ACS Catalysis 最新文献

{"title":"Atomic Insights into Catalyst–Substrate Interfaces of Self-Supported Electrodes for Energy Conversion and Fuel Synthesis","authors":"Sahanaz Parvin, Mamoni Maji, Rahul Majee, Sayan Bhattacharyya","doi":"10.1021/acscatal.5c01508","DOIUrl":"https://doi.org/10.1021/acscatal.5c01508","url":null,"abstract":"Recent breakthroughs in electrocatalyst design have advanced key redox reactions for large-scale green hydrogen, carbon-based fuel and ammonia production, while rechargeable metal-ion batteries continue to transform the mobility sector. However, charge and mass transfer limitations hinder the efficiency of several electrocatalysts at high current densities, prompting the growing adoption of self-supported electrodes as a solution. These self-supported flexible electrodes, with catalysts directly grown on metal or nonmetal substrates, provide superior conductivity and extended stability under extreme conditions. This approach lowers overpotential, increases current density and electrochemically active surface area (ECSA), and enhances the intrinsic activity through improved turnover frequency (TOF), mass activity and specific activity. This perspective explores the atomic-level electronic structure at catalyst–substrate interfaces, with a focus on orbital interactions that govern reaction pathways and active sites in the anchored electrocatalysts. It also explores the fabrication methods and structural variations of self-supported electrodes in key electrochemical processes, including oxygen evolution reaction (OER), hydrogen evolution reaction (HER), metal–air batteries, CO₂ reduction reaction (CRR), nitrogen reduction reaction (NRR), nitrate reduction reaction (NO₃RR), and electrochemical urea synthesis. Alongside a market survey and overview of existing self-supported systems, it also addresses catalyst–substrate interfacial challenges and experimental methodologies critical to advancing this field.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"26 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521523","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":"Emulsion of Benzene and Water Phases by an Amphiphilic Hematite/Carbon Nitride Photocatalyst for Phenol Synthesis","authors":"Ningxi Su, Dexi Yu, Shengyang Zhong, Meirong Huang, Yidong Hou, Masakazu Anpo, Jimmy C. Yu, Jinshui Zhang, Xinchen Wang","doi":"10.1021/acscatal.5c02352","DOIUrl":"https://doi.org/10.1021/acscatal.5c02352","url":null,"abstract":"Photocatalytic hydroxylation of benzene in water using H₂O₂ as the oxidant is a green approach toward phenol synthesis. However, the immiscibility of benzene in water results in poor photocatalytic performance and a low efficiency of H₂O₂ utilization. To enhance drastically the affinity between the aqueous and nonaqueous phases, an amphiphilic heterojunction (Fe₂O₃/crystalline carbon nitride (CCN)) has been synthesized by intimately immobilizing hematite (Fe₂O₃) nanoparticles on a CCN surface for the photocatalytic hydroxylation of benzene to phenol. The unique amphiphilicity of Fe₂O₃/CCN allows the formation and stabilization of homogeneous emulsions in a benzene/water mixture to increase the effective oil/water interface area for more efficient mass transport. Moreover, the well-established type II heterojunction between Fe₂O₃ and CCN facilitates the fast separation and transfer of photoelectrons from CCN to Fe₂O₃ for the photo-Fenton activation of H₂O₂ with high utilization efficiency. We recorded a maximum phenol conversion of 31.6% by using a stoichiometric amount of H₂O₂ (10 mmol) on the photocatalytic hydroxylation of benzene. The apparent quantum yield of phenol production at λ = 420 nm was determined to be 47.1%. This amphiphilic photocatalyst approach would be useful for realizing other advanced oxidation reactions involving immiscible components.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521258","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":"Atomically Dispersed Fe–N–C-Catalyzed Intermolecular Reductive Coupling toward the Synthesis of Benzimidazoles","authors":"Zhuang Ma, Binyu Zhang, Zhuo He, Ting Xu, Yuhe Cheng, Yanbin Cui, Zupeng Chen","doi":"10.1021/acscatal.5c03077","DOIUrl":"https://doi.org/10.1021/acscatal.5c03077","url":null,"abstract":"Benzimidazoles are privileged structural motifs in pharmaceuticals due to their diverse biological activities. Herein, we report an atomically dispersed iron catalyst (Fe-NC-800) for the reductive coupling of 2-nitroacetanilides with various aldehydes to synthesize structurally diverse benzimidazoles. The catalyst is synthesized through a template-sacrificial strategy and contains atomically dispersed Fe–N₄ active sites embedded in a nitrogen-doped carbon matrix. This transformation proceeds with high efficiency (conversion: 100%; yield: up to 89%), broad substrate scope (>50 samples), and functional group tolerance, delivering valuable benzimidazoles with good yields. Notably, this method achieves benzimidazole synthesis via an intermolecular coupling rather than an intramolecular cyclization process, distinguishing it from conventional strategies. Mechanistic studies reveal a stepwise hydrogenation pathway involving imine and amine intermediates, with Fe–N sites playing a crucial catalytic role. Additionally, the catalyst demonstrates great recyclability and stability, making it a promising platform for modern organic synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"19 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521524","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":"Stabilizing High-Valence Ni/Fe Through Li Vacancy Engineering in Li(1–x)NiFeO2/NiFeOOH Heterostructures for Enhanced Oxygen Evolution Reaction","authors":"Wei Liu, Ruiqi Zhang, Chengyu Li, Xingwu Liu, Shuheng Tian, Xiao Ren, Ding Ma","doi":"10.1021/acscatal.5c01469","DOIUrl":"https://doi.org/10.1021/acscatal.5c01469","url":null,"abstract":"Ni/Fe (oxy)hydroxides have been extensively studied as highly effective electrocatalysts for oxygen evolution reactions (OERs) in alkaline media. The ability of stable, higher-valence Ni/Fe ions (Ni³⁺/Fe³⁺) to enhance the OER activity has been well documented. In this work, we propose a cost-effective strategy for fabricating efficient OER catalysts through the electrochemical in situ delithiation of layered LiNi_1–<i>x</i>Fe_<i>x</i>O₂ (LNFO) in an alkaline solution. This process leads to the formation of a NiFeOOH phase with highly oxidative Ni³⁺/Fe³⁺ species at the catalyst surface. The ingenious heterostructure, resulting from the lithium vacancies generated on the LNFO surface, stabilizes the high-valence Ni and Fe species, significantly enhancing the intrinsic OER activity. The as-prepared NiFeOOH/LNFO catalyst shows good OER performance, achieving a current density of 10 mA cm^–2 at an overpotential (η) of 250 mV. In situ Raman and quasi-in situ XPS analyses reveal that the continuous electrochemical delithiation process resulted in the presence of highly oxidative Ni^3+δ/Fe^3+δ species and more amorphous defective structures on the surface of NiFeOOH/LNFO during OER. The high activity (<i>U</i> = 1.72 V at 1 A cm^–2) and durability (continuous 45 h at 500 mA cm^–2) of a membrane electrode assembly (MEA) cell also highlight its potential for practical large-scale applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"78 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521516","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":"Mesoporous Amorphous High-Entropy Oxide Films: Unlocking Enhanced Redox Activity","authors":"Qingju Wang, Meijia Li, Kevin M. Siniard, Darren M. Driscoll, Alexander S. Ivanov, Jue Liu, Shize Yang, Junyan Zhang, Felipe Polo-Garzon, Austin Houston, Gerd Duscher, Zhenzhen Yang, Sheng Dai","doi":"10.1021/acscatal.5c01591","DOIUrl":"https://doi.org/10.1021/acscatal.5c01591","url":null,"abstract":"High-entropy oxides (HEOs) represent a frontier in catalyst design via entropy-stabilized solid solution formation. However, their catalytic efficiency is limited by their bulk and dense nature. This work presents a strategic approach to tackle this challenge by fabricating mesoporous amorphous HEO films (MA-HEOF) possessing maximized active site utilization efficiency. The success hinges on the as-developed geometric engineering strategy via controlled deposition–precipitation to confine the amorphous HEO thin film on the surface of mesoporous channels. The unique structure of MA-HEOF was elucidated via microscopy-, X-ray-, and neutron-based techniques, which were manifested by enriched surface-activated lattice oxygen and enhanced redox activity, as confirmed by isotope studies. Besides, the MA-HEOF could stabilize and modulate the properties of integrated noble metal sites, enhancing their redox activity in diverse reactions. The approaches and insights presented herein provide guidance on maximizing the utilization efficiency of high-entropy materials in catalysis and beyond.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"34 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144371251","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":"Activated-Carbon-Supported Clusters Consisting of Four Planarly Arranged Palladium Atoms as Highly Active and Alkene-Selective Hydrogenation Catalysts","authors":"Chikako Yanagisawa, Rinako Miyauchi, Risa Nishiura, Yoshimasa Wada, Seiji Yamazoe, Atsushi Tahara, Yusuke Sunada","doi":"10.1021/acscatal.5c00339","DOIUrl":"https://doi.org/10.1021/acscatal.5c00339","url":null,"abstract":"The development of metal catalysts that require a minimum amount of precious metals is highly desirable due to the high cost and scarcity of noble metals. In this study, we synthesized a heterogeneous catalyst consisting of a cluster of four planarly arranged Pd atoms (Pd₄) immobilized onto activated carbon. The obtained catalyst exhibited high catalytic activity in the hydrogenation of various alkenes, whereby the highest TON was 455,556 per Pd atom. This catalyst is characterized by high alkene selectivity, while intramolecular −NO₂, −CN, −OCH₂Ph, epoxy, ester, ketone, and halogen groups remained intact. An X-ray absorption fine structure analysis revealed that the Pd₄ framework was maintained on activated carbon after catalysis. This heterogeneous catalyst structure provides a platform for the development of catalysts that combine good catalytic activity with high chemoselectivity, recyclability, and good substrate compatibility based on a minimum amount of palladium atoms.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2020 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144370763","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":"Zinc Doping Boosts the Reactivity and Anti-Coking Ability of Cobalt-Based Catalysts for Propane Dehydrogenation","authors":"Dandan Qin, Lili Cai, Shuailong Zhang, Wenling Chu, Weishen Yang","doi":"10.1021/acscatal.5c02743","DOIUrl":"https://doi.org/10.1021/acscatal.5c02743","url":null,"abstract":"The development of environmentally friendly non-noble-metal catalysts for propane dehydrogenation (PDH) has attracted significant attention. CoO_<i>x</i> and ZnO_<i>x</i> catalysts, known for their relatively high C–H bond activation ability, show great potential. Bimetallic oxide catalysts with dual active sites are particularly promising because of their unique intrinsic properties for PDH. In this study, we synthesized high-performance ZnCoO_<i>x</i> oxides supported on Silicalite-1 (S-1) zeolite via a complexation-impregnation method with citric acid. The optimized ZnCoO_<i>x</i>/S-1 catalyst demonstrated a propylene formation rate approximately twice as high as that of monometallic CoO_<i>x</i>/S-1 or ZnO_<i>x</i>/S-1 catalysts. The kinetic analysis and in situ spectroscopy confirmed that bimetallic ZnCoO_<i>x</i> species exhibited superior selective activation ability for propane C–H bonds compared to those of monometallic CoO_<i>x</i> and ZnO_<i>x</i> catalysts. Furthermore, these results demonstrated the dominant role of metallic Co⁰ sites as the primary active centers for PDH. These features contributed to minimal coke deposition, further improving the catalytic performance. Additionally, reversible transformation between metallic Co⁰ and the ZnCoO_<i>x</i> spinel phase under redox conditions accounts for the good regeneration stability of this catalytic system.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"66 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144371201","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":"Promoting Interfacial Electron Transfer by In Situ Generated Asymmetric Sn–Ov–Bi Sites for Selective CO2 Photoreduction","authors":"Qin Ren, Ye He, Yuxin Zhang, Lili Zhang, Yanjuan Sun, Fan Dong","doi":"10.1021/acscatal.5c02719","DOIUrl":"https://doi.org/10.1021/acscatal.5c02719","url":null,"abstract":"Photocatalytic CO₂ reduction offers a promising pathway for carbon neutrality, which fundamentally depends on the transfer of photoexcited electrons to the symmetric O═C═O bonds. However, precisely adjusting the electronic structure of active sites to promote the activation of the CO₂ molecules is still challenging. Herein, we demonstrate a light-driven engineering strategy for in situ construction of a dynamic active site, where the strain-induced asymmetric Sn–O–Bi units could evolve into self-optimized Sn–O_v–Bi triatomic sites under irradiation. These in situ generated photosensitive O_vs increase the electron density of neighboring Sn atoms and adjacent Bi atoms to form unique Sn–O_v–Bi triatomic sites, creating a polarized built-in electric field (IEF) that can accelerate charge separation and transfer. In situ electron paramagnetic resonance spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy further reveal that the strong electron transfer between the Sn–O_v–Bi sites and reactant molecules highly promotes the activation of the CO₂ molecules and the formation of H* species, thus facilitating the generation of critical COOH* intermediates. As a result, the in situ-generated asymmetric Sn–O_v–Bi sites enable BiOBr to achieve a stable and high CO production rate with 100% selectivity. This work provides a paradigm for the structural design of dynamic asymmetric active sites and highlights the importance of in situ electronic manipulation in a catalytic reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144371207","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":"Structural Insights into Ni–Fe Layered Double Hydroxides as Anode Catalysts for Pairing CO2 Reduction and Ethylene Glycol Oxidation","authors":"Jiefeng Liu, Yuwei Yang, Eddy Petit, Valérie Bonniol, Zakaria Anfar, Bertrand Rebiere, Bonito Aristide Karamoko, Wensen Wang, Huali Wu, Mathilde Moderne, Robin Guéret, Philippe Miele, Nicholas M. Bedford, Chrystelle Salameh, Damien Voiry","doi":"10.1021/acscatal.5c02291","DOIUrl":"https://doi.org/10.1021/acscatal.5c02291","url":null,"abstract":"Harnessing renewable electricity for CO₂ electroreduction is essential for the low-carbon production of chemicals and fuels. Traditional methods combine the CO₂ reduction reaction (CO₂RR) with the oxygen evolution reaction (OER), which has high energy consumption and low-value products. Here, we propose using anodic ethylene glycol oxidation reaction (EGOR) instead of OER, which has a lower oxidation potential and valuable product. Nickel–iron layered double hydroxide (NiFe-LDH) is identified as an efficient EGOR catalyst. Using systematic electrochemical measurements and both ex situ and operando spectroscopy revealed that NiFe-LDH undergoes distinct structural evolution under EGOR and the OER. We found that metal–oxygen hybridization enhances EGOR selectivity and reduces the OER selectivity. Pairing EGOR with CO₂RR allowed achieving a low electrical consumption of 6.2 kWh Nm^–3 at 300 mA cm^–2 for CO production using Ag as the cathode. This strategy was successfully applied to the conversion of CO₂ to multicarbon products, demonstrating a partial current density of 364 mA cm^–2 for C₂₊ production using Cu₂O as the cathode.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"99 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521464","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":"To Alloy or Not to Alloy? The Unexpected Power of Pd–Au Catalyst Physical Mixtures in Efficient HMF Oxidation to FDCA","authors":"Yani Peng, Xinyue Zhou, Xuzhao Liu, Min Hu, Boya Qiu, Yilai Jiao, Carmine D’Agostino, Jesus Esteban, Christopher M. A. Parlett, Xiaolei Fan","doi":"10.1021/acscatal.5c02908","DOIUrl":"https://doi.org/10.1021/acscatal.5c02908","url":null,"abstract":"Bimetallic palladium (Pd) and gold (Au) systems are active for promoting the selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a key building block for producing polyethylene furanoate, a biobased polymer to substitute poly(ethylene terephthalate). Here, an FDCA yield of ∼99% was achieved over a physical mixture of 1.5 wt % Au/C and 1.5 wt % Pd/C (Pd/Au molar ratio of 5:1) under mild conditions (90 °C, 1 bar O₂), outperforming bimetallic core–shell Au@Pd/C (∼90% FDCA yield) or alloyed AuPd/C (∼73% FDCA yield) systems. To gain insights into the synergy between the two monometallic catalysts, a series of kinetic studies were conducted employing either HMF or its intermediates as substrates in catalytic oxidation systems over either Pd/C or Au/C. The results show distinct selectivity preference of the two catalysts: Pd/C favors the 2,5-diformylfuran pathway (DFF), while Au/C follows the 5-hydroxymethyl-2-furancarboxylic acid (HFCA) pathway, as well as the presence of base-induced Cannizzaro disproportionation (CD) reactions. The advantage of the physical mixture system is largely attributed to the synergy between the two metals, which promotes the DFF pathway (over the HFCA route) and suppresses CD reactions, facilitating a more rapid progression of the overall oxidation cascade process. Catalyst recycling studies reveal deactivation of the physical mixture system (FDCA yield dropped to 62% after 3 cycles), with detailed comparative characterization of the fresh and used catalysts identifying operando Pd leaching and subsequent deposition onto Au/C, forming a core (Au)–shell (Pd) structure, as the origin of the diminished activity. Our findings challenge the conventional view regarding the alloy superiority in the selective oxidation of HMF, showing that systems based on simple physical mixtures of monometallic catalysts could be a more effective and practical strategy for progressing FDCA production via selective HMF oxidation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144521526","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}