Pub Date : 2025-12-27DOI: 10.1016/j.mcat.2025.115686
Bingrong Chen , Saili Xu , Qidong Pan , Rongchuan Hong , Wei Zhu , Xiaoxia Liu , Miaolin Ke , Zhiran Ju , Fener Chen
A highly efficient chemo-enzymatic approach has been developed for the synthesis of mirabegron-a selective β₃-adrenergic receptor agonist indicated for overactive bladder treatment. Starting from styrene, an engineered styrene monooxygenase (SMO) catalyzes the critical epoxidation step, yielding the key chiral intermediate with excellent enantioselectivity (>99 % ee) and a moderate yield of 36 %. This enzymatic process obviates the need for intermediate isolation and reduces the use of toxic reagents, offering distinct advantages over traditional chemical synthesis in terms of sustainability and atom economy. Subsequent eco-friendly chemical transformations of the intermediate afford mirabegron. This optimized protocol, which is efficient and scalable, achieves a final mirabegron yield of 17.7 %, underscoring the potential of enzymatic systems for the efficient synthesis of this therapeutic agent.
{"title":"Chemoenzymatic synthesis of mirabegron using an engineered styrene monooxygenase","authors":"Bingrong Chen , Saili Xu , Qidong Pan , Rongchuan Hong , Wei Zhu , Xiaoxia Liu , Miaolin Ke , Zhiran Ju , Fener Chen","doi":"10.1016/j.mcat.2025.115686","DOIUrl":"10.1016/j.mcat.2025.115686","url":null,"abstract":"<div><div>A highly efficient chemo-enzymatic approach has been developed for the synthesis of mirabegron-a selective β₃-adrenergic receptor agonist indicated for overactive bladder treatment. Starting from styrene, an engineered styrene monooxygenase (SMO) catalyzes the critical epoxidation step, yielding the key chiral intermediate with excellent enantioselectivity (>99 % ee) and a moderate yield of 36 %. This enzymatic process obviates the need for intermediate isolation and reduces the use of toxic reagents, offering distinct advantages over traditional chemical synthesis in terms of sustainability and atom economy. Subsequent eco-friendly chemical transformations of the intermediate afford mirabegron. This optimized protocol, which is efficient and scalable, achieves a final mirabegron yield of 17.7 %, underscoring the potential of enzymatic systems for the efficient synthesis of this therapeutic agent.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115686"},"PeriodicalIF":4.9,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838960","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 : 2025-12-27DOI: 10.1016/j.mcat.2025.115688
Jiangkun Wang , Yuxi Tu , Yuan Yang , Xia Wang , Junsen Tong , Jianzhuang Yao
The escalating environmental burden of PET waste has prompted the pursuit of efficient enzymatic solutions for its degradation. This research successfully engineered the H218S/F222I variant based on a variant of the leaf and branch compost cutinase (ICCG), enhancing its PET hydrolysis capabilities through both computational and experimental studies. The variant demonstrated superior thermostability and catalytic efficiency, attributes crucial for industrial-scale PET recycling. Comprehensive kinetic analyses, utilizing both conventional and inverse Michaelis-Menten equations, underscored the variant's improved PET substrate affinity and reaction velocity. In particular, the reaction rate of ICCG-H218S/F222I are higher than that of ICCG across a range of temperatures (30–70 °C). Upon substrate normalization, the mutant delivered 96 % PET conversion within 24 h under high-loading conditions, substantially outperforming ICCG at 85 %, thus corroborating the engineered variant’s superior catalytic efficiency. Structural and QM/MM MD and free energy simulations studies elucidated the enzyme's reaction mechanisms, revealing temperature-dependent pathways that inform future enzyme optimizations. This work not only advances our understanding of PET hydrolases but also paves the way for developing more effective biocatalysts to combat plastic pollution.
{"title":"Biochemical characterization, crystal structure, and catalytic mechanism of a PET-hydrolase double mutant","authors":"Jiangkun Wang , Yuxi Tu , Yuan Yang , Xia Wang , Junsen Tong , Jianzhuang Yao","doi":"10.1016/j.mcat.2025.115688","DOIUrl":"10.1016/j.mcat.2025.115688","url":null,"abstract":"<div><div>The escalating environmental burden of PET waste has prompted the pursuit of efficient enzymatic solutions for its degradation. This research successfully engineered the H218S/F222I variant based on a variant of the leaf and branch compost cutinase (ICCG), enhancing its PET hydrolysis capabilities through both computational and experimental studies. The variant demonstrated superior thermostability and catalytic efficiency, attributes crucial for industrial-scale PET recycling. Comprehensive kinetic analyses, utilizing both conventional and inverse Michaelis-Menten equations, underscored the variant's improved PET substrate affinity and reaction velocity. In particular, the reaction rate of ICCG-H218S/F222I are higher than that of ICCG across a range of temperatures (30–70 °C). Upon substrate normalization, the mutant delivered 96 % PET conversion within 24 h under high-loading conditions, substantially outperforming ICCG at 85 %, thus corroborating the engineered variant’s superior catalytic efficiency. Structural and QM/MM MD and free energy simulations studies elucidated the enzyme's reaction mechanisms, revealing temperature-dependent pathways that inform future enzyme optimizations. This work not only advances our understanding of PET hydrolases but also paves the way for developing more effective biocatalysts to combat plastic pollution.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115688"},"PeriodicalIF":4.9,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838903","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 : 2025-12-26DOI: 10.1016/j.mcat.2025.115683
Salma A. Al-Zahrani , Naga Suresh Enjamuri , Hamid Ahmed , Maha Awjan Alreshidi , Ahmed Al Otaibi , Hessah Difallah A. Al-Enazy , Nuha Othman S Alsaif , Rawesh Kumar , Ahmed S. Al-Fatesh
Utilization of greenhouse gas methane (CH4) to obtain hydrogen-rich syngas using partial oxidation of methane (POM) plays a noteworthy role in view of the reduction of methane emissions and the production of sustainable energy. Sm (0-3wt.%) promoted tungsten-zirconia (10W+Zr) supported Ni-based catalysts are prepared by using the impregnation method, and these prepared catalysts are characterized by PXRD, N2 adsorption-desorption, H2-TPR-O2-TPO-H2-TPR cycle experiment, and Raman study. Along with the POM, the current catalysts also get amorphous carbon deposit which is oxidized easily and does not hinder the active sites. The carbon deposit over samarium promoted catalyst has relatively higher degree of graphitization. Samarium addition up to 2wt.% over 5Ni-10W+Zr limits the size of Ni to minimum, acquires highest surface area and improves the population of terminal Wδ+=O2-. Over 5Ni+2Sm-10W+Zr catalyst, the active sites Ni are in close contact with WOx-Sm2O3-ZrO2 matrix. Smallest crystallites of Ni in accompany with terminal Wδ+=O2- bring most effective C-H’s dissociation and its subsequent oxidation through POM reaction over 5Ni+2Sm-10W+Zr catalyst. Amongst catalysts, the 5Ni+2Sm-10W+Zr catalyst outperforms and attains an H2/CO ratio of 2.7 with a 61.7-56.7% H2 yield at 600°C during 275 min on stream. In long time-on-stream test (24 h) over 5Ni+2Sm-10W+Zr catalyst, the nature of carbon deposit is changed to more oxidisable and degree of graphitization of carbon is also dropped. Such carbon deposits are more easily oxidized and left the active sites exposed and 5Ni+2Sm-10W+Zr retains about 50% H2 yield (H2/CO ratio of 2.8) at 600°C during 24 h time-on-stream. This study paves the path for achieving hydrogen-rich syngas over Sm promoted tungsten-zirconia supported Ni catalyst at low reaction temperature through POM reaction.
{"title":"Hydrogen Rich Syngas Production from Methane using Partial Oxidation over Sm-promoted Tungsten-zirconia Supported Ni Catalysts","authors":"Salma A. Al-Zahrani , Naga Suresh Enjamuri , Hamid Ahmed , Maha Awjan Alreshidi , Ahmed Al Otaibi , Hessah Difallah A. Al-Enazy , Nuha Othman S Alsaif , Rawesh Kumar , Ahmed S. Al-Fatesh","doi":"10.1016/j.mcat.2025.115683","DOIUrl":"10.1016/j.mcat.2025.115683","url":null,"abstract":"<div><div>Utilization of greenhouse gas methane (CH<sub>4</sub>) to obtain hydrogen-rich syngas using partial oxidation of methane (POM) plays a noteworthy role in view of the reduction of methane emissions and the production of sustainable energy. Sm (0-3wt.%) promoted tungsten-zirconia (10W+Zr) supported Ni-based catalysts are prepared by using the impregnation method, and these prepared catalysts are characterized by PXRD, N<sub>2</sub> adsorption-desorption, H<sub>2</sub>-TPR-O<sub>2</sub>-TPO-H<sub>2</sub>-TPR cycle experiment, and Raman study. Along with the POM, the current catalysts also get amorphous carbon deposit which is oxidized easily and does not hinder the active sites. The carbon deposit over samarium promoted catalyst has relatively higher degree of graphitization. Samarium addition up to 2wt.% over 5Ni-10W+Zr limits the size of Ni to minimum, acquires highest surface area and improves the population of terminal W<sup>δ+</sup>=O<sup>2-</sup>. Over 5Ni+2Sm-10W+Zr catalyst, the active sites Ni are in close contact with WO<sub>x</sub>-Sm<sub>2</sub>O<sub>3</sub>-ZrO<sub>2</sub> matrix. Smallest crystallites of Ni in accompany with terminal W<sup>δ+</sup>=O<sup>2-</sup> bring most effective C-H’s dissociation and its subsequent oxidation through POM reaction over 5Ni+2Sm-10W+Zr catalyst. Amongst catalysts, the 5Ni+2Sm-10W+Zr catalyst outperforms and attains an H<sub>2</sub>/CO ratio of 2.7 with a 61.7-56.7% H<sub>2</sub> yield at 600°C during 275 min on stream. In long time-on-stream test (24 h) over 5Ni+2Sm-10W+Zr catalyst, the nature of carbon deposit is changed to more oxidisable and degree of graphitization of carbon is also dropped. Such carbon deposits are more easily oxidized and left the active sites exposed and 5Ni+2Sm-10W+Zr retains about 50% H<sub>2</sub> yield (H<sub>2</sub>/CO ratio of 2.8) at 600°C during 24 h time-on-stream. This study paves the path for achieving hydrogen-rich syngas over Sm promoted tungsten-zirconia supported Ni catalyst at low reaction temperature through POM reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115683"},"PeriodicalIF":4.9,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838961","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}
The active center of rare-earth (RE) zirconate catalysts for the dehydration of seven alkanediols, such as 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-pentanediol, 3-methyl-1,3-butanediol, and 2-methyl-2,4-pentanediol, was systematically unveiled. The correlation between the formation rate of dehydration products, i.e., unsaturated alcohols (UOLs), and their acid-base properties, corroborated by the poisoning experiments of the active centers, suggests that the active site for the dehydration of these alkanediols is a base-acid pair site. These sites were formed by the generation of oxygen vacancies resulting from the incorporation of RE into the ZrO2 lattice structure. We also demonstrated that the same active site served as the active center for the dehydration of different alkanediols, regardless of the carbon chain length, the position of OH groups, or the presence or absence of methyl branching. Using the established active sites, it is also possible to calculate the turnover frequency for each alkanediol.
{"title":"Active centers of rare-earth zirconate catalysts for the vapor-phase dehydration of alkanediols","authors":"Taiga Harada, Enggah Kurniawan, Fumihiro Okusa, Rena Endo, Takayoshi Hara, Yasuhiro Yamada, Satoshi Sato","doi":"10.1016/j.mcat.2025.115673","DOIUrl":"10.1016/j.mcat.2025.115673","url":null,"abstract":"<div><div>The active center of rare-earth (RE) zirconate catalysts for the dehydration of seven alkanediols, such as 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-pentanediol, 3-methyl-1,3-butanediol, and 2-methyl-2,4-pentanediol, was systematically unveiled. The correlation between the formation rate of dehydration products, i.e., unsaturated alcohols (UOLs), and their acid-base properties, corroborated by the poisoning experiments of the active centers, suggests that the active site for the dehydration of these alkanediols is a base-acid pair site. These sites were formed by the generation of oxygen vacancies resulting from the incorporation of RE into the ZrO<sub>2</sub> lattice structure. We also demonstrated that the same active site served as the active center for the dehydration of different alkanediols, regardless of the carbon chain length, the position of OH groups, or the presence or absence of methyl branching. Using the established active sites, it is also possible to calculate the turnover frequency for each alkanediol.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115673"},"PeriodicalIF":4.9,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838958","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 : 2025-12-24DOI: 10.1016/j.mcat.2025.115674
Keyi Zhao , Zhou Zhou , Yang Chen , Haiting Yan , Jinxin Yu , Liwei Qiu , Songjian Zhao
Carbon monoxide (CO), a typical toxic industrial pollutant, requires efficient low-temperature catalytic oxidation for effective air pollution control. Although copper-doped octahedral molecular sieve manganese oxide (Cu-OMS-2) shows promising CO oxidation activity, it suffers from rapid deactivation in flue gas containing SO2 and H2O. In this study, a plasma modification strategy was employed to enhance the catalytic performance of Cu-OMS-2. The effects of plasma atmosphere (CO, N2, O2, H2), power (20–80 W), and treatment duration (15 min–4 h) were systematically investigated. Results revealed that the catalyst treated with H2 plasma at 60 W for 2 h (Cu-OMS-2-H2–60W-2 h) exhibited optimal performance, achieving 100% CO conversion for 23 h under conditions of 60,000 mL·g-1·h-1 gas hourly space velocity, 15 vol% H2O, and 50 ppm SO2, significantly outperforming the untreated sample. Characterization via XRD, SEM, BET, TGA, H2-TPR, FT-IR, and XPS indicated that H2 plasma treatment introduced oxygen vacancies and surface defects, promoted the redox cycling of Cu2+/Cu+ and Mn4+/Mn3+, increased surface hydroxyl groups, and optimized pore structure and metal dispersion. Furthermore, plasma modification mitigated SO2 poisoning of active sites, thereby improving sulfur resistance and long-term stability. This work provides novel insights and practical strategies for developing non-precious metal catalysts for CO oxidation in complex industrial flue gas environments.
一氧化碳（CO）是一种典型的有毒工业污染物，需要高效的低温催化氧化才能有效控制大气污染。虽然铜掺杂八面体分子筛氧化锰（Cu-OMS-2）表现出良好的CO氧化活性，但在含SO2和H2O的烟气中会迅速失活。在本研究中，采用等离子体修饰策略来提高Cu-OMS-2的催化性能。系统考察了等离子体气氛（CO、N2、O2、H2）、功率（20 ~ 80 W）和处理时间（15 min ~ 4 h）的影响。结果表明，60W等离子体处理2 h （Cu-OMS-2-H2-60W-2 h）催化剂表现出最佳性能，在60000 mL·g-1·h-1气体小时空速、15 vol% H2O和50 ppm SO2的条件下，23 h的CO转化率达到100%，显著优于未处理样品。通过XRD、SEM、BET、TGA、H2- tpr、FT-IR和XPS表征表明，H2等离子体处理引入了氧空位和表面缺陷，促进了Cu2+/Cu+和Mn4+/Mn3+的氧化还原循环，增加了表面羟基，优化了孔隙结构和金属分散。此外，等离子体修饰减轻了活性位点的SO2中毒，从而提高了抗硫性和长期稳定性。这项工作为在复杂的工业烟气环境中开发用于CO氧化的非贵金属催化剂提供了新的见解和实用策略。
{"title":"Enhanced CO oxidation of hydrogen plasma-modified Cu-OMS-2 catalysts under complex sulfur and moisture conditions","authors":"Keyi Zhao , Zhou Zhou , Yang Chen , Haiting Yan , Jinxin Yu , Liwei Qiu , Songjian Zhao","doi":"10.1016/j.mcat.2025.115674","DOIUrl":"10.1016/j.mcat.2025.115674","url":null,"abstract":"<div><div>Carbon monoxide (CO), a typical toxic industrial pollutant, requires efficient low-temperature catalytic oxidation for effective air pollution control. Although copper-doped octahedral molecular sieve manganese oxide (Cu-OMS-2) shows promising CO oxidation activity, it suffers from rapid deactivation in flue gas containing SO<sub>2</sub> and H<sub>2</sub>O. In this study, a plasma modification strategy was employed to enhance the catalytic performance of Cu-OMS-2. The effects of plasma atmosphere (CO, N<sub>2</sub>, O<sub>2</sub>, H<sub>2</sub>), power (20–80 W), and treatment duration (15 min–4 h) were systematically investigated. Results revealed that the catalyst treated with H<sub>2</sub> plasma at 60 W for 2 h (Cu-OMS-2-H<sub>2</sub>–60W-2 h) exhibited optimal performance, achieving 100% CO conversion for 23 h under conditions of 60,000 mL·g<sup>-1</sup>·h<sup>-1</sup> gas hourly space velocity, 15 vol% H<sub>2</sub>O, and 50 ppm SO<sub>2</sub>, significantly outperforming the untreated sample. Characterization via XRD, SEM, BET, TGA, H<sub>2</sub>-TPR, FT-IR, and XPS indicated that H<sub>2</sub> plasma treatment introduced oxygen vacancies and surface defects, promoted the redox cycling of Cu<sup>2+</sup>/Cu<sup>+</sup> and Mn<sup>4+</sup>/Mn<sup>3+</sup>, increased surface hydroxyl groups, and optimized pore structure and metal dispersion. Furthermore, plasma modification mitigated SO<sub>2</sub> poisoning of active sites, thereby improving sulfur resistance and long-term stability. This work provides novel insights and practical strategies for developing non-precious metal catalysts for CO oxidation in complex industrial flue gas environments.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115674"},"PeriodicalIF":4.9,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838863","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 : 2025-12-24DOI: 10.1016/j.mcat.2025.115651
Tamára A. Branco, Ana C. Fernandes
This work presents a novel method for the valorization of polyester and polycarbonate plastic waste through the catalytic depolymerization into borylated diols or diols. The process employs WO2Cl2 as a catalyst and pinacolborane (HBpin) as the reducing agent. The HBpin/WO₂Cl₂ catalytic system exhibited high efficiency in the reductive depolymerization of the polyesters PCL, P4HB, PBS, PES, and PBA into the corresponding borylated alcohols, with yields ranging from 60 % to 91 %. Moreover, the conversion of the polyester PCL into 1,6-hexanediol was successfully achieved, affording an overall yield of 87 % through hydroboration of this polyester followed by hydrolysis. This catalytic system was also investigated in the depolymerization of the polycarbonate PC.BPA, leading to the formation of borylated bisphenol and MeOBpin, with moderate yields. Notably, WO2Cl2 retained its catalytic activity over at least ten consecutive depolymerization reactions of polycaprolactone (PCL), consistently delivering excellent yields.
{"title":"WO2Cl2-promoted chemical recycling of plastics into valuable products","authors":"Tamára A. Branco, Ana C. Fernandes","doi":"10.1016/j.mcat.2025.115651","DOIUrl":"10.1016/j.mcat.2025.115651","url":null,"abstract":"<div><div>This work presents a novel method for the valorization of polyester and polycarbonate plastic waste through the catalytic depolymerization into borylated diols or diols. The process employs WO<sub>2</sub>Cl<sub>2</sub> as a catalyst and pinacolborane (HBpin) as the reducing agent. The HBpin/WO₂Cl₂ catalytic system exhibited high efficiency in the reductive depolymerization of the polyesters PCL, P4HB, PBS, PES, and PBA into the corresponding borylated alcohols, with yields ranging from 60 % to 91 %. Moreover, the conversion of the polyester PCL into 1,6-hexanediol was successfully achieved, affording an overall yield of 87 % through hydroboration of this polyester followed by hydrolysis. This catalytic system was also investigated in the depolymerization of the polycarbonate PC.BPA, leading to the formation of borylated bisphenol and MeOBpin, with moderate yields. Notably, WO<sub>2</sub>Cl<sub>2</sub> retained its catalytic activity over at least ten consecutive depolymerization reactions of polycaprolactone (PCL), consistently delivering excellent yields.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115651"},"PeriodicalIF":4.9,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838864","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 : 2025-12-24DOI: 10.1016/j.mcat.2025.115672
Bing Han, Yongchao Liang, Qian Chen, Xiaoxiao Li
The gradual exhaustion of fossil fuels underscores the urgency of developing photocatalytic hydrogen evolution as a sustainable energy alternative. This first-principles study computationally designs an S-scheme Hf2CO2/ZrS2 van der Waals heterojunction and systematically evaluates its potential for solar-driven water splitting. Our calculations demonstrate that the heterostructure possesses not only robust interfacial stability but also a built-in electronic field that promotes efficient electron transfer from Hf2CO2 to ZrS2. This unique architecture, confirmed to be an S-scheme mechanism, coupled with high charge carrier mobility, leads to the effective spatial separation of photogenerated electron-hole pairs. Remarkably, the heterojunction achieves a superior solar-to-hydrogen (STH) efficiency of 34.15%, with enhanced light absorption and outstanding catalytic performance in both the hydrogen and oxygen evolution reactions, as evidenced by Gibbs free energy analysis. Furthermore, the photocatalytic activity can be precisely optimized through biaxial strain, which effectively modulates the band structure. These findings highlight Hf2CO2/ZrS2 as a highly promising candidate material for efficient photocatalytic water splitting.
{"title":"First-principles insight into an efficient S-scheme Hf2CO2/ZrS2 photocatalyst: Electronic structure and sunlight-driven H2 evolution performance","authors":"Bing Han, Yongchao Liang, Qian Chen, Xiaoxiao Li","doi":"10.1016/j.mcat.2025.115672","DOIUrl":"10.1016/j.mcat.2025.115672","url":null,"abstract":"<div><div>The gradual exhaustion of fossil fuels underscores the urgency of developing photocatalytic hydrogen evolution as a sustainable energy alternative. This first-principles study computationally designs an S-scheme Hf<sub>2</sub>CO<sub>2</sub>/ZrS<sub>2</sub> van der Waals heterojunction and systematically evaluates its potential for solar-driven water splitting. Our calculations demonstrate that the heterostructure possesses not only robust interfacial stability but also a built-in electronic field that promotes efficient electron transfer from Hf<sub>2</sub>CO<sub>2</sub> to ZrS<sub>2</sub>. This unique architecture, confirmed to be an S-scheme mechanism, coupled with high charge carrier mobility, leads to the effective spatial separation of photogenerated electron-hole pairs. Remarkably, the heterojunction achieves a superior solar-to-hydrogen (STH) efficiency of 34.15%, with enhanced light absorption and outstanding catalytic performance in both the hydrogen and oxygen evolution reactions, as evidenced by Gibbs free energy analysis. Furthermore, the photocatalytic activity can be precisely optimized through biaxial strain, which effectively modulates the band structure. These findings highlight Hf<sub>2</sub>CO<sub>2</sub>/ZrS<sub>2</sub> as a highly promising candidate material for efficient photocatalytic water splitting.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115672"},"PeriodicalIF":4.9,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838901","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 : 2025-12-23DOI: 10.1016/j.mcat.2025.115660
Anastasia V. Orlova , Vladislava Yu. Kozhevnikova , Alexander I. Dalinger , Liubov O. Tcelykh , Zhipeng Guo , Yanan Zhu , Sergey Z. Vatsadze , Valentina V. Utochnikova
Lanthanide complexes are widely used in both luminescent thermometry and catalysis, yet their integration into a single material remains a major challenge. Herein, we report novel terbium and europium complexes with a bispidine-based ligand conjugated to benzoic acid via a triazole linker. These complexes exhibit dual functionality: they act as homogeneous catalysts for the Michael addition reaction and simultaneously serve as ratiometric luminescent thermometers. The mixed-metal complex (Eu0.1Tb0.9)(L)(TFA)2·H2O demonstrates bright emission with quantum yields up to 56 %, and europium lifetime-based thermometry shows a relative sensitivity of 1.7 %/ °C with a temperature uncertainty below 0.5 °C. Notably, the catalytic activity arises only in the metal-ligand complex form, as neither the ligand nor lanthanide salts alone promote the reaction. To the best of our knowledge, this is the first report of a rare-earth complex combining homogeneous catalysis with luminescent thermometry in solution.
{"title":"Terbium and europium complexes with bispidine-based ligand as integrated luminescent thermometers and homogeneous catalysts","authors":"Anastasia V. Orlova , Vladislava Yu. Kozhevnikova , Alexander I. Dalinger , Liubov O. Tcelykh , Zhipeng Guo , Yanan Zhu , Sergey Z. Vatsadze , Valentina V. Utochnikova","doi":"10.1016/j.mcat.2025.115660","DOIUrl":"10.1016/j.mcat.2025.115660","url":null,"abstract":"<div><div>Lanthanide complexes are widely used in both luminescent thermometry and catalysis, yet their integration into a single material remains a major challenge. Herein, we report novel terbium and europium complexes with a bispidine-based ligand conjugated to benzoic acid via a triazole linker. These complexes exhibit dual functionality: they act as homogeneous catalysts for the Michael addition reaction and simultaneously serve as ratiometric luminescent thermometers. The mixed-metal complex (Eu<sub>0.1</sub>Tb<sub>0.9</sub>)(L)(TFA)<sub>2</sub>·H<sub>2</sub>O demonstrates bright emission with quantum yields up to 56 %, and europium lifetime-based thermometry shows a relative sensitivity of 1.7 %/ °C with a temperature uncertainty below 0.5 °C. Notably, the catalytic activity arises only in the metal-ligand complex form, as neither the ligand nor lanthanide salts alone promote the reaction. To the best of our knowledge, this is the first report of a rare-earth complex combining homogeneous catalysis with luminescent thermometry in solution.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115660"},"PeriodicalIF":4.9,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838902","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 : 2025-12-22DOI: 10.1016/j.mcat.2025.115671
Xuhui Wang , Yiwei Su , Jinxian Zhao , Fuzhen Wang , Zhengnan Cao
The hydrogenation of CO₂ to ethanol can both alleviate climate problems and solve energy issues. However, due to the easy formation of by-products such as methane and methanol during the reaction, the selectivity for ethanol remains low. In this study, Cu4 cluster loaded on graphene (Cu4/SVG) was designed by density functional theory (DFT) calculations. To enhance ethanol selectivity, single–atom Co and Fe doped into Cu4/SVG catalyst were marked as CoCu3/SVG and FeCu3/SVG, respectively. The results showed that Co and Fe doping enhanced the adsorption of species and acted as the active sites. The studies on the reaction mechanism have shown that CoCu3/SVG reduced the energy barrier by 28.4 kJ/mol and FeCu3/SVG slightly increased the energy barrier by 2.4 kJ/mol, but both catalysts effectively inhibited the formation of by-products of methane and methanol. The results of microkinetic analysis indicate that the doping of Co and Fe effectively enhances the ethanol formation rate, while suppressing the production of methanol and methane, thus making ethanol the optimal product. Electronic structure analysis demonstrated that the incorporation of Fe and Co enhanced the electron transfer capability, which significantly promoted the adsorption and activation of CO₂ and improved the stability of the catalyst. These findings provide critical insights into the rational design of high-performance catalysts for selective CO₂ hydrogenation to ethanol.
{"title":"Enhanced catalytic performance of the graphene supported Cu-based cluster for CO2 hydrogenation to ethanol: The role of single-atom Co and Fe doping","authors":"Xuhui Wang , Yiwei Su , Jinxian Zhao , Fuzhen Wang , Zhengnan Cao","doi":"10.1016/j.mcat.2025.115671","DOIUrl":"10.1016/j.mcat.2025.115671","url":null,"abstract":"<div><div>The hydrogenation of CO₂ to ethanol can both alleviate climate problems and solve energy issues. However, due to the easy formation of by-products such as methane and methanol during the reaction, the selectivity for ethanol remains low. In this study, Cu<sub>4</sub> cluster loaded on graphene (Cu<sub>4</sub>/SVG) was designed by density functional theory (DFT) calculations. To enhance ethanol selectivity, single–atom Co and Fe doped into Cu<sub>4</sub>/SVG catalyst were marked as CoCu<sub>3</sub>/SVG and FeCu<sub>3</sub>/SVG, respectively. The results showed that Co and Fe doping enhanced the adsorption of species and acted as the active sites. The studies on the reaction mechanism have shown that CoCu<sub>3</sub>/SVG reduced the energy barrier by 28.4 kJ/mol and FeCu<sub>3</sub>/SVG slightly increased the energy barrier by 2.4 kJ/mol, but both catalysts effectively inhibited the formation of by-products of methane and methanol. The results of microkinetic analysis indicate that the doping of Co and Fe effectively enhances the ethanol formation rate, while suppressing the production of methanol and methane, thus making ethanol the optimal product. Electronic structure analysis demonstrated that the incorporation of Fe and Co enhanced the electron transfer capability, which significantly promoted the adsorption and activation of CO₂ and improved the stability of the catalyst. These findings provide critical insights into the rational design of high-performance catalysts for selective CO₂ hydrogenation to ethanol.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115671"},"PeriodicalIF":4.9,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838957","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 : 2025-12-20DOI: 10.1016/j.mcat.2025.115668
Payal Tyagi, Rajender Singh Malik
The CO2 cycloaddition with epoxides to form cyclic carbonate is environmentally benign and a 100 % atom-economic reaction for CO2 mitigation. A heterogeneous bifunctional nanomaterial, (1,1',1''-(1,3,5-triazine-2,4,6-triyl) tris(3-(3-(triethoxysilyl) propyl)-1H-imidazol-3-ium) chloride incorporated periodic mesoporous organosilica (PMO@TIT) was designed via a surfactant-templated co-condensation method. A series of PMO@TIT was prepared based on the molar ratio of TIT-organosilica precursor and tetraethyl orthosilicate (TEOS) [i.e., 1:10, 1:20 and 1:30] and structurally characterized. The obtained PMO@TIT have ordered mesoporous channels, high surface area, high structural stability and offered synergistic effect of hydrogen bond donor groups and quaternary ammonium moieties for CO2 adsorption and conversion under cycloaddition reaction. Moreover, the PMO@TIT samples exhibit appreciable CO₂ adsorption capacities, with uptake values reaching approximately 1000 mmol g⁻¹ at 273 K and ∼700 mmol g⁻¹ at 293 K (1 bar). These high capacities highlight the cooperative contribution of the highly accessible pore network, the enriched nitrogen-containing organic domains, and the embedded Lewis basic sites, collectively enabling efficient CO₂ capture and its subsequent transformation. The optimal combination of high surface area and multiple active sites made PMO@TIT-20 a more effective catalyst than the other two. It featured excellent catalytic activity having 98 % conversion with 96 % selectivity of chloropropene carbonate (CPC) at 5 bar pressure and 100 °C temperature within 8 h under solvent and co-catalyst-free conditions. 1H-NMR was used to analyse the catalytic activity of the catalyst. A 96 % conversion of epichlorohydrin with 90 % selectivity for chloropropene carbonate was observed even after five cycles, signifying its reusability. Moreover, PMO@TIT-20 exhibits exciting versatility, catalysing several epoxide conversions. Finally, a PMO@TIT-catalysed mechanism for cycloaddition reaction was proposed.
{"title":"Triazine–imidazole functionalized periodic Mesoporous Organosilica (PMO): A next-generation catalyst for CO₂ transformation","authors":"Payal Tyagi, Rajender Singh Malik","doi":"10.1016/j.mcat.2025.115668","DOIUrl":"10.1016/j.mcat.2025.115668","url":null,"abstract":"<div><div>The CO<sub>2</sub> cycloaddition with epoxides to form cyclic carbonate is environmentally benign and a 100 % atom-economic reaction for CO<sub>2</sub> mitigation. A heterogeneous bifunctional nanomaterial, (1,1',1''-(1,3,5-triazine-2,4,6-triyl) tris(3-(3-(triethoxysilyl) propyl)-1H-imidazol-3-ium) chloride incorporated periodic mesoporous organosilica (PMO@TIT) was designed via a surfactant-templated co-condensation method. A series of PMO@TIT was prepared based on the molar ratio of TIT-organosilica precursor and tetraethyl orthosilicate (TEOS) [i.e., 1:10, 1:20 and 1:30] and structurally characterized. The obtained PMO@TIT have ordered mesoporous channels, high surface area, high structural stability and offered synergistic effect of hydrogen bond donor groups and quaternary ammonium moieties for CO<sub>2</sub> adsorption and conversion under cycloaddition reaction. Moreover, the PMO@TIT samples exhibit appreciable CO₂ adsorption capacities, with uptake values reaching approximately 1000 mmol g⁻¹ at 273 K and ∼700 mmol g⁻¹ at 293 K (1 bar). These high capacities highlight the cooperative contribution of the highly accessible pore network, the enriched nitrogen-containing organic domains, and the embedded Lewis basic sites, collectively enabling efficient CO₂ capture and its subsequent transformation. The optimal combination of high surface area and multiple active sites made PMO@TIT-20 a more effective catalyst than the other two. It featured excellent catalytic activity having 98 % conversion with 96 % selectivity of chloropropene carbonate (CPC) at 5 bar pressure and 100 °C temperature within 8 h under solvent and co-catalyst-free conditions. <sup>1</sup>H-NMR was used to analyse the catalytic activity of the catalyst. A 96 % conversion of epichlorohydrin with 90 % selectivity for chloropropene carbonate was observed even after five cycles, signifying its reusability. Moreover, PMO@TIT-20 exhibits exciting versatility, catalysing several epoxide conversions. Finally, a PMO@TIT-catalysed mechanism for cycloaddition reaction was proposed.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115668"},"PeriodicalIF":4.9,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838959","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