ACS Catalysis 最新文献

{"title":"Origin of Electrocatalytic Selectivity during the Oxygen Reduction Reaction on Au(111)","authors":"Elias Diesen, Alexandra M. Dudzinski, Karsten Reuter, Vanessa J. Bukas","doi":"10.1021/acscatal.4c04413","DOIUrl":"https://doi.org/10.1021/acscatal.4c04413","url":null,"abstract":"A puzzling observation during the oxygen reduction reaction (ORR) on weak-binding electrodes such as Au is the preference to form hydrogen peroxide (H₂O₂) instead of the thermodynamically favored water product. This selectivity cannot be explained on the basis of thermodynamic reaction models that simply assume a series of proton-coupled electron transfers (PCETs). Here, we use ab initio molecular dynamics along with umbrella sampling to obtain free energy profiles for competing key ORR steps on Au(111). Our comparison includes not only PCETs but also “chemical” reaction steps that do not include an explicit faradaic charge transfer, such as desorption or surface dissociation. This allows one to explore favorable reaction paths while varying the capacitive charging to represent realistic ORR potentials. Our results show that all reaction steps competing with H₂O₂ formation have sizable kinetic barriers and are thus prohibited, even though they may be thermodynamically favored. We find that this situation does not change under more reducing conditions and specifically determines the “nobleness” of Au as playing a decisive role in preventing O–O bond scission. It is thus not the applied potential but the underlying chemistry that drives the ORR selectivity. Our study overall further highlights the kinetic competition between PCET and non-PCET steps that cannot be resolved via simple Bro̷nsted–Evans–Polanyi scaling relations.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654000","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":"Surface Structure-Dependent Mechanistic Modulation of the Selective Oxidative Dehydrogenation of Ethane with CO2 over Iron Oxide Catalysts","authors":"Li Kang, Feigang Zhao, Jingyang Zhang, Tiantian Xiao, Shengping Wang, Xinbin Ma","doi":"10.1021/acscatal.4c08099","DOIUrl":"https://doi.org/10.1021/acscatal.4c08099","url":null,"abstract":"The selective oxidative dehydrogenation of ethane with CO₂ (CO₂–ODHE) catalyzed by iron oxide (FeO_<i>x</i>) provides a CO₂-utilizing route for ethylene production, simultaneously utilizing greenhouse gases and enabling the efficient conversion of light alkanes. However, the diverse phases formed by FeO_<i>x</i> catalysts under the reaction conditions expose surface structures with distinct Fe and O atom arrangements, complicating the identification of reactive active sites. In this study, we demonstrate the pivotal role of surface structures of FeO_<i>x</i> catalysts in governing the ethylene formation activity and selectivity. Among various phases, Fe₃O₄ with octahedrally coordinated Fe terminations (Fe₃O₄–B2) is characterized by frustrated Lewis pair (FLP) and low oxygen vacancy formation energy, which synergistically promote ethane activation and facilitate the CO₂-mediated regeneration of active sites via the Mars-van Krevelen mechanism. Additionally, the coordination geometry of surface Fe atoms optimizes the interaction between the Fe 4s orbitals and the π* orbitals of the ethyl group (C₂H₅), stabilizing C₂H₅ adsorption. This electronic stabilization is complemented by spatial confinement imposed by FLP, effectively suppressing C₂H₅ migration and inhibiting the formation of CH₃CH intermediates in the dry reforming of ethane, thereby enhancing the ethylene selectivity. The synergistic role of electronic and geometric effects of the Fe₃O₄–B2 surface structure remarkably enhances ethylene selectivity while maintaining high catalytic activity. These findings provide mechanistic insights into the structure–activity–selectivity relationships of FeO_<i>x</i> catalysts and offer a solid theoretical foundation for designing advanced catalysts for efficient, CO₂-integrated hydrocarbon conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640420","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":"Z-Selective Semihydrogenation of Alkynes Catalyzed by a Co(I)PCNHCP Pincer Complex: A Simple, Fast, and Practical Methodology","authors":"Tofayel Sheikh Mohammad, Pavel Sakharov, Sakthi Raje, Graham de Ruiter","doi":"10.1021/acscatal.5c00792","DOIUrl":"https://doi.org/10.1021/acscatal.5c00792","url":null,"abstract":"The stereoselective synthesis of alkenes from their corresponding internal alkynes is a highly desirable and atom-economical reaction that is typically performed via transfer hydrogenation. Very few practical methods have been developed that allow for the direct hydrogenation of alkynes under mild reaction conditions and with high stereoselectivities. Here, we demonstrated that a well-defined cobalt catalyst [(PC_NHCP)Co(N₂)][BAr₄^F] (<b>1</b>) catalyzes the semihydrogenation of alkynes under mild conditions (25 °C; 1 bar H₂) and with high stereoselectivities (&gt;99:1). The reaction does not require any additives, is fast (&lt;60 min), and is compatible with a variety of functional groups that include aldehydes, ketones, esters, and alcohols. Even natural products can be used with our hydrogenation protocol highlighting its versatility. Our mechanistic studies indicate the presence of a transient Co(III)-dihydride that is responsible for the hydrogenation of the herein reported internal and terminal alkynes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"55 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640419","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":"Influence of the Mn Promoter on the Composition and Activity of the Adsorbed Phase in the Carbon Paths of the CO Hydrogenation Reaction on 20 wt % Co/MnOx-Al2O3: An Operando-SSITKA and Transient Kinetic Study","authors":"Michalis A. Vasiliades, Denzil Moodley, Renier Crous, Jana Potgieter, Thys Botha, Angelos M. Efstathiou","doi":"10.1021/acscatal.4c07921","DOIUrl":"https://doi.org/10.1021/acscatal.4c07921","url":null,"abstract":"Herein, we explored the influence of the Mn/Co molar ratio (0.011–0.268) on the composition and activity of the adsorbed phase established during CO hydrogenation at 230 °C (P_T = 1.2 bar) over a 20 wt % Co/MnO_<i>x</i>-Al₂O₃ industrially relevant catalyst as a function of time-on-stream, TOS (2–50 h). Correlations between surface coverages of active and inactive carbonaceous species, site activity (k, s^–1) for methanation and chain growth, and the Mn/Co molar ratio for optimum performance were derived. ¹³CO-SSITKA revealed that the Mn/Co molar ratio and TOS significantly influenced the dynamic net rate of CO chemisorption and that of −CH_<i>x</i> formation, θ_CO, θ_CHx, TOF_CH4, and k (s^–1) of methanation and chain growth kinetic parameters in a diverse way. An optimum Mn/Co ratio of 0.111 was found for chain growth (C₂–C₅ hydrocarbons) and which was related to the dependence of θ_CO and θ_CHx on the Mn/Co ratio. Dynamic hydrogen chemisorption at 100 °C and H₂-TPD studies indicated the increase of θ_H and alteration of H-chemisorption site distribution with increasing Mn/Co ratio. <i>Operando</i> DRIFTS-mass spectrometry transient hydrogenation of two linear type adsorbed CO-s revealed the influence of Mn/Co ratio on their relative hydrogenation activity (k), highlighting the importance of the population of CO chemisorption sites of lower hydrogenation activity toward methane. Structural and topological information for the presence of the MnO_<i>x</i> promoter in Co/γ-Al₂O₃ was obtained via HRTEM/EDX (RGB mapping). Highly dispersed MnO_<i>x</i> clusters were formed on the cobalt surface for low Mn/Co ratios (ca. 0.011), while for higher Mn/Co ratios both MnO_<i>x</i> particles surrounded the Co particles (10–12 nm) and Mn chemically interacted with the Co surface (e.g., Co-MnO clusters and agglomerates). It is proposed that optimum chain growth is the result of a balance between unpromoted and Mn-promoted cobalt surface regions for the present 20 wt % Co/MnO_<i>x</i>-Al₂O₃ catalytic system. This work paved the way for deriving reliable correlations between important kinetic parameters of CO hydrogenation that control the chain growth in FTS for Mn-based and other promoted Co-based FTS catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"54 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635467","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":"Coupling Plastic Upgrading and Photocatalysis: Catalytic Mechanisms and Design Principles","authors":"Zongyang Ya, Shengbo Zhang, Dong Xu, Hua Wang, Mei Li","doi":"10.1021/acscatal.5c00139","DOIUrl":"https://doi.org/10.1021/acscatal.5c00139","url":null,"abstract":"Converting plastic wastes into valuable chemicals and fuels provides an attractive alternative solution. However, current catalytic technologies often require rigorous conditions such as high temperature, high pressure, and caustic bases, resulting in high energy costs and secondary environmental contamination. Recently, integrating plastic upgrading with photocatalysis into one reaction system has been proven to be an effective approach that can sufficiently utilize photogenerated electrons and holes to achieve sustainable economic development. In this review, we summarize current advances in coupling plastic upgrading and photocatalysis by focusing on the catalyst selection, design principles of these integrated systems, including photoreforming H₂ evolution, photocoupling CO₂ reduction, and photo-oxidation, and the underlying catalytic mechanisms, including holes and reactive oxygen species mechanisms. We also assess the economic feasibility and environmental impact of these integrated technologies based on techno-economic analysis and life cycle assessment. The ongoing challenges and future research directions in this field are critically discussed. We believe that this review will inspire more creativity in designing such win–win coupled photoredox reaction systems.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640005","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":"Unlocking Isonitrile Insertion with N-Centered Radicals: A General Synthetic Strategy toward Quinazolinone Alkaloids by Synergistic Photo/Copper Catalysis","authors":"Xiaoyu Guo, Hui Wang, Zhongyan Hu, Yu Zhao, Jinhuan Dong, Kangbao Zhong, Yu Lan, Xianxiu Xu","doi":"10.1021/acscatal.5c00608","DOIUrl":"https://doi.org/10.1021/acscatal.5c00608","url":null,"abstract":"Significant progress has been achieved in radical isonitrile insertion reactions, yet the reactivity of isonitriles toward <i>N</i>-centered radicals remains underexplored. Herein, we report an efficient method that enables isonitrile insertion into <i>N</i>-centered radicals, facilitated by a synergistic photocatalyst/copper catalytic system. This insertion triggers a highly efficient cascade cyclization that constitutes a flexible strategy for synthesizing alkaloids with a fused quinolizinone scaffold. Alkaloids, including luotonin A, rutaecarpine, and 2-methoxy-13-methylrutaecarpine, along with 37 natural product-like molecules, were synthesized by this method in a single step, starting from readily synthesizable <i>ortho</i>-isocyano-<i>N</i>-tosylbenzamides as <i>N</i>-radical precursors. Mechanistic investigations, encompassing photophysical, electrochemical, Einstein–Podolsky–Rosen studies, and density functional theory calculations, imply that arylisonitrile-Cu(I) complexes serve as effective reductants, quenching the excited iridium photocatalyst via single-electron transfer at the onset of the reaction. Crucially, the Cu(I)/Cu(II)/Cu(III) catalytic cycle plays a key role in sustaining the photocatalytic process and driving the radical cascade cyclization.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"55 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635465","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":"Cooperative Ligand-Enabled Facile Synthesis of γ-C(sp3)–H Alkenylated Aliphatic Amides: A Comprehensive Protocol to Free N–H Tolerance","authors":"Suparna Dutta, Nikunj Kumar, Minhajul Islam, Wajid Ali, Puneet Gupta, Debabrata Maiti","doi":"10.1021/acscatal.4c07905","DOIUrl":"https://doi.org/10.1021/acscatal.4c07905","url":null,"abstract":"Site-selective distal C(<i>sp³</i>)–H functionalization of aliphatic amides is one of the longstanding challenges in synthetic methodology. Herein, we report a palladium-catalyzed <i>γ</i>-C(<i>sp³</i>)–H alkenylation of native aliphatic amide, exploiting a cooperative ligand approach to harness the weak coordinating ability of the amide functional group. Apart from tertiary amides, the protocol developed by us is also suitable for secondary, primary, and relatively unbiased <i>β</i>-C–H bond-containing amides, which remain unexplored till date. Theoretical calculations revealed that the combination of ligands is crucial for the reaction. Monoprotected amino acid (MPAA) ligand is essential for the concerted metalation–deprotonation (CMD) step of the C–H activation, occurring <i>via</i> a distinctive [5,6]-palladacyclic transition state. Meanwhile, the pyridone ligand plays a key role in forming the catalyst resting state, promoting <i>β</i>-hydride elimination, and facilitating product release. Both experimental and computational mechanistic studies confirm that C–H activation is the rate-limiting step in this process, providing crucial insights into the factors governing regioselective functionalization at the distant <i>γ</i>-site.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"136 3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627384","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":"CatTSunami: Accelerating Transition State Energy Calculations with Pretrained Graph Neural Networks","authors":"Brook Wander, Muhammed Shuaibi, John R. Kitchin, Zachary W. Ulissi, C. Lawrence Zitnick","doi":"10.1021/acscatal.4c04272","DOIUrl":"https://doi.org/10.1021/acscatal.4c04272","url":null,"abstract":"Direct access to transition state energies at low computational cost unlocks the possibility of accelerating catalyst discovery. We show that the top performing graph neural network potential trained on the OC20 data set, a related but different task, is able to find transition states energetically similar (within 0.1 eV) to density functional theory (DFT) 91% of the time with a 28× speedup. This speaks to the generalizability of the models, having never been explicitly trained on reactions, the machine learned potential approximates the potential energy surface well enough to be performant for this auxiliary task. We introduce the Open Catalyst 2020 Nudged Elastic Band (OC20NEB) data set, which is made of 932 DFT nudged elastic band calculations, to benchmark machine learned model performance on transition state energies. To demonstrate the efficacy of this approach, we for the first time explicitly treated a large reaction network with 61 intermediates and 174 dissociation reactions at DFT resolution (40 meV). To find low energy transition states we densely enumerate many possible NEBs. Using DFT this would have taken 52 GPU years. With ML we realized a 1500× speedup for dense enumerations, using just 12 GPU days of compute. Similar searches for complete reaction networks could become routine using the approach presented here. Finally, we constructed an ammonia synthesis activity volcano and systematically found lower energy configurations of the transition states and intermediates on six stepped unary surfaces than had previously been reported. This scalable approach offers a more complete treatment of configurational space to improve and accelerate catalyst discovery.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619060","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":"The Implementation and Impact of Chemical High-Throughput Experimentation at AstraZeneca","authors":"James J. Douglas, Andrew D. Campbell, David Buttar, Gary Fairley, Magnus J. Johansson, Allyson C. Mcintyre, Anthony J. Metrano, Richard S. Morales, Rachel H. Munday, Thanh V. Q. Nguyen, Samantha Staniland, Michele Tavanti, Erik Weis, Simon D. Yates, Zirong Zhang","doi":"10.1021/acscatal.4c07969","DOIUrl":"https://doi.org/10.1021/acscatal.4c07969","url":null,"abstract":"High-throughput experimentation (HTE) is a critical tool in modern pharmaceutical discovery and development. The ability to perform multiple parallel experiments in miniaturized plate-based formats has revolutionized how chemical reactions are optimized. HTE has been especially enabling for catalytic reactions, where the complexity of factors influencing the outcome makes the HTE approach especially suitable. We detail AstraZeneca’s 20-year journey with HTE, from early beginnings to a global community of HTE specialists that are critical to the delivery of our complex portfolio with reduced environmental impact. With an emphasis on catalytic reactions, we provide relevant case study examples from across discovery and development, discuss current technology, data science and workflows, and provide insights into where we see future advances in HTE.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"183 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608371","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":"Monomer Discrimination in the Enantioselective Living Coordinative Chain Transfer Polymerization of α,ω-Nonconjugated Dienes vs α-Olefins","authors":"Cole M. Burrows,&nbsp;Peter Y. Zavalij and Lawrence R. Sita*,&nbsp;","doi":"10.1021/acscatal.5c0055810.1021/acscatal.5c00558","DOIUrl":"https://doi.org/10.1021/acscatal.5c00558https://doi.org/10.1021/acscatal.5c00558","url":null,"abstract":"<p >The stereoselective living coordinative polymerization (LCP) of α-olefins and α,ω-nonconjugated dienes can be achieved using initiators derived from the homochiral, configurationally stable, monocyclopentadienyl, 7- and 9-membered-ring <i>cycloamidinate</i> group 4 metal complexes, <b>1</b>–<b>3</b>, respectively, as preinitiators in combination with borate <b>B1</b> as activating co-initiator. However, yield, molar mass (<i>M</i>_n), and degree of stereoregularity in these LCPs were found to be highly dependent upon initial monomer concentration due to decreased magnitudes for monomer complexation and site isomerization, <i>K</i>_M, and <i>K</i>_SI, respectively. The <i>enantioselective</i> living coordinative chain transfer polymerization (LCCTP) of 1,5-hexadiene using the initiator derived from <b>1</b>/<b>B1</b> and excess equivalents of ZnEt₂ as chain transfer agent (CTA) provides isotactic <i>cis</i>/<i>trans</i> poly(methylene-1,3-cyclopentane) (PMCP) in high yield. In contrast, under identical conditions, all attempts to carry out the enantioselective LCCTP of 1-hexene failed. It is proposed that this unprecedented discrimination of polymerizability between the two monomer types for LCCTP is due to stark differences in conformational freedom of the growing polyolefin chains. More specifically, in the case of the rigid-rod nature of growing PMCP, reversible chain transfer is not sterically impeded and can occur as required, whereas the unrestricted conformational flexibility of side chains in poly(1-hexene) creates a steric barrier that prohibits chain transfer to occur after just a few monomer insertions. Collectively, these results provide insights for designs of the next generation of enantiopure and configurationally stable cycloamidinate preinitiators that can potentially lead to the successful enantioselective LCCTP of both α,ω-nonconjugated dienes and α-olefins with high stereoregularity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 6","pages":"5219–5228 5219–5228"},"PeriodicalIF":11.3,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666824","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}