ACS Catalysis 最新文献

{"title":"Fundamental Insights into Photoelectrochemical Carbon Dioxide Reduction: Elucidating the Reaction Pathways","authors":"Lujie Zuo, Yuchao Deng, Lu Chen, Ting He, Jinhu Yang, Jiansheng Zhang","doi":"10.1021/acscatal.4c04795","DOIUrl":"https://doi.org/10.1021/acscatal.4c04795","url":null,"abstract":"The photoelectrochemical (PEC) reduction of carbon dioxide (CO₂) to produce solar fuels presents a sustainable strategy to mitigate CO₂ emissions and alleviate the global energy crisis. While significant research efforts have been dedicated to optimizing cell system configurations and designing efficient photoelectrocatalysts, there remains a lack of in-depth understanding of the CO₂ reduction pathway. This review provides a comprehensive overview of the fundamental insights of PEC CO₂ reduction with a focus on CO₂ reduction pathways from the perspectives of final products and adsorption modes. First, key challenges are identified and analyzed, including the initial activation of CO₂, the competitive hydrogen evolution reaction (HER), and the complex carbon–carbon (C–C) coupling process. The review then examines the fundamental aspects of the reduction process, covering state-of-the-art cell devices, their operational principles, and methodologies for capturing reaction intermediates. The initial activation of CO₂ through concerted or sequential proton–electron transfer mechanisms is discussed in detail. Furthermore, potential PEC CO₂ reduction pathways are systematically identified and categorized on the basis of the final products and distinct adsorption modes that drive the reduction process, including CO₂ insertion, carbon-coordinated and oxygen-coordinated monodentate adsorption, oxygen-coordinated bidentate adsorption, and adsorption on oxygen vacancies. Detailed pathways leading to the formation of C₁, C₂, and C₃ compounds are elucidated, with an emphasis on strategies that enhance selectivity toward C₁ and C₂₊ products. In particular, understanding the CO₂ reduction pathways aids in catalyst design. For C₁ production, catalyst design focuses on promoting adsorption and activation, as the rate-determining step (RDS) is the initial CO₂ activation. In contrast, for C₂₊ formation, catalyst design strategies aim to increase intermediate concentration, thereby enhancing the lateral interaction of intermediates, which is crucial for C–C coupling. Finally, the review summarizes potential future breakthroughs from electron, interfacial, and ionic pathways, thereby offering insights into the ongoing evolution of PEC reduction technologies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556055","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":"Brønsted Acid-Triggered Fast Synthesis Pathway of Furfural to Ethyl Levulinate by PtZn Supported on ZSM-5 Nanosheets","authors":"Longbin Deng, Zongyuan Wang, Xin Yu, Congzhen Qiao, Shuaishuai Zhou, Qiang Deng, Yong Zhao, Yajie Tian","doi":"10.1021/acscatal.4c03794","DOIUrl":"https://doi.org/10.1021/acscatal.4c03794","url":null,"abstract":"Furfural (FUR) is widely used to synthesize alkyl levulinate (AL), an important biomass-derived compound for industrial use. Traditional synthesis pathways, including hydrogenation, etherification, and hydrolysis, are slow due to high activation energy requirements. This study presents a pathway using ethyl levulinate (EL) as a model AL. The process starts with the acetalization of FUR to produce 2-(diethoxymethyl)furan (DEMF) using a Brønsted acid–based ZSM-5 nanosheet-supported PtZn (PtZn/ZSM-NS) catalyst. DEMF is then hydrogenolyzed to form 2-(ethoxymethyl)furan (EMF), which is hydrolyzed to produce EL at a rate of 29.8 mmol·g^–1h^–1, over 20 times faster than with a Lewis acid–based catalyst. In the initial step, Brønsted acid sites on the PtZn/ZSM-NS activate ethanol to generate an acetate-like intermediate (COO^θ), which facilitates the acetalization of FUR to produce DEMF. This step is crucial for efficiently producing EL using the PtZn/ZSM-NS catalyst. Subsequently, EMF is easily formed through the hydrogenolysis of DEMF instead of through the etherification of furfuryl alcohol. Additionally, highly dispersed PtZn alloys on PtZn/ZSM-NS are essential for optimizing the adsorption strength, thereby accelerating the overall reaction. Using this pathway, the PtZn/ZSM-NS catalyst achieves an EL yield of up to 89.5 wt % at 200 °C in just 1 h.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541962","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":"Electronic and Structural Property Comparison of Iridium-Based OER Nanocatalysts Enabled by Operando Ir L3-Edge X-ray Absorption Spectroscopy","authors":"Marianne van der Merwe, Romualdus Enggar Wibowo, Catalina E. Jimenez, Carlos Escudero, Giovanni Agostini, Marcus Bär, Raul Garcia-Diez","doi":"10.1021/acscatal.4c03562","DOIUrl":"https://doi.org/10.1021/acscatal.4c03562","url":null,"abstract":"In this study, we investigate the electronic and structural behavior of a newly developed and of a commercially available Ir-based oxygen evolution reaction (OER) catalyst under relevant conditions employing an <i>operando</i> Ir L₃-edge X-ray absorption near-edge structure and extended X-ray absorption fine structure approach. The newly developed Kopernikus P2X amorphous IrO_<i>x</i>/TiO₂ catalyst is compared to the current commercial benchmark catalyst: crystalline IrO₂/TiO₂, Umicore Elyst. Analysis of the redox behavior of the catalysts shows distinct electronic differences between the amorphous and crystalline oxides, with the former exhibiting significant reversible electronic transformations. Employing an equivalent charge transfer approach following Faraday’s law of electrolysis, we study the behavior of the catalysts under equivalent OER conditions (chronopotentiometric steps), as opposed to the conventional chronoamperometric approach. This enables the derivation of property–structure relationships under equivalent OER conditions for materials exhibiting distinctly different activities. The P2X IrO_<i>x</i>/TiO₂ catalyst undergoes substantial electronic structure changes, with larger reduction in the Ir–O bond lengths compared to that of the commercial benchmark catalyst. The correlation between electronic states and local geometric information highlights diverse OER pathways, suggesting that the newly developed P2X IrO_<i>x</i>/TiO₂ catalyst and the benchmark IrO₂/TiO₂ commercial catalyst follow mechanisms akin to those of amorphous iridium oxide (am-IrO_<i>x</i>) and rutile-IrO₂, respectively. These results shed light on the intrinsic activities of different iridium oxide-based catalysts and provide crucial insights for enhancing their performances in proton exchange membrane water electrolyzers.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541961","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":"Selective Hydrolysis of Heterooligosaccharides by Poly(acrylate) Gel Catalysts","authors":"Susanne Striegler","doi":"10.1021/acscatal.4c04697","DOIUrl":"https://doi.org/10.1021/acscatal.4c04697","url":null,"abstract":"Natural glycoside hydrolases are distinguished by their ability to hydrolyze glycosidic bonds with high efficiency and selectivity. This feature is achieved through specific interactions in the active site during catalytic turnover and is not just facilitated by two catalytically active amino acids. Intrigued by these features, a biomimetic α-galactosidase mimic was developed using an empirical catalyst design. Starting with a library of 704 gels of which 250 have a unique composition synthesized from TEGDMA cross-linker and 7 selected monomers, 238 monomodal gels are evaluated for their ability to hydrolyze the 1→6 α-glycosidic bond in the disaccharide melibiose. Among those, 13 polyacrylate gels with the potential for high catalytic activity are identified using spectrophotometric screening assays based on Schiff bases formed with toluidine. The best-performing polyacrylate (gel A) was found to have a 1500-fold higher proficiency to hydrolyze the 1→6 α-glycosidic bond in melibiose over the 1→2 α-glycosidic bond in sucrose, translating to selective hydrolysis of the glycosidic linkages in the trisaccharide raffinose. The matrix of gel A is composed of 25 mol % TEGDMA cross-linker and equimolar amounts of cyclohexyl, butyl, and benzyl acrylate accounting for CH-π and hydrophobic interaction in the surrounding of a hydrolytic binuclear Cu(II) complex. The combined observations underline a paramount influence of matrix-stabilizing effects on the transition state of the hydrolysis of glycosidic bonds and may pave the way for the rapid development of catalysts transforming biomass.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541963","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":"Activity Enhancement of Molybdenum Carbide in Alkaline Hydrogen Evolution Reaction through Oxidation-Gradient Modulation","authors":"Yifan Li, Xueying Wan, Zhigang Chen, Ding Ding, Hao Li, Ning Zhang, Dong Liu, Yi Cui","doi":"10.1021/acscatal.4c01779","DOIUrl":"https://doi.org/10.1021/acscatal.4c01779","url":null,"abstract":"Featured by their Pt-like electronic structure, molybdenum carbides have been widely developed for efficiently catalyzing the hydrogen evolution reaction (HER). It is noteworthy that the oxophilicity of transition-metal atoms can give rise to the inevitable surface oxidation of molybdenum carbides, which has a noticeable impact on their HER activities. However, such a significant detail was usually documented in theory simulations and rarely explored by well-controlled experiments. Herein, advanced surface-science techniques using vacuum-connected setups are performed to deliberately prepare oxidation-gradient molybdenum carbide-oxide model electrocatalysts and evaluate the corresponding alkaline HER performance. The performance evaluations demonstrate that the minimal oxygen-modified Mo₂C exhibits the best alkaline HER activity among all model electrocatalysts. In situ XPS combined with quasi in situ XPS under different applied negative potentials reveals that tailoring the Mo₂C surface decorated with oxygen-containing species can facilitate the desorption of produced OH* intermediates from water activation, thus avoiding the deep oxidation issue of the catalyst surface and accelerating the regeneration of active sites in the alkaline HER process. Moreover, a comparable trend of HER performance is also observed on the synthetically practical Mo₂C powder catalysts, which further proves our hypothesis deduced from the model system. Our strategy of oxygen-terminated Mo₂C model electrocatalysts and the utilization of advanced spectroscopy characterizations may pave an interesting route for the rational design of low-cost but highly efficient oxygen-modified molybdenum carbide catalysts for practical water electrolysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541960","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":"Enabling Automation of de Novo Catalyst Design: An Experimentally Validated, Multifactor Design Metric for Olefin Metathesis","authors":"Jonas B. Ekeli, Marco Foscato, Christian O. Blanco, Giovanni Occhipinti, Deryn E. Fogg, Vidar R. Jensen","doi":"10.1021/acscatal.4c06212","DOIUrl":"https://doi.org/10.1021/acscatal.4c06212","url":null,"abstract":"Automated methods for molecular design navigate chemical space by ranking candidate compounds against predefined, numerical design metrics. To date, metrics for homogeneous catalysts focus on catalyst activity as the sole criterion, neglecting performance-critical factors such as stability and degradation. Here we introduce a general, multifactor design metric for molecular catalysts, and highlight the opportunities created by mechanistically-based de novo design by implementing this metric within the showcase application of olefin metathesis. Ruthenium-catalyzed olefin metathesis offers a prominent context within which the central importance of catalyst degradation is now widely acknowledged, and mechanistic understanding of the decomposition pathways has reached an advanced stage. A numerical figure of merit (or “fitness score”) for these catalysts is generated by combining functions based on DFT-calculated relative energies, which describe (i) catalyst initiation, (ii) catalyst activity in the metathesis of terminal olefins, (iii) catalyst stability–specifically, resistance to decomposition via β-hydride elimination, (iv) the synthetic accessibility of the precatalyst, and (v) its thermodynamic stability in the <i>trans</i>-anionic geometry essential for high activity. By comparing calculated fitness scores with catalytic turnovers measured in benchmark olefin metathesis reactions, we demonstrate that this multifactor fitness function reproduces the experimental ranking and productivity trend for catalysts known to exhibit profoundly different susceptibilities to decomposition. The trend cannot be reproduced by considering in isolation any of the individual factors, including catalytic activity or resistance to β-hydride elimination. The fitness formulation presented here establishes a foundation for automated screening and design of improved catalysts for olefin metathesis. More broadly, it establishes a general strategy for development of multifactor design metrics for molecular catalysts that incorporate mechanistic understanding of catalyst activity, stability, and synthetic accessibility.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541965","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":"Practical Considerations for Understanding Surface Reaction Mechanisms Involved in Heterogeneous Catalysis","authors":"Daniyal Kiani, Israel E. Wachs","doi":"10.1021/acscatal.4c05188","DOIUrl":"https://doi.org/10.1021/acscatal.4c05188","url":null,"abstract":"Acquiring useful knowledge about the active site(s) of a catalyst, nature of reactant–catalyst interactions, nature of reactive intermediates, rate-determining step, reaction rate orders that affect various process parameters, and reaction mechanism as a whole is exceedingly challenging. This is especially true in the case of heterogeneous catalysts due to the complexity of the nature of surface active sites and their nonstatic behavior. Here, we present our perspective on differentiating between various surface reaction mechanisms in light of pioneering studies by leaders in the field, with the aim of clarifying some of the confusion associated with these complex mechanisms, especially the Eley–Rideal mechanism. Using bibliometric analysis, we identify and discuss the following four reactions that most commonly invoke the Eley–Rideal mechanism: H₂ activation, CO oxidation, esterification of alcohols by acids, and selective catalytic reduction (SCR) of NO_<i>x</i> with NH₃. Our analysis of studies utilizing well-suited experimental and computational methodologies for differentiating surface reaction mechanisms suggests that the above-mentioned four reactions do not occur via the Eley–Rideal mechanism. Instead, each reaction occurs via the Langmuir–Hinshelwood mechanism with nonidealities present. Lastly, we highlight practical considerations regarding select experimental (characterization methods and differential kinetics) and computational modeling that we believe can provide useful insights to accurately discern between the various possible reaction mechanisms in heterogeneous catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142541964","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":"Chiral N-Hydroxyalkyl Pyrid-2-Ylidenes: A New Class of Ligands for Copper-Catalyzed Asymmetric Allylic Alkylation","authors":"Dylan Bouëtard, Ziyun Zhang, Thomas Vives, Marie Cordier, Luigi Cavallo, Lucie Jarrige, Laura Falivene, Marc Mauduit","doi":"10.1021/acscatal.4c05243","DOIUrl":"https://doi.org/10.1021/acscatal.4c05243","url":null,"abstract":"A class of chiral <i>N</i>-heterocyclic carbenes derived from pyridine, namely <i>N</i>-hydroxyalkyl pyrid-2-ylidenes, was developed. Capitalizing the remarkable steric and electronic features of the pyrid-2-ylidene core with the presence of a chiral hydroxyalkyl-chelating arm on the nitrogen atom, these ligands demonstrated high performance in copper-catalyzed asymmetric allylic alkylation of dialkylzincs to various allylic or dienic phosphates with high γ-selectivity (&gt;98%) and enantioselectivity (up to 95% ee). Importantly, the catalyst loading can be decreased to below 0.5 mol% without any loss of catalyst efficiency, thus outperforming <i>N</i>-hydroxyalkyl imidazoline-2-ylidene congeners. Moreover, thanks to the versatile post-transformation of the resulting enantioenriched skipped 1,4-dienes, various relevant building blocks were synthesized, notably a key intermediate in the total synthesis of (+)-Phorbasin C. Furthermore, by involving a transient oxazolidine, which acts as a masked carbene before the insertion of the metal center, a well-defined but air-sensitive <i>N</i>-hydroxyalkyl pyrid-2-ylidene copper(I) chloride complex was isolated. Deuteration experiments and computational studies provided valuable insights into the formation of the oxazolidine and the corresponding copper complex.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556099","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":"Single-Atom Manganese-Based Catalysts for the Oxidative Dehydrogenation of Propane","authors":"Carly Byron, Patricia Anne Ignacio-de Leon, Jacob Bryant, Ryan Langeslay, Louisa Savereide, Jianguo Wen, Jeffrey Camacho-Bunquin, Justin M. Notestein, Massimiliano Delferro, Magali Ferrandon","doi":"10.1021/acscatal.4c06021","DOIUrl":"https://doi.org/10.1021/acscatal.4c06021","url":null,"abstract":"Combinatorial screening of 150 supported metal oxide (manganese and additives) catalysts was carried out via a high-throughput synthesis platform and parallel reactors for the oxidative dehydrogenation (ODH) of propane to propylene. Specifically, an organomanganese (0.05–2.5 Mn atoms/nm²) complex was grafted on metal oxide supports (Al₂O₃, SiO₂, TiO₂, and ZrO₂) premodified with either Lewis acid (Al, Ti, Zn, and Zr) or redox-active (Cu, Cr, Ga Ni, V) additives at various surface coverages (25, 50, and 75%). Catalysts were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, and UV–vis spectroscopy. Catalysts 0.05 Mn/V(50%)/Al₂O₃ and 0.05 Mn/Ni(50%)/ZrO₂ showed the highest combined propane conversion and propylene selectivities (31/41% and 15/85%), with excellent stability at 500 °C for 25 h. The presence of Ni in Mn/Ni/ZrO₂ resulted in a 6-fold increase in turnover frequency (TOF) over the Mn/ZrO₂. HRTEM identified single Mn atoms after 500 °C heat treatment. For the Mn/Ni/ZrO₂ system, Mn was incorporated into the support lattice due to the similar ionic radius of Mn²⁺ and Zr⁴⁺, which was also enhanced by the presence of Ni. For the Mn/V/Al₂O₃ system, highly active MnO was prevalent as observed by Raman. Both V and Mn contributed to an increase in mutual dispersion, but both species remained on the surface. It is proposed that the highly dispersed atom and interactions between Mn with either Ni or V are responsible for the ODH performance and stability.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142542153","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":"Double-Shell Confinement Strategy Enhancing Durability of PtFeTi Intermetallic Catalysts for the Oxygen Reduction Reaction","authors":"Su-Min Chen, Lai-Ke Chen, Na Tian, Sheng-Nan Hu, Shuang-Li Yang, Jun-Fei Shen, Jing-Xiao Tang, De-Yin Wu, Ming-Shu Chen, Zhi-You Zhou, Shi-Gang Sun","doi":"10.1021/acscatal.4c04779","DOIUrl":"https://doi.org/10.1021/acscatal.4c04779","url":null,"abstract":"The development of Pt-based catalysts with enhanced activity and stability for the oxygen reduction reaction (ORR) is crucial for fuel cell applications. Pt-M (M = Fe, Co, Ni, Cu, etc.) catalysts exposed to prolonged acidic environments in fuel cells suffer from the leaching of transition metals, leading to accelerated catalyst degradation. Here, we present a double-shell confinement strategy to stabilize ORR catalysts by introducing a Ti-rich layer beneath the Pt skin. This design aims to prevent the leaching of Fe atoms, thus protecting the inner PtFeTi intermetallic structure. The resistance of Ti to acid and corrosion allows it to act as a physical protective layer, inhibiting the leaching of Fe and stabilizing the ordered structure of the internal PtFeTi intermetallic. Density functional theory calculations support that the Ti layer can effectively elevate the vacancy formation energy of Fe, thereby enhancing the structural stability. Mass activity (MA) of the double-shell L1₀-PtFe_0.6Ti_0.4/P–C catalyst is up to 1.04 A mg_Pt^–1. Even after 30,000 potential cycles of accelerated durability test, the MA decreases by only 13.5%. As the fuel cell cathode catalyst, it achieves a peak power density of 1.10 W cm^–2, and the voltage drop at 0.8 A cm^–2 is only 14 mV after 30,000 square-wave potential cycles. These performance metrics surpass the DOE 2025 target and exceed the stability data of many of the representative catalysts. Moreover, this double-shell confinement strategy is also applicable to PtCo-based and PtNi-based catalysts, demonstrating its broad applicability.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536345","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}