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Chinese Journal of Catalysis
2025, Vol. 74
Online: 18 July 2025

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Cover: Prof. Yao Fu's group at the University of Science and Technology of China developed a Cu@MFI bifunctional catalyst through zeolite pore-confined architecture. By synergizing binuclear Cu active sites with spatial confinement effects, this innovative design precisely restricts transition-state configurations, achieving 100% conversion and exclusive selectivity in aqueous-phase furfural hydrogenation to furfuryl alcohol. This breakthrough resolves the "activity-selectivity" trade-off in conventional catalysis, establishing a new paradigm for biomass valorization and sustainable industrial catalysis. Read more about the article behind the cover on page 71–81.

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Dynamic hydrogen intercalation catalysis Hao Zhang, Xiaosong Xiong, Tao Wang, Yuping Wu 2025, 74:  1-3.  DOI: 10.1016/S1872-2067(25)64742-5 Abstract ( 60 )   HTML ( 20 )   PDF (601KB) ( 50 )

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Advances in iron-based Fischer-Tropsch synthesis with high carbon efficiency Xueqing Zhang, Wusha Jiye, Yuhua Zhang, Jinlin Li, Li Wang 2025, 74:  4-21.  DOI: 10.1016/S1872-2067(25)64738-3 Abstract ( 136 )   HTML ( 10 )   PDF (3589KB) ( 37 )   Fischer-Tropsch synthesis offers a promising route to convert carbon-rich resources such as coal, natural gas, and biomass into clean fuels and high-value chemicals via syngas. Catalyst development is crucial for optimizing the process, with cobalt- and iron-based catalysts being widely used in industrial applications. Iron-based catalysts, in particular, are favored due to their low cost, broad temperature range, and high water-gas shift reaction activity, making them ideal for syngas derived from coal and biomass with a low H2/CO ratio. However, despite their long history of industrial use, iron-based catalysts face two significant challenges. First, the presence of multiple iron phases-metallic iron, iron oxides, and iron carbides-complicates the understanding of the reaction mechanism due to dynamic phase transformations. Second, the high water-gas shift activity of these catalysts leads to increased CO2 selectivity, thereby reducing overall carbon efficiency. In Fischer-Tropsch synthesis, CO2 can arise as primary CO2 from CO disproportionation (the Boudouard reaction) and as secondary CO2 from the water-gas shift reaction. The accumulation of CO2 formation further compromises overall carbon efficiency, which is particularly undesirable given the current focus on minimizing carbon emissions and achieving carbon neutrality. This review focus on the ongoing advancements of iron-based catalysts for Fischer-Tropsch synthesis, with particular emphasis on overcoming these two critical challenges for iron-based catalysts: regulating the active phases and minimizing CO2 selectivity. Addressing these challenges is essential for enhancing the overall catalytic efficiency and selectivity of iron-based catalysts. In this review, recent efforts to suppress CO2 selectivity of iron-based catalysts, including catalyst hydrophobic modification and graphene confinement, are explored for their potential to stabilize active phases and prevent unwanted side reactions. This innovative approach offers new opportunities for developing catalysts with high activity, low CO2 selectivity, and enhanced stability, which are key factors for enhancing both the efficiency and sustainability for Fischer-Tropsch synthesis. Such advancements are crucial for advancing more efficient and sustainable Fischer-Tropsch synthesis technologies, supporting the global push for net-zero emissions goals, and contributing to carbon reduction efforts worldwide.

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Properties, applications, and challenges of copper- and zinc-based multinary metal sulfide photocatalysts for photocatalytic hydrogen evolution Xinlong Zheng, Yiming Song, Chongtai Wang, Qizhi Gao, Zhongyun Shao, Jiaxin Lin, Jiadi Zhai, Jing Li, Xiaodong Shi, Daoxiong Wu, Weifeng Liu, Wei Huang, Qi Chen, Xinlong Tian, Yuhao Liu 2025, 74:  22-70.  DOI: 10.1016/S1872-2067(25)64720-6 Abstract ( 94 )   HTML ( 6 )   PDF (10015KB) ( 21 )   The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen, which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature. In this regard, photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method. The recently developed copper- and zinc-based multinary metal sulfide (MMS) semiconductor photocatalysts exhibit the advantages of suitable bandgap, wide light-harvesting range, and flexible elemental composition, thus possessing great potential for achieving considerable photocatalytic hydrogen evolution (PHE) performance. Despite great progress has been achieved, the current photocatalysts still cannot meet the commercial application demands, which highlights the mechanisms understanding and optimization strategies for efficient PHE. Herein, the basic mechanisms of PHE, and effective optimization strategies are firstly introduced. Afterwards, the research process and the performance of copper- and zinc-based MMS photocatalysts, are thoroughly reviewed. Finally, the unresolved issues, and challenges hindering the achievement of overall water splitting have been discussed.

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Accurate restricted transition-state shape selective hydrogenation of furfural over zeolite confined Cu catalyst Wanying Liang, Guangyue Xu, Yao Fu 2025, 74:  71-81.  DOI: 10.1016/S1872-2067(25)64741-3 Abstract ( 94 )   HTML ( 9 )   PDF (2506KB) ( 45 )   Supporting Information Transition-state shape selectivity plays a crucial role in catalytic systems where reactants and products exhibit comparable molecular dimensions, as it restricts the accessible configuration space of reaction intermediates. Herein, we designed a Cu@MFI catalyst by encapsulating Cu active sites within the well-defined micropores of MFI zeolite through a pore confinement strategy. This architecture preserves the zeolite framework integrity while maintaining unhindered internal mass transport, thereby enabling precise spatial control over transition-state configurations. Employing furfural hydrogenation as a probe reaction, the metal-zeolite synergy in Cu@MFI endowed the catalyst with exceptional activity (100% furfural conversion) and quantitative selectivity (100% furfuryl alcohol) at 70 °C, sustained across a broad temperature window. Mechanistic studies reveal that the transition-state shape selectivity effectively prevented H2O interaction with the furan ring, offering valuable insights for other reaction systems seeking to exploit shape selectivity for specific transformations.

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Co particles separated by immiscible Ag on yttria-stabilized zirconia as durable methane dry reforming catalyst under pressurized conditions Shi-Ning Li, Juntao Yao, Shuxin Pang, Jing-Peng Zhang, Shiying Li, Zhicheng Liu, Lu Han, Weibin Fan, Kake Zhu, Yi-An Zhu 2025, 74:  82-96.  DOI: 10.1016/S1872-2067(25)64677-8 Abstract ( 139 )   HTML ( 5 )   PDF (2768KB) ( 31 )   Supporting Information It is economical to perform methane and carbon dioxide reforming (DRM) under industrially relevant high-pressure conditions, but the harsh operation condition poses a grand challenge for coke-resistant catalyst design. Here, we propose to boost the coke- tolerance of Co catalyst by applying a contact potential introduced by immiscible Ag clusters. We demonstrate that Co clusters separated by neighboring Ag on Yttria-stabilized zirconia (YSZ) support can serve as a coke- and sintering-resistant DRM catalyst under diluent gas-free, stoichiometric CH4 and CO2 feeding, 1123 K and 20 bar. Since immiscible metals are ubiquitous and metal contact influences surface work function in general, this new design concept may have general implications for tailoring catalytic properties of metals.

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Benefits of H-ZSM-5 zeolite from fluoride-mediated acidic synthesis for liquid-phase conversion of cyclohexanol Qisong Yi, Lu Lin, Huawei Geng, Shaohua Chen, Yuanchao Shao, Ping He, Zhifeng Liu, Haimei Xu, Tiehong Chen, Yuanshuai Liu, Valentin Valtchev 2025, 74:  97-107.  DOI: 10.1016/S1872-2067(25)64718-8 Abstract ( 114 )   HTML ( 4 )   PDF (2157KB) ( 36 )   Supporting Information The hydrothermal stability of zeolites is essential for their potential applications in biomass conversion, especially in processes involving elevated temperatures alongside the use or generation of H2O. In this study, we employed F- ions as mineralizers to synthesize hydrothermally stable ZSM-5 zeolites under acidic conditions. The acidic synthesis system promotes zeolites with fewer silanol-terminated lattice defects (ZSM-5(A)) compared to the traditional basic conditions (ZSM-5(B)), endowing materials with substantially higher structural integrity and hydrophobicity. After 10 days of autoclave treatment at 200 °C in aqueous phase, H-ZSM-5(A) demonstrated nearly unchanged reaction rates in the dehydration of cyclohexanol, while H-ZSM-5(B) lost > 50% of the dehydration activity. Additionally, H-ZSM-5(A) delivered higher initial dehydration rates compared to H-ZSM-5(B). The different measured activation energies further revealed variations in reaction pathways during cyclohexanol dehydration, i.e., the monomer- or dimer-mediated routes depending on the concentration of alcohol molecule within zeolite pores, providing additional evidence for the strengthened hydrophobic nature of H-ZSM-5(A). Beyond this, the zeolite surface properties and the strength of cyclohexanol-zeolite interactions may impose additional transport/adsorption barriers attributed to multi-phase phenomena on the more polar H-ZSM-5(B) zeolite surfaces. More importantly, the hydrothermal treatment did not induce significant desilication and dealumination in H-ZSM-5(A), thereby preserving its active acid sites and ensuring exceptional hydrothermal stability. The present work fundamentally studies the synthesis of hydrothermally stable zeolites in an acidic medium using fluorides and expands the understanding of polar interactions in catalysis, characterized by the dehydration of cyclohexanol, for future application in biomass conversion.

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Understanding the reaction-induced restructuring of CoOx species in silicalite-1 to control selectivity in non-oxidative dehydrogenation of propane Qiyang Zhang, Vita A. Kondratenko, Xiangnong Ding, Jana Weiss, Stephan Bartling, Elizaveta Fedorova, Dan Zhao, Dmitry E. Doronkin, Dongxu Wang, Christoph Kubis, Evgenii V. Kondratenko 2025, 74:  108-119.  DOI: 10.1016/S1872-2067(25)64724-3 Abstract ( 124 )   HTML ( 5 )   PDF (1450KB) ( 38 )   Supporting Information Non-oxidative dehydrogenation of propane (PDH) is an important route for large-scale on purpose propene production. Although cobalt-based catalysts are promising alternatives to currently used platinum- or chromium oxide-based catalysts, their further developments are hindered by the uncertainties related to the kind of the active sites involved in the desired and side reactions. To contribute to closing such a gap, we systematically investigate the role of oxidized CoOx and metallic Co0 species in the PDH reaction over catalysts based in Silicalite-1 with supported CoOx species differing in their redox properties. C3H8 pulse experiments with sub-millisecond and second resolution at pulse sizes of about 13 and 2200 nmol, respectively, combined with in-depth catalyst characterization and PDH tests at different propane conversions enabled us to understand how the reaction-induced reduction of CoOx affects product selectivity. Propane readily reacts with CoOx to yield propene, carbon oxides and water. The formed Co0 species show high activity to coking and cracking reactions. However, if the size of such species is below 2 nm, these undesired reactions are significantly hindered due to the coverage of the active sites by carbon-containing species. The remaining uncovered surface Co0 sites selectively dehydrogenate propane to propene. The best-performing catalyst showed higher activity than a commercial-like K-CrOx/Al2O3 and operated durable in a series of 10 dehydrogenation/regeneration cycles under industrial relevant conditions. The space time yield of propene formation of 0.97 kg·h-1·kgcat-1 was achieved at 550 °C, 52% equilibrium propane conversion and 95% propene selectivity.

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Regulating the local environment of Ni single-atom catalysts with heteroatoms for efficient CO2 electroreduction Gang Wang, Imran Muhammad, Hui-Min Yan, Jun Li, Yang-Gang Wang 2025, 74:  120-129.  DOI: 10.1016/S1872-2067(25)64679-1 Abstract ( 95 )   HTML ( 3 )   PDF (1084KB) ( 61 )   Supporting Information The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO2 reduction to CO, yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials. Herein, we report P- and S- doped Ni single-atom catalysts, i.e. symmetric Ni1/PN4 and asymmetric Ni1/SN3C can exhibit high catalytic activity of CO2 reduction with stable potential windows. It is revealed that the key intermediate *COOH in CO2 electroreduction is stabilized by heteroatom doping, which stems from the upward shift of the axial dz2 orbital of the active metal Ni atom. Furthermore, we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni1/SN3C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model. Based on the potential-dependent microkinetic model, we predict that S-atom doped Ni SAC shifts the onset potential of CO2 electroreduction from -0.88 to -0.80 V vs. RHE, exhibiting better activity. Overall, this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems, and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.

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Surface oxygen vacancies of BiOBr regulating piezoelectricity for enhancing efficiency and selectivity of photocatalytic CO2 reduction Cunjun Li, Jie He, Tianle Cai, Xianlei Chen, Hengcong Tao, Yingtang Zhou, Mingshan Zhu 2025, 74:  130-143.  DOI: 10.1016/S1872-2067(25)64649-3 Abstract ( 128 )   HTML ( 10 )   PDF (5082KB) ( 23 )   Supporting Information Although defect engineering has been widely used to boost catalytic CO2 photoreduction, the piezoelectric polarized properties induced by structure changes through introducing defects are always ignored. Here we report a new kind of bismuth oxybromide (BiOBr, BOB) with piezoelectric property regulated by oxygen vacancies (OVs). Compared with pure BOB, BOB with OVs (BOB-OV) could enhance photocatalytic CO2 reduction efficiency under the ultrasonic force, achieving durable CO2 reduction process to superior production rates of CO (54.4 µmol g-1 h-1) with a high selectivity (92%). Moderate OVs concentration changed the degree of Bi-Br stretching in the BOB-OV to produce strong dipole moments, which endowed BOB-OV with strong spontaneous piezoelectric polarization ability under external force. Ultrasonic piezoelectric effects were innovatively integrated into the photocatalytic reaction, which not only provided an alternating force field to modulate the spontaneous polarization of BOB-OV, thereby maintaining efficient photogenerated charge separation, but also lowered the reaction energy barrier of CO2 by high stress, ultimately improving CO product selectivity. This study is the first to leverage OVs-induced piezoelectric polarization effects to enhance the performance and product selectivity of photocatalytic CO2 reduction, providing new directions and insights for defect engineering to contribute to photocatalysis.

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Highly conjugated and chemically stable three-dimensional covalent organic frameworks for efficient photocatalytic CO2 reduction Lin Zhang, Hui Zhang, Jinghong Fang, Jialin Cui, Jie Liu, Hui Liu, Lishui Sun, Qiong Sun, Lifeng Dong, Yingjie Zhao 2025, 74:  144-154.  DOI: 10.1016/S1872-2067(25)64717-6 Abstract ( 193 )   HTML ( 2 )   PDF (3757KB) ( 51 )   Supporting Information Covalent organic frameworks (COFs), as efficient photocatalysts, can convert CO2 and H2O into value-added fuel, thus improving the deteriorating ecological environment. However, achieving high photocatalytic efficiency and selectivity without relying on noble metals or sacrificial agents remains a significant challenge. Here, a highly conjugated three-dimensional (3D) COF 3D-COF-1 with imine linkage is constructed by the combination of two rigid and conjugated orthogonal building blocks (spirobifluorene and bicarbazole) with good photoactivites. Through a simple post-synthetic reduction, a chemically stable and amine-linked 3D-COF-2 which maintains excellent crystallinity and porosity can be obtained. Notably, the 3D-COF-2 exhibits excellent performance in CO2 reduction and exceptional selectivity of CO due to the highly conjugated structure and abundant amine groups as chemisorption sites for selectively capturing CO2. Under the irradiation of visible light and without noble metals and sacrificial agents, 3D-COF-2 produces 1070 μmol g-1 of carbon monoxide in 4.5 h, and the selectivity is close to 100%.

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Engineering coordination microenvironments of polypyridine Ni catalysts embedded in covalent organic frameworks for efficient CO2 photoreduction Ya-Hui Li, Yu Chen, Jin-Yu Guo, Rui Wang, Shu-Na Zhao, Gang Li, Shuang-Quan Zang 2025, 74:  155-166.  DOI: 10.1016/S1872-2067(25)64666-3 Abstract ( 126 )   HTML ( 2 )   PDF (2893KB) ( 26 )   Supporting Information The coordination engineering of catalytic centers emerges as a pivotal strategy for precise electronic configuration modulation in photocatalytic CO2 reduction. Herein, the electronic structure of active sites in polypyridine nickel catalysts is well modified through strategic ligand variation (bipyridine, terpyridine (TPY), 2,6-di(1-pyrazolyl)pyridine) and anion coordination (NO3-, Cl-, and CH3COO-), achieving enhanced CO2 performance. Crucially, covalent immobilization of these molecular catalysts within the COF-OH framework not only preserves their precisely defined and structurally adaptable characteristics but also demonstrates synergistic enhancement of CO2 adsorption capacity and charge transfer kinetics, as verified by CO2 adsorption isothermal analysis and ultrafast time-resolved transient absorption spectroscopy. Remarkably, COF-O-TPYNi(NO3-) catalyst exhibits a CO2-to-CO reduction activity of 9006.0 μmol·g-1·h-1 with 95.9% selectivity, superior to its counterpart catalysts, directly validating the mechanistic significance of precisely tailored coordination microenvironments around Ni active sites. Mechanistic studies through in situ XAFS, in situ ATR-SEIRAS and theoretical calculations reveal that this performance improvement over COF-O-TPYNi(NO3-) is attributed to the reduced reaction energy barrier of *COOH generation. This work pioneers a coordination shell engineering paradigm for rational design of molecularly defined catalytic architectures.

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A spatial-resolved online MS study on OCM reaction catalyzed by Mn-Na2WO4/SiO2 system for radicals coupling mechanistic insight Ningxujin Ding, Danyu Wang, Shihui Zou, Jie Fan, Lyubov Alexandrovna Isupova, Junyu Lang, Yong Yang 2025, 74:  167-176.  DOI: 10.1016/S1872-2067(25)64694-8 Abstract ( 74 )   HTML ( 2 )   PDF (1616KB) ( 27 )   Supporting Information Oxidative coupling of methane (OCM) is a catalytic partial oxidation process that directly converts methane into C2 products. For this high temperature reaction, understanding the radical behavior through experimental investigation is important in correlating the catalytic activity and the products. In this work, a spatial resolution online mass spectrometry (MS) system was developed and applied to a Mn-Na2WO4/SiO2 catalyzed OCM system. In addition to the residue gas analysis, the system obtained the distribution information of the reactants and products in the reactor. At various setting temperatures, all species online MS signals were collected at different positions, mapping the reaction activity covering parameters including temperature, time and space. The distribution behavior of the catalytic activity, selectivity, and apparent activation energy were kinetically analyzed. Selectivity and additional carbon balance analysis strongly supported the radical coupling model of OCM and indicated that after the catalytic bed layer, there is a significant length in the reactor (> 2 mm) filled with radicals. Based on the result, a designed new method by tuning the temperature field in the reactor was found effectively to improve the catalytic activity, especially the C2 yield from 702 to 773 °C.

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Electronic enrichment on Ni atoms at Ni-CeO2 interfaces: Unraveling the catalytic role in CO methanation and its volcano-type relation with the CeO2 content Xinli Li, Xiaonan Zhang, Zhenzhen Du, Feixue Han, Zhihui Fan, Shaokang Zhang, Zhenzhou Zhang, Weifeng Tu, Yi-Fan Han 2025, 74:  177-190.  DOI: 10.1016/S1872-2067(25)64688-2 Abstract ( 74 )   HTML ( 3 )   PDF (2346KB) ( 23 )   Supporting Information Tuning the metal-oxide interface to achieve optimal catalytic performance represents a classic yet fast-growing area in catalysis research. This work demonstrated that the decoration of CeO2 clusters onto Ni particles creates electron-enriched Ni sites at the Ni-CeO2 interface with highly efficient CO methanation, by kinetics, chemical titration, and a series of in situ/operando spectroscopic characterizations. These electron-enriched Ni atoms facilitate the back-donation of electrons into the orbital of CO and thus reduce the reaction barrier of CH4 formation, but do not alter the catalytic steps and their kinetic relevance as well as the evolution of surface intermediates during CO methanation. The amount of electron-enriched Ni atoms increases significantly to a maximum value and then decreases as the content of CeO2 increases, leading the formation rates of CH4 to increase in a volcano-type relation with CeO2 contents in xCeNi/Al2O3 catalysts. These insights provide a comprehensive understanding of the nature and the role of the metal-oxide interface and could potentially guide the rational design of highly efficient oxide-supported catalysts for CO methanation.

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A water-resistant and stable Pd-Co3O4 catalytic interface for complete methane oxidation with insights on active structures and reaction pathway Yuanjie Xu, Run Hou, Kunxiang Chi, Bo Liu, Zemin An, Lizhi Wu, Li Tan, Xupeng Zong, Yihu Dai, Zailai Xie, Yu Tang 2025, 74:  191-201.  DOI: 10.1016/S1872-2067(25)64728-0 Abstract ( 101 )   HTML ( 2 )   PDF (1617KB) ( 36 )   Supporting Information Palladium-based catalysts have long been considered the benchmark for methane combustion; however, the authentic phase of catalytic active sites remains a subject of ongoing debate. Additionally, challenges like water-poisoning and long-term stability need to be addressed to advance catalyst performance. Herein, we investigate Pd on Co3O4 nanorods as a highly effective catalyst for catalytic oxidation of methane, demonstrating long-term stability and water tolerance during a 100-h continuous operation at 350 °C. Comprehensive characterizations reveal the presence of an active Pd-oxygen vacancy (Ov)-cobalt interface in Pd/Co3O4, which effectively adsorbs molecular O2. The absorbed oxygen species on this interface are activated and directly participate in methane combustion. Moreover, near-ambient pressure X-ray photoelectron spectroscopy demonstrates that Pd nanoparticles undergo a rapid phase transition and predominantly remain in the metallic state during the reaction. This behavior is attributed to the electronic metal-support interaction between Pd and Co3O4. Furthermore, in situ Fourier transformed infrared spectrum reveals that under reaction conditions, HCO3* species are formed initially and subsequently transformed into formate species, indicating that the formate pathway is the dominant mechanism for CH4 oxidation.

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CO2-H2O co-electrolysis to CO/O2 for safe oxidative double carbonylation of ethylene/acetylene Yanwei Cao, Yunhao Qu, Bin Su, Gongwei Wang, Yang Huang, Zhenmin Luo, Lin Zhuang, Lin He 2025, 74:  202-210.  DOI: 10.1016/S1872-2067(25)64739-5 Abstract ( 49 )   HTML ( 1 )   PDF (1845KB) ( 22 )   Supporting Information Upgrading carbon dioxide (CO2) into value-added bulk chemicals offers a dual-benefit strategy for the carbon neutrality and circular carbon economy. Herein, we develop an integrated CO2 valorization strategy that synergizes CO2-H2O co-electrolysis (producing CO/O2 feeds) with oxidative double carbonylation of ethylene/acetylene to synthesize CO2-derived C4 diesters (dimethyl succinate, fumarate, and maleate). A group of versatile building blocks for manufacturing plasticizers, biodegradable polymers, and pharmaceutical intermediates. Remarkably, CO2 exhibits dual functionality: serving simultaneously as a CO/O2 source and an explosion suppressant during the oxidative carbonylation process. We systematically investigated the explosion-suppressing efficacy of CO2 in flammable gas mixtures (CO/O2, C2H4/CO/O2, and C2H2/CO/O2) across varying concentrations. Notably, the mixed gas stream from CO2/H2O co-electrolysis at an industrial-scale current densities of 400 mA/cm2, enabling direct utilization in oxidative double carbonylation reactions with exceptional compatibility and inherent safety. Extended applications were demonstrated through substrate scope expansion and gram-scale synthesis. This study establishes not only a safe protocol for oxidative carbonylation processes, but also opens an innovative pathway for sustainable CO2 valorization, including CO surrogate and explosion suppressant.

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Data-driven framework based on machine learning and optimization algorithms to predict oxide-zeolite-based composite and reaction conditions for syngas-to-olefin conversion Mansurbek Urol ugli Abdullaev, Woosong Jeon, Yun Kang, Juhwan Noh, Jung Ho Shin, Hee-Joon Chun, Hyun Woo Kim, Yong Tae Kim 2025, 74:  211-227.  DOI: 10.1016/S1872-2067(25)64733-4 Abstract ( 166 )   HTML ( 9 )   PDF (3747KB) ( 48 )   Supporting Information Bifunctional oxide-zeolite-based composites (OXZEO) have emerged as promising materials for the direct conversion of syngas to olefins. However, experimental screening and optimization of reaction parameters remain resource-intensive. To address this challenge, we implemented a three-stage framework integrating machine learning, Bayesian optimization, and experimental validation, utilizing a carefully curated dataset from the literature. Our ensemble-tree model (R2 > 0.87) identified Zn-Zr and Cu-Mg binary mixed oxides as the most effective OXZEO systems, with their light olefin space-time yields confirmed by physically mixing with HSAPO-34 through experimental validation. Density functional theory calculations further elucidated the activity trends between Zn-Zr and Cu-Mg mixed oxides. Among 16 catalyst and reaction condition descriptors, the oxide/zeolite ratio, reaction temperature, and pressure emerged as the most significant factors. This interpretable, data-driven framework offers a versatile approach that can be applied to other catalytic processes, providing a powerful tool for experiment design and optimization in catalysis.

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Unconventional metastable cubic 2D LaMnO3 for efficient alkaline seawater oxygen evolution Ji’ao Dai, Jinglin Xian, Kaisi Liu, Zhiao Wu, Miao Fan, Shutong Qin, Huiyu Jiang, Weilin Xu, Huanyu Jin, Jun Wan 2025, 74:  228-239.  DOI: 10.1016/S1872-2067(25)64667-5 Abstract ( 82 )   HTML ( 0 )   PDF (2713KB) ( 17 )   Supporting Information The electrolysis of alkaline seawater is critical for sustainable hydrogen production but is hindered by the sluggish oxygen evolution reaction in saline environments. Advanced electrocatalysts with tailored structures and electronic properties are essential, and phase engineering provides a transformative approach by modulating crystallographic symmetry and electronic configurations. Two-dimensional (2D) LaMnO3 perovskites show promise due to their exposed active sites and tunable electronic properties. However, the conventional stable rhombohedral phase limits oxygen diffusion despite good electron transport. Unconventional metastable phases with superior symmetry enhance lattice oxygen activity in saline environments but are challenging to synthesize. Herein, we propose a microwave shock method incorporating Co atoms to rapidly produce 2D LaMnO3 in rhombohedral, hexagonal, and metastable cubic phases. This strategy circumvents the limitations of high-temperature synthesis, preserving the 2D morphology while enabling the formation of metastable cubic phases. The metastable cubic phase exhibits superior OER activity and stability even in alkaline seawater due to optimal symmetry, interlayer spacing, and Mn-O covalency. X-ray absorption spectroscopy and theoretical calculations further highlight its balanced oxygen adsorption and desorption. This work underscores the role of metastable phase engineering in advancing seawater electrolysis and establishes a scalable route for designing high-performance 2D electrocatalysts.

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Ru single atoms-induced interfacial water structure regulation for efficient alkaline hydrogen oxidation reaction Yiming Jin, Wenjing Cheng, Wei Luo 2025, 74:  240-249.  DOI: 10.1016/S1872-2067(24)60283-4 Abstract ( 99 )   HTML ( 0 )   PDF (2565KB) ( 29 )   Supporting Information The employment of single atom catalysts (SACs) remarkably increases atomic utilization and catalytic efficiency in various electrochemical processes, especially when coupled with metal clusters/nanoparticles. However, the synergistic effects mainly focus on the energetics of key intermediates during the electrocatalysis, while the properties of electrode surface and electric-double-layer (EDL) structure are largely overlooked. Herein, we report the synthesis of Ru nanoparticles integrated with neighboring Ru single atoms on nitrogen doped carbon (Ru1,n/NC) as efficient catalysts toward hydrogen oxidation reaction (HOR) under alkaline electrolytes. Electrochemical data, in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy, and density functional theory calculations reveal that the positively charged Ru single atoms could lead to the dynamically regulated proportion of strongly hydrogen-bonded interfacial water structure with O-down conformation and optimized connectivity of the hydrogen-bond network in the EDL region, which contribute to the accelerated diffusion of hydroxide ions to the electrified interfaces. Consequently, the obtained Ru1,n/NC catalyst displays remarkable HOR performance with the mass activity of 1.15 mA μgPGM-1 under alkaline electrolyte. This work demonstrates the promise of single atoms for interfacial water environment adjustment and mass transfer process modulation, providing new insights into rational design of highly-effective SAC-based electrocatalysts.

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Revealing the dynamics of charge carriers in organic/inorganic hybrid FS-COF/WO3 S-scheme heterojunction for boosted photocatalytic hydrogen evolution Yunchao Zhang, Jinkang Pan, Xiang Ni, Feiqi Mo, Yuanguo Xu, Pengyu Dong 2025, 74:  250-263.  DOI: 10.1016/S1872-2067(25)64664-X Abstract ( 101 )   HTML ( 1 )   PDF (4131KB) ( 43 )   Supporting Information Designing high-efficiency photocatalysts by the construction of organic/inorganic heterojunctions is considered to be an effective approach for improving photocatalytic hydrogen evolution reaction (HER) activity. This work designed and built unique S-scheme heterojunctions by in-situ growing inorganic WO3 nanoparticles with excellent oxidation ability on fused-sulfone-modified covalent organic frameworks (FS-COF) with strong reduction ability. It is found that FS-COF and WO3 have a well-matched staggered band alignment. The best-designed FS-COF/WO3-20% exhibits a maximum photocatalytic HER rate of 24.7 mmol g-1 h-1 under visible light irradiation, which is 1.4 times greater than the pure FS-COF. Moreover, photogenerated electron-hole pairs can be separated and utilized more efficiently thanks to the FS-COF/WO3 heterojunction's ability to create a favorable internal electric field resulting from the difference in work functions between FS-COF and WO3, which speeds up the transfer dynamics of photoinduced electrons from WO3 to FS-COF through an additional interfacial electron-transfer channel obeying the directional S-scheme migration mechanism. Furthermore, the S-scheme migration mechanism of photoinduced charge carriers instead of the type-II mechanism was confirmed by the signal intensity of •O2− species from spin-trapping electron paramagnetic resonance spectra over the single component and the formed heterojunction. It ensures the photoexcited electrons maintain on the lowest unoccupied molecular orbital of FS-COF with a strong reduction ability to participate in photocatalytic HER, resulting in a significantly boosted H2 evolution rate. Based on organic/inorganic coupling, this work offers a strategy for creating particular S-scheme heterojunction photocatalysts.

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Developing a stable and high-performance W-CoMnP electrocatalyst by mitigating the Jahn-Teller effect through W doping strategy Bohan An, Xin Li, Weilong Liu, Jipeng Dong, Ruichao Bian, Luyao Zhang, Ning Li, Yangqin Gao, Lei Ge 2025, 74:  264-278.  DOI: 10.1016/S1872-2067(25)64669-9 Abstract ( 117 )   HTML ( 1 )   PDF (5173KB) ( 21 )   Supporting Information Manganese-based materials are influenced by the Jahn-Teller effect, causing the spontaneous dismutation of Mn3+ (2Mn3+ → Mn2+ + Mn4+) and the dissolution of Mn2+, which often results in diminished activity. This study uniquely employs a W doping strategy to suppress this effect. Externally, a simple template-free method was initially used to prepare cobalt- and manganese-based precursors, followed by a W doping process during the synthesis of transition bimetallic phosphides. Ultimately, W-doped bimetallic phosphides (W-CoMnP) were obtained. The W-CoMnP material demonstrates excellent HER and OER performance with low overpotentials of 95 mV (η₁₀ HER) and 225 mV (η₅₀ OER), and can achieve overall water splitting at a voltage of 1.52 V while maintaining stable cycling for 24 h. To enable commercial application, W-CoMnP was incorporated into an anion exchange membrane (AEM) electrolysis water device, demonstrating continuous and stable hydrogen production under ambient temperature conditions. This study offers a promising strategy for the future development of catalysts for AEM electrolysis water devices.

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Z-scheme heterojunction Zn3(OH)2(V2O7)(H2O)2/V-Zn(O,S) for enhanced visible-light photocatalytic N2 fixation via synergistic heterovalent vanadium states and oxygen vacancy defects Pengkun Zhang, Qinhan Wu, Haoyu Wang, Dong-Hau Kuo, Yujie Lai, Dongfang Lu, Jiqing Li, Jinguo Lin, Zhanhui Yuan, Xiaoyun Chen 2025, 74:  279-293.  DOI: 10.1016/S1872-2067(25)64716-4 Abstract ( 66 )   HTML ( 1 )   PDF (4157KB) ( 17 )   Supporting Information Herein, we established a Zn3(OH)2(V2O7)(H2O)2/V-Zn(O,S) Z-scheme heterojunction (labeled ZnVO/V-Zn(O,S) with a heterovalent V4+/V5+ states and oxygen vacancies in both phases via a one-step in-situ hydrolysis method. The NaBH4 regulated the ZnVO/V-Zn(O,S)-3 with rich Vo and suitable n(V4+)/n(V5+) ratio achieved an excellent photocatalytic nitrogen fixation activity of 301.7 μmol/(g•h) and apparent quantum efficiency of 1.148% at 420 nm without any sacrificial agent, which is 11 times than that of V-Zn(O,S). The Vo acts as the active site to trap and activate N2 molecules and to trap and activate H2O to produce the H for N2 molecules photocatalytic reduction. The rich Vo defects can also reduce the competitive adsorption of H2O and N2 molecules on the surface active site of the catalyst. The heterovalent vanadium states act as the photogenerated electrons, quickly hopping between V4+ and V5+ to transfer for the photocatalytic N2 reduction reaction. Additionally, the Z-scheme heterojunction effectively minimizes photogenerated carrier recombination. These synergistic effects collectively boost the photocatalytic nitrogen fixation activity. This study provides a practical method for designing Z-scheme heterojunctions for efficient photocatalytic N2 fixation under mild conditions.

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Custom exposed crystal facets: Synergistic effect of optimum crystal facet anisotropy and Ohmic heterojunction boosting photocatalytic hydrogen evolution Zhengyu Zhou, Zhiliang Jin 2025, 74:  294-307.  DOI: 10.1016/S1872-2067(25)64690-0 Abstract ( 89 )   HTML ( 2 )   PDF (3847KB) ( 13 )   Supporting Information The design of customized crystal plane heterojunction can effectively leverage the optimal anisotropic interaction of crystal plane, thereby enhancing photocatalytic activity. In this study, Co3O4 exposed (111), (110), and (100) crystal planes (designated as HCO, NCO, and CCO, respectively) were synthesized and successfully coupled with Cd0.5Zn0.5S (CZS). Among these composites, the HCO/CZS exhibited best hydrogen evolution activity. In conjunction with DFT calculations and femtosecond transient absorption spectroscopy, it has been found that: the crystal plane interaction between HCO and CZS enabled the composite catalyst to exhibit optimal anisotropy in crystal plane carrier transport, crystal plane active sites, and crystal plane electronic structure. This interaction induces a redistribution of electrons at their contact interface, thereby establishing a built-in electric field that facilitates the formation of ohmic heterojunction between HCO and CZS. The synergistic effect of the ohmic heterojunction and crystal plane anisotropy not only decreases the Gibbs free energy of hydrogen adsorption but also facilitates the efficient spatial separation and rapid transfer of electron-hole pairs. This study offers valuable insights into the customization of crystal plane heterojunctions, aiming to maximize anisotropic interactions between crystal planes in order to enhance photocatalytic hydrogen evolution.

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Sustainable co-production of H2 and lactic acid from lignocellulose photoreforming using Pt-C3N4 single-atom catalyst Eryu Wang, Yi-Chun Chu, Wenjun Zhang, Yanping Wei, Chuanling Si, Regina Palkovits, Xin-Ping Wu, Zupeng Chen 2025, 74:  308-318.  DOI: 10.1016/S1872-2067(25)64698-5 Abstract ( 117 )   HTML ( 4 )   PDF (1973KB) ( 38 )   Supporting Information The co-production of hydrogen and value-added biochemicals from lignocellulose utilizing solar energy has been regarded as one of the technologies most potentially able to alleviate the current energy crisis. Here, we demonstrate a cost-effective photoreforming strategy for lignocellulose valorization using a carbon nitride-supported platinum single-atom photocatalyst. An advanced H2 evolution rate of 6.34 mmol molPt-1 h-1 is achieved over the optimal catalyst, which is around 4.6 and 30.5 times higher compared with the nanosized Pt counterpart and pristine carbon nitride, respectively. Meanwhile, the monosaccharides are oxidized to value-added lactic acid with >99% conversion and extraordinary selectivity up to 97%. The theoretical calculations show that with Pt incorporation, the photogenerated holes are predominantly localized on the metal sites while the photogenerated electrons are concentrated on C3N4, thus enhancing the effective separation of charge carriers. This work provides a promising avenue for the simultaneous production of green H2 and bio-based chemicals by biomass photorefinery.

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Constructing dual-cocatalyst-directed quantifiable electron and hole transfer for enhanced photocatalytic performance Wenjing Gao, Yuchan Liu, Chenyao Chen, Ziqi Lian, Rongkai Ye, Chaorong Qi, Jianqiang Hu 2025, 74:  319-328.  DOI: 10.1016/S1872-2067(25)64729-2 Abstract ( 41 )   HTML ( 0 )   PDF (2611KB) ( 6 )   Supporting Information Photocatalysts are essential for the preparation of wanted fine chemical and biomedical intermediates via visible photocatalysis, but existing photocatalysts with low catalytic efficiency limit their wide applications. Herein, CdS/Ti3C2Tx/MBI nanocomposites have been successfully fabricated through anchoring reduction cocatalyst Ti3C2Tx with electron-drawing ability and oxidation cocatalyst 2-mercaptobenzimidazole (MBI) with hole-capturing capacity on CdS nanoparticles. The Ti3C2Tx and MBI of CdS/Ti3C2Tx/MBI nanocomposites can extract electrons and holes from CdS nanoparticles to come true electron-hole separation, respectively. Moreover, the electron-drawing and hole-capturing abilities of the CdS/Ti3C2Tx/MBI nanocomposites depend on Ti3C2Tx and MBI contents, and the quantifiable electron and hole transfers finally determine photocatalytic efficiency of the CdS/Ti3C2Tx/MBI nanocomposites. The transient photocurrent density of the CdS/Ti3C2Tx/MBI nanocomposites is 6-fold higher than that of the CdS nanoparticles. The CdS/Ti3C2Tx/MBI nanocomposites with strong electron-hole separation capability exhibit outstanding visible photocatalytic organic transformation properties. The CdS/Ti3C2Tx/MBI nanocomposites produce (E)-N-benzyl-1-phenylmethylimine in ~96% yield (~8000 μmol·g-1·h-1), which is 3-fold higher than the CdS nanoparticles (~2500 μmol·g-1·h-1, 30%). This work provides a new strategy for constructing efficient and stable photocatalysts that can be used for efficient visible light-driven organic transformations.

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Dual O2 reduction centers of COFs boosting H2O2 photosynthesis Chongbei Wu, Feihong Chu, Yongchao Hao, Xuan Li, Xiaoyue Jia, Yifan Sun, Jiaxuan Gu, Pengfei Jia, Aobing Wang, Jizhou Jiang 2025, 74:  329-340.  DOI: 10.1016/S1872-2067(25)64740-1 Abstract ( 88 )   HTML ( 2 )   PDF (2584KB) ( 25 )   Supporting Information The two-electron oxygen reduction reaction (ORR) for H2O2 photosynthesis is often hindered by sluggish charge kinetics and a limited number of activation sites. Theoretical predictions based on dipole moment analysis indicate that introducing pyrazine units enhances charge migration, leading to increased accumulation of photoinduced electrons on these units, thereby facilitating the two-site, two-electron ORR. Inspired by these theoretical insights, this work designed and fabricated a triazine-pyrazine-based covalent organic framework materials (TTDN-COFs) for H2O2 photosynthesis via a polarity-functionalization strategy. The TTDN-COFs demonstrate a significant improvement in the photocatalytic H2O2 production rate, reaching 2757.6 μmol h-1 g-1 in pure water-3.2 times higher than that of the triazine-based COFs (TTPH-COFs). Experimental results and theoretical calculations confirm that the incorporation of pyrazine units not only enhances polarization, promoting the separation and migration of charge carriers, but also facilitates the formation of endoperoxide at both the triazine and pyrazine units. The dual adsorption activation sites lower the activation energy barrier for O2, thereby accelerating the overall reaction kinetics. These findings highlight the potential of functional-group-mediated polarization engineering as a promising strategy for developing COFs-based H2O2 photosynthesis with dual activation sites.

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Facet-oriented surface modification for enhancing photocatalytic hydrogen production on Sm2Ti2O5S2 nanosheets Zihao Zhang, Jiaming Zhang, Haifeng Wang, Meng Liu, Yao Xu, Kaiwei Liu, Boyang Zhang, Ke Shi, Jifang Zhang, Guijun Ma 2025, 74:  341-351.  DOI: 10.1016/S1872-2067(25)64745-0 Abstract ( 30 )   HTML ( 1 )   PDF (3501KB) ( 11 )   Supporting Information Oxysulfide semiconductors are promising photocatalysts for visible light-driven water splitting. For a widely studied narrow-bandgap Sm2Ti2O5S2 (STOS), limited bulk charge separation and slow surface reaction heavily restrict its photocatalytic performance. Here, well-crystallized STOS oxysulfide nanosheets, synthesized by a flux-assisted solid-state reaction, were proved to show prominent facet-oriented charge transport property, in which photogenerated electrons migrated to {101} planes and holes to {001} planes of each particle. Hydrogen evolution cocatalysts were therefore precisely positioned on the electron-rich facets to boost the water reduction reaction. In particular, in-situ formation of a Ptshell@Ircore core-shell structure on the electron-rich {101} facets and an IrO2 on the hole-accumulated {001} facets greatly assisted the sacrificial photocatalytic H2 production over STOS, resulting in an apparent quantum yield as high as 35.9% at 420 nm. By using the highly-active STOS as H2 evolution photocatalyst, a Mo:BiVO4 as oxygen evolution photocatalyst, and a [Co(bpy)3]2+/3+ as redox shuttle, a Z-Scheme overall water splitting system was constructed to achieve a solar-to-hydrogen conversion efficiency of 0.175%. This work not only elucidates the facet-dependent charge transfer mechanism on STOS but also proposes an ideal strategy for enhancing its photocatalytic performance.

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Oxidative depolymerization of lignin enhanced by synergy of polyoxometalate and acetic acid Jiaming Cao, Yuting Liu, Huifang Liu, Chunguang Liu, Junyou Shi, Ning Li 2025, 74:  352-364.  DOI: 10.1016/S1872-2067(25)64737-1 Abstract ( 85 )   HTML ( 1 )   PDF (3022KB) ( 20 )   Supporting Information Oxidative catalysis enables lignin depolymerization to yield carbonyl-containing aromatic chemicals for sustainable lignocellulose valorization. The oxidative depolymerization of lignin requires high oxygen pressure and harsh conditions to trade off lignin’s structural complexity and limited solubility. Herein, we developed an oxidation system for lignin depolymerization using a single phosphomolybdic acid (H3PMo12O40) catalyst in acetic acid solvent to address the aforementioned issues. The entire catalytic system was operated under only 0.1 MPa O2 pressure, providing over 20 wt% of aromatic compounds containing aldehydes and carboxylic acids. Theoretical calculations combined with experimental analyses reveal structural transformations and redox behavior driven by the synergistic interaction between H3PMo12O40 and acetic acid. Mechanistic studies detected superoxide radicals, confirming the joint role of catalyst and solvent in oxygen activation, radicals stabilization, and enhanced reaction efficiency. A low-cost, commercially available catalyst with minimal oxygen demand offers a promising route to industrial-scale biomass refining.

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Hydrogen production via ammonia decomposition on molybdenum carbide catalysts: Exploring the Mo/C ratio and phase transition dynamics Bowen Sun, Siyun Mu, Bingbing Chen, Guojun Hu, Rui Gao, Chuan Shi 2025, 74:  365-376.  DOI: 10.1016/S1872-2067(25)64726-7 Abstract ( 77 )   HTML ( 0 )   PDF (2134KB) ( 18 )   Supporting Information The deployment of non-precious metal catalysts for the production of COx-free hydrogen via the ammonia decomposition reaction (ADR) presents a promising yet great challenge. In the present study, two crystal structures of α-MoC and β-Mo2C catalysts with different Mo/C ratios were synthesized, and their ammonia decomposition performance as well as structural evolution in ADR was investigated. The β-Mo2C catalyst, characterized by a higher Mo/C ratio, demonstrated a remarkable turnover frequency of 1.3 s-1, which is over tenfold higher than that of α-MoC (0.1 s-1). An increase in the Mo/C ratio of molybdenum carbide revealed a direct correlation between the surface Mo/C ratio and the hydrogen yield. The transient response surface reaction indicated that the combination of N* and N* derived from NH3 dissociation represents the rate-determining step in the ADR, and β-Mo2C exhibited exceptional proficiency in facilitating this pivotal step. Concurrently, the accumulation of N* species on the carbide surface could induce the phase transition of molybdenum carbide to nitride, which follows a topological transformation. It is discovered that such phase evolution was affected by the Mo-C surface and reaction temperature simultaneously. When the kinetics of combination of N* was accelerated by rising temperatures and its accumulation on the carbide surface was mitigated, β-Mo2C maintained its carbide phase, preventing nitridation during the ADR at 810 °C. Our results contribute to an in-depth understanding of the molybdenum carbides’ catalytic properties in ADR and highlight the nature of the carbide-nitride phase transition in the reaction.

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Efficient synthesis of flexible SCR catalysts utilizing graphene oxide as a bridging agent without calcination: Catalytic performance, mechanism and kinetics studies Tingkai Xiong, Fengyu Gao, Jiajun Wen, Honghong Yi, Shunzheng Zhao, Xiaolong Tang 2025, 74:  377-393.  DOI: 10.1016/S1872-2067(25)64722-X Abstract ( 77 )   HTML ( 0 )   PDF (4531KB) ( 18 )   Supporting Information The mechanical performance of flexible catalysts remains a significant challenge for industrial applications. In this study, graphene oxide (GO) functions as both a binder and a redox mediator, serving as a crucial "bridge" between metal species and the organic foam, thereby substantially enhancing NOx conversion efficiency. Catalytic activity tests demonstrate that the GO-modified MnCo-MS@0.05GO catalyst achieves a NOx conversion rate exceeding 95%. The incorporation of GO strengthens the adhesion between the organic foam and metal components, increases the surface roughness of the sponge, and ensures the uniform and stable distribution of metal active sites. Additionally, GO enhances the content of effective catalytic species, improves electron transfer efficiency in the selective catalytic reduction reaction, and reduces diffusion resistance. To elucidate the NO reduction mechanism, in situ diffuse reflectance infrared Fourier transform spectroscopy and transient reaction studies were performed. The results indicate that as the reaction temperature increases, both the Eley-Rideal and Langmuir-Hinshelwood mechanisms contribute to promoting the SCR reaction rate.

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Dual-shell hollow nanospheres NiCo2S4@CoS2/MoS2: Enhancing catalytic activity for oxygen evolution reaction and achieving water splitting via the unique synergistic effects of mechanisms of adsorption-desorption and lattice oxygen oxidation Yang Chen, Yu Tang, Leiyun Han, Jiayan Liu, Yingjie Hua, Xudong Zhao, Xiaoyang Liu 2025, 74:  394-410.  DOI: 10.1016/S1872-2067(25)64727-9 Abstract ( 86 )   HTML ( 1 )   PDF (5718KB) ( 14 )   Supporting Information Activating both metal and lattice oxygen sites for efficient oxygen evolution reactions (OER) is a critical challenge. This study pioneers a novel approach, employing cobalt-nickel glycerate solid spheres (CoNi-G SSs) as self-sacrificial templates to synthesize yolk-shell structured CoNi-G SSs@ZIF-67 nanospheres. The derived NiCo2S4@CoS2/MoS2 double-shelled hollow nanospheres integrate the adsorbate evolution mechanism (AEM) and lattice oxygen mechanism (LOM), enabling synergistic dual catalytic pathways. Nickel modulation facilitates active species reconstruction in NiCo2S4, enhancing lattice oxygen activity and optimizing the LOM pathway. Characterization results indicate that anode activation triggered the redox processes of metal and lattice oxygen sites, involving the formation and re-filling of oxygen vacancies. Additionally, the CoS2/MoS2 heterostructure enhances the AEM pathway, as supported by density functional theory calculations, which demonstrate optimized adsorption of intermediates for both hydrogen evolution reaction and OER. The assembled anion exchange membrane water splitting device can deliver a catalytic current of 500 mA cm-2 at 1.74 V under commercial catalytic operating conditions (1 mol L-1 KOH) for 150 h, with negligible degradation. This work provides important insights into the understanding of OER mechanisms and the design of high-performance water-splitting electrocatalysts, while also opening new avenues for developing multifunctional materials with multi-shell structures.

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Insights into the couple-decouple spin state shifting of graphdiyne-supported d8 state Fe dual-atom catalysts Xiaohui Zhu, Haoran Xing, Guangyu He, Hai Xiao, Yinjuan Chen, Jun Li 2025, 74:  411-424.  DOI: 10.1016/S1872-2067(25)64691-2 Abstract ( 69 )   HTML ( 1 )   PDF (3233KB) ( 30 )   Supporting Information Dual-atom catalysts (DACs), a natural extension of single-atom catalysts (SACs), have emerged as a prominent focal point in the field of heterogeneous catalysis, particularly in the context of chemical and energy conversion processes. Despite the fact that the catalytic activity of DACs is significantly modulated by the electronic structure of the catalyst, understanding how electron spin states are affected by variations in topology and geometric structure remains challenging and relatively unexplored. Herein, we propose the rational design of stable DACs composed of two iron atoms anchored on pristine graphdiyne (GDY), Fe2-GDYn. A comprehensive and systematic investigation was carried out to elucidate the electronic configuration and spin states involved in the deliberate convergence towards the magnetic ground state, with the aim of uncovering the structure-spin relationship. Through an in-depth analysis of spin populations, electronic localization/delocalization, and the chemical bonding characteristics of the central metal atoms and the GDY skeleton, it was revealed that the spin coupling between the two iron atoms is preponderantly dictated by adjacent short-range Fe-Fe interactions. Conversely, spin decoupling can be attributed to the long-range π-bond component within the linkage. Moreover, geometric and chemical bonding asymmetries were found to induce orbital and spin splitting in iron atoms possessing an electronic configuration of d8. These findings provide important insights into the relationship between topology and spin, thereby presenting novel strategies for the rational design of spin-manipulated DACs.

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Simultaneously achieving ultrahigh loading and ultrasmall particle size of Pt/C catalysts Xiaoyang Wang, Ziqi Fu, Ziyi Luo, Weidi Liu, Jia Ding, Jianrong Zeng, Yanan Chen, Wenbin Hu 2025, 74:  425-437.  DOI: 10.1016/S1872-2067(25)64673-0 Abstract ( 100 )   HTML ( 1 )   PDF (3138KB) ( 20 )   Supporting Information High-loading Pt/C catalysts play an important role in the fabrication of membrane electrode assemblies with thin catalytic layer, which enhance mass transport and maintain the balance of water and heat. Unfortunately, as the loading increases, the agglomeration and growth of Pt nanoparticles (NPs) occur, causing unsatisfactory performance. Here, we present an efficient method for preparing of highly dispersed and small-sized Pt/C catalysts with Pt loadings varying from 39.01 wt% to 66.48 wt% through the high-temperature shock technique. The high density and ultrafine (~2.5 nm) Pt NPs are successfully anchored onto Vulcan XC-72R carbon black without the use of additional capping agents or surfactants. The modified carbon supports enhance the affinity for Pt precursors, contributing to loading efficiencies of 95% or more, while also providing abundant sites for the nucleation and fixation of Pt NPs, thus preventing agglomeration. In the context of the hydrogen evolution reaction in acidic media, the as-synthesized high-loading Pt/C catalysts show remarkable activity and stability, outperforming the state-of-the-art commercial Pt/C. This is mainly because the combined effects of ultrasmall and uniform Pt NPs, optimized electronic structure of Pt site, superhydrophilicity and effective anchoring of Pt NPs. The polymer electrolyte membrane electrolyzer integrated with Pt60/OX72R and commercial IrO2 reaches 1 A cm-2 at 1.77 V and operates stably for 120 hours with a negligible voltage decay. This new strategy is fast, scalable and cost-effective for large-scale production of metal-supported catalysts, especially for the high-loading ones.