Chinese Journal of Catalysis最新文献

{"title":"Cation effects in electrocatalytic reduction reactions: Recent advances","authors":"Qinghui Ren ,&nbsp;Liang Xu ,&nbsp;Mengyu Lv ,&nbsp;Zhiyuan Zhang ,&nbsp;Zhenhua Li ,&nbsp;Mingfei Shao ,&nbsp;Xue Duan","doi":"10.1016/S1872-2067(24)60080-X","DOIUrl":"10.1016/S1872-2067(24)60080-X","url":null,"abstract":"<div><p>Electrocatalytic reduction reactions, powered by clean energy sources such as solar energy and wind, offer a sustainable method for converting inexpensive feedstocks (e.g., CO₂, N₂/NO_<em>x</em>, organics, and O₂) into high-value-added chemicals or fuels. The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions. However, bottlenecks are encountered, making it challenging to further improve performance through catalyst development alone. Recently, cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions. This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions. First, we introduce the mechanisms underlying cation effects. We then provide a comprehensive overview of their application in electroreduction reactions. Characterization techniques and theoretical calculation methods for studying cation effects are also discussed. Finally, we address remaining challenges and future perspectives in this field. We hope that this review offers fundamental insights and design guidance for utilizing cation effects, thereby advancing their development.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 16-32"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142049208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Conjugated microporous polymers-scaffolded enzyme cascade systems with enhanced catalytic activity","authors":"Zhenhua Wu ,&nbsp;Jiafu Shi ,&nbsp;Boyu Zhang ,&nbsp;Yushuai Jiao ,&nbsp;Xiangxuan Meng ,&nbsp;Ziyi Chu ,&nbsp;Yu Chen ,&nbsp;Yiran Cheng ,&nbsp;Zhongyi Jiang","doi":"10.1016/S1872-2067(24)60088-4","DOIUrl":"10.1016/S1872-2067(24)60088-4","url":null,"abstract":"<div><p>Enhancing catalytic activity of multi-enzyme <em>in vitro</em> through substrate channeling effect is promising yet challenging. Herein, conjugated microporous polymers (CMPs)-scaffolded integrated enzyme cascade systems (I-ECSs) are constructed through co-entrapping glucose oxidase (GOx) and horseradish peroxidase (HRP), in which hydrogen peroxide (H₂O₂) is the intermediate product. The interplay of low-resistance mass transfer pathway and appropriate pore wall-H₂O₂ interactions facilitates the directed transfer of H₂O₂, resulting in 2.4-fold and 5.0-fold elevation in catalytic activity compared to free ECSs and separated ECSs, respectively. The substrate channeling effect could be regulated by altering the mass ratio of GOx to HRP. Besides, I-ECSs demonstrate excellent stabilities in harsh environments and multiple recycling.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 213-223"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050390","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H2O2 production by using femtosecond transient absorption spectroscopy","authors":"Yanyan Zhao ,&nbsp;Chunyan Yang ,&nbsp;Shumin Zhang ,&nbsp;Guotai Sun ,&nbsp;Bicheng Zhu ,&nbsp;Linxi Wang ,&nbsp;Jianjun Zhang","doi":"10.1016/S1872-2067(24)60069-0","DOIUrl":"10.1016/S1872-2067(24)60069-0","url":null,"abstract":"<div><p>Hydrogen peroxide (H₂O₂) has gained widespread attention as a versatile oxidant and a mild disinfectant. Here, an electrostatic self-assembly method is applied to couple ZnSe quantum dots (QDs) with a flower-like covalent organic framework (COF) to form a step-scheme (S-scheme) photocatalyst for H₂O₂ production. The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF. The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and <em>in-situ</em> X-ray photoelectron and femtosecond transient absorption spectroscopies. Photoluminescence, time-resolved photoluminescence, photocurrent response, electrochemical impedance spectroscopy, and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability, resulting in enhanced photocatalytic performance. Remarkably, a 10%-ZnSe QD/COF has excellent photocatalytic H₂O₂-production activity, and the optimal S-scheme composite with ethanol as the hole scavenger yields a H₂O₂-production rate of 1895 mol g^–1 h^–1. This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H₂O₂ production.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 258-269"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050447","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Superposition of dual electric fields in covalent organic frameworks for efficient photocatalytic hydrogen evolution","authors":"Chao Li ,&nbsp;Shuo Wang ,&nbsp;Yuan Liu ,&nbsp;Xihe Huang ,&nbsp;Yan Zhuang ,&nbsp;Shuhong Wu ,&nbsp;Ying Wang ,&nbsp;Na Wen ,&nbsp;Kaifeng Wu ,&nbsp;Zhengxin Ding ,&nbsp;Jinlin Long","doi":"10.1016/S1872-2067(24)60075-6","DOIUrl":"10.1016/S1872-2067(24)60075-6","url":null,"abstract":"<div><p>Covalent organic frameworks (COFs) are promising materials for converting solar energy into green hydrogen. However, limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction (HER). In this study, the intrinsically tunable internal bond electric field (IBEF) at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field (IMEF) induced by the donor-acceptor (D-A) structure for an efficient HER. The aligned orientation of IBEF and IMEF resulted in a remarkable H₂ evolution rate of 57.3 mmol·g^–1·h^–1 on TNCA, which was approximately 520 times higher than that of TCNA (0.11 mmol·g^–1·h^–1) with the opposing electric field orientation. The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer, kinetically facilitating the migration of photogenerated electrons from D to A. Furthermore, theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only provides a strong driving force for carrier transfer but also effectively hinders the return of free electrons to the valence band, improving the utilization of photoelectrons. This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 164-175"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytically altering the redox pathway of sulfur in propylene carbonate electrolyte using dual-nitrogen/oxygen-containing carbon","authors":"Linghui Yu ,&nbsp;Heng Zhang ,&nbsp;Luyuan Paul Wang ,&nbsp;Samuel Jun Hoong Ong ,&nbsp;Shibo Xi ,&nbsp;Bo Chen ,&nbsp;Rui Guo ,&nbsp;Ting Wang ,&nbsp;Yonghua Du ,&nbsp;Wei Chen ,&nbsp;Ovadia Lev ,&nbsp;Zhichuan J. Xu","doi":"10.1016/S1872-2067(24)60096-3","DOIUrl":"10.1016/S1872-2067(24)60096-3","url":null,"abstract":"<div><p>Carbonate electrolytes are one of the most desirable electrolytes for high-energy lithium-sulfur batteries (LSBs) because of their successful implementation in commercial Li-ion batteries. The low-polysulfide-solubility feature of some carbonate solvents also makes them very promising for overcoming the shuttle effects of LSBs. However, regular sulfur electrodes experience undesired electrochemical mechanisms in carbonate electrolytes due to side reactions. In this study, we report a catalytic redox mechanism of sulfur in propylene carbonate (PC) electrolyte based on a comparison study. The catalytic mechanism is characterized by the interactions between polysulfides and dual N/O functional groups on the host carbon, which largely prevents side reactions between polysulfides and the carbonate electrolyte. Such a mechanism coupled with the low-polysulfide-solubility feature leads to stable cycling of LSBs in PC electrolyte. Favorable dual N/O functional groups are identified <em>via</em> a density functional theory study. This work provides an alternative route for enabling LSBs in carbonate electrolytes.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 224-233"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050391","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Identification of origin of insulating polymer maneuvered photoredox catalysis","authors":"Qiao-Ling Mo ,&nbsp;Rui Xiong ,&nbsp;Jun-Hao Dong,&nbsp;Bai-Sheng Sa,&nbsp;Jing-Ying Zheng,&nbsp;Qing Chen,&nbsp;Yue Wu,&nbsp;Fang-Xing Xiao","doi":"10.1016/S1872-2067(24)60070-7","DOIUrl":"10.1016/S1872-2067(24)60070-7","url":null,"abstract":"<div><p>Solid non-conjugated polymers have long been regarded as insulators due to deficiency of delocalized π electrons along the molecular chain framework. Up to date, origin of insulating polymer regulated charge transfer has not yet been uncovered. In this work, we unleash the root origin of charge transport capability of insulating polymer in photocatalysis. We ascertain that insulating polymer plays crucial roles in fine tuning of electronic structure of transition metal chalcogenides (TMCs), which mainly include altering surface electron density of TMCs for accelerating charge transport kinetics, triggering the generation of defect over TMCs for prolonging carrier lifetime, and acting as hole-trapping mediator for retarding charge recombination. These synergistic roles contribute to the charge transfer of insulating polymer. Our work opens a new vista of utilizing solid insulating polymers for maneuvering charge transfer toward solar energy conversion.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 109-123"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Is platinum-loaded titania the best material for dye-sensitized hydrogen evolution under visible light?","authors":"Haruka Yamamoto ,&nbsp;Langqiu Xiao ,&nbsp;Yugo Miseki ,&nbsp;Hiroto Ueki ,&nbsp;Megumi Okazaki ,&nbsp;Kazuhiro Sayama ,&nbsp;Thomas E. Mallouk ,&nbsp;Kazuhiko Maeda","doi":"10.1016/S1872-2067(24)60092-6","DOIUrl":"10.1016/S1872-2067(24)60092-6","url":null,"abstract":"<div><p>A dye-sensitized photocatalyst combining Pt-loaded TiO₂ and Ru(II) tris-diimine sensitizer (<strong>RuP</strong>) was constructed and its activity for photochemical hydrogen evolution was compared with that of Pt-intercalated HCa₂Nb₃O₁₀ nanosheets. When the sacrificial donor ethylenediaminetetraacetic acid (EDTA) disodium salt dihydrate was used, <strong>RuP</strong>/Pt/TiO₂ showed higher activity than <strong>RuP</strong>/Pt/HCa₂Nb₃O₁₀. In contrast, when NaI (a reversible electron donor) was used, <strong>RuP</strong>/Pt/TiO₂ showed little activity due to back electron transfer to the electron acceptor (I₃^–), which was generated as the oxidation product of I^–. By modification with anionic polymers (sodium poly(styrenesulfonate) or sodium polymethacrylate) that could inhibit the scavenging of conduction band electrons by I₃^–, the H₂ production activity from aqueous NaI was improved, but it did not exceed that of <strong>RuP</strong>/Pt/HCa₂Nb₃O₁₀. Transient absorption measurements showed that the rate of semiconductor-to-dye back electron transfer was slower in the case of TiO₂ than HCa₂Nb₃O₁₀, but the electron transfer reaction to I₃^– was much faster. These results indicate that Pt/TiO₂ is useful for reactions with sacrificial reductants (e.g., EDTA), where the back electron transfer reaction to the more reducible product can be neglected. However, more careful design of the catalyst will be necessary when a reversible electron donor is employed.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 124-132"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring the microenvironment of Ti sites in Ti-containing materials for synergizing with Au sites to boost propylene epoxidation","authors":"Shudong Shi ,&nbsp;Zhihua Zhang ,&nbsp;Yundao Jing,&nbsp;Wei Du,&nbsp;Xuezhi Duan,&nbsp;Xinggui Zhou","doi":"10.1016/S1872-2067(24)60083-5","DOIUrl":"10.1016/S1872-2067(24)60083-5","url":null,"abstract":"<div><p>Au sites supported on Ti-containing materials (Au/Ti-containing catalyst) are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermediates and contributes to the formation of propylene oxide (PO). In principle, thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials. Consequently, the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction. Herein, we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion, and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups. The Ti^VI material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H₂ efficiency compared to the Ti^VI material that possessed more hydroxyls, offering a 7-fold and 4-fold increase, respectively. As expected, the Ti^VI+IV and Ti^IV materials also exhibit a similar phenomenon to the Ti^VI materials through the same thermal treatment, which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO conversion and enhancing catalytic performance. These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 133-143"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A dendritic Cu/Cu2O structure with high curvature enables rapid and efficient reduction of carbon dioxide to C2 in an H-cell","authors":"Lei shao,&nbsp;Bochen Hu,&nbsp;Jinhui Hao,&nbsp;Junjie Jin,&nbsp;Weidong Shi,&nbsp;Min Chen","doi":"10.1016/S1872-2067(24)60079-3","DOIUrl":"10.1016/S1872-2067(24)60079-3","url":null,"abstract":"<div><p>Electrocatalytic reduction of CO₂ (CO₂RR) to multicarbon products is an efficient approach for addressing the energy crisis and achieving carbon neutrality. In H-cells, achieving high-current C₂ products is challenging because of the inefficient mass transfer of the catalyst and the presence of the hydrogen evolution reaction (HER). In this study, dendritic Cu/Cu₂O with abundant Cu⁰/Cu⁺ interfaces and numerous dendritic curves was synthesized in a CO₂ atmosphere, resulting in the high selectivity and current density of the C₂ products. Dendritic Cu/Cu₂O achieved a C₂ Faradaic efficiency of 69.8% and a C₂ partial current density of 129.5 mA cm^‒2 in an H-cell. Finite element simulations showed that a dendritic structure with a high curvature generates a strong electric field, leading to a localized CO₂ concentration. Additionally, DRT analysis showed that a dendritic structure with a high curvature actively adsorbed the surrounding high concentration of CO₂, enhancing the mass transfer rate and achieving a high current density. During the experiment, the impact of the electronic structure on the performance of the catalyst was investigated by varying the atomic ratio of Cu⁰/Cu⁺ on the catalyst surface, which resulted in improved ethylene selectivity. Under the optimal atomic ratio of Cu⁰/Cu⁺, the charge transfer resistance was minimized, and the desorption rate of the intermediates was low, favoring C₂ generation. Density functional theory calculations indicated that the Cu⁰/Cu⁺ interfaces exhibited a lower Gibbs free energy for the rate-determining step, enhancing C₂H₄ formation. The Cu/Cu₂O catalyst also exhibited a low Cu d-band center, which enhanced the adsorption stability of *CO on the surface and facilitated C₂ formation. This observation explained the higher yield of C₂ products at the Cu⁰/Cu⁺ interface than that of H₂ under rapid mass transfer. The results of the net present value model showed that the H-cell holds promising industrial prospects, contingent upon it being a catalyst with both high selectivity and high current density. This approach of integrating the structure and composition provides new insights for advancing the CO₂RR towards high-current C₂ products.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 144-153"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Amorphous core-shell NiMoP@CuNWs rod-like structure with hydrophilicity feature for efficient hydrogen production in neutral media","authors":"Jiayong Xiao ,&nbsp;Chao Jiang ,&nbsp;Hui Zhang,&nbsp;Zhuo Xing,&nbsp;Ming Qiu,&nbsp;Ying Yu","doi":"10.1016/S1872-2067(24)60086-0","DOIUrl":"10.1016/S1872-2067(24)60086-0","url":null,"abstract":"<div><p>Using interface engineering, a highly efficient catalyst with a shell@core structure was successfully synthesized by growing an amorphous material composed of Ni, Mo, and P on Cu nanowires (NiMoP@CuNWs). This catalyst only requires an overpotential of 35 mV to reach a current density of 10 mA cm^–2. The exceptional hydrogen evolution reaction (HER) activity is attributed to the unique amorphous rod-like nature of NiMoP@CuNWs, which possesses a special hydrophilic feature, enhances mass transfer, promotes effective contact between the electrode and electrolyte solution, and exposes more active sites during the catalytic process. Density functional theory revealed that the introduction of Mo weakens the binding strength of the Ni site on the catalyst surface with the H atom and promotes the desorption process of the H₂ product significantly. Owing to its facile synthesis, low cost, and high catalytic performance, this electrocatalyst is a promising option for commercial applications as a water electrolysis catalyst.</p></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"63 ","pages":"Pages 154-163"},"PeriodicalIF":15.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142050419","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}