Molecular Catalysis最新文献_第9页

Selective oxidation of benzyl alcohols photocatalyzed by asymmetric cobalt thioporphyrazine supported on alumina 氧化铝支撑的不对称硫代卟嗪钴光催化苯甲醇的选择性氧化作用

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-13 DOI: 10.1016/j.mcat.2024.114608

Wenyao Zhou, Rongjiao Tan, Changjun Yang, Bingguang Zhang, Kejian Deng

{"title":"Selective oxidation of benzyl alcohols photocatalyzed by asymmetric cobalt thioporphyrazine supported on alumina","authors":"Wenyao Zhou, Rongjiao Tan, Changjun Yang, Bingguang Zhang, Kejian Deng","doi":"10.1016/j.mcat.2024.114608","DOIUrl":"10.1016/j.mcat.2024.114608","url":null,"abstract":"<div><div>The sunlight-powered transformation of alcohols to corresponding carboxylic acids offers a feasible route for fine chemical synthesis. In this work, the asymmetric cobalt tri(2,3-bis(butylthio)maleonitrile)-(1,4-dithiin) porphyrazine (CoPz(SBu)6(dtn)) was synthesized, more importantly, its single crystal was further obtained by the solvent evaporation method. Then the asymmetric CoPz(SBu)6(dtn) supported on neutral Al2O3 particles to form composite photocatalyst CoPz(SBu)6(dtn)@Al2O3, which possessed strong visible light absorption. Under simulated sunlight irradiation using a xenon lamp, the composite photocatalyst CoPz(SBu)6(dtn)@Al2O3 exhibited excellent photocatalytic activity for selective oxidation of benzyl alcohol to benzoic acid in water under conditions of green H2O2 as oxidant and K2CO3 as additive. The conversion of benzyl alcohol was up to 53.8 % together with 99 % selectivity of benzoic acid over composite photocatalyst CoPz(SBu)6(dtn)@Al2O3. Meanwhile, this photocatalytic system had feasible substrate generalizability and excellent photocatalytic activity for substituted benzyl alcohols containing both electron-donating and electron-withdrawing substituents. The composite photocatalyst CoPz(SBu)6(dtn)@Al2O3 exhibited excellent photocatalytic durability, which was confirmed by the recycling experiments. This work manifests the asymmetric thioporphyrazine as photocatalyst is feasible in implementing sunlight-powered selective transformation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114608"},"PeriodicalIF":3.9,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142433769","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}

引用次数: 0

Mechanistic insights of surface OH* modulation on methanol production with CO2 hydrogenation by iron-based catalyst 铁基催化剂表面 OH* 调制对二氧化碳加氢制甲醇的机理启示

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-11 DOI: 10.1016/j.mcat.2024.114599

Fugui He , Xiangbin Kong , Tong Zhang , Yongning Yuan , Jianli Zhang , Xinhua Gao , Yurong He , Tiansheng Zhao

{"title":"Mechanistic insights of surface OH* modulation on methanol production with CO2 hydrogenation by iron-based catalyst","authors":"Fugui He , Xiangbin Kong , Tong Zhang , Yongning Yuan , Jianli Zhang , Xinhua Gao , Yurong He , Tiansheng Zhao","doi":"10.1016/j.mcat.2024.114599","DOIUrl":"10.1016/j.mcat.2024.114599","url":null,"abstract":"<div><div>The conversion of CO2 into high-value-added chemicals via the Fischer-Tropsch Synthesis (FTS) reaction has gathered a lot of attention. The surface oxygenation environment is a significant factor affecting the catalyst performance. In this work, spin-polarized density-functional theory calculations have been used to investigate the adsorption and reactions of CO2 and H to generate CH4 and CH3OH on Fe5C2(510) surfaces with varying OH* coverage. On the pure Fe5C2(510) surface, CO2 preferentially dissociates via direct dissociation, and the major C1 species generated is CH4. At low OH* coverage, the preferential pathway for CO2 dissociation changes from direct dissociation to the H-assisted route by the formation of COOH*. The major C1 product of the reaction in this state is transferred to CH3OH. In addition, CO2 hydrogenation reactions are facilitated by the OH* species. At high OH coverage, CO2 preferentially dissociates through the HCOO* intermediates. However, it appears that the CO2 hydrogenation reaction activity is suppressed. The results demonstrate that maintaining the surface environment with OH* and H* could be an indispensable measure to obtain the target product in the iron-based CO2 Fischer-Tropsch Synthesis system.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114599"},"PeriodicalIF":3.9,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424037","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}

引用次数: 0

Laser-engraved defects in TiO2 support: Enhancing reducibility and redox capability of Pt/TiO2 catalyst for reactive and selective hydrogenation 二氧化钛载体中的激光刻蚀缺陷：提高 Pt/TiO2 催化剂的还原性和氧化还原能力，用于反应性和选择性氢化

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-10 DOI: 10.1016/j.mcat.2024.114602

Yuan Zhang , Ali Kamali , Sheng Zhang , Tong Wang , Sooyeon Hwang , Aiysha Ashfaq , Lorelis Gonzalez-Lopez , Harrison Kraus , Jiayi Fu , Wenfei Zhang , Dionisios G. Vlachos , Mohamad I. Al-Sheikhly , Dongxia Liu

{"title":"Laser-engraved defects in TiO2 support: Enhancing reducibility and redox capability of Pt/TiO2 catalyst for reactive and selective hydrogenation","authors":"Yuan Zhang , Ali Kamali , Sheng Zhang , Tong Wang , Sooyeon Hwang , Aiysha Ashfaq , Lorelis Gonzalez-Lopez , Harrison Kraus , Jiayi Fu , Wenfei Zhang , Dionisios G. Vlachos , Mohamad I. Al-Sheikhly , Dongxia Liu","doi":"10.1016/j.mcat.2024.114602","DOIUrl":"10.1016/j.mcat.2024.114602","url":null,"abstract":"<div><div>Titanium dioxide (TiO2) has been studied as catalyst or catalyst support in catalysis. Its synthesis or modification approach controls the structural, optical, and electronic properties. Here we applied laser engraving to the anatase TiO2 and studied the consequent changes in its structure and property as well as the properties of TiO2 supported platinum (i.e., Pt/TiO2) catalyst. The laser engraving enlarged the particle size, formed rutile phase and created defects (i.e., oxygen vacancy (Ov) and Ti3+) in anatase TiO2. This induced band gap change and enhanced visible light absorption. The defects created by laser engraving are stable and more reducible than those existed in the pristine TiO2. The defective TiO2 is structurally stable and has great redox properties. The metal-support interaction in the Pt/defective TiO2 catalyst is stronger than that of the pristine Pt/TiO2 catalyst, which enabled higher reactivity and selectivity in hydrogenation of 3-nitrostyrene and furfuryl alcohol. Laser-engraved TiO2 has been rarely studied for thermal catalysis. This work provides basic understanding of material properties and catalysis application of laser-engraved catalyst supports and catalysts in field of thermal catalysis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114602"},"PeriodicalIF":3.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424035","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}

引用次数: 0

Inverse supported Al2O3/Coº catalysts for enhanced CO2 hydrogenation 用于增强二氧化碳加氢的反相支撑 Al2O3/Coº 催化剂

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-10 DOI: 10.1016/j.mcat.2024.114598

Weijie Fu , Yiming He , Shuilian Liu , Jian Chen , Jie Ren , Ruiyan Sun , Zhenchen Tang , Chalachew Mebrahtu , Huanhao Chen , Feng Zeng

{"title":"Inverse supported Al2O3/Coº catalysts for enhanced CO2 hydrogenation","authors":"Weijie Fu , Yiming He , Shuilian Liu , Jian Chen , Jie Ren , Ruiyan Sun , Zhenchen Tang , Chalachew Mebrahtu , Huanhao Chen , Feng Zeng","doi":"10.1016/j.mcat.2024.114598","DOIUrl":"10.1016/j.mcat.2024.114598","url":null,"abstract":"<div><div>Inverse catalysts, characterized by their distinctive interfaces, demonstrate exceptional catalytic activity for CO2 conversion. This study explores the synthesis of an Al-Co oxide/Co0 inverse catalyst through the reduction of a Co-Al oxide with a high Co content, achieved by modulating the Co/Al ratio in the oxide precursor. The resulting inverse catalyst significantly enhances CO2 hydrogenation, yielding increased production of methane, methanol, and ethanol, with a notable amplification in ethanol output. Amongst, the catalyst with a Co/Al ratio of 9:1 achieves high yields for methane (32,131 μmol/g, methanol (461 μmol/g), and ethanol (123 μmol/g). To elucidate the structure and reaction mechanism, the inverse catalyst was also characterized using a suite of techniques. It is posited that the abundance of active sites on the inverse catalyst, coupled with its moderate H binding affinity, facilitates CO2 activation and conversion. This is particularly evident in the enhanced coupling of *HCOO and *CH3 intermediates, which promotes ethanol synthesis. This research not only sheds light on the interactions between metal and metal oxide within Co-based catalysts for CO2 hydrogenation but also proposes a facile method for crafting efficient catalysts for such processes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114598"},"PeriodicalIF":3.9,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424036","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}

引用次数: 0

Zr-based MOF as a support for lipase immobilization to enhance enzymatic transesterification for biodiesel production 以 Zr 基 MOF 为支撑固定脂肪酶，增强生物柴油生产中的酶促酯交换反应

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-09 DOI: 10.1016/j.mcat.2024.114603

Xiangsheng Zheng, Xiaohong Hao, Yan Wang, Siyu Gao, Dantong Wen, Jinchuan Wang

{"title":"Zr-based MOF as a support for lipase immobilization to enhance enzymatic transesterification for biodiesel production","authors":"Xiangsheng Zheng, Xiaohong Hao, Yan Wang, Siyu Gao, Dantong Wen, Jinchuan Wang","doi":"10.1016/j.mcat.2024.114603","DOIUrl":"10.1016/j.mcat.2024.114603","url":null,"abstract":"<div><div>The development of novel biocatalysts is essential to promote the commercialization of biodiesel production by transesterification reaction. In this paper, Rhizopus oryzae lipase (ROL) was immobilized on an amino-functionalized zirconium-based metal organoskeleton by interfacial adsorption. The immobilization conditions were optimized and the enzymatic properties were tested, and the resulting novel biocatalysts exhibited higher stability and heat resistance. SEM, XRD and BET analyses were used to characterize the biocatalysts and carrier materials. The catalytic performance of ROL@UiO-66-NH2 in the production of biodiesel by transesterification reaction was explored, and the production process was optimized by response surface method. The results showed that the conversion rate of FAEE reached 82.05% at molar ratio of ethanol/oil of 15.43:1, reaction temperature of 50.28°C, reaction time of 120.9 min, DES addition of 48.08 wt%, biocatalyst addition of 3 wt%, and ultrasonic power of 90 W. In addition, ROL@UiO-66-NH2 demonstrated good recyclability, with the catalytic efficiency remaining at 71.87% after five cycles.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114603"},"PeriodicalIF":3.9,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424030","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}

引用次数: 0

Synthesis of SCD3-containing bicyclo[1.1.1]pentanes enabled by photocatalyzed difunctionalization of [1.1.1]propellane 通过光催化[1.1.1]丙烷的二官能化合成含 SCD3 的双环[1.1.1]戊烷

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-09 DOI: 10.1016/j.mcat.2024.114592

Yumiao Liu , Qing Pang , Binbin Chen , Zizhen Zhu , Jiabin Shen , Pengfei Zhang

引用次数: 0

Engineering an alcohol dehydrogenase from Gluconobacter oxydans for improved production of a bulky Ezetimibe intermediate 从氧葡萄糖杆菌中改造出一种醇脱氢酶，以改进大体积依折麦布中间体的生产

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-09 DOI: 10.1016/j.mcat.2024.114586

Yuqinxin Xie (谢雨沁欣), Dongzhi Wei (魏东芝), Jinping Lin (林金萍)

{"title":"Engineering an alcohol dehydrogenase from Gluconobacter oxydans for improved production of a bulky Ezetimibe intermediate","authors":"Yuqinxin Xie (谢雨沁欣), Dongzhi Wei (魏东芝), Jinping Lin (林金萍)","doi":"10.1016/j.mcat.2024.114586","DOIUrl":"10.1016/j.mcat.2024.114586","url":null,"abstract":"<div><div>(4S)-3-[(5S)-5-(4-fluorophenyl)-5‑hydroxy-valyl]-4-phenyl-1,3-oxazacyclopentane-2-one ((S)-Fop alcohol) is a key chiral intermediate for the synthesis of ezetimibe, and could be synthesized via asymmetric reduction of (S)-4-phenyl-3-[5-(4-fluorophenyl)-5-oxopentanoyl]-2-oxazolidione (Fop dione). However, discovering and engineering of ketoreductases toward bulky-bulky (diaryl) ketones is still challenging. Previously, we identified an alcohol dehydrogenase Gox0525 from Gluconobacter oxydans DSM2343 which possessed strict diastereoselectivity (d.e. value > 99%) but low activity toward Fop dione. In this study, a semi-rational design based on the focused rational iterative site-specific mutagenesis (FRISM) based on site-directed saturation mutagenesis was performed to improve the catalytic efficiency of Gox0525. The variant M4 (Y92G/P93M/Y94P/L151V) shows a 64-fold enhanced catalytic efficiency (Kcat/Km) and 47-fold in specific activity compared with the wild type Gox0525. Engineered Escherichia coli cells co-expressing the variant M4 and glucose dehydrogenase from Bacillus subtilis (BsGDH) for NADPH regeneration were employed as biocatalysts for gram-scale reaction of Fop dione. As a result,95 mM (33.76 g/L) Fop dione was completely transformed within 4 h, affording (S)-Fop alcohol with > 99% d.e. value, the yield of 96%, and the space-time yield of 195.6 g/L/d.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114586"},"PeriodicalIF":3.9,"publicationDate":"2024-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424032","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}

引用次数: 0

Illuminating tandem reactions characterized by temporal separation of catalytic activities via DFT calculations: A case study of Ni-catalyzed alkyne semi-hydrogenation 通过 DFT 计算阐明以催化活性的时间分离为特征的串联反应：镍催化炔烃半氢化案例研究

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-08 DOI: 10.1016/j.mcat.2024.114600

Yiying Yang , Xiaotai Wang , Dongju Zhang

{"title":"Illuminating tandem reactions characterized by temporal separation of catalytic activities via DFT calculations: A case study of Ni-catalyzed alkyne semi-hydrogenation","authors":"Yiying Yang , Xiaotai Wang , Dongju Zhang","doi":"10.1016/j.mcat.2024.114600","DOIUrl":"10.1016/j.mcat.2024.114600","url":null,"abstract":"<div><div>The concept of “temporal separation of catalytic activities” outlines a scenario where multiple transformations within a catalytic tandem reaction proceed sequentially over time without mutual interference. After presenting several examples of such reactions, we specifically focus on an example of the Ni-catalyzed alkyne semi-hydrogenation as a significant case study. By performing density functional theory (DFT) calculations, we illuminate the unique dynamic character of the reaction that the intermediate remains dormant until the reactant exhausted. The insights gained from the present calculations have led us to propose a comprehensive energy landscape model for the catalytic tandem reactions with temporal separation of catalytic activities, which offers a logical explanation for the temporal dormancy of the intermediate. This class of reactions is expected to be highly valuable as it presents the opportunity to fine-tune individual reaction steps, thereby introducing fresh concepts for precise control of reactions in one-pot chemistry.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114600"},"PeriodicalIF":3.9,"publicationDate":"2024-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424029","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}

引用次数: 0

Catalytic amination of 1,6-hexanediol for synthesis of N, N, N’, N’-tetramethyl-1,6-hexanediamine over Cu/Ni/Zn catalysts 在铜/镍/锌催化剂上催化 1,6-己二醇胺化以合成 N,N,N',N'-四甲基-1,6-己二胺

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-08 DOI: 10.1016/j.mcat.2024.114601

Zhifei Wang , Jun Li , Yakui Wang , Hongbin Ju , Lu Zhang , Yajie Jiang

引用次数: 0

Theoretical insight into the mechanism of Li-mediated nitrogen reduction reaction by density functional theory 通过密度泛函理论深入了解锂介导的氮还原反应机理

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2024-10-07 DOI: 10.1016/j.mcat.2024.114593

Ji Zhang , Aimin Yu , Dong-sheng Li , Chenghua Sun

{"title":"Theoretical insight into the mechanism of Li-mediated nitrogen reduction reaction by density functional theory","authors":"Ji Zhang , Aimin Yu , Dong-sheng Li , Chenghua Sun","doi":"10.1016/j.mcat.2024.114593","DOIUrl":"10.1016/j.mcat.2024.114593","url":null,"abstract":"<div><div>Lithium-mediated electrochemical nitrogen reduction reaction (NRR) as an alternative to the Haber-Bosch process has attracted increasing attention because of its high faradaic efficiency and reproducibility. However, the limited understanding of the mechanism has hampered further improvement of its catalytic performance. This work has endeavored to study the process of Li-mediated NRR and its underlying mechanism using density functional theory. It is founded that the Li6N2, Li7N2 atom groups, Li3N (001) and Li3N (110) layer stably exist on the deposited Li (001) layer. The replacing model has been established to describe the hydrogenation process with ethanol as a proton source, revealing that the replacement between Li and H atom is a spontaneously thermal process. Based on the replacing mechanism, the structure of interface and coverage rate of reactive sites are the two main factors that determine the ammonia formation. These findings further our understanding of Li-mediated NRR mechanism and will be helpful for the rational design of experiments of Li-mediated NRR.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114593"},"PeriodicalIF":3.9,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142424026","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}

引用次数: 0