Journal of Catalysis最新文献

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Thermosensitive four-arm star-shaped copolymers with phthalocyanine as core and porphyrin copolymer as arms was used as visible light photocatalyst
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-13 DOI: 10.1016/j.jcat.2025.116009
Shan Wu , Jian Shi , Qian Duan , Ludan Shang , Xiaodong Zhang , Yuhan Duan
{"title":"Thermosensitive four-arm star-shaped copolymers with phthalocyanine as core and porphyrin copolymer as arms was used as visible light photocatalyst","authors":"Shan Wu ,&nbsp;Jian Shi ,&nbsp;Qian Duan ,&nbsp;Ludan Shang ,&nbsp;Xiaodong Zhang ,&nbsp;Yuhan Duan","doi":"10.1016/j.jcat.2025.116009","DOIUrl":"10.1016/j.jcat.2025.116009","url":null,"abstract":"<div><div>Porphyrins and phthalocyanines are considered as visible light catalysts with great development potential due to their unique π-conjugated structure, strong visible light absorption and structural tunability. However, they are easy to aggregate and difficult to dissolve, and their application in the field of photocatalysis is limited. Based on the above problems, in this study, three four-arms star-shaped thermosensitive copolymers (PcZn-(PNIPAM<sub>n</sub>-co-PUMPP<sub>m</sub>)<sub>4</sub>) photocatalysts with zinc phthalocyanine as the core and porphyrin thermosensitive copolymer as the arms was constructed by using RAFT polymerization technology and the ’core first’ route. The visible light catalytic activity of the prepared star-shaped copolymers was evaluated by using 1,5-dihydroxynaphthalene (DHN) and methylene blue (MB) as model pollutants. The three copolymers were found to be effective in oxidizing DHN to juglone and degrading MB. Among them, PcZn-(PNIPAM<sub>33.5</sub>-co-PUMPP<sub>1.6</sub>)<sub>4</sub> (P3) showed the highest DHN conversion efficiency (100.0 %), reaction yield (70.0 %) and MB degradation (96.9 %). <sup>1</sup>O<sub>2</sub> and O<sub>2</sub>·<sup>-</sup> are the main active substances in the visible photocatalytic process. Based on UV–vis absorption spectra, Fluorescence spectra, EIS Nyquist plots and transient photocurrents, it is confirmed that P3 has a wider range of visible light absorption, and there is effective energy and electron transfer between TTPcZn and UMPP units in P3, which makes it have higher catalytic activity. More importantly, the lower critical solution temperature (32.6 ∼ 32.9 °C) of P3 makes it possible to achieve homogeneous catalysis and heterogeneous recovery through simple temperature regulation in the catalytic process, which makes P3 have good reusability. This work paves a way for the construction of high-performance and recyclable visible polymer photocatalyst.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"445 ","pages":"Article 116009"},"PeriodicalIF":6.5,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418465","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}
引用次数: 0
Ten recommendations for literature data generation for chemical process optimization in renewable feedstock conversion
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-13 DOI: 10.1016/j.jcat.2025.116004
Siddhant M. Lambor , Dionisios G. Vlachos
{"title":"Ten recommendations for literature data generation for chemical process optimization in renewable feedstock conversion","authors":"Siddhant M. Lambor ,&nbsp;Dionisios G. Vlachos","doi":"10.1016/j.jcat.2025.116004","DOIUrl":"10.1016/j.jcat.2025.116004","url":null,"abstract":"<div><div>Process development of recyclable and renewable feedstocks entails intensive and tedious catalyst and solvent screening and multiparameter process exploration. The solid nature of these feedstocks necessitates highly time-consuming, batch experiments, leading to limited published datasets. Our ability to rapidly advance process development requires a systematic approach to the simultaneous optimization of catalysts, solvents, and processing conditions. One approach toward this goal is to harness and analyze accumulated literature data to develop performance-process correlations. With this goal, we study a prototype biomass reaction, the fructose dehydration to 5-hydroxymethyl furfural (HMF) over zeolite catalysts. We explore literature data to optimize the vast descriptor space of zeolite characteristics, solvents, and process conditions using correlation analysis. We assess the quality of reported literature data and identify where provenance is lacking. We develop apparent kinetic analysis to correlate performance with solvent and catalyst properties. We showcase that solvents and to an extent processing conditions dominate HMF yield; in contrast, zeolites play a secondary role for this chemistry. We provide ten recommendations for improving this methodology to extract further knowledge and improve process optimization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 116004"},"PeriodicalIF":6.5,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418464","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}
引用次数: 0
Proton shuttle mediated by ionic liquid promotes aldol condensation
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-11 DOI: 10.1016/j.jcat.2025.116001
Tianhao Zhang , Hanwen Yan , Chong Zhang , Yiqian Yang , Jie Li , Guoliang Zhang , Junping Zhang , Gang Wang , Chunshan Li
{"title":"Proton shuttle mediated by ionic liquid promotes aldol condensation","authors":"Tianhao Zhang ,&nbsp;Hanwen Yan ,&nbsp;Chong Zhang ,&nbsp;Yiqian Yang ,&nbsp;Jie Li ,&nbsp;Guoliang Zhang ,&nbsp;Junping Zhang ,&nbsp;Gang Wang ,&nbsp;Chunshan Li","doi":"10.1016/j.jcat.2025.116001","DOIUrl":"10.1016/j.jcat.2025.116001","url":null,"abstract":"<div><div>Effective strategy is intensively desired to construct efficient and durable catalytic system for mild aldol condensation between aldehydes, considering the profound significance in synthesis of high-valued <em>α</em>, <em>β</em>-unsaturated aldehydes. Although series of mild catalytic systems using secondary amine-based catalysts have been proposed, the compatibility of high catalytic selectivity and durability still troubles the researchers in this field. Here, we developed a protonated diethanolamine ionic liquid catalyzed mild aldol reaction system with reasonable regulation of ion pair strength and ionic cluster microenvironment based on the deep insights into proton shuttle effects to improve catalytic selectivity and durability for the probed methacrolein synthesis. The interplay between the cation and anion mediated proton shuttle was elucidated by detailed kinetics derived from <em>in situ</em> Raman spectroscopy and theoretical calculations. Further experimental and characterization facts combined with molecular dynamic simulations identify the weak interaction of cation–anion pair and metastable worm-like cluster microenvironment facilitate proton shuttle and thus improve catalytic performance and durability. Consequently, the formation rate of methacrolein was enhanced by one fold, while overall side reaction rates were reduced by 27.5% compared to the conventional <em>sec</em>-amine catalyst. Additionally, this strategy also exhibited significant promotion in catalytic activity, selectivity, and durability in synthesis of the other representative <em>α</em>, <em>β</em>-unsaturated aldehydes. These findings will offer reference for the construction and modulation of ionic liquid catalyzed mild aldol reaction system utilizing proton shuttle effects.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 116001"},"PeriodicalIF":6.5,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393982","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}
引用次数: 0
Insights into the catalytic synthesis of 2,5-hexanedione from the novel biomass-derived platform compound 5-chloromethylfurfural using NiMo@HZSM-5 catalyst
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-11 DOI: 10.1016/j.jcat.2025.116000
Shibo Yang , Wenbo Liao , Hangwei Qin , Tong Sun , Yadong Liu , Xiaokai Li , Wenlong Jia , Xing Tang , Lu Lin , Yong Sun
{"title":"Insights into the catalytic synthesis of 2,5-hexanedione from the novel biomass-derived platform compound 5-chloromethylfurfural using NiMo@HZSM-5 catalyst","authors":"Shibo Yang ,&nbsp;Wenbo Liao ,&nbsp;Hangwei Qin ,&nbsp;Tong Sun ,&nbsp;Yadong Liu ,&nbsp;Xiaokai Li ,&nbsp;Wenlong Jia ,&nbsp;Xing Tang ,&nbsp;Lu Lin ,&nbsp;Yong Sun","doi":"10.1016/j.jcat.2025.116000","DOIUrl":"10.1016/j.jcat.2025.116000","url":null,"abstract":"<div><div>Currently, there exists a significant deficiency of reports addressing the direct synthesis of 2,5-hexanedione (HD) from biomass a derivatives 5-Chloromethylfurfural (CMF). The in-situ generation of hydrochloric acid during the hydrogenation process of CMF necessitates catalysts with exceptional acid resistance, which has compelled previous studies to rely on noble-metal catalysts—an approach that poses challenges for scaling up HD production. Herein, this study presents the inaugural report of a non-noble metal nickel-based alloy catalyst synthesized through a straightforward wet impregnation method, which facilitates the efficient catalytic hydrogenation of CMF to produce HD under mild conditions. The results demonstrate that complete conversion of CMF was achieved and an 81.6 % yield of HD was obtained under optimal reaction conditions. In addition, the reaction pathway for synthesizing HD from CMF was elucidated based on the reaction kinetics and gas chromatography-mass spectrometry analysis, accompanied by an in-depth investigation into the reaction mechanism. The molybdenum was incorporated into the catalyst to form alloy components, which significantly enhanced the stability and acid resistance of the catalyst, thereby improving its catalytic performance. This study presents a novel approach for non-noble metal alloy catalysts to efficiently facilitate the conversion of biomass derivatives into downstream chemicals in an acidic environment.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 116000"},"PeriodicalIF":6.5,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143393954","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}
引用次数: 0
Positive shift of the d-Band center in Cu nanoparticles facilitates electrocatalytic hydrogenation of furfural under mild pH conditions
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-10 DOI: 10.1016/j.jcat.2025.116003
Huabin Lian , Riming Hu , Lin Zheng , Daowei Gao , Shuai Wang , Rongyao Wang , Bin Wang , Guozhu Chen
{"title":"Positive shift of the d-Band center in Cu nanoparticles facilitates electrocatalytic hydrogenation of furfural under mild pH conditions","authors":"Huabin Lian ,&nbsp;Riming Hu ,&nbsp;Lin Zheng ,&nbsp;Daowei Gao ,&nbsp;Shuai Wang ,&nbsp;Rongyao Wang ,&nbsp;Bin Wang ,&nbsp;Guozhu Chen","doi":"10.1016/j.jcat.2025.116003","DOIUrl":"10.1016/j.jcat.2025.116003","url":null,"abstract":"<div><div>The electrocatalytic reduction of biomass-derived furfural represents a sustainable pathway for the production of furfuryl alcohol and 2-methylfuran, serving respectively as value-added chemicals and biofuels. However, the production of these high-value-added products under mild conditions is hampered by low Faradaic efficiency. In this study, we develop a strategy to establish strong metal-support interactions, enabling Cu/NC (nitrogen-doped carbon) catalysts to efficiently produce value-added products under mild conditions. Specifically, we prepare a cost-effective NC support with highly dispersed ultrafine nano-Cu particles of approximately 1 nm in diameter. Under mild pH conditions, our comparative experiments show that the Faradaic efficiency for value-added products (furfuryl alcohol and 2-methylfuran) is nearly four times higher than that of commercial foam copper. We elucidate the influence of nitrogen-doped supports on the behavior of the supported metal Cu. Comprehensive in-situ infrared reflection absorption spectroscopy characterization and DFT theoretical calculations reveal a positive shift in the d-band center of the Cu 3d orbitals. This shift enhances the adsorption of furfural C1=O1 bonds on the Cu/NC catalyst and improves its capacity to bind active hydrogen, thereby increasing the Faradaic efficiency of the value-added products. Our findings advance theoretical understanding and providing practical insights for electrocatalytic hydrogenation of furfural under mild pH conditions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 116003"},"PeriodicalIF":6.5,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385449","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}
引用次数: 0
Toward selective electrooxidation of HMF to FDCA: Suppressing non-Faradaic transformations via low temperature electrolysis
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-10 DOI: 10.1016/j.jcat.2025.116002
Gui-Rong Zhang , Zhiyuan Sun , Xinyu Liu , Jiansong Wang , He Li , Xiaoliang Qu , Hui Yu , Liu-Liu Shen , Donghai Mei
{"title":"Toward selective electrooxidation of HMF to FDCA: Suppressing non-Faradaic transformations via low temperature electrolysis","authors":"Gui-Rong Zhang ,&nbsp;Zhiyuan Sun ,&nbsp;Xinyu Liu ,&nbsp;Jiansong Wang ,&nbsp;He Li ,&nbsp;Xiaoliang Qu ,&nbsp;Hui Yu ,&nbsp;Liu-Liu Shen ,&nbsp;Donghai Mei","doi":"10.1016/j.jcat.2025.116002","DOIUrl":"10.1016/j.jcat.2025.116002","url":null,"abstract":"<div><div>Electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a promising strategy for biomass valorization. However, a significant challenge arises from the substantial carbon loss due to spontaneous HMF degradation in alkaline electrolytes, particularly at high concentrations. In this study, we present a straightforward approach to mitigating carbon loss during the electrochemical conversion of HMF to FDCA by suppressing non-Faradaic degradation through low-temperature electrolysis. Notably, under conventional room temperature conditions, carbon losses of up to 25 % can occur, whereas our low-temperature electrolysis method reduces carbon loss to negligible levels (&lt; 1 %) even at high HMF concentrations (up to 500 mM) in highly alkaline electrolyte (2.0 M KOH). This strategy effectively addresses the long-standing challenge of balancing the enhanced kinetics of HMF electrooxidation with the accelerated degradation of HMF as its concentration increases in alkaline media. Our findings highlight the critical role of suppressing non-Faradaic degradation in the efficient conversion of HMF and demonstrate that low-temperature electrolysis offers a viable solution to the challenges of industrial-scale electrochemical biomass valorization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 116002"},"PeriodicalIF":6.5,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385450","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}
引用次数: 0
Systematic study on efficient transfer hydrogenation of levulinate esters to γ-valerolactone over robust catalyst
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-08 DOI: 10.1016/j.jcat.2025.115999
Liangqing Zhang , Hong Xiao , Ben Zhou , Yonglin Hong , Qiaomei Wu , Jiarong Qiu , Jianfeng Chen
{"title":"Systematic study on efficient transfer hydrogenation of levulinate esters to γ-valerolactone over robust catalyst","authors":"Liangqing Zhang ,&nbsp;Hong Xiao ,&nbsp;Ben Zhou ,&nbsp;Yonglin Hong ,&nbsp;Qiaomei Wu ,&nbsp;Jiarong Qiu ,&nbsp;Jianfeng Chen","doi":"10.1016/j.jcat.2025.115999","DOIUrl":"10.1016/j.jcat.2025.115999","url":null,"abstract":"<div><div>The CuMgZrO<sub>x</sub> oxide catalysts were employed with economical 2-PrOH as the hydrogen donor for catalytic transfer hydrogenation of ethyl levulinate (EL) to γ-valerolactone (GVL). The cost-effective Cu<sub>1</sub>Mg<sub>1.15</sub>Zr<sub>2</sub>O<sub>x</sub> catalyst exhibited excellent physicochemical properties, with 99.8% EL conversion and 88.0% GVL yield. Studies have shown that sufficient basic sites of the catalyst, along with the maintenance of the Cu<sup>2+</sup>/Cu<sup>+</sup> state rather than Cu<sup>0</sup>, are crucial for achieving high GVL yields. Optimization of the substrate-to-hydrogen donor ratio (1:3), along with recycling tests and characterization, demonstrated excellent activity (99.5% EL conversion and 90.0% GVL yield) and cycle stability for the Cu<sub>1</sub>Mg<sub>1.15</sub>Zr<sub>2</sub>O<sub>x</sub> catalyst, highlighting its strong potential for practical applications. The mechanism for GVL production from EL via the metal hydride as the dominant route was proposed based on rigorous experimental studies and in-depth characterization. Substrate scope evaluation showed that the Cu<sub>1</sub>Mg<sub>1.15</sub>Zr<sub>2</sub>O<sub>x</sub> catalyst also exhibited outstanding activity in converting methyl levulinate and butyl levulinate to GVL.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 115999"},"PeriodicalIF":6.5,"publicationDate":"2025-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143367602","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}
引用次数: 0
The importance of alkali cations in manganese-catalyzed enantioselective transfer hydrogenation of ketones: An insight into the effect of “NH” and “CN” groups in ligands
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-07 DOI: 10.1016/j.jcat.2025.115998
Zechen Wang , Yuanyuan Wang , Quanming Lyu , Dongzhi Zhu , Zhifeng Ma , Badral Gansukh , Libin Li , Huimin Liu , Ning Ma , Zheng Wang
{"title":"The importance of alkali cations in manganese-catalyzed enantioselective transfer hydrogenation of ketones: An insight into the effect of “NH” and “CN” groups in ligands","authors":"Zechen Wang ,&nbsp;Yuanyuan Wang ,&nbsp;Quanming Lyu ,&nbsp;Dongzhi Zhu ,&nbsp;Zhifeng Ma ,&nbsp;Badral Gansukh ,&nbsp;Libin Li ,&nbsp;Huimin Liu ,&nbsp;Ning Ma ,&nbsp;Zheng Wang","doi":"10.1016/j.jcat.2025.115998","DOIUrl":"10.1016/j.jcat.2025.115998","url":null,"abstract":"<div><div>A family of new ferrocene-based chiral PNN ligands and two novel manganese(I) PNN-pincer complexes (<strong>Mn1</strong> and <strong>Mn2</strong>) with the “NH” or“C=N”group have been established, enabling the asymmetric transfer hydrogenations of (hetero)aryl alkyl ketones (33 examples) with high activity (up to 1250 TON) and excellent enantioselectivity (up to &gt; 96 % ee). The catalytic studies and DFT investigations led to the conclusion that the alkali cation, especially, Li<sup>+</sup> is an important player in the ligand-assisted hydrogen-transfer step and supports a new preferred NLi/MH instead of NH/MH bifunctional mechanism. Furthermore, humidity sensitivity experiments and DFT calculations highlight the superior binding properties of the imine pincer ligand in <strong>Mn2</strong> over its amine-containing counterpart in <strong>Mn1</strong>. Overall, the lithium effect in the manganese (I) catalytic system has proved useful for enhancing the ATH of ketones.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 115998"},"PeriodicalIF":6.5,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143367603","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}
引用次数: 0
Understanding the synergetic catalytic functions of Cu–Pt active sites in the bimetallic CuPt/ZrO2 catalyst in CO oxidation
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-07 DOI: 10.1016/j.jcat.2025.115995
Lianxin Xu , Peng Zheng , Junbo Tian , Tengfei Zhang , Renzheng Jiang , Jiajian Gao , Lili Zhang , Guangwen Xu , Ziyi Zhong , Fabing Su
{"title":"Understanding the synergetic catalytic functions of Cu–Pt active sites in the bimetallic CuPt/ZrO2 catalyst in CO oxidation","authors":"Lianxin Xu ,&nbsp;Peng Zheng ,&nbsp;Junbo Tian ,&nbsp;Tengfei Zhang ,&nbsp;Renzheng Jiang ,&nbsp;Jiajian Gao ,&nbsp;Lili Zhang ,&nbsp;Guangwen Xu ,&nbsp;Ziyi Zhong ,&nbsp;Fabing Su","doi":"10.1016/j.jcat.2025.115995","DOIUrl":"10.1016/j.jcat.2025.115995","url":null,"abstract":"<div><div>Catalytic oxidation processes for carbon monoxide (CO) typically rely on catalysts made from noble metals. However, due to the scarcity and high cost of noble metals, developing low–cost, highly active, and stable catalysts with low noble metal loading is highly demanded but challenging. Herein, we synthesized ZrO<sub>2</sub>–supported CuPt alloy nanoparticle (NP) catalyst (0.3Cu0.1Pt/ZrO<sub>2</sub>), with a Cu loading of 0.3 wt% and a Pt loading of 0.1 wt%, using a straightforward impregnation method. This catalyst structure enables the well-mixing of Cu and Pt atoms in the pristine and partially oxidized catalysts during the CO oxidation. The temperature for 0.3Cu0.1Pt/ZrO<sub>2</sub> to reach 90 % CO conversion is 160 °C, which is much lower than those for 0.1Pt/ZrO<sub>2</sub> (220 °C) and 0.4Cu/ZrO<sub>2</sub> (195 °C). Extensive characterizations were conducted, particularly for the pristine catalysts. The experiments and density functional theory (DFT) calculations results reveal that the interaction between the two metals significantly modified the electronic property of the catalyst. On CuPt bimetallic sites, the electron transfer from Cu to Pt weakens the strong adsorption of CO, and Cu species provide sites for O<sub>2</sub> adsorption, which synergistically promotes the CO oxidation on the surface of CuPt NPs. This research provides deep insights into the relationship between the catalyst structure and their catalytic performance and paves the way for developing highly active bimetallic synergistic catalysts for CO oxidation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"444 ","pages":"Article 115995"},"PeriodicalIF":6.5,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143367604","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}
引用次数: 0
Mechanism of CO2 Conversion to Methanol on a Highly Representative Model Cu/ZnO Interface
IF 6.5 1区 化学
Journal of Catalysis Pub Date : 2025-02-05 DOI: 10.1016/j.jcat.2025.115997
David A. Jurado A. , Michael D. Higham , Yong Rui Poh , C. Richard A. Catlow , Ingo Krossing
{"title":"Mechanism of CO2 Conversion to Methanol on a Highly Representative Model Cu/ZnO Interface","authors":"David A. Jurado A. ,&nbsp;Michael D. Higham ,&nbsp;Yong Rui Poh ,&nbsp;C. Richard A. Catlow ,&nbsp;Ingo Krossing","doi":"10.1016/j.jcat.2025.115997","DOIUrl":"10.1016/j.jcat.2025.115997","url":null,"abstract":"<div><div>The mechanism of CO<sub>2</sub> hydrogenation to methanol is modelled using plane-wave DFT applied to a representative model Cu<sub>8</sub>-ZnO catalyst system (CZ), obtained via unbiased Monte Carlo exploration of Cu cluster growth over a reconstructed polar ZnO surface. Enhanced CO<sub>2</sub> adsorption and activation is found at the active Cu/ZnO interfacial site – resembling a V<sub>O</sub> vacancy – compared to sites on other Cu-based systems. Three competing methanol formation mechanisms (the formate, carboxyl and CO hydrogenation pathways) are investigated; the least energy-demanding pathway followed the formate mechanism: CO<sub>2</sub>* → HCOO* → H<sub>2</sub>COO* → H<sub>2</sub>COOH* → H<sub>2</sub>CO* → H<sub>3</sub>CO* → H<sub>3</sub>COH. We report the coexistence of several formate adsorbates, some of which being highly stable spectators that were observed spectroscopically. Only one higher energy interfacial Cu/ZnO formate species is a true intermediate relevant for catalysis, undergoing subsequent hydrogenation to methanol. The methoxy intermediate is also highly stable, in agreement with its spectroscopic observation. The most energy-demanding elementary process is hydrogenation of methoxy to methanol (<em>E</em><sub>a</sub> = 1.20 eV). Furthermore, the calculations indicate the possible role of CO and H<sub>2</sub>CO* in scavenging surface O* by forming CO<sub>2</sub>* or H<sub>2</sub>COO*, thus preventing the poisoning of active sites. Finally, water is expected to form from O* on a pure Cu site only, but not the Cu/ZnO interfacial site relevant for MeOH production. The calculations presented provide valuable new insights that allow a more complete rationalisation of experimental observations. They suggest the key steps to enhance catalysis involves destabilizing the long-lived H<sub>3</sub>CO* favouriting its hydrogenation and fast desorption or stabilizing competing intermediates such as H<sub>2</sub>COH*.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"446 ","pages":"Article 115997"},"PeriodicalIF":6.5,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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