Chinese Journal of Catalysis最新文献

{"title":"Solar-driven H2O2 production by S-scheme heterojunction photocatalyst","authors":"Han Li ,&nbsp;Wang Wang ,&nbsp;Kaiqiang Xu ,&nbsp;Bei Cheng ,&nbsp;Jingsan Xu ,&nbsp;Shaowen Cao","doi":"10.1016/S1872-2067(24)60257-3","DOIUrl":"10.1016/S1872-2067(24)60257-3","url":null,"abstract":"<div><div>Hydrogen peroxide (H₂O₂), as an essential and green chemical, is extensively used in energy and environmental applications. However, the production of H₂O₂ primarily relies on the anthraquinone method, which is an energy-intensive method involving multi-step reactions, producing harmful by-product wastes. Solar-driven H₂O₂ production, an alternative route for H₂O₂ generation, is a green and sustainable technology since it only utilizes water and oxygen as feedstock. However, the rapid recombination of charge carriers as well as insufficient redox capability limit the photocatalytic H₂O₂ production performance. Constructing step-scheme (S-scheme) heterojunction photocatalysts has been regarded as an effective strategy to address these drawbacks because it not only achieves spatially separated charge carriers, but also preserves redox capability of the photocatalytic system. This paper covers the recent advances of S-scheme heterojunction photocatalysts for H₂O₂ production in terms of basic principles, characterization techniques, and preparation strategies. Moreover, the mechanism and advantages of S-scheme heterojunction for photocatalytic H₂O₂ generation are systematically discussed. The recent S-scheme heterojunction designs, including inorganic-organic heterojunction, inorganic-inorganic heterojunction, and organic-organic heterojunction, are summarized. Lastly, the challenges and research directions of S-scheme photocatalysts for H₂O₂ generation are presented.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 24-47"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144105655","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An experimental and computational investigation on structural evolution of the In2O3 catalyst during the induction period of CO2 hydrogenation","authors":"Zhangqian Wei ,&nbsp;Mingxiu Wang ,&nbsp;Xinnan Lu ,&nbsp;Zixuan Zhou ,&nbsp;Ziqi Tang ,&nbsp;Chunran Chang ,&nbsp;Yong Yang ,&nbsp;Shenggang Li ,&nbsp;Peng Gao","doi":"10.1016/S1872-2067(25)64657-2","DOIUrl":"10.1016/S1872-2067(25)64657-2","url":null,"abstract":"<div><div>As one of the most important industrially viable methods for carbon dioxide (CO₂) utilization, methanol synthesis serves as a platform for production of green fuels and commodity chemicals. For sustainable methanol synthesis, In₂O₃ is an ideal catalyst and has garnered significant attention. Herein, cubic In₂O₃ nanoparticles were prepared via the precipitation method and evaluated for CO₂ hydrogenation to produce methanol. During the initial 10 h of reaction, CO₂ conversion gradually increased, accompanied by a slow decrease of methanol selectivity, and the reaction reached equilibrium after 10-20 h on stream. This activation and induction stage may be attributed to the sintering of In₂O₃ nanoparticles and the creation of more oxygen vacancies on In₂O₃ surfaces. Further experimental studies demonstrate that hydrogen induction created additional oxygen vacancies during the catalyst activation stage, enhancing the performance of In₂O₃ catalyst for CO₂ hydrogenation. Density functional theory calculations and microkinetic simulations further demonstrated that surfaces with higher oxygen vacancy coverages or hydroxylated surfaces formed during this induction period can enhance the reaction rate and increase the CO₂ conversion. However, they predominantly promote the formation of CO instead of methanol, leading to reduced methanol selectivity. These predictions align well with the above-mentioned experimental observations. Our work thus provides an in-depth analysis of the induction stage of the CO₂ hydrogenation process on In₂O₃ nano-catalyst, and offers valuable insights for significantly improving the CO₂ reactivity of In₂O₃-based catalysts while maintaining long-term stability.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 301-313"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient carbon integration of CO2 in propane aromatization over acidic zeolites","authors":"Cheng Li ,&nbsp;Xudong Fang ,&nbsp;Bin Li ,&nbsp;Siyang Yan ,&nbsp;Zhiyang Chen ,&nbsp;Leilei Yang ,&nbsp;Shaowen Hao ,&nbsp;Hongchao Liu ,&nbsp;Jiaxu Liu ,&nbsp;Wenliang Zhu","doi":"10.1016/S1872-2067(25)64680-8","DOIUrl":"10.1016/S1872-2067(25)64680-8","url":null,"abstract":"<div><div>Direct converting carbon dioxide (CO₂) and propane (C₃H₈) into aromatics with high carbon utilization offers a desirable opportunity to simultaneously mitigate CO₂ emission and adequately utilize C₃H₈ in shale gas. Owing to their thermodynamic resistance, converting CO₂ and C₃H₈ respectively remains difficult. Here, we achieve 60.2% aromatics selectivity and 48.8% propane conversion over H-ZSM-5-25 <em>via</em> a zeolite-catalyzing the coupling of CO₂ and C₃H₈. Operando dual-beam FTIR spectroscopy combined with ¹³C-labeled CO₂ tracing experiments revealed that CO₂ is directly involved in the generation of aromatics, with its carbon atoms selectively embedded into the aromatic ring, bypassing the reverse water-gas shift pathway. Accordingly, a cooperative aromatization mechanism is proposed. Thereinto, lactones, produced from CO₂ and olefins, are proven to be the key intermediate. This work not only provides an opportunity for simultaneous conversion of CO₂ and C₃H₈, but also expends coupling strategy designing of CO₂ and alkanes over acidic zeolites.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 314-322"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106079","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In-situ distortion of Bi lattice in Bi28O32(SO4)10 cluster boosted electrocatalytic CO2 reduction to formate","authors":"Jinghan Sun ,&nbsp;Zhengrong Xu ,&nbsp;Deng Liu ,&nbsp;Aiguo Kong ,&nbsp;Qichun Zhang ,&nbsp;Rui Liu","doi":"10.1016/S1872-2067(24)60287-1","DOIUrl":"10.1016/S1872-2067(24)60287-1","url":null,"abstract":"<div><div>To convert carbon dioxide into high-value-added liquid products such as formate with renewable electricity (CO₂RR) is a promising strategy of CO₂ resource utilization. The key is to find a highly efficient and selective electrocatalyst for CO₂RR. Herein, clustered Bi₂₈O₃₂(SO₄)₁₀ was found to show a high formate Faradaic efficiency (FE_formate) of 96.2% at –1.1 V_RHE and FE_formate above 90% in a wide potential range from –0.9 to –1.3 V_RHE in H-type cell, surpassing the corresponding layered Bi₂O₂SO₄ (85.6% FE_formate at –1.1 V_RHE). The advantageous CO₂RR performance of Bi₂₈O₃₂(SO₄)₁₀ over Bi₂O₂SO₄ was ascribed to a special two-step <em>in-situ</em> reconstruction process, consisting of Bi₂₈O₃₂(SO₄)₁₀ → Bi_–2.1/Bi₂O₂CO₃ → Bi_–2.1/Bi_–0.6 during CO₂RR. It gave metallic Bi_–2.1 with lattice distortion of –2.1% at the first step and metallic Bi_–0.6 with lattice distortion of –0.6% at the second step. In contrast, the usual layered Bi₂O₂SO₄ only formed metallic Bi_–0.6 with weaker lattice strain. The metallic Bi_–2.1 revealed higher efficiency in stabilizing *CO₂ intermediate and reducing the energy barrier of CO₂RR, while suppressing hydrogen evolution reaction and CO formation. This work delivers a high-performance cluster-type Bi₂₈O₃₂(SO₄)₁₀ electrocatalyst for CO₂RR, and elucidates the origin of superior performance of clustered Bi₂₈O₃₂(SO₄)₁₀ electrocatalysts compared with layered Bi₂O₂SO₄.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 199-210"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A theoretical study of the role of K on the reverse water-gas shift reaction on Hägg carbide","authors":"Xianxuan Ren ,&nbsp;Rozemarijn D.E. Krösschell ,&nbsp;Zhuowu Men ,&nbsp;Peng Wang ,&nbsp;Ivo A.W. Filot ,&nbsp;Emiel J.M. Hensen","doi":"10.1016/S1872-2067(24)60278-0","DOIUrl":"10.1016/S1872-2067(24)60278-0","url":null,"abstract":"<div><div>Potassium (K) is known to enhance the catalytic performance of Fe-based catalysts in the reverse water-gas shift (rWGS) reaction, which is highly relevant during Fischer-Tropsch (FT) synthesis of CO₂-H₂ mixtures. To elucidate the mechanistic role of K promoter, we employed density functional theory (DFT) calculations in conjunction with microkinetic modelling for two representative surface terminations of Hägg carbide (χ-Fe₅C₂), i.e., (010) and (510). K₂O results in stronger adsorption of CO₂ and H₂ on Hägg carbide and promotes C–O bond dissociation of adsorbed CO₂ by increasing the electron density on Fe atoms close to the promoter oxide. The increased electron density of the surface Fe atoms results in an increased electron-electron repulsion with bonding orbitals of adsorbed CO₂. Microkinetics simulations predict that K₂O increases the CO₂ conversion during CO₂-FT synthesis. K₂O also enhances CO adsorption and dissociation, facilitating the formation of methane, used here as a proxy for hydrocarbons formation during CO₂-FT synthesis. CO dissociation and O removal via H₂O compete as the rate-controlling steps in CO₂-FT.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 289-300"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Single [Ga(OH)]2+ species supported on mesoporous hollow-structured H-ZSM-5: A highly efficient light alkanes aromatization catalyst","authors":"Dezhi Shi ,&nbsp;Yanyan Chen ,&nbsp;Xiao Chen ,&nbsp;Sen Wang ,&nbsp;Qiang Wang ,&nbsp;Pengfei Wang ,&nbsp;Huaqing Zhu ,&nbsp;Mei Dong ,&nbsp;Jun Xu ,&nbsp;Feng Deng ,&nbsp;Jianguo Wang ,&nbsp;Weibin Fan","doi":"10.1016/S1872-2067(25)64678-X","DOIUrl":"10.1016/S1872-2067(25)64678-X","url":null,"abstract":"<div><div>Aromatization of light alkanes is a value-added process in both petrochemical and coal chemical industries. Here, single [Ga(OH)]²⁺ ion-exchanged mesoporous hollow-structured ZSM-5 (Ga-MH-ZSM-5) material was prepared, and it shows unprecedented catalytic performance in light alkane aromatization, considering activity, product selectivity and catalytic stability. The average aromatics yields in ethane aromatization at 600 °C and WHSV of 0.8 h^–1 within 28 h and in propane aromatization at 580 °C and WHSV of 1.1 h^–1 within 20 h reach ~18.4% and ~70.8% with benzene, toluene and xylenes (BTX) accounting for <em>~</em>96% and ~88% of aromatics, respectively. Ga-MH-ZSM-5-0.41 gave a TON for formation of aromatics (TON_aromatics) from propane as high as 57479, whereas the reported catalysts maximally show a TON_aromatics of 5514. This also holds true for ethane aromatization; the TON_aromatics obtained on Ga-MH-ZSM-5-0.41 was ≥ 3845 in contrast to ≤ 392 on reported non-noble metal catalysts. The catalytic activity of Ga-MH-ZSM-5 highly depends on Ga species structures. [Ga(OH)]²⁺ ions are predominant species at Ga loading ≤ 0.3 wt%, while more [Ga(OH)₂]⁺ and GaO_<em>x</em> oligomers are formed with increasing Ga content. Upon reduction with H₂, [Ga(OH)]²⁺ and [Ga(OH)₂]⁺ are transformed into [GaH]²⁺ and [GaH₂]⁺ species, which show a propane dehydrogenation rate of 300 and 15 times of that of Brønsted acid sites respectively. The light alkanes are mainly dehydrogenated into light olefins on [GaH]²⁺ species, and then, oligomerized and cyclized into (alkyl)cycloalkanes on H⁺ sites, which is followed by possible ring expansion on H⁺ and sequential dehydrogenations into aromatics primarily on [GaH]²⁺.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 359-375"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering of sulfate ions migration in Fe2O3-doped NiSO4/Al2O3 catalysts to enhance the selective trimerization of propylene","authors":"Xu Liu ,&nbsp;Yu Ling ,&nbsp;Xiao Chen ,&nbsp;Changhai Liang","doi":"10.1016/S1872-2067(25)64663-8","DOIUrl":"10.1016/S1872-2067(25)64663-8","url":null,"abstract":"<div><div>Propylene, a readily accessible and economically viable light olefin, has garnered substantial interest for its potential conversion into valuable higher olefins through oligomerization processes. The distribution of products is profoundly influenced by the catalyst structure. In this study, Fe₂O₃-doped NiSO₄/Al₂O₃ catalysts have been meticulously developed to facilitate the selective trimerization of propylene under mild conditions. Significantly, the 0.25Fe₂O₃-NiSO₄/Al₂O₃ catalyst demonstrates an enhanced reaction rate (48.5 mmol_C3/(g_cat.·h)), alongside a high yield of C9 (~ 32.2%), significantly surpassing the performance of the NiSO₄/Al₂O₃ catalyst (C9: ~24.1%). The incorporation of Fe₂O₃ modifies the migration process of sulfate ions, altering the Lewis acidity of the electron-deficient Ni and Fe sites on the catalyst and resulting a shift in product distribution from a Schulz-Flory distribution to a Poisson distribution. This shift is primarily ascribed to the heightened energy barrier for the β-H elimination reaction in the C6 alkyl intermediates on the doped catalyst, further promoting polymerization to yield a greater quantity of Type II C9. Furthermore, the validation of the Cossee-Arlman mechanism within the reaction pathway has been confirmed. It is noteworthy that the 0.25Fe₂O₃-NiSO₄/Al₂O₃ catalyst exhibits remarkable stability exceeding 80 h in the selective trimerization of propylene. These research findings significantly enhance our understanding of the mechanisms underlying olefin oligomerization reactions and provide invaluable insights for the development of more effective catalysts.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 376-391"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Driving selective photoelectrocatalytic oxidation of seawater to oxygen via regulating interfacial water structures on titanium oxides","authors":"Qisen Jia ,&nbsp;Yanan Wang ,&nbsp;Yan Zhao ,&nbsp;Zhenming Tian ,&nbsp;Luyao Ren ,&nbsp;Xuejing Cui ,&nbsp;Guangbo Liu ,&nbsp;Xin Chen ,&nbsp;Wenzhen Li ,&nbsp;Luhua Jiang","doi":"10.1016/S1872-2067(24)60282-2","DOIUrl":"10.1016/S1872-2067(24)60282-2","url":null,"abstract":"<div><div>Photoelectrocatalytic (PEC) seawater splitting as a green and sustainable route to harvest hydrogen is attractive yet hampered by low activity of photoanodes and unexpected high selectivity to the corrosive and toxic chlorine. Especially, it is full of challenges to unveil the key factors influencing the selectivity of such complex PEC processes. Herein, by regulating the energy band and surface structure of the anatase TiO₂ nanotube array photoanode <em>via</em> nitrogen-doping, the seawater PEC oxidation shifts from Cl^– oxidation reaction (ClOR) dominant on the TiO₂ photoanode (61.6%) to oxygen evolution reaction (OER) dominant on the N-TiO₂ photoanode (62.9%). Comprehensive investigations including <em>operando</em> photoelectrochemical FTIR and DFT calculations unveil that the asymmetric hydrogen-bonding water at the N-TiO₂ electrode/electrolyte interface enriches under illumination, facilitating proton transfer and moderate adsorption strength of oxygen-intermediates, which lowers the energy barrier for the OER yet elevates the energy barrier for the ClOR, resulting to a promoted selectivity towards the OER. The work sheds light on the underlying mechanism of the PEC water oxidation processes, and highlights the crucial role of interfacial water on the PEC selectivity, which could be regulated by controlling the energy band and the surface structure of semiconductors.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 154-163"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144106181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering metalloenzymes for new-to-nature carbene and nitrene transfer biocatalysis","authors":"Wenjin Pan ,&nbsp;Xinlong Fan ,&nbsp;Wantong Jiang ,&nbsp;Sirui Xin ,&nbsp;Ningzhi Wang ,&nbsp;Qian Wang ,&nbsp;Keyang Yu ,&nbsp;Xinkun Ren","doi":"10.1016/S1872-2067(25)64659-6","DOIUrl":"10.1016/S1872-2067(25)64659-6","url":null,"abstract":"<div><div>Biocatalysis, which involves using enzymes to address synthetic challenges of significance to humans, has rapidly developed into a pivotal technology for chemical innovation. Over the past decade, there has been a notable increase in the use of metalloproteins as catalysts for abiotic, synthetically valuable carbene and nitrene transfer reactions. This trend highlights the adaptability of protein-based catalysts and our growing ability to harness this potential for novel enzyme chemistry. This review focuses on the most recent advancements in metalloenzyme-catalyzed carbene and nitrene transfer reactions, including cyclopropanation, carbene Y–H and C–H insertions, Doyle-Kirmse reactions, aldehyde olefinations, nitrene azide-to-aldehyde conversions, and nitrene C–H insertion. A variety of protein scaffolds have been engineered to offer varied levels of reactivity and selectivity towards pharmaceutically relevant compounds. The application of these new catalysts in preparative-scale synthesis underscores their emerging biotechnological significance. Furthermore, insights into key intermediate and determining factors in stereochemistry are offering valuable guidance for engineering metalloproteins, thereby expanding the scope and utility of these non-natural activities.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 4-23"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144105654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A de novo biomimetic enzyme-nanozyme hybrid system for advancing lignin valorization","authors":"Xinying Wang ,&nbsp;Qing Tian ,&nbsp;Yao Chen ,&nbsp;Aipeng Li ,&nbsp;Lianbing Zhang ,&nbsp;Mingming Zhang ,&nbsp;Changzhi Li ,&nbsp;Qiang Fei","doi":"10.1016/S1872-2067(25)64656-0","DOIUrl":"10.1016/S1872-2067(25)64656-0","url":null,"abstract":"<div><div>Directed degradation of abundant renewable lignin into small aromatic compounds is crucial for lignin valorization but challenging. The degradation of lignin in natural environments typically involves multienzyme synergy. However, the proteinaceous characteristics of lignin-degrading enzymes restrict their accessibility to certain regions of intricate lignin, resulting in the multienzyme systems being unable to fully demonstrate their effectiveness. Herein, a <em>de novo</em> biomimetic enzyme-nanozyme hybrid system was constructed by combining λ-MnO₂ nanozyme with laccase CotA from <em>Bacillus subtilis</em>, aimed at facilitating lignin degradation under mild conditions. The lignin degradation rate of the CotA + λ-MnO₂ hybrid system was determined to be 25.15%, which was much higher than those of the lignin degradation systems with only laccase CotA (15.32%) or λ-MnO₂ nanozyme (14.90%). Notably, the proportion of aromatic chemicals in the products derived from the hybrid system reached as much as 48%, which was 41.2% and 118.2% higher than those of the CotA- and λ-MnO₂-catalyzed systems, respectively. Analysis of products mapping and lignin structure changes suggested that the higher proportion of aromatic compounds in the CotA + λ-MnO₂ hybrid system was more likely to benefit from the laccase-mediated methoxylation. Moreover, electron paramagnetic resonance analysis indicated that the intensity and kind of free radicals such as •OH and •O₂^– are closely linked to the degradation rate and reaction type. This work is the inaugural application of an enzyme-nanozyme hybrid system for lignin degradation, demonstrating the potential of the synergistic interaction between enzyme and nanozyme in the directed degradation of lignin.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"72 ","pages":"Pages 84-94"},"PeriodicalIF":15.7,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144105657","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}