Molecular Catalysis最新文献

{"title":"Theoretical study on the performance of g-C3N4 loaded silver nanoparticles (Ag4, Ag8, Ag13) catalysts and their electrocatalytic reduction mechanism of CO2","authors":"Xin-Long Zhang,&nbsp;Ya-Yuan Shi,&nbsp;Xiao-Min Liang,&nbsp;Laicai Li","doi":"10.1016/j.mcat.2024.114705","DOIUrl":"10.1016/j.mcat.2024.114705","url":null,"abstract":"<div><div>In this study, density functional theory (DFT) was employed to model Ag₄, Ag₈, and Ag₁₃ nanoparticle-supported g-C₃N₄ catalysts. The stability of the Ag₄, Ag₈, and Ag₁₃ nanoparticle-supported g-C₃N₄ catalysts was rigorously confirmed, followed by the computation of electron density and differential charge density profiles. The adsorption configuration of CO₂ on the catalyst surfaces was optimized, revealing that the adsorption process is predominantly governed by chemisorption. It was determined that the activation of this process is intricately linked to the electronic interactions between CO₂ molecules and the catalyst surface. Furthermore, the study explored the mechanisms underlying the electrochemical reduction of CO₂, with a focus on elucidating the production pathways of four key products: HCOOH, CO, CH₃OH, and CH₄, across the three catalysts. The free energy profiles along the reaction pathways were analyzed to compare the selectivity and catalytic activity of the three catalysts for various reduction products. Among the catalysts studied, the Ag₄-supported g-C₃N₄ catalyst exhibited the highest selectivity for the electrochemical reduction of CO₂ to HCOOH. Additionally, the study demonstrated that an increase in the size of the Ag nanoparticles correlates with an enhanced selectivity for CO as a two-electron reduction product, while the catalytic activity for multi-electron reduction products such as HCOOH, CH₃OH, and CH₄ decreases. Band structure and density of states calculations for the three Ag nanoparticle-supported catalysts revealed an inverse correlation between band gap values and catalytic activity, with smaller band gaps associated with higher catalytic activity. This work provides critical insights into the relationship between Ag nanoparticle size and CO₂ electrocatalytic reduction activity, offering a theoretical foundation for the design of advanced CO₂ reduction catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114705"},"PeriodicalIF":3.9,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700277","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}

{"title":"Universal increase in catalytic hydrogenation performance for lanthanide-modified Pd/Al2O3 catalysts by hydrogen transfer","authors":"Zhe Zhang ,&nbsp;Jianan Zhang ,&nbsp;Shuai Chen ,&nbsp;Yanan Liu ,&nbsp;Yufei He ,&nbsp;Dianqing Li","doi":"10.1016/j.mcat.2024.114704","DOIUrl":"10.1016/j.mcat.2024.114704","url":null,"abstract":"<div><div>Hydrogen spillover phenomenon can significantly impact the activity in hydrogenation reaction, but the spillover is limited in a very short range on non-reducible Al₂O₃, a most widely used industrial support. Herein, Al₂O₃ doped with different lanthanides (ln) was prepared by co-precipitation, which was then used to produce Pd/ln-Al₂O₃ catalysts. These catalysts display much higher hydrogenation activity towards alkylated anthraquinone than undoped Pd/Al₂O₃ catalyst and those modified by non-lanthanide elements. After the introduction of lanthanides, the reaction order of H₂ decreases from 1 to 0. Further characterization and DFT calculation show that H₂ storage ability is increased for ln-doped catalysts due to the low activation energy of H transfer and low adsorption energy of H on O(-ln) sites. In addition, a reasonable relationship between reducibility of ln³⁺ in catalysts and the catalytic performance is found.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114704"},"PeriodicalIF":3.9,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700283","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}

{"title":"Synergistic catalysis for converting α-pinene to camphene via carbon-based solid acid derived from eucalyptus wood","authors":"Tao Lv ,&nbsp;Kexin Wei ,&nbsp;Ting Wang ,&nbsp;Xiao Wang ,&nbsp;Zuguang Liu","doi":"10.1016/j.mcat.2024.114717","DOIUrl":"10.1016/j.mcat.2024.114717","url":null,"abstract":"<div><div>A carbon-based acid was prepared by the sulfonation of activated carbon derived from eucalyptus wood waste, a solid waste from wood processing, and characterized by SEM, BET, FT-IR, Raman, XRD and XPS. Due to activation by phosphoric acid and subsequent sulfonation, the resultant carbon-based solid acid can obtain a porous structure, medium surface area and abundant functional groups including sulfonic groups, carboxyl, hydroxyl and other oxygen-containing groups, which provides excellent mass transfer channels and sufficient reactive sites for catalytic reactions. So, the carbon-based solid acid showed excellent catalytic performance for converting <em>α</em>-pinene to camphene with a conversion of up to 99.8 % and a selectivity of 51.2 %, respectively. Quantum chemical theoretical calculations (electrostatic potential, Gibbs free enthalpy of intermediates, molecular size) are used to further analyze the catalytic mechanism of carbon-based solid acids. Theoretical analysis of the carbon positive ions and their energies as well as experimental results under electron-donating co-catalysts suggests that oxygen-containing functional groups on carbon-based solid acids play an important role in improving <em>α-</em>pinene adsorption onto catalyst as well as camphene selectivity. This work provides a promising approach for converting <em>α</em>-pinene to camphene catalyzed by carbon-based solid catalyst.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114717"},"PeriodicalIF":3.9,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700275","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}

{"title":"Efficient biosynthesis of bilirubin by overexpressing heme oxygenase, biliverdin reductase and 5-aminolevulinic acid dehydratase in Escherichia coli","authors":"Zhe Liu,&nbsp;Peng Xiong,&nbsp;Ning Guo,&nbsp;Huaxin Chen","doi":"10.1016/j.mcat.2024.114714","DOIUrl":"10.1016/j.mcat.2024.114714","url":null,"abstract":"<div><div>Bilirubin IXα (BR) offers health benefits in cardiovascular health, stroke, diabetes and metabolic syndrome. BR is mainly extracted from pig bile, bringing potential risks due to infectious viruses. In this study, an efficient pathway for BR biosynthesis was constructed by overexpression of heme oxygenase (HO1) and biliverdin reductase (BvdR) in <em>Escherichia coli</em>. Co-expression of 5-aminolevulinic acid (ALA) dehydratase improved BR production by the recombinant <em>E. coli</em>. In addition, glutamate supplementation in culture media enhanced BR production. Interestingly, it was discovered that ALA exhibited inhibitory effects on HO1 activity and reduced BR production. Culture conditions including post-induction temperature, IPTG concentration, pH of TB media and induction start time were optimized. Finally, fed-batch fermentation was carried out for the strain SH2, producing a BR titer of 62.1 mg/L in a 20 L bioreactor. This study lays foundation for future scalable production of BR in recombinant <em>E. coli</em>.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114714"},"PeriodicalIF":3.9,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700280","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}

{"title":"N, N-Mn(I)-catalyzed transfer hydrogenation of ketones","authors":"Renshi Luo ,&nbsp;Jinghui Tong ,&nbsp;Liang Liu ,&nbsp;Lu Ouyang ,&nbsp;Jianhua Liao","doi":"10.1016/j.mcat.2024.114707","DOIUrl":"10.1016/j.mcat.2024.114707","url":null,"abstract":"<div><div>Compared with other inexpensive metals-based catalysts for transfer hydrogenation, the use of manganese is rather more limited. Herein, a series of <em>N, N</em>-Mn(I)-Catalysts based on previous work were synthesized for transfer hydrogenation of ketones. Differential aromatic, heterocyclic ketones, as well as aliphatic ketones could be employed in this catalytic system, delivering the desired alcohol products in moderate to excellent yields. This <em>N, N</em>-Mn(I)-based catalytic system provides an alternative protocol for transfer hydrogenation of ketones to produce alcoholic products.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114707"},"PeriodicalIF":3.9,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700281","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}

{"title":"Regulating electrons transfer through Pd-O-Bi bridges for boosting photocatalytic CO2 reduction","authors":"Chi Ma,&nbsp;Zhiyong Zhong,&nbsp;Quanjun Xiang","doi":"10.1016/j.mcat.2024.114700","DOIUrl":"10.1016/j.mcat.2024.114700","url":null,"abstract":"<div><div>The photocatalytic efficiency of bismuth-based metal-organic framework (Bi-MOF) is extremely restricted by the rapid recombination of photogenerated electron-hole pairs, which reduce the number of electrons involved in the photocatalytic reduction reaction. Constructing precise interfacial bond bridges between metal nanoparticles (NPs) and MOFs has emerged as an effective strategy to address the above-mentioned issues, promoting the electrons transfer. Herein, this study improves the sluggish dynamics of photogenerated charge in Bi-MOF by inducing the Pd-O-Bi bond bridges at the interface on a Pd NPs-decorated Bi-MOF (Pd/Bi-MOF) nanosheets. This phenomenon results in an interaction between Pd NPs and the Bi-MOF support. And Pd-O-Bi bond bridges provide the fast electron transfer channels, triggering the directional migration of photogenerated electrons from Pd to Bi node, then enhancing the spatial separation of photogenerated electron-hole pairs, finally facilitating overall photocatalytic CO₂ reduction. The presence of these bond bridges leads to higher enhancement in CO production for Pd/Bi-MOF nanosheets compared to the Bi-MOF nanosheets under visible light irradiation after 4.5 h. This research demonstrates the importance of interfacial bond bridges and provides a reasonable guide to design efficient photocatalyst for reduction of CO₂ to CO.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114700"},"PeriodicalIF":3.9,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699766","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}

{"title":"Influence of MIL-53 on the catalytic performance of metallocene in propylene polymerization","authors":"Jeong Suk Lee ,&nbsp;Clinton Manianglung ,&nbsp;Hye In Jeon ,&nbsp;Young Soo Ko","doi":"10.1016/j.mcat.2024.114719","DOIUrl":"10.1016/j.mcat.2024.114719","url":null,"abstract":"<div><div>In this study, we investigate the application of metal-organic frameworks (MOFs) as a support for metallocene catalysts in the polymerization of propylene. MOFs such as MIL-53 and other conventional supports, SBA-15 and SiO₂, were employed to immobilize the Me₂Si(2-Me-4-PhInd)₂ZrCl₂ catalyst activated with methylaluminoxane (MAO). The effects of the physicochemical properties of these supports on catalytic performance and polymer properties were investigated. MIL-53, characterized by its channel structure, facilitated higher molecular weight polypropylene production and exhibited double the catalytic activity of SBA-15 and SiO₂ supports. The MIL-53/MAO/Me₂Si(2-Me-4-PhInd)₂ZrCl₂ catalyst also demonstrated higher comonomer incorporation and lower polymer melting points. The higher activity, elevated molecular weight, and increased reactivity towards 1-hexene of the MIL-53/MAO/Me₂Si(2-Me-4-PhInd)₂ZrCl₂ catalyst are attributed to the electronic and steric effects of MIL-53. This study underscores the significant role of MOF structure in influencing polymerization behavior and highlights the potential of MOF-supported catalysts for tailored polymer properties.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114719"},"PeriodicalIF":3.9,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700282","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}

{"title":"RuxMoS2 interfacial heterojunctions achieve efficient overall water splitting and stability in both alkaline and acidic media under large current density exceeding 100 mA cm-2","authors":"Pingping Li ,&nbsp;Songwen Luo ,&nbsp;Zhihui Xiong ,&nbsp;Hanyue Xiao ,&nbsp;Xinning Wang ,&nbsp;Kai Peng ,&nbsp;Xinmeng Xie ,&nbsp;Ziqing Zhang ,&nbsp;Guowei Deng ,&nbsp;Min Yang ,&nbsp;Cuijuan Wang","doi":"10.1016/j.mcat.2024.114710","DOIUrl":"10.1016/j.mcat.2024.114710","url":null,"abstract":"<div><div>RuO₂ has attracted considerable attention as a potential acid-alkali OER electrocatalyst. Exploring highly active Ru_x/MoS₂@NF (<em>x</em> = 1, 2, 3 mmol) electrocatalysts for acidic oxygen evolution reaction (OER) is critical for advancing H₂ production <em>via</em> water electrolysis using proton exchange membrane electrolyzer. For an alkaline current density of 10 mA cm⁻², Ru₂/MoS₂@NF has severely low HER and OER overpotentials of -38.44 and 39.42 mV. Tafel has a smaller slope of 43.32 and 24.58 mV dec⁻¹ and exceptional stability exceeding 600 h At 0.5 M H₂SO₄, Ru₂/MoS₂@NF at 100 mA cm⁻² current density, OER is only 336.2 mV, considerably better than commercial Pt/C. In addition, doping Ru into MoO₆ induces structural defects to generate oxygen vacancies, increasing the Mo⁶⁺/Mo⁴⁺ ratio. In situ Raman analyses showed that Ru doping has numerous structural defects, there was an increase in Mo−O active species at octahedral sites in Ru_x/MoS₂, indicating accelerated generation of the key *O intermediates for enhanced OER kinetics. This work provides insight into the design of Ru based electrocatalysts that can considerably improve the performance of acidic OER, provides a roadmap for achieving efficient, economical and sustainable electrolysis of water for hydrogen production, and provides a roadmap for the design and commercialization of materials.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114710"},"PeriodicalIF":3.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142698274","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}

{"title":"Silver- and gold-catalyzed azide−alkyne cycloaddition by functionalized NHC-based polynuclear catalysts: Computational investigation and mechanistic insights","authors":"Ali A Khairbek ,&nbsp;Mohammad Abd Al-Hakim Badawi ,&nbsp;Abdullah Yahya Abdullah Alzahrani ,&nbsp;Rajimon KJ ,&nbsp;Renjith Thomas","doi":"10.1016/j.mcat.2024.114708","DOIUrl":"10.1016/j.mcat.2024.114708","url":null,"abstract":"<div><div>This study evaluated the catalytic efficiency of Au(I), Ag(I), and Cu(I) complexes in the azide‒alkyne cycloaddition (<strong>AAC</strong>) reaction through density functional theory (<strong>DFT</strong>) calculations. Cu(I) complexes exhibit superior catalytic performance, with lower energy barriers (8.8 kcal/mol) and a favorable Gibbs free energy of -0.9 kcal/mol in the key cycloaddition step, significantly outperforming Ag and Au complexes. Structural analysis revealed that shorter M−C bond lengths in the Cu complex contributed to increased stability. Additionally, the copper complex has a more negative Gibbs free energy for the formed metallacycle, indicating a thermodynamically favorable reaction pathway. Noncovalent interaction (NCI) and reduced density gradient (RDG) analyses of the Cu, Ag, and Au systems highlighted distinct interaction patterns influencing the reactivity. Furthermore, electron localization function (ELF) and localized orbital locator (LOL) analyses revealed bonding characteristics in those complexes. This study offers valuable insights into the mechanistic differences among Au(I), Ag(I), and Cu(I) complexes, paving the way for future research on enhancing the catalytic activity of copper, silver and gold complexes through ligand modification.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114708"},"PeriodicalIF":3.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142698267","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}

{"title":"Tuning of isobutylene polymerization by Lewis acid catalytic Systems: Is a duo better than one?","authors":"Qinghua Guo ,&nbsp;Xing Guo ,&nbsp;Jiale Niu ,&nbsp;Xinyi Yang ,&nbsp;Boping Liu ,&nbsp;Zhen Liu","doi":"10.1016/j.mcat.2024.114692","DOIUrl":"10.1016/j.mcat.2024.114692","url":null,"abstract":"<div><div>The FeCl₃·phenetole/TiCl₄·H₂O catalytic system was investigated for the synthesis of medium molecular weight polyisobutylene (MPIB). The dual Lewis acid system showed a remarkable synergistic effect on the catalytic efficiency. The much higher monomer conversion was achieved with the dual Lewis acid system than that with the FeCl₃·phenetole system. Notably, the PIB with number average molecular weight up to 18,500 g mol^-1 was obtained with 93 % conversion in 10 min by the dual Lewis acid system. DFT calculations revealed a dimeric FeCl₃/TiCl₄ geometry for the FeCl₃·phenetole/TiCl₄·H₂O complex, in which H₂O simultaneously binds to the Fe center and the Ti center. The most plausible mechanism for the initiation reaction follows a proton transfer from the H₂O molecule to a nearby isobutylene molecule in the FeCl₃·phenetole/TiCl₄·H₂O system, which is favored in terms of energy barrier with comparison to the reaction initiated by the FeCl₃·phenetole system.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"571 ","pages":"Article 114692"},"PeriodicalIF":3.9,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700279","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}