Molecular Catalysis最新文献

{"title":"Light alkanes dehydrogenation over silica supported gallium catalysts","authors":"Yury A. Agafonov,&nbsp;Oleg L. Eliseev","doi":"10.1016/j.mcat.2024.114646","DOIUrl":"10.1016/j.mcat.2024.114646","url":null,"abstract":"<div><div>The present work is devoted to the studies of Ga/Silica catalysts in the paraffins dehydrogenation of natural gas - propane and ethane to produce valuable products - olefins and hydrogen. The gallium oxide supported on silica gel (2–10 %wt. of Ga) have been studied using XRD, TPR-H₂ and STEM/EDS methods, it has been shown that the dispersion of gallium oxide over the silica surface is very effective, the support actively reacts with a gallium salt to form surface particles that are more easily reduced than pure gallium oxide. Under steady and no-stationary state the negative effect of oxidative pre-treatment and the addition of CO₂ to the reaction mixture on catalytic activity was detected. On the contrary, pre-treatment of the catalysts in hydrogen (at 650–700 °C) or CO addition to the reaction mixture was accompanied by an increase in their propane dehydrogenation activities and stabilities at 600 °C. In the ethane dehydrogenation conditions (650 to 700 °C) catalysts is effective treated by hydrogen during the experiment. At 700 °C, the Ga/Silica activity may even increase during ethane dehydrogenation. By TPR-H₂ it was observed that with an increase in the temperature of pre-treatment of Ga/Silica in hydrogen from 650 to 700 °C, the proportion of oxidized Ga-containing phase significantly decreases.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114646"},"PeriodicalIF":3.9,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657065","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":"Proper NCoordination improves catalytic activity of graphene edge anchored Pt single atom for conversion of methane and carbon dioxide to acetic acid","authors":"Baoyu Huang ,&nbsp;Xiaomei Zhao ,&nbsp;Yang Ma ,&nbsp;Zhengjun Fang","doi":"10.1016/j.mcat.2024.114688","DOIUrl":"10.1016/j.mcat.2024.114688","url":null,"abstract":"<div><div>The reaction of directly converting CH₄ and CO₂ into acetic acid has a wide and important application in the chemical industry. In this work, we carried out systematically computational chemistry study on the catalytic performance of the single Pt atom catalyst anchored at the edge of N-doped graphene for the direct co-conversion of CH₄ and CO₂ to acetic acid based on density functional theory (DFT) calculations. The DFT calculation results show the catalytic activity of single Pt atom is significantly tuned by the local N-atom coordination. The Pt-N₁C exhibits the best catalytic performance of CH₄ and CO₂ conversion with a low rate-determining free energy barrier of 0.69 eV The microkinetic modeling shows that the TOF of CH₃COOH on Pt-N₁C catalyst reaches 7.63×10² <em>s</em>⁻¹ at 600 K and 2 bar Further analysis shows that the adsorption strength of reactant CH₄ and CO₂ is linearly correlated with the energy level of d_xy orbital center of Pt atom. A moderate adsorption strength of CH₄ and CO₂ over the Pt-N₁C leads to easier activation of methane and migration of H and CH₃ during the conversion reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114688"},"PeriodicalIF":3.9,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657062","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":"On the Mechanism of Acrylate and Propionate Silyl Esters Synthesis by Ruthenium-Catalyzed Coupling of CO2 with C2H4 in the Presence of Hydrosilanes: Combined Experimental and Computational Investigations","authors":"Kana Kunihiro ,&nbsp;Thayalan Rajeshkumar ,&nbsp;Laurent Maron ,&nbsp;Svetlana Heyte ,&nbsp;Sébastien Paul ,&nbsp;Thierry Roisnel ,&nbsp;Jean-François Carpentier ,&nbsp;Evgueni Kirillov","doi":"10.1016/j.mcat.2024.114660","DOIUrl":"10.1016/j.mcat.2024.114660","url":null,"abstract":"<div><div>The upcycling of CO₂ to value-added chemicals using catalytic approaches constitutes a challenge in the topical area of sustainable development and use of renewable resources. We report herein on a Ru(II)-catalyzed reductive carboxylation of ethylene in the presence of hydrosilane (Et₃SiH) affording acrylate and propionate silyl esters. Upon using high-throughput screening (HTS) and batch-reactor techniques, some promising catalyst systems incorporating 1,4-bis(dicyclohexylphosphino)butane (DCPB) as ligand, namely monohydrido-chloro complex Ru(H)(Cl)(CO)(DCPB)(PPh₃) (<strong>Ru-2</strong>) or dihydride complex Ru(H)₂(CO)(DCPB)(PPh₃) (<strong>Ru-5</strong>), were identified among a few others. Detailed mechanistic studies involving the isolation of a Ru(II)-acrylate intermediate and computational investigations unveiled the possible operational mechanism leading to the construction of the acrylate platform from CO₂ and ethylene. The selectivity toward the desired silyl esters is affected by side-processes (mainly CO₂ hydrosilylation, ethylene hydrosilylation and dehydrogenative coupling of ethylene with hydrosilane) and could be improved by varying the substrates’ concentrations (CO₂/ethylene/hydrosilane ratios), while the acrylate vs. propionate selectivity depends on the processes producing in situ H₂, which is responsible for the reduction of the acrylate C=C double bond. In particular, a marked role of water on the selectivity was rationalized as a potential H₂ source when used in combination with hydrosilane. A better selectivity towards the production of triethylsilyl acrylate could be achieved using dihydride complex <strong>Ru-5</strong> as discrete precatalyst (up to 47% vs. 15% with <strong>Ru-1</strong>/DCPB), in line with the mechanistic studies.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114660"},"PeriodicalIF":3.9,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657064","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":"Spiro-linked hanging group cobalt phthalocyanine for CO2-to-methanol electrocatalysis unveiled by grand canonical density functional theory","authors":"Beibei Tang ,&nbsp;Chao Ma ,&nbsp;Zhiyuan Xu ,&nbsp;Qi Zhang","doi":"10.1016/j.mcat.2024.114689","DOIUrl":"10.1016/j.mcat.2024.114689","url":null,"abstract":"<div><div>Heterogeneous cobalt phthalocyanine (CoPc) is one of the few favorable molecular catalysts for the electrocatalytic reduction of carbon dioxide to methanol. In-plane substituent modification of planar conjugated phthalocyanine ligands is a key way to establish the structure-activity relationship and enhance the catalytic performance of cobalt phthalocyanines. While steric hanging substituents inspired by efficient enzymes' catalytic architectures are prevalent in metalloporphyrin systems, their application in metal phthalocyanines remains underexplored. Herein, we carried out a systematic constant potential theoretical study on heterogeneous hanging group substituted CoPc electrocatalytic carbon dioxide reduction reaction. Notably, a phenol-based hanging group-modified tetra amino cobalt phthalocyanine was found to have excellent activity and selectivity for the methanol production. Intriguingly, the hanging group substituent connects to the ligand through a spirocyclic structure (rather than the conventional C-N single bond), which can reduce spatial steric hindrance and maintain hydrogen bonding. The phenolic H atoms in the hanging group form effective hydrogen bonds with the O atoms in the key structures of *CHO and *CH₂O, resulting in a strong stabilizing effect that facilitates the selectivity-determining *CO → *CHO and rate-determining *CHO → *CH₂O over a wide potential range. Our findings offer a theoretically effective hanging group substituent for metal phthalocyanine catalysts, broadening the scope and complexity of substituent design.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114689"},"PeriodicalIF":3.9,"publicationDate":"2024-11-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657063","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 active Pd-only three-way catalysts: The balance between surface composition and oxygen vacancies of ceria-zirconia support","authors":"Zixuan Zheng ,&nbsp;Xinyi Yin ,&nbsp;Zhiwei Zhou ,&nbsp;Linmei Wang ,&nbsp;Wei Wang ,&nbsp;Shanshan Li ,&nbsp;Jianli Wang ,&nbsp;Yaoqiang Chen","doi":"10.1016/j.mcat.2024.114682","DOIUrl":"10.1016/j.mcat.2024.114682","url":null,"abstract":"<div><div>CeO₂-based catalysts have attracted widespread attention in gasoline vehicle exhaust purification, and their catalytic performance is often intimately associated with the supports used. In this work, a series CeO₂-ZrO₂ (CZ) supports with varying composition and phase structure (with or without partial κ-Ce₂Zr₂O₈ structure) have been employed for Pd-only three-way catalysts (TWCs), and the corresponding activities were evaluated. It was found that for catalysts without κ-Ce₂Zr₂O₈ structure, the activity is positively related with the content of CeO₂ in CZ due to the increased Pd-O-Ce interfaces. However, as the formation of κ-Ce₂Zr₂O₈ structure is accompanied by the increased surface oxygen vacancies but decreased surface Ce-O_x species, for catalysts with κ-Ce₂Zr₂O₈ structure, there exists a balance between the reasonable concentration of oxygen vacancies and surface Ce-O_x species in determining the corresponding activities. Among these catalysts, only the Pd-only TWC with medium content of CeO₂ and partial κ-Ce₂Zr₂O₈ structure (Pd/κMC) exhibits superior activity than that in the same composition but without κ-Ce₂Zr₂O₈ structure (Pd/MC). This may be associated with the obviously increased surface oxygen vacancies introduced in κMC, which could compensate the slight decrease of its surface Ce-O_x species to stabilize the supported Pd species in smaller size and higher oxidation states. This finding enhances the understanding of support effects to rationally design efficient heterogeneous catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114682"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657170","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":"Emerging molecular sieve regulation strategy for the adsorption and catalysis: Silicon hydroxyl engineering","authors":"Zehao Pei ,&nbsp;Zhenghao Feng ,&nbsp;Zhitian Yao ,&nbsp;Yongming Luo ,&nbsp;Jichang Lu","doi":"10.1016/j.mcat.2024.114667","DOIUrl":"10.1016/j.mcat.2024.114667","url":null,"abstract":"<div><div>As a widely used aluminosilicate material, molecular sieves are modified to enhance performance according to the requirements of different practical working conditions. One of the main functional groups, the silicon hydroxyl group, is crucial to the unique chemical characteristics and adsorption capacity of molecular sieves, because of silicon hydroxyl group has inherent hydrogen bonding, which can give molecular sieves more adsorption and catalytic sites. Moreover, silicon hydroxyl groups are crucial for regulating the performance of molecular sieves and operate as a channel for the insertion of extra active compounds. Various regulating tactics include grafting ionic liquids and organic molecules, are utilized to create silicon hydroxyl nests to either directly or indirectly anchor active metals, and forming silicon hydroxyl groups to engage in adsorption and catalysis. The classification methods and characterization techniques of silicon hydroxyl groups have been summarized, and the introduction methods and applications in regulating the performance of molecular sieves have been reviewed. The key factors that need attention in regulating silicon hydroxyl groups have been analyzed. Finally, the development trend for the performance and application of silicon hydroxyl groups controlled molecular sieves in the future was discussed.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114667"},"PeriodicalIF":3.9,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657066","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 novel approach for the preparation of furandiamines utilizing biomass platform chemicals as substrates via Gabriel synthesis","authors":"Tong Sun ,&nbsp;Shibo Yang ,&nbsp;Yadong Liu ,&nbsp;Xiaokai Li ,&nbsp;Wenbo Liao ,&nbsp;Shuxia Wei ,&nbsp;Yong Sun","doi":"10.1016/j.mcat.2024.114679","DOIUrl":"10.1016/j.mcat.2024.114679","url":null,"abstract":"<div><div>Primary diamines are significant chemical intermediates and raw materials for high-added-value chemical products, which are regarded as essential monomers in the synthesis of polyamides and polyurethanes. Primary diamines are also particularly pronounced in the automotive, aerospace, and pharmaceutical fields. Among them, 2,5-bis(aminomethyl)furan (BAF) has garnered grant attention as a highly promising renewable diamine. In this work, a new route for the reduction preparation of BAF using a platform compound 5-chloromethylfurfural (CMF) utilizing the Gabriel method was developed, which reasonably avoids the disadvantage of molecular internal polymerization that often occurs in traditional routes that converting BAF from 5-hydroxymethylfurfural (HMF) and HMF derivatives. Additionally, under mild reaction conditions, this novel route yields BAF efficiently by employing Ni/SiO₂ as the catalyst. According to the kinetic analysis the reduction process was proved to be predominant. In addition, the analysis of the mechanism showed that compared to other catalysts, Ni/SiO₂ contains more active sites and more hydrogen active components (Ni⁰), achieving an impressive yield of 82.35 % under mild conditions. This work provides a pioneering method for the preparation of BAF, which is crucial for the development of primary diamine preparation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114679"},"PeriodicalIF":3.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657068","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":"Unveiling the role of N species in Co/NC catalysts for photothermal CO2 hydrogenation","authors":"Pengcheng Wang ,&nbsp;Qingqing Jiang ,&nbsp;XingYu Li,&nbsp;Xuedong Wang,&nbsp;Juncheng Hu","doi":"10.1016/j.mcat.2024.114686","DOIUrl":"10.1016/j.mcat.2024.114686","url":null,"abstract":"<div><div>Generally, researchers focus on the regulation of metal sites rather than surrounding nonmetals in photothermal CO₂ hydrogenation reaction. Herein, concerning the role of non-metallic N species, a series of Co/NC-T catalysts have been fabricated <em>via</em> high-temperature pyrolysis of Zeolitic Imidazolate Frameworks-67. The CO₂ conversion rate shows a consistent tendency with the ratio of graphitized-N species while the product selectivity is closely related to the coordination state of Co-N_x species. Co/NC-800 catalyst achieves high CO₂ conversion rate of 758 mmol g_cat^-1 h^-1 with CH₄ selectivity of 99.6 %. After adding extra graphitized-N species, the CO₂ conversion rate could further enhance to 80.2 % for N-Co/NC-2. The role of N species in photothermal CO₂ hydrogenation reaction has been investigated in details, providing new insights for the design of metal organic frameworks derived metal/N-doped carbon catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114686"},"PeriodicalIF":3.9,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657067","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":"Bio-based mesoporous carbon-modified Co3O4 quantum dots as efficient electrocatalyst for freshwater, seawater and urea oxidation reaction","authors":"Xintong Li,&nbsp;Min Gao,&nbsp;Shenglong Li,&nbsp;Zhichuan Yang,&nbsp;Xin Zhao,&nbsp;Yu Liu","doi":"10.1016/j.mcat.2024.114678","DOIUrl":"10.1016/j.mcat.2024.114678","url":null,"abstract":"<div><div>The combination of quantum dots (QDs) with carbon materials has garnered significant attention as electrocatalysts owing to their exceptional catalytic activity and robust thermodynamic stabilities. The present study utilizes bio-based mesoporous carbon as a carbon source to synthesize QDs carbon nanostructures (Co₃O₄/BMC<em>_-400</em>) through hydrothermal and carbonization methods. Due to the abundance of active sites and limited availability of Co, the size of Co particles is confined to the QDs level, ranging from 2 to 3 nm. The anodic oxidation reaction of the Co₃O₄/BMC<em>_-400</em> was investigated in freshwater, seawater, and urea. The prepared Co₃O₄/BMC<em>_-400</em> exhibits an oxygen evolution reaction overpotential of 235 mV at 10 mA cm⁻² in 1.0 M KOH. The catalytic activity is reduced as a result of the competitive oxidation and corrosion caused by chloride ions in seawater. For the urea oxidation reaction, Co₃O₄/BMC<em>_-400</em> exhibits superior catalytic performance, requiring only a potential of 1.371 V at 10 mA cm⁻², while exhibiting remarkable long-term stability for up to 30 h. More significantly, in comparison to Co₃O₄ nanosheets and nanoparticles, QDs can effectively reduce the transport pathways of alkali metal ions, thereby affording an increased number of catalytic active sites while simultaneously enhancing stability and prolonging service life. These findings may facilitate further exploration of metal-QDs/carbon materials in a wide range of electrocatalytic application.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114678"},"PeriodicalIF":3.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657237","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":"Insight into crystal-plane-dependent of cobalt catalysts for ethylene glycol amination","authors":"Kai Li ,&nbsp;De Zhang ,&nbsp;Heqin Guo ,&nbsp;Xinqi Yang ,&nbsp;Congcong Liang ,&nbsp;Xu Wu ,&nbsp;Qiang Wang ,&nbsp;Debao Li ,&nbsp;Litao Jia","doi":"10.1016/j.mcat.2024.114655","DOIUrl":"10.1016/j.mcat.2024.114655","url":null,"abstract":"<div><div>Co possesses outstanding dehydrogenation and hydrogenation activitiy and is a suitable catalyst for the amination of ethylene glycol. Nevertheless, the catalytic activity of Co's different crystal surfaces remains unclear, which hinders the further advancements in its catalytic efficiency. This research comprehensively examines the influence of Co's crystal plane effect on the amination of ethylene glycol employing both experimental and theoretical methodologies. Three single-crystal Co catalysts with mainly exposed (10−11), (0001) and (11−20) crystal planes were synthesized by a hydrothermal method and evaluated for ethylene glycol amination. The experimental results indicated that the c-Co-R catalyst with exposed Co (11–20) crystal facets exhibits optimal performance, with a 55.4 % ethylene glycol conversion and a 43.7 % primary amines (ethylenediamine and ethanolamine) selectivity. Combined with density-functional theory calculations and experimental characterization, the results showed that the Co (11−20) surface exhibited robust C-H bond dissociation and strong adsorption of ethylene glycol, which markedly improved the dehydrogenation efficiency of ethylene glycol and improved ethylene glycol conversion. Furthermore, the weak adsorption capacity of NH₃ further promoted the selectivity of the target products.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"570 ","pages":"Article 114655"},"PeriodicalIF":3.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657236","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}