Pub Date : 2024-10-21DOI: 10.1016/j.checat.2024.101155
Jing Ouyang, Hongyi Tao, Zhiyi Yang, Yim Kwan Wong, Wei Shen Aik, Herman Ho-Yung Sung, Ian Williams, Yangjian Quan
Pursuing both structural uniformity/crystallinity and functional complexity is a long-term goal in functional materials engineering. Often, efforts to enhance one attribute may compromise the other. Herein, we report an elaborate strategy of integrating a catalytic center into a modulator, which enables the one-pot synthesis of a bifunctional metal-organic framework (MOF), Zr-TBAPy-TSA (TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene; TSA = o-thiosalicylic acid). TSA serves as both a modulator for metal-organic framework (MOF) preparation and a catalytic center. Zr-TBAPy-TSA is distinguished by its highly uniform and crystalline structure, as evidenced by detailed characterizations including single-crystal X-ray diffraction. Additionally, Zr-TBAPy-TSA incorporating both photosensitizer and thiol active centers showcases superior catalytic performance in the activation of element–H bonds (elements include C, B, Si, and P). Due to its less defective structure, extra high turnover numbers of up to 14,200 and good catalyst recyclability are obtained.
{"title":"Modulator engineering of bifunctional metal-organic framework for synergistic catalysis","authors":"Jing Ouyang, Hongyi Tao, Zhiyi Yang, Yim Kwan Wong, Wei Shen Aik, Herman Ho-Yung Sung, Ian Williams, Yangjian Quan","doi":"10.1016/j.checat.2024.101155","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101155","url":null,"abstract":"Pursuing both structural uniformity/crystallinity and functional complexity is a long-term goal in functional materials engineering. Often, efforts to enhance one attribute may compromise the other. Herein, we report an elaborate strategy of integrating a catalytic center into a modulator, which enables the one-pot synthesis of a bifunctional metal-organic framework (MOF), <strong>Zr-TBAPy-TSA</strong> (TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene; TSA = <em>o</em>-thiosalicylic acid). TSA serves as both a modulator for metal-organic framework (MOF) preparation and a catalytic center. <strong>Zr-TBAPy-TSA</strong> is distinguished by its highly uniform and crystalline structure, as evidenced by detailed characterizations including single-crystal X-ray diffraction. Additionally, <strong>Zr-TBAPy-TSA</strong> incorporating both photosensitizer and thiol active centers showcases superior catalytic performance in the activation of element–H bonds (elements include C, B, Si, and P). Due to its less defective structure, extra high turnover numbers of up to 14,200 and good catalyst recyclability are obtained.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"12 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452301","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 : 2024-10-17DOI: 10.1016/j.checat.2024.101151
Lin Zuo, Gonghong Qiu, Yan Liu, Xiaolan Chen, Kai Sun, Igor B. Krylov, Lingbo Qu, Alexander O. Terent’ev, Bing Yu
Heterogeneous photocatalysts present notable benefits over homogeneous systems. However, their application is often hindered by spontaneous electron-hole recombination, undermining photoconversion efficiency. Addressing this, our study introduces a diversity-oriented synthesis of electron-donor-acceptor (D-A)-type polyimides via N-amidation of aromatic dianhydrides with anilines. These polyimides exhibit segregated D-A alignments that facilitate enhanced charge separation, rapid electron transfer, and long-lived photogenerated electron-hole pairs, attributed to superior electron-donating and -accepting capabilities alongside predictable π-π stacking. Their efficacy is demonstrated in catalyzing visible-light-driven redox-neutral C–H trifluoromethylation, transforming pharmaceuticals and bioactive molecules into trifluoromethyl-functionalized products with high yield and selectivity. A continuous-flow fixed-bed photoreactor supports gram-scale synthesis, and the photocatalyst maintains activity through at least four recycling rounds. Time-dependent density functional theory (TD-DFT) and non-covalent interaction (NCI) analyses suggest that the observed performance enhancement is due to controlled photoinduced electron transfer within the D-A system and intrachain π-π stacking.
{"title":"Electron-acceptor-controlled polyimides for photoredox-neutral trifluoromethylation","authors":"Lin Zuo, Gonghong Qiu, Yan Liu, Xiaolan Chen, Kai Sun, Igor B. Krylov, Lingbo Qu, Alexander O. Terent’ev, Bing Yu","doi":"10.1016/j.checat.2024.101151","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101151","url":null,"abstract":"Heterogeneous photocatalysts present notable benefits over homogeneous systems. However, their application is often hindered by spontaneous electron-hole recombination, undermining photoconversion efficiency. Addressing this, our study introduces a diversity-oriented synthesis of electron-donor-acceptor (D-A)-type polyimides via N-amidation of aromatic dianhydrides with anilines. These polyimides exhibit segregated D-A alignments that facilitate enhanced charge separation, rapid electron transfer, and long-lived photogenerated electron-hole pairs, attributed to superior electron-donating and -accepting capabilities alongside predictable π-π stacking. Their efficacy is demonstrated in catalyzing visible-light-driven redox-neutral C–H trifluoromethylation, transforming pharmaceuticals and bioactive molecules into trifluoromethyl-functionalized products with high yield and selectivity. A continuous-flow fixed-bed photoreactor supports gram-scale synthesis, and the photocatalyst maintains activity through at least four recycling rounds. Time-dependent density functional theory (TD-DFT) and non-covalent interaction (NCI) analyses suggest that the observed performance enhancement is due to controlled photoinduced electron transfer within the D-A system and intrachain π-π stacking.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"231 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444437","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 : 2024-10-17DOI: 10.1016/j.checat.2024.101125
Jiamiao Jin, Shi-Chao Ren
Recently, Li’s group designed a conceptually novel radical strategy for site-selective functionalization of ultra-remote arene C–H bond. The arenes were activated by intramolecular nitrogen-centered radical instead of generally used C–H metalation. The NHC-catalyzed radical cross-coupling acts as the key step to forging C–C bond at the para position of the arenes.
{"title":"NHC-catalyzed remote site-selective arene C–H acylations","authors":"Jiamiao Jin, Shi-Chao Ren","doi":"10.1016/j.checat.2024.101125","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101125","url":null,"abstract":"Recently, Li’s group designed a conceptually novel radical strategy for site-selective functionalization of ultra-remote arene C–H bond. The arenes were activated by intramolecular nitrogen-centered radical instead of generally used C–H metalation. The NHC-catalyzed radical cross-coupling acts as the key step to forging C–C bond at the para position of the arenes.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"79 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444238","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 : 2024-10-17DOI: 10.1016/j.checat.2024.101161
Francesca Pallini, Luca Beverina
In this issue of Chem Catalysis, Joanna Wencel-Delord et al.1 present a new surfactant featuring a specific ligation motif for selective coordination of Ru catalysts. This surfactant enables direct arylation reactions on highly functionalized substrates under exceptionally mild conditions, showcasing the potential for micellar catalysis to become a precision chemistry tool.
{"title":"A new functional surfactant enables direct C−H arylation in water under mild conditions","authors":"Francesca Pallini, Luca Beverina","doi":"10.1016/j.checat.2024.101161","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101161","url":null,"abstract":"In this issue of <em>Chem Catalysis</em>, Joanna Wencel-Delord et al.<span><span><sup>1</sup></span></span> present a new surfactant featuring a specific ligation motif for selective coordination of Ru catalysts. This surfactant enables direct arylation reactions on highly functionalized substrates under exceptionally mild conditions, showcasing the potential for micellar catalysis to become a precision chemistry tool.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"79 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444287","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 : 2024-10-17DOI: 10.1016/j.checat.2024.101152
Zhaole Lu, Rong Yang, Yingchao Yu, Yuting Wang, Bin Zhang, Lingjun Kong
The electrochemical reduction of nitrate to ammonia can serve as an effective complement to the traditional Haber-Bosch process. Currently, rapid and continuous ammonia production is challenging because of the multistep hydrogenation process and the constant alkalinization of the electrolyte. Herein, Ru atoms are incorporated into the octahedral sites of Co3O4 to achieve an ammonia yield rate of 24.6 mg h−1 cm−2. Electrochemical in situ spectroscopic analyses and theoretical calculations reveal that Ru sites improve water molecule coverage and facilitate the production of active hydrogen atoms, leading to stable and orderly ammonia production. Furthermore, a peak power density of 32.28 mW cm−2, a high ammonia Faradaic efficiency of 98.2%, and excellent durability (91 h) are achieved in a Ru-Co3O4-based Zn-nitrate battery, indicating its practical applicability. This work may provide a method for efficient nitrate reduction to ammonia or other hydrogenation reactions via the synergistic modulation of active sites.
{"title":"Boosting active hydrogen generation by anchored Ru sites in Co3O4 for nitrate-to-ammonia electrosynthesis","authors":"Zhaole Lu, Rong Yang, Yingchao Yu, Yuting Wang, Bin Zhang, Lingjun Kong","doi":"10.1016/j.checat.2024.101152","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101152","url":null,"abstract":"The electrochemical reduction of nitrate to ammonia can serve as an effective complement to the traditional Haber-Bosch process. Currently, rapid and continuous ammonia production is challenging because of the multistep hydrogenation process and the constant alkalinization of the electrolyte. Herein, Ru atoms are incorporated into the octahedral sites of Co<sub>3</sub>O<sub>4</sub> to achieve an ammonia yield rate of 24.6 mg h<sup>−1</sup> cm<sup>−2</sup>. Electrochemical <em>in situ</em> spectroscopic analyses and theoretical calculations reveal that Ru sites improve water molecule coverage and facilitate the production of active hydrogen atoms, leading to stable and orderly ammonia production. Furthermore, a peak power density of 32.28 mW cm<sup>−2</sup>, a high ammonia Faradaic efficiency of 98.2%, and excellent durability (91 h) are achieved in a Ru-Co<sub>3</sub>O<sub>4</sub>-based Zn-nitrate battery, indicating its practical applicability. This work may provide a method for efficient nitrate reduction to ammonia or other hydrogenation reactions via the synergistic modulation of active sites.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"3 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444429","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 : 2024-10-17DOI: 10.1016/j.checat.2024.101150
Jihyeon Park, Drew Higgins
The quest for low-cost, Earth-abundant catalysts for hydrogen oxidation reactions (HORs) in anion-exchange membrane fuel cells (AEMFCs) has led to significant advancements in recent years, yet challenges pertaining to the stability of non-platinum-group metal catalysts operational conditions still remain. The study by Zhou et al. in Nature Energy presents an innovative approach to enhance the stability and performance of nickel (Ni) catalysts for the HOR by using quantum confinement effects to suppress Ni oxidation. This research not only addresses surface passivation of Ni-based catalysts but also unlocks new possibilities for designing advanced catalysts for energy conversion technologies.
{"title":"Quantum confinement for stable nickel catalyst in hydrogen oxidation","authors":"Jihyeon Park, Drew Higgins","doi":"10.1016/j.checat.2024.101150","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101150","url":null,"abstract":"The quest for low-cost, Earth-abundant catalysts for hydrogen oxidation reactions (HORs) in anion-exchange membrane fuel cells (AEMFCs) has led to significant advancements in recent years, yet challenges pertaining to the stability of non-platinum-group metal catalysts operational conditions still remain. The study by Zhou et al. in <em>Nature Energy</em> presents an innovative approach to enhance the stability and performance of nickel (Ni) catalysts for the HOR by using quantum confinement effects to suppress Ni oxidation. This research not only addresses surface passivation of Ni-based catalysts but also unlocks new possibilities for designing advanced catalysts for energy conversion technologies.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"10 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444432","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 : 2024-10-17DOI: 10.1016/j.checat.2024.101143
Hai Wang, Liang Wang
In the current issue of Chem Catalysis, Zhu and co-workers report the construction of a neotype strong metal-support interaction between Ni nanoparticle and BaCO3 via H2 reduction and CO2 hydrogenation. The migration of BaCO3 onto Ni nanoparticles leads to the formation of porous overlayers, which not only stabilized the Ni nanoparticles against sintering but also formed abundant Ni-BaCO3 interfaces for CO2 enrichment, thereby enhancing CO2 hydrogenation to methane.
在本期《化学催化》（Chem Catalysis）杂志上，Zhu 及其合作者报告了通过 H2 还原和 CO2 加氢，在 Ni 纳米粒子和 BaCO3 之间构建了一种新型强金属-支撑相互作用。BaCO3 在镍纳米粒子上的迁移导致多孔覆盖层的形成，这不仅稳定了镍纳米粒子以防止烧结，还形成了丰富的 Ni-BaCO3 界面以富集 CO2，从而促进 CO2 加氢制甲烷。
{"title":"Strong metal-support interaction between Ni and BaCO3 boosts CO2 hydrogenation","authors":"Hai Wang, Liang Wang","doi":"10.1016/j.checat.2024.101143","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101143","url":null,"abstract":"In the current issue of <em>Chem Catalysis</em>, Zhu and co-workers report the construction of a neotype strong metal-support interaction between Ni nanoparticle and BaCO<sub>3</sub> via H<sub>2</sub> reduction and CO<sub>2</sub> hydrogenation. The migration of BaCO<sub>3</sub> onto Ni nanoparticles leads to the formation of porous overlayers, which not only stabilized the Ni nanoparticles against sintering but also formed abundant Ni-BaCO<sub>3</sub> interfaces for CO<sub>2</sub> enrichment, thereby enhancing CO<sub>2</sub> hydrogenation to methane.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"68 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142444430","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}
The hydrogenation and hydrodeoxygenation (HDO) of organic mixtures are important processes in bio-oil conversion and plastics upcycling. Understanding how the presence of co-reactants in organic mixtures affects the kinetics is critical for designing reactors that can convert these mixtures into desired products. Here, we discuss cases in (electro)catalysis where the presence of a co-reactant R2 enhances the rate of hydrogenation or HDO of another reactant R1 beyond the rate if only R1 is present. We divide the discussion into simple and complex mutual influences. Simple mutual influences occur when the presence of R2 does not change the mechanism or values of rate constants of elementary steps for R1. A complex mutual influence of R2 on R1 occurs if the presence of R2 changes the rate constants of elementary steps involving R1. We discuss challenges and opportunities in discerning the different mutual influences and increasing their synergistic effects in organic mixtures.
{"title":"Synergistic effects in organic mixtures for enhanced catalytic hydrogenation and hydrodeoxygenation","authors":"Ankit Mathanker, Sahil Halarnkar, Bolton Tran, Nirala Singh, Bryan R. Goldsmith","doi":"10.1016/j.checat.2024.101135","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101135","url":null,"abstract":"The hydrogenation and hydrodeoxygenation (HDO) of organic mixtures are important processes in bio-oil conversion and plastics upcycling. Understanding how the presence of co-reactants in organic mixtures affects the kinetics is critical for designing reactors that can convert these mixtures into desired products. Here, we discuss cases in (electro)catalysis where the presence of a co-reactant <em>R</em><sub>2</sub> enhances the rate of hydrogenation or HDO of another reactant <em>R</em><sub>1</sub> beyond the rate if only <em>R</em><sub>1</sub> is present. We divide the discussion into simple and complex mutual influences. Simple mutual influences occur when the presence of <em>R</em><sub>2</sub> does not change the mechanism or values of rate constants of elementary steps for <em>R</em><sub>1</sub>. A complex mutual influence of <em>R</em><sub>2</sub> on <em>R</em><sub>1</sub> occurs if the presence of <em>R</em><sub>2</sub> changes the rate constants of elementary steps involving <em>R</em><sub>1</sub>. We discuss challenges and opportunities in discerning the different mutual influences and increasing their synergistic effects in organic mixtures.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"66 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440410","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 : 2024-10-16DOI: 10.1016/j.checat.2024.101149
Pavitra Laohapaisan, Ipshita Roy, David A. Nagib
Radical C–H aminations enable rapid access to the most common heterocycles in medicines (e.g., pyrrolidines), yet stereocontrol of these powerful transformations remains a challenge. Here, we report the discovery of the first enantio- and regioselective C–H imination, which readily converts ketones to enantioenriched pyrrolidines. This enantioselective Hofmann-Löffler-Freytag reaction mechanism entails iminyl radical generation from an oxime by a chiral Cu catalyst that facilitates 1,5-H-atom transfer (HAT) to form a remote C-radical regioselectively. The selective capture of this alkyl radical as an organocopper(III) complex then mediates highly stereoselective reductive elimination to unprotected pyrrolines. The broad steric and electronic scope of this remote C–H amination has been probed systematically, along with key mechanistic aspects of enantiodetermination, radical intermediacy, and atypical Cu(III) ligands that enable this uniquely selective C–N coupling. Importantly, either (1) reductions or (2) nucleophilic additions to these enantioenriched pyrrolines provide the most rapid syntheses of chiral pyrrolidines to date.
{"title":"Chiral pyrrolidines via an enantioselective Hofmann-Löffler-Freytag reaction","authors":"Pavitra Laohapaisan, Ipshita Roy, David A. Nagib","doi":"10.1016/j.checat.2024.101149","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101149","url":null,"abstract":"Radical C–H aminations enable rapid access to the most common heterocycles in medicines (e.g., pyrrolidines), yet stereocontrol of these powerful transformations remains a challenge. Here, we report the discovery of the first enantio- and regioselective C–H imination, which readily converts ketones to enantioenriched pyrrolidines. This enantioselective Hofmann-Löffler-Freytag reaction mechanism entails iminyl radical generation from an oxime by a chiral Cu catalyst that facilitates 1,5-H-atom transfer (HAT) to form a remote C-radical regioselectively. The selective capture of this alkyl radical as an organocopper(III) complex then mediates highly stereoselective reductive elimination to unprotected pyrrolines. The broad steric and electronic scope of this remote C–H amination has been probed systematically, along with key mechanistic aspects of enantiodetermination, radical intermediacy, and atypical Cu(III) ligands that enable this uniquely selective C–N coupling. Importantly, either (1) reductions or (2) nucleophilic additions to these enantioenriched pyrrolines provide the most rapid syntheses of chiral pyrrolidines to date.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"124 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142440409","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}
Inducing the rapid and deep self-reconstruction of anodes has the potential to achieve the desired structure for effective oxygen evolution reactions (OERs) in seawater, but it is challenging. Herein, sulfur-assisted structural reconstruction of transition metal molybdates was fabricated. Benefiting from the electronic escape effect that occurs due to metal–O/–S bonding orbitals in the pre-catalyst, deep electrochemical reconstruction to highly active S-doped oxyhydroxides was achieved via rational S–metal hybridization and phase transition in the pre-catalyst. Meanwhile, combining the theoretical calculations and spectroscopic tests, it was found that introducing S atoms into oxyhydroxides activated lattice oxygen atoms, thereby boosting the intrinsic OER activity following the lattice oxygen mechanism pathway. As tested, the final S-doped oxyhydroxide catalysts exhibited excellent electrocatalytic activity with an ultralow overpotential of 166 mV at 10 mA cm−2 in alkaline seawater oxidation. This work showcased a feasible strategy of sulfur-assisted structural reconstruction to fabricate highly efficient and chemically stable materials for seawater splitting.
诱导阳极进行快速而深入的自我重构，有可能实现在海水中进行有效氧进化反应（OER）所需的结构，但这具有挑战性。在此，我们制作了硫辅助的过渡金属钼酸盐结构重构。利用前催化剂中金属-O/-S 键轨道产生的电子逸出效应，通过前催化剂中合理的 S 金属杂化和相变，实现了高活性 S 掺杂氧氢氧化物的深度电化学重构。同时，结合理论计算和光谱测试发现，在氧氢氧化物中引入 S 原子可激活晶格氧原子，从而按照晶格氧机制途径提高固有的 OER 活性。经测试，最终的掺 S 氧氢氧化物催化剂表现出优异的电催化活性，在碱性海水氧化过程中，10 mA cm-2 的过电位仅为 166 mV。这项工作展示了一种可行的硫辅助结构重构策略，可用于制造高效且化学性质稳定的海水分离材料。
{"title":"Sulfur-facilitated in situ deep reconstruction of transition metal molybdates toward superior electrocatalytic oxidation of alkaline seawater","authors":"Zhan Zhao, Shiyu Qin, Xiang Li, Jianpeng Sun, Zizhen Li, Xiangchao Meng","doi":"10.1016/j.checat.2024.101144","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101144","url":null,"abstract":"Inducing the rapid and deep self-reconstruction of anodes has the potential to achieve the desired structure for effective oxygen evolution reactions (OERs) in seawater, but it is challenging. Herein, sulfur-assisted structural reconstruction of transition metal molybdates was fabricated. Benefiting from the electronic escape effect that occurs due to metal–O/–S bonding orbitals in the pre-catalyst, deep electrochemical reconstruction to highly active S-doped oxyhydroxides was achieved via rational S–metal hybridization and phase transition in the pre-catalyst. Meanwhile, combining the theoretical calculations and spectroscopic tests, it was found that introducing S atoms into oxyhydroxides activated lattice oxygen atoms, thereby boosting the intrinsic OER activity following the lattice oxygen mechanism pathway. As tested, the final S-doped oxyhydroxide catalysts exhibited excellent electrocatalytic activity with an ultralow overpotential of 166 mV at 10 mA cm<sup>−2</sup> in alkaline seawater oxidation. This work showcased a feasible strategy of sulfur-assisted structural reconstruction to fabricate highly efficient and chemically stable materials for seawater splitting.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"66 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142435996","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}
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