Pub Date : 2024-11-21DOI: 10.1016/j.checat.2024.101195
Marc Robert
In a recent issue of Nature Catalysis, Yu and Shao-Horn et al. describe the impact of cations on the electrochemical reduction of CO2 to methanol with Co phthalocyanine complexes deposited onto carbon nanotubes. Their findings that the catalysis is enhanced opens wide and stimulating perspectives.
在最近一期的《自然催化》（Nature Catalysis）杂志上，Yu 和 Shao-Horn 等人描述了阳离子对沉积在碳纳米管上的酞菁钴复合物电化学还原 CO2 到甲醇的影响。他们的发现增强了催化作用，开辟了广阔而令人振奋的前景。
{"title":"Cations in molecular electrochemical catalysis","authors":"Marc Robert","doi":"10.1016/j.checat.2024.101195","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101195","url":null,"abstract":"In a recent issue of <em>Nature Catalysis</em>, Yu and Shao-Horn et al. describe the impact of cations on the electrochemical reduction of CO<sub>2</sub> to methanol with Co phthalocyanine complexes deposited onto carbon nanotubes. Their findings that the catalysis is enhanced opens wide and stimulating perspectives.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"193 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679036","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reduction of CO2 emissions and conversion of CO2 to valuable chemicals is an urgent mission, as it is vital to the global environment and sustainable development. The activation of CO2 is always considered to be the key step for its transformation. Herein, we verified that the activation and dissociation behavior of H2 was the controlling step for CO2 reduction. PdIn alloy was an active center and played a pivotal role in CO2 hydrogenation to the methyl reagent of HCOO∗. H2 split to active Hδ− species on PdIn alloy sites. Strong nucleophilic Hδ− reacted with the CO2 adsorbed on oxygen defects to form ∗HCOO in situ. A high yield of up to 99% was achieved for the cascade fixation of CO2 to valuable amines. The new insights into the activation of CO2 and H2 and their contributions to CO2 conversion that we present will attract the attention of researchers in catalysis, synthesis, surface, and interface chemistry.
减少二氧化碳排放和将二氧化碳转化为有价值的化学品是一项紧迫的任务，因为这对全球环境和可持续发展至关重要。二氧化碳的活化一直被认为是其转化的关键步骤。在此，我们验证了 H2 的活化和解离行为是二氧化碳还原的控制步骤。PdIn 合金是一个活性中心，在 CO2 加氢为 HCOO∗ 的甲基试剂过程中发挥了关键作用。H2 在 PdIn 合金位点上分裂成活性 Hδ- 物种。强亲核 Hδ- 与吸附在氧缺陷上的 CO2 发生反应，在原位生成 ∗HCOO。在将 CO2 级联固定为有价值的胺时，产量高达 99%。我们提出的关于 CO2 和 H2 活化及其对 CO2 转化贡献的新见解将吸引催化、合成、表面和界面化学研究人员的关注。
{"title":"Hydrogen dissociation and CO2 activation in cascade CO2 fixation on PdIn/TiO2 catalyst","authors":"Leilei Zhou, Ying Wang, Yinze Yang, Liyan Zhang, Jingrong Li, Tingting Xiao, Peikai Luo, Xinluona Su, Haiyang Cheng, Fengyu Zhao","doi":"10.1016/j.checat.2024.101116","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101116","url":null,"abstract":"Reduction of CO<sub>2</sub> emissions and conversion of CO<sub>2</sub> to valuable chemicals is an urgent mission, as it is vital to the global environment and sustainable development. The activation of CO<sub>2</sub> is always considered to be the key step for its transformation. Herein, we verified that the activation and dissociation behavior of H<sub>2</sub> was the controlling step for CO<sub>2</sub> reduction. PdIn alloy was an active center and played a pivotal role in CO<sub>2</sub> hydrogenation to the methyl reagent of HCOO∗. H<sub>2</sub> split to active H<sup>δ−</sup> species on PdIn alloy sites. Strong nucleophilic H<sup>δ−</sup> reacted with the CO<sub>2</sub> adsorbed on oxygen defects to form ∗HCOO <em>in situ</em>. A high yield of up to 99% was achieved for the cascade fixation of CO<sub>2</sub> to valuable amines. The new insights into the activation of CO<sub>2</sub> and H<sub>2</sub> and their contributions to CO<sub>2</sub> conversion that we present will attract the attention of researchers in catalysis, synthesis, surface, and interface chemistry.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"81 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679037","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-21DOI: 10.1016/j.checat.2024.101133
Bo M. Couture, Ru Cui, Jia-Min Chu, Zhuofan Shen, Sagar D. Khare, Yong Zhang, Rudi Fasan
Indolines are ubiquitous structural motifs occurring in pharmaceuticals and natural products. Here, we report a strategy for regio- and stereoselective C(sp3)–H functionalization of N-substituted indolines via carbene transfer chemistry mediated by engineered CYP119-based catalysts. These systems offer high enantioselectivity and high catalytic efficiency, as well as regiodivergent selectivity, furnishing an efficient and convenient route for diversification of these important scaffolds via direct C(sp3)–H functionalization. Selective functionalization of exocyclic C(sp3)–H bond in N-methyl indolines was also achieved, and a biocatalytic cascade combining enzyme-mediated α- and β-C(sp3)–H functionalization yielded a polycyclic indoline-containing motif found in drugs. Mechanistic and computational studies support a radical-mediated C–H functionalization pathway and provide insights into protein-mediated regiodivergent selectivity. Altogether, this work offers a direct and tunable strategy to access functionalized indolines as key building blocks for medicinal chemistry and natural product synthesis and provides first insights into the mechanism of P450-catalyzed C(sp3)–H carbene insertion.
{"title":"Radical-mediated regiodivergent C(sp3)–H functionalization of N-substituted indolines via enzymatic carbene transfer","authors":"Bo M. Couture, Ru Cui, Jia-Min Chu, Zhuofan Shen, Sagar D. Khare, Yong Zhang, Rudi Fasan","doi":"10.1016/j.checat.2024.101133","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101133","url":null,"abstract":"Indolines are ubiquitous structural motifs occurring in pharmaceuticals and natural products. Here, we report a strategy for regio- and stereoselective C(<em>sp</em><sup><em>3</em></sup>)–H functionalization of <em>N</em>-substituted indolines via carbene transfer chemistry mediated by engineered CYP119-based catalysts. These systems offer high enantioselectivity and high catalytic efficiency, as well as regiodivergent selectivity, furnishing an efficient and convenient route for diversification of these important scaffolds via direct C(<em>sp</em><sup><em>3</em></sup>)–H functionalization. Selective functionalization of exocyclic C(<em>sp</em><sup><em>3</em></sup>)–H bond in <em>N</em>-methyl indolines was also achieved, and a biocatalytic cascade combining enzyme-mediated α- and β-C(<em>sp</em><sup><em>3</em></sup>)–H functionalization yielded a polycyclic indoline-containing motif found in drugs. Mechanistic and computational studies support a radical-mediated C–H functionalization pathway and provide insights into protein-mediated regiodivergent selectivity. Altogether, this work offers a direct and tunable strategy to access functionalized indolines as key building blocks for medicinal chemistry and natural product synthesis and provides first insights into the mechanism of P450-catalyzed C(<em>sp</em><sup><em>3</em></sup>)–H carbene insertion.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"23 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-21DOI: 10.1016/j.checat.2024.101185
Siddhartha Subramanian, Hugo-Pieter Iglesias van Montfort, Thomas Burdyny
CO2 electrolyzers show promise as a cleaner alternative to produce value-added chemicals. In the last decade, research has shifted from classifying CO2 reduction activity and selectivity as a catalytic property (zero-dimensional [0D]) to one that includes the complex interactions of gas, liquid, and solid species between the cathode and anode (1D). To scale CO2 electrolyzers, however, 2D and 3D spatial variations in product selectivity, activity, and stability arise due to the design of reactor components, as well as concentration variations of the reactants, intermediates, and products. Conventional “black-box” measurement protocols are then insufficient to characterize CO2 electrolyzers. Here, we discuss the critical multi-dimensional phenomena occurring inside these electrochemical systems, which impact the observed performance. Recent literature is used to demonstrate how a spatial perspective is essential for proper data interpretation, designing effective catalysts, and prolonging CO2 electrolyzer lifetimes. Researchers should then define CO2 electrolysis systems in multiple dimensions (2D and 3D).
{"title":"Spatial effects define CO2 electrolysis systems","authors":"Siddhartha Subramanian, Hugo-Pieter Iglesias van Montfort, Thomas Burdyny","doi":"10.1016/j.checat.2024.101185","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101185","url":null,"abstract":"CO<sub>2</sub> electrolyzers show promise as a cleaner alternative to produce value-added chemicals. In the last decade, research has shifted from classifying CO<sub>2</sub> reduction activity and selectivity as a catalytic property (zero-dimensional [0D]) to one that includes the complex interactions of gas, liquid, and solid species between the cathode and anode (1D). To scale CO<sub>2</sub> electrolyzers, however, 2D and 3D spatial variations in product selectivity, activity, and stability arise due to the design of reactor components, as well as concentration variations of the reactants, intermediates, and products. Conventional “black-box” measurement protocols are then insufficient to characterize CO<sub>2</sub> electrolyzers. Here, we discuss the critical multi-dimensional phenomena occurring inside these electrochemical systems, which impact the observed performance. Recent literature is used to demonstrate how a spatial perspective is essential for proper data interpretation, designing effective catalysts, and prolonging CO<sub>2</sub> electrolyzer lifetimes. Researchers should then define CO<sub>2</sub> electrolysis systems in multiple dimensions (2D and 3D).","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"8 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-21DOI: 10.1016/j.checat.2024.101189
Yufeng Li, Zhenwei Li, Nan Wang, Yajun Zha, Ke Zheng, Yuebing Xu, Bing Liu, Xiaohao Liu
The dry reforming of methane (DRM) reaction holds significance for efficient conversion of CH4 and CO2 into syngas for the subsequent production of premium fuels and high-value chemicals. However, catalyst deactivation is easily caused by carbon deposition over Ni-based catalysts. Here, we investigated the effects of ultrasmall CeO2 nano-islands on the DRM reaction and found a strong volcano-type relationship between CeO2 content and reaction activity over Ni/CeO2-SiO2 catalysts. A suitable CeO2 amount can only slightly suppress CH4 dissociation but largely promote carbon species elimination. More importantly, the presence of these CeO2 nano-islands positively affected the types and location of coke species by “carbon-phobic effect” and thus alleviated coverage of Ni active sites. As a result, a higher TOFCH4 was obtained by an increase of about 82% and a continuous 2,000-h run almost without any side reaction, and deactivation was achieved along with CO2 and CH4 conversions at about 96% and 92%, respectively.
{"title":"Strong activity-based volcano-type relationship for dry reforming of methane through modulating Ni-CeO2 interaction over Ni/CeO2-SiO2 catalysts","authors":"Yufeng Li, Zhenwei Li, Nan Wang, Yajun Zha, Ke Zheng, Yuebing Xu, Bing Liu, Xiaohao Liu","doi":"10.1016/j.checat.2024.101189","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101189","url":null,"abstract":"The dry reforming of methane (DRM) reaction holds significance for efficient conversion of CH<sub>4</sub> and CO<sub>2</sub> into syngas for the subsequent production of premium fuels and high-value chemicals. However, catalyst deactivation is easily caused by carbon deposition over Ni-based catalysts. Here, we investigated the effects of ultrasmall CeO<sub>2</sub> nano-islands on the DRM reaction and found a strong volcano-type relationship between CeO<sub>2</sub> content and reaction activity over Ni/CeO<sub>2</sub>-SiO<sub>2</sub> catalysts. A suitable CeO<sub>2</sub> amount can only slightly suppress CH<sub>4</sub> dissociation but largely promote carbon species elimination. More importantly, the presence of these CeO<sub>2</sub> nano-islands positively affected the types and location of coke species by “carbon-phobic effect” and thus alleviated coverage of Ni active sites. As a result, a higher TOF<sub>CH4</sub> was obtained by an increase of about 82% and a continuous 2,000-h run almost without any side reaction, and deactivation was achieved along with CO<sub>2</sub> and CH<sub>4</sub> conversions at about 96% and 92%, respectively.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"74 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-21DOI: 10.1016/j.checat.2024.101194
Pavel A. Kots
In a recent article, Conk and colleagues report a new pathway for closed-loop chemical recycling of polyolefin plastic waste. The authors discovered a new catalytic composition for tandem cracking and ethenolysis that yields 90% propylene from polyethylene at 320°C.
{"title":"Close-loop chemical recycling unlocked via waste polyolefins-ethylene co-metathesis","authors":"Pavel A. Kots","doi":"10.1016/j.checat.2024.101194","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101194","url":null,"abstract":"In a recent article, Conk and colleagues report a new pathway for closed-loop chemical recycling of polyolefin plastic waste. The authors discovered a new catalytic composition for tandem cracking and ethenolysis that yields 90% propylene from polyethylene at 320°C.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"19 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142679035","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-18DOI: 10.1016/j.checat.2024.101187
Léa Thai-Savard, Jason R. Zbieg, Jack A. Terrett
The direct employment of widely available alcohol feedstocks as synthons in nucleophilic couplings is a long-standing objective within the synthetic community. Traditional methods utilizing alcohols require the preactivation of one coupling partner due to the inherent mismatched electronics for C–O bond formation. Here, free alcohols are leveraged as carbocation precursors via in situ activation, reversing their traditional nucleophilic behavior and avoiding the need for prefunctionalization. The direct catalytic deoxygenative coupling of alcohols toward selective C–O heterocoupling is described. Mechanistic studies support the intermediacy of a discrete carbocation, which can be intercepted by a diverse array of simple nucleophiles. Application of this protocol toward natural products and complex active pharmaceutical ingredients is also demonstrated. The compatibility toward a large breadth of nucleophiles enables the construction of C–O, C–S, C–C, and C–N bonds in a single step, showcasing the broad applicability of this alcohol activation platform.
{"title":"Deoxygenative alcohol–nucleophile coupling via carbocations","authors":"Léa Thai-Savard, Jason R. Zbieg, Jack A. Terrett","doi":"10.1016/j.checat.2024.101187","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101187","url":null,"abstract":"The direct employment of widely available alcohol feedstocks as synthons in nucleophilic couplings is a long-standing objective within the synthetic community. Traditional methods utilizing alcohols require the preactivation of one coupling partner due to the inherent mismatched electronics for C–O bond formation. Here, free alcohols are leveraged as carbocation precursors via <em>in situ</em> activation, reversing their traditional nucleophilic behavior and avoiding the need for prefunctionalization. The direct catalytic deoxygenative coupling of alcohols toward selective C–O heterocoupling is described. Mechanistic studies support the intermediacy of a discrete carbocation, which can be intercepted by a diverse array of simple nucleophiles. Application of this protocol toward natural products and complex active pharmaceutical ingredients is also demonstrated. The compatibility toward a large breadth of nucleophiles enables the construction of C–O, C–S, C–C, and C–N bonds in a single step, showcasing the broad applicability of this alcohol activation platform.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"13 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665561","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-15DOI: 10.1016/j.checat.2024.101184
Upasana Mukherjee, Jagrut A. Shah, Ming-Yu Ngai
The use of visible light to drive chemical transformations has a history spanning over a century. However, the development of photo-redox catalysts to efficiently harness light energy is a more recent advancement, evolving over the past 2 decades. While Ru- and Ir-based photocatalysts dominate due to their photostability, long excited-state lifetimes, and high redox potentials, concerns about sustainability and cost have shifted attention to first-row transition metals. Luminescent Cu(I) complexes have emerged as promising alternatives, offering open-shell reactivity and tunable photoelectrochemical properties. This review (1) provides an overview of the structural, photophysical, and electrochemical properties governing Cu(I) complexes; (2) highlights advances in Cu(I)-BINAP catalysis for C–C and C–heteroatom bond formations under mild conditions; and (3) analyzes the trajectory of this catalytic system, addressing challenges and identifying opportunities for further development.
{"title":"Visible light-driven excited-state copper-BINAP catalysis for accessing diverse chemical reactions","authors":"Upasana Mukherjee, Jagrut A. Shah, Ming-Yu Ngai","doi":"10.1016/j.checat.2024.101184","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101184","url":null,"abstract":"The use of visible light to drive chemical transformations has a history spanning over a century. However, the development of photo-redox catalysts to efficiently harness light energy is a more recent advancement, evolving over the past 2 decades. While Ru- and Ir-based photocatalysts dominate due to their photostability, long excited-state lifetimes, and high redox potentials, concerns about sustainability and cost have shifted attention to first-row transition metals. Luminescent Cu(I) complexes have emerged as promising alternatives, offering open-shell reactivity and tunable photoelectrochemical properties. This review (1) provides an overview of the structural, photophysical, and electrochemical properties governing Cu(I) complexes; (2) highlights advances in Cu(I)-BINAP catalysis for C–C and C–heteroatom bond formations under mild conditions; and (3) analyzes the trajectory of this catalytic system, addressing challenges and identifying opportunities for further development.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"98 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142637859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-13DOI: 10.1016/j.checat.2024.101183
Fatima Mahnaz, Balaji C. Dharmalingam, Jasan Robey Mangalindan, Jenna Vito, Jithin John Varghese, Manish Shetty
We demonstrate that the exchange of zeolitic Brønsted acid sites (BASs) with cations from metal oxides plays a pivotal role in the propagation of hydrocarbon pools (HCPs) during CO2 hydrogenation. We probed the likelihood of In2O3, ZnZrOx, and Cr2O3 migration and their cation exchange with BASs of a silicoaluminophosphate, SAPO-34, by integrating them at nanoscale proximity (∼1,400 nm). Analysis with NH3 temperature-programmed desorption and transmission Fourier transform infrared spectroscopy showed ion exchange of BASs with Inδ+ and Znδ+ but not for Crδ+. We measured the C3/C2 hydrocarbon ratio (indicating relative propagation of olefin to aromatic cycles) and paraffin-to-olefin ratio, which revealed that Inδ+ species inhibited HCPs inside the channels of SAPO-34, while Znδ+ species enhanced hydrogen transfer and secondary hydrogenation. Combining reactivity data with occluded hydrocarbon analysis and 13C solid-state nuclear magnetic resonance spectroscopy, we show that ion-exchanged species affect HCP propagation. Overall, our work provides insights for the rational integration of bifunctional catalysts.
{"title":"Metal cation exchange with zeolitic acid sites modulates hydrocarbon pool propagation during CO2 hydrogenation","authors":"Fatima Mahnaz, Balaji C. Dharmalingam, Jasan Robey Mangalindan, Jenna Vito, Jithin John Varghese, Manish Shetty","doi":"10.1016/j.checat.2024.101183","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101183","url":null,"abstract":"We demonstrate that the exchange of zeolitic Brønsted acid sites (BASs) with cations from metal oxides plays a pivotal role in the propagation of hydrocarbon pools (HCPs) during CO<sub>2</sub> hydrogenation. We probed the likelihood of In<sub>2</sub>O<sub>3</sub>, ZnZrO<sub>x</sub>, and Cr<sub>2</sub>O<sub>3</sub> migration and their cation exchange with BASs of a silicoaluminophosphate, SAPO-34, by integrating them at nanoscale proximity (∼1,400 nm). Analysis with NH<sub>3</sub> temperature-programmed desorption and transmission Fourier transform infrared spectroscopy showed ion exchange of BASs with In<sup>δ+</sup> and Zn<sup>δ+</sup> but not for Cr<sup>δ+</sup>. We measured the C<sub>3</sub>/C<sub>2</sub> hydrocarbon ratio (indicating relative propagation of olefin to aromatic cycles) and paraffin-to-olefin ratio, which revealed that In<sup>δ+</sup> species inhibited HCPs inside the channels of SAPO-34, while Zn<sup>δ+</sup> species enhanced hydrogen transfer and secondary hydrogenation. Combining reactivity data with occluded hydrocarbon analysis and <sup>13</sup>C solid-state nuclear magnetic resonance spectroscopy, we show that ion-exchanged species affect HCP propagation. Overall, our work provides insights for the rational integration of bifunctional catalysts.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"3 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-12DOI: 10.1016/j.checat.2024.101169
Canhui Zhang, Xu Liu, Cheng Zhen, Hanxu Yao, Liangliang Xu, Haibing Ye, Yue Wang, Xingkun Wang, M. Danny Gu, Minghua Huang, Heqing Jiang
A self-driven seawater splitting system could efficiently produce hydrogen from abundant seawater. However, high Cl− concentrations in seawater lead to catalyst corrosion and deactivation, impairing performance in the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Here, we adopted single-atom Co-N-C-based catalysts, in which the electronic structure around the central Co site can be controlled and adjusted at an atomic level. Experimentally, the target N and S co-doped hollow carbon sphere (Co-N/S-HCS) catalyst, featuring asymmetric Co-N3S1 sites, shows excellent ORR/OER/HER performance. By employing density functional theory and molecular dynamics simulations of real-time simulations, we reveal that the S doped in the asymmetric Co-N3S1 model leads to a customized electronic structure around the central Co site, enabling weakened adsorption of the corrosive Cl− and excellent ORR/OER/HER activities. Moreover, the seawater-based Zn-air batteries (S-ZABs) assembled by the Co-N/S-HCS deliver a cycling performance exceeding 650 h, and the overall seawater splitting system can run continuously for 1,100 h.
自驱动海水分离系统可从丰富的海水中高效制氢。然而，海水中高浓度的 Cl- 会导致催化剂腐蚀和失活，影响氧还原反应（ORR）、氧进化反应（OER）和氢进化反应（HER）的性能。在这里，我们采用了基于 Co-N-C 的单原子催化剂，在这种催化剂中，围绕中心 Co 位点的电子结构可以在原子水平上进行控制和调整。实验结果表明，目标 N 和 S 共掺杂空心碳球（Co-N/S-HCS）催化剂具有不对称 Co-N3S1 位点，显示出优异的 ORR/OER/HER 性能。通过采用密度泛函理论和分子动力学实时模拟，我们发现在非对称 Co-N3S1 模型中掺杂的 S 会导致围绕中心 Co 位点的定制电子结构，从而削弱对腐蚀性 Cl- 的吸附，实现优异的 ORR/OER/HER 活性。此外，Co-N/S-HCS 组装的海水型锌空气电池（S-ZABs）的循环性能超过 650 小时，整个海水分裂系统可连续运行 1100 小时。
{"title":"Symmetry-breaking CoN3S1 centers enable inert chloride ion adsorption for facilitating self-driven overall seawater splitting","authors":"Canhui Zhang, Xu Liu, Cheng Zhen, Hanxu Yao, Liangliang Xu, Haibing Ye, Yue Wang, Xingkun Wang, M. Danny Gu, Minghua Huang, Heqing Jiang","doi":"10.1016/j.checat.2024.101169","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101169","url":null,"abstract":"A self-driven seawater splitting system could efficiently produce hydrogen from abundant seawater. However, high Cl<sup>−</sup> concentrations in seawater lead to catalyst corrosion and deactivation, impairing performance in the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Here, we adopted single-atom Co-N-C-based catalysts, in which the electronic structure around the central Co site can be controlled and adjusted at an atomic level. Experimentally, the target N and S co-doped hollow carbon sphere (Co-N/S-HCS) catalyst, featuring asymmetric Co-N<sub>3</sub>S<sub>1</sub> sites, shows excellent ORR/OER/HER performance. By employing density functional theory and molecular dynamics simulations of real-time simulations, we reveal that the S doped in the asymmetric Co-N<sub>3</sub>S<sub>1</sub> model leads to a customized electronic structure around the central Co site, enabling weakened adsorption of the corrosive Cl<sup>−</sup> and excellent ORR/OER/HER activities. Moreover, the seawater-based Zn-air batteries (S-ZABs) assembled by the Co-N/S-HCS deliver a cycling performance exceeding 650 h, and the overall seawater splitting system can run continuously for 1,100 h.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"71 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：