{"title":"Cover Feature: Ambient CO2 Hydrogenation to Formate Over NiPd Catalyst (ChemCatChem 17/2025)","authors":"Jayashree Parthiban, Bhanu Priya, Rohit Kumar Rai, Satoshi Suganuma, Kiyotaka Nakajima, Sanjay Kumar Singh","doi":"10.1002/cctc.70300","DOIUrl":"10.1002/cctc.70300","url":null,"abstract":"<p><b>The Cover Feature</b> highlights a two-step integrated strategy for direct air capture (DAC) and subsequent conversion of CO<sub>2</sub> into formate by using a bimetallic Ni<sub>9</sub>Pd<sub>1</sub> catalytic system. To address the global challenge of rising atmospheric CO<sub>2</sub> concentrations, S. K. Singh and co-workers have developed a non-noble-metal-based bimetallic heterogeneous catalyst that enables the conversion of low-concentration CO<sub>2</sub> from air into formate. The catalyst demonstrates remarkable activity under ambient temperature, underscoring its potential for practical implementation in carbon capture and utilization (CCU) technologies. More information can be found in Research Article 10.1002/cctc.202500771.\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.70300","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144998949","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Front Cover: Sustainable Production of 1-Propanol via the Selective Hydrogenolysis of Glycerol Over a Tailored Iridium–Rhenium Oxide Catalyst Supported on HUSY Zeolite (ChemCatChem 17/2025)","authors":"Supphathee Chaowamalee, Atikhun Chotirattanachote, Wongsakorn Khammee, Chanoknun Kalvibool, Chawalit Ngamcharussrivichai","doi":"10.1002/cctc.70297","DOIUrl":"10.1002/cctc.70297","url":null,"abstract":"<p><b>The Front Cover</b> presents a sustainable one-pot transformation of glycerol to 1-propanol by selective hydrogenolysis. A multifunctional Ir-ReO<sub>x</sub>/HUSY catalyst has been rationally designed to synergize three key functions: a metallic iridium site (yellow) promotes hydrogenation, oxophilic ReO<sub>x</sub> (blue) enhances glycerol activation, and the acidic HUSY zeolite (red and white) facilitates dehydration, resulting in improved 1-propanol productivity. More information can be found in the Research Article by C. Ngamcharussrivichai and co-workers (DOI: 10.1002/cctc.202500885).\u0000\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure></p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.70297","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemCatChemPub Date : 2025-09-03DOI: 10.1002/cctc.202501086
Claudio Righetti, Antonio Recupido, Mehdi Yemloul, Pierre Rousselot-Pailley, Ally Aukauloo, Winfried Leibl, Elise Courvoisier-Dezord, A. Jalila Simaan, Thierry Tron, Yasmina Mekmouche
{"title":"Electron Relay Boosts Ruthenium-Laccase System Photo-Epoxidation","authors":"Claudio Righetti, Antonio Recupido, Mehdi Yemloul, Pierre Rousselot-Pailley, Ally Aukauloo, Winfried Leibl, Elise Courvoisier-Dezord, A. Jalila Simaan, Thierry Tron, Yasmina Mekmouche","doi":"10.1002/cctc.202501086","DOIUrl":"https://doi.org/10.1002/cctc.202501086","url":null,"abstract":"<p>We report here the light-driven oxidation of olefin to epoxide using a [Ru(bipyridine)<sub>3</sub>]<sup>2+</sup>/laccase (Ru<sup>II</sup>/LAC3)-based system, enhanced by the presence of methyl viologen (MV<sup>2+</sup>) as an electron relay. This approach leads to a fivefold increase in the conversion yield of sodium <i>p</i>-styrene sulfonate (pSS) oxidation (from 3% to 14% in the presence of MV<sup>2+</sup>), and favors chemoselectivity toward epoxidation. We demonstrate that laccase plays a crucial role in steering product selectivity, favoring epoxidation due to its ability to scavenge superoxide (O<sub>2</sub><sup>•−</sup>). In contrast, in the absence of laccase, the reaction predominantly yields sodium <i>p</i>-benzaldehyde sulfonate (A) and the sodium α-hydroxyketone <i>p</i>-phenyl sulfonate (α-HK). Mechanistic insights, supported by reactive intermediate trapping, isotope labeling, and product distribution analysis, suggest a reaction pathway involving both molecular oxygen and water as the oxygen sources.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202501086","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145316697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemCatChemPub Date : 2025-09-03DOI: 10.1002/cctc.202500975
Mohammed Ali Saif Al-Shaibani, Saksham Verma, Dr. Luka A. Zivkovic, Dr. Tanja Vidakovic-Koch
{"title":"Revisiting the Reaction Mechanism of Electrochemical 1,4-NADH Regeneration on Carbon Electrodes","authors":"Mohammed Ali Saif Al-Shaibani, Saksham Verma, Dr. Luka A. Zivkovic, Dr. Tanja Vidakovic-Koch","doi":"10.1002/cctc.202500975","DOIUrl":"https://doi.org/10.1002/cctc.202500975","url":null,"abstract":"<p>The direct electrochemical regeneration of 1,4-NADH, an essential cofactor in many enzymatic reactions, has emerged as a promising approach due to its compatibility with renewable electricity, reduced CO<sub>2</sub> emissions, and significantly lower environmental impact (E-factor). However, its application is challenged by low selectivity and high overpotentials. This process is primarily studied on metal electrodes, where it often overlaps with the hydrogen evolution reaction (HER). The occurrence of HER is considered important, as most proposed mechanisms for NAD<sup>+</sup> reduction reaction (NADRR) suggest that adsorbed hydrogen is a necessary step for 1,4-NADH formation. However, on carbon materials, appears to be a region where NADRR and HER do not overlap. According to current understanding, this would lead only to dimer formation on carbon, contrary to experimental findings from our research and other literature. In this study, we propose a new mechanism for 1,4-NADH formation at low overpotentials with proton donation occurring directly from the buffer, bypassing the formation of adsorbed hydrogen (H<sub>ads</sub>). We identified optimal conditions for achieving high selectivity of 1,4-NADH regeneration, resulting in 91% selectivity at 77% conversion, with no HER occurrence and low E-factor. These conditions include low catalyst loadings, low initial NAD⁺ concentrations, and low overpotentials.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500975","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145316698","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemCatChemPub Date : 2025-09-03DOI: 10.1002/cctc.202500992
Kapil Dhaka, Stephane Kenmoe, Achim Füngerlings, Rossitza Pentcheva, Kristina Tschulik, Kai S. Exner
{"title":"Trends in Oxygen Evolution Reaction Activity and Limiting Steps for Different Active Sites on Co3O4(001)","authors":"Kapil Dhaka, Stephane Kenmoe, Achim Füngerlings, Rossitza Pentcheva, Kristina Tschulik, Kai S. Exner","doi":"10.1002/cctc.202500992","DOIUrl":"https://doi.org/10.1002/cctc.202500992","url":null,"abstract":"<p>Cobalt spinel (Co<sub>3</sub>O<sub>4</sub>) is a dynamically restructuring catalyst under oxygen evolution reaction (OER) conditions. So far, little is known about the mechanistic complexity of the OER at different active sites of Co<sub>3</sub>O<sub>4</sub> at the atomic level. Using the A- and B-terminations of a single-crystal Co<sub>3</sub>O<sub>4</sub>(001) model electrode, we apply a combination of density functional theory calculations and <i>ab initio</i> molecular dynamics simulations to identify three main types of active sites of Co<sub>3</sub>O<sub>4</sub> under OER conditions. In addition to tetrahedral and octahedral surface sites, we report the formation of pseudo-octahedral sites due to a change in the local environment upon adsorption of intermediate species. For all these active sites, we analyze the elementary steps of the OER by descriptor-based analysis and the concept of degree of span control. While octahedral and pseudo-octahedral sites are catalytically more active than tetrahedral sites, we show structural sensitivity with respect to the key limiting reaction step, which ranges from O─O bond formation to O<sub>2</sub> desorption and *OH oxidation. Our modeling strategy, which captures changes in the local environment, elementary steps of the OER, and the contribution of different reaction steps to the current density, provides an integrated and comprehensive framework for describing complex oxide materials under applied bias.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500992","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237257","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Review on the Pivotal Role of Interfacial Sites in Multicomponent Catalysts for Promoting Selective COx Hydrogenation to Ethanol","authors":"Jinyan Zhang, Feng Zeng, Xiaolei Fan, Huanhao Chen","doi":"10.1002/cctc.202501092","DOIUrl":"https://doi.org/10.1002/cctc.202501092","url":null,"abstract":"<p>With growing emphasis on circular carbon economy, catalytic CO<i><sub>x</sub></i> (CO/CO<sub>2</sub>) conversion offers a sustainable route for ethanol synthesis, yet challenges persist in achieving high selectivity due to competing single-carbon products formation (e.g., CO, methane, and methanol formation). Multicomponent catalysts, which consist of two or more distinct metal species with cooperative synergistic interactions between discrete active sites, exhibit high ethanol selectivity in CO<sub>x</sub> hydrogenation reactions. Here, this review comments on the critical role of interfacial sites, where metal–metal or metal–oxide interactions modulate electronic and geometric properties, in multicomponent bifunctional catalysts for selective CO<sub>x</sub> hydrogenation to ethanol. We first highlight how engineered metal–oxide interfaces and nanoscale metal intimacy (e.g., in Rh-, Cu-, Co-, and in-based multicomponent bifunctional catalysts) synergistically activate CO<i><sub>x</sub></i>, stabilize key intermediates (e.g., CH<i><sub>x</sub>*</i>, CO*, and CH<sub>x</sub>O*), and thereby promoting C─C coupling. Advanced strategies, including atomic layer deposition (ALD), surface organometallic chemistry (SOMC), and strong electrostatic adsorption (SEA), for engineering interfacial sites are then discussed. The mechanistic insights (obtained from advanced characterization) into these catalytic systems are then discussed, followed by the proposed future research avenues for the field. This review serves as the roadmap for developing efficient catalysts to advance CO<sub>x</sub>-to-ethanol technology.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 19","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202501092","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemCatChemPub Date : 2025-09-02DOI: 10.1002/cctc.202500991
Hengyu Zhao, Jing Zhao, Xue Li, Bate Nasen, Yang Wu, Xinlong Wang, Jinxiong Wu, Yaya Wang
{"title":"Ni–O–Ca Interfacial Electron Transfer Channels Engineered From Electroplating Sludge for Ultrafast 4-Nitrophenol Reduction","authors":"Hengyu Zhao, Jing Zhao, Xue Li, Bate Nasen, Yang Wu, Xinlong Wang, Jinxiong Wu, Yaya Wang","doi":"10.1002/cctc.202500991","DOIUrl":"https://doi.org/10.1002/cctc.202500991","url":null,"abstract":"<p>The catalytic reduction of 4-nitrophenol (4-NP), a persistent environmental pollutant faces dual challenges reliance on noble metals and inefficient utilization of hydrogen radicals (H*). Meanwhile, nickel-containing sludge generated by the electroplating industry, classified as hazardous waste has long posed significant disposal conundrums. Herein, we developed a noble metal-free pyroxene-type CaNi(Si<sub>2</sub>O<sub>6</sub>) catalyst, synthesized from electroplating sludge, that simultaneously addresses these challenges through dynamically reconstructed Ni–O–Ca interface with oxygen vacancies and interfacial electron transfer channels. Ni@Ca-195/20 establishes a self-sustaining catalytic system, achieving a remarkable conversion of 96.8% with 0.1 mM NaBH<sub>4</sub> and 0.05 mg catalyst, while maintaining stability over 31 cycles in low concentration regimes. Integrated characterization combined with catalytic performance evaluation reveals an interfacial electron transfer mechanism: the engineered interface enables in situ reduction of Ni<sup>2+</sup> generates metallic electron-deficient Ni<sup>δ+</sup> species, enhancing 4-NP<sup>−</sup> and BH<sub>4</sub><sup>−</sup> adsorption through dual-site coordination. Oxygen vacancies accelerate BH<sub>4</sub><sup>−</sup> hydrolysis, while electron transfer channels sustain H* flux via Ca<sup>2+</sup> modulated charge equilibration. This work establishes a waste-to-functionality paradigm for designing defect-engineered catalysts while advancing sustainable remediation of nitroaromatic pollutants.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145316693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemCatChemPub Date : 2025-09-02DOI: 10.1002/cctc.202500720
Ellen Held, Dr. Paul Knüpfer, Prof. Dr. Sven Kureti
{"title":"Coking of Extruded H-ZSM-5 Zeolite Catalyst in Methanol to Gasoline","authors":"Ellen Held, Dr. Paul Knüpfer, Prof. Dr. Sven Kureti","doi":"10.1002/cctc.202500720","DOIUrl":"https://doi.org/10.1002/cctc.202500720","url":null,"abstract":"<p>The present study deals with the production of sustainable fuels by the methanol to gasoline (MtG) process. As the conversion suffers from catalyst coking, this work investigated the effect of local coke deposits on the MtG performance using H-ZSM-5 zeolite extrudates. Spent catalysts were taken from defined sections of an MtG pilot plant after an operation time of 1000 h. The samples were evaluated toward MtG performance and physicochemical properties employing N<sub>2</sub> physisorption, X-ray diffraction, temperature-programmed desorption of ammonia and isopropylamine, thermogravimetry, UV/Vis spectroscopy, Raman spectroscopy, and laser desorption and ionization coupled with mass spectrometry. The catalyst characterization showed substantial deposition of polyaromatic hard coke decreasing from 0.129 to 0.046 g/g along the catalyst bed. The strong coking at the inlet was associated with the initially high MtG rate and the recycling of short-chain olefins, enhancing the presence of coke precursors. The coke deposits blocked active Brønsted acid sites of the zeolite, which decreased from 43 to 15 µmol/g toward the inlet. Consequently, the MtG activity and selectivity were clearly affected by the axial position, with the lowest performance in the inlet section due to loss of hydrocarbon coupling activity of the zeolite.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500720","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145316660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A Multicomponent Synthetic Strategy for 2-Pyrazolines and Pyrimidines Through Activation of Renewable Alcohols by a Versatile Fe(III) Catalyst and Friedländer Quinoline Synthesis","authors":"Prashant Kukreti, Rahul Chauhan, Abhishek Panwar, Yutaka Hitomi, Kaushik Ghosh","doi":"10.1002/cctc.202500620","DOIUrl":"https://doi.org/10.1002/cctc.202500620","url":null,"abstract":"<p>In this study, we have reported the first Fe(III) catalyzed eco-friendly, practical, and less expensive multicomponent synthesis (MCS) of pyrazolines and pyrimidines by dehydrogenation of greener benzyl alcohols. A well-defined bimetallic μ-oxo iron(III) was synthesized and characterized by a number of spectroscopic techniques. The molecular structure of the complex was determined by single-crystal X-ray diffraction. The iron(III) complex (<b>C1</b>) has been utilized as a catalyst for the MCS of pyrazolines from sustainable benzyl alcohols, aromatic ketones, and phenylhydrazine. The catalyst was further utilized for the MCS of pyrimidines from phenylacetylene, amidine derivatives via activation of alcohols. The efficiency of this catalyst was also scrutinized for quinoline synthesis from acceptorless dehydrogenative (AD) coupling of 2-aminobenzyl alcohol with aromatic ketones. A wide range of substrates with diverse functionality was explored, and a total of 44 derivatives of 1,3,5-trisubstituted pyrazolines, 38 derivatives of 2,4,6-trisubstituted pyrimidines, and 35 derivatives of quinolines were explored and characterized, having an isolated yield up to 95%. The current methodology is also utilized for gram-scale synthesis for large-scale applicability. Various controlled experiments and DFT optimized study were performed to reveal the possible intermediates and explain the plausible reaction mechanism.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145316694","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemCatChemPub Date : 2025-08-29DOI: 10.1002/cctc.202501024
Luchao Huang, Dr. Qian Xu, Dr. Yi Tu, Dr. Xingwang Cheng, Dr. Dongling Zhang, Dr. Jun Hu, Dr. Honghe Ding, Prof.Dr. Junfa Zhu
{"title":"O2 Activation on Au/CeOX(111) Model Catalysts and Its Role in CO Oxidation","authors":"Luchao Huang, Dr. Qian Xu, Dr. Yi Tu, Dr. Xingwang Cheng, Dr. Dongling Zhang, Dr. Jun Hu, Dr. Honghe Ding, Prof.Dr. Junfa Zhu","doi":"10.1002/cctc.202501024","DOIUrl":"https://doi.org/10.1002/cctc.202501024","url":null,"abstract":"<p>The O<sub>2</sub> activation mechanism of Au/CeO<i><sub>x</sub></i> (111) (1.5 < <i>x </i>≤ 2) model catalysts has been systematically studied through an integrated surface science approach that combines infrared reflection absorption spectroscopy (IRAS), low-energy electron diffraction (LEED), resonant photoemission spectroscopy (RPES), work function measurements, and isotope-labeled temperature‒programmed desorption (TPD). The key findings reveal that, in contrast to the fully oxidized CeO<sub>2</sub>(111) and Au/CeO<sub>2</sub>(111) surfaces, which are inert toward O<sub>2</sub> adsorption, superoxide species (O<sub>2</sub><sup>−</sup>) are detected on the oxygen-deficient CeO<sub>1.85</sub>(111) and Au/CeO<sub>1.85</sub>(111) surfaces upon O<sub>2</sub> adsorption at 105 K, which subsequently undergo dissociation as the surfaces are annealed, leading to formation of atomic oxygen, which reoxidizes the reduced ceria surfaces. Isotopic labeling TPD experiments using <sup>13</sup>C<sup>16</sup>O and <sup>18</sup>O<sub>2</sub> uncover the critical role of <sup>18</sup>O<sub>2</sub> activation in <sup>13</sup>C<sup>16</sup>O oxidation on the Au/CeO<sub>1.85</sub>(111) surface, which proceeds in the dual pathways: i) reaction of adsorbed <sup>13</sup>C<sup>16</sup>O on the Au nanoparticles with lattice oxygen (<sup>16</sup>O) of the ceria to form <sup>13</sup>C<sup>16</sup>O<sub>2</sub>, generating oxygen vacancies, and ii) activation of <sup>18</sup>O<sub>2</sub> at vacancies to form O<sub>2</sub><sup>-</sup>, which dissociates and oxidizes <sup>13</sup>C<sup>16</sup>O to <sup>13</sup>C<sup>16</sup>O<sup>18</sup>O while replenishing lattice oxygen. These findings establish superoxide as the key intermediate and highlight the Mars–van Krevelen redox mechanism in sustaining catalytic CO oxidation.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 20","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145317811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}