Pub Date : 2025-11-29DOI: 10.1016/j.mcat.2025.115631
Yu-Chin Chiu , Hui-Lung Chen , Hsin-Tsung Chen
In this work, density functional theory (DFT) calculations were conducted to explore the electrocatalytic CO₂ reduction reaction (CO₂RR) on metal-doped fullerenes (TM@C59, TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn). The thermodynamic and electrochemical stabilities were systematically evaluated through formation, binding, cohesive, and dissolution energy analyses, confirming that all TM@C₅₉ structures are stable, particularly those doped with Ti, Mn, Fe, Co, Ni, and Cu. CO₂ adsorption and activation studies revealed that most catalysts favor end-on adsorption, inducing moderate C=O bond elongation indicative of molecular activation. Reaction free-energy analyses identified *OCHO and *COOH as key intermediates, with the *OCHO pathway dominating across most metals. Ni@C59 and Co@C59 exhibit the most favorable limiting potentials for formic acid and methane formation, respectively. A volcano-type correlation between the limiting potential and electronic descriptor ϕ highlights Ni@C59 as the most active catalyst, providing valuable insight for designing fullerene-based single-atom catalysts for CO2 conversion.
{"title":"Electrocatalytic CO2 reduction on metal-doped fullerenes: Mechanistic insights from DFT calculations","authors":"Yu-Chin Chiu , Hui-Lung Chen , Hsin-Tsung Chen","doi":"10.1016/j.mcat.2025.115631","DOIUrl":"10.1016/j.mcat.2025.115631","url":null,"abstract":"<div><div>In this work, density functional theory (DFT) calculations were conducted to explore the electrocatalytic CO₂ reduction reaction (CO₂RR) on metal-doped fullerenes (TM@C<sub>59</sub>, TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn). The thermodynamic and electrochemical stabilities were systematically evaluated through formation, binding, cohesive, and dissolution energy analyses, confirming that all TM@C₅₉ structures are stable, particularly those doped with Ti, Mn, Fe, Co, Ni, and Cu. CO₂ adsorption and activation studies revealed that most catalysts favor end-on adsorption, inducing moderate C=O bond elongation indicative of molecular activation. Reaction free-energy analyses identified *OCHO and *COOH as key intermediates, with the *OCHO pathway dominating across most metals. Ni@C<sub>59</sub> and Co@C<sub>59</sub> exhibit the most favorable limiting potentials for formic acid and methane formation, respectively. A volcano-type correlation between the limiting potential and electronic descriptor ϕ highlights Ni@C<sub>59</sub> as the most active catalyst, providing valuable insight for designing fullerene-based single-atom catalysts for CO<sub>2</sub> conversion.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115631"},"PeriodicalIF":4.9,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-28DOI: 10.1016/j.mcat.2025.115625
Kaili Zhang , Wenfeng Zhang , Kui Wang , Jianchun Jiang
As a major by-product of pulp and paper making and biorefinery industries, industrial lignin has large output and wide sources, but its complex structure, broad molecular weight distribution and strong heterogeneity hinder high-value utilization, with most incinerated or discarded as low-value products. Fractionation technology is key to transforming it into high-value raw materials by regulating structural homogeneity and molecular weight distribution. This paper reviews the latest research progress, elaborates on two mainstream technologies (solvent and membrane fractionation), and summarizes applications of fractionated components in polymers, fuels, chemicals, functional materials, etc. It also analyzes core challenges (poor repeatability, high industrialization cost, lack of unified evaluation standards), highlights high-value application opportunities (e.g., composite materials), and prospects future directions: efficient green technology development, molecular weight homogenization, integrated process construction, and standardized system establishment.
{"title":"Fractionation of industrial lignins: Technical advances, application prospects, and critical challenges","authors":"Kaili Zhang , Wenfeng Zhang , Kui Wang , Jianchun Jiang","doi":"10.1016/j.mcat.2025.115625","DOIUrl":"10.1016/j.mcat.2025.115625","url":null,"abstract":"<div><div>As a major by-product of pulp and paper making and biorefinery industries, industrial lignin has large output and wide sources, but its complex structure, broad molecular weight distribution and strong heterogeneity hinder high-value utilization, with most incinerated or discarded as low-value products. Fractionation technology is key to transforming it into high-value raw materials by regulating structural homogeneity and molecular weight distribution. This paper reviews the latest research progress, elaborates on two mainstream technologies (solvent and membrane fractionation), and summarizes applications of fractionated components in polymers, fuels, chemicals, functional materials, etc. It also analyzes core challenges (poor repeatability, high industrialization cost, lack of unified evaluation standards), highlights high-value application opportunities (e.g., composite materials), and prospects future directions: efficient green technology development, molecular weight homogenization, integrated process construction, and standardized system establishment.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115625"},"PeriodicalIF":4.9,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615333","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-28DOI: 10.1016/j.mcat.2025.115628
Bo Sheng , Huaiming Zhang , Jiarui Li , Yunlong Wang , Jinzhao Wang , Feng Zhou , Jing Zhang
Beyond efficient charge separation, the overall efficiency of H2O2 photosynthesis from water and O2 is also limited by the kinetic mismatch between the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR), which leads to an insufficient proton supply and low electron transfer density. To overcome this limitation, we incorporated proton-reservoir motifs into quinone-amine polymer (QAP)-based photocatalysts, thereby alleviating the kinetic imbalance between the two half-reactions. This approach suppressed the formation of superoxide (O2•−) intermediates and facilitated the direct two-electron pathway for H2O2 synthesis. Our results demonstrate that hydroquinone units and specific side-chain groups, such as hydroxyl, methoxy, and methyl, play a critical role in determining the photocatalytic H2O2 production performance. Notably, the hydroxyl‑functionalized QAP exhibited a 5.3-fold higher H2O2 production rate compared to its methyl-substituted analogue. Moreover, under an air atmosphere rather than pure O2, the hydroxyl‑modified QAP maintained high H2O2 productivity with no significant decline, indicating efficient utilization of low-concentration O2. This robustness under ambient conditions enables continuous H2O2 production without the need for external gas input. Our work underscores the significance of dual proton–electron regulation in enhancing the efficiency of photocatalytic H2O2 synthesis.
{"title":"Side-chain engineering of quinone-amine polymers for high-efficiency H2O2 photosynthesis","authors":"Bo Sheng , Huaiming Zhang , Jiarui Li , Yunlong Wang , Jinzhao Wang , Feng Zhou , Jing Zhang","doi":"10.1016/j.mcat.2025.115628","DOIUrl":"10.1016/j.mcat.2025.115628","url":null,"abstract":"<div><div>Beyond efficient charge separation, the overall efficiency of H<sub>2</sub>O<sub>2</sub> photosynthesis from water and O<sub>2</sub> is also limited by the kinetic mismatch between the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR), which leads to an insufficient proton supply and low electron transfer density. To overcome this limitation, we incorporated proton-reservoir motifs into quinone-amine polymer (QAP)-based photocatalysts, thereby alleviating the kinetic imbalance between the two half-reactions. This approach suppressed the formation of superoxide (O<sub>2</sub><sup>•−</sup>) intermediates and facilitated the direct two-electron pathway for H<sub>2</sub>O<sub>2</sub> synthesis. Our results demonstrate that hydroquinone units and specific side-chain groups, such as hydroxyl, methoxy, and methyl, play a critical role in determining the photocatalytic H<sub>2</sub>O<sub>2</sub> production performance. Notably, the hydroxyl‑functionalized QAP exhibited a 5.3-fold higher H<sub>2</sub>O<sub>2</sub> production rate compared to its methyl-substituted analogue. Moreover, under an air atmosphere rather than pure O<sub>2</sub>, the hydroxyl‑modified QAP maintained high H<sub>2</sub>O<sub>2</sub> productivity with no significant decline, indicating efficient utilization of low-concentration O<sub>2</sub>. This robustness under ambient conditions enables continuous H<sub>2</sub>O<sub>2</sub> production without the need for external gas input. Our work underscores the significance of dual proton–electron regulation in enhancing the efficiency of photocatalytic H<sub>2</sub>O<sub>2</sub> synthesis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115628"},"PeriodicalIF":4.9,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615407","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-27DOI: 10.1016/j.mcat.2025.115590
Mengjia Zhang , Jialin Xu , Yiqin Su, Xing Huang, Jiayao Chen, Jianghui Lin, Guohui Cai, Ling Li
Dimethyl carbonate (DMC) is an essential organic chemical and versatile intermediate with widespread industrial applications. However, conventional synthesis routes for DMC faced harsh reaction conditions, equipment corrosion from by-products, and the catalysts easily dissolve in the reaction system. To address these challenges, we developed a heterogeneous catalyst (Im-TDB-COFs), synthesised by immobilizing the ionic liquid ( [BMIm]Br) on covalent organic frameworks (TDB-COFs). This catalyst was successfully applied in the two-step transesterification of CO₂ for DMC synthesis. Notably, this bifunctional catalyst simultaneously catalyzed the CO2 cycloaddition and CH3OH transesterification without any co-catalyst. Through systematic optimization, we achieved 99.3 % yield of propylene carbonate (PC) under the conditions of 160 °C, 2.0 MPa, 2.0 wt%, and 6 h, and 60.0 % yield of for dimethyl carbonate (DMC) under the conditions of 140 °C, 2.0 wt%, 6 h, nCH₃OH:nPC = 15:1. Comprehensive studies (such as reusability tests, kinetic experiments) were performed to evaluate the catalyst's performance. Furthermore, the potential reaction mechanism for Im-TDB-COFs catalyzed the two-step transesterification was also proposed. This work provided a new strategy for designing porous catalysts for two-step transesterification of CO2 to DMC.
碳酸二甲酯（DMC）是一种重要的有机化工中间体，具有广泛的工业用途。然而，传统的DMC合成路线面临着反应条件恶劣、副产物对设备的腐蚀以及催化剂易溶解在反应体系中的问题。为了解决这些挑战，我们开发了一种多相催化剂（Im-TDB-COFs），通过将离子液体（[BMIm]Br）固定在共价有机框架（TDB-COFs）上合成。该催化剂成功地应用于CO₂的两步酯交换合成DMC。值得注意的是，该双功能催化剂无需任何助催化剂即可同时催化CO2环加成和CH3OH酯交换反应。通过系统优化,我们取得了99.3 %收益率碳酸丙烯酯(PC)条件下160 °C, 2.0 MPa, 2.0 wt %,和6 h,和60.0 %产量为碳酸二甲酯(DMC)条件下140 °C, 2.0 wt %, 6 h, nCH₃哦:人大 = 15:1。对催化剂的性能进行了综合研究（如可重用性测试、动力学实验）。此外，还提出了Im-TDB-COFs催化两步酯交换反应的潜在机理。本研究为设计CO2两步酯交换制DMC的多孔催化剂提供了新的思路。
{"title":"Synthesis of DMC via two-step transesterification of CO2 catalyzed by imidazole ionic liquid covalent organic frameworks","authors":"Mengjia Zhang , Jialin Xu , Yiqin Su, Xing Huang, Jiayao Chen, Jianghui Lin, Guohui Cai, Ling Li","doi":"10.1016/j.mcat.2025.115590","DOIUrl":"10.1016/j.mcat.2025.115590","url":null,"abstract":"<div><div>Dimethyl carbonate (DMC) is an essential organic chemical and versatile intermediate with widespread industrial applications. However, conventional synthesis routes for DMC faced harsh reaction conditions, equipment corrosion from by-products, and the catalysts easily dissolve in the reaction system. To address these challenges, we developed a heterogeneous catalyst (Im-TDB-COFs), synthesised by immobilizing the ionic liquid ( [BMIm]Br) on covalent organic frameworks (TDB-COFs). This catalyst was successfully applied in the two-step transesterification of CO₂ for DMC synthesis. Notably, this bifunctional catalyst simultaneously catalyzed the CO<sub>2</sub> cycloaddition and CH<sub>3</sub>OH transesterification without any co-catalyst. Through systematic optimization, we achieved 99.3 % yield of propylene carbonate (PC) under the conditions of 160 °C, 2.0 MPa, 2.0 wt%, and 6 h, and 60.0 % yield of for dimethyl carbonate (DMC) under the conditions of 140 °C, 2.0 wt%, 6 h, n<sub>CH₃OH</sub>:n<sub>PC</sub> = 15:1. Comprehensive studies (such as reusability tests, kinetic experiments) were performed to evaluate the catalyst's performance. Furthermore, the potential reaction mechanism for Im-TDB-COFs catalyzed the two-step transesterification was also proposed. This work provided a new strategy for designing porous catalysts for two-step transesterification of CO<sub>2</sub> to DMC.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115590"},"PeriodicalIF":4.9,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-27DOI: 10.1016/j.mcat.2025.115626
Sára Spátay , Vencel Hahn , Dorka Szegedi , Bálint Árpád Ádám , Zsombor Mohácsi , Balázs Simon , Péter Huszthy , György Tibor Balogh , Ádám Golcs
We report herein the first application of a silica gel bound enantiopure crown ether as a catalyst in a continuous-flow enantioselective Strecker reaction. The model transformation – among benzaldehyde, aniline, and KCN – was conducted in a packed-bed reactor containing functionalized silica gel covalently modified with an enantiopure acridino-crown ether. The transient phase preceding steady-state conditions was systematically examined under isothermal conditions using dichloromethane and ethanol as solvents. By collecting and analyzing time-resolved fractions, we studied how solvent polarity affects both conversion and enantioselectivity throughout the startup period. Surprisingly, ethanol provided superior conversion and enantioselectivity, despite expectations suggesting less polar environments. These findings are supported by mechanistic considerations involving ion pairing and solvation effects within the confined environment of the immobilized catalyst. This study highlights the dynamic nature of asymmetric induction under flow conditions and offers early insights into a previously unexplored class of catalytic systems.
{"title":"Asymmetric induction in motion: Transient dynamics in the first crown ether-catalyzed enantioselective flow Strecker reaction","authors":"Sára Spátay , Vencel Hahn , Dorka Szegedi , Bálint Árpád Ádám , Zsombor Mohácsi , Balázs Simon , Péter Huszthy , György Tibor Balogh , Ádám Golcs","doi":"10.1016/j.mcat.2025.115626","DOIUrl":"10.1016/j.mcat.2025.115626","url":null,"abstract":"<div><div>We report herein the first application of a silica gel bound enantiopure crown ether as a catalyst in a continuous-flow enantioselective Strecker reaction. The model transformation – among benzaldehyde, aniline, and KCN – was conducted in a packed-bed reactor containing functionalized silica gel covalently modified with an enantiopure acridino-crown ether. The transient phase preceding steady-state conditions was systematically examined under isothermal conditions using dichloromethane and ethanol as solvents. By collecting and analyzing time-resolved fractions, we studied how solvent polarity affects both conversion and enantioselectivity throughout the startup period. Surprisingly, ethanol provided superior conversion and enantioselectivity, despite expectations suggesting less polar environments. These findings are supported by mechanistic considerations involving ion pairing and solvation effects within the confined environment of the immobilized catalyst. This study highlights the dynamic nature of asymmetric induction under flow conditions and offers early insights into a previously unexplored class of catalytic systems.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115626"},"PeriodicalIF":4.9,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-25DOI: 10.1016/j.mcat.2025.115618
Lihong Zhao , Yuanli Jiang , Yuqing Li , Yuwei Wang , Fei Wang , Guoqin Hu , Jinghui Liu , Bin Zhao , Xu Liang
Achieving high selectivity toward dimethyl carbonate (DMC) in CO oxidative esterification remains a central challenge in C1 chemistry. While recent studies have identified electronic effects as the primary factor controlling product selectivity, systematic strategies to optimize DMC formation remain limited. Building on prior evidence that PdML/AgML/Al(111) catalysts exhibit DMC favor selectivity, we investigate Ag‑based multilayer architectures as platforms for electronic modulation. We systematically examine PdML/XML/Ag(111) catalysts (X = Ag, Al, Cu, Zn, Au) using density functional theory (DFT) calculations to establish structure-performance relationships for enhanced DMC selectivity. Among the studied systems, PdML/AgML/Ag(111) exhibits the most favorable DMC selectivity, featuring the lowest CO coupling barrier and the largest thermodynamic driving force. Energy barrier decomposition analysis confirms that selectivity control operates primarily through electronic modulation of methoxycarbonyl intermediate stability rather than geometric constraints. A clear correlation between d-band characteristics and catalytic performance provides a predictive framework for rational catalyst design. Overall, Ag‑based multilayer architectures emerge as a promising strategy for highly DMC‑selective catalysis in CO oxidative esterification, providing fundamental insight into electronic control and practical guidance for catalyst optimization.
{"title":"Ab initio investigation of electronic effects in Pd catalysts for enhanced dimethyl carbonate selectivity","authors":"Lihong Zhao , Yuanli Jiang , Yuqing Li , Yuwei Wang , Fei Wang , Guoqin Hu , Jinghui Liu , Bin Zhao , Xu Liang","doi":"10.1016/j.mcat.2025.115618","DOIUrl":"10.1016/j.mcat.2025.115618","url":null,"abstract":"<div><div>Achieving high selectivity toward dimethyl carbonate (DMC) in CO oxidative esterification remains a central challenge in C1 chemistry. While recent studies have identified electronic effects as the primary factor controlling product selectivity, systematic strategies to optimize DMC formation remain limited. Building on prior evidence that Pd<sub>ML</sub>/Ag<sub>ML</sub>/Al(111) catalysts exhibit DMC favor selectivity, we investigate Ag‑based multilayer architectures as platforms for electronic modulation. We systematically examine Pd<sub>ML</sub>/X<sub>ML</sub>/Ag(111) catalysts (<em>X</em> = Ag, Al, Cu, Zn, Au) using density functional theory (DFT) calculations to establish structure-performance relationships for enhanced DMC selectivity. Among the studied systems, Pd<sub>ML</sub>/Ag<sub>ML</sub>/Ag(111) exhibits the most favorable DMC selectivity, featuring the lowest C<img>O coupling barrier and the largest thermodynamic driving force. Energy barrier decomposition analysis confirms that selectivity control operates primarily through electronic modulation of methoxycarbonyl intermediate stability rather than geometric constraints. A clear correlation between <span>d</span>-band characteristics and catalytic performance provides a predictive framework for rational catalyst design. Overall, Ag‑based multilayer architectures emerge as a promising strategy for highly DMC‑selective catalysis in CO oxidative esterification, providing fundamental insight into electronic control and practical guidance for catalyst optimization.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115618"},"PeriodicalIF":4.9,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615406","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-25DOI: 10.1016/j.mcat.2025.115613
Yong Jia , Hang Chen , Tao Wen , Zhihang Chen , Lina Guo , Shenghua Wu , Fanyu Meng , Zhongming Wang , Jin Jiang , Shule Zhang
A catalyst TiO2 supported phosphomolybdic acid modified fascicular CeO2(F-CeO2-HPMo/TiO2) catalysts for low-temperature NH3-SCR denitration was developed. Experimental results revealed that the catalytic activity of F-CeO2/TiO2 was remarkably enhanced by HPMo modification. The denitrification efficiency of F-CeO2/TiO2 was 49.5 % at 200 °C, whereas that of F-CeO2(2)-HPMo/TiO2 reached 87 % at the same temperature and rose to almost 100 % at 240 °C. HPMo also enhanced the SO2 resistance of F-CeO2/TiO2. The characterization results indicated that the F-CeO2 was integrated with HPMo. The stable (111) facet of CeO2 with high chemical activity is exposed on the surface of F-CeO2(2)-HPMo. The HPMo modification induced charge imbalance in the F-CeO2, thereby increasing the oxygen vacancies and enhancing the redox properties of the catalysts. Moreover, the modification of HPMo not only enhances the surface acidity but also facilitates the formation of unstable nitrate species, thereby effectively boosting the NH3-SCR catalytic activity of F-CeO2/TiO2. Finally, the in-situ DRIFTS results further demonstrated that the reduction of NOx over F-CeO2(2)-HPMo/TiO2 proceeds via both the E-R and l-H mechanisms.
{"title":"Low-temperature NH3-SCR De-NOx performance of HPMo-modified fascicular CeO2: Boosting catalytic activity and SO2 tolerance","authors":"Yong Jia , Hang Chen , Tao Wen , Zhihang Chen , Lina Guo , Shenghua Wu , Fanyu Meng , Zhongming Wang , Jin Jiang , Shule Zhang","doi":"10.1016/j.mcat.2025.115613","DOIUrl":"10.1016/j.mcat.2025.115613","url":null,"abstract":"<div><div>A catalyst TiO<sub>2</sub> supported phosphomolybdic acid modified fascicular CeO<sub>2</sub>(F-CeO<sub>2</sub>-HPMo/TiO<sub>2</sub>) catalysts for low-temperature NH<sub>3</sub>-SCR denitration was developed. Experimental results revealed that the catalytic activity of F-CeO<sub>2</sub>/TiO<sub>2</sub> was remarkably enhanced by HPMo modification. The denitrification efficiency of F-CeO<sub>2</sub>/TiO<sub>2</sub> was 49.5 % at 200 °C, whereas that of F-CeO<sub>2</sub>(2)-HPMo/TiO<sub>2</sub> reached 87 % at the same temperature and rose to almost 100 % at 240 °C. HPMo also enhanced the SO<sub>2</sub> resistance of F-CeO<sub>2</sub>/TiO<sub>2</sub>. The characterization results indicated that the F-CeO<sub>2</sub> was integrated with HPMo. The stable (111) facet of CeO<sub>2</sub> with high chemical activity is exposed on the surface of F-CeO<sub>2</sub>(2)-HPMo. The HPMo modification induced charge imbalance in the F-CeO<sub>2</sub>, thereby increasing the oxygen vacancies and enhancing the redox properties of the catalysts. Moreover, the modification of HPMo not only enhances the surface acidity but also facilitates the formation of unstable nitrate species, thereby effectively boosting the NH<sub>3</sub>-SCR catalytic activity of F-CeO<sub>2</sub>/TiO<sub>2</sub>. Finally, the in-situ DRIFTS results further demonstrated that the reduction of NO<em><sub>x</sub></em> over F-CeO<sub>2</sub>(2)-HPMo/TiO<sub>2</sub> proceeds via both the E-R and <span>l</span>-H mechanisms.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115613"},"PeriodicalIF":4.9,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615403","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-24DOI: 10.1016/j.mcat.2025.115615
Xinrui Wang , Wei Xia , Yanli Zhang , Di Wang , Mingyuan Dong , Kun Chen , Dong Liu , Baowang Lu
The catalytic conversion of CO2 to CO via the reverse water-gas shift (RWGS) reaction, followed by Fischer-Tropsch synthesis of CO into valuable chemicals, is a promising CO2 utilization pathway. In this paper, mesoporous Ni/CeO2 catalysts with different NiO contents were prepared by calcination method, and characterized by BET, XRD and BJH. Results showed NiO effectively occupied CeO2 pores, with pore size independent of NiO content. Catalyst performance tests revealed NiO/CeO2 achieved a 50.9 % CO2 conversion, and 100 % CO selectivity when NiO/CeO2 molar ratio <7 % (monodispersed NiO). Density functional theory (DFT) investigations explored effects of oxygen vacancies and Ni loading on CeO2 catalytic activity. Calculations (differential charge density, adsorption energy, DOS, d-band density, etc.) demonstrated CeO2-x (with vacancies) and Ni/CeO2 outperformed CeO2, promoting RWGS and CO selectivity. Ni/CeO2 facilitated oxygen vacancy formation, elevated Fermi levels, and modified CeO2 electronic states (via O atomic orbitals near Ni). DFT analysis of Ni loading content (Ni/CeO2, Ni2/CeO2, Ni4/CeO2) showed single Ni sites optimized reactant activation, Ni utilization, and CO selectivity. This study highlights critical roles of oxygen vacancies and Ni loading in CeO2-catalyzed RWGS, providing a theoretical basis for catalyst design.
{"title":"Tailoring CeO2 catalysts via oxygen vacancies and Ni loading: Boosting RWGS reaction performance and uncovering underlying mechanisms","authors":"Xinrui Wang , Wei Xia , Yanli Zhang , Di Wang , Mingyuan Dong , Kun Chen , Dong Liu , Baowang Lu","doi":"10.1016/j.mcat.2025.115615","DOIUrl":"10.1016/j.mcat.2025.115615","url":null,"abstract":"<div><div>The catalytic conversion of CO<sub>2</sub> to CO via the reverse water-gas shift (RWGS) reaction, followed by Fischer-Tropsch synthesis of CO into valuable chemicals, is a promising CO<sub>2</sub> utilization pathway. In this paper, mesoporous Ni/CeO<sub>2</sub> catalysts with different NiO contents were prepared by calcination method, and characterized by BET, XRD and BJH. Results showed NiO effectively occupied CeO<sub>2</sub> pores, with pore size independent of NiO content. Catalyst performance tests revealed NiO/CeO<sub>2</sub> achieved a 50.9 % CO<sub>2</sub> conversion, and 100 % CO selectivity when NiO/CeO<sub>2</sub> molar ratio <7 % (monodispersed NiO). Density functional theory (DFT) investigations explored effects of oxygen vacancies and Ni loading on CeO<sub>2</sub> catalytic activity. Calculations (differential charge density, adsorption energy, DOS, d-band density, etc.) demonstrated CeO<sub>2-x</sub> (with vacancies) and Ni/CeO<sub>2</sub> outperformed CeO<sub>2</sub>, promoting RWGS and CO selectivity. Ni/CeO<sub>2</sub> facilitated oxygen vacancy formation, elevated Fermi levels, and modified CeO<sub>2</sub> electronic states (via O atomic orbitals near Ni). DFT analysis of Ni loading content (Ni/CeO<sub>2</sub>, Ni<sub>2</sub>/CeO<sub>2</sub>, Ni<sub>4</sub>/CeO<sub>2</sub>) showed single Ni sites optimized reactant activation, Ni utilization, and CO selectivity. This study highlights critical roles of oxygen vacancies and Ni loading in CeO<sub>2</sub>-catalyzed RWGS, providing a theoretical basis for catalyst design.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115615"},"PeriodicalIF":4.9,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two C(sp2)–H trifluoroacetylation methods based on masked trifluoroacyl reagents have been developed: a thermally driven protocol using (NH4)2S2O8 as the oxidant and a light-mediated approach employing PhI(OCOMe)2. Both methods exhibit high efficiency and broad applicability toward various heterocyclic substrates, including quinazolin-4(3H)-ones, quinoxalin-2(1H)-ones, and pyrazin-2(1H)-ones. Notably, the visible-light-mediated transformation proceeds smoothly under photosensitizer-free conditions, offering operational simplicity and aligning with the principles of green chemistry. Furthermore, density functional theory (DFT) calculations support a newly proposed iodine(III)-mediated radical pathway, providing mechanistic insight into the photochemical C–H trifluoroacetylation process.
{"title":"Trifluoroacetylation of C(sp2)–H bonds using masked trifluoroacyl reagents: Photoinitiated (Photosensitiser-free) vs. thermal","authors":"Shenyuan Gao, Yujie Huang, Menglu Cai, Xixue Liu, Dapeng Jiang, Xiaozhong Wang, Liyan Dai","doi":"10.1016/j.mcat.2025.115620","DOIUrl":"10.1016/j.mcat.2025.115620","url":null,"abstract":"<div><div>Two C(sp<sup>2</sup>)–H trifluoroacetylation methods based on masked trifluoroacyl reagents have been developed: a thermally driven protocol using (NH<sub>4</sub>)<sub>2</sub>S<sub>2</sub>O<sub>8</sub> as the oxidant and a light-mediated approach employing PhI(OCOMe)<sub>2</sub>. Both methods exhibit high efficiency and broad applicability toward various heterocyclic substrates, including quinazolin-4(3H)-ones, quinoxalin-2(1H)-ones, and pyrazin-2(1H)-ones. Notably, the visible-light-mediated transformation proceeds smoothly under photosensitizer-free conditions, offering operational simplicity and aligning with the principles of green chemistry. Furthermore, density functional theory (DFT) calculations support a newly proposed iodine(III)-mediated radical pathway, providing mechanistic insight into the photochemical C–H trifluoroacetylation process.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115620"},"PeriodicalIF":4.9,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615402","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-22DOI: 10.1016/j.mcat.2025.115617
G. Anandha babu , B. Kayalvizhi , P. Hemalatha , Tae Hwan Oh , Subramaniyan Ramasundaram , Krishna Prakash Arunachalam
The rational structural design techniques of Binary metal telluride (BMT) and their component adjustments could become highlighted as potentially appealing and difficult for developing materials with various functions for hydrogen generation from water electrolysis. The fabrication of a bimetal Co-Ni composition with tellurides (Te) structure composed of different Co-NiTe nanostructures via hydrothermal reactions. The best and optimized Co-NiTe/NF compositions than Co-Ni2Te/NF and Co-NiTe2/NF results uniform nanoflowers assembly which could provide prolonged catalytic sites. In comparison to Co-Ni2Te/NF and Co-NiTe2/NF, Co-NiTe/NF had a smaller overpotential (62 mV) at 10 mAcm−2 and a lower Tafel slope (135 mV dec−1) for HER. The superior catalytic activity of Co-NiTe/NF could be related to the peculiar electron configuration with abundant active surface sites. After a 15-hour continuous reaction, Co-NiTe/NF proved the catalyst's exceptional compositional robustness, confirming that there was no catalyst dispersion or other contaminant accumulation in the electrolyte even after long-term operation. This research reveals about using rational architecture and constituent design to create low-cost and effective electrocatalysts for HER.
二元金属碲化物（Binary metal telluride， BMT）的合理结构设计技术及其组分调整将成为开发具有多种功能的水电解制氢材料的潜在吸引力和难点。通过水热反应制备了由不同纳米结构的碲化物（Te）结构的双金属钴镍化合物。与Co-Ni2Te/NF和Co-NiTe2/NF相比，优化后的Co-NiTe/NF组分的纳米花组装均匀，可提供较长的催化位点。与Co-Ni2Te/NF和Co-NiTe2/NF相比，Co-NiTe/NF在10 mAcm−2时具有较小的过电位（62 mV）和较低的Tafel斜率（135 mV dec−1）。Co-NiTe/NF之所以具有优异的催化活性，可能与其具有丰富的表面活性位点的特殊电子构型有关。经过15小时的连续反应，Co-NiTe/NF证明了催化剂的特殊组成稳健性，证实了即使在长期运行后，电解质中也没有催化剂分散或其他污染物积聚。本研究揭示了利用合理的结构和组成设计来制造低成本和高效的HER电催化剂。
{"title":"Rational structural engineering of binary metal tellurides for advanced hydrogen evolution electrocatalysis","authors":"G. Anandha babu , B. Kayalvizhi , P. Hemalatha , Tae Hwan Oh , Subramaniyan Ramasundaram , Krishna Prakash Arunachalam","doi":"10.1016/j.mcat.2025.115617","DOIUrl":"10.1016/j.mcat.2025.115617","url":null,"abstract":"<div><div>The rational structural design techniques of Binary metal telluride (BMT) and their component adjustments could become highlighted as potentially appealing and difficult for developing materials with various functions for hydrogen generation from water electrolysis. The fabrication of a bimetal Co-Ni composition with tellurides (Te) structure composed of different Co-NiTe nanostructures via hydrothermal reactions. The best and optimized Co-NiTe/NF compositions than Co-Ni<sub>2</sub>Te/NF and Co-NiTe<sub>2</sub>/NF results uniform nanoflowers assembly which could provide prolonged catalytic sites. In comparison to Co-Ni<sub>2</sub>Te/NF and Co-NiTe<sub>2</sub>/NF, Co-NiTe/NF had a smaller overpotential (62 mV) at 10 mAcm<sup>−2</sup> and a lower Tafel slope (135 mV dec<sup>−1</sup>) for HER. The superior catalytic activity of Co-NiTe/NF could be related to the peculiar electron configuration with abundant active surface sites. After a 15-hour continuous reaction, Co-NiTe/NF proved the catalyst's exceptional compositional robustness, confirming that there was no catalyst dispersion or other contaminant accumulation in the electrolyte even after long-term operation. This research reveals about using rational architecture and constituent design to create low-cost and effective electrocatalysts for HER.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"589 ","pages":"Article 115617"},"PeriodicalIF":4.9,"publicationDate":"2025-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145615404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号