ACS Catalysis 最新文献

{"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 (>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":"Hydrogen Evolution and Oxygen Reduction on OH/F-Terminated Titanium Nitride MXene Reveal the Role of the Surface Termination Group in Electrocatalysis","authors":"Eugenie Pranada, Bright Ngozichukwu, Ray Yoo, Denis Johnson, Mark A. Barteau, Ahmed Abdel-Wahab, Abdoulaye Djire","doi":"10.1021/acscatal.4c05247","DOIUrl":"https://doi.org/10.1021/acscatal.4c05247","url":null,"abstract":"MXenes, a class of two-dimensional (2D) carbides and/or nitrides, are increasingly utilized in various electrochemical reduction reactions owing to their electronic conductivity, specific surface area, and tunable surface chemistry. Previous studies have indicated that the performance of MXenes in catalyzing the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is influenced by their surface termination groups. However, our understanding of how these groups affect electrocatalytic performance remains limited, especially for nitride MXenes. This work investigates the effects of termination group modification on the HER and ORR activity of Ti₄N₃ nitride MXene in alkaline media. Ti₄N₃ MXene was synthesized via oxygen-assisted molten salt fluoride etching and delaminated using different solvents, including tetramethylammonium hydroxide (TMAOH), dimethyl sulfoxide (DMSO), water (H₂O), and tetrabutylammonium hydroxide (TBAOH). Characterization through FTIR, EDS, and XPS revealed that all delaminated MXenes have hydroxyl and fluoro terminations, with the former being the predominant group. Among the samples, Ti₄N₃ delaminated with TBAOH (referred to as Ti₄N₃-TBAOH) had the highest −OH surface coverage. While the initial HER activity was comparable for all the nitride samples, we observed different onset and overpotentials after activation through chronopotentiometry, likely due to the removal of the passivation layer and the consequent increase in the −OH surface coverage. Ti₄N₃-TMAOH demonstrated the highest improvement, with a nearly 300-mV decrease in the overpotential at −10 mA/cm². For the ORR activity, all OH-terminated Ti₄N₃ MXenes exhibited very similar onset and half-wave potentials despite having different surface coverages. Overall, our results show that while varying the delamination agent alters the coverage of OH/F functional groups, it does not significantly affect the overall catalytic performance, which offers flexibility when preparing nitride MXenes for these applications. These insights provide an experimental basis to further exploration of surface modification of nitride MXenes for fuel cell and water splitting applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"203 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912044","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}

{"title":"Advancing the Synthesis for Perdeuterated Small Organic Chemicals via Electrochemical CO2 Reduction","authors":"Bjørt Óladóttir Joensen, Qiucheng Xu, Kasper Enemark-Rasmussen, Victoria Frankland, Arun Prakash Periasamy, John R. Varcoe, Ib Chorkendorff, Brian Seger","doi":"10.1021/acscatal.4c06353","DOIUrl":"https://doi.org/10.1021/acscatal.4c06353","url":null,"abstract":"High deuteration yields are difficult to attain with conventional chemical synthesis methods. In this work, we demonstrate that deuterated chemicals can be produced using electrochemical CO₂ reduction in the presence of D₂O. The absence of H₂O enables deuteration yields over 99% for products such as ethanol-<i>d</i>₆ and formate-<i>d</i>. With a D₂O solvent, the competing D₂ evolution reaction is completely suppressed at low current densities while being kept &lt;10% at a higher 300 mA/cm².","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"48 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917801","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":"Biocatalytic Efficient and Enantiocomplementary Synthesis of 3-Hydroxy-3-hydroxymethyloxindoles by Combining Halohydrin Dehalogenase and Epoxide Hydrolase","authors":"Run-Ping Miao, Hai-Xia Zhang, Kui-De Lu, Tong-Qiu Lu, Hui-Hui Wang, Yong-Zheng Chen, Nan-Wei Wan","doi":"10.1021/acscatal.4c07482","DOIUrl":"https://doi.org/10.1021/acscatal.4c07482","url":null,"abstract":"Enantiopure 3-hydroxyoxindoles are one class of basic functional molecules that hold particular interest in medicinal chemistry and drug discovery due to their diverse pharmacological properties. While many chemical methods have been developed for producing these molecules, there remains a continuous demand for more efficient and greener approaches. Herein, we present a novel dual-enzyme biocatalytic platform for the enantiocomplementary synthesis of chiral 3-hydroxy-3-hydroxymethyloxindoles, compounds that have not previously been synthesized stereoselectively. This biocatalytic platform involves the halohydrin dehalogenase-catalyzed kinetic resolution of racemic spiro-epoxyoxindoles with nitrite, paired with the epoxide hydrolase-catalyzed enantiospecific hydrolysis of the residual enantiopure spiro-epoxyoxindoles. Both enzymatic processes demonstrate high catalytic selectivity and efficiency, enabling the preparative synthesis of various (<i>R</i>)- and (<i>S</i>)-3-hydroxy-3-hydroxymethyloxindoles with high yields (up to 50%) and optical purities (up to &gt;99% <i>ee</i>). In addition, useful transformations of the chiral products were conducted to further showcase the scalability and applicability of the biocatalytic platform.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"67 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142912049","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":"Shaping the Future of Green Hydrogen Production: Overcoming Conventional Challenges with Molecular Catalysts, Immobilization, and Scalable Electrolyzers","authors":"Suhana Karim, Niharika Tanwar, Srewashi Das, Rounak Ranjit, Anwesha Banerjee, Gulafshan, Aryan Gupta, Akshai Kumar, Arnab Dutta","doi":"10.1021/acscatal.4c05986","DOIUrl":"https://doi.org/10.1021/acscatal.4c05986","url":null,"abstract":"The energy crisis is a daunting global problem that calls for innovative and supportable solutions to ensure future energy security and environmental stability. To counter this energy uncertainty, accelerating renewable-driven hydrogen production stands as a vital option to foster carbon-neutral energy infrastructure. This review conveys an overview of worldwide hydrogen generation techniques (steam methane reformation, thermochemical, biological, and electrolytic), highlighting the key features, indicating the pros and cons, and unraveling the potential environmental consequences. Herein, the conventional gray and cutting-edge green hydrogen production technologies are compared, with a focus on sustainable water electrolysis utilizing renewable energy sources. The existing difficulties with conventional electrolysis, including the usage of expensive catalysts in both cathode and anode, are discussed along with the possible gateway with cost-effective and sustainable electrocatalysts. This review focuses on the potential of three types of 3d transition metal-based molecular catalysts─cobaloximes, iron porphyrins, and nickel bis-phosphines─for hydrogen evolution reactions (HER), stressing their strategic synthetic designs, mechanistic routes, and catalytic parameters. Despite their high activity and selectivity, these molecular systems confront stability and scalability issues, limiting their practical applicability. To address this, the immobilization of these catalysts into solid matrices is studied, simplifying their integration into membrane electrode assembly (MEA) water electrolyzers for industrial-scale renewable-driven hydrogen production. To bridge the gap between lab-scale investigations and commercial implementation, several design components of the MEA stack are examined, such as flow patterns and scaling methodologies. A comprehensive approach to catalyst development and deployment is ensured by highlighting the significance of Life Cycle Assessment (LCA) and Techno-Economic Analysis (TEA) in assessing environmental sustainability and economic viability. The review closes with a call for multidisciplinary research and innovation to improve electrochemical water-splitting technology and accelerate the transition to an enduring hydrogen economy.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917800","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":"Poly(triazine imide) Crystals for Efficient CO2 Photoreduction: Surface Pyridine Nitrogen Dominates the Performance","authors":"Feng Liu, Jing Deng, Bo Su, Kang-Shun Peng, Kunlong Liu, Xiahui Lin, Sung-Fu Hung, Xiong Chen, Xue Feng Lu, Yuanxing Fang, Guigang Zhang, Sibo Wang","doi":"10.1021/acscatal.4c06685","DOIUrl":"https://doi.org/10.1021/acscatal.4c06685","url":null,"abstract":"Polymeric carbon nitrides (PCNs), usually the melon phase, have been extensively applied as photocatalysts for CO₂ reduction; however, their performance is still unsatisfactory. The condensed allotrope, namely, poly(triazine imide) (PTI) with extended conjugation and a crystallized structure, indeed holds more favorable compositional and structural advantages for photocatalytic CO₂ reduction but remains to be fully exploited. Herein, hexagonal prism-shaped PTI crystals were synthesized and developed as a high-performance photocatalyst for CO₂ reduction. With Co(bpy)₃²⁺ as a cocatalyst, the PTI crystals exhibit a CO evolution rate of 44 μmol h^–1 (i.e., 1467 μmol g^–1 h^–1) with 93% selectivity, markedly superior to that of the melon counterpart. Moreover, PTI crystals manifest an apparent quantum efficiency of 12.9% at 365 nm, representing the state-of-the-art value by PCN photocatalysts for CO₂-to-CO reduction without using noble metals. The surface pyridine N species of PTI are exposed as active sites to dominate CO₂ activation and conversion, which, together with the high crystallinity to facilitate charge separation and transport, endows high CO₂ reduction efficiency. In situ diffuse reflectance infrared Fourier transform spectroscopy determines the key intermediates during the CO₂ reduction reaction and, consequently, constructs the possible reaction mechanism.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"92 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917802","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}