Journal of Catalysis最新文献

{"title":"Large-scale, continuous preparation of MnO2 for highly efficient oxidative coupling of amines to imines under mild conditions","authors":"Jia-qi Bai ,&nbsp;Huangfei Liu ,&nbsp;Mei Ma,&nbsp;Zhangkai Qian,&nbsp;Durui Liu,&nbsp;Mengdie Cai,&nbsp;Jingshuai Chen,&nbsp;Lisheng Guo,&nbsp;Yuxue Wei,&nbsp;Fang Chen,&nbsp;Song Sun","doi":"10.1016/j.jcat.2025.116209","DOIUrl":"10.1016/j.jcat.2025.116209","url":null,"abstract":"<div><div>Aerobic oxidation self-coupling of amines is an important method to prepare imines, however, the reported catalyst suffered from expensive price, complex preparation method and harsh reaction condition. Herein, large-scale, continuous preparation of MnO₂ was achieved by cheap microfluidic method and applied in the oxidative coupling of amines to imines. The δ-MnO₂ showed 98.0 % yield with initial TOF of 4.17 h⁻¹ under 343 K and 0.1 MPa O₂, which was the maximum among the reported non-noble metallic based catalysts under mild reaction conditions. Moreover, the δ-MnO₂ can be reused at least 7 times and exhibited wide substrate applicability. Furthermore, the various characterizations showed that the superior catalytic performance can be ascribed to the high concentration of surface Mn³⁺, rich oxygen vacancies and more acidic and basic sites. Additionally, the reaction path and mechanism were proposed based on the kinetics and <em>in-situ</em> DRIFTS. This work provided a feasible approach to prepare large-scale MnO₂ for highly efficient oxidative coupling of amines to imines under mild conditions with low cost.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116209"},"PeriodicalIF":6.5,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143932584","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":"HOF-to-MOF transformation strategy for Porphyrin-based MOF photocatalysts","authors":"Mengting Wu ,&nbsp;Zhipeng Xie ,&nbsp;Jiaxu Qi ,&nbsp;Jie Hu ,&nbsp;Lele Wang ,&nbsp;Weikang Wang ,&nbsp;Qinqin Liu ,&nbsp;Yazhou Zhou ,&nbsp;Jimmy C. Yu","doi":"10.1016/j.jcat.2025.116207","DOIUrl":"10.1016/j.jcat.2025.116207","url":null,"abstract":"<div><div>Photocatalysis is a sustainable and eco-friendly technology for solar energy conversion. However, the development of advanced photocatalysts remains challenging due to slow exciton dynamics and limited active site accessibility. Herein, we present a novel transformation strategy for synthesizing metal–organic frameworks (MOFs) from hydrogen-bonded organic frameworks (HOFs). This transformation is driven by the in-situ conversion of hydrogen bonds to coordination bonds. A series of 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl) tetra benzoic acid (TCPP)-based MOFs, denoted as H_III-MT (M = Cu, Zn, Fe, Ce, and Mg), were successfully synthesized from TCPP HOF (H_III). The HOF offers a flexible framework that guides the precise assembly of porphyrin ligands and metal centers, making it possible to develop a highly ordered molecular arrangement with abundant metal active sites. The resulting H_III-CuT exhibits remarkable photocatalytic performance and achieves 88 % carbamazepine degradation under solar light. This efficiency surpasses template-free CuT, H_III, and aggregated TCPP by 2.4, 3.6, and 8 times, respectively. The enhanced performance is due to prolonged electron lifetimes and improved substrate adsorption. This work provides a new pathway for designing high-performance MOF photocatalysts with controlled orientation and tailored structure, opening great opportunities environmental remediation and sustainable energy applications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116207"},"PeriodicalIF":6.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143931117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Promoting activation of N2 and H2O via dual active sites synergistically for efficient photocatalytic ammonia synthesis","authors":"Hao Du ,&nbsp;Huimin Li ,&nbsp;Zufan Yang ,&nbsp;Shengjie Xia ,&nbsp;Jing Chen ,&nbsp;Yue Meng ,&nbsp;Litong Bian ,&nbsp;Geng Yang ,&nbsp;Guanhua Zhang","doi":"10.1016/j.jcat.2025.116197","DOIUrl":"10.1016/j.jcat.2025.116197","url":null,"abstract":"<div><div>Photocatalytic nitrogen fixation is a green synthetic process for the direct conversion of N₂ and H₂O to ammonia using solar energy. However, the scarcity of N₂ and H₂O active sites is a limiting factor in the kinetics of nitrogen fixation reactions. The construction of spatially synergistic dual active sites is a feasible strategy to overcome this challenge. Herein, Fe-doped CdS (FCS) photocatalysts containing S vacancy have been prepared by a simple one-step solvothermal method. The results show that S vacancy in FCS preferentially adsorb H₂O molecules and activate them to active hydrogen (H*) for nitrogen reduction. Fe sites tend to adsorb N₂ molecules and promote the d− band center of CdS to move to Fermi level (E_f), which significantly improves the activation ability of N₂ molecules. The unique dual active sites greatly reduce Gibbs free energy of N₂ and H₂O activation and improve surface reaction kinetics of nitrogen reduction reaction. NH₄⁺ production rate of FCS reached 13.39 μmol · h⁻¹ without sacrificial reagent, which was 13.2 times higher than that of CdS. This study proves the significance of synergy between active sites for improving reaction efficiency and provides inspiration for the construction of dual active systems in photocatalytic nitrogen reduction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116197"},"PeriodicalIF":6.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143931116","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":"Radical-mediated Cα-Cβ cleavage by ZnIn2S4-based heterojunction materials in photo-electro-catalysis","authors":"Jifang Zhang ,&nbsp;Chengcheng Suo,&nbsp;Xinchi Hao,&nbsp;Xingyu Zhu,&nbsp;Yiheng Zhuang,&nbsp;Cunyuan Hu,&nbsp;Wei Li,&nbsp;Sha Luo,&nbsp;Bing Tian,&nbsp;Chunhui Ma,&nbsp;Shouxin Liu","doi":"10.1016/j.jcat.2025.116189","DOIUrl":"10.1016/j.jcat.2025.116189","url":null,"abstract":"<div><div>The selective cleavage of lignin specific linkages for production of high-value chemicals remains a significant challenge due to inherent inertness and complex structure. In this study, we developed a Photo-Electro-Catalysis (PEC) strategy utilizing radicals, which achieved high catalytic efficiency for lignin depolymerization at room temperature (from 10 °C to 35 °C). A heterojunction material composed of 2D ZnIn₂S₄ nanosheets and carbon nanoparticles was synthesized to facilitate efficient electron transfer and radical generation. The quantum yield (2.1858) exceeding 1 suggested a radical chain mechanism in the PEC process. Mechanistic studies revealed that oxygen radical combine with C-centered radicals to form a C_β-OOH peroxide intermediate, leading to C<img>C bond cleavage. Notably, chlorine radicals (•Cl) were introduced for the first time in lignin PEC depolymerization, initiating C_β-H functionalization, cyclization and ring-opening reactions. This approach achieved 100 % C_α-C_β cleavage and over 90 % mass conversion of native G-units lignin. The highest product yields were 233.34 mg g⁻¹ (benzaldehyde), 66.03 mg g⁻¹ (acetophenone), and 54.98 mg g⁻¹ (phenol) from the β-O-4 dimer. This study provides novel insights into radical mechanisms and catalytic strategies for lignin depolymerization into high-value chemicals.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116189"},"PeriodicalIF":6.5,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927183","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":"Predicting a generalized mechanism of branched alkane hydrogenolysis on Ru, Ir, and Pt surfaces relevant to polymer upcycling applications","authors":"Andy Simonson, Lydia Thies, David Hibbitts","doi":"10.1016/j.jcat.2025.116200","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116200","url":null,"abstract":"Here, we present a fundamental study investigating the mechanisms governing C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C hydrogenolysis of branch points within small alkanes on Ir, Pt, and Ru surfaces using Density Functional Theory (DFT). Previous work has shown that activation of unsubstituted C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C bonds occurs through the dehydrogenation of the C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C bond to form a bound alkyne, followed by a kinetically relevant C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C activation and the hydrogenation of the cleaved intermediates to form smaller alkane products. Substituted bonds, in contrast, involve the dehydrogenation of the C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C bond being cleaved, as well as other C atoms near the reacting center. This leads to the counterintuitive observation, that reactions of unsubstituted C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C bonds (having more H to lose) are less inhibited by H&lt;sub&gt;2&lt;/sub&gt; than reactions of substituted C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C bonds (having less H atoms to lose). These prior studies of branched alkane activation, however, focused on Ir catalysts and on methyl-substituted alkanes and cycloalkanes, such that the impact of catalyst identity or of long branches (i.e., like those found in some polymers) on substituted C&lt;img alt=\"single bond\" src=\"https://sdfestaticassets-us-east-1.sciencedirectassets.com/shared-assets/55/entities/sbnd.gif\" style=\"vertical-align:middle\"/&gt;C hydrogenolysis mechanisms is largely unexplored. Here, we consider isobutane activation mechanisms on Ir, Ru, and Pt catalysts, and use these results to predict how a larger branched alkane, 3-ethylpentane, would react, as that molecule is more reminiscent of the branches in polyethylene. DFT-estimated free energy barriers and turnover rates indicate that hydrogenolysis activity and rate inhibition from hydrogen pressure follow a general trend with catalysts following a reactivity trend of Ru &gt; Ir &gt; Pt, where Ru is the most active and most inhibited by H&lt;sub&gt;2&lt;/sub&gt;, with Pt being the least reactive and least inhibited by H&lt;sub&gt;2&lt;/sub&gt; pressure. By categorizing the","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"53 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927184","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":"Role of oxygen vacancies employing GaxZr1-xO2-y / ZrO2 in isobutene generation from ethanol","authors":"Mariana G.S. Pinheiro ,&nbsp;Luciano H. Chagas ,&nbsp;Eugenio F. Souza ,&nbsp;Guilherme G. Gonzalez ,&nbsp;Priscila C. Zonetti ,&nbsp;Odivaldo C. Alves ,&nbsp;Liane M. Rossi ,&nbsp;Omar Ginoble Pandoli ,&nbsp;Roberto R. de Avillez ,&nbsp;Luiz E.P. Borges ,&nbsp;Lucia G. Appel","doi":"10.1016/j.jcat.2025.116205","DOIUrl":"10.1016/j.jcat.2025.116205","url":null,"abstract":"<div><div>This study advances the understanding of oxygen vacancies (Vo) in heterogeneous catalysis, focusing on isobutene synthesis from ethanol. Ga-doped ZrO₂ was investigated and compared with Zn-doped ZrO₂. Characterization techniques, including EPR, XRD, XPS, H₂O dissociation, and Raman spectroscopy, revealed that Ga substitutes Zr in the m-ZrO₂ lattice, generating more Vo than Zn. DFT calculations supported these findings, showing that incorporating two Ga atoms into monoclinic ZrO₂ leads to spontaneous defect formation, with energies more negative than those for Zn-doped ZrO₂. The isobutene synthesis from ethanol involves three steps: the acetaldehyde generation from ethanol, acetone synthesis from this aldehyde, and isobutene formation from acetone, the rate-limiting step (rls). Catalytic tests and CO₂-TPD showed that the Lewis basicity of the ZrO₂-based catalysts is not relevant for the isobutene formation. Experiments with Ga-doped t-ZrO₂ (tetragonal) highlighted the relevance of ZrO₂′s structure in the isobutene synthesis. It was observed that Ga-doped catalysts generate much more isobutene from acetone when compared with Zn-based catalysts. Moreover, the isobutene yield shows a linear correlation with Ga at. %, and consequently, with the Vo concentration. The superior performance of Ga-doped ZrO₂ compared to Zn-doped ZrO₂ might be attributed not only to Ga’s greater ability to generate Vo but also to the formation of a Ga(2)-Vo atomic ensemble, proposed by the DFT studies, which likely participates in the rls of this synthesis. This study offers new insights into the role of Vo in catalytic processes, providing perspectives for improving isobutene synthesis from ethanol and advancing the design of Vo-rich catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116205"},"PeriodicalIF":6.5,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927187","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":"Application of machine learning interatomic potentials in heterogeneous catalysis","authors":"Gbolagade Olajide,&nbsp;Khagendra Baral,&nbsp;Sophia Ezendu,&nbsp;Ademola Soyemi,&nbsp;Tibor Szilvási","doi":"10.1016/j.jcat.2025.116202","DOIUrl":"10.1016/j.jcat.2025.116202","url":null,"abstract":"<div><div>Heterogeneous catalysts are crucial in modern societies as they promote sustainability by enabling lower-energy pathways for various chemical reactions. While Density Functional Theory (DFT) computations can provide critical insights into how heterogeneous catalysts operate at the atomic level, they are limited by computational costs and unfavorable scaling with system size. Recently, machine learning interatomic potentials (MLIPs) have emerged as a promising alternative to DFT, offering near-DFT accuracy at significantly reduced cost. In this perspective, we discuss the application of MLIPs in heterogeneous catalyst modeling as a surrogate for DFT. We detail how MLIPs have been applied in thermal catalysis to probe active sites, enable studying complex metallic and nanoporous catalysts, and investigate the reconstruction of catalytic surfaces. We review the use of MLIPs in electrocatalysis and photocatalysis, emphasizing their capabilities in studying transition metal oxide surfaces and solid–liquid interfaces. We also discuss the current limitations of MLIPs, particularly their challenges with transferability and description of non-local interactions. Finally, we conclude by identifying promising and underexplored domains in which MLIPs can further advance our understanding of heterogeneous catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116202"},"PeriodicalIF":6.5,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927185","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":"Influence of alkali and chloride promoters on silver catalysts in ethylene epoxidation","authors":"Claudia J. Keijzer ,&nbsp;Naud M.T. van de Ven ,&nbsp;Remco Dalebout ,&nbsp;Tracy L. Lohr ,&nbsp;John R. Lockemeyer ,&nbsp;Peter van den Brink ,&nbsp;Petra E. de Jongh","doi":"10.1016/j.jcat.2025.116206","DOIUrl":"10.1016/j.jcat.2025.116206","url":null,"abstract":"<div><div>Commercial ethylene epoxidation catalysts consist of Ag particles supported with α-alumina and contain a mixture of promoters. High activity catalysts typically contain Cs in combination with other alkali promoters and a gaseous organochloride. We studied a series of Ag catalysts that were individually promoted with different alkali species (Li, Na, K, Rb and Cs) at equimolar loadings of 2.5 mol% (mol_alkali/(mol_alkali + mol_Ag)). O₂-TPD experiments revealed that the absorption strength of oxygen onto the silver surface was influenced by the presence of the alkali species. Ethylene epoxidation experiments were performed both in the absence and presence of the industrially vital ethyl chloride promoter. Without the chloride, the alkali-promoted catalysts were less active than the silver reference catalyst and showed a decreased primary ethylene oxide (EO) selectivity. Introducing ethyl chloride to the feed increased the primary EO selectivity of all catalysts to ca. 80% without sacrificing the activity for the alkali-promoted catalysts. Systematic EO isomerization experiments revealed that the secondary reactions of EO are inhibited by alkali promoters on the silver surface rather than on the support. Larger/less electronegative alkali species such as Rb and Cs inhibited EO degradation to a greater extent than Li and Na. However, when ethyl chloride was introduced to the feed the EO conversion of all catalysts was blocked. This study hence demonstrates how the combination of chloride and alkali promoters affects the Ag sites, specifically suppressing both undesired combustion and promoting desired ethylene epoxidation when increasing the conversion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116206"},"PeriodicalIF":6.5,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143927186","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":"Elucidating the role of potassium in methane steam reforming using first-principles-based kinetic Monte Carlo simulations","authors":"Sai Sharath Yadavalli ,&nbsp;Glenn Jones ,&nbsp;Carlos Fonte ,&nbsp;Michail Stamatakis","doi":"10.1016/j.jcat.2025.116203","DOIUrl":"10.1016/j.jcat.2025.116203","url":null,"abstract":"<div><div>In the chemical industry, potassium is commonly employed as a promoter to reduce coke formation on the Ni catalyst surface and has been demonstrated to significantly improve the productivity of the methane steam reforming (MSR) reaction. Despite numerous studies, a detailed understanding of the potassium effect at steam reforming conditions is lacking. In this contribution, we have developed a first-principles-based KMC model of MSR on Ni(1 1 1) and potassium-doped Ni(1 1 1) surfaces. The cluster expansion (CE) methodology was employed to systematically capture adsorbate–adsorbate interactions between MSR species and their effects on reaction rates. We performed KMC simulations with different loadings of potassium (0.5–3 %) on Ni(1 1 1) to understand the effect on MSR net turnover rates and macroscopic coverages. At high temperatures, we found that potassium strongly promotes the oxidation of CH and carbon adsorbates. For instance, at 1273.0 K, we observe that the MSR net turnover rate on the potassium-doped Ni(1 1 1) system (K-Ni(1 1 1)-2.8 %) is around 13.6 times higher than on Ni(1 1 1). The KMC process statistics analysis reveals that key oxidation events such as the formation of CHO, CHOH, COH and CO occur significantly faster on the potassium sites compared to Ni sites. Furthermore, on K-Ni(1 1 1)-2.8 % at 1273.0 K, the CO pathway on the potassium sites, which entails complete dehydrogenation of methane to C and oxidation of the latter to CO, makes the highest contribution (around 57 %) to the MSR net turnover rate. Our KMC simulations provide a deeper mechanistic-level understanding of the role of potassium in MSR and can potentially aid in the design of next-generation Ni-based catalysts that exhibit high activity and stability at steam reforming conditions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116203"},"PeriodicalIF":6.5,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915827","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":"Study of the surface species of CePr-supported Cu, Ni and CuNi catalysts at different Water Gas Shift reaction conditions","authors":"E. Poggio-Fraccari ,&nbsp;R. Jiménez ,&nbsp;A. Karelovic ,&nbsp;L. Alemany ,&nbsp;F. Mariño","doi":"10.1016/j.jcat.2025.116201","DOIUrl":"10.1016/j.jcat.2025.116201","url":null,"abstract":"<div><div>The catalytic performance for Water Gas Shift Reaction and surface species at reaction conditions were studied by operando-DRIFTS of the bare Pr-promoted Ce oxide support, two supported monometallic Cu and Ni, and a bimetallic CuNi catalyst. All samples were thoroughly characterised by Operando-DRIFTS across a range of temperatures (150–375 °C) and two distinct reaction atmospheres: CO–H₂O and CO–H₂O–H₂. The results demonstrated that the nature of the surrounding atmosphere significantly influences the surface chemistry and product distribution. The reactivity was as follows: CePr &lt; Cu/CePr &lt; CuNi/CePr &lt; Ni/CePr. However, the selectivity towards CO₂ was CePr=Cu/CePr &gt; CuNi/CePr &gt; Ni/CePr due to the tendency to produce CH₄ (on Ni-containing catalysts) when H₂ was present in the reaction feed.</div><div>Hence, under oxidising conditions (absence of hydrogen), formate species were stabilised on CePr and Ni/CePr surfaces, indicating a predominant associative mechanism. In contrast, Cu-containing catalysts (Cu/CePr and CuNi/CePr) favoured carbonate formation and suppressed formate accumulation, promoting a redox-type pathway. Under reducing conditions (presence of H₂), Ni facilitated CH₄ formation via methanation, particularly on Ni/CePr. The bimetallic CuNi/CePr catalyst behaved similarly to Cu/CePr under CO–H₂O feed, showing no stable formates, but in the presence of H₂, methane formation and surface-stabilised formates were observed—mimicking the behaviour of Ni/CePr. These findings highlight the role of Cu in modulating the electronic and adsorptive properties of Ni, weakening formate adsorption and delaying methanation, thus enhancing CO₂ selectivity. Overall, the CuNi/CePr system emerges as a complex multimetallic catalyst that adapts to both oxidising and reducing environments, improving WGS performance through a balanced interplay between redox and hydrogenation pathways.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"448 ","pages":"Article 116201"},"PeriodicalIF":6.5,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915825","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}