-022-2279-3
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Phase change materials are potential candidates for the application of latent heat storage. Herein, we fabricated porous capsules as shape-stable materials from cellulose-based polyelectrolyte complex, which were first prepared using cellulose 6-(N-pyridinium)hexanoyl ester as the cationic polyelectrolyte and carboxymethyl cellulose as the anionic polyelectrolyte to encapsulate polyethylene glycol by the vacuum impregnation method. Furthermore, the multi-walled carbon nanotube or graphene oxide, which were separately composited into the polyelectrolytes complex capsules to enhance thermal conductivity and light-to-thermal conversion efficiency. These capsules owned a typical core–shell structure, with an extremely high polyethylene glycol loading up to 34.33 g∙g‒1. After loading of polyethylene glycol, the resulted cellulose-based composite phase change materials exhibited high thermal energy storage ability with the latent heat up to 142.2 J∙g‒1, which was 98.5% of pure polyethylene glycol. Further results showed that the composite phase change materials demonstrated good form-stable property and thermal stability. Moreover, studies involving light-to-thermal conversion determined that composite phase change materials exhibited outstanding light-to-thermal conversion performance. Considering their exceptional comprehensive features, innovative composite phase change materials generated from cellulose presented a highly interesting choice for thermal management and renewable thermal energy storage.

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Corrosion behavior of Fe–Cr–Ni based alloys exposed to molten MgCl2–KCl–NaCl salt with over-added Mg corrosion inhibitor
Rui Yu, Qing Gong, Hao Shi, Yan Chai, Alexander Bonk, Alfons Weisenburger, Dihua Wang, Georg Müller, Thomas Bauer, Wenjin Ding
Front. Chem. Sci. Eng.    2023, 17 (10): 1608-1619.   https://doi.org/10.1007/s11705-023-2349-1
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MgCl2–NaCl–KCl salts mixture shows great potential as a high-temperature (> 700 °C) thermal energy storage material in next-generation concentrated solar power plants. Adding Mg into molten MgCl2–NaCl–KCl salt as a corrosion inhibitor is one of the most effective and cost-effective methods to mitigate the molten salt corrosion of commercial Fe–Cr–Ni alloys. However, it is found in this work that both stainless steel 310 and Incoloy 800H samples were severely corroded after 500 h immersion test at 700 °C when the alloy samples directly contacted with the over-added Mg in the liquid form. The corrosion attack is different from the classical impurity-driven corrosion in molten chloride salts found in previous work. Microscopic analysis indicates that Ni preferentially leaches out of alloy matrix due to the tendency to form MgNi2/Mg2Ni compounds. The Ni-depletion leads to the formation of a porous corrosion layer on both alloys, with the thickness around 204 µm (stainless steel 310) and 1300 µm (Incoloy 800H), respectively. These results suggest that direct contact of liquid Mg with Ni-containing alloys should be avoided during using Mg as a corrosion inhibitor for MgCl2–NaCl–KCl or other chlorides for high temperature heat storage and transfer.

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Durable and recyclable BiOBr/silk fibroin-cellulose acetate composite film for efficient photodegradation of dyes under visible light irradiation
Jialiang Xu, Jian Jian, Yixiao Dan, Jie Song, Lingxi Meng, Pei Deng, Weijie Sun, Yusheng Zhang, Jinhua Xiong, Zhengqiu Yuan, Hu Zhou
Front. Chem. Sci. Eng.    2023, 17 (11): 1765-1775.   https://doi.org/10.1007/s11705-023-2323-y
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A stable and recyclable of BiOBr/silk fibroin-cellulose acetate composite film was prepared by blending-wet phase transformation and in situ precipitate technology. The cellulose acetate film modified by silk fibroin formed a finger-shaped porous structure, which provided a large space for the uniform growth of BiOBr nanosheets and facilitated the shuttle flow of dyes in film. The morphology, phase structure, and optical properties of the composite films were characterized using various techniques, and their photocatalytic performance for dye wastewater was evaluated under visible light irradiation. Results showed that the BiOBr/SF-CA composite film exhibited efficient photocatalytic activity with 99.9% of rhodamine B degradation rate. Moreover, the composite film maintained high catalytic stability because Bi as the active species deposited on the film showed almost no loss. Finally, the possible photocatalytic mechanisms in the BiOBr/SF-CA composite film were speculated through radical-trapping experiments and electron spin resonance testing.

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Cuprous oxide/copper oxide interpenetrated into ordered mesoporous cellulose-based carbon aerogels for efficient photocatalytic degradation of methylene blue
Rui Cui, Dongnv Jin, Gaojie Jiao, Zhendong Liu, Jiliang Ma, Runcang Sun
Front. Chem. Sci. Eng.    2023, 17 (7): 918-929.   https://doi.org/10.1007/s11705-023-2305-0
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The casual discharge of dyes from industrial settings has seriously polluted global water systems. Owing to the abundance of biomass resources, preparing photocatalysts for photocatalytic degradation of dyes is significant; however, it still remains challenging. In this work, a cuprous oxide/copper oxide composite was interpenetrated onto carbon nanosheets of cellulose-based flexible carbon aerogels (Cu2O/CuO@CAx) via a simple freeze-drying-calcination method. The introduction of the carbon aerogel effectively prevents the aggregation of the cuprous oxide/copper oxide composite. In addition, Cu2O/CuO@CA0.2 has a larger specific surface area, stronger charge transfer capacity, and lower recombination rate of photogenerated carriers than copper oxide. Moreover, Cu2O/CuO@CA0.2 exhibited high photocatalytic activity in decomposing methylene blue, with a degradation rate reaching up to 99.09% in 60 min. The active oxidation species in the photocatalytic degradation process were systematically investigated by electron spin resonance characterization and poisoning experiments, among which singlet oxygen played a major role. In conclusion, this work provides an effective method for preparing photocatalysts using biomass resources in combination with different metal oxides. It also promotes the development of photocatalytic degradation of dyes.

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Effect of different acid anions on highly efficient Ce-based catalysts for selective catalytic reduction of NO with NH3
De Fang, Guanlin Huang, Jingyi Yang, Shengxing Pan, Caihong Lv, Da Li
Front. Chem. Sci. Eng.    2023, 17 (10): 1399-1411.   https://doi.org/10.1007/s11705-023-2345-5
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Three kinds of Ce-based catalysts (CePO4, CeVO4, Ce2(SO4)3) were synthesized and used for the selective catalytic reduction (SCR) of NO by NH3. NH3-SCR performances were conducted in the temperature range of 80 to 400 °C. The catalytic efficiencies of the three catalysts are as follow: CePO4 > CeVO4 > Ce2(SO4)3, which is in agreement with their abilities of NH3 adsorption capacities. The highest NO conversion rate of CePO4 could reach about 95%, and the catalyst had more than 90% NO conversion rate between 260 and 320 °C. The effect of PO43–, VO43– and SO42– on NH3-SCR performances of Ce-based catalysts was systematically investigated by the X-ray photoelectron spectroscopy analysis, NH3 temperature programmed desorption, H2 temperature programmed reduction and field emission scanning electron microscopy tests. The key factors that can enhance the SCR are the existence of Ce4+, large NH3 adsorption capacity, high and early H2 consumptions, and suitable microstructures for gas adsorption. Finally, CePO4 and CeVO4 catalysts also exhibited relatively strong tolerance of SO2, and the upward trend about 8% was detected due to the sulfation enhancement by SO2 for Ce2(SO4)3.

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Multiple input self-organizing-map ResNet model for optimization of petroleum refinery conversion units
Jiannan Zhu, Vladimir Mahalec, Chen Fan, Minglei Yang, Feng Qian
Front. Chem. Sci. Eng.    2023, 17 (6): 759-771.   https://doi.org/10.1007/s11705-022-2269-5
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This work introduces a deep-learning network, i.e., multi-input self-organizing-map ResNet (MISR), for modeling refining units comprised of two reactors and a separation train. The model is comprised of self-organizing-map and the neural network parts. The self-organizing-map part maps the input data into multiple two-dimensional planes and sends them to the neural network part. In the neural network part, residual blocks enhance the convergence and accuracy, ensuring that the structure will not be overfitted easily. Development of the MISR model of hydrocracking unit also benefits from the utilization of prior knowledge of the importance of the input variables for predicting properties of the products. The results show that the proposed MISR structure predicts more accurately the product yields and properties than the previously introduced self-organizing-map convolutional neural network model, thus leading to more accurate optimization of the hydrocracker operation. Moreover, the MISR model has smoother error convergence than the previous model. Optimal operating conditions have been determined via multi-round-particle-swarm and differential evolution algorithms. Numerical experiments show that the MISR model is suitable for modeling nonlinear conversion units which are often encountered in refining and petrochemical plants.

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Investigation of the roles of lignin in biomass-based hydrogel for efficient desalination
Qizhao Shao, Lan Sun, Xinzhou Wu, Dafeng Zheng
Front. Chem. Sci. Eng.    2023, 17 (7): 954-965.   https://doi.org/10.1007/s11705-023-2311-2
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The shortage of freshwater has become a global challenge, and solar-driven interfacial evaporation for desalination is a promising way to alleviate the crisis. To develop highly efficient and environmentally friendly photothermal evaporator, the hydroxyethyl cellulose (HEC)/alkaline lignin (AL)/graphene oxide (GO) hydrogels (CLGs) with remarkable evaporative performance were successfully fabricated by a facile sol–gel method using biomass residues. The influence of AL content on the physicochemical properties of the evaporator was investigated. The increasing content of AL improves the mechanical properties, saturated water content and crosslink density of the hydrogels. The designed materials exhibit outstanding thermal insulation capacity (the thermal conductivity of less than 0.05 W·m–1·K–1) and high light absorption capacity of more than 97%. The solar evaporation efficiency and water evaporation rate of the HEC/64 wt % of AL/GO hydrogels (CLG4) achieve 92.1% and 2.55 kg·m–2·h–1 under 1 sun, respectively. The salt resistance test results reveal that the evaporation rate of the CLG4 can still reach 2.44 kg·m–2·h–1 in 3.5 wt % NaCl solution. The solar evaporation rate of the CLG4 can maintain in the range of 2.45–2.59 kg·m–2·h–1 in five cycles. This low-cost lignin-based photothermal evaporator offers a sustainable strategy for desalination.

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“Charging” the cigarette butt: heteroatomic porous carbon nanosheets with edge-induced topological defects for enhanced oxygen evolution performance
Qing-Hui Kong, Xian-Wei Lv, Jin-Tao Ren, Hao-Yu Wang, Xin-Lian Song, Feng Xu, Zhong-Yong Yuan
Front. Chem. Sci. Eng.    2023, 17 (11): 1755-1764.   https://doi.org/10.1007/s11705-023-2318-8
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Owing to the complexity of electron transfer pathways, the sluggish oxygen evolution reaction process is defined as the bottleneck for the practical application of Zn–air batteries. In this effort, metal nanoparticles (Co, Ni, Fe, etc.) encapsulated within nitrogen-doped carbon materials with abundant edge sites were synthesized by one-step pyrolysis treatment using cigarette butts as raw materials, which can drastically accelerate the overall rate of oxygen evolution reaction by facilitating the adsorption of oxygenated intermediates by the edge-induced topological defects. The prepared catalyst of nitrogen-doped carbon porous nanosheets loaded with Co nanoparticles (Co@NC-500) exhibits enhanced catalytic activity toward oxygen evolution reaction, with a low overpotential of 350 mV at the current density of 10 mA·cm–2. Furthermore, the Zn–air battery assembled with Co@NC-500 catalyst demonstrates a desirable performance affording an open-circuit potential of 1.336 V and power density of 33.6 mW·cm–2, indicating considerable practical application potential.

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Efficient conversion of lignin to alkylphenols over highly stable inverse spinel MnFe2O4 catalysts
Yi Qi, Xuezhi Zeng, Lingyingzi Xiong, Xuliang Lin, Bowen Liu, Yanlin Qin
Front. Chem. Sci. Eng.    2023, 17 (8): 1085-1095.   https://doi.org/10.1007/s11705-022-2236-1
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The aromatic properties of lignin make it a promising source of valuable chemicals and fuels. Developing efficient and stable catalysts to effectively convert lignin into high-value chemicals is challenging. In this work, MnFe2O4 spinel catalysts with oxygen-rich vacancies and porous distribution were synthesized by a simple solvothermal process and used to catalyze the depolymerization of lignin in an isopropanol solvent system. The specific surface area was 110.5 m2∙g–1, which substantially increased the active sites for lignin depolymerization compared to Fe3O4. The conversion of lignin reached 94%, and the selectivity of alkylphenols exceeded 90% after 5 h at 250 °C. Underpinned by characterizations, products, and density functional theory analysis, the results showed that the catalytic performance of MnFe2O4 was attributed to the composition of Mn and Fe with strong Mn–O–Fe synergy. In addition, the cycling experiments and characterization showed that the depolymerized lignin on MnFe2O4 has excellent cycling stability. Thus, our work provides valuable insights into the mechanism of lignin catalytic depolymerization and paves the way for the industrial-scale application of this process.

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