EES catalysis最新文献

{"title":"Transport-induced voltage penalties of aqueous electrochemical reactions involving proton or hydroxide transfer in non-extreme pH conditions.","authors":"Gerard Prats Vergel, Yvette Ziggers, Min Li, David A Vermaas, Thomas Burdyny","doi":"10.1039/d6ey00240d","DOIUrl":"https://doi.org/10.1039/d6ey00240d","url":null,"abstract":"<p><p>Electrolyzers operating in non-extreme pH conditions are gaining interest as they offer advantages in stability and compatibility with different feedstocks, reactants and products. However, the cell voltages reported are often substantially higher than their thermodynamic equilibrium potential, undermining their energy efficiency and scalability. Here, we show that this discrepancy originates from ionic transport through the cell and applies to any electrochemical reaction involving H⁺ or OH^-, such as water, CO₂ and nitrate reduction or water oxidation. These transport-induced penalties are usually not accounted for until much later in the development process. While strongly acidic and alkaline electrolyzers can sustain current while maintaining pH symmetry between the electrodes, non-extreme pH electrolyzers inevitably develop local large pH gradients that lead to asymmetric conditions. This local pH asymmetry generates concentration overpotentials that can reach 0.5-1 V depending on the applied current density and temperature. Finally, we discuss strategies to minimize local pH shifts, assess their risks for industrial implementation, and identify pathways to reduce the transport-induced pH-asymmetry voltage penalties of non-extreme pH electrolyzers.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" ","pages":""},"PeriodicalIF":9.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13628322/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149119471","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":"CO-tolerant hydrogen oxidation on Pt enabled by ultrathin silica overlayers.","authors":"Christos Englezos, Marco Altomare, Guido Mul, Bastian Mei, Georgios Katsoukis","doi":"10.1039/d6ey00101g","DOIUrl":"10.1039/d6ey00101g","url":null,"abstract":"<p><p>Low-temperature electrochemical hydrogen compression can combine H₂ compression and purification, but CO impurities in practical H₂ feeds rapidly poison Pt anodes. Here, we use sputter- and electrodeposited Pt on Ti disk model electrodes to assess whether ultrathin polydimethylsiloxane (PDMS)-derived amorphous silica overlayers can improve CO tolerance during the hydrogen oxidation reaction (HOR). Fourier-transform infrared reflection-absorption and low-energy ion-scattering spectroscopy confirmed conformal and amorphous silica overlayer formation on Pt. Nominal thickness-dependent measurements revealed a narrow activity-protection window within the sub-10 nm regime. 2-3 nm silica overlayers provided limited CO tolerance, whereas increasing the nominal thickness from 7 to 8 nm strongly suppressed HOR activity. Benchmarking against active electrochemical regeneration showed that bare Pt operated at 0.15 V <i>vs</i>. RHE with 15 s CO-stripping pulses at 0.85 V <i>vs</i>. RHE delivered a 1.8 times higher time-averaged HOR power density than silica-coated Pt. However, the pulses introduced an 8% energy-efficiency loss and rely on repeated high-potential cycling that accelerates electrode degradation. Importantly, under fixed-current operation, silica-coated Pt reduced the cumulative HOR energy demand under CO contamination by a factor of up to 3.6. These results establish ultrathin silica overlayers as a promising interfacial design strategy for CO-tolerant hydrogen oxidation and motivate translation to gas-diffusion electrodes (GDEs), where homogeneous and selective coating of porous electrodes remains the key challenge.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" ","pages":""},"PeriodicalIF":9.8,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13573285/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148972487","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":"Balancing selectivity retention and catalyst restructuring in pulsed CO₂ electroreduction on silver.","authors":"Claudia Bissattini Alessi, Richa Rajadhyax, Alessandro Senocrate, Corsin Battaglia","doi":"10.1039/d6ey00140h","DOIUrl":"10.1039/d6ey00140h","url":null,"abstract":"<p><p>Pulsed electrochemical CO₂ reduction has emerged as a strategy to extend electrolyzer lifetime by periodically interrupting reductive operation with short oxidative pulses. Here we investigate the effect of oxidative pulse potential, pulse frequency, and pulse duration on the selectivity and structural integrity of electrospun polymer-based silver gas diffusion electrodes over extended periods of operation. We show that the threshold potential for anodic dissolution of silver at 0.55 V <i>vs.</i> SHE defines an upper boundary for the pulse potential: pulses with a potential below this threshold enable periodic local acidification of the electrolyte in the vicinity of the catalyst promoting partial dissolution of (bi)carbonate precipitates, while pulses with a potential above the threshold drive a silver dissolution-redeposition cycle that restructures the catalyst into silver clusters promoting the hydrogen evolution reaction. Systematic exploration of the pulse parameter space identifies an optimal protocol consisting of 10-seconds-long oxidative pulses applied every 30 minutes, yielding a duty cycle exceeding 99%. Under these conditions, carbon product faradaic efficiency is maintained in the range of 70-80% over 100 hours of operation, representing a five-fold improvement in selectivity relative to continuous electrolysis. Our results demonstrate the potential of pulsed electrolysis to maintain high CO selectivity over long operational periods, thus representing an important step towards the industrialization of CO₂ electrolysis.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" ","pages":""},"PeriodicalIF":9.8,"publicationDate":"2026-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13509025/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148835322","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":"EES Catalysis 2025 Outstanding Papers","authors":"None","doi":"10.1039/D6EY90010K","DOIUrl":"https://doi.org/10.1039/D6EY90010K","url":null,"abstract":"<p >A graphical abstract is available for this content</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 3","pages":" 495-501"},"PeriodicalIF":0.0,"publicationDate":"2026-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ey/d6ey90010k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147923962","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":"Platinum surface oxides govern the cathodic overpotential of the oxygen reduction reaction","authors":"Alfred Larsson, Andrea Grespi, Ozbej Vodeb, Karen van den Akker, Auden Ti, Claire Berschauer, Alexandra M. Imre, Philip Miguel Kofoed, Estephania Lira, Mahesh Ramakrishnan, Stuart Ansell, Justus Just, Henrik Grönbeck, Ulrike Diebold, Edvin Lundgren, Lindsay R. Merte, Dusan Strmcnik, Rik Mom and Marc T. M. Koper","doi":"10.1039/D6EY00014B","DOIUrl":"10.1039/D6EY00014B","url":null,"abstract":"<p >The oxygen reduction reaction (ORR) on platinum is limited by a substantial overpotential, which hampers the efficiency of fuel cell technologies. While adsorbate binding energies have been widely used to explain ORR kinetics, we here illustrate a more complex role of platinum surface oxides, which are often ambiguously defined in the literature. We use <em>operando</em> total reflection X-ray absorption fine structure spectroscopy (RefleXAFS), supported by X-ray photoelectron spectroscopy, density functional theory, and microkinetic modeling, to resolve the surface oxides on polycrystalline platinum and their impact on ORR. We identify the formation of a surface oxide as early as 1 V<small>_RHE</small> in 0.1 M HClO<small>₄</small> and demonstrate that platinum spontaneously oxidizes at the open-circuit potential (OCP) under O<small>₂</small> saturation. Furthermore, we show that the oxide coverage increases with upper vertex potential, slower scan rates, and extended hold times at OCP, illustrating how oxides inhibit ORR during fuel cell start-up. Crucially, we demonstrate that the ORR onset is delayed until these oxides are reduced, establishing a direct, negative relationship between oxide coverage and ORR activity. This reveals a revised mechanism in which the potential-determining step is the reduction of surface oxides, and the slow kinetics of this restructuring ultimately determine when surface sites become catalytically available.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 3","pages":" 754-765"},"PeriodicalIF":0.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12997406/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147488616","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":"Anodic activation-mediated formation of a crystalline–amorphous heterojunction of CoNi(O)OH for improved urea oxidation activity","authors":"Toufik Ansari, Manshu Dhillon, Vijay Patel, Aviru Kumar Basu and Arindam Indra","doi":"10.1039/D5EY00367A","DOIUrl":"https://doi.org/10.1039/D5EY00367A","url":null,"abstract":"<p >The urea oxidation reaction (UOR) has been proposed as an alternative to anodic oxygen evolution for an improved cell voltage and cost-effective H<small>₂</small> production by water electrolysis. However, the progress in this field is limited by the lack of efficient UOR electrocatalysts. Herein, we report two different active catalysts, [CoNi(O)OHs], formed by the <em>in situ</em> anodic activation of the cyanide-bridged polymer [CoNi(O)OH-1] and CoNi-layered double hydroxide [CoNi(O)OH-2] for the electrochemical UOR. In CoNi(O)OH-1, the Co-leaching during the anodic activation produced a Ni-rich CoNi(O)OH phase, forming a crystalline–amorphous heterojunction with a highly disordered structure. The defect-rich structure of CoNi(O)OH-1 facilitates the oxidation of Ni<small>²⁺</small> to Ni<small>³⁺</small>, stabilizes the Ni<small>³⁺</small> valence state, and thereby provides dynamically accessible active sites for the UOR. As a result, CoNi(O)OH-1 achieved a current density of 400 mA cm<small>⁻²</small> at a potential of 1.34 V <em>vs.</em> RHE, far better than that of CoNi(O)OH-2 (1.45 V <em>vs.</em> RHE) and Ni(O)OH (1.57 V <em>vs.</em> RHE). Furthermore, <em>operando</em> Raman spectroscopy reveals the adsorption of urea molecules on the catalyst surface, followed by dehydrogenation, and C–N bond cleavage during the UOR.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 3","pages":" 788-795"},"PeriodicalIF":0.0,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ey/d5ey00367a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147924014","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":"Spatially extended asymmetry directs electron transfer and modulates water oxidation deprotonation behavior on dual-atom catalysts","authors":"Jixuan Yang, Yaxin Cheng, Hao Ma, Zirui Wang, Ting Wang and Yuanmiao Sun","doi":"10.1039/D5EY00362H","DOIUrl":"https://doi.org/10.1039/D5EY00362H","url":null,"abstract":"<p >Introducing local coordination asymmetry through heteroatom substitution in homonuclear dual-atom catalysts (DACs) is an effective strategy to modulate the electronic state of metal centers. However, this approach often results in chaotic and unpredictable changes in electron transfer between the metals and coordinating atoms, which limits precise adjustment of the intermediate adsorption. In this study, we propose a spatially extended asymmetric coordination design strategy that enables simultaneous and precise regulation of electron transfer and differentiation of metal electronic states. Based on first-principles calculations, the constructed homonuclear DACs embedded in a hexagonal boron nitride/graphene (h-BN/Gra) heterostructure demonstrate well-defined electron transfer. The electronegativity differences among B, N, and C coordination atoms lead to distinct d-orbital configurations at the metal centers, which in turn modulate the *OH–*OH deprotonation behavior, following the trend of N coordination &gt; C coordination &gt; B coordination. The constructed volcano plot using the descriptor of Δ<em>G</em><small>_*O–*OH</small> − Δ<em>G</em><small>_*OH–*OH</small> provides clear theoretical guidance and design principles for optimizing oxygen evolution reaction activity. This work establishes a conceptual transition from local to spatially extended asymmetric coordination, offering a new theoretical framework for the rational design of asymmetric DACs.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 3","pages":" 686-695"},"PeriodicalIF":0.0,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ey/d5ey00362h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147923969","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":"Natural-sunlight-harvesting benzothiadiazole-based molecular photocatalyst for H2O2 production: a recyclable homogeneous biphasic system","authors":"Ajeet Singh, Aditya Mohan Shukla and Saumi Ray","doi":"10.1039/D6EY00008H","DOIUrl":"https://doi.org/10.1039/D6EY00008H","url":null,"abstract":"<p >Photocatalytic hydrogen peroxide (H<small>₂</small>O<small>₂</small>) synthesis offers a sustainable route for solar-to-chemical energy conversion to address the increasing global energy demand. However, developing an efficient and sustainable photocatalytic system for H<small>₂</small>O<small>₂</small> synthesis remains a critical bottleneck. Herein, we report a unique toluene–water two-phase system for highly efficient H<small>₂</small>O<small>₂</small> synthesis, employing a benzothiadiazole-based small organic photocatalyst, Py–BT–Th. Py–BT–Th shows a high H<small>₂</small>O<small>₂</small> production rate of 107.18 mmol g<small>⁻¹</small> h<small>⁻¹</small>, with a turnover frequency of ∼32 h<small>⁻¹</small>, under natural sunlight irradiation in the toluene–water biphasic system, which uses triethylamine as a sacrificial agent. The biphasic system promotes H<small>₂</small>O<small>₂</small> mass transport, leading to rapid kinetics across the toluene–water interface. Experimental studies reveal that the superior photocatalytic performance of the catalyst Py–BT–Th is attributed to its donor–acceptor-type molecular architecture, which promotes efficient exciton separation, high molar absorptivity (<em>ε</em> = 12.27 × 10<small>³</small> M<small>⁻¹</small> cm<small>⁻¹</small>), long exciton lifetime (12.9 ns) and broad light-harvesting capacity. Scavenger and <em>in situ</em> EPR spectroscopic studies confirm that Py–BT–Th produces H<small>₂</small>O<small>₂</small> by following a dual mechanistic route: (1) indirect two-step one-electron ORR <em>via</em> an electron transfer pathway and (2) singlet-oxygen generation <em>via</em> an energy transfer pathway. In both the routes, ˙O<small>₂</small><small>⁻</small> is the key intermediate that ultimately gets converted into hydrogen peroxide, in association with the oxidation of triethylamine by photogenerated holes. Overall, this work disentangles the dilemma associated with small organic photocatalysts for H<small>₂</small>O<small>₂</small> synthesis through a recyclable toluene–water biphasic system.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 3","pages":" 777-787"},"PeriodicalIF":0.0,"publicationDate":"2026-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ey/d6ey00008h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147924013","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":"Quantifying buffer transport-limited water electrolysis under non-extreme pH conditions via numerical simulations","authors":"Melody Wada, Keisuke Obata and Kazuhiro Takanabe","doi":"10.1039/D6EY00006A","DOIUrl":"https://doi.org/10.1039/D6EY00006A","url":null,"abstract":"<p >Water electrolysis carried out under non-extreme pH conditions is expected to play an essential role in a sustainable society as it significantly broadens the choice of materials available for cell components. Buffer species are commonly introduced into electrolytes to minimize local pH gradients through their buffering action; however, the fundamental limitations imposed by buffer transport remain poorly understood. This study focuses on both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) under non-extreme pH conditions. Limiting current densities associated with mass transport of buffer species were quantitatively evaluated. The generalized modified Poisson–Nernst–Planck (GMPNP) model was employed to model achievable mass transport limits of buffer ions and their distribution near the electrode surface. While a buffer's p<em>K</em><small>_a</small> value affects the limiting current of each half-reaction, consideration of a coupled HER and OER reveals that diffusion of buffer species plays a decisive role in determining the overall performance. Increasing buffer concentration and temperature, assisted by electrolyte convection, effectively enhances the attainable limiting current density beyond industrially relevant thresholds, demonstrating that <em>electrolyte engineering</em> through control of buffer chemistry and transport enables buffer-based water electrolysis under non-extreme pH conditions.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 3","pages":" 766-776"},"PeriodicalIF":0.0,"publicationDate":"2026-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ey/d6ey00006a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147924012","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":"Correction: Phosphate modification of Pd/Al2O3 enhances activity and stability in aromatic hydrogenation under CO-contaminated hydrogen","authors":"Adrian Seitz, Yaoci Sheng, Ian Backes, Phillip Nathrath, Dennis Weber, Tanja Franken, Roberto Félix, Angelo Rillera, Johannes Frisch, Marcus Bär, Tanja Retzer and Patrick Schühle","doi":"10.1039/D6EY90005D","DOIUrl":"https://doi.org/10.1039/D6EY90005D","url":null,"abstract":"<p >Correction for ‘Phosphate modification of Pd/Al<small>₂</small>O<small>₃</small> enhances activity and stability in aromatic hydrogenation under CO-contaminated hydrogen’ by Adrian Seitz <em>et al.</em>, <em>EES Catal.</em>, 2026, <strong>4</strong>, 118–133, https://doi.org/10.1039/D5EY00231A.</p>","PeriodicalId":72877,"journal":{"name":"EES catalysis","volume":" 2","pages":" 483-483"},"PeriodicalIF":0.0,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/ey/d6ey90005d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147429365","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}