EES catalysis最新文献

{"title":"Probing the structure–property relationships of supported copper oxide nanoclusters for methane activation†","authors":"Xijun Wang, Kaihang Shi, Anyang Peng and Randall Q. Snurr","doi":"10.1039/D3EY00234A","DOIUrl":"10.1039/D3EY00234A","url":null,"abstract":"<p >Supported metal oxide nanoclusters (MeO-NCs) have gained significant attention for their remarkable versatility in various energy and sustainability applications. Despite rapid advancements in atomic-scale synthesis and characterization techniques, the rational design of MeO-NCs with desired catalytic properties remains challenging. This challenge arises from the elusive and difficult-to-quantify structure-catalytic property relationships, particularly in the case of amorphous nanoclusters. Exploiting first-principles calculations at the density functional theory (DFT) level, we conducted a systematic investigation into the growth, geometries, and catalytic performance of a series of tetra-copper oxide nanoclusters (Cu<small>₄</small>O-NCs) for methane activation. Focusing on the most representative geometries, we applied machine learning to extract two physically insightful descriptors involving the spin density, the p-band center of the oxygen site, and the d-band center of adjacent Cu sites. These descriptors enable us to predict free energy barriers associated with both the homolytic and heterolytic mechanisms of methane activation. This descriptor-driven approach enables rapid and intuitive prediction of the preferred reaction mechanism. Our findings lay a solid foundation for future advancements in catalysts based on amorphous nanoclusters and provide valuable insights into the mechanistic landscape of methane activation.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00234a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138542512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced H2 production at the atomic Ni–Ce interface following methanol steam reforming†","authors":"Yaqi Hu, Zhong Liang, Yabin Zhang, Yaping Du and Hongbo Zhang","doi":"10.1039/D3EY00225J","DOIUrl":"10.1039/D3EY00225J","url":null,"abstract":"<p >Hydrogen production with high efficiency and low CO selectivity in methanol steam reforming (MSR) is of pivotal importance. However, there is limited understanding of the active sites and reaction mechanisms during catalysis. In this study, we maximized the interfacial site, known as the active component in MSR, of Ni–CeO<small>_<em>x</em></small> by atomically dispersed Ni and Ce over the carbon–nitrogen support to generate the Ni and Ce dual-atomic catalyst (DAC), which achieved 6.5 μmol<small>_{H<small>₂</small>}</small> g<small>_cat.</small><small>⁻¹</small> s<small>⁻¹</small> H<small>₂</small> generation rate and 0.8% CO selectivity at 99.1% methanol conversion at 513 K. The finely dispersed Ni and Ce structure was confirmed by systematic characterization of AC HAADF-STEM and EXAFS. Electron transfer from Ce to Ni was confirmed simultaneously by quasi-<em>in situ</em> XPS analysis. Moreover, the reaction mechanism of methanol steam reforming was clarified by combining kinetic studies with isotope-tracing/exchange analysis (<em>i.e.</em>, KIEs and steady-state isotopic transient kinetic analysis (SSITKA)), which suggests that the steam reforming consists of two tandem reaction processes: methanol decomposition (MD) and water–gas shift (WGS) reaction, with methanol and water activation at independent active sites (<em>e.g.</em>, Ni and oxygen vacancy over CeO<small>_<em>x</em></small>), and that hydrogen generation was primarily determined by both C–H bond rupture and O<small>_L</small>–H (O<small>_L</small> represents the lattice oxygen) cleavage within methoxy and hydroxyl groups, respectively, with the catalytic surface mainly covered by CO and methoxy groups. A shift of WGS involvement in hydrogen generation from negligibly influenced to significantly promoted was selectively observed once modifying the reaction from differential conditions to a high methanol conversion regime, and two quantification methods have been established by comparing the molecule ratio between CO and CO<small>₂</small> or H<small>₂</small>.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00225j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138515492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modified Cu–Zn–Al mixed oxide dual function materials enable reactive carbon capture to methanol†","authors":"Chae Jeong-Potter, Martha A. Arellano-Treviño, W. Wilson McNeary, Alexander J. Hill, Daniel A. Ruddy and Anh T. To","doi":"10.1039/D3EY00254C","DOIUrl":"10.1039/D3EY00254C","url":null,"abstract":"<p >Reactive carbon capture (RCC), an integrated CO<small>₂</small> capture and conversion process that does not require generating a purified CO<small>₂</small> stream, is an attractive carbon management strategy that can reduce costs and energy requirements associated with traditionally separate capture and conversion processes. Dual function materials (DFMs) comprised of co-supported sorbent sites and catalytic sites have emerged as a promising material design to enable RCC. DFMs have been extensively studied for methane production, but the noncompetitive economics of methane necessitates the development of DFMs to target more valuable, useful, and versatile products, like methanol. Herein, we report the development of modified Cu–Zn–Al mixed oxide (Alk/CZA, Alk = K, Ca) DFMs for combined capture and conversion of CO<small>₂</small> to methanol. CO<small>₂</small> chemisorption, <em>in situ</em> DRIFTS characterization, and co-fed hydrogenation performance revealed that K and Ca have different effects on the CO<small>₂</small> capture and catalytic behavior of the parent CZA. K-modification resulted in the greatest promotional effect on capture capacity but the most detrimental effect on co-fed hydrogenation catalytic activity. Interestingly, when used in a cyclic temperature-and-pressure-swing RCC operation, K/CZA exhibited a greater conversion of adsorbed CO<small>₂</small> (94.4%) with high methanol selectivity (46%), leading to greater methanol production (59.0 μmol g<small>_DFM</small><small>⁻¹</small>) than the parent CZA or Ca/CZA (13.2 and 18.9 μmol g<small>_DFM</small><small>⁻¹</small>, respectively). This study presents the foundational methodology for the design and evaluation of novel DFMs to target renewable methanol synthesis, highlighted by a critical learning that co-fed CO<small>₂</small> hydrogenation performance is not an effective indicator of RCC performance.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00254c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138515490","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective catalytic reduction of NOx with NH3 over copper-based catalysts: recent advances and future prospects","authors":"Guoquan Liu, He Zhang, Yi Li, Pengfei Wang and Sihui Zhan","doi":"10.1039/D3EY00210A","DOIUrl":"10.1039/D3EY00210A","url":null,"abstract":"<p >Selective catalytic reduction of NO with NH<small>₃</small> (NH<small>₃</small>-SCR) is a promising technology to reduce the emission of nitrogen oxides (NO<small>_<em>x</em></small>) from diesel engines and industrial flue gases. Due to their advantages of variable valence and high stability, Cu-based catalysts exhibit superior activity and have been widely employed in the NH<small>₃</small>-SCR reaction. Herein, we expound the reaction mechanism of NH<small>₃</small>-SCR, and summarize the comprehensive advances of Cu-based catalysts (Cu-based small-pore zeolites and Cu-containing metal oxides) developed in the last decade. In this review, the challenges and prospects for Cu-based catalysts are presented to meet the industrial need, and efficient design strategies for promoting the NH<small>₃</small>-SCR performance of Cu-based catalysts through support derivation, precursor optimization engineering, secondary metal doping, crystal structure regulation, preparation method modification and interaction and interface engineering are comprehensively proposed and discussed. These proposed strategies are confirmed to be beneficial for enhancing catalysis by accelerating acid and redox cycles. Besides, we sum up the poisoning mechanism of impurities from flue gas on active sites, and provide the corresponding anti-inactivation measures to inhibit the deactivation of catalysts. Finally, we hope to focus on the current opportunities and challenges faced by Cu-based catalysts, further promoting their development and achieving practical applications.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00210a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138515507","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activating iodine redox by enabling single-atom coordination to dormant nitrogen sites to realize durable zinc–iodine batteries†","authors":"Jisung Lee, Wooseok Lee, Seungho Back, Seung Yeop Yi, Seonggyu Lee, Seongseop Kim, Joonhee Moon, Dong-Yeun Koh, Kyeounghak Kim, Seoin Back and Jinwoo Lee","doi":"10.1039/D3EY00228D","DOIUrl":"10.1039/D3EY00228D","url":null,"abstract":"<p >Aqueous rechargeable static zinc–iodine (Zn–I<small>₂</small>) batteries are regarded as competitive candidates for next-generation energy storage devices owing to their safety and high energy density. However, their inherent limitations such as the shuttle effect, sluggish electrochemical kinetics, and the poor electrical conductivity of iodine have been challenging to mitigate when using methods that confer polarity to the surface of the carbon host through nitrogen doping. Moreover, the considerable prevalence of inactive pyridinic N sites significantly impedes the establishment of approaches to overcome issues associated with redox kinetics and iodine utilization. Herein, single Ni atoms were incorporated into an electrochemically inactive N-doped carbon matrix by carbonizing a zeolitic imidazolate framework and then thermally activating the Ni ions adsorbed onto the carbonized product. The single Ni atoms modulated the electronic structure of the surrounding N-doped carbon matrix, thereby improving its ability to adsorb polyiodides and exhibit bifunctional catalytic activity for iodine reduction and oxidation reactions. Consequently, the assembled Zn–I<small>₂</small> battery delivered an outstanding rate performance (193 mA h g<small>⁻¹</small> at a current density of 6 A g<small>⁻¹</small>) and ultralong cyclability (10 000 cycles at a current density of 4 A g<small>⁻¹</small>). Overall, this study illuminates the merits of using single-atom catalysts to revitalize inactive N pyridinic sites, thereby providing a promising direction for further advancement of Zn–I<small>₂</small> batteries.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00228d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135506946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recent progress in understanding the catalyst layer in anion exchange membrane electrolyzers – durability, utilization, and integration","authors":"Emily K. Volk, Melissa E. Kreider, Stephanie Kwon and Shaun M. Alia","doi":"10.1039/D3EY00193H","DOIUrl":"10.1039/D3EY00193H","url":null,"abstract":"<p >Anion exchange membrane water electrolyzers (AEMWEs) are poised to play a key role in reducing capital cost and materials criticality concerns associated with traditional low-temperature electrolysis technologies. To accelerate the development and deployment of this technology, an in-depth understanding of cell materials integration is essential. Notably, the complex chemistries and interactions within the catalyst layer (consisting of the anode/cathode catalyst, anion exchange ionomer, and their interfaces with the transport layers and membrane) collectively influence overall cell performances, lifetimes, and costs. This review outlines recent advances in understanding the catalyst layer in AEMWEs. Specifically, electrode development strategies (including catalyst deposition techniques and configurations as well as transport layer design strategies) and our current understanding of catalyst–ionomer interactions are discussed. Effects of cell assembly and operational variables (including compression, temperature, pressure, and electrolyte conditions) on cell performance are also discussed. Lastly, we consider cutting-edge <em>in situ</em> and <em>ex situ</em> diagnostic techniques to study the complex chemistries within the catalyst layer as well as discuss degradation mechanisms that arise due to the integration of cell components. Simultaneously, comparisons are made to proton exchange membrane water electrolyzers (PEMWEs) and liquid alkaline water electrolyzers (LAWE) throughout the review to provide context to researchers transitioning into the AEMWE space. We also include recommendations for standard operating procedures, configurations, and metrics for comparing activity and stability.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00193h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135506047","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rational element-doping of FeOOH-based electrocatalysts for efficient ammonia electrosynthesis†","authors":"Haifan Wang, Menglei Yuan, Jingxian Zhang, Yiling Bai, Ke Zhang, Bin Li and Guangjin Zhang","doi":"10.1039/D3EY00208J","DOIUrl":"10.1039/D3EY00208J","url":null,"abstract":"<p >Electrocatalysis has been intensively studied in nitrogen (N<small>₂</small>) reduction for its sustainable power and stable catalytic performance, but it is still limited by weak activation of N<small>₂</small> at the catalytic sites, and the competition from the hydrogen evolution reaction (HER). The special d-orbital electron arrangement of transition metals and the tuning of the microenvironment provide possible strategies to enhance the activation of N<small>₂</small>, while improving the selectivity of the eNRR. Herein, FeO(OH, S) with high spin state and Mo–FeOOH with low spin state were designed around the FeOOH-based catalysts through elemental doping, which could achieve excellent ammonia yield performance of 80.1 ± 4.0 μg h<small>⁻¹</small> mg<small>_cat</small><small>⁻¹</small> (FE 36.9 ± 0.5%) and 86.8 ± 4.1 μg h<small>⁻¹</small> mg<small>_cat</small><small>⁻¹</small> (FE 29.1 ± 0.8%) in 0.1 M LiClO<small>₄</small> at −0.6 V <em>vs.</em> RHE, respectively, coupled with polyethylene glycol (PEG) to inhibit the HER. Based on theoretical calculations to investigate the adsorption of N<small>₂</small> on Fe sites, the FeO(OH, S) catalyst has stronger adsorption ability, which may originate from the high spin effect, which means that the more isolated and highly active e<small>_g</small> orbital electrons are more beneficial to realize the electronic feedback mechanism, promoting the d–π* orbital interaction with N<small>₂</small>.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00208j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138515493","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cobalt-free layered perovskites RBaCuFeO5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction†","authors":"Elena Marelli, Jike Lyu, Mickaël Morin, Maxime Leménager, Tian Shang, N. Sena Yüzbasi, Dino Aegerter, Jinzhen Huang, Niéli D. Daffé, Adam H. Clark, Denis Sheptyakov, Thomas Graule, Maarten Nachtegaal, Ekaterina Pomjakushina, Thomas J. Schmidt, Matthias Krack, Emiliana Fabbri and Marisa Medarde","doi":"10.1039/D3EY00142C","DOIUrl":"10.1039/D3EY00142C","url":null,"abstract":"<p >Co-based perovskite oxides are intensively studied as promising catalysts for electrochemical water splitting in an alkaline environment. However, the increasing Co demand by the battery industry is pushing the search for Co-free alternatives. Here we report a systematic study of the Co-free layered perovskite famil<em>y</em> RBaCuFeO<small>_{5+<em>δ</em>}</small> (R = 4f lanthanide), where we uncover the existence of clear correlations between electrochemical properties and several physicochemical descriptors. Using a combination of advanced neutron and X-ray synchrotron techniques with <em>ab initio</em> DFT calculations we demonstrate and rationalize the positive impact of a large R ionic radius in their oxygen evolution reaction (OER) activity. We also reveal that, in these materials, Fe<small>³⁺</small> is the transition metal cation the most prone to donate electrons. We also show that similar R<small>³⁺</small>/Ba<small>²⁺</small> ionic radii favor the incorporation and mobility of oxygen in the layered perovskite structure and increase the number of available O diffusion paths, which have an additional, positive impact on both, the electric conductivity and the OER process. An unexpected result is the observation of a clear surface reconstruction exclusively in oxygen-rich samples (<em>δ</em> &gt; 0), a fact that could be related to their superior OER activity. The encouraging intrinsic OER values obtained for the most active electrocatalyst (LaBaCuFeO<small>_5.49</small>), together with the possibility of industrially producing this material in nanocrystalline form should inspire the design of other Co-free oxide catalysts with optimal properties for electrochemical water splitting.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00142c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138515489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multidisciplinary approaches for enzyme biocatalysis in pharmaceuticals: protein engineering, computational biology, and nanoarchitectonics","authors":"Suhyeon Kim, Seongmin Ga, Hayeon Bae, Ronald Sluyter, Konstantin Konstantinov, Lok Kumar Shrestha, Yong Ho Kim, Jung Ho Kim and Katsuhiko Ariga","doi":"10.1039/D3EY00239J","DOIUrl":"10.1039/D3EY00239J","url":null,"abstract":"<p >Enzyme biocatalysis is reshaping pharmaceutical synthesis, offering sustainable and efficient pathways for drug discovery and production. This paradigm shift towards eco-friendly methodologies addresses concerns inherent in traditional chemical synthesis. Enzymes, celebrated for their precision and adaptability to mild conditions, are poised as ideal candidates for pharmaceutical applications. Their versatility facilitates the synthesis of diverse pharmaceutical compounds, ensuring precise drug design and minimizing environmental impact. The integration of multidisciplinary approaches, including protein engineering, computational biology, and nanoarchitectonics, holds the potential to propel enzyme biocatalysis even further. Protein engineering utilizes directed evolution and rational design to customize enzymes, enhancing their stability and efficacy. Computational biology aids in deciphering enzymatic mechanisms, while nanoarchitectonics introduces innovative enzyme integration strategies into continuous flow systems. This comprehensive review explores how these multidisciplinary approaches can revolutionize pharmaceutical research and production. The synergy among these disciplines promises to expedite pharmaceutical processes, promote sustainability, optimize efficiency, and elevate precision—aligning perfectly with the evolving requirements of the pharmaceutical industry.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00239j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"134883771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Operando insights into correlating CO coverage and Cu–Au alloying with the selectivity of Au NP-decorated Cu2O nanocubes during the electrocatalytic CO2 reduction†","authors":"Clara Rettenmaier, Antonia Herzog, Daniele Casari, Martina Rüscher, Hyo Sang Jeon, David Kordus, Mauricio Lopez Luna, Stefanie Kühl, Uta Hejral, Earl M. Davis, See Wee Chee, Janis Timoshenko, Duncan T.L. Alexander, Arno Bergmann and Beatriz Roldan Cuenya","doi":"10.1039/D3EY00162H","DOIUrl":"10.1039/D3EY00162H","url":null,"abstract":"<p >Electrochemical reduction of CO<small>₂</small> (CO<small>₂</small>RR) is an attractive technology to reintegrate the anthropogenic CO<small>₂</small> back into the carbon cycle driven by a suitable catalyst. This study employs highly efficient multi-carbon (C<small>₂₊</small>) producing Cu<small>₂</small>O nanocubes (NCs) decorated with CO-selective Au nanoparticles (NPs) to investigate the correlation between a high CO surface concentration microenvironment and the catalytic performance. Structure, morphology and near-surface composition are studied <em>via operando</em> X-ray absorption spectroscopy and surface-enhanced Raman spectroscopy, <em>operando</em> high-energy X-ray diffraction as well as quasi <em>in situ</em> X-ray photoelectron spectroscopy. These <em>operando</em> studies show the continuous evolution of the local structure and chemical environment of our catalysts during reaction conditions. Along with its alloy formation, a CO-rich microenvironment as well as weakened average CO binding on the catalyst surface during CO<small>₂</small>RR is detected. Linking these findings to the catalytic function, a complex compositional interplay between Au and Cu is revealed in which higher Au loadings primarily facilitate CO formation. Nonetheless, the strongest improvement in C<small>₂₊</small> formation appears for the lowest Au loadings, suggesting a beneficial role of the Au–Cu atomic interaction for the catalytic function in CO<small>₂</small>RR. This study highlights the importance of site engineering and <em>operando</em> investigations to unveil the electrocatalyst's adaptations to the reaction conditions, which is a prerequisite to understand its catalytic behavior.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2023-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/ey/d3ey00162h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135212409","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}