ACS Catalysis 最新文献_第6页

Promoter-Guided Reaction Intermediate Dynamics Enhance Perhydro-benzyltoluene Dehydrogenation

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-20 DOI: 10.1021/acscatal.4c07703

Eui-Rim On, Kimoon Lee, Yeonsu Kwak, Chan Kim, Quan Dao, Hyuntae Sohn, Suk Woo Nam, Joohoon Kim, Yongmin Kim, Hyangsoo Jeong

{"title":"Promoter-Guided Reaction Intermediate Dynamics Enhance Perhydro-benzyltoluene Dehydrogenation","authors":"Eui-Rim On, Kimoon Lee, Yeonsu Kwak, Chan Kim, Quan Dao, Hyuntae Sohn, Suk Woo Nam, Joohoon Kim, Yongmin Kim, Hyangsoo Jeong","doi":"10.1021/acscatal.4c07703","DOIUrl":"https://doi.org/10.1021/acscatal.4c07703","url":null,"abstract":"The dehydrogenation of perhydrobenzyltoluene (H12-BT) as a liquid organic hydrogen carrier presents significant challenges in reaction kinetics and catalyst stability. The reaction pathway involves multiple intermediates and isomeric variations, creating an intricate network that influences both catalytic activity and deactivation mechanisms. While sulfur modification of Pt/θ-Al2O3 catalysts enhances reaction rates and stability, the underlying mechanisms governing catalyst–intermediate interactions have remained elusive. To unravel these complex interactions, we developed a surrogate approach using single-ring model compounds (methylcyclohexane, dimethylcyclohexane, toluene, and xylene) as surrogates for two-ring intermediates. This strategy enabled systematic analysis of intermediate behavior without requiring challenging intermediate synthesis. Using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) at 320 °C, we examined how sulfur modification transforms reaction pathways and surface chemistry. Our results reveal that successful dehydrogenation depends on controlled intermediate readsorption patterns. Sulfur modification promotes favorable readsorption via aliphatic moieties, facilitating complete dehydrogenation while minimizing aromatic species retention. In contrast, unmodified Pt/θ-Al2O3 exhibits preferential readsorption of dehydrogenated aromatic species, leading to active-site blockage and carbon formation. Postreaction analyses confirm that sulfur maintains catalyst integrity by redirecting reaction pathways, demonstrating a broader strategy for controlling surface chemistry in complex dehydrogenation systems through selective adsorption modification.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"56 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661093","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}

引用次数: 0

Copper Phyllosilicate-Derived Cu Catalyst for the Water–Gas Shift Reaction: Insight into the Role of Cu+–Cu0 and Reaction Mechanism

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-20 DOI: 10.1021/acscatal.4c07785

Chunjin Huang, Yue Chen, Huihuang Fang, Guo Zhi, Chongqi Chen, Yu Luo, Xingyi Lin, Lilong Jiang

{"title":"Copper Phyllosilicate-Derived Cu Catalyst for the Water–Gas Shift Reaction: Insight into the Role of Cu+–Cu0 and Reaction Mechanism","authors":"Chunjin Huang, Yue Chen, Huihuang Fang, Guo Zhi, Chongqi Chen, Yu Luo, Xingyi Lin, Lilong Jiang","doi":"10.1021/acscatal.4c07785","DOIUrl":"https://doi.org/10.1021/acscatal.4c07785","url":null,"abstract":"Cu-based catalysts have been extensively researched for hydrogen production via water–gas shift (WGS, CO+H2O↔CO2+H2) reaction. Yet, the catalyst easily suffers from performance degradation due to Cu+/Cu0 transformation and particle aggregation. Herein, copper phyllosilicate with different morphologies, i.e., tubular and lamellar, was fabricated by a modified hydrothermal method for the WGS reaction. Compared with the catalyst derived from lamellar copper phyllosilicate (30Cu/SiO2-L), the one derived from the tubular phyllosilicate (30Cu/SiO2-T) demonstrates better performance due to the high Cu+/(Cu0+Cu+) ratio. In situ characterizations were conducted to unveil the transformation between Cu+ and Cu0, which is highly correlated to the CO and H2O activation. Cu+ is primarily responsible for the activation of CO, while Cu0 mainly facilitates the dissociation of H2O. The results show that 30Cu/SiO2-T follows the redox mechanism, where CO reduces Cu+ to Cu0 and H2O oxidizes Cu0 to Cu+, maintaining the reaction cycle.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"61 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666703","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}

引用次数: 0

Preventing Loss of Selectivity during the Oxidative Dehydrogenation of Propane over Supported Vanadium Catalysts

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-20 DOI: 10.1021/acscatal.5c00720

Abdullah J. Al Abdulghani, Unni Kurumbail, Son Dong, Natalie R. Altvater, Rick W. Dorn, Melissa C. Cendejas, William P. McDermott, Theodore O. Agbi, Collin M. Queen, Matias Alvear, Ashley R. Head, Aaron J. Rossini, Ive Hermans

{"title":"Preventing Loss of Selectivity during the Oxidative Dehydrogenation of Propane over Supported Vanadium Catalysts","authors":"Abdullah J. Al Abdulghani, Unni Kurumbail, Son Dong, Natalie R. Altvater, Rick W. Dorn, Melissa C. Cendejas, William P. McDermott, Theodore O. Agbi, Collin M. Queen, Matias Alvear, Ashley R. Head, Aaron J. Rossini, Ive Hermans","doi":"10.1021/acscatal.5c00720","DOIUrl":"https://doi.org/10.1021/acscatal.5c00720","url":null,"abstract":"Supported vanadium materials are promising catalysts for the oxidative dehydrogenation of propane to propylene (ODHP), but a lack of mechanistic understanding limits the rational design of catalysts with improved propylene selectivity. Adding Ta to V/SiO2 increases the propylene selectivity, as well as the activity, leading to superior performance compared to state-of-the-art boron-based systems. In this contribution, we utilize this surprising promotional effect of Ta to elucidate key elements of the mechanistic cycle. Through a combination of characterization techniques, computational modeling, and kinetic experiments, we show that the catalytic cycle over V/SiO2 likely involves the formation of an isopropyl alcohol intermediate, the fate of which is in kinetic competition between subsequent dehydration to propylene or further oxidation. Furthermore, we show that the relatively facile propylene overoxidation observed for these materials occurs via the epoxidation of propylene by a proposed peroxovanadium intermediate, rather than the abstraction of propylene’s allylic C–H bond as previously assumed. Using these key mechanistic features, we rationalize the enhanced selectivity and activity of Ta promotion. Our mechanistic framework offers avenues for future catalyst development to improve supported vanadium materials for ODHP.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"27 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666704","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}

引用次数: 0

Unveiling the Nature of High Catalytic Activity of the Zr1@Mo2TiC2 Single-Atom Catalyst for N2-to-NH3 Thermal Conversion

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-19 DOI: 10.1021/acscatal.5c00809

Yu-Ling Tang, Cong Zhang, Haiyan Wang, Jin-Xia Liang, Chun Zhu, Jun Li

{"title":"Unveiling the Nature of High Catalytic Activity of the Zr1@Mo2TiC2 Single-Atom Catalyst for N2-to-NH3 Thermal Conversion","authors":"Yu-Ling Tang, Cong Zhang, Haiyan Wang, Jin-Xia Liang, Chun Zhu, Jun Li","doi":"10.1021/acscatal.5c00809","DOIUrl":"https://doi.org/10.1021/acscatal.5c00809","url":null,"abstract":"Two-dimensional (2D) MXene nanomaterial-supported single-atom catalysts (SACs) have attracted extensive attention due to their high stability and catalytic performance in ammonia synthesis. Herein, density functional theory (DFT) calculations were performed to systematically investigate the structural stability and electronic properties of M1@Mo2TiC2 SACs. Among these SACs, Zr1@Mo2TiC2 was screened as the most stable SAC, on which N2 can be directly activated well, akin to its activation on Fe(211) C7 (iron atoms with seven nearest neighbors) and Ru(0001) B5 sites, and H2 can also be adsorbed dissociatively. Further calculations indicated that N2 can be directly converted to NH3 on Zr1@Mo2TiC2 through a dissociation mechanism with a low energy barrier of 1.13 eV in the rate-determining step (RDS). Moreover, microkinetic simulations showed that the turnover frequency (TOF) of ammonia synthesis on Zr1@Mo2TiC2 is as high as 1.01 × 10–2 s–1 site–1 at 51 bar and 700 K. The nature of high catalytic activity stems from the effective σ donation from N2(3σg) → Zr(4d) and the three π back-donation from Mo(4d) → N2(1πg), yielding the well-activated *N2 with the N–N bond order of 1.5 on the Zr1Mo3 single-cluster site, which is effectively converted into NH3. Our work provides a theoretical understanding of the stability and catalytic mechanism of Zr1@Mo2TiC2 and guidance for further designing and fabricating MXene-based metal SACs for N2 fixation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"61 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654001","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}

引用次数: 0

Synthesis, Molecular Structure, and Water Electrolysis Performance of TiO2-Supported Raney-IrOx Nanoparticles for the Acidic Oxygen Evolution Reaction

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-19 DOI: 10.1021/acscatal.4c06385

Jiaqi Kang, Xingli Wang, Sebastian Möhle, Shima Farhoosh, Miklós Márton Kovács, Johannes Schmidt, Liang Liang, Matthias Kroschel, Sören Selve, Michael Haumann, Dominik Dworschak, Holger Dau, Peter Strasser

{"title":"Synthesis, Molecular Structure, and Water Electrolysis Performance of TiO2-Supported Raney-IrOx Nanoparticles for the Acidic Oxygen Evolution Reaction","authors":"Jiaqi Kang, Xingli Wang, Sebastian Möhle, Shima Farhoosh, Miklós Márton Kovács, Johannes Schmidt, Liang Liang, Matthias Kroschel, Sören Selve, Michael Haumann, Dominik Dworschak, Holger Dau, Peter Strasser","doi":"10.1021/acscatal.4c06385","DOIUrl":"https://doi.org/10.1021/acscatal.4c06385","url":null,"abstract":"Developing low-cost, highly active, and stable catalysts for the acidic oxygen evolution reaction (OER) at the proton exchange membrane (PEM) water electrolyzer anodes remains a scientific priority. Reducing the iridium loading while increasing the intrinsic activity of the catalysts is essential for cost-effective hydrogen production. Here, we address a family of TiO2-supported Raney-IrOx catalysts with low iridium loading and high activity in single-cell PEM water electrolyzer anode environments. A controlled Raney-type Ni leaching process of pristine, supported IrNi alloy phases forms crystalline IrOx nanoparticles (NPs) featuring metallic Ir-rich cores surrounded by more amorphous IrOx surfaces. This structure is shown to be conducive to catalytic activity and the suppression of membrane poisoning due to Ni degradation. The trace amounts of Ni remaining after leaching in the IrOx NPs result in heterogeneous crystal structure and induce local lattice strain. Further, we synthetically strike a balance between conductivity and activity and succeed to narrow down the notorious large performance gap between liquid electrolyte rotating disk electrodes (RDEs) and single-cell membrane electrode assembly (MEA) electrolyzer measurements. OER stability numbers (S-numbers) of the identified Raney-IrOx anode catalysts surpass commercial IrO2 catalysts, confirming the stability of these catalysts. The PEM electrolyzer tests reveal that Raney-IrOx anodes achieve 3 A cm–2 at 1.8 V with a low geometric Ir loading of ca. 0.3 mgIr cm–2, meeting the technically important power specific Ir utilization target of 0.05 gIr/kW.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"200 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653997","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}

引用次数: 0

Applications of Cobalt Phosphide-Based Materials in Electrocatalysis

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-19 DOI: 10.1021/acscatal.5c00623

Wei Zhang, Ning Han, Yuhai Dou, Xuan Zhang, Jiangshui Luo, Shixue Dou, Jan Fransaer

{"title":"Applications of Cobalt Phosphide-Based Materials in Electrocatalysis","authors":"Wei Zhang, Ning Han, Yuhai Dou, Xuan Zhang, Jiangshui Luo, Shixue Dou, Jan Fransaer","doi":"10.1021/acscatal.5c00623","DOIUrl":"https://doi.org/10.1021/acscatal.5c00623","url":null,"abstract":"Electrocatalysis plays a pivotal role in advancing clean energy technologies to address pressing environmental and energy challenges. However, the design and fabrication of cost-effective electrocatalysts with high activity and long-term stability remain significant hurdles. Among the reported electrocatalysts, Co-P-based materials such as Co2P, CoP, and CoP2 have emerged as promising candidates for various applications, including water splitting, polysulfide electrocatalysis, and oxygen reduction reactions. Their appeal lies in their advantageous electronic structures, cost-effectiveness, excellent electrocatalytic performance, and robust chemical stability. This review begins with an overview of diverse electrocatalytic processes and their fundamental mechanisms. It then explores various synthesis strategies for Co-P-based materials, highlighting their applications across different electrocatalytic systems. A comprehensive discussion of prevalent strategies for optimizing Co-P-based materials in electrocatalysis is provided, with water splitting serving as a representative example. Following an in-depth analysis of active sites in Co-P-based materials relevant to water splitting, insights from our research are presented. Additionally, the critical influence of precursor materials and their transformation pathways on the properties of the resulting oxygen evolution reaction electrocatalysts is thoroughly discussed. Finally, the review concludes by outlining the challenges and future perspectives for designing highly efficient Co-P-based electrocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"19 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143653998","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}

引用次数: 0

Excited-State Palladium-Catalyzed Radical Allylic Alkylation: Rapid Access to C2-Allyl Carbohydrates

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-19 DOI: 10.1021/acscatal.5c00555

Wang Yao, Jaclyn N. Mauro, Yue Fu, Hang Chen, Peng Liu, Ming-Yu Ngai

引用次数: 0

Ligand Design for Aerobic Pd-Catalyzed Styrene Production via the One-Step C–H/C–H Coupling of Benzene and Ethylene

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-19 DOI: 10.1021/acscatal.5c00054

Frederick Martens, Conrad Bonné, Igor Beckers, Luxuan Guo, Sam Van Minnebruggen, Harry Poels-Ryckeboer, Jeremy Harvey, Aram Bugaev, Jannick Vercammen, Dirk E. De Vos

引用次数: 0

Electron-Deficient Coδ+ Induced by Synergistic Co–ZnO–ZnAl2O4 Interface Interactions for Enhanced N-Propylcarbazole Hydrogenation

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-19 DOI: 10.1021/acscatal.4c07988

Yinheng Zhao, Ting Zhu, Jiaqi Li, Chenggen Li, Wenxin Lu, Jia Liu, Dazhou Zhang, Yuan Dong, Ming Yang

{"title":"Electron-Deficient Coδ+ Induced by Synergistic Co–ZnO–ZnAl2O4 Interface Interactions for Enhanced N-Propylcarbazole Hydrogenation","authors":"Yinheng Zhao, Ting Zhu, Jiaqi Li, Chenggen Li, Wenxin Lu, Jia Liu, Dazhou Zhang, Yuan Dong, Ming Yang","doi":"10.1021/acscatal.4c07988","DOIUrl":"https://doi.org/10.1021/acscatal.4c07988","url":null,"abstract":"Developing efficient and cost-effective hydrogenation catalysts is essential for advancing liquid organic hydrogen carrier (LOHC) technology. In this study, ZnO-modified Co/Al2O3 catalysts were synthesized via coprecipitation and evaluated for N-propylcarbazole (NPCZ) hydrogenation. Among them, Co50Zn2Al8 achieved complete hydrogenation within 60 min under mild conditions (150 °C, 7 MPa), demonstrating outstanding activity. This performance is attributed to the synergistic Co–ZnO–ZnAl2O4 interface, which induces electron transfer from Co to ZnO, generating electron-deficient Coδ+ species. These species enhance hydrogen dissociation and NPCZ adsorption, accelerating the reaction. ZnO also forms a protective layer around Co particles, preventing strong Co–Al2O3 interactions and suppressing inactive CoAl2O4 formation, thereby improving the Co reducibility and dispersion. Advanced characterization and density functional theory calculations provided insights into the electronic and structural effects of ZnO on the catalytic mechanism. Stability tests confirmed that Co50Zn2Al8 retained high activity over five cycles without significant deactivation. The synergistic Co–ZnO interaction reduces the activation energy and improves reaction rates, making Co50Zn2Al8 a highly efficient and durable catalyst. With its low cost, high activity, and remarkable stability, Co50Zn2Al8 shows great potential for LOHC hydrogenation, offering a promising pathway for efficient hydrogen storage and utilization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661094","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}

引用次数: 0

Recent Advances in Asymmetric Synthesis of Chiral-at-Sulfur Sulfoximines

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-03-19 DOI: 10.1021/acscatal.5c01027

Muhammad Suleman, Tianming Huang, Tao Zhou, Zhiyuan Chen, Bingfeng Shi

引用次数: 0