Molecular Catalysis最新文献

{"title":"Molecular complex inspired design of an efficient copper(II)-containing robust porous polymers for electrochemical water oxidation","authors":"Aodi Wang,&nbsp;Jiani Peng,&nbsp;Lijuan Wang,&nbsp;Guang Tan,&nbsp;Lei Wang","doi":"10.1016/j.mcat.2024.114659","DOIUrl":"10.1016/j.mcat.2024.114659","url":null,"abstract":"<div><div>Homogeneous copper-bipyridine complexes have been reported as effective catalysts for water oxidation, demonstrating significant potential as alternatives to precious metal-based complexes. However, these complexes face long-term stability and product separation challenges similar to many homogeneous catalysts. Meanwhile, recent studies have underscored the potential of metalated polymer networks, which integrate the structural advantages of polymers with the functional benefits of metal species, making them highly attractive for various applications. Herein, we integrated copper-bipyridine units into porous polymer networks to overcome the limitations of copper-bipyridine complexes. We prepared a series of copper-incorporated polymers (TpBpy-Cu_x) for electrochemical water oxidation. The electrochemical properties of these polymers were tuned by varying the copper content, with TpBpy-Cu₃ presenting the best performance among the samples studied. TpBpy-Cu₃ demonstrated a low Tafel slope of 69 mV/decade, achieved a high Faradaic efficiency (FE) of 94 %, and exhibited exceptional stability over 1000 cyclic scans. This study offers insights into the design and optimization of metal-incorporated porous polymer networks building on the foundational understanding of their molecular counterparts for advanced catalytic applications.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114659"},"PeriodicalIF":3.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142592977","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":"Optimizing reverse water gas shift catalysis: Minimizing metal loading and enhancing performance with Pt/ZrO2 catalysts through Rh incorporation","authors":"Renée S. García-Orozco,&nbsp;Rodrigo Linares-Arroyo,&nbsp;Trino A. Zepeda,&nbsp;Alfredo Solís-García","doi":"10.1016/j.mcat.2024.114661","DOIUrl":"10.1016/j.mcat.2024.114661","url":null,"abstract":"<div><div>In this study, the optimization of catalysts for the reverse water gas shift reaction by minimizing metal loading and enhancing the performance of supported Pt catalysts through Rh incorporation was done. The catalysts were synthesized by the wet impregnation method, in which the metal noble load in bimetallic samples decreased by approximately one-third compared to the reference platinum catalyst, with varying Rh-Pt ratios. In all materials, m-ZrO₂, obtained by the hydrothermal method, was used as support. In the catalytic tests in a continuous packed-bed flow reactor at atmospheric pressure, all samples were active to catalyze CO₂ reduction between 200 and 300 °C. Bimetallic samples, particularly those with an Rh-Pt atomic ratio of 20–80, exhibited superior performance in the RWGS reaction despite their lower metal content. Based on the results of H<em>₂</em>-TPR, FTIR <em>in situ</em>, and XPS, we propose that the enhanced CO production in bimetallic samples compared to Pt/ZrO₂ catalysts can be attributed to Rh increasing the reduction extent of supported Pt. This enhancement facilitates the hydrogenation of bicarbonate species into formate species, which subsequently evolve into Pt⁰-CO and ultimately into CO. Additionally, Rh incorporation enables an alternative pathway for CO generation, where Pt⁰-carbonyls, known for their CO-producing capability, are formed via CO₂ dissociation on the Pt⁰ surface. However, higher Rh concentrations favor the CO₂ methanation rather than the RWGS reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114661"},"PeriodicalIF":3.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"F-modified Cu/electrolyte interface boosts CO2 electroreduction into C2H4 and C2H5OH products via an alternative CC coupling mechanism","authors":"Lihui Ou","doi":"10.1016/j.mcat.2024.114662","DOIUrl":"10.1016/j.mcat.2024.114662","url":null,"abstract":"<div><div>A <em>F</em>⁻-modified Cu(111) electrocatalysts exhibited an ultrahigh Faradaic efficiency and product selectivity towards CO₂ electroreduction into C₂ products. Thus, CO₂ electroreduction mechanisms towards C₂H₄ and C₂H₅OH products at <em>F</em>⁻-modified Cu(111)/H₂O interface based on DFT calculations are studied in this work, by which the influencing mechanism of specifically adsorbed <em>F</em>⁻ on electroreduction activity, product selectivity and a alternative C<img>C coupling mechanism can be revealed. Our present studies indicate that the presence of <em>F</em>⁻ can notably enhance CO₂ electroreduction activity towards key intermediate CO because of significantly changed CO₂ adsorption configuration and weakening effect of <em>F</em>⁻ on COOH adsorption strength. CO dimerization into dimer OCCO through Langmuir-Hinshelwood mechanism is more favorable than CHO formation in the presence of the <em>F</em>⁻. Thus, it can be concluded that C<img>C coupling reaction occurs via CO dimerization. More CO adsorption strength because of modification of <em>F</em>⁻ can explain easier occurrence of C<img>C coupling reaction, thus leading to change of product selectivity. The parallel OCCOH and OCCHO pathways are proposed for CO₂ electroreduction into C₂H₄ and C₂H₅OH products at <em>F</em>⁻-modified Cu(111)/H₂O interface, in which CO dimerization is regarded as the rate-determining step. Ou present studies can unveil CO₂ electroreduction mechanisms and significant role of the specifically adsorbed <em>F</em>⁻ at Cu/electrolyte interface for promoting CO₂ electroreduction activity and improving product selectivity towards C₂ products.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114662"},"PeriodicalIF":3.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142587055","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":"VSI in memory of Prof. Rosario Pietropaolo (1941–2022): the man, the scientist, and the enlightened founder","authors":"A. Pietropaolo ,&nbsp;E. Paone ,&nbsp;P. Mastrorilli ,&nbsp;R. Luque ,&nbsp;F. Mauriello","doi":"10.1016/j.mcat.2024.114626","DOIUrl":"10.1016/j.mcat.2024.114626","url":null,"abstract":"","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114626"},"PeriodicalIF":3.9,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656331","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":"Development of an efficient biocatalytic three-component reaction for synthesizing pyrrole derivatives","authors":"YaoYao,&nbsp;Ming-Liang Shi,&nbsp;Xin-Yue Fan,&nbsp;Kun Li,&nbsp;Jing Li,&nbsp;Na Wang","doi":"10.1016/j.mcat.2024.114638","DOIUrl":"10.1016/j.mcat.2024.114638","url":null,"abstract":"<div><div>Multi-component reactions (MCRs) enable the development of efficient and atom-economic methods for synthesizing pyrrole derivatives. However, the current MCRs methods for synthesizing pyrrole derivatives in the enzymatic process have been unexploited. Herein, we developed a one-pot three-component enzymatic promiscuous catalytic system with green, efficient, and atom-economic to construct pyrrole derivatives. In this system, amines and 1,3-dicarbonyl compounds formed enamines with subsequent Michael addition with nitroolefins catalyzed by trypsin. A series of pyrrole derivatives were successfully obtained with moderate to good yield (up to 92 %). In addition, molecular simulations were conducted to gain insight into the source of differing tolerance of aromatic amides and fatty amines and the intrinsic effect of solvents in this system. This enzymatic catalytic one-pot three-component system has excellent functional tolerance, simple operation, and application potential for industrial production demonstrated by the gram scale experiment.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114638"},"PeriodicalIF":3.9,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554785","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":"Heterogeneous visible-light photoredox catalysis with NiCl2@g-C3N4 for induced C(sp2)-H/NH cross-dehydrogenative coupling","authors":"Lipeng Li ,&nbsp;Xiuzhi Xu ,&nbsp;Jin Wang,&nbsp;Jianjun Kang,&nbsp;Yan Chen,&nbsp;Fang Ke","doi":"10.1016/j.mcat.2024.114633","DOIUrl":"10.1016/j.mcat.2024.114633","url":null,"abstract":"<div><div>A novel photoactive NiCl₂@g-C₃N₄ catalyst system, which effectively drives C(sp²)-H/N<img>H bond formation between quinolin-2(1<em>H</em>)-ones, primary and secondary aliphatic amines under blue light irradiation. The NiCl₂@g-C₃N₄ composite with a NiCl₂ loading of 0.7wt% had the highest photoactivity, and the calculated band gap energy value is 2.56 eV The nickel ion could act as an electron acceptor enhancing carrier separation and transfer efficiency, greatly enhanced the photoreaction efficiency of g-C₃N₄. Preliminary mechanistic studies indicate upon visible light irradiation, the photo-generated electrons and holes act as oxidants, thereby generating amine radicals in the absence of external chemical oxidants. This provides a straightforward and efficient approach for directly 3-aminating quinoxalines-2(1<em>H</em>)-ones. Moreover, the heterogeneous catalyst can be recycled at least six times without significant activity loss.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114633"},"PeriodicalIF":3.9,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554786","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":"Copper single atoms decorated iridium nanoparticles for the selective hydrogenation of bromonitrobenzene","authors":"Zhifeng Yu ,&nbsp;Chenqi Zhao ,&nbsp;Zhelun Xiong ,&nbsp;Zicheng Xiao ,&nbsp;Meng He ,&nbsp;Yining Wu ,&nbsp;Yu Wang ,&nbsp;Pingfan Wu ,&nbsp;Wei Guo ,&nbsp;Ning Zhang ,&nbsp;Minghui Liang","doi":"10.1016/j.mcat.2024.114631","DOIUrl":"10.1016/j.mcat.2024.114631","url":null,"abstract":"<div><div>The interaction between metals is an important factor to modify the catalytic roles of metallic catalysts, and it is highly desirable to reveal the relationship between metal-metal interaction and catalytic performance. Three types of Ir-Cu catalysts including Cu single atoms modified Ir nanoparticles and Ir-Cu alloy catalysts are prepared to observe the modifying role of Cu on Ir. Under relatively high temperature treatment, Ir-Cu alloy can be produced from Cu single atoms and Ir nanoparticles. The selectivity to bromoaniline (BAN) over Cu/C-Ir catalyst can be up to 99.9 % at the 100 % conversion of bromonitrobenzene (BNB), which is higher than that over Ir/C (94.3 %) and Ir-Cu/C alloy catalyst (98.5 %). The turnover frequencies (TOFs) of Cu/C-Ir catalysts are evidently lower than that of the Ir-Cu/C alloy catalyst, though their dispersions are higher than that of Ir-Cu/C alloy catalyst. The electronic transfer from Cu single atoms to Ir nanoparticles not only weakens the hydrogen adsorption ability but reduces the number of active sites available for splitting hydrogen molecules into hydrogen atoms, leading to a decrease in the catalytic activity for the selective hydrogenation of BNB. The interaction exerted by unalloyed Cu single atoms on Ir nanoparticles differs from that of alloyed Cu on Ir, which may be the possible reason for the different catalytic performance between Cu single atoms modified Ir nanoparticles and Ir-Cu alloy.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114631"},"PeriodicalIF":3.9,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554864","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":"A superior Mn5CeTi5Ox catalysts for synergistic catalytic removal of chlorobenzene and NOx: Performance enhancement and mechanism studies","authors":"Bo Yang,&nbsp;Liuying Wang,&nbsp;Qiuxiang Gu,&nbsp;Yujie Lei,&nbsp;Qiong Huang,&nbsp;Mindong Chen","doi":"10.1016/j.mcat.2024.114634","DOIUrl":"10.1016/j.mcat.2024.114634","url":null,"abstract":"<div><div>The transition metal titanium-doped Mn-Ce-O_x catalysts catalyst were employed to achieve synergetic removal of NO and CB at 180–220 °C. The Mn₅CeTi₅O_x catalyst with a molar ratio of Mn/Ce/Ti = 5:1:5 exhibits excellent activity, and the NO_x and CB removal efficiencies reach 96 % and 89 % at 160–220 °C, respectively. The selectivity for N₂ and CO₂ are 93 % and 78 %, respectively. The N₂-physisorption, NH₃-TPD, H₂-TPR and XPS results show that Ti doping makes the catalyst possess a mesoporous structure, suitable particle sizes, and excellent redox and Lewis site properties. All of these features contribute to the observed high NO and CB removal efficiency. The synergetic removal of CB and NO over Mn₅CeTi₅O_x results from the synergistic catalysis between the redox and the solid acid. On the one hand, in the synergistic removal process, CB and NH₃ are competitively adsorbed on the catalyst surface, resulting in a decrease in the NH₃-SCR activity. On the other hand, the removal of NO and CB has a synergetic effect. The byproduct NO₂ produced by the NH₃-SCR reaction promotes the oxidation of CB, which is beneficial for CB removal. Moreover, the consumption of NO₂ indirectly promotes the NH₃-SCR reaction, which partially compensates for the decrease in the NO removal efficiency caused by competitive adsorption between NH₃ and CB. Ti doping promotes the participation of the SCR byproduct NO₂ in the CBCO reaction and promotes the formation of maleic acid, an intermediate product of CB oxidation. In summary, the Mn₅CeTi₅O_x catalyst exhibits good activity for the synergistic removal of NO_x and CB and is a promising candidate for the effective and economical removal of NO and CB during waste incineration.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114634"},"PeriodicalIF":3.9,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554784","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":"Impact of the key residues of 1-Deoxy-D-Xylulose-5-Phosphate synthase on its catalysis","authors":"Yan-Fei Liang ,&nbsp;Shuai Feng ,&nbsp;Dan Wu,&nbsp;Meng Ma,&nbsp;Jin-Tao Ren,&nbsp;Qian Zhao,&nbsp;Wen-Yun Gao,&nbsp;Heng Li","doi":"10.1016/j.mcat.2024.114639","DOIUrl":"10.1016/j.mcat.2024.114639","url":null,"abstract":"<div><div>1-Deoxy-<span>D-</span>xylulose-5-phosphate synthase (DXS) is the first rate-limiting enzyme in the 2-methyl-<span>D-</span>erythritol-4-phosphate (MEP) terpenoid biosynthetic pathway. To explore the active sites of the protein, we made a series of mutations to the key amino acid residues of <em>Escherichia coli</em> DXS including H49, R420, D427, and R478. The results show that several mutants including H49Q lose almost all their catalytic activity in DXP synthesis, but the double-point mutants H49QD427H and H49QD427 N recover 100 % activity of the wild type enzyme. The kinetic characterization displays that the affinity of the double-point mutants for pyruvate and <span>D-</span>glyceraldehyde-3-phosphate only slightly decreases. We also assessed impact of the mutation on the oxidative decarboxylation activity of all the mutants. Despite the fact that H49QD427H and H49QD427 N get back the full activity with regard to DXP synthesis, their oxidase activity remains unrestored. Furthermore, we assayed the acceptor substrate spectrum of the mutants and the results show that a large portion of them catalyzes ligation between pyruvate and nitrosobenzene to form N-phenyl-N-hydroxyacetamide, whereas R420D, R420F, and D427H exhibit activity in connection of pyruvate and benzaldehyde to afford phenylacetocarbinol (PAC), with the first two mutants yielding (<em>S</em>)-PAC (yields 21 %-25 %, <em>ee</em> values 71–75 %) while D427H furnishing (<em>R</em>)-PAC (yield 41 %, <em>ee</em> value 91 %), implying the key role of D427 for the acceptor substrate recognition and the stereoselectivity of the enzyme. It is worth noting that this is the first report of DXS mutants that can recognize benzaldehyde as an acceptor substrate and generate both enantiomers of PAC.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114639"},"PeriodicalIF":3.9,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554863","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":"Synthesis and evaluation of new mono- and binuclear salen complexes for the Cα-alkylation reaction of amino acid substrates as chiral phase transfer catalysts","authors":"Anahit M. Hovhannisyan ,&nbsp;Anna S. Tovmasyan ,&nbsp;Anna F. Mkrtchyan ,&nbsp;Karapet R. Ghazaryan ,&nbsp;Ela V. Minasyan ,&nbsp;Olgert L. Dallakyan ,&nbsp;Mikayel S. Chobanyan ,&nbsp;Hayk Zakaryan ,&nbsp;Giovanni N. Roviello ,&nbsp;Ashot S. Saghyan","doi":"10.1016/j.mcat.2024.114618","DOIUrl":"10.1016/j.mcat.2024.114618","url":null,"abstract":"<div><div>In this study, we present a series of Zn(II) mono- and Cu(II) binuclear salen complexes synthesized and assessed for their effectiveness in the Cα-alkylation reaction. Through systematic experimentation, it was observed that the introduction of a methoxy group at position 3 of the phenyl group in the salicylidene ligand led to a notable enhancement in asymmetric yield, while an allyl group reduced yield. Computational DFT calculations supported the involvement of the binuclear complex in the transition state of the reaction, elucidating the underlying mechanisms governing the observed catalytic behavior. A newly synthesized binuclear complex exhibited significantly higher catalytic activity compared to its mononuclear counterpart which could potentially be explained by increased intramolecular rigidity. This comprehensive investigation not only advances our understanding of structure-activity relationships in chiral salen complexes but also provides valuable insights for the rational design and optimization of catalysts for the asymmetric Cα-alkylation reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"569 ","pages":"Article 114618"},"PeriodicalIF":3.9,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}