ACS Catalysis 最新文献

{"title":"Enhanced Three-Component Chloro-/Azido-Fluoroalkylation of Unactivated Alkenes via the Proximity Effect in a Heterogenous Metallaphotocatalyst","authors":"Xiaolin Shi, Maolin Li, Yuanjun Zhao, Yifan Liu, Xin Zhou, Bo Yu, Yong Yang","doi":"10.1021/acscatal.4c06960","DOIUrl":"https://doi.org/10.1021/acscatal.4c06960","url":null,"abstract":"Heterogeneous metallaphotocatalytic chemical transformations employing a recyclable catalyst are highly desirable for organic synthesis. However, the rational design and controlled preparation of well-defined, site-isolated metal/photo bifunctional heterogeneous catalysts to achieve this goal remain a significant challenge. In this study, we demonstrate the covalent attachment of a homogeneous molecular MnSalen complex (where Salen = <i>N</i>,<i>N</i>′-bis(salicylidene)ethylenediamine) onto the surface of graphitic carbon nitride (CN) via an amide bond for visible-light-driven chloro- and azido-fluoroalkylation of unactivated alkenes. The amide covalent linkage between MnSalen and CN not only facilitates electron delocalization and enhances the light-harvesting capabilities of the CN photosensitizer but also exerts a proximity effect that markedly enhances the ability of the Mn sites to capture alkyl radical intermediates during the reaction process. A diverse set of unactivated alkenes could be efficiently chloro- and azido-fluoroalkylated to their corresponding difunctionalized products in moderate to high yields with good functional group compatibility. Furthermore, the practicability of the heterogeneous protocol is illustrated through the late-stage diversification of various bioactive compounds and pharmaceuticals. Notably, this integrated photocatalyst demonstrates high stability and can be recycled at least 10 times without loss of activity and selectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Redox-Neutral Photocatalytic Germylative Difunctionalization of Unactivated Olefins via Selective Radical Capture by Ge(II)","authors":"Wen-Jing Zhou, Zequn Yang, Bin Xiao","doi":"10.1021/acscatal.4c06681","DOIUrl":"https://doi.org/10.1021/acscatal.4c06681","url":null,"abstract":"This study reports the development of a photocatalytic germanyl functionalization of unactivated olefins. A modular approach to alkylgermanium trihalides was realized through a three-component radical reaction involving fluoroalkyl bromides and commercially available GeBr₂ in a redox-neutral process. The target organogermanes were readily obtained via one-pot derivatization using various Grignard reagents, demonstrating good functional group compatibility with amides, esters and ketones. This work highlights the utility of Ge(II) reagents in constructing C–Ge bonds via photoredox catalysis. Notably, the selectivity in capturing electrophilic or nucleophilic radicals by Ge(II) was found to be significantly influenced by the halide ligands on GeX₂.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A General Amino–(Hetero)arylation of Simple Olefins with (Hetero)aryl Sulfonamides Enabled by an N-Triazinyl Group","authors":"Jaxon L. Barney, Andrew J. Wolfram, Rose Litvak, Eric D. Nacsa","doi":"10.1021/acscatal.5c00157","DOIUrl":"https://doi.org/10.1021/acscatal.5c00157","url":null,"abstract":"(Hetero)arylethylamines are privileged substructures in pharmaceuticals, agrochemicals, and other bioactive compounds. In principle, the amino–(hetero)arylation of olefins represents an ideal strategy for the rapid preparation of these pharmacophores, which could accelerate the discovery of valuable new products. Established amino–(hetero)arylation methods, however, do not accommodate several important classes of olefins and (hetero)aromatic structures, which precludes access to an appreciable range of molecular architectures. To address these limitations, we have developed a radical-mediated reaction that adds the amino and (hetero)aryl groups from a simple and stable (hetero)aryl sulfonamide across an alkene. The identification of a readily available triazine as an original <i>N</i>-protecting group was critical to the development of this transformation. The reaction features good regio- and stereoselectivity and succeeds with classes of olefins and medicinally valuable (hetero)aryl groups that are unproductive with alternate protocols. Lastly, we highlighted these advances by synthesizing TMP269, a class IIa histone deacetylase inhibitor that would otherwise be challenging to prepare by olefin amino–arylation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"74 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient Photoelectrocatalysis of Glycerol to Dihydroxyacetone and Synergistic Hydrogen Generation via Dual Oxidation Pathways Using Co-LDH/Bi2O3/TiO2 Ternary Array","authors":"Lu Niu, Rufeng Tian, Wanggang Zhang, Hongxia Wang, Jian Wang, Yiming Liu","doi":"10.1021/acscatal.4c05193","DOIUrl":"https://doi.org/10.1021/acscatal.4c05193","url":null,"abstract":"Replacing the oxygen evolution reaction (OER) in photoelectrocatalytic (PEC) water splitting with glycerol oxidation reaction (GOR) not only enhances hydrogen production but also generates high-value glycerol byproducts. In this study, we developed a ternary photoanode, Co-LDH/Bi₂O₃/TiO₂, by loading particulate Bi₂O₃ and linear Co-LDH onto a TiO₂ nanorod for glycerol conversion and hydrogen production. The characterization results confirm the formation of coupled interfaces between Co-LDH and Bi₂O₃ and TiO₂, which improves the visible light utilization and promotes the formation of type II heterojunctions, resulting in a significant suppression of electron–hole recombination and an improvement in the PEC performance. Fourier transform infrared (FT-IR) spectroscopy revealed that the Co-LDH/Bi₂O₃/TiO₂ photoanode exhibited stronger adsorption of glycerol intermediate hydroxyl group and more effective desorption of DHA compared to TiO₂ and binary photoanodes (Co-LDH/TiO₂ and Bi₂O₃/TiO₂), resulting in high-selectivity glycerol conversion to DHA. Mechanistic studies and density function theory calculations have shown that the binary photoanode Co-LDH/TiO₂ oxidizes glycerol mainly through hole oxidation, and the binary photoanode Bi₂O₃/TiO₂ oxidizes glycerol mainly through hydroxyl radical (^•OH) oxidation. Therefore, the ternary photoanode constructed (Co-LDH/Bi₂O₃/TiO₂) with a dual heterojunction converts glycerol through the dual pathways of hole oxidation and ^•OH oxidation. This work demonstrates a promising strategy for developing high-performance photoanodes in PEC systems for glycerol oxidation and hydrogen production, leveraging the synergistic effects of multisemiconductor heterojunctions and multiple oxidation pathways, offering significant potential for practical applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"45 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Time-Domain NMR: Generating Unique Insights into the Characterization of Heterogeneous Catalysis in Liquid Phase","authors":"Murilo T. Suekuni, Carmine D’Agostino, Alan M. Allgeier","doi":"10.1021/acscatal.4c04789","DOIUrl":"https://doi.org/10.1021/acscatal.4c04789","url":null,"abstract":"Time-domain (TD) nuclear magnetic resonance (NMR) comprises a family of tools for characterizing wetted porosity and surface area, fluid-catalyst surface adsorption energy, liquid distribution in packed beds, and transport of fluids in catalyst materials. These methods are differentiated from NMR spectroscopy in that the data are not analyzed in the frequency domain and often benefit from the use of low magnetic field strength. The increased accessibility of commercial, low-field, benchtop NMR instruments has supported substantial growth in TD NMR research in catalysis. This perspective offers a tutorial on physical phenomena critical to TD NMR methods, a summary of applications in both ex situ and in situ settings, and commentaries on ensuring experimental rigor and opportunities for growth in the field. The unique insights accessible from TD NMR often cover length scales in the tens of nanometers to tens of micrometers and are complementary to other catalyst characterization methods probing molecular structure and identity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct Syngas-To-Ethanol Conversion over Lithium-Promoted Rh/MgO Catalysts","authors":"Abdellah Ait El Fakir, Pengfei Du, Li Wan, HongLi Pan, Shirun Zhao, Nazmul Hasan M.D. Dostagir, Akihiko Anzai, Shinya Mine, Evgeny A. Pidko, Ken-ichi Shimizu, Takashi Toyao","doi":"10.1021/acscatal.4c05085","DOIUrl":"https://doi.org/10.1021/acscatal.4c05085","url":null,"abstract":"Significant efforts have been dedicated to the direct syngas conversion into ethanol, however, achieving a high ethanol yield remains a formidable task. In this study, we present the direct syngas-to-ethanol conversion over Li-promoted RhO_<i>x</i>/MgO catalyst (RhO_<i>x</i>/Li₂O/MgO). The ethanol space-time yield (EtOH STY) and selectivity reached 12.2 mmol g_cat^–1 h^–1 and 20%, respectively, at a 35% CO conversion over the RhO_<i>x</i>/Li₂O/MgO catalyst. The RhO_<i>x</i>/Li₂O/MgO catalyst demonstrated superior performance in terms of both ethanol selectivity and STY compared to Rh/Li₂O catalysts on other support materials and Rh/MgO catalysts promoted with other alkali metals. In situ/operando spectroscopic techniques, combined with other characterisations and theoretical calculations, have elucidated the interactions between Li₂O and Rh on the MgO surface. These interactions promote the formation of new active sites and weaken CO adsorption on the Rh surface, thereby enhancing ethanol production. This work provides a promising strategy for improving ethanol yield in syngas conversion processes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990834","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pickering Interfacial Tandem Catalysis of Alkenes to 1,2-Diols over Manganese Oxide Catalysts at Room Temperature","authors":"Shihao Su, Guojun Lv, Jialing Shen, Fuxin Wang, Lachgar Oussama, Yan Chen, Shengnan Xu","doi":"10.1021/acscatal.4c06225","DOIUrl":"https://doi.org/10.1021/acscatal.4c06225","url":null,"abstract":"In the tandem synthesis of 1,2-cyclohexanediol, solvents such as acetonitrile are often added to eliminate the immiscibility of cyclohexene with water and accordingly strengthen the interphase mass transfer; however, the usage of solvents artificially increases the solvent separation procedure, enhancing the energy consumption and decreasing the economic benefits of the reaction process. Hence, the development of the solvent-free Pickering interfacial tandem catalysis of cyclohexene to 1,2-cyclohexanediol is extremely appealing. In this study, β-MnO₂ and Mn₂O₃ were prepared by calcining γ-MnO₂ synthesized with the hydrothermal synthesis method and concurrently served as a colloidal emulsifier and a heterogeneous catalyst in the Pickering interfacial tandem catalysis of cyclohexene to 1,2-cyclohexanediol at room temperature in the presence of the oxidant molecular oxygen and the co-oxidant isobutyraldehyde. The prepared β₄₅₀-MnO₂ sample revealed the best tandem catalysis performance, achieving a cyclohexene conversion of 99.4% and a 1,2-cyclohexanediol selectivity of 83.6% within 4 h of reaction, which can be ascribed to the highest Mn⁴⁺/Mn³⁺ ratio and the greatest concentration of oxygen vacancies as well as the most stable Pickering emulsion. At the same time, density functional theory (DFT) studies further confirmed that isobutyraldehyde and molecular oxygen could be more easily adsorbed and activated by β₄₅₀-MnO₂ in comparison with the other catalyst samples, benefiting its eminent catalytic epoxidation performance. In addition, a possible reaction mechanism for the β₄₅₀-MnO₂ catalyst catalyzing cyclohexene into 1,2-cyclohexanediol in the Pickering interfacial tandem catalytic reaction system was put forward and validated through quenching experiments as well as in situ infrared characterization. The synthesized β₄₅₀-MnO₂ catalyst exhibited reusability for greater than 5 cycles, and meanwhile, the Pickering interfacial tandem catalytic reaction system can be expanded to a spread of linear and cyclic alkene substrates, highlighting the superiority of the β₄₅₀-MnO₂ catalyst. These findings verify that the synthesized β₄₅₀-MnO₂ catalyst is capable of being utilized as an efficient and stable catalyst for the Pickering interfacial catalytic conversion of alkenes into 1,2-diols at room temperature.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"102 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultrathin ZSM-5 Shell Constructed on an S-1 Crystal Surface for Prins Reaction to Boost Methanol Aromatization with High Catalytic Stability","authors":"Qian Ma, Tingjun Fu, Chuntao Cao, Xueqing Wu, Zhong Li","doi":"10.1021/acscatal.4c07004","DOIUrl":"https://doi.org/10.1021/acscatal.4c07004","url":null,"abstract":"The conversion of methanol to aromatic over acid zeolite is a promising route to increase the supply of aromatic via a nonpetroleum route. However, the low conversion rate of the hydrogen transfer route between olefins over conventional ZSM-5 leads to a low efficiency of the aromatization process. Herein, a thin ZSM-5 shell with high Lewis/Brønsted was coated on the silicalite-1 surface by seed-induced stepwise crystallization. The thin ZSM-5 shell and Lewis acid sites promoted the formation of formaldehyde by hydrogen transfer between methanol and the olefin. Formaldehyde underwent a Prins reaction with olefin to generate long-chain unsaturated hydrocarbons, which accelerated the aromatization process of olefins. The aromatic selectivity increased to 33.9% from 26.6% of hydrogen transfer routes between olefins, and the alkene selectivity decreased from 16.1% to 9.4%. The diffusion promoted by ultrathin shell slowed down the formation of polycyclic aromatic, achieving stable conversion of methanol to aromatics. Appropriately increasing the amount of Brønsted acid in the catalyst or introducing additional olefin into the reaction system could promote the formation of dimethylcyclopentene intermediates and the conversion to aromatic, further improving the aromatic selectivity. This study extended insights into the regulation of acidity and diffusion length over ZSM-5 for promoting aromatic production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"137 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992651","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ethane Oxidative Dehydrogenation over TiO2 and M/TiO2 Catalysts: Unraveling the Surface Structure Evolution, Oxygen Species Type, and Role of Doped Metal in Tuning Catalytic Performance","authors":"Mifeng Xue, Baojun Wang, Maohong Fan, Lixia Ling, Riguang Zhang","doi":"10.1021/acscatal.4c07213","DOIUrl":"https://doi.org/10.1021/acscatal.4c07213","url":null,"abstract":"TiO₂ has better catalytic performance toward alkane oxidative dehydrogenation (ODH) due to adjustable surface oxygen species; however, identifying the dynamic evolution process of the TiO₂ surface structure and its effect on the type of surface oxygen species is still challenging. In this work, the combined methods of density functional theory calculations and kinetic Monte Carlo simulations were employed to fully investigate the catalytic performance of ethane ODH over TiO₂ and 15 types of single-atom metal-doped TiO₂ (M/TiO₂) catalysts. The results clearly unravel the evolution mechanism of the TiO₂ surface structure and the type of surface oxygen species formed during the evolution process in tuning ethane ODH catalytic performance. Surface oxygen vacancies enhance catalytic performance with unsaturated Ti_4CN as the active site, while surface-adsorbed oxygen species limit catalytic performance. Single-atom metal-doped TiO₂ can change the O₂(g) adsorption mode and dissociation activity to adjust the type of surface oxygen species and further regulate the catalytic performance by tuning electronic properties of adsorbed oxygen atoms. Interestingly, the screened V/TiO₂–O* catalyst exhibits high C₂H₄(g) production activity and selectivity at the optimal temperature of 873.15 K and a C₂H₆(g) partial pressure of 0.2 bar, which thoroughly eliminates the negative effect of adsorbed oxygen species over the TiO₂ catalyst in the process of ethane ODH due to more charge transfer from V to the adsorbed oxygen atom. This work provides the theoretical basis and structural clue for designing an alkane ODH catalyst by regulating the types and electronic properties of surface oxygen species over metal oxide.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"9 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992652","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Adaptive Morphing of Hydroxyl Groups on Covalency Competing Spinel Oxides Boosting Oxygen Evolution Reactions","authors":"Jiali Gou, Xin Lei, Bifa Ji, Shanshan Zhang, Yongping Zheng, Yongbing Tang","doi":"10.1021/acscatal.4c07014","DOIUrl":"https://doi.org/10.1021/acscatal.4c07014","url":null,"abstract":"Spinel oxides based on first-row transition metals (M_<i>d</i>) have been recognized as cost-effective alternatives to noble metal catalysts in oxygen evolution reactions (OERs), and a multimetal strategy is usually employed to enhance their OER activity. However, it is challenging to rely solely on the combination of these 3<i>d</i> metals to achieve optimal OER activity as their similar metal–oxygen covalency cannot provide sufficient intermodulation to obtain the desirable electronic structure. Here we report that the incorporation of <i>p</i>-block single atoms (M_<i>p</i>, Bi, Sn, and Sb) into octahedral sites of a model spinel oxide NiFe₂O₄ (NFO) can effectively induce asymmetric M_<i>p</i>-O-M_<i>d</i> covalency competition, where the M_<i>p</i>-O covalency acts as an electron reservoir that adaptively modulates the reactivity of M_<i>d</i> sites. This allows surface hydroxyl groups to morph dynamically with each electron transfer step, leading to near-optimal formation energies of the OER intermediates. The subsequent experiments as well as in situ and ex situ characterizations have successfully validated the theoretical predictions, especially since the design of Bi-doped NFO (Bi-NFO) shows significant improvement in specific activity compared to pristine spinel NFO. Our work provides important insights into the design principle of earth-abundant oxide catalysts for the OER by leveraging covalency competition, which may be extended to other catalytic reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"35 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990877","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}