Journal of Catalysis最新文献_第7页

Proton shuttle mediated by ionic liquid promotes aldol condensation

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

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

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 α, β-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 in situ 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 sec-amine catalyst. Additionally, this strategy also exhibited significant promotion in catalytic activity, selectivity, and durability in synthesis of the other representative α, β-unsaturated aldehydes. These findings will offer reference for the construction and modulation of ionic liquid catalyzed mild aldol reaction system utilizing proton shuttle effects.

{"title":"Proton shuttle mediated by ionic liquid promotes aldol condensation","authors":"Tianhao Zhang , Hanwen Yan , Chong Zhang , Yiqian Yang , Jie Li , Guoliang Zhang , Junping Zhang , Gang Wang , 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 Q2 CHEMISTRY, PHYSICAL

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

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.

{"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 , Wenbo Liao , Hangwei Qin , Tong Sun , Yadong Liu , Xiaokai Li , Wenlong Jia , Xing Tang , Lu Lin , 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 Q2 CHEMISTRY, PHYSICAL

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

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.

{"title":"Positive shift of the d-Band center in Cu nanoparticles facilitates electrocatalytic hydrogenation of furfural under mild pH conditions","authors":"Huabin Lian , Riming Hu , Lin Zheng , Daowei Gao , Shuai Wang , Rongyao Wang , Bin Wang , 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 Q2 CHEMISTRY, PHYSICAL

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

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 (< 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.

{"title":"Toward selective electrooxidation of HMF to FDCA: Suppressing non-Faradaic transformations via low temperature electrolysis","authors":"Gui-Rong Zhang , Zhiyuan Sun , Xinyu Liu , Jiansong Wang , He Li , Xiaoliang Qu , Hui Yu , Liu-Liu Shen , 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 (< 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 Q2 CHEMISTRY, PHYSICAL

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

The CuMgZrO_x 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 Cu₁Mg_1.15Zr₂O_x 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 Cu²⁺/Cu⁺ state rather than Cu⁰, 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 Cu₁Mg_1.15Zr₂O_x 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 Cu₁Mg_1.15Zr₂O_x catalyst also exhibited outstanding activity in converting methyl levulinate and butyl levulinate to GVL.

{"title":"Systematic study on efficient transfer hydrogenation of levulinate esters to γ-valerolactone over robust catalyst","authors":"Liangqing Zhang , Hong Xiao , Ben Zhou , Yonglin Hong , Qiaomei Wu , Jiarong Qiu , 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 Q2 CHEMISTRY, PHYSICAL

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

A family of new ferrocene-based chiral PNN ligands and two novel manganese(I) PNN-pincer complexes (Mn1 and Mn2) 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 > 96 % ee). The catalytic studies and DFT investigations led to the conclusion that the alkali cation, especially, Li⁺ 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 Mn2 over its amine-containing counterpart in Mn1. Overall, the lithium effect in the manganese (I) catalytic system has proved useful for enhancing the ATH of ketones.

{"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 , Yuanyuan Wang , Quanming Lyu , Dongzhi Zhu , Zhifeng Ma , Badral Gansukh , Libin Li , Huimin Liu , Ning Ma , 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 > 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 Q2 CHEMISTRY, PHYSICAL

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

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 ZrO₂–supported CuPt alloy nanoparticle (NP) catalyst (0.3Cu0.1Pt/ZrO₂), 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/ZrO₂ to reach 90 % CO conversion is 160 °C, which is much lower than those for 0.1Pt/ZrO₂ (220 °C) and 0.4Cu/ZrO₂ (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 O₂ 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.

{"title":"Understanding the synergetic catalytic functions of Cu–Pt active sites in the bimetallic CuPt/ZrO2 catalyst in CO oxidation","authors":"Lianxin Xu , Peng Zheng , Junbo Tian , Tengfei Zhang , Renzheng Jiang , Jiajian Gao , Lili Zhang , Guangwen Xu , Ziyi Zhong , 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 7.3 1区化学 Q2 CHEMISTRY, PHYSICAL

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

The mechanism of CO₂ hydrogenation to methanol is modelled using plane-wave DFT applied to a representative model Cu₈-ZnO catalyst system (CZ), obtained via unbiased Monte Carlo exploration of Cu cluster growth over a reconstructed polar ZnO surface. Enhanced CO₂ adsorption and activation is found at the active Cu/ZnO interfacial site – resembling a V_O 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: CO₂*→ HCOO*→ H₂COO*→ H₂COOH*→ H₂CO*→ H₃CO*→ H₃COH. 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 (E_a = 1.20 eV). Furthermore, the calculations indicate the possible role of CO and H₂CO* in scavenging surface O* by forming CO₂* or H₂COO*, 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 H₃CO* favouriting its hydrogenation and fast desorption or stabilizing competing intermediates such as H₂COH*.

{"title":"Mechanism of CO2 conversion to methanol on a highly representative model Cu/ZnO interface","authors":"David A. Jurado A, Michael D. Higham, Yong Rui Poh, C. Richard A. Catlow, Ingo Krossing","doi":"10.1016/j.jcat.2025.115997","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115997","url":null,"abstract":"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*.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"40 1","pages":""},"PeriodicalIF":7.3,"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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Efficient photocatalytic oxidation of cyclohexane to KA oil by carbon nitride hybridized decatungstate under visible light

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-03 DOI: 10.1016/j.jcat.2025.115996

Jue Wang , Jinyi Yang , Siyu Zeng , Huitao Liu , Fei Li , Haijiao Xie , Senpei Tang , Zaihui Fu , Youji Li

The highly selective synthesis of KA oil (cyclohexanol and cyclohexanone) from the oxidation of cyclohexane (CHA) with O₂ under mild conditions is still a very important and challenging research topic. This paper discloses that the hybrid (DTCN) is easily prepared by inducing carbon nitride (CN) in the synthesis of decatungstate (DT) and is found to be efficiently photo-catalyst for the above selective oxidation in acetonitrile. After illumination (LED of 405 nm) for 2 h, the best DTCN-0.5 can achieve 41.03 % CHA conversion and greater than 95 % KA oil selectivity with an apparent quantum efficiency of 25.52 %, which is much superior to the pure DT (12.46 % CHA conversion). Also, it is active for the selective oxidation of other substrates containing inert C(sp³)-H bonds. A series of characterizations, free radical trapping and isotope tracing tests as well as DFT calculations support that the doped CN can construct a built-in electric field with DT to accelerate the separation of the photo-generated charge, thus hoisting the photo-excited quantum efficiency of DT. Furthermore, it also plays a key role in converting O₂ into superoxide (•O₂^–) radical as the active oxygen donor. Additionally, the doped CN also contributes to the limited participation of water as a weak oxygen donor in the selective oxidation of CHA to cyclohexanol. It is hoped that this work will be informative for advancing the key technology of selective oxidation of saturated hydrocarbons under mild conditions.

{"title":"Efficient photocatalytic oxidation of cyclohexane to KA oil by carbon nitride hybridized decatungstate under visible light","authors":"Jue Wang , Jinyi Yang , Siyu Zeng , Huitao Liu , Fei Li , Haijiao Xie , Senpei Tang , Zaihui Fu , Youji Li","doi":"10.1016/j.jcat.2025.115996","DOIUrl":"10.1016/j.jcat.2025.115996","url":null,"abstract":"<div><div>The highly selective synthesis of KA oil (cyclohexanol and cyclohexanone) from the oxidation of cyclohexane (CHA) with O<sub>2</sub> under mild conditions is still a very important and challenging research topic. This paper discloses that the hybrid (DTCN) is easily prepared by inducing carbon nitride (CN) in the synthesis of decatungstate (DT) and is found to be efficiently photo-catalyst for the above selective oxidation in acetonitrile. After illumination (LED of 405 nm) for 2 h, the best DTCN-0.5 can achieve 41.03 % CHA conversion and greater than 95 % KA oil selectivity with an apparent quantum efficiency of 25.52 %, which is much superior to the pure DT (12.46 % CHA conversion). Also, it is active for the selective oxidation of other substrates containing inert C(sp<sup>3</sup>)-H bonds. A series of characterizations, free radical trapping and isotope tracing tests as well as DFT calculations support that the doped CN can construct a built-in electric field with DT to accelerate the separation of the photo-generated charge, thus hoisting the photo-excited quantum efficiency of DT. Furthermore, it also plays a key role in converting O<sub>2</sub> into superoxide (•O<sub>2</sub><sup>–</sup>) radical as the active oxygen donor. Additionally, the doped CN also contributes to the limited participation of water as a weak oxygen donor in the selective oxidation of CHA to cyclohexanol. It is hoped that this work will be informative for advancing the key technology of selective oxidation of saturated hydrocarbons under mild conditions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"443 ","pages":"Article 115996"},"PeriodicalIF":6.5,"publicationDate":"2025-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077433","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

Heterogeneous catalysts prepared by loading homogeneous α-diimide nickel complexes with asymmetric N-aryl substituents onto carbon nanotubes for 1,3-butadiene polymerization 在碳纳米管上负载具有不对称n -芳基取代基的均相α-二亚胺镍配合物制备1,3-丁二烯聚合非均相催化剂

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis

Pub Date : 2025-02-01 DOI: 10.1016/j.jcat.2024.115891

Mingyu Zhang , Dong Yan , Yuqi Tang , Shuangping Xu , Yanqing Qu , Boyu Du , Qiping Cao , Jingyu Xu , Jun Chen , Hongge Jia

Inexpensive and reusable transition metal heterogeneous catalysts demonstrate excellent polybutadiene performance and are appealing substitutes for precious metal and homogeneous catalysts. Here, a variety of homogeneous nickel catalysts were designed and synthesized by a two-step Schiff base reaction involving dinaphthones and different aniline derivatives. These homogeneous nickel catalysts are also known as novel α-diimine ligands with asymmetric N-aryl substituents (Ni1-Ni3). Under the optimal reaction conditions ([BD]/[Ni] = 6000, [Al]/[Ni] = 600, 0 °C, 4 h), Ni3 exhibited the best catalytic effect (PBD yields obtained averaged 96.5 %). The PBD in question possesses a molecular weight of 5.53 × 10⁴. The cis-structural ratio aligns with the Ziegler-Natta catalytic system. The corresponding heterogeneous nickel catalysts (Ni1/CNT-Ni3/CNT) were prepared by attaching these ligands to the carbon nanotube surfaces via amidation reactions of carboxyl and amino groups. Under the optimal conditions, Ni3/CNT exhibited the best catalytic effect (the obtained PBD yield reached 99.4 % on average). The PBD in question possess a molecular weight of 5.30 × 10⁴. No significant decrease in activity was observed after five reuse cycles. The homogeneous catalyst (Ni3/CNT) prepared in this experiment not only improves production efficiency and economic benefits but also reduces energy consumption and environmental pollution.

廉价且可重复使用的过渡金属多相催化剂具有优异的聚丁二烯性能，是贵金属和均相催化剂的理想替代品。本文采用二萘醌和不同苯胺衍生物为原料，采用两步希夫碱反应，设计并合成了多种均相镍催化剂。这些均相镍催化剂也被称为具有不对称n -芳基取代基（Ni1-Ni3）的新型α-二亚胺配体。在最佳反应条件（[BD]/[Ni] = 6000,[Al]/[Ni] = 600,0 °C, 4 h）下，Ni3的催化效果最好（PBD产率平均为96.5 %）。所讨论的PBD分子量为5.53 × 104。顺式结构比与齐格勒-纳塔催化体系一致。通过羧基和氨基的酰胺化反应，将这些配体附着在碳纳米管表面，制备了相应的非均相镍催化剂Ni1/CNT- ni3 /CNT。在最佳条件下，Ni3/CNT表现出最佳的催化效果（得到的PBD产率平均达到99.4 %）。所讨论的PBD分子量为5.30 × 104。经过5次循环使用后，活性没有明显下降。本实验制备的均相催化剂（Ni3/CNT）不仅提高了生产效率和经济效益，而且降低了能耗和环境污染。

{"title":"Heterogeneous catalysts prepared by loading homogeneous α-diimide nickel complexes with asymmetric N-aryl substituents onto carbon nanotubes for 1,3-butadiene polymerization","authors":"Mingyu Zhang , Dong Yan , Yuqi Tang , Shuangping Xu , Yanqing Qu , Boyu Du , Qiping Cao , Jingyu Xu , Jun Chen , Hongge Jia","doi":"10.1016/j.jcat.2024.115891","DOIUrl":"10.1016/j.jcat.2024.115891","url":null,"abstract":"<div><div>Inexpensive and reusable transition metal heterogeneous catalysts demonstrate excellent polybutadiene performance and are appealing substitutes for precious metal and homogeneous catalysts. Here, a variety of homogeneous nickel catalysts were designed and synthesized by a two-step Schiff base reaction involving dinaphthones and different aniline derivatives. These homogeneous nickel catalysts are also known as novel α-diimine ligands with asymmetric N-aryl substituents (<strong>Ni1-Ni3</strong>). Under the optimal reaction conditions ([BD]/[Ni] = 6000, [Al]/[Ni] = 600, 0 °C, 4 h), <strong>Ni3</strong> exhibited the best catalytic effect (PBD yields obtained averaged 96.5 %). The PBD in question possesses a molecular weight of 5.53 × 10<sup>4</sup>. The <em>cis</em>-structural ratio aligns with the Ziegler-Natta catalytic system. The corresponding heterogeneous nickel catalysts (<strong>Ni1/CNT-Ni3/CNT</strong>) were prepared by attaching these ligands to the carbon nanotube surfaces via amidation reactions of carboxyl and amino groups. Under the optimal conditions, <strong>Ni3/CNT</strong> exhibited the best catalytic effect (the obtained PBD yield reached 99.4 % on average). The PBD in question possess a molecular weight of 5.30 × 10<sup>4</sup>. No significant decrease in activity was observed after five reuse cycles. The homogeneous catalyst (<strong>Ni3/CNT</strong>) prepared in this experiment not only improves production efficiency and economic benefits but also reduces energy consumption and environmental pollution.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"442 ","pages":"Article 115891"},"PeriodicalIF":6.5,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777046","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