Pub Date : 2025-03-06DOI: 10.1021/acscatal.5c00304
Liqun Hu, Yao Xiang, Qing Huang, Hui Zhou, Youwei Xie
We describe in this work a Re2O7-catalyzed nondirected C–H deuteration of arenes and heteroarenes. This process was facilitated via a network of deuterium bonds with AcOD that also serves as an inexpensive deuterium source. With this operationally facile protocol, various arenes could be deuterated with a high level of isotope incorporation. Compared to other acid-mediated C–H deuterations, rhenium catalysis makes weak acid AcOD a powerful deuterium reagent for a broad substrate scope and at the same time shows significantly improved functional group tolerance due to its relatively low acidity, which was exemplified in the late-stage isotopic labeling of various pharmaceuticals and biologically active molecules. 1H NMR and DFT calculations were carried out to study the role of deuterium bonding.
{"title":"Late-Stage C–H Deuteration of (Hetero)Arenes via Deuterium-Bonding Enhanced Rhenium Catalysis","authors":"Liqun Hu, Yao Xiang, Qing Huang, Hui Zhou, Youwei Xie","doi":"10.1021/acscatal.5c00304","DOIUrl":"https://doi.org/10.1021/acscatal.5c00304","url":null,"abstract":"We describe in this work a Re<sub>2</sub>O<sub>7</sub>-catalyzed nondirected C–H deuteration of arenes and heteroarenes. This process was facilitated via a network of deuterium bonds with AcOD that also serves as an inexpensive deuterium source. With this operationally facile protocol, various arenes could be deuterated with a high level of isotope incorporation. Compared to other acid-mediated C–H deuterations, rhenium catalysis makes weak acid AcOD a powerful deuterium reagent for a broad substrate scope and at the same time shows significantly improved functional group tolerance due to its relatively low acidity, which was exemplified in the late-stage isotopic labeling of various pharmaceuticals and biologically active molecules. <sup>1</sup>H NMR and DFT calculations were carried out to study the role of deuterium bonding.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"36 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1021/acscatal.5c00439
Ming Yan, Jia-wei Zou, Dong-mei Fang, Shi-qi Zhang, Xin Cui, Zhuo Tang, Guang-xun Li
Enantioselective desymmetrization of phosphinic acid with two completely different carbon substituents on the P atom is an efficient way to obtain chiral P(V) compounds with high structural diversity. Herein, we reported a Cu-catalyzed asymmetric arylation of phosphinic acid, which turns the P-center to be a versatile electrophile for obtaining a series of chiral P(V) compounds, including phosphinates, phosphinamides, and tertiary phosphine oxides, in good yields and high enantioselectivities.
{"title":"Enantioselective Desymmetrization of Phosphinic Acids via Cu-Catalyzed O-Arylation","authors":"Ming Yan, Jia-wei Zou, Dong-mei Fang, Shi-qi Zhang, Xin Cui, Zhuo Tang, Guang-xun Li","doi":"10.1021/acscatal.5c00439","DOIUrl":"https://doi.org/10.1021/acscatal.5c00439","url":null,"abstract":"Enantioselective desymmetrization of phosphinic acid with two completely different carbon substituents on the P atom is an efficient way to obtain chiral P(V) compounds with high structural diversity. Herein, we reported a Cu-catalyzed asymmetric arylation of phosphinic acid, which turns the P-center to be a versatile electrophile for obtaining a series of chiral P(V) compounds, including phosphinates, phosphinamides, and tertiary phosphine oxides, in good yields and high enantioselectivities.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"34 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561125","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}
Electrocatalytic upgrading of plastic waste and biomass into value-added chemicals offers a sustainable approach for resource utilization. However, it remains challenging to realize adjustable and efficient C–C activation behavior during electrooxidation. Herein, by designing Pt@Ni(OH)2–x electrocatalyst consisting of Ni–O–Pt interface and abundant oxygen vacancies, the intelligent switchover between C–C maintained and broken products was successfully achieved in electrooxidation of ethylene glycol (EG from PET) and glycerol (GLY from biodiesel). Especially, for EG electrooxidation, Pt@Ni(OH)2–x delivers remarkable selectivity and activity toward C2 (CH2OHCOOH) and C1 (HCOOH) (95 and 92%, respectively) with industrial-scaled current densities at moderate potentials (355.1 mA cm–2 at 0.9 V and 382.3 mA cm–2 at 1.6 V, respectively). Experimental and theoretical results reveal that (1) the tunable C–C activation ability strongly depends on the oxidation state of Pt@Ni(OH)2–x, and *CH2OHCOOH intermediate is the key factor determining the selectivity of C2 and C1; (2) the strong coupling interface induced by Ni–O–Pt bridge and oxygen vacancies activate the synergistic effect, enriching EG and OH–, and facilitating the reversibility of Ni2+/Ni3+ species. Additionally, a solar-powered reactor with an Internet system was designed for upcycling real-world PET bottles, which realized the controllable switchover between C1 and C2 products by “one click”. This study underlines the tunable C–C activation capability, laying the way for the design of bifunctional catalysts toward polyhydric alcohol electrooxidation.
{"title":"Selectively Steering the Retention and Cleavage of C–C Bond in Electrooxidation of PET Plastic and Biomass-Derived Alcohols by Defective Ni(OH)2–x-Supported Pt","authors":"Fahao Ma, Chunhuan Zhang, Wenbo Li, Riming Hu, Zengqi Wang, Junpeng Wang, Jinkai Li, Yong Nie, Zhaoke Zheng, Xuchuan Jiang","doi":"10.1021/acscatal.4c07644","DOIUrl":"https://doi.org/10.1021/acscatal.4c07644","url":null,"abstract":"Electrocatalytic upgrading of plastic waste and biomass into value-added chemicals offers a sustainable approach for resource utilization. However, it remains challenging to realize adjustable and efficient C–C activation behavior during electrooxidation. Herein, by designing Pt@Ni(OH)<sub>2–<i>x</i></sub> electrocatalyst consisting of Ni–O–Pt interface and abundant oxygen vacancies, the intelligent switchover between C–C maintained and broken products was successfully achieved in electrooxidation of ethylene glycol (EG from PET) and glycerol (GLY from biodiesel). Especially, for EG electrooxidation, Pt@Ni(OH)<sub>2–<i>x</i></sub> delivers remarkable selectivity and activity toward C<sub>2</sub> (CH<sub>2</sub>OHCOOH) and C<sub>1</sub> (HCOOH) (95 and 92%, respectively) with industrial-scaled current densities at moderate potentials (355.1 mA cm<sup>–2</sup> at 0.9 V and 382.3 mA cm<sup>–2</sup> at 1.6 V, respectively). Experimental and theoretical results reveal that (1) the tunable C–C activation ability strongly depends on the oxidation state of Pt@Ni(OH)<sub>2–<i>x</i></sub>, and *CH<sub>2</sub>OHCOOH intermediate is the key factor determining the selectivity of C<sub>2</sub> and C<sub>1</sub>; (2) the strong coupling interface induced by Ni–O–Pt bridge and oxygen vacancies activate the synergistic effect, enriching EG and OH<sup>–</sup>, and facilitating the reversibility of Ni<sup>2+</sup>/Ni<sup>3+</sup> species. Additionally, a solar-powered reactor with an Internet system was designed for upcycling real-world PET bottles, which realized the controllable switchover between C<sub>1</sub> and C<sub>2</sub> products by “one click”. This study underlines the tunable C–C activation capability, laying the way for the design of bifunctional catalysts toward polyhydric alcohol electrooxidation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"20 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1021/acscatal.5c00899
Weiye Qu, Pranav Roy, Canhui Wang, Lu Ma, Fan Bu, Xinsui Zhang, Zimin He, Michael Tsapatsis, Brandon C. Bukowski, Chao Wang
Developing advanced catalytic materials for mild-condition ammonia (NH3) synthesis is essential for improving the energy efficiency of the industrial Haber-Bosch process. Here, we report a ζ-phase manganese nitride (MnN0.43) catalyst for low-temperature NH3 synthesis. The as-synthesized MnN0.43 catalyst is protected by a carbon shell, allowing for the storage and processing of the air-sensitive metal nitride under ambient conditions. After activation in situ, the MnN0.43 catalyst exhibits high activity for NH3 synthesis at 250–350 °C, surpassing the conventional noble metal based Ru/MgO catalyst. A combination of kinetic, chemisorption, isotope labeling and computational studies indicate that a nitrogen vacancy-mediated associative mechanism accounts for the catalytic enhancements. Our work highlights the great potential of earth-abundant transition metal nitrides for catalyzing mild-condition NH3 synthesis.
{"title":"Earth-Abundant Manganese Nitride Catalysts for Mild-Condition Ammonia Synthesis","authors":"Weiye Qu, Pranav Roy, Canhui Wang, Lu Ma, Fan Bu, Xinsui Zhang, Zimin He, Michael Tsapatsis, Brandon C. Bukowski, Chao Wang","doi":"10.1021/acscatal.5c00899","DOIUrl":"https://doi.org/10.1021/acscatal.5c00899","url":null,"abstract":"Developing advanced catalytic materials for mild-condition ammonia (NH<sub>3</sub>) synthesis is essential for improving the energy efficiency of the industrial Haber-Bosch process. Here, we report a ζ-phase manganese nitride (MnN<sub>0.43</sub>) catalyst for low-temperature NH<sub>3</sub> synthesis. The as-synthesized MnN<sub>0.43</sub> catalyst is protected by a carbon shell, allowing for the storage and processing of the air-sensitive metal nitride under ambient conditions. After activation <i>in situ</i>, the MnN<sub>0.43</sub> catalyst exhibits high activity for NH<sub>3</sub> synthesis at 250–350 °C, surpassing the conventional noble metal based Ru/MgO catalyst. A combination of kinetic, chemisorption, isotope labeling and computational studies indicate that a nitrogen vacancy-mediated associative mechanism accounts for the catalytic enhancements. Our work highlights the great potential of earth-abundant transition metal nitrides for catalyzing mild-condition NH<sub>3</sub> synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"23 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-05DOI: 10.1021/acscatal.4c07187
Xiaorui Du, Chongshuai Gao, Jiaxin Huang, Yanbin Cui, Shijun Liu, Chenguang Wang
Controlling both the hydrogenation performance and the activation of Schiff base intermediate in catalysts is crucial for attaining high slectivity toward primary amine in the reduction amination of furfural. However, it remains pending for Pt-based catalysts, on which the reduction amination reactions rarely generate primary amines so far. In this work, we developed a Pt/TiO2 nanocluster (NC) catalyst with a size distribution independent of the reduction temperature and loading amount. The reductive amination performance was investigated by regulating the surface electronic state and the distance between Pt NCs, and the results, attractively, revealed that the catalyst with a lower loading amount exhibited a higher furfurylamine (FAM) yield. Further studies unraveled that the catalyst with a larger Pt NC proximity had more abundant effective adsorption sites for the key intermediate Schiff base, i.e., the surface Ti4+ sites adjacent to the Pt NC, promoting the transformation of the Schiff base. Meanwhile, reducing the surface density of Pt NCs helped control the intensity of hydrogen spillover, thereby inhibiting the occurrence of overhydrogenation reactions. Optimal activity for primary amine generation from furfural reductive amination was achieved with a Pt NC catalyst reduced at 500 °C and with a loading amount of only 0.1 wt %, resulting in a FAM yield exceeding 93% and a production rate of 297.9 gFAM gPt h–1. The reaction mechanism, involving the competitive relationship between NH3 and H2, was elucidated through kinetic studies and theoretical calculations. This work provides insights for the designation of catalysts with controllable hydrogenation activity and adsorption selectivity and contributes to the understanding of the mechanism of the reductive amination reaction.
{"title":"Efficient Reductive Amination of Furfural to a Primary Amine on a Pt/TiO2 Catalyst: A Manifestation of the Nanocluster Proximity Effect","authors":"Xiaorui Du, Chongshuai Gao, Jiaxin Huang, Yanbin Cui, Shijun Liu, Chenguang Wang","doi":"10.1021/acscatal.4c07187","DOIUrl":"https://doi.org/10.1021/acscatal.4c07187","url":null,"abstract":"Controlling both the hydrogenation performance and the activation of Schiff base intermediate in catalysts is crucial for attaining high slectivity toward primary amine in the reduction amination of furfural. However, it remains pending for Pt-based catalysts, on which the reduction amination reactions rarely generate primary amines so far. In this work, we developed a Pt/TiO<sub>2</sub> nanocluster (NC) catalyst with a size distribution independent of the reduction temperature and loading amount. The reductive amination performance was investigated by regulating the surface electronic state and the distance between Pt NCs, and the results, attractively, revealed that the catalyst with a lower loading amount exhibited a higher furfurylamine (FAM) yield. Further studies unraveled that the catalyst with a larger Pt NC proximity had more abundant effective adsorption sites for the key intermediate Schiff base, i.e., the surface Ti<sup>4+</sup> sites adjacent to the Pt NC, promoting the transformation of the Schiff base. Meanwhile, reducing the surface density of Pt NCs helped control the intensity of hydrogen spillover, thereby inhibiting the occurrence of overhydrogenation reactions. Optimal activity for primary amine generation from furfural reductive amination was achieved with a Pt NC catalyst reduced at 500 °C and with a loading amount of only 0.1 wt %, resulting in a FAM yield exceeding 93% and a production rate of 297.9 g<sub>FAM</sub> g<sub>Pt</sub> h<sup>–1</sup>. The reaction mechanism, involving the competitive relationship between NH<sub>3</sub> and H<sub>2</sub>, was elucidated through kinetic studies and theoretical calculations. This work provides insights for the designation of catalysts with controllable hydrogenation activity and adsorption selectivity and contributes to the understanding of the mechanism of the reductive amination reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"13 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-05DOI: 10.1021/acscatal.4c07962
Fabio Juliá
Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected for many decades by careful selection of metal centers and ligands, giving rise to synthetic methods with unparalleled efficiency and chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful tool to dramatically alter the outcome of catalytic reactions, providing access to innovative pathways with remarkable synthetic potential. In this context, the adoption of photochemical conditions as a mainstream strategy to drive organic reactions has unveiled exciting opportunities to exploit the rich excited-state framework of transition metals for catalytic applications. This Perspective examines advances in the application of transition metal complexes as standalone photocatalysts, exploiting the innate reactivity of their excited states beyond their common use as photoredox catalysts. An account of relevant examples is dissected to provide a discussion on the electronic reorganization, the orbitals involved, and the associated reactivity of different types of excited states. This analysis aims to provide practitioners with fundamental principles and guiding strategies to understand, design, and apply light-activation strategies to homogeneous transition metal catalysis for organic synthesis.
{"title":"Catalysis in the Excited State: Bringing Innate Transition Metal Photochemistry into Play","authors":"Fabio Juliá","doi":"10.1021/acscatal.4c07962","DOIUrl":"https://doi.org/10.1021/acscatal.4c07962","url":null,"abstract":"Transition metal catalysis is an indispensable tool for organic synthesis that has been harnessed, modulated, and perfected for many decades by careful selection of metal centers and ligands, giving rise to synthetic methods with unparalleled efficiency and chemoselectivity. Recent developments have demonstrated how light irradiation can also be recruited as a powerful tool to dramatically alter the outcome of catalytic reactions, providing access to innovative pathways with remarkable synthetic potential. In this context, the adoption of photochemical conditions as a mainstream strategy to drive organic reactions has unveiled exciting opportunities to exploit the rich excited-state framework of transition metals for catalytic applications. This Perspective examines advances in the application of transition metal complexes as standalone photocatalysts, exploiting the innate reactivity of their excited states beyond their common use as photoredox catalysts. An account of relevant examples is dissected to provide a discussion on the electronic reorganization, the orbitals involved, and the associated reactivity of different types of excited states. This analysis aims to provide practitioners with fundamental principles and guiding strategies to understand, design, and apply light-activation strategies to homogeneous transition metal catalysis for organic synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"58 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561206","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-05DOI: 10.1021/acscatal.5c00788
Chengyu Liu, Titus de Haas, Francesco Buda, Sylvestre Bonnet
Molecular catalysts offer an ideal platform for conducting mechanistic studies of the hydrogen evolution reaction (HER) due to their electronic tunability. This study explores a series of anionic M═Co(III)- and M═Zn(II)-porphyrin complexes with electron-donating ([M(OMeP)]n−, [M(MeP)]n−) and electron-withdrawing ([M(F8P)]n−, [M(F16P)]n−) substituents. The activity of these complexes for the HER was analyzed in homogeneous photocatalytic conditions using [Ru(bpy)3]2+ as a photosensitizer under blue light (450 nm) irradiation. The substituent-induced electronic effects were found to tightly control the activity and mechanism of the photocatalytic HER. As expected, the electron-rich [Co(OMeP)]3– catalyst showed higher activity in acidic media (pH 4.1) with a maximum TOF of 7.2 ± 0.4 h–1 and TON of 175 ± 5 after 39.5 h. DFT calculations were performed to investigate the HER mechanism. H2 formation was found to initiate following proton-coupled reduction of a CoIII–H hydride intermediate in such conditions. More surprisingly, however, the electron-poor [Co(F16P)]3– catalyst was more active at neutral pH (7.0), achieving a maximum TOF of 6.7 ± 0.3 h–1 and TON of 70 ± 3 after 39.5 h. Instead of forming the CoIII–H hydride, an additional ligand-based reduction led to a ligand-protonated intermediate. This work demonstrates that electron-poor HER catalysts can outperform electron-rich catalysts near neutral pH conditions.
{"title":"Electron-Withdrawing Effects in Cobalt Porphyrin Catalysts Boost Homogeneous Photocatalytic Hydrogen Evolution in Neutral Aqueous Solutions","authors":"Chengyu Liu, Titus de Haas, Francesco Buda, Sylvestre Bonnet","doi":"10.1021/acscatal.5c00788","DOIUrl":"https://doi.org/10.1021/acscatal.5c00788","url":null,"abstract":"Molecular catalysts offer an ideal platform for conducting mechanistic studies of the hydrogen evolution reaction (HER) due to their electronic tunability. This study explores a series of anionic M═Co(III)- and M═Zn(II)-porphyrin complexes with electron-donating ([M(OMeP)]<sup><i>n</i>−</sup>, [M(MeP)]<sup><i>n</i>−</sup>) and electron-withdrawing ([M(F8P)]<sup><i>n</i>−</sup>, [M(F16P)]<sup><i>n</i>−</sup>) substituents. The activity of these complexes for the HER was analyzed in homogeneous photocatalytic conditions using [Ru(bpy)<sub>3</sub>]<sup>2+</sup> as a photosensitizer under blue light (450 nm) irradiation. The substituent-induced electronic effects were found to tightly control the activity and mechanism of the photocatalytic HER. As expected, the electron-rich [Co(OMeP)]<sup>3–</sup> catalyst showed higher activity in acidic media (pH 4.1) with a maximum TOF of 7.2 ± 0.4 h<sup>–1</sup> and TON of 175 ± 5 after 39.5 h. DFT calculations were performed to investigate the HER mechanism. H<sub>2</sub> formation was found to initiate following proton-coupled reduction of a Co<sup>III</sup>–H hydride intermediate in such conditions. More surprisingly, however, the electron-poor [Co(F16P)]<sup>3–</sup> catalyst was more active at neutral pH (7.0), achieving a maximum TOF of 6.7 ± 0.3 h<sup>–1</sup> and TON of 70 ± 3 after 39.5 h. Instead of forming the Co<sup>III</sup>–H hydride, an additional ligand-based reduction led to a ligand-protonated intermediate. This work demonstrates that electron-poor HER catalysts can outperform electron-rich catalysts near neutral pH conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"38 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-05DOI: 10.1021/acscatal.4c07573
Heng Zhang, Jinxin Zhang, Shijie Yu, Dongfang Wu
Exploiting stable active structures and investigating the intrinsic mechanism are of great importance for heterogeneous catalysis. Especially for CO2 hydrogenation to methanol, efficient and affordable catalysts are desired to exert the value of this reaction in promoting the development of the circular carbon economy. In this work, a CoIn3 intermetallic compound (IMC) catalyst with a regular arrangement of atoms was prepared, which manifests the prominent catalytic performance for CO2 hydrogenation to methanol. Systematic atomic-scale investigations reveal the critical role of the unique interatomic interactions in the ordered atomically aligned CoIn3 IMC catalyst, particularly in propelling the adsorption and conversion of reactants while preserving the desired durability. In situ measurements and density functional theory calculations further demonstrate that the hydrogenation path of CO2 can encounter a low activation energy barrier on CoIn3 IMC, thus allowing for smooth and productive methanol synthesis along the HCOO* path. This work provides valuable insights for designing efficient catalysts and investigating the inherent mechanism for CO2 hydrogenation.
开发稳定的活性结构和研究其内在机理对于异相催化具有重要意义。特别是在 CO2 加氢制甲醇的过程中，需要高效且价格合理的催化剂，以发挥该反应在促进循环碳经济发展中的价值。本研究制备了一种原子排列规整的 CoIn3 金属间化合物 (IMC) 催化剂，该催化剂在 CO2 加氢制甲醇反应中具有突出的催化性能。系统的原子尺度研究揭示了有序原子排列的 CoIn3 IMC 催化剂中独特的原子间相互作用的关键作用，特别是在保持所需的耐久性的同时促进反应物的吸附和转化。现场测量和密度泛函理论计算进一步证明，CO2 的氢化路径在 CoIn3 IMC 上会遇到较低的活化能障碍，从而使 HCOO* 路径上的甲醇合成顺利且富有成效。这项工作为设计高效催化剂和研究 CO2 加氢的内在机理提供了宝贵的见解。
{"title":"Unique Interatomic Interaction Assisted CoIn Intermetallic Compound for Efficient Hydrogenation of CO2 into Methanol","authors":"Heng Zhang, Jinxin Zhang, Shijie Yu, Dongfang Wu","doi":"10.1021/acscatal.4c07573","DOIUrl":"https://doi.org/10.1021/acscatal.4c07573","url":null,"abstract":"Exploiting stable active structures and investigating the intrinsic mechanism are of great importance for heterogeneous catalysis. Especially for CO<sub>2</sub> hydrogenation to methanol, efficient and affordable catalysts are desired to exert the value of this reaction in promoting the development of the circular carbon economy. In this work, a CoIn<sub>3</sub> intermetallic compound (IMC) catalyst with a regular arrangement of atoms was prepared, which manifests the prominent catalytic performance for CO<sub>2</sub> hydrogenation to methanol. Systematic atomic-scale investigations reveal the critical role of the unique interatomic interactions in the ordered atomically aligned CoIn<sub>3</sub> IMC catalyst, particularly in propelling the adsorption and conversion of reactants while preserving the desired durability. In situ measurements and density functional theory calculations further demonstrate that the hydrogenation path of CO<sub>2</sub> can encounter a low activation energy barrier on CoIn<sub>3</sub> IMC, thus allowing for smooth and productive methanol synthesis along the HCOO* path. This work provides valuable insights for designing efficient catalysts and investigating the inherent mechanism for CO<sub>2</sub> hydrogenation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"48 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143560923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-04DOI: 10.1021/acscatal.5c00112
Hye-Min Jeong, Hee Seo Jung, Dong Gyu Kim, Jae Yeon Kim, Do Hyun Ryu
The wide spectrum of biological activities of tetrahydroquinolines (THQs) has prompted the extensive development of synthetic strategies. While photoredox catalysis has emerged as a powerful approach for THQ synthesis, achieving asymmetry remains challenging due to the high reactivity of the radicals. Here we report enantio- and diastereoselective tandem Giese addition/homolytic aromatic substitution reactions via visible-light photoredox catalysis. Using a chiral oxazaborolidinium ion catalyst and photosensitizer, the reaction of α-aminoalkyl radicals with α,β-unsaturated esters provided high yields (up to 97%) of the desired THQs with high enantio- and diastereoselectivities (up to 99% ee and formation of only trans-diastereomer) in a single step.
{"title":"Enantio- and Diastereoselective Tandem Giese Addition/Homolytic Aromatic Substitution Reaction via Visible-Light Photoredox Catalysis","authors":"Hye-Min Jeong, Hee Seo Jung, Dong Gyu Kim, Jae Yeon Kim, Do Hyun Ryu","doi":"10.1021/acscatal.5c00112","DOIUrl":"https://doi.org/10.1021/acscatal.5c00112","url":null,"abstract":"The wide spectrum of biological activities of tetrahydroquinolines (THQs) has prompted the extensive development of synthetic strategies. While photoredox catalysis has emerged as a powerful approach for THQ synthesis, achieving asymmetry remains challenging due to the high reactivity of the radicals. Here we report enantio- and diastereoselective tandem Giese addition/homolytic aromatic substitution reactions via visible-light photoredox catalysis. Using a chiral oxazaborolidinium ion catalyst and photosensitizer, the reaction of α-aminoalkyl radicals with α,β-unsaturated esters provided high yields (up to 97%) of the desired THQs with high enantio- and diastereoselectivities (up to 99% ee and formation of only <i>trans</i>-diastereomer) in a single step.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"48 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546822","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-04DOI: 10.1021/acscatal.5c00647
Junxi Zhang, An Pei, Huayue Yang, Weiwei Zhou, Zhenzhen Feng, Han Tian, Yun Zhao, Guangxu Chen, Jian Peng
An effective design of a bimetallic cobalt-based spinel oxide catalyst to selectively convert 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA), replacing the oxygen evolution reaction (OER), demonstrates broad application prospects. However, the oxidation mechanisms differ markedly among various catalysts, and the structural transformations of transition metals within cobalt oxides remain insufficiently understood. Here we synthesized a Cu0.29Co2.71O4 model catalyst using a facile solvothermal method. As the applied potential increased, Co(OH)2 was generated on the surface of Cu0.29Co2.71O4 and subsequently transformed into (Cu)CoOxHy via electrooxidation, followed by a rapid (nonelectrochemical) chemical oxidation reaction with HMF, achieving high selectivity (99.8%) and Faraday efficiency (91.6%) for the production of FDCA. Through comprehensive characterization coupled with electrochemical measurements and theoretical simulations, we found that the incorporation of copper effectively modulates the active sites of the cobalt oxide, which enhances OH– adsorption and improves conductivity, thereby achieving superior HMF oxidation activity. This work provides valuable insights into designing highly active bimetallic spinel oxide electrocatalysts to accelerate the anode oxidation reaction, offering a promising alternative to the OER and promoting efficient biomass conversion.
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