Transition metal-catalyzed asymmetric hydrogenation of ketones has been well established; however, the asymmetric hydrogenation of sterically unbiased ketones remains a major challenge, primarily due to difficulties in controlling enantioselectivity. Here, we report a highly practical and efficient protocol for the asymmetric hydrogenation of such substrates, delivering chiral cyclic diaryl alcohols (including the baloxavir intermediate) in up to a 99% yield and 99% enantiomer excess (ee). Mechanistic studies show that [Ir(cod)Cl]2 undergoes intramolecular oxidative C–H activation with an oxa-spirocyclic ligand, forming a rigid, butterfly-shaped Ir–PNNC complex, as confirmed by single-crystal X-ray diffraction. In our understanding, this tetradentate binding both prevents catalyst poisoning by sulfur-containing substrates and maximizes enantioselectivity, aided by crucial π-π interactions (as revealed by density functional theory [DFT] and non-covalent bond interaction [NCI] analyses). The synthetic practicality is demonstrated by gram-scale hydrogenation with excellent stereocontrol, underscoring the potential of this approach for the efficient preparation of valuable enantiopure compounds.
{"title":"π-π interaction-directed asymmetric hydrogenation of sterically unbiased aromatic ketones","authors":"Jingyuan Song, Renwei Xiao, Hui He, Li Wang, Fanping Huang, Menglong Zhao, Donghuang Liu, Shao-Fei Ni, Gen-Qiang Chen, Xumu Zhang","doi":"10.1016/j.checat.2025.101438","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101438","url":null,"abstract":"Transition metal-catalyzed asymmetric hydrogenation of ketones has been well established; however, the asymmetric hydrogenation of sterically unbiased ketones remains a major challenge, primarily due to difficulties in controlling enantioselectivity. Here, we report a highly practical and efficient protocol for the asymmetric hydrogenation of such substrates, delivering chiral cyclic diaryl alcohols (including the baloxavir intermediate) in up to a 99% yield and 99% enantiomer excess (ee). Mechanistic studies show that [Ir(cod)Cl]<sub>2</sub> undergoes intramolecular oxidative C–H activation with an <em>oxa</em>-spirocyclic ligand, forming a rigid, butterfly-shaped Ir–PNNC complex, as confirmed by single-crystal X-ray diffraction. In our understanding, this tetradentate binding both prevents catalyst poisoning by sulfur-containing substrates and maximizes enantioselectivity, aided by crucial π-π interactions (as revealed by density functional theory [DFT] and non-covalent bond interaction [NCI] analyses). The synthetic practicality is demonstrated by gram-scale hydrogenation with excellent stereocontrol, underscoring the potential of this approach for the efficient preparation of valuable enantiopure compounds.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"27 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547468","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}
Proton exchange membrane (PEM) water splitting is a cutting-edge technology that can produce clean and renewable hydrogen fuel. However, sluggish oxygen evolution reaction (OER) kinetics remain a challenge for the trade-off between catalytic activity and stability in acidic media. Currently, ruthenium dioxide (RuO2) materials show great potential for the OER, which still suffers from a major drawback of low durability due to the severe dissolution of metal atoms in acidic electrolytes. Herein, we report a RuO2 nanoparticle material modified with atomic Co and Pd to enhance OER stability while boosting catalytic activity in acidic environments. We demonstrate that Co atoms facilitate OOH∗ deprotonation, thereby lowering the OER energy barrier, while Pd atoms stabilize the Ru sites by effectively suppressing their over-oxidation and dissolution during the acidic OER.
{"title":"Stabilization of highly active Ru sites toward acidic water oxidation by dual-atom doping","authors":"Jialin Tang, Qisheng Zeng, Qiu Jiang, Haoyuan Wang, Sunpei Hu, Yuan Ji, Hongliang Zeng, Chunxiao Liu, Hong-Jie Peng, Xu Li, Tingting Zheng, Chih-Wen Pao, Xinyan Liu, Chuan Xia","doi":"10.1016/j.checat.2025.101441","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101441","url":null,"abstract":"Proton exchange membrane (PEM) water splitting is a cutting-edge technology that can produce clean and renewable hydrogen fuel. However, sluggish oxygen evolution reaction (OER) kinetics remain a challenge for the trade-off between catalytic activity and stability in acidic media. Currently, ruthenium dioxide (RuO<sub>2</sub>) materials show great potential for the OER, which still suffers from a major drawback of low durability due to the severe dissolution of metal atoms in acidic electrolytes. Herein, we report a RuO<sub>2</sub> nanoparticle material modified with atomic Co and Pd to enhance OER stability while boosting catalytic activity in acidic environments. We demonstrate that Co atoms facilitate OOH∗ deprotonation, thereby lowering the OER energy barrier, while Pd atoms stabilize the Ru sites by effectively suppressing their over-oxidation and dissolution during the acidic OER.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"70 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547470","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}
Renewable energy conversion is pivotal for decarbonization via a carbon-neutral energy cycle. Solid oxide cells (SOCs) offer efficient energy conversion for power generation, hydrogen production, and CO2 electrolysis. These devices benefit from favorable thermodynamic and catalytic mechanisms enabled by high-temperature operation. Perovskite oxides are key SOC catalysts due to their tunable lattice structures, which influence electronic properties, defect chemistry, and catalytic activity. Perovskite surface reconstruction attracts much attention as a critical strategy to enhance reaction kinetics by tailoring surface properties and improving electrode performance. This review explores the unique adaptability of perovskite oxides for surface modification, along with the relationships between lattice structures, surface characteristics, and catalytic performance. It highlights methods for atomic-level reconstruction and summarizes recent experimental and theoretical progress, offering insights for designing next-generation SOC catalysts and advancing the application of perovskite oxides in renewable energy.
{"title":"Surface reconstruction of versatile perovskites via in situ nanoparticle engineering for solid oxide cells","authors":"Boshen Xu, Jiufeng Ruan, Pengxi Zhu, Sidong Lei, Hanping Ding, Pei Dong","doi":"10.1016/j.checat.2025.101432","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101432","url":null,"abstract":"Renewable energy conversion is pivotal for decarbonization via a carbon-neutral energy cycle. Solid oxide cells (SOCs) offer efficient energy conversion for power generation, hydrogen production, and CO<sub>2</sub> electrolysis. These devices benefit from favorable thermodynamic and catalytic mechanisms enabled by high-temperature operation. Perovskite oxides are key SOC catalysts due to their tunable lattice structures, which influence electronic properties, defect chemistry, and catalytic activity. Perovskite surface reconstruction attracts much attention as a critical strategy to enhance reaction kinetics by tailoring surface properties and improving electrode performance. This review explores the unique adaptability of perovskite oxides for surface modification, along with the relationships between lattice structures, surface characteristics, and catalytic performance. It highlights methods for atomic-level reconstruction and summarizes recent experimental and theoretical progress, offering insights for designing next-generation SOC catalysts and advancing the application of perovskite oxides in renewable energy.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"19 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521329","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 : 2025-06-30DOI: 10.1016/j.checat.2025.101430
Yichen Li, Dongfang Cheng, Giyeong Son, Anna V. Shneidman, Kang Rui Garrick Lim, Joanna Aizenberg, Philippe Sautet
Au supported on TiO2 is a promising photocatalyst due to its ability to catalyze reactions under illumination and store electrons for sustained reactivity in the dark. Using density functional theory (DFT), we investigate the structural evolution and reactivity of the Au/anatase-TiO2(001) interface under realistic conditions. Phase diagrams and charge analysis reveal that the Au nanoparticles supported on TiO₂ (Au/TiO2) interface can reversibly store electrons by transitioning between different charge states and structures via oxidation and reduction. This electron storage and the associated reducing potential, along with the atomic arrangement, promote key photoelectrochemical reactions, such as the oxygen reduction reaction (ORR) and the CO2 reduction reaction (CO2RR). Lattice titanium and oxygen vacancies act as active sites, with the two-electron (2e)-ORR pathway (H2O2 formation) kinetically favored due to a lower proton-coupled electron transfer barrier. The interface also facilitates CO2 activation, which is challenging on bare Au. These findings provide a foundation for optimizing Au/TiO2 composites for energy storage and conversion.
{"title":"Modeling electron storage at the interface between Au and anatase-TiO2 under ambient conditions","authors":"Yichen Li, Dongfang Cheng, Giyeong Son, Anna V. Shneidman, Kang Rui Garrick Lim, Joanna Aizenberg, Philippe Sautet","doi":"10.1016/j.checat.2025.101430","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101430","url":null,"abstract":"Au supported on TiO<sub>2</sub> is a promising photocatalyst due to its ability to catalyze reactions under illumination and store electrons for sustained reactivity in the dark. Using density functional theory (DFT), we investigate the structural evolution and reactivity of the Au/anatase-TiO<sub>2</sub>(001) interface under realistic conditions. Phase diagrams and charge analysis reveal that the Au nanoparticles supported on TiO₂ (Au/TiO<sub>2</sub>) interface can reversibly store electrons by transitioning between different charge states and structures via oxidation and reduction. This electron storage and the associated reducing potential, along with the atomic arrangement, promote key photoelectrochemical reactions, such as the oxygen reduction reaction (ORR) and the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). Lattice titanium and oxygen vacancies act as active sites, with the two-electron (2e)-ORR pathway (H<sub>2</sub>O<sub>2</sub> formation) kinetically favored due to a lower proton-coupled electron transfer barrier. The interface also facilitates CO<sub>2</sub> activation, which is challenging on bare Au. These findings provide a foundation for optimizing Au/TiO<sub>2</sub> composites for energy storage and conversion.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"29 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516251","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 precise design of highly efficient nanocatalysts with traditional ensemble methodologies faces a challenge. Here, we demonstrate the first precise guidance of basic research on carbon supports at the single-particle level for designing Pt/C nanoelectrocatalysts. With single-molecule fluorescence microscopy to measure redox electron transfer (ET) rates on individual graphene sheets (GSs), we reveal that the reductive ET rate increases with the thickness decrease of GSs, while the oxidative ET increases with the thickness decrease first and reaches a constant on thinner GSs. Notably, O=C-OH accelerates reductive ET while slowing oxidative ET. All these insights are further confirmed on carbon nanospheres. Guided by these unprecedented insights, two high-efficiency Pt/C nanoelectrocatalysts for the hydrogen evolution reaction and hydrogen oxidation reaction are designed. Compared to traditional ensemble methods, our single-particle-level research on carbon supports provides a deeper understanding of the support effect, enabling precise nanocatalyst design and reducing unnecessary research and development costs.
{"title":"Design of highly efficient catalysts guided by redox of individual carbon supports","authors":"Dezheng Zhang, Jing Cao, Xuanhao Mei, Huimin Zhang, Shaoqing Zhang, Yaheng Gu, Ce Han, Ping Song, Weilin Xu","doi":"10.1016/j.checat.2025.101436","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101436","url":null,"abstract":"The precise design of highly efficient nanocatalysts with traditional ensemble methodologies faces a challenge. Here, we demonstrate the first precise guidance of basic research on carbon supports at the single-particle level for designing Pt/C nanoelectrocatalysts. With single-molecule fluorescence microscopy to measure redox electron transfer (ET) rates on individual graphene sheets (GSs), we reveal that the reductive ET rate increases with the thickness decrease of GSs, while the oxidative ET increases with the thickness decrease first and reaches a constant on thinner GSs. Notably, O=C-OH accelerates reductive ET while slowing oxidative ET. All these insights are further confirmed on carbon nanospheres. Guided by these unprecedented insights, two high-efficiency Pt/C nanoelectrocatalysts for the hydrogen evolution reaction and hydrogen oxidation reaction are designed. Compared to traditional ensemble methods, our single-particle-level research on carbon supports provides a deeper understanding of the support effect, enabling precise nanocatalyst design and reducing unnecessary research and development costs.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"74 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516252","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}
Methane and carbon dioxide catalytic conversion through dry reforming is crucial both technically and academically because it generates syngas solely from greenhouse gas emissions. Given that this is an energy-intensive endothermic process, the integration of photothermal catalysis is essential for reducing or replacing fossil energy input. Nanoscale heat transfer within catalysts influenced by various encapsulation strategies plays a key role in overall catalytic efficiency. In this regard, different thermal environments are generated using nickel-based catalysts embedded in the thermally insulating TS-1 zeolite matrix. TS-1 zeolite limits the growth of nickel particles and regulates internal energy, achieving a remarkable photothermal CO2 conversion rate of 53.6% in a single pass at 450°C, exceeding the thermodynamic equilibrium limit by 300%. It also demonstrates excellent stability over more than 300 h of testing, with a near-ideal 1:1 stoichiometric ratio of H2 to CO.
{"title":"Nanoscale heat management enhanced photothermal methane dry reforming with carbon dioxide","authors":"Jiakun Wang, Jianheng Xu, Zeshu Zhang, Zhongyi Chen, Kaijie Liu, Cheng Rao, Yong Men, Mengjia Li, Junan Lai, Liwei Sun, Xiaolu Zhuo, Lu Wang, Xiangguang Yang, Yibo Zhang, Wuping Liao","doi":"10.1016/j.checat.2025.101437","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101437","url":null,"abstract":"Methane and carbon dioxide catalytic conversion through dry reforming is crucial both technically and academically because it generates syngas solely from greenhouse gas emissions. Given that this is an energy-intensive endothermic process, the integration of photothermal catalysis is essential for reducing or replacing fossil energy input. Nanoscale heat transfer within catalysts influenced by various encapsulation strategies plays a key role in overall catalytic efficiency. In this regard, different thermal environments are generated using nickel-based catalysts embedded in the thermally insulating TS-1 zeolite matrix. TS-1 zeolite limits the growth of nickel particles and regulates internal energy, achieving a remarkable photothermal CO<sub>2</sub> conversion rate of 53.6% in a single pass at 450°C, exceeding the thermodynamic equilibrium limit by 300%. It also demonstrates excellent stability over more than 300 h of testing, with a near-ideal 1:1 stoichiometric ratio of H<sub>2</sub> to CO.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"47 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144516253","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 : 2025-06-26DOI: 10.1016/j.checat.2025.101433
Yan-Fei Mu, Ji-Li Zhou, Su-Xian Yuan, Meng-Ran Zhang, Huan Pang, Min Zhang, Tong-Bu Lu
Photocatalytic conversion of N2 and CO2 into urea is a highly desirable yet formidable challenge given the inherent inertness of N2/CO2 and poor C–N coupling activity. Herein, we introduce a Cu single-atom-decorated porous Fe2O3 nanorod (Cu-Fe2O3) photocatalyst with a Cu–O–Fe configuration for efficient photocatalytic N2/CO2 co-reduction to urea. Because the d-orbitals of the Cu/Fe sites are close to the molecular orbitals of CO2/N2, the CuFe dual active sites can selectively adsorb and activate N2/CO2, thereby facilitating efficient C–N coupling. The incorporation of the high-electrostatic-potential Cu creates a localized electrostatic-potential difference over Fe2O3, enabling the sequential activation of CO2 and N2. Consequently, Cu-Fe2O3 offers the highest urea activity (171 ± 12 μmol g−1 h−1) and selectivity (>90%) reported to date. This work showcases a promising avenue for green urea synthesis as well as the asymmetric coupling reaction.
{"title":"Efficient urea photosynthesis via CuFe dual-atom synergistic catalysis","authors":"Yan-Fei Mu, Ji-Li Zhou, Su-Xian Yuan, Meng-Ran Zhang, Huan Pang, Min Zhang, Tong-Bu Lu","doi":"10.1016/j.checat.2025.101433","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101433","url":null,"abstract":"Photocatalytic conversion of N<sub>2</sub> and CO<sub>2</sub> into urea is a highly desirable yet formidable challenge given the inherent inertness of N<sub>2</sub>/CO<sub>2</sub> and poor C–N coupling activity. Herein, we introduce a Cu single-atom-decorated porous Fe<sub>2</sub>O<sub>3</sub> nanorod (Cu-Fe<sub>2</sub>O<sub>3</sub>) photocatalyst with a Cu–O–Fe configuration for efficient photocatalytic N<sub>2</sub>/CO<sub>2</sub> co-reduction to urea. Because the d-orbitals of the Cu/Fe sites are close to the molecular orbitals of CO<sub>2</sub>/N<sub>2</sub>, the CuFe dual active sites can selectively adsorb and activate N<sub>2</sub>/CO<sub>2</sub>, thereby facilitating efficient C–N coupling. The incorporation of the high-electrostatic-potential Cu creates a localized electrostatic-potential difference over Fe<sub>2</sub>O<sub>3</sub>, enabling the sequential activation of CO<sub>2</sub> and N<sub>2</sub>. Consequently, Cu-Fe<sub>2</sub>O<sub>3</sub> offers the highest urea activity (171 ± 12 μmol g<sup>−1</sup> h<sup>−1</sup>) and selectivity (>90%) reported to date. This work showcases a promising avenue for green urea synthesis as well as the asymmetric coupling reaction.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"10 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144488406","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 : 2025-06-23DOI: 10.1016/j.checat.2025.101428
Yong Yuan, Bipin Lamichhane, William N. Porter, Sooyeon Hwang, Lu Ma, Dali Yang, Akhil Tayal, Nebojsa S. Marinkovic, Shyam Kattel, Jingguang G. Chen
Converting CO2 into carbon nanotubes (CNTs) offers a promising method of CO2 utilization and sequestration, potentially mitigating environmental impacts from anthropogenic emissions. This study reports that bimetallic CoFe catalysts can increase CNT production from the reaction of CO2 and C2H6 by an order of magnitude compared to their monometallic counterparts. The active sites and CNT morphologies are composition dependent: Co-rich catalysts (Co/Fe ratio ≥ 5) form stable face-centered cubic (fcc) CoFe alloys, producing cylindrical CNTs, and Fe-containing catalysts (Co/Fe ≤ 2) favor body-centered cubic (bcc) CoFe alloys upon reduction, which transforms into carbides, resulting in bamboo-like CNTs. Experimental evidence and density functional theory (DFT) calculations reveal that adjacent Fe and Co atoms modulate CO and CxHy adsorption, regulating CNT production pathways through the CO Boudouard reaction and C2H6 decomposition. These results highlight the dual benefits of bimetallic catalysts in enhancing CNT yield and controlling CNT morphology through adjustment of catalyst compositions.
{"title":"Enhancing carbon nanotube production from carbon dioxide and ethane using bimetallic catalysts","authors":"Yong Yuan, Bipin Lamichhane, William N. Porter, Sooyeon Hwang, Lu Ma, Dali Yang, Akhil Tayal, Nebojsa S. Marinkovic, Shyam Kattel, Jingguang G. Chen","doi":"10.1016/j.checat.2025.101428","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101428","url":null,"abstract":"Converting CO<sub>2</sub> into carbon nanotubes (CNTs) offers a promising method of CO<sub>2</sub> utilization and sequestration, potentially mitigating environmental impacts from anthropogenic emissions. This study reports that bimetallic CoFe catalysts can increase CNT production from the reaction of CO<sub>2</sub> and C<sub>2</sub>H<sub>6</sub> by an order of magnitude compared to their monometallic counterparts. The active sites and CNT morphologies are composition dependent: Co-rich catalysts (Co/Fe ratio ≥ 5) form stable face-centered cubic (fcc) CoFe alloys, producing cylindrical CNTs, and Fe-containing catalysts (Co/Fe ≤ 2) favor body-centered cubic (bcc) CoFe alloys upon reduction, which transforms into carbides, resulting in bamboo-like CNTs. Experimental evidence and density functional theory (DFT) calculations reveal that adjacent Fe and Co atoms modulate CO and C<sub>x</sub>H<sub>y</sub> adsorption, regulating CNT production pathways through the CO Boudouard reaction and C<sub>2</sub>H<sub>6</sub> decomposition. These results highlight the dual benefits of bimetallic catalysts in enhancing CNT yield and controlling CNT morphology through adjustment of catalyst compositions.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"51 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341409","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 : 2025-06-23DOI: 10.1016/j.checat.2025.101429
Jun Guan, Ruihao Zhou, Hengxue Shi, Shenghan Zhang, Chaowei He, Muqing Cao, Lei Jiao, Huaping Xu
Carboradical reservoirs are non-radical precursors that controllably release stored radicals to directly participate in product formation, making them critically important in organic chemistry. However, no aryl radical reservoir has been reported to date. Here, we have constructed an aryl radical reservoir via polytelluroxane (PTeO)-mediated activation of arylboronic acids under white light. PTeO, featuring an inorganic Te–O backbone with organic side chains, facilitates the transfer of aryl substituents from boronic acids to Te sites, thereby storing them as reactive Te–C bonds and forming the reservoir. The stored radicals can be responsively released through the homolysis of Te–C bonds under white light or heating. Furthermore, air re-oxidizes the remaining Te radicals, restoring the Te–O backbone, regenerating PTeO, and imparting catalytic capability to PTeO. This work broadens the scope of synthetic methodologies and highlights the significant potential of PTeO in advancing organic synthesis.
{"title":"An aryl radical reservoir based on the activation of organoboronic acids by polytelluroxane","authors":"Jun Guan, Ruihao Zhou, Hengxue Shi, Shenghan Zhang, Chaowei He, Muqing Cao, Lei Jiao, Huaping Xu","doi":"10.1016/j.checat.2025.101429","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101429","url":null,"abstract":"Carboradical reservoirs are non-radical precursors that controllably release stored radicals to directly participate in product formation, making them critically important in organic chemistry. However, no aryl radical reservoir has been reported to date. Here, we have constructed an aryl radical reservoir via polytelluroxane (PTeO)-mediated activation of arylboronic acids under white light. PTeO, featuring an inorganic Te–O backbone with organic side chains, facilitates the transfer of aryl substituents from boronic acids to Te sites, thereby storing them as reactive Te–C bonds and forming the reservoir. The stored radicals can be responsively released through the homolysis of Te–C bonds under white light or heating. Furthermore, air re-oxidizes the remaining Te radicals, restoring the Te–O backbone, regenerating PTeO, and imparting catalytic capability to PTeO. This work broadens the scope of synthetic methodologies and highlights the significant potential of PTeO in advancing organic synthesis.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"51 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341410","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 : 2025-06-19DOI: 10.1016/j.checat.2025.101396
Huayu Gu, Dongshuang Wu
Single-atom catalysts (SACs) have demonstrated remarkable potential in heterogeneous catalytic reactions. However, elucidating and precisely predicting the structure-activity relationships of SACs remain critical yet challenging for the rational design of high-performance catalysts. Reporting recently in Nature, Shi et al. uncover a linear relationship between the acetylene semi-hydrogenation activity of palladium (Pd1) SACs and the lowest unoccupied molecular orbital (LUMO) of oxide supports.
{"title":"Unveiling the support LUMO-activity correlation in single-atom catalysis","authors":"Huayu Gu, Dongshuang Wu","doi":"10.1016/j.checat.2025.101396","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101396","url":null,"abstract":"Single-atom catalysts (SACs) have demonstrated remarkable potential in heterogeneous catalytic reactions. However, elucidating and precisely predicting the structure-activity relationships of SACs remain critical yet challenging for the rational design of high-performance catalysts. Reporting recently in <em>Nature</em>, Shi et al. uncover a linear relationship between the acetylene semi-hydrogenation activity of palladium (Pd<sub>1</sub>) SACs and the lowest unoccupied molecular orbital (LUMO) of oxide supports.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"12 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319657","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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