List of Issues

Chinese Journal of Catalysis
2025, Vol. 70
Online: 18 March 2025

Previous Issue    Next Issue

Cover: In recent years, covalent organic frameworks (COF) materials have garnered significant attention in the field of solar-to-chemical energy conversion due to their unique properties. Professors Xin Li, Hongjun Dong, and co-workers have comprehensively reviewed the latest advancements in COF-based photocatalytic materials, including the historical overview, fundamental principles, design concepts, synthesis strategies, structural characteristics, and diversity of COF materials in the photocatalysis field. Additionally, they provided an in-depth discussion of the practical applications of COF materials in various photocatalytic reactions. Read more about the article behind the cover on page 142–206.

For Selected:

Download Citations EndNote Ris BibTeX

Toggle Thumbnails

Highlights

Select

Enhanced O2 adsorption at Au sites and improved H2O2 production Xuejiao Wang, Kezhen Qi, Kaiqiang Xu 2025, 70:  1-4.  DOI: 10.1016/S1872-2067(24)60246-9 Abstract ( 152 )   HTML ( 20 )   PDF (1153KB) ( 92 )

Select

S-scheme heterojunction with intraband defect levels for artificial photosynthesis Xiaoming Liu, Zhifeng Jiang 2025, 70:  5-7.  DOI: 10.1016/S1872-2067(24)60223-8 Abstract ( 93 )   HTML ( 6 )   PDF (1102KB) ( 39 )

Reviews

Select

Advances in metal-free carbon catalysts for acetylene hydrochlorination: From heteroatom doping to intrinsic defects over the past decade Shuhao Wei, Guojun Lan, Yiyang Qiu, Di Lin, Wei Kong, Ying Li 2025, 70:  8-43.  DOI: 10.1016/S1872-2067(24)60245-7 Abstract ( 191 )   HTML ( 9 )   PDF (7788KB) ( 86 )   The development of metal-free carbon catalysts has garnered significant attention as a promising approach to address the challenges of sustainable catalysis, particularly in the replacement of toxic and environmentally hazardous mercury-based systems for the coal-based PVC industry. Within a decade of development, the catalytic performance of carbon catalysts has been improved greatly and even shows superiorities over metal catalysts in some cases, which have demonstrated great potential as sustainable alternatives to mercury catalysts. This review provides a comprehensive summary of the recent advancements in carbon catalysts for acetylene hydrochlorination. It encompasses a wide range of aspects, including the identification of active sites from heteroatom doping to intrinsic carbon defects, the various synthetic strategies employed, the reaction and deactivation mechanisms of carbon catalysts, and the current insights into the key challenges that are encountered on the journey from laboratory research to scalable commercialization within the field of carbon catalysts. The review offers foundational insights and practical guidelines for designing green carbon catalysts systems, not only for acetylene hydrochlorination but also for other heterogeneous catalytic reactions.

Select

Photocatalytic water splitting versus H2 generation coupled with organic synthesis: A large critical review Oleksandr Savateev, Jingru Zhuang, Sijie Wan, Chunshan Song, Shaowen Cao, Junwang Tang 2025, 70:  44-114.  DOI: 10.1016/S1872-2067(24)60216-0 Abstract ( 180 )   HTML ( 11 )   PDF (11486KB) ( 84 )   Photocatalytic water splitting using natural solar light is considered as a sustainable approach to generate H2 and O2. While H2 has high market value, the by-product of water splitting, oxygen, is less valuable. To make H2 produced by means of photocatalysis more economically competitive to that generated from methane, its generation is studied together with synthesis of organic compounds that have higher market value. This review summarizes and analyzes critically dehydrogenation reactions that were developed since 1980s. Photocatalytic dehydrogenation reactions are classified and the results are collected in the online database. Performance of homogeneous and heterogenous photocatalysts in dehydrogenation reactions, such as yield rates of organic products on analytical and preparative scales, and quantum efficiencies are compared. Current limitations of the existing methods and photocatalytic systems are identified and directions for the future developments are outlined.

Select

Heterogeneous Co-based catalytic systems for alkene hydroformylation Chao-an Liang, Bo Zeng, Baolin Feng, Huibing Shi, Fengqi Zhang, Jianhua Liu, Lin He, Yuxiao Ding, Chungu Xia 2025, 70:  115-141.  DOI: 10.1016/S1872-2067(24)60238-X Abstract ( 114 )   HTML ( 2 )   PDF (4391KB) ( 30 )   Hydroformylation of olefins is one of the highest-volume industrial reactions to meet the vast demands for aldehydes as well as their derivatives. Homogeneous Co complexes were the original catalysts industrialized since 1960s. Heterogeneous catalysis is considered superior owing to the facile separation of catalysts from products, shorter technical process, and reduced manufacturing costs. Unexpectedly, there has not been a single case of plant using heterogenized Co-based catalyst successfully. To address the separation issue and understand the catalytic mechanism of the reactions, this review summarizes the progress in heterogeneous systems and provides a detailed discussion of their catalytic performance. Strategies for stabilizing Co species through support modification and additive incorporation are carefully considered to elucidate why heterogeneous systems have not yet succeeded on an industrial scale. Furthermore, we provide our insights for the development of heterogeneous catalytic hydroformylation, including the challenges, opportunities, and outlooks. The aim is to deepen the fundamental understanding of heterogeneous alkene hydroformylation, guiding the community's research efforts towards realizing its successful application in the future.

Select

Recent advances of covalent organic frameworks-based photocatalysts: Principles, designs, and applications Hongjun Dong, Chunhong Qu, Chunmei Li, Bo Hu, Xin Li, Guijie Liang, Jizhou Jiang 2025, 70:  142-206.  DOI: 10.1016/S1872-2067(24)60184-1 Abstract ( 217 )   HTML ( 5 )   PDF (8722KB) ( 82 )   Covalent organic frameworks (COFs) semiconductor materials have garnered significant attention in solar to chemical energy conversion owing to their unique properties, including structural tunability, pre-design capability, large surface area, abundant pore structures, high crystallinity, excellent chemical stability, suitable energy-band structure, fast charge carrier transfer and so on. These intrinsic features endow COFs with the remarkable candidates for various photocatalytic applications including photocatalytic H2 generation from water reduction, CO2 reduction, degradation of organic pollutants, N2 fixation, H2O2 evolution, and even organic synthesis. Here, this review comprehensively summarizes the recent advancements in COF-based materials for the above photocatalytic reactions, including the historic overview of the COF in the photocatalysis field, the fundamentals and design philosophy of COF-based photocatalysts, the advances of synthesis strategies, the structural characteristics and diversities, the practical applications in various photocatalytic fields as well as the challenges and future development direction in terms of COFs material and application perspectives. We sincerely hope this review can offer symbolic guidelines for future development COF semiconductor materials in this promising field.

Select

Photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane to alcohol Yu Huang, Lei Zou, Yuan-Biao Huang, Rong Cao 2025, 70:  207-229.  DOI: 10.1016/S1872-2067(24)60212-3 Abstract ( 90 )   HTML ( 0 )   PDF (5001KB) ( 45 )   The conversion of the greenhouse gas methane to value-added chemicals such as alcohols is a promising technology to mitigate environmental issue and the energy crisis. Especially, the sustainable photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane at ambient conditions is regarded as an alternative technology to replace with thermocatalysis. In this review, we summarize recent advances in photocatalytic, electrocatalytic and photoelectrocatalytic conversion of methane into alcohols. We firstly introduce the general principles of photocatalysis, electrocatalysis and photoelectrocatalysis. Then, we discuss the mechanism for selective activation of C-H bond and following oxygenation over metal, inorganic semiconductor, organic semiconductor, and heterojunction composite systems in the photocatalytic, electrocatalytic and photoelectrocatalytic methane oxidation in detail. Later, we present insights into the construction of effective photocatalyst, electrocatalyst and photoelectrocatalyst for methane conversion into alcohols from the perspective of band structures and active sites. Finally, the challenges and outlook for future designs of photocatalytic, electrocatalytic and photoelectrocatalytic methane oxidation systems are also proposed.

Select

1D-based nanostructures in photocatalytic CO2 reduction Farideh Kolahdouzan, Nahal Goodarzi, Mahboobeh Setayeshmehr, Dorsa Sadat Mousavi, Alireza Z. Moshfegh 2025, 70:  230-259.  DOI: 10.1016/S1872-2067(24)60214-7 Abstract ( 64 )   HTML ( 3 )   PDF (5535KB) ( 23 )   Air pollution and global warming have aroused great interest in CO2 conversion research, as CO2 is the most important greenhouse gas. Photocatalytic CO2 reduction reaction (CRR) is a key carbon capture and utilization (CCU) technology aimed at transforming CO2 into valuable products like fuels and chemicals. However, many semiconductor photocatalysts used in CRR face challenges such as low optical absorption, poor charge carrier separation, and electron-hole recombination, leading to low reaction yields. Some important solutions to these issues include reducing nanostructure dimensions, cocatalyst decoration, as well as metal/nonmetal doping, and heterojunction construction. One-dimensional (1D) nanostructures like nanorods, nanotubes, nanowires, and nanofibers are prominent photocatalysts for CO2 reduction process due to their excellent light absorption capability, high electron-hole separation efficiency, high aspect ratio, and abundant exposed active surface sites. In this research, after studying CO2 reduction mechanism, we first discuss 1D nanomaterials growth methods based on the growing environment. Types of 1D nanostructures in photocatalytic CRR, have been also investigated. Two main strategies to improve 1D-based photocatalysts in CRR including surface modification and heterojunction construction are reviewed. Finally, the report presents some important challenges of the CRR and their solutions for future applications.

Articles

Select

The curvature structure unlocks an ultra-efficient metal-free carbon catalyst surpassing gold for acetylene hydrochlorination Shuhao Wei, Ye Chen, Yiyang Qiu, Wei Kong, Di Lin, Jiarong Li, Guojun Lan, Yi Jia, Xiucheng Sun, Zaizhe Cheng, Jian Liu, P. Hu, Ying Li 2025, 70:  260-271.  DOI: 10.1016/S1872-2067(24)60250-0 Abstract ( 186 )   HTML ( 12 )   PDF (2085KB) ( 83 )   Supporting Information Metal-free carbon catalysts have garnered significant attention since their inception. Despite substantial advancements, including widely adopted strategies such as heteroatom doping and defect engineering, their catalytic performance remains inferior to that of metal-based catalysts. In this study, we have predicted and demonstrated that the curvature of carbon plays a pivotal role in the adsorption of acetylene and the overall catalytic performance. First-principles calculations suggest that a tip-enhanced local electric field at the defect site on the curved carbon catalyst enhances the reaction kinetics for acetylene hydrochlorination. The experimental results highlight the structural advantages of the curved defect site, revealing that high-curvature defective carbon (HCDC) demonstrates an adsorption capacity for acetylene that is almost two orders of magnitude higher than that of defective carbon. Notably, HCDC achieves an acetylene conversion of up to 90% at 220 °C under a gas hourly space velocity of 300 h-1, significantly surpassing the performance of the benchmark 0.25% Au/AC catalyst. This proof-of-concept study reveals the fundamental mechanisms driving the superior performance of carbon catalysts with curved nanostructures and presents a straightforward, environmentally friendly method for large-scale production of carbon materials with precisely controlled nanostructures. It highlights the potential for commercializing metal-free carbon catalysts in acetylene hydrochlorination and related heterogenous catalytic reactions.

Select

Synergistic sites over the ZnxZrO catalyst for targeted cleavage of the C-H bonds of ethane in tandem with CO2 activation Wenjun Qiang, Duohua Liao, Maolin Wang, Lingzhen Zeng, Weiqi Li, Xuedong Ma, Liang Yang, Shuang Li, Ding Ma 2025, 70:  272-284.  DOI: 10.1016/S1872-2067(24)60235-4 Abstract ( 93 )   HTML ( 3 )   PDF (3347KB) ( 34 )   Supporting Information The CO2-assisted oxidative dehydrogenation of ethane (CO2-ODHE) provides a promising way to produce ethylene and utilize CO2. Simultaneous upgrading of ethane into the high value-added chemical products and the reduction of greenhouse gas CO2 emissions could be achieved. However, the targeted breaking of the C-C/C-H bonds of ethane is still a challenge for the designed catalysts. In this paper, ZnO-doped ZrO2 bifunctional catalysts (ZnxZrO) with different Zn/Zr molar ratios were prepared by the deposition-precipitation method, and the functions of various sites for CO2-ODHE reaction were revealed by in situ characterizations and ethane pulse experiment: the medium-strength acidic Zn-O-Zr sites are responsible for the purposefully cracking of ethane C-H bonds to ethylene, while the more oxygen vacancies (OV) created by the introduction of Zn2+ are responsible for the efficient activation C=O bonds of CO2, thus promoting the RWGS reaction. In addition, the Zn0.2ZrO catalyst demonstrated excellent catalytic performances, with C2H6 conversion, C2H4 yield, and CO2 conversion about 19.1%, 10.5%, and 10.6% within 5 h, respectively (600 °C, GHSV = 3000 mL/(g·h)). Especially, the initial ethylene space-time yield of 355.5 μmol/(min·g) was obtained under 6000 mL/(g·h); Finally, the tandem reaction mechanism of ethane dehydrogenation and RWGS was revealed.

Select

Proximity electronic effect of adjacent Ni Site enhances compatibility of hydrogenation and deoxygenation over Cu Site to boost nitrate electroreduction to ammonia Xue-Feng Cheng, Qing Liu, Qi-Meng Sun, Huilong Dong, Dong-Yun Chen, Ying Zheng, Qing-Feng Xu, Jian-Mei Lu 2025, 70:  285-298.  DOI: 10.1016/S1872-2067(24)60221-4 Abstract ( 84 )   HTML ( 3 )   PDF (3187KB) ( 29 )   Supporting Information Electrocatalytic conversion of nitrate to ammonia (NITRR) can simultaneously achieve the removal of nitrate and the synthesis of value-added ammonia, a promising candidate to replace Haber-Bosch process with low carbon dioxide emissions. However, high hydrogenation energy barrier for *NO intermediates and insufficient supply of active hydrogen cause slow hydrogenation process, and further result in low efficiency of nitrate conversion and ammonia synthesis. Herein, a series of tandem catalysts, one-dimensional coordination polymers (1D CCPs) with dual sites are synthesized and obtained 190.4 mg h-1 mgcat-1 ammonia production rate with Faradaic efficiency of 97.16%, outperforming to the most of recent reported catalysts. The catalytic performances are well-maintained even after a long-term stability test of 1200 h, laying the foundation for practical applications. Density functional theory results reveal that the stationary adsorbed *NO on Ni site induced proximity electronic effect could reduce the energy barrier for hydrogenation of *NO intermediates over Cu site. In addition, the Ni site in the dual sites 1D CCPs is conducive to generating active hydrogen, providing rich proton source to boost the hydrogenation of *NO, and further enhancing the compatibility of deoxygenation and hydrogenation process. Our work paves a new insight into the mechanism of NITRR process and will inspire more research interests in exploring the proximity electronic effect in catalytic process.

Select

Modulation of the electronic structure of CoP active sites by Er-doping for nitrite reduction for ammonia electrosynthesis Donglin Zhao, Keyu Zhou, Li Zhan, Guangyin Fan, Yan Long, Shuyan Song 2025, 70:  299-310.  DOI: 10.1016/S1872-2067(24)60224-X Abstract ( 54 )   HTML ( 0 )   PDF (2935KB) ( 13 )   Supporting Information The electrochemical conversion of toxic nitrite (NO2-) is a promising approach for the simultaneous removal of nitrogen contaminants and synthesis of ammonia (NH3). In this study, we present the Er-doping-induced electronic modulation of CoP integrated with nitrogen-doped carbon (CN) nanosheets supported on a titanium mesh (Er-CoP@NC/TM) for the electrocatalytic NO2- reduction reaction (eNO2-RR) for NH3 synthesis. The catalyst demonstrates a high Faraday efficiency of 97.08 ± 2.22% and a high yield of 2087.60 ± 17.10 µmol h-1 cm-2 for NH3 production. Characterization and theoretical calculations revealed that Er-doping facilitated the electronic modulation of CoP in Er-CoP@NC/TM, which regulated the adsorption behaviors of intermediates and was the rate-limiting step for the eNO2-RR, thereby enhancing the electrocatalytic performance. Quenching experiments and electron paramagnetic resonance tests suggest that both direct electrocatalytic reduction by active hydrogen and electron transfer are critical for the eNO2-RR for NH3 synthesis. Furthermore, Er-CoP@NC/TM exhibited high performance across a wide range of NO2- concentrations (0.05-0.1 mol L-1) and pH values (4-13). In addition, the catalyst demonstrated strong resistance to anions and a long cycle life in simulated wastewater environments. This study offers a powerful approach for the remediation of NO2- wastewater and recovery of valuable inorganic compounds.

Select

Machine learning-assisted screening of SA-FLP dual-active-site catalysts for the production of methanol from methane and water Tao Ban, Jian-Wei Wang, Xi-Yang Yu, Hai-Kuo Tian, Xin Gao, Zheng-Qing Huang, Chun-Ran Chang 2025, 70:  311-321.  DOI: 10.1016/S1872-2067(24)60225-1 Abstract ( 153 )   HTML ( 5 )   PDF (2127KB) ( 67 )   Supporting Information One-step direct production of methanol from methane and water (PMMW) under mild conditions is challenging in heterogeneous catalysis owing to the absence of highly effective catalysts. Herein, we designed a series of “Single-Atom” - “Frustrated Lewis Pair” (SA-FLP) dual active sites for the direct PMMW via density functional theory (DFT) calculations combined with a machine learning (ML) approach. The results indicate that the nine designed SA-FLP catalysts are capable of efficiently activate CH4 and H2O and facilitate the coupling of OH* and CH3* into methanol. The DFT-based microkinetic simulation (MKM) results indicate that CH3OH production on Co1-FLP and Pt1-FLP catalysts can reach the turnover frequencies (TOFs) of 1.01 × 10−3 s-1 and 8.80 × 10−4 s-1, respectively, which exceed the experimentally reported values by three orders of magnitude. ML results unveil that the gradient boosted regression model with 13 simple features could give satisfactory predictions for the TOFs of CH3OH production with RMSE and R2 of 0.009 s-1 and 1.00, respectively. The ML-predicted MKM results indicate that four catalysts including V1-, Fe1-, Ti1-, and Mn1-FLP exhibit higher TOFs of CH3OH production than the value that the most relevant experiments reported, indicating that the four catalysts are also promising catalysts for the PMMW. This study not only develops a simple and efficient approach for design and screening SA-FLP catalysts but also provides mechanistic insights into the direct PMMW.

Select

Identification of stable and selective nickel alloy catalyst for acceptorless dehydrogenation of ethane Guomin Li, Teng Li, Bin Wang, Yong Ding, Xinjiang Cui, Feng Shi 2025, 70:  322-332.  DOI: 10.1016/S1872-2067(24)60229-9 Abstract ( 71 )   HTML ( 3 )   PDF (2666KB) ( 24 )   Supporting Information Modifying the electronic density of states and the synergistic effect of the active centers by introducing a second metal present an efficient strategy to tune physi/chemi-sorption, probably lead to improving catalytic performances. Herein, bimetallic Ni3Mo/Al2O3 catalyst was demonstrated and exhibited over 5 times more active than Pt/Al2O3 toward the ethane dehydrogenation (EDH) as well as 2-10 times activity enhancement compared with their monometallic Ni and Mo counterparts and other Ni-based bimetallic nanoparticles. Kinetic studies revealed that the activation energy over Ni3Mo/Al2O3 (111 kJ mol-1) was much lower than that of Ni (157 kJ mol-1) and Mo (171 kJ·mol-1). DFT calculations showed ethane was adsorbed on the Ni or Mo surface in a more parallel configuration, whereas over Ni3Mo it adopted an inclined configuration. This change promoted ethane adsorption and pre-activation of the C-H bond, thereby benefiting the ethane dehydrogenation process on the Ni3Mo surface.

Select

Rational construction of S-scheme CdS quantum dots/In2O3 hollow nanotubes heterojunction for enhanced photocatalytic H2 evolution Yong-Hui Wu, Yu-Qing Yan, Yi-Xiang Deng, Wei-Ya Huang, Kai Yang, Kang-Qiang Lu 2025, 70:  333-340.  DOI: 10.1016/S1872-2067(24)60213-5 Abstract ( 126 )   HTML ( 1 )   PDF (2271KB) ( 60 )   Supporting Information The rapid recombination of photogenerated carriers poses a significant limitation on the use of CdS quantum dots (QDs) in photocatalysis. Herein, the construction of a novel S-scheme heterojunction between cubic-phase CdS QDs and hollow nanotube In2O3 is successfully achieved using an electrostatic self-assembly method. Under visible light irradiation, all CdS-In2O3 composites exhibit higher hydrogen evolution efficiency compared to pure CdS QDs. Notably, the photocatalytic H2 evolution rate of the optimal CdS-7%In2O3 composite is determined to be 2258.59 μmol g−1 h−1, approximately 12.3 times higher than that of pure CdS. The cyclic test indicates that the CdS-In2O3 composite maintains considerable activity even after 5 cycles, indicating its excellent stability. In situ X-ray photoelectron spectroscopy and density functional theory calculations confirm that carrier migration in CdS-In2O3 composites adheres to a typical S-scheme heterojunction mechanism. Additionally, a series of characterizations demonstrate that the formation of S-scheme heterojunctions between In2O3 and CdS inhibits charge recombination and accelerates the separation and migration of photogenerated carriers in the CdS QDs, thus achieving enhanced photocatalytic performance. This work elucidates the pivotal role of S-scheme heterojunctions in photocatalytic H2 production and offers novel insights into the construction of effective composite photocatalysts.

Select

Atomically dispersed Ba sites as electron promoters to enhance the performance for photoreduction of CO2 Lina Zhang, Guowei Liu, Xinyan Deng, Qiuye Li, Jianjun Yang 2025, 70:  341-352.  DOI: 10.1016/S1872-2067(24)60226-3 Abstract ( 54 )   HTML ( 1 )   PDF (2236KB) ( 13 )   Supporting Information The highly photocatalytic conversion of CO2 into valuable products is a promising method for mitigating the global greenhouse effect and increasing the energy supply. However, the utilization of electron-deficient active sites to activate CO2 leads to lower photocatalytic efficiency and selectivity. One effective strategy to improve CO2 photoreduction performance is making precise adjustments to the electronic structure of the photocatalyst. Herein, the defective TiO2 modified with Cu, Ba, and CuBa metal sites is synthesized via a simple photo-deposition method and applied for photoreduction of CO2. Among the prepared catalysts, Cu1Ba3/TiO2-SBO (TiO2-SBO: TiO2 with surface and bulk oxygen vacancies) has been demonstrated to possess excellent photocatalytic conversion of CO2, with the activity levels of the CO and CH4 that are 8 and 6 times higher than the bare TiO2-SBO, and the electron selectivity of CO is up to 53%. The results reveal that oxygen vacancies and CuBa bimetallic sites have a synergistic ability to facilitate the separation of photogenerated carriers. Furthermore, the electron-donor Ba metal enables modulation of the electronic structure of Cu co-catalysts, generating electron-rich Cu metal sites that accelerate the activation of CO2. Meanwhile, the theoretical calculations prove that the Cu1Ba3/TiO2-SBO has the stronger CO2 adsorption energy, and its strengthened binding of *COOH and the markedly reduced formation energy of CO and *CO intermediates boost the conversion of COOH to CO and enhance the selectivity of CO. Thereby, the defective TiO2 modified with CuBa bimetal represents a more effective measure for CO2 reduction into valuable products.

Select

Isomorphous substitution in CaAl-hydrotalcite to construct high density single-atom catalysts for selective N-Heteroarene hydrogenation Jieting He, Yu Liang, Binbin Zhao, Lei Liu, Qian He, Dingsheng Wang, Jinxiang Dong 2025, 70:  353-362.  DOI: 10.1016/S1872-2067(24)60217-2 Abstract ( 50 )   HTML ( 0 )   PDF (2346KB) ( 14 )   Supporting Information Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications, but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging. Herein, we report an innovative strategy for the fabrication of high-density single-atoms (Rh, Ru, Pd) catalysts on CaAl-layered double hydroxides (CaAl-LDH) via isomorphous substitution. The Rh species have occupied Ca2+ vacancies within CaAl-LDH laminate by ion-exchange, facilitating a substantial loading of isolated Rh single-atoms. Such catalysts displayed superior performance in the selective hydrogenation to quinoline, pivotal for liquid organic hydrogen storage, and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified. Combining the experimental results and density functional theory calculations, the pathway of quinoline hydrogenation over Rh1CaAl-LDH was proposed. This synthetic strategy marks a significant advancement in the field of single-atom catalysts, expanding their horizons in green chemical processes.

Select

Bimetallic NixFe2-xP cocatalyst with tunable electronic structure for enhanced photocatalytic benzyl alcohol oxidation coupled with H2 evolution over red phosphorus Shuang Li, Haili Lin, Xuemei Jia, Xin Jin, Qianlong Wang, Xinyue Li, Shifu Chen, Jing Cao 2025, 70:  363-377.  DOI: 10.1016/S1872-2067(24)60236-6 Abstract ( 70 )   HTML ( 1 )   PDF (6314KB) ( 33 )   Supporting Information Although bimetallic phosphide cocatalysts have attracted considerable interest in photocatalysis research owing to their advantageous thermodynamic characteristics, superstable and efficient cocatalysts have rarely been produced through the modulation of their structure and composition. In this study, a series of bimetallic nickel-iron phosphide (NixFe2-xP, where 0 < x < 2) cocatalysts with controllable structures and overpotentials were designed by adjusting the atomic ratio of Ni/Fe onto nonmetallic elemental red phosphorus (RP) for the photocatalytic selective oxidation of benzyl alcohol (BA) coupled with hydrogen production. The catalysts exhibited an outstanding photocatalytic activity for benzaldehyde and a high H2 yield. The RP regulated by bimetallic phosphide cocatalysts (NixFe2-xP) demonstrated higher photocatalytic oxidation-reduction activity than that regulated by monometallic phosphide cocatalysts (Ni2P and Fe2P). In particular, the RP regulated by Ni1.25Fe0.75P exhibited the best photocatalytic performance. In addition, experimental and theoretical calculations further illustrated that Ni1.25Fe0.75P, with the optimized electronic structure, possessed good electrical conductivity and provided strong adsorption and abundant active sites, thereby accelerating electron migration and lowering the reaction energy barrier of RP. This finding offers valuable insights into the rational design of highly effective cocatalysts aimed at optimizing the photocatalytic activity of composite photocatalysts.

Select

TiO2-facet-dependent effect on methane combustion over Ir/TiO2 catalysts Huimei Duan, Xiaofei Li, Chuanhui Wang, Congyun Zhang, Kaiwen Yu, Lei Chen, Yunshang Zhang, Jiabin Ji, Xianfeng Yang, Dongjiang Yang 2025, 70:  378-387.  DOI: 10.1016/S1872-2067(24)60227-5 Abstract ( 56 )   HTML ( 1 )   PDF (2799KB) ( 14 )   Supporting Information Engineering the morphology of the support is effective in tuning the redox properties of active metals for efficient catalytic methane combustion via tailoring the metal-support interaction. Herein, uniform Ir nanoparticles supported on anatase TiO2 with different morphologies predominantly exposing {100}, {101}, and {001} planes were synthesized and tested for methane combustion. The CH4 catalytic activity shows a remarkable TiO2-facet-dependent effect and follows the order of Ir/TiO2-{100} > Ir/TiO2-{101} >> Ir/TiO2-{001}. Detailed characterizations and DFT calculations reveal that compared with Ir-TiO2-{101} and Ir-TiO2-{001} interfaces, the superior Ir-TiO2-{100} interface facilitates the generation of electron-rich Ir species through more profound charge transfer from TiO2-{100} to Ir atoms. The electron-rich Ir structure, featuring abundant defect oxygen vacancies, significantly enhances the redox properties of active Ir species and reduces the activation energy for breaking the initial C-H bond in CH4, resulting in the superior catalytic activity for methane combustion. These findings deepen fundamental insights into the TiO2-facet-dependent reactivity of different Ir/TiO2 nanomaterials in methane oxidation and pave the way for designing efficient Ir-based methane oxidation catalysts.

Select

Electrochemistry assisted chlorine corrosion strategy: The minute-level fabrication of lattice Cl- functioned high spin-polarized Ni/Fe-LDH array for enhanced anti-Cl- OER performance Bo Zhang, Ru Xiao, Liyuan Liu, Xiaobin Liu, Ying Deng, Qingliang Lv, Zexing Wu, Yunmei Du, Yanyan Li, Zhenyu Xiao, Lei Wang 2025, 70:  388-398.  DOI: 10.1016/S1872-2067(24)60215-9 Abstract ( 79 )   HTML ( 2 )   PDF (2395KB) ( 24 )   Supporting Information Although the intermittent energy-driven direct seawater splitting technology provides an unparalleled approach to achieving sustainable development, the severe corrosion via aggressive Cl- severely affects the stability and efficiency of the anode catalyst and limits its industrial application. Herein, a lattice Cl- functioned NiFe-LDH electrode (E-NF-LDHCl or E-NF-LDHSW) is firstly constructed by a minute-level electrochemistry assisted chlorine corrosion strategy, which presents enhanced oxygen evolution reaction (OER) performance and excellent anti-Cl- corrosion behavior for seawater splitting. The optimized E-NF-LDHCl and E-NF-LDHSW deliver low OER overpotential of 355 and 384 mV to reach 1 A cm−2 current density in the 1 mol L-1 KOH and 1 mol L-1 KOH seawater, respectively, as well as excellent stability of E-NF-LDHCl is maintained at 1 A cm-2 for 400 h in the 1 mol L-1 KOH and 1 mol L-1 KOH + 0.5 mol L-1 NaCl. MD (molecular dynamics) simulation and DFT (density functional theory) calculation confirmed that strong common-ion repulsion effect in IHP region repels free Cl-, forming high spin polarization centers and more single electrons to enhance the intrinsic activity of OER.

Select

Carbon diffusion mechanism as an effective stability enhancement strategy: The case study of Ni-based catalyst for photothermal catalytic dry reforming of methane Dezheng Li, Huimin Liu, Xuewen Xiao, Manqi Zhao, Dehua He, Yiming Lei 2025, 70:  399-409.  DOI: 10.1016/S1872-2067(24)60249-4 Abstract ( 114 )   HTML ( 2 )   PDF (1776KB) ( 42 )   Supporting Information Photothermal catalytic methane dry reforming (DRM) technology can convert greenhouse gases (i.e. CH4 and CO2) into syngas (i.e. H2 and CO), providing more opportunities for reducing the greenhouse effect and achieving carbon neutrality. In the DRM field, Ni-based catalysts attract wide attention due to their low cost and high activity. However, the carbon deposition over Ni-based catalysts always leads to rapid deactivation, which is still a main challenge. To improve the long-term stability of Ni-based catalysts, this work proposes a carbon-atom-diffusion strategy under photothermal conditions and investigates its effect on a Zn-doped Ni-based photothermal catalyst (Ni3Zn@CeO2). The photothermal catalytic behavior of Ni3Zn@CeO2 can maintain more than 70 h in DRM reaction. And the photocatalytic DRM activity of Ni3Zn@CeO2 is 1.2 times higher than thermal catalytic activity. Density functional theory (DFT) calculation and experimental characterizations indicate that Ni3Zn promotes the diffusion of carbon atoms into the Ni3Zn to form the Ni3ZnC0.7 phase with body-centered cubic (bcc) structure, thus inhibiting carbon deposition. Further, in-situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and DFT calculation prove Ni3Zn@CeO2 benefits the CH4 activation and inhibits the carbon deposition during the DRM process. Through inducing carbon atoms diffusion within the Ni3Zn lattice, this work provides a straightforward and feasible strategy for achieving efficient photothermal catalytic DRM and even other CH4 conversion implementations with long-term stability.

Select

Role of Y2O3 in Cu/ZnO/Y2O3 catalysts for CO2 hydrogenation to methanol Ziguo Cai, Xuefeng Yu, Penglong Wang, Huifang Wu, Ruifeng Chong, Limin Ren, Tao Hu, Xiang Wang 2025, 70:  410-419.  DOI: 10.1016/S1872-2067(24)60220-2 Abstract ( 126 )   HTML ( 6 )   PDF (1525KB) ( 57 )   Supporting Information CuZn-based catalyst is an attractive catalyst for methanol synthesis from CO2 hydrogenation, but it early deactivates and its methanol yield still needs to improve. In this study, Y2O3 was introduced to Cu/ZnO using a one-pot hydrothermal method, and exhibits a synergistic effect of ZnO and Y2O3 on enhancing methanol yield and the stability. We found that the interaction between Y2O3 and ZnO results in abundant oxygen vacancies formation, thereby enhancing CO2 adsorption and activation. Kinetic analysis and in situ DRIFTS suggest that RWGS forming CO and methanol formation compete for a mutual intermediate HCOO*, and the introduction of Y2O3 to Cu/ZnO raises the energy barrier for the CO formation but lowers that for methanol formation, thus enhancing the methanol yield on Cu/ZnO/Y2O3.

Select

Decoding the mechanism of P450-catalyzed aromatic hydroxylation: Uncovering the arene oxide pathway and insights into the regioselectivity Qun Huang, Xuan Zhang, Guangwu Sun, Rui-ying Qiu, Lan Luo, Cuizhen Wang, Longwei Gao, Bing Gao, Bo Chen, Binju Wang, Jian-bo Wang 2025, 70:  420-430.  DOI: 10.1016/S1872-2067(24)60234-2 Abstract ( 98 )   HTML ( 2 )   PDF (1893KB) ( 31 )   Supporting Information P450 enzymes-catalyzed aromatic hydroxylation plays an important role in detoxification, biosynthesis, and potential carcinogenic effect of aromatic compounds. Though it has been explored for decades, the actual process of aromatic hydroxylation and mechanism of regioselectivity catalyzed by cytochrome P450 monooxygenases remained ambiguous. Here, we have resolved these issues. With a stable chiral organofluorine probe, and especially with X-ray data of two isolated arene oxides derivatives, we demonstrate that an arene oxide pathway is definitely involved in P450-catalyzed aromatic hydroxylation. By the capture, isolation, identification and reactivity exploration of the arene 1,2-oxide and arene 2,3-oxide intermediates, together with advanced QM calculations, the mechanism of how two intermediates go to the same product has been elucidated. In addition to the model substrate, we also confirmed that an arene oxide intermediate is involved in the P450-catalyzed hydroxylation pathway of a natural product derivative methyl cinnamate, which indicates that this intermediate appears to be universal in P450-catalyzed aromatic hydroxylation. Our work not only provides the most direct evidence for the arene oxide pathway and new insights into the regioselectivity involved in P450-catalyzed aromatic hydroxylation, but also supplies a new synthetic approach to achieve the dearomatization of aromatic compounds.

Select

Constructing S-scheme heterojunction between porphyrinyl covalent organic frameworks and Nb2C MXene for photocatalytic H2O2 production Mingyang Xu, Zhenzhen Li, Rongchen Shen, Xin Zhang, Zhihong Zhang, Peng Zhang, Xin Li 2025, 70:  431-443.  DOI: 10.1016/S1872-2067(24)60247-0 Abstract ( 84 )   HTML ( 3 )   PDF (2811KB) ( 29 )   Supporting Information We have developed a novel S-scheme heterojunction photocatalyst for the photocatalytic production of hydrogen peroxide (H2O2) via a two-electron (2e−) oxygen reduction reaction. This S-scheme heterojunction Tph-Dha-COF@Nb2C was fabricated via the in-situ solvothermal growth of Tph-Dha-COF nanostructures on amino-functionalized Nb2C MXene nanoflakes (Nb2C-NH2). The integration of Nb2C significantly extended the visible light absorption of Tph-Dha-COF into the near-infrared region for photocatalytic H2O2 production. The Tph-Dha-COF@Nb2C composite demonstrated efficient charge separation, rapid electron transfer, and enhanced oxygen adsorption. Consequently, the Tph-Dha-COF@Nb2C heterojunction exhibited a high H2O2 production rate of 1833 μmol g‒1 h‒1 without sacrificial agents. In-situ Fourier transformed infrared spectroscopy and density functional theory calculations revealed the photocatalytic H2O2 production mechanism. The generated H2O2 demonstrated enhanced antibacterial activity. This work presents the first application of Nb2C in the photocatalytic synthesis of H2O2 and provides a novel strategy for constructing COF-based heterojunctions for photocatalytic H2O2 generation and wastewater treatment.

Select

Unified construction of prenylated and reverse-prenylated oxindoles from isoprene launched by Ni catalysis Ying-Ying Liu, Ying Li, Xue-Ting Li, Su-Yang Xu, Ding-Wei Ji, Xiang-Ping Hu, Qing-An Chen 2025, 70:  444-454.  DOI: 10.1016/S1872-2067(24)60218-4 Abstract ( 63 )   HTML ( 1 )   PDF (2099KB) ( 26 )   Supporting Information As important natural and pharmaceutical motifs, the catalytic construction of structurally diverse 3,3-disubstituted oxindoles often requires elaborate synthetic efforts on optimizations. Herein, we developed a simple and divergent approach for constructing reverse-prenylated and prenylated oxindoles launched by Ni catalysis with bulk chemical isoprene. Using C3-unsubstituted oxindoles as starting materials, mono reverse-prenylation was demonstrated in high chemo- and regioselectivities facilitated by the combination of Ni(0) and monodentate phosphine ligand. Using the obtained reverse-prenylated oxindoles as versatile synthon, substitutions at the pseudobenzylic position with various electrophiles created vicinal quaternary centers in a concise way. With the help of additives (PPh3 and NaH), air could be directly used as green oxidant to construct prenylated and reverse-prenylated α-hydroxy-oxindoles divergently from the same substrates. In situ esterification of prenylated α-hydroxy-oxindoles allowed subsequent Friedel-Crafts substitutions with diverse nucleophiles to deliver prenyl substituted dimeric or spiro-oxindoles. This protocol provides a divergent synthetic approach for the construction of highly functionalized 3,3-disubstituted oxindoles, which have been otherwise difficult to access in a unified approach.