Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64759-0
Yuxing Xu , Leilei Wang , Qin Liu , Botao Teng , Chuanqiang Wu , Binghui Ge , Wentuan Bi , Minghui Gu , Mengkai Zhang , Huan Yan , Junling Lu
Electrocatalytic conversion of carbon dioxide (CO2) offers an effective method of CO2 fixation to mitigate global warming and the energy crisis. However, for supported Ni single-atom catalysts (SACs), which are among the most promising candidates for this application, the relationship between Ni coordination structure and catalytic properties is still under strong debate. Here, we fabricated a series of Ni SACs through precise-engineering of anchor sites on nitrogen-doped carbon (NC) followed by Ni atom anchoring using atomic layer deposition. Among them, a Ni1/NC SAC, with a coordination number (CN) of four but less pyridinic nitrogen (Npyri), achieved over 90% faradaic efficiency for CO at potentials from –0.7 to –1.0 V and a mass activity of 6.5 A/mgNi at –0.78 V along with high stability, outperforming other Ni SACs with lower CN and more Npyri. Theoretical calculations of various three and four-coordinated Ni1-NxCy structures revealed a linear correlation between the reaction Gibbs free energy for the potential–limiting step and the highest occupied molecular orbital (HOMO) position of Ni-3d orbitals, therein the four-coordinated Ni1-N1C3 with the highest HOMO position is identified as the active site for the electrocatalytic CO2-to-CO process, in line with the experimental results.
二氧化碳的电催化转化为减缓全球变暖和能源危机提供了一种有效的二氧化碳固定方法。然而，对于负载型镍单原子催化剂（SACs）来说，镍配位结构与催化性能之间的关系仍然存在激烈的争论。在这里，我们通过在氮掺杂碳（NC）上精确设计锚点，然后使用原子层沉积技术将Ni原子锚定，从而制备了一系列Ni SACs。其中，配位数（CN）为4而吡啶氮（Npyri）较少的Ni1/NC SAC在-0.7 ~ -1.0 V电势下对CO的法拉第效率超过90%，在-0.78 V电势下的质量活度为6.5 a /mgNi，稳定性好，优于其他CN较低、Npyri较高的Ni SAC。对各种三配位和四配位Ni1-NxCy结构的理论计算表明，限制电位步骤反应的吉布斯自由能与Ni-3d轨道的最高占据分子轨道（HOMO）位置呈线性相关，其中HOMO位置最高的四配位Ni1-N1C3被确定为电催化CO2-to-CO过程的活性位点，与实验结果一致。
{"title":"Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO2 reduction","authors":"Yuxing Xu , Leilei Wang , Qin Liu , Botao Teng , Chuanqiang Wu , Binghui Ge , Wentuan Bi , Minghui Gu , Mengkai Zhang , Huan Yan , Junling Lu","doi":"10.1016/S1872-2067(25)64759-0","DOIUrl":"10.1016/S1872-2067(25)64759-0","url":null,"abstract":"<div><div>Electrocatalytic conversion of carbon dioxide (CO<sub>2</sub>) offers an effective method of CO<sub>2</sub> fixation to mitigate global warming and the energy crisis. However, for supported Ni single-atom catalysts (SACs), which are among the most promising candidates for this application, the relationship between Ni coordination structure and catalytic properties is still under strong debate. Here, we fabricated a series of Ni SACs through precise-engineering of anchor sites on nitrogen-doped carbon (NC) followed by Ni atom anchoring using atomic layer deposition. Among them, a Ni<sub>1</sub>/NC SAC, with a coordination number (CN) of four but less pyridinic nitrogen (N<sub>pyri</sub>), achieved over 90% faradaic efficiency for CO at potentials from –0.7 to –1.0 V and a mass activity of 6.5 A/mg<sub>Ni</sub> at –0.78 V along with high stability, outperforming other Ni SACs with lower CN and more N<sub>pyri</sub>. Theoretical calculations of various three and four-coordinated Ni<sub>1</sub>-N<sub><em>x</em></sub>C<sub><em>y</em></sub> structures revealed a linear correlation between the reaction Gibbs free energy for the potential–limiting step and the highest occupied molecular orbital (HOMO) position of Ni-3<em>d</em> orbitals, therein the four-coordinated Ni<sub>1</sub>-N<sub>1</sub>C<sub>3</sub> with the highest HOMO position is identified as the active site for the electrocatalytic CO<sub>2</sub>-to-CO process, in line with the experimental results.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 68-77"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64844-3
Yinhong Niu , Zhen Shi , Zhiquan Yu , Qiang Guo , Junju Mu , Yafei Liang , Zhixin Zhang , Sheng Wang , Feng Wang
Vanadium phosphorus oxide (VPO) catalyst is a promising candidate for the condensation reaction of formaldehyde (FA) and acetic acid (HAc) to produce acrylic acid (AA). However, the complexity of the active phases and their dynamic interconversion under redox conditions has led to controversies regarding the actual active phase in this reaction. To address this, this study systematically investigates the phase transition and underlying mechanism of VPO catalysts under reaction conditions. X-ray diffraction (XRD) patterns, Raman spectra, transmission electron microscopy images and X-ray photoelectron spectroscopy collectively demonstrated that the V4+ phase (VO)2P2O7 retained the bulk phase structure throughout the reaction, with only minor surface phase transition observed. In contrast, the V5+ phase underwent reduction to other phases in both bulk and surface regions. Specifically, the δ-VOPO4 phase rapidly transformed into the αII-VOPO4 phase, which could reversibly convert into the R1-VOHPO4 phase (V4+). Controlled variable experiments, H2-temperature programmed reduction and in-situ XRD experiments in a hydrogen atmosphere further demonstrated that these phase transitions were primarily attributed to the loss of lattice oxygen. The presence of V4+ phase in VPO catalysts enhanced the selectivity of acrylic acid, while the existence of V5+ phase promoted the activation of acetic acid. This work elucidates the redox-driven phase evolution of VPO catalysts and offers valuable insights for designing efficient catalysts for FA-HAc cross-condensation by balancing phase stability and activity.
{"title":"Lattice oxygen transfer induced active phase transition of VPO catalysts in cross condensation of acetic acid and formaldehyde","authors":"Yinhong Niu , Zhen Shi , Zhiquan Yu , Qiang Guo , Junju Mu , Yafei Liang , Zhixin Zhang , Sheng Wang , Feng Wang","doi":"10.1016/S1872-2067(25)64844-3","DOIUrl":"10.1016/S1872-2067(25)64844-3","url":null,"abstract":"<div><div>Vanadium phosphorus oxide (VPO) catalyst is a promising candidate for the condensation reaction of formaldehyde (FA) and acetic acid (HAc) to produce acrylic acid (AA). However, the complexity of the active phases and their dynamic interconversion under redox conditions has led to controversies regarding the actual active phase in this reaction. To address this, this study systematically investigates the phase transition and underlying mechanism of VPO catalysts under reaction conditions. X-ray diffraction (XRD) patterns, Raman spectra, transmission electron microscopy images and X-ray photoelectron spectroscopy collectively demonstrated that the V<sup>4+</sup> phase (VO)<sub>2</sub>P<sub>2</sub>O<sub>7</sub> retained the bulk phase structure throughout the reaction, with only minor surface phase transition observed. In contrast, the V<sup>5+</sup> phase underwent reduction to other phases in both bulk and surface regions. Specifically, the <em>δ</em>-VOPO<sub>4</sub> phase rapidly transformed into the <em>α</em><sub>II</sub>-VOPO<sub>4</sub> phase, which could reversibly convert into the R1-VOHPO<sub>4</sub> phase (V<sup>4+</sup>). Controlled variable experiments, H<sub>2</sub>-temperature programmed reduction and <em>in-situ</em> XRD experiments in a hydrogen atmosphere further demonstrated that these phase transitions were primarily attributed to the loss of lattice oxygen. The presence of V<sup>4+</sup> phase in VPO catalysts enhanced the selectivity of acrylic acid, while the existence of V<sup>5+</sup> phase promoted the activation of acetic acid. This work elucidates the redox-driven phase evolution of VPO catalysts and offers valuable insights for designing efficient catalysts for FA-HAc cross-condensation by balancing phase stability and activity.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 112-126"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64817-0
Haotian Guo , Lulu Zhao , Xinyu Liu , Jing Li , Pengfei Wang , Zonglin Liu , Linlin Wang , Jie Shu , Tingfeng Yi
Metal-organic frameworks (MOFs) are porous materials formed by the coordination of organic and inorganic components through coordination bonds. MOF-derived materials preserve the large surface area and inherent porosity of their parent structures, while simultaneously offering enhanced electrical conductivity and more efficient charge transport. Studies have shown that integrating electrospinning with MOFs into continuous nanofiber networks can effectively address issues such as MOF structural collapse, low conductivity, and leaching of active sites. Moreover, the electrospinning technique enables fine-tuning of the product’s morphology, architecture, and chemical composition, thereby unlocking new possibilities for advancing high-performance ZABs. This review provides a systematic overview of recent advances in non-precious metal electrocatalysts derived from electrospun-MOF composites and examines the unique advantages of combining electrospinning with MOF precursors in the design of oxygen electrocatalysts. It also investigates the morphological regulation of various fiber structures, including porous, hollow, core-shell, and beaded structures, as well as their influence on the catalytic performance. Finally, the performance enhancement strategies of electrospun-MOF catalyst materials are examined, and the development prospects along with future research directions related to oxygen electrocatalysts based on electrospun nanofibers are emphasized. This thorough review aims to offer meaningful insights and practical guidance for advancing the understanding, design, and fabrication of next-generation devices for energy conversion and storage.
{"title":"Electrospinning technology combined with MOFs: Bridging the development of high-performance zinc-air batteries","authors":"Haotian Guo , Lulu Zhao , Xinyu Liu , Jing Li , Pengfei Wang , Zonglin Liu , Linlin Wang , Jie Shu , Tingfeng Yi","doi":"10.1016/S1872-2067(25)64817-0","DOIUrl":"10.1016/S1872-2067(25)64817-0","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) are porous materials formed by the coordination of organic and inorganic components through coordination bonds. MOF-derived materials preserve the large surface area and inherent porosity of their parent structures, while simultaneously offering enhanced electrical conductivity and more efficient charge transport. Studies have shown that integrating electrospinning with MOFs into continuous nanofiber networks can effectively address issues such as MOF structural collapse, low conductivity, and leaching of active sites. Moreover, the electrospinning technique enables fine-tuning of the product’s morphology, architecture, and chemical composition, thereby unlocking new possibilities for advancing high-performance ZABs. This review provides a systematic overview of recent advances in non-precious metal electrocatalysts derived from electrospun-MOF composites and examines the unique advantages of combining electrospinning with MOF precursors in the design of oxygen electrocatalysts. It also investigates the morphological regulation of various fiber structures, including porous, hollow, core-shell, and beaded structures, as well as their influence on the catalytic performance. Finally, the performance enhancement strategies of electrospun-MOF catalyst materials are examined, and the development prospects along with future research directions related to oxygen electrocatalysts based on electrospun nanofibers are emphasized. This thorough review aims to offer meaningful insights and practical guidance for advancing the understanding, design, and fabrication of next-generation devices for energy conversion and storage.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 32-67"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64841-8
Yan Wang , Xiaorui Yan , Zeyang Sun , Jinjun Liu , Yiwen Wang , Chenchao Hu , Yilin Deng , Meng Xie , Jimin Xie , Wei Zhang , Yuanguo Xu
The regulation of peroxymonosulfate (PMS) activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle. This work demonstrates a strategy to constructed ethylene glycol (EG) well-coupled S-scheme heterojunction of NiFe2O4–x/NiS with oxygen vacancy (VO)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation, a 99% PMS decomposition efficiency is achieved. Photoassisted Kelvin probe force microscopy and in-situ electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe2O4–x/NiS with an S-scheme heterojunction, which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation. The S-scheme NiFe2O4–x/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate (0.15 min–1) at a low PMS dosage of 0.1 g/L, which is 19 times greater than that of the pristine NiS (0.0077 min–1). Density functional theory calculations confirmed that VO in NiFe2O4–x/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer. Moreover, in-situ experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation, unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe2O4–x/NiS during the reaction. This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation, providing a promising solution the cost-effective and efficient treatment of organic wastewater.
{"title":"Synergistic catalysis of oxygen vacancy and S-scheme heterojunction in NiFe2O4–x/NiS regulates peroxymonosulfate activation forenhanced photo-Fenton-like reaction","authors":"Yan Wang , Xiaorui Yan , Zeyang Sun , Jinjun Liu , Yiwen Wang , Chenchao Hu , Yilin Deng , Meng Xie , Jimin Xie , Wei Zhang , Yuanguo Xu","doi":"10.1016/S1872-2067(25)64841-8","DOIUrl":"10.1016/S1872-2067(25)64841-8","url":null,"abstract":"<div><div>The regulation of peroxymonosulfate (PMS) activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle. This work demonstrates a strategy to constructed ethylene glycol (EG) well-coupled S-scheme heterojunction of NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS with oxygen vacancy (V<sub>O</sub>)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation, a 99% PMS decomposition efficiency is achieved. Photoassisted Kelvin probe force microscopy and <em>in-situ</em> electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS with an S-scheme heterojunction, which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation. The S-scheme NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate (0.15 min<sup>–1</sup>) at a low PMS dosage of 0.1 g/L, which is 19 times greater than that of the pristine NiS (0.0077 min<sup>–1</sup>). Density functional theory calculations confirmed that V<sub>O</sub> in NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer. Moreover, <em>in-situ</em> experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation, unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS during the reaction. This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation, providing a promising solution the cost-effective and efficient treatment of organic wastewater.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 186-204"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64839-X
Ziye Zheng , Yi Ren , Meng Dai , Hongsheng Li , Huizhen Cui , Sen Wang , Shuguang Wang , Zuoli He
Since conventional photocatalytic technology fails to achieve complete elimination of chlorophenol contaminants from aqueous environments, this study presents a synergistic photocatalysis-capacitive deionization (PC-CDI) system as an advanced solution for industrial chlorophenol wastewater remediation. The PC-CDI system, employing boron nitride/carbon nitride (BN/CN) heterojunction electrodes, demonstrates exceptional degradation performance toward chlorophenols. The high-surface-area porous BN/CN heterojunction facilitates electro-adsorption and charge carrier separation, thereby synergistically optimizing both photocatalytic (PC) and capacitive deionization (CDI) functionalities. Remarkably, the integrated system achieves a 2,4-DCP degradation efficiency of 97.15% and a 2,4,6-TCP degradation efficiency of 100% in 2 h. The CDI component enables spatial separation through the electro-adsorption of Cl– ions at the anode, effectively mitigating their interference and suppressing chlorinated byproduct formation. Concurrently, the electro-adsorption of positively charged chlorophenol pollutants accelerates their diffusion to catalytic sites, promoting the reactive oxygen species (ROS)-driven degradation of chlorophenol pollutants. The PC-CDI system exhibits robust stability (> 95% efficiency retention over five cycles) and broad applicability across various chlorophenol derivatives. By circumventing Cl–-induced side reactions and inhibiting chlorine radical generation during photocatalysis, this strategy minimizes the environmental risks associated with chlorinated byproducts during chlorophenol wastewater treatment. These findings establish the PC-CDI system as a sustainable and eco-friendly technology for industrial wastewater treatment.
{"title":"An eco-friendly photocatalytic coupling capacitive deionization system for efficient chlorophenol wastewater treatment","authors":"Ziye Zheng , Yi Ren , Meng Dai , Hongsheng Li , Huizhen Cui , Sen Wang , Shuguang Wang , Zuoli He","doi":"10.1016/S1872-2067(25)64839-X","DOIUrl":"10.1016/S1872-2067(25)64839-X","url":null,"abstract":"<div><div>Since conventional photocatalytic technology fails to achieve complete elimination of chlorophenol contaminants from aqueous environments, this study presents a synergistic photocatalysis-capacitive deionization (PC-CDI) system as an advanced solution for industrial chlorophenol wastewater remediation. The PC-CDI system, employing boron nitride/carbon nitride (BN/CN) heterojunction electrodes, demonstrates exceptional degradation performance toward chlorophenols. The high-surface-area porous BN/CN heterojunction facilitates electro-adsorption and charge carrier separation, thereby synergistically optimizing both photocatalytic (PC) and capacitive deionization (CDI) functionalities. Remarkably, the integrated system achieves a 2,4-DCP degradation efficiency of 97.15% and a 2,4,6-TCP degradation efficiency of 100% in 2 h. The CDI component enables spatial separation through the electro-adsorption of Cl<sup>–</sup> ions at the anode, effectively mitigating their interference and suppressing chlorinated byproduct formation. Concurrently, the electro-adsorption of positively charged chlorophenol pollutants accelerates their diffusion to catalytic sites, promoting the reactive oxygen species (ROS)-driven degradation of chlorophenol pollutants. The PC-CDI system exhibits robust stability (> 95% efficiency retention over five cycles) and broad applicability across various chlorophenol derivatives. By circumventing Cl<sup>–</sup>-induced side reactions and inhibiting chlorine radical generation during photocatalysis, this strategy minimizes the environmental risks associated with chlorinated byproducts during chlorophenol wastewater treatment. These findings establish the PC-CDI system as a sustainable and eco-friendly technology for industrial wastewater treatment.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 148-161"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532508","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64828-5
Linhai He , Caiyi Lou , Lu Sun , Jing Niu , Shutao Xu , Yingxu Wei , Zhongmin Liu
Porous molecular sieve catalysts, including aluminosilicate zeolites and silicoaluminophosphate (SAPO) molecular sieves, have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development. Given the ubiquitous presence of water during catalyst synthesis, storage, and application, the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention. These effects are inherently complex and highly dependent on various factors such as temperature, water phase, and partial pressure. In this review, we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis, based on both experimental and theoretical calculation results. Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level, underscoring the dynamic and labile nature of these frameworks in water environments. The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives: (1) its participation in reaction through hydrogen bonding interactions, such as competitive adsorption at active sites, stabilization of ground and transition states, and proton transfer bridge; (2) its role as a direct reactant forming new species via reactions with other guest molecules. Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.
{"title":"Water interactions in molecular sieve catalysis: Framework evolution and reaction modulation","authors":"Linhai He , Caiyi Lou , Lu Sun , Jing Niu , Shutao Xu , Yingxu Wei , Zhongmin Liu","doi":"10.1016/S1872-2067(25)64828-5","DOIUrl":"10.1016/S1872-2067(25)64828-5","url":null,"abstract":"<div><div>Porous molecular sieve catalysts, including aluminosilicate zeolites and silicoaluminophosphate (SAPO) molecular sieves, have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development. Given the ubiquitous presence of water during catalyst synthesis, storage, and application, the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention. These effects are inherently complex and highly dependent on various factors such as temperature, water phase, and partial pressure. In this review, we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis, based on both experimental and theoretical calculation results. Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level, underscoring the dynamic and labile nature of these frameworks in water environments. The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives: (1) its participation in reaction through hydrogen bonding interactions, such as competitive adsorption at active sites, stabilization of ground and transition states, and proton transfer bridge; (2) its role as a direct reactant forming new species via reactions with other guest molecules. Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 9-31"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532391","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64822-4
Mingdong Zhang, Xueshuang Wu, Guiying Li, Changwei Hu
The direct oxidation of cyclohexane to adipic acid (AA) without the use of HNO3 is important but still challenging. Herein, hierarchical manganese-containing TS-1 zeolite (HMTS) was prepared using an improved direct synthesis method, in which titanium and manganese coexist within the zeolite matrix, as characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet, extended X-ray absorption fine structure etc. The introduction of matrix Mn species (Mn3+, Mn4+) not only increased the surface oxygen vacancies, but also generated medium-strong acid sites, which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination. On HMTS-3, one-pot oxidation of cyclohexane at 140 °C and 2 MPa O2 gave 81.6% conversion and 71.5% AA selectivity, the highest value obtained at present. Control experiments with single-component samples confirmed that matrix Ti4+ catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol (KA oil), and matrix Mn favored the conversion of KA oil to AA. The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity. Specifically, the matrix Ti4+ might activate oxygen to form Ti-O22– which facilitated the activation of the C–H bond of cyclohexane. The activation of O2 on matrix Mn3+ formed Mn4+-O2– favoring the breaking of the C–C bond of cyclohexanone. The hierarchical structure not only exposed more active sites and promoted mass transfer, but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti, which facilitated the overall reaction. This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.
{"title":"Hierarchical manganese-containing TS-1 zeolite for the direct oxidation of cyclohexane to adipic acid with molecular oxygen: Synergy between matrix Ti and Mn species","authors":"Mingdong Zhang, Xueshuang Wu, Guiying Li, Changwei Hu","doi":"10.1016/S1872-2067(25)64822-4","DOIUrl":"10.1016/S1872-2067(25)64822-4","url":null,"abstract":"<div><div>The direct oxidation of cyclohexane to adipic acid (AA) without the use of HNO<sub>3</sub> is important but still challenging. Herein, hierarchical manganese-containing TS-1 zeolite (HMTS) was prepared using an improved direct synthesis method, in which titanium and manganese coexist within the zeolite matrix, as characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet, extended X-ray absorption fine structure <em>etc</em>. The introduction of matrix Mn species (Mn<sup>3+</sup>, Mn<sup>4+</sup>) not only increased the surface oxygen vacancies, but also generated medium-strong acid sites, which endowed HMTS catalysts with the ability to efficiently activate oxygen and facilitate substrate coordination. On HMTS-3, one-pot oxidation of cyclohexane at 140 °C and 2 MPa O<sub>2</sub> gave 81.6% conversion and 71.5% AA selectivity, the highest value obtained at present. Control experiments with single-component samples confirmed that matrix Ti<sup>4+</sup> catalyzed the conversion of cyclohexane to a mixture of cyclohexanone and cyclohexanol (KA oil), and matrix Mn favored the conversion of KA oil to AA. The synergy between matrix Ti and Mn inside the hierarchical structure were the key factor for the superior activity. Specifically, the matrix Ti<sup>4+</sup> might activate oxygen to form Ti-O<sub>2</sub><sup>2–</sup> which facilitated the activation of the C–H bond of cyclohexane. The activation of O<sub>2</sub> on matrix Mn<sup>3+</sup> formed Mn<sup>4+</sup>-O<sub>2</sub><sup>–</sup> favoring the breaking of the C–C bond of cyclohexanone. The hierarchical structure not only exposed more active sites and promoted mass transfer, but also provided a better microenvironment for the matrix Mn to synergize with the matrix Ti, which facilitated the overall reaction. This work demonstrated the practical application potential of HMTS and provided useful insights into the direct oxidation of cyclohexane to AA.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 127-147"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64818-2
Guangmei Gan , Lin Yin , Xiaotian Wang, Juyuan Xing, Yuan Li, Gaoke Zhang
Developing efficient photocatalysts for CO2 conversion under full-spectrum irradiation remains a key challenge for solar-to-chemical energy conversion. In this study, a novel S-scheme heterojunction composed of reduction Cs0.32WO3 (CWO) nanosheets with hexagonal structure and oxidation WO3·2H2O (WO) nanorods with monoclinic structure photocatalyst was successfully constructed via an ultrasound strategy. Under full-spectrum irradiation for 4 h, the optimized 2D/1D of heterostructure CWO/WO-0.8 exhibited superior photocatalytic performance, achieving CO and CH3OH yields of 29.74 and 63.71 μmol·g–1, respectively. The enhanced activity is primarily ascribed to the formation of an S-scheme charge transfer pathway, which facilitates efficient separation and directional migration of photogenerated charge carriers through the internal electric field at the CWO/WO interface. This process facilitates the electron enrichment on the CWO surface and significantly enhances its CO2 reduction ability. Besides, the results of various characterizations show that CWO/WO-0.8 possesses enhanced optical response capability. The results of density functional theory calculations and CO2-temperature programmed desorption analysis confirmed that the CWO/WO heterojunction exhibits stronger CO2 adsorption and activation abilities compared to the pristine CWO and WO. The reaction pathway for CH3OH production was elucidated by in-situ diffused reflectance Fourier transformed infrared tests. This work provides new insights into the rational design of S-scheme photocatalysts for efficient and selective CO2 conversion.
{"title":"Interface-engineered S-scheme 2D/1D heterojunction of Cs0.32WO3/WO3·2H2O for boosted CO2 photoreduction: Synergistic charge separation and activation","authors":"Guangmei Gan , Lin Yin , Xiaotian Wang, Juyuan Xing, Yuan Li, Gaoke Zhang","doi":"10.1016/S1872-2067(25)64818-2","DOIUrl":"10.1016/S1872-2067(25)64818-2","url":null,"abstract":"<div><div>Developing efficient photocatalysts for CO<sub>2</sub> conversion under full-spectrum irradiation remains a key challenge for solar-to-chemical energy conversion. In this study, a novel S-scheme heterojunction composed of reduction Cs<sub>0.32</sub>WO<sub>3</sub> (CWO) nanosheets with hexagonal structure and oxidation WO<sub>3</sub>·2H<sub>2</sub>O (WO) nanorods with monoclinic structure photocatalyst was successfully constructed via an ultrasound strategy. Under full-spectrum irradiation for 4 h, the optimized 2D/1D of heterostructure CWO/WO-0.8 exhibited superior photocatalytic performance, achieving CO and CH<sub>3</sub>OH yields of 29.74 and 63.71 μmol·g<sup>–1</sup>, respectively. The enhanced activity is primarily ascribed to the formation of an S-scheme charge transfer pathway, which facilitates efficient separation and directional migration of photogenerated charge carriers through the internal electric field at the CWO/WO interface. This process facilitates the electron enrichment on the CWO surface and significantly enhances its CO<sub>2</sub> reduction ability. Besides, the results of various characterizations show that CWO/WO-0.8 possesses enhanced optical response capability. The results of density functional theory calculations and CO<sub>2</sub>-temperature programmed desorption analysis confirmed that the CWO/WO heterojunction exhibits stronger CO<sub>2</sub> adsorption and activation abilities compared to the pristine CWO and WO. The reaction pathway for CH<sub>3</sub>OH production was elucidated by <em>in-situ</em> diffused reflectance Fourier transformed infrared tests. This work provides new insights into the rational design of S-scheme photocatalysts for efficient and selective CO<sub>2</sub> conversion.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 219-230"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532533","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-27DOI: 10.1016/S1872-2067(25)64797-8
Wenhui Miao , Jingya Hao , Wenqin Zhou , Guoqing Jia , Can Li
G-quadruplex DNA (G4) can function as a kind of nucleic acid apoenzyme for constructing G4/hemin biocatalyst to mimic the catalytic function of hemoprotein. However, achieving stereoselective control with G4/hemin remains a persistent challenge. Here, we report that a PW17/hemin (PW17: 5’-GGGTAGGGCGGGTTGGG-3’), adopting the 5’-5’ stacked dimeric parallel G4 topology, can realize the enantioselective induction in intramolecular cyclopropanation of allyl diazoacetates with enantioselectivity up to 87% ee. Spectroscopic characterization and catalytic results demonstrate that the relatively open G-quartet of the 3’ terminal in dimeric PW17 contributes a catalytic pocket for hemin accommodation and plays a pivotal role in enantioselective control. This finding expands the unique repertoire of heme enzyme using biological scaffolds from proteins to nucleic acids and resolves the long-standing challenge of stereochemical control in G4/hemin catalysis.
g -四重体DNA （G4）可作为核酸脱酶，用于构建G4/血红蛋白生物催化剂，模拟血红蛋白的催化作用。然而，实现G4/hemin的立体选择性控制仍然是一个持续的挑战。本文报道了一种PW17/hemin （PW17: 5′-GGGTAGGGCGGGTTGGG-3′），采用5′-5′堆叠二聚体平行G4拓扑结构，可实现重氮乙酸丙烯基环丙化的分子内对映选择性诱导，对映选择性高达87% ee。光谱表征和催化结果表明，二聚体PW17的3′端相对开放的g -四重奏为血红蛋白的调节提供了一个催化口袋，并在对映选择性控制中起关键作用。这一发现扩大了血红素酶使用生物支架从蛋白质到核酸的独特库，并解决了G4/血红素催化中立体化学控制的长期挑战。
{"title":"Enantioselective induction by G-quadruplex DNA/hemin in intramolecular cyclopropanation","authors":"Wenhui Miao , Jingya Hao , Wenqin Zhou , Guoqing Jia , Can Li","doi":"10.1016/S1872-2067(25)64797-8","DOIUrl":"10.1016/S1872-2067(25)64797-8","url":null,"abstract":"<div><div>G-quadruplex DNA (G4) can function as a kind of nucleic acid apoenzyme for constructing G4/hemin biocatalyst to mimic the catalytic function of hemoprotein. However, achieving stereoselective control with G4/hemin remains a persistent challenge. Here, we report that a PW17/hemin (PW17: 5’-GGGTAGGGCGGGTTGGG-3’), adopting the 5’-5’ stacked dimeric parallel G4 topology, can realize the enantioselective induction in intramolecular cyclopropanation of allyl diazoacetates with enantioselectivity up to 87% <em>ee</em>. Spectroscopic characterization and catalytic results demonstrate that the relatively open G-quartet of the 3’ terminal in dimeric PW17 contributes a catalytic pocket for hemin accommodation and plays a pivotal role in enantioselective control. This finding expands the unique repertoire of heme enzyme using biological scaffolds from proteins to nucleic acids and resolves the long-standing challenge of stereochemical control in G4/hemin catalysis.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 138-143"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-27DOI: 10.1016/S1872-2067(25)64824-8
Anton L. Maximov , Mikhail P. Egorov
Catalysis is a cornerstone of modern chemistry, enabling the development of sustainable processes and the production of essential chemicals. However, a fundamental challenge in catalysis lies in understanding the nature of the catalytic species and active centers, particularly the key mechanistic understanding of homogeneous and heterogeneous systems. This review describes the concept of “cocktail”-type catalysis, demonstrating that catalytic active species are not static but evolve through the interconversion of molecular complexes, clusters, and nanoparticles. By bridging homogeneous and heterogeneous catalysis, this paradigm challenges conventional mechanistic views and initiates discussions for a universal theory of catalysis. The findings highlight the importance of adaptive catalyst behavior, leading to more efficient, selective, and robust catalytic systems. The impact of the “cocktail”-type approach extends beyond fundamental research, offering practical applications in industrial catalysis, green chemistry, and synthetic methodologies. By embracing catalytic dynamics, new opportunities arise for designing next-generation catalysts that are both versatile and highly effective in diverse transformations.
{"title":"Discovery and development of cocktail-type catalysis","authors":"Anton L. Maximov , Mikhail P. Egorov","doi":"10.1016/S1872-2067(25)64824-8","DOIUrl":"10.1016/S1872-2067(25)64824-8","url":null,"abstract":"<div><div>Catalysis is a cornerstone of modern chemistry, enabling the development of sustainable processes and the production of essential chemicals. However, a fundamental challenge in catalysis lies in understanding the nature of the catalytic species and active centers, particularly the key mechanistic understanding of homogeneous and heterogeneous systems. This review describes the concept of “cocktail”-type catalysis, demonstrating that catalytic active species are not static but evolve through the interconversion of molecular complexes, clusters, and nanoparticles. By bridging homogeneous and heterogeneous catalysis, this paradigm challenges conventional mechanistic views and initiates discussions for a universal theory of catalysis. The findings highlight the importance of adaptive catalyst behavior, leading to more efficient, selective, and robust catalytic systems. The impact of the “cocktail”-type approach extends beyond fundamental research, offering practical applications in industrial catalysis, green chemistry, and synthetic methodologies. By embracing catalytic dynamics, new opportunities arise for designing next-generation catalysts that are both versatile and highly effective in diverse transformations.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"78 ","pages":"Pages 7-24"},"PeriodicalIF":17.7,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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