ACS Catalysis 最新文献

{"title":"Modeling-Assisted Elucidation of the Organosolv Lignin Depolymerization: Lessons Learned from β-Ether Cleavage over Ni/C","authors":"Tina Ročnik Kozmelj, Edita Jasiukaitytė-Grojzdek, Matej Huš, Miha Grilc, Blaž Likozar","doi":"10.1021/acscatal.4c06058","DOIUrl":"https://doi.org/10.1021/acscatal.4c06058","url":null,"abstract":"The complexity of lignin is a major challenge to overcome in order to develop a complete biorefinery concept for the biobased community. Therefore, the lignin model compound 2-phenoxy-1-phenylethanol was used to design lignin depolymerization. We proposed a two-step mechanism involving predehydrogenation at the C_α-position, removal of the OH group, and subsequent cleavage of the β-<i>O</i>-4 bond at the C_β-position into phenol and ethylbenzene. The study was supported by density functional theory and kinetic modeling to evaluate the activation barriers for the cleavage of the β-<i>O</i>-4 bond in the dimeric lignin compound. The activation energies for predehydrogenation and cleavage at the C_β-position of phenethoxybenzene were predicted to be 71 kJ mol^–1 and 9 kJ mol^–1, respectively, suggesting that the predehydrogenation is beneficial for the cleavage of the β-<i>O</i>-4 bond as it lowers the activation energy. Additionally, the removal of the OH group at the C_α-position increased the reaction rate constant for the β-<i>O</i>-4 bond cleavage to 0.68 min^–1. By comparing lignin depolymerization and the cleavage of the β-<i>O</i>-4 bond in the dimeric lignin compound, the study provided mechanistic insights and suggested process- and structure-dependent correlations. Similarities were found in the process mechanism of aliphatic OH group removal and cleavage at the C_β-position, while the temperature increase contributed more to the enhanced cleavage of the β-<i>O</i>-4 bond in the lignin model compound compared to the lignin macromolecule. On the other hand, the reaction conditions affected the structural characteristics of the products after lignin depolymerization, especially the molecular weight and functionality of the oligomeric fragments. We have found that using a lignin model component is beneficial for fundamental research, but correlating the results with the real lignin sample is essential to improve the potential of lignin in the biorefinery concept.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935392","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":"Dynamic Catalysis Multiscale Simulations for Nonoxidative Coupling of Methane Using Light and Heat","authors":"Juganta K. Roy, Mona Abdelgaid, Henrik Grönbeck, Giannis Mpourmpakis","doi":"10.1021/acscatal.4c04312","DOIUrl":"https://doi.org/10.1021/acscatal.4c04312","url":null,"abstract":"Methane (CH₄) activation and conversion under mild reaction conditions are a great challenge for the chemical industry. Photocatalysis is attractive for activating inert C–H bonds of CH₄ at room temperature. Specifically, photocatalytic nonoxidative coupling of CH₄ (NOCM) is a promising process to produce ethane (C₂-hydrocarbon) and H₂. Different oxide-based photocatalysts have been used for room-temperature NOCM, and TiO₂ is a potential photocatalyst with a bandgap that can capture photons in the UV region. However, a fundamental understanding of the NOCM mechanism on TiO₂ is still missing. Herein, we apply multiscale modeling, combining density functional theory (DFT) calculations with kinetic Monte Carlo (kMC) simulations to investigate the photocatalytic NOCM on a rutile TiO₂(110) surface. DFT calculations revealed that the photogenerated holes mediate the homolytic activation of CH₄ via the formation of methyl radicals with an activation barrier that is 70% lower than that of the conventional thermocatalytic route. The generated methyl radicals further recombine to form ethane. The detailed reaction pathway energetics investigated with DFT-based kMC simulations revealed that ethane can be formed at 315.15 K, but the dissociated hydrogens poison the catalyst surface. Further thermocatalytic simulations revealed that increasing the temperature by thermal heating (ca. 690.15 K) facilitated H₂ formation and catalyst regeneration. Importantly, we demonstrate how photo- and thermocatalytic modes can be combined, facilitating NOCM on TiO₂ and a route to enable dynamic catalysis simulations through multiscale modeling, opening alternative avenues in computational catalyst discovery.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935380","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":"Pt–Co Single-Atom Alloy toward Furfural Hydrogenation–Rearrangement Tandem Reaction in the Aqueous Phase","authors":"Yuanjing Zhang, Guanyi Zhang, Quandong Hou, Shiquan Zhao, Si Wang, Enze Xu, Lei Wang, Xin Zhang, Feng Li, Yusen Yang, Min Wei","doi":"10.1021/acscatal.4c07190","DOIUrl":"https://doi.org/10.1021/acscatal.4c07190","url":null,"abstract":"Aqueous-phase tandem reactions, as a fundamental aspect of green chemistry, hold a crucial position in the contemporary synthesis of fine chemicals, wherein the advancement of high-performance heterogeneous catalysts remains a formidable challenge. Herein, we report a Pt₁Co_<i>n</i> single-atom alloy (SAA) catalyst in which Pt single atoms are immobilized onto the surface of Co nanoparticles through Pt–Co coordination. The Pt₁Co_<i>n</i> SAA catalyst exhibits a high chemoselectivity for the aqueous-phase hydrogenation–rearrangement reaction of furfural (FAL) to cyclopentanol (CPL) (yield: &gt;93%, considering the carbon loss), with a TOF value of 2257 h^–1 (based on Pt). A joint investigation based on reaction dynamics, isotope-label tracing experiments, EPR, and <i>in situ</i> FT-IR verifies a five-step consecutive tandem reaction pathway for the formation of CPL. Notably, during the reaction, the rapid exchange of hydrogen atoms would occur between activated hydrogen species and the water solvent. Furthermore, the water molecule does not serve as a H-donor but is involved in the rearrangement reaction in the side chain of the furan ring. Kinetic studies combined with DFT calculations substantiate that the Pt–Co interface sites effectively lower the energy barrier of the cyclopentanone (CPO) hydrogenation step via facilitating activation adsorption of the carbonyl group, accounting for the largely enhanced catalytic behavior. This study sheds light on the advancement of a highly efficient and stable heterogeneous catalyst for a biomass upgrading reaction in the aqueous phase.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"35 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935383","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":"Mechanistic Insights into Nitrile and Alkyne Covalent Inhibitors of the SARS-CoV-2 Main Protease","authors":"Ashim Nandi, Mojgan Asadi, Aoxuan Zhang, Zhen T. Chu, Arieh Warshel","doi":"10.1021/acscatal.4c06020","DOIUrl":"https://doi.org/10.1021/acscatal.4c06020","url":null,"abstract":"The treatment of SARS-CoV-2 can be accomplished by effective suppression of its 3CL protease (3CL^pro), also known as the main protease (M^pro) and nonstructural protein 5 (nsp5). Covalent inhibitors can irreversibly and selectively disable the protease, particularly when they are highly exothermic. Herein we investigated the distinct kinetic behaviors exhibited by two covalently linked SARS-CoV-2 inhibitors. One of these inhibitors features a nitrile reactive group, while the other has this group replaced by an alkyne group, a less reactive electrophile. Our investigations involve the assessment of the free energy surfaces of the key feasible mechanisms: that is, direct and water-assisted mechanisms involved in the rate-determining proton-transfer nucleophilic attack step through the utilization of both ab initio and empirical valence bond (EVB) simulations. The calculated free energy profiles show that substituting the nitrile group with alkyne increases the chemical barrier but leads to very exothermic reaction energy and is an irreversible process as opposed to nitrile, which is moderately exothermic and reversible. We also examine the time dependence of IC50 inhibition by applying an innovative kinetic simulation approach, which is particularly important in studies of covalent inhibitors with a very exothermic bonding step. Our computational approach provides a good agreement between the calculated and observed values of the time dependence results for the nitrile and alkyne inhibitors. Our approach, which is rather unique in combining calculations of the chemical barriers and the binding energy is likely to be very effective in studies of the effectiveness of other covalent inhibitors related cases.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"38 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929621","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":"Bioinspired Molecular Catalyst for Photocatalytic Semihydrogenation of Acetylene with Water as a Proton Source","authors":"Yangguang Hu, Song Wang, Zifan Jiang, Wanbing Gong, Aobo Chen, Qiaoxi Liu, Guangyu Liu, Zhiqiang Shen, Jingxiang Low, Jun Ma, Jun Jiang, Chao Gao, Yujie Xiong","doi":"10.1021/acscatal.4c04763","DOIUrl":"https://doi.org/10.1021/acscatal.4c04763","url":null,"abstract":"Selective semihydrogenation of acetylene to ethylene in ethylene-rich gas streams is a significant industrial process for obtaining high-quality polyethylene products. The conventional thermal hydrogenation route requires high temperature (&gt;100 °C), excess H₂, and noble metal Pd to achieve satisfactory conversion efficiency. Therefore, the development of a more efficient and economical low-energy method for acetylene semihydrogenation is greatly desired yet challenging. Here, we report a noble-metal-free molecular system consisting of a bioinspired [Co^II(N₄S₂)](ClO₄)₂ catalyst and a copper photosensitizer, which achieves photocatalytic semihydrogenation of acetylene to ethylene with over 96% selectivity and 96–99.9% conversion under ambient conditions for both pure acetylene and industrially relevant ethylene cofeed (containing 1% acetylene) conditions using water as a proton source. In addition, our catalytic system in deuterium oxide exhibits ability for deuterated ethylene production, which is an important building block for various deuterated polyolefins and chemicals.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"116 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917799","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":"Highly Active and Stable Al-Doped NiFe Self-Supported Oxygen Evolution Reaction Electrode for Alkaline Water Electrolysis","authors":"Byung-Jo Lee, Sang-Mun Jung, Gwonho Yu, Hyun-Yup Kim, Jaesub Kwon, Kyu-Su Kim, Jaeik Kwak, Wooseok Lee, Dong Hyeon Mok, Seoin Back, Yong-Tae Kim","doi":"10.1021/acscatal.4c04393","DOIUrl":"https://doi.org/10.1021/acscatal.4c04393","url":null,"abstract":"Alkaline water electrolysis (AWE), a predominant technology for large-scale industrial hydrogen production, faces limitations in commercialization owing to the inadequate catalytic activity and stability of oxygen evolution reaction (OER) electrocatalysts. This study introduces a NiFeAl self-supported electrode characterized by high activity and stability for the OER and outlines a rational design strategy for NiFe (oxy)hydroxide-based self-supported electrodes. The introduction of Al, a ternary dopant with relatively low electronegativity and a small ionic radius, into the NiFe electrode effectively controls the adsorption energy of O-intermediates and facilitates the deprotonation of adsorbed OH*, thereby accelerating the OER. Remarkably, the NiFeAl self-supported electrode demonstrates approximately 50% enhanced operational activity (0.71 A cm^–2 at 1.8 V) compared to NiFe alongside exceptional stability (&gt;72 h at 0.6 A cm^–2) in OER within an AWE single cell. These findings highlight the significant potential of the NiFeAl electrode for application in AWE for efficient, large-scale hydrogen production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917796","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":"Construction of Highly Active Fe5C2–FeCo Interfacial Sites for Oriented Synthesis of Light Olefins from CO2 Hydrogenation","authors":"Teng Li, Heng Zhao, Lisheng Guo, Guangbo Liu, Jinhu Wu, Tao Xing, Tao Li, Qiang Liu, Jiancai Sui, Yitong Han, Jiaming Liang, Yingluo He, Noritatsu Tsubaki","doi":"10.1021/acscatal.4c06001","DOIUrl":"https://doi.org/10.1021/acscatal.4c06001","url":null,"abstract":"The hydrogenation of CO₂ into high-value chemistry is seen as one of the viable strategies for solving the energy crisis of the future. Light olefins have attracted considerable attention as basic feedstocks in the industry. In this work, a series of Fe–Co bimetallic active site catalysts were constructed by a typical sol–gel strategy. The synergistic regulation layout of the Fe–Co bimetallic active site catalyst constructed highly active interfaces and exhibited high conversion (56.9%) of CO₂, low CO selectivity (3.6%), high selectivity (40.5%) of light olefins, and remarkable light olefins yield (22.2%). The results of the associated characterization analysis indicate that the high activity interfaces formed by the synergistic regulation layout of the Fe–Co bimetallic active sites are the fundamental reason for the high yield of light olefins. The high activity interfaces formed by the introduction of cobalt drive the RWGS reaction forward (Le Chatelier’s Principle), which further enhances the CO₂ conversion. In addition, the dynamic evolution of the physical phase structure, elemental composition and valence, CO₂ and H₂ adsorption ability, and the formation process of light olefins during the reaction of Fe–Co bimetallic catalysts were analyzed by in situ DRIFT spectra and other characterizations, and a potential mechanism for the high selectivity of CO₂ hydrogenation to light olefins is further proposed. This work provides an effective and rational design strategy for the synergistic regulation layout of Fe–Co bimetals with highly active interfaces to promote efficient hydrogenation of CO₂ for the oriented synthesis of light olefins.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917843","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":"Dynamic Kinetic Reductive Grignard-Type Addition for the Construction of Axial and Central Chirality","authors":"Ya-Ping Shao, Yong-Min Liang","doi":"10.1021/acscatal.4c07172","DOIUrl":"https://doi.org/10.1021/acscatal.4c07172","url":null,"abstract":"This study describes a photoredox/cobalt dual-catalyzed asymmetric Grignard-type addition reaction, enabling the synthesis of axially chiral hexatomic (six–six) N-heterobiaryls bearing the extra chiral secondary alcohol unit via an efficient dynamic kinetic asymmetric transformation of racemic N-heterobiaryl triflate substrates. The conversion facilitated via both photoredox and classical reductive reaction conditions exhibits good functional group tolerance, a broad substrate scope, and satisfactory stereoselectivity. Furthermore, control experiments and density functional theory calculations provide preliminary mechanistic insights.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"34 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924799","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":"Regulating Heteroatom Doping-Induced Embedded Pt-M Bimetallic Sites Coupled with Ce3+-OVs for Efficient Low-Temperature Methanol Steam Reforming","authors":"Zheng Wei, Shengfang Shi, Fei Dong, Hekun Jia, Zhiling Chen, Bifeng Yin","doi":"10.1021/acscatal.4c05507","DOIUrl":"https://doi.org/10.1021/acscatal.4c05507","url":null,"abstract":"Platinum-based metal oxide catalysts confront huge challenges in achieving efficient low-temperature methanol steam reforming below 200 °C. Here, the highly dispersed metal (M) dopants coordinated with embedded Pt species at Pt-CeM (110) interface is exploited. This arrangement shortens the geometric distance between embedded Pt and doped M atoms, enabling Pt-M coordination and facilitating the formation of atomically dispersed Pt-M bimetallic sites on the catalyst surface. This unique structure promotes electron transfer across interfaces, intensifying Pt-support interactions that enhanced methanol decomposition. Meanwhile, enhanced hydrogen spillover forms Ce³⁺-OVs pairs (where OV denotes an oxygen vacancy) at the hydrogen activation stage, which promotes H₂O dissociation. Thus, the proposed mechanisms suggest the formation of dual-function centers consisting of Pt–M and Ce³⁺-OVs, which facilitated methanol decomposition and H₂O dissociation, respectively. This process involved successive dehydrogenation of methanol followed by WGS reaction via the *CO route, with the rate-determining step of *CO + *OH → *COOH being enhanced based on DFT calculations. The optimal Pt-CeCo (H₂) catalyst exhibited an extremely low start-up temperature of 140 °C and a remarkable H₂ production rate below 200 °C. This study presents an approach for synthesizing atomically dispersed bimetallic active sites with strong interfacial interactions, leading to the development of an efficient catalytic system for low-temperature methanol reforming.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"31 24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912048","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":"Dehydrogenase versus Oxidase Function: The Interplay between Substrate Binding and Flavin Microenvironment","authors":"Teresa Benedetta Guerriere, Alessandro Vancheri, Ilaria Ricotti, Stefano A. Serapian, Daniel Eggerichs, Dirk Tischler, Giorgio Colombo, Maria L. Mascotti, Marco W. Fraaije, Andrea Mattevi","doi":"10.1021/acscatal.4c05944","DOIUrl":"https://doi.org/10.1021/acscatal.4c05944","url":null,"abstract":"Redox enzymes, mostly equipped with metal or organic cofactors, can vary their reactivity with oxygen by orders of magnitude. Understanding how oxygen reactivity is controlled by the protein milieu remains an open issue, with broad implications for mechanistic enzymology and enzyme design. Here, we address this problem by focusing on a widespread group of flavoenzymes that oxidize phenolic compounds derived from microbial lignin degradation, using either oxygen or cytochrome c as an electron acceptor. A comprehensive phylogenetic analysis revealed conserved amino acid motifs in the flavin-binding site. Using a combination of kinetic, mutagenesis, structural, and computational methods, we examined the role of these residues. Our results demonstrate that subtle and localized changes in the flavin environment can drastically impact oxygen reactivity. These effects are afforded through the creation or blockade of pathways for oxygen diffusion. Substrate binding plays a crucial role by potentially obstructing oxygen access to the flavin, thus influencing the enzyme’s reactivity. The switch between oxidase and dehydrogenase functionalities is thereby achieved through targeted, site-specific amino acid replacements that finely tune the microenvironment around the flavin. Our findings explain how very similar enzymes can exhibit distinct functional properties, operating as oxidases or dehydrogenases. They further provide valuable insights for the rational design and engineering of enzymes with tailored functions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917798","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}