Molecular Catalysis最新文献_第5页

Ammonia decomposition using barrier discharge Ru/Fe bed reactor: plasma catalytic synergy effect study on all-metal catalyst

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-20 DOI: 10.1016/j.mcat.2025.115036

Zhijun Wang , Jiyou Deng , Guangjiu Lei , Huilin He , Yi Duan , Guoyao Zheng , Shaofei Geng , Ke Zhang , Xiayu Qiu , Kun Zhang , Bin Zhao

{"title":"Ammonia decomposition using barrier discharge Ru/Fe bed reactor: plasma catalytic synergy effect study on all-metal catalyst","authors":"Zhijun Wang , Jiyou Deng , Guangjiu Lei , Huilin He , Yi Duan , Guoyao Zheng , Shaofei Geng , Ke Zhang , Xiayu Qiu , Kun Zhang , Bin Zhao","doi":"10.1016/j.mcat.2025.115036","DOIUrl":"10.1016/j.mcat.2025.115036","url":null,"abstract":"<div><div>Plasma-catalytic ammonia decomposition has witnessed substantial progress over the past decade, focusing on improving catalytic efficiency and achieving rapid start-stop operation capabilities under practical conditions. Despite these advancements, the mechanistic understanding of plasma-catalyst synergy remains a critical gap. This study investigates the synergy effects in a hybrid ammonia decomposition reaction utilizing dielectric barrier discharge (DBD) plasma coupled with Ru/Fe pellet catalysts. Through comprehensive analysis of this rarely understudied all-metal catalyst system, we reveal that plasma discharge primarily occurs along the ceramic reactor wall periphery rather than within the catalyst bed, as evidenced by high-speed imaging diagnostics. The predominant energy conversion pathway involves heating activation of thermal catalytic process, demonstrating an absence of synergistic enhancement in the one-stage reactor configuration. Notably, a two-stage reactor design exhibited plasma-induced pre-activation of NH<sub>3</sub>, leading to observable synergistic effects. However, the overall efficiency for hydrogen production deceased in the two-stage reactor configuration. This study provides valuable insights into the development of all-metal catalysts or catalysts with high metal loading for plasma catalytic ammonia decomposition or other potential applications.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115036"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143684662","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

A comparative study of CeO2 and Nb2O5-based supports for ethanol steam reforming (ESR) catalysts

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-20 DOI: 10.1016/j.mcat.2025.115015

I. Dancini-Pontes , M. de Souza , R.M. Pontes , N.R.C. Fernandes

{"title":"A comparative study of CeO2 and Nb2O5-based supports for ethanol steam reforming (ESR) catalysts","authors":"I. Dancini-Pontes , M. de Souza , R.M. Pontes , N.R.C. Fernandes","doi":"10.1016/j.mcat.2025.115015","DOIUrl":"10.1016/j.mcat.2025.115015","url":null,"abstract":"<div><div>Ethanol steam reforming (ESR) over CeO<sub>2</sub> and Nb<sub>2</sub>O<sub>5</sub>-based supports was studied in order to determine the role played by the support in the processs of hydrogen generation for fuel cells. Temperature of calcination as well as the presence of dopants influence the chemical and physical characteristics of the supports with impact in the product mixture distribution. The CeO<sub>2</sub> support calcined at 800 °C and the Nb<sub>2</sub>O<sub>5</sub>-Na support calcined at 500 °C presented the best results in ESR, both in terms of acidity, conversion and selectivity. While CeO<sub>2</sub> gives predominantly hydrogen and acetone, Nb<sub>2</sub>O<sub>5</sub> produces mores ethylene. In the two cases, however, conversion is low (<span><math><mrow><mo>∼</mo><mn>15</mn></mrow></math></span> %), so that the undesired products generated by the supports may not impact too much the product mixture under the presence of an active metallic phase. Density functional calculations (DFT) show that the preference for ethylene formation in Nb<sub>2</sub>O<sub>5</sub> comes from the thermodynamic stability of the products, but not directly from acidic catalysis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115015"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143684660","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

Foamed copper-based three-dimensional monolithic Cu6Mo5O18-X/CuInS2 microreactor for photocatalytic nitrogen fixation

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-20 DOI: 10.1016/j.mcat.2025.115033

Xianxin Fang , Rui Liu , Chaojie Li , Yunlong Qu , Mengqi Bian , Qinghai Zhang , Jihai Duan

{"title":"Foamed copper-based three-dimensional monolithic Cu6Mo5O18-X/CuInS2 microreactor for photocatalytic nitrogen fixation","authors":"Xianxin Fang , Rui Liu , Chaojie Li , Yunlong Qu , Mengqi Bian , Qinghai Zhang , Jihai Duan","doi":"10.1016/j.mcat.2025.115033","DOIUrl":"10.1016/j.mcat.2025.115033","url":null,"abstract":"<div><div>Photocatalytic nitrogen fixation often exhibits low efficiency due to the inert N<img>N triple bond and limitations in conventional reactor designs, which hinder reduction activation and photon utilization. To address these challenges, this study introduces microreactor technology into photocatalytic systems, leveraging a three-dimensional monolithic catalyst (CuInS<sub>2</sub>/Cu<sub>6</sub>Mo<sub>5</sub>O<sub>18-X</sub>@CF) where oxygen vacancy (OV)-induced localized surface plasmon resonance (LSPR) and an S-scheme heterojunction synergistically enhance charge separation. The monolithic microreactor significantly improved mass transfer by optimizing reactant flow dynamics, achieving an ammonia yield of 63.61 μmol·g<sub>cat</sub><sup>-1</sup>·h<sup>-1</sup> under visible light irradiation 8.1-fold higher than conventional quartz tube reactors. Furthermore, the system demonstrated remarkable stability and durability over multiple cycles. This work provides a promising strategy for advancing photocatalytic microreaction technologies, offering a pathway to efficient nitrogen fixation through integrated catalyst and reactor design.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115033"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143684658","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

Unification of Ru and carbon support in catalytic aqueous 1,6-hexanediol amination

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-20 DOI: 10.1016/j.mcat.2025.115030

Phillip Palenicek , Hafila S. Khairun , Navneet Kumar Gupta , Sandeep Yadav , Aby Cheruvathoor Poulose , Aristides Bakandritsos , Jörg J. Schneider , Marcus Rose

{"title":"Unification of Ru and carbon support in catalytic aqueous 1,6-hexanediol amination","authors":"Phillip Palenicek , Hafila S. Khairun , Navneet Kumar Gupta , Sandeep Yadav , Aby Cheruvathoor Poulose , Aristides Bakandritsos , Jörg J. Schneider , Marcus Rose","doi":"10.1016/j.mcat.2025.115030","DOIUrl":"10.1016/j.mcat.2025.115030","url":null,"abstract":"<div><div>The aqueous-phase reductive amination of 1,6-hexanediol (HDO) to amines is reported in the presence of Ru supported over various carbon materials with efficient product selectivity even under mild conditions (463 K, 25 bar H<sub>2</sub>). Activated carbon with an optimal balance of amorphous and graphitic configurations proved to be an outstanding support for achieving the highest selectivity towards total amines. Furthermore, adding Ba(OH)<sub>2</sub> in the Ru supported on different carbon materials notably improved the conversion of HDO and boosted the selectivity towards amines by around 1.3 times. This enhancement led to impressive yields, with hexamethylenediamine (HMDA) reaching up to 29%, azepane at 24%, and 6-amino-1-hexanol (AH) at 15% when using Ru-supported on activated carbon. A detailed examination and control experiments demonstrated the significance of the synergistic relationship between graphitic and amorphous sites within carbon materials, resulting in enhanced selectivity towards amination. Increasing the alkyl chain length of mono alcohols consistently produced higher yields with longer carbon chains, thus suggesting the crucial role of alkyl chain adsorption on amorphous carbon material in the HDO amination process, with Ru acting as the pivotal active site.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115030"},"PeriodicalIF":3.9,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143684661","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

Unravelling the reaction mechanism and structure-performance relationship for selective oxidation of ethylene glycol over Pt/Al2O3 catalyst

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-19 DOI: 10.1016/j.mcat.2025.115035

Shiping Wu , Yanhong Quan , Shunan Yin , Jun Ren

{"title":"Unravelling the reaction mechanism and structure-performance relationship for selective oxidation of ethylene glycol over Pt/Al2O3 catalyst","authors":"Shiping Wu , Yanhong Quan , Shunan Yin , Jun Ren","doi":"10.1016/j.mcat.2025.115035","DOIUrl":"10.1016/j.mcat.2025.115035","url":null,"abstract":"<div><div>A series of Pt/Al<sub>2</sub>O<sub>3</sub> catalysts were fabricated by finely adjusting the amount of platinum and investigated in the selective oxidative of ethylene glycol (EG) to glycolic acid (GA) under mild neutral conditions. The 0.90Pt/Al<sub>2</sub>O<sub>3</sub> catalyst showed the maximum turnover frequency (TOF: 1106.6 h<sup>−1</sup>) with the EG conversion of 74.2 % and GA selectivity of 90.2 %. A strong linear relationship between TOF values and Pt<sup>0</sup>concentration was revealed, confirming that Pt<sup>0</sup> species serves as the active sites for GA formation. In addition, <em>in situ</em> diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) results verify the reaction pathways of EG oxidation as follows: C<sub>2</sub>H<sub>6</sub>O<sub>2</sub> → HOCH<sub>2</sub>CHO → HOCH<sub>2</sub>COOH. This work unraveled structure-performance relationship for the selective EG oxidation over Pt/Al<sub>2</sub>O<sub>3</sub> catalyst, providing important guidance for the design of efficient noble catalysts especially for the oxidation reaction of polyols.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115035"},"PeriodicalIF":3.9,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643702","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

Theoretical investigation of Co(II)-catalyzed inert C–H bond functionalization in pyridine amide derivatives

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-18 DOI: 10.1016/j.mcat.2025.115027

Yi Sun, Yong Wang

{"title":"Theoretical investigation of Co(II)-catalyzed inert C–H bond functionalization in pyridine amide derivatives","authors":"Yi Sun, Yong Wang","doi":"10.1016/j.mcat.2025.115027","DOIUrl":"10.1016/j.mcat.2025.115027","url":null,"abstract":"<div><div>Density functional theory (DFT) calculations were used to investigate the mechanism of Co(II)-catalyzed functionalization of inert C<img>H bonds in pyridine amide derivatives. The research focused on the influence of substituents on the benzene ring and product selectivity. When the benzene ring contains <em>tert</em>‑butyl and isopropyl substituents, the reaction yields indoline and benzoxazine derivatives, respectively. Through calculations, the distinct mechanisms of these two reaction pathways were revealed: the formation of indoline derivatives follows a concerted metalation/deprotonation (CMD) mechanism, while the formation of benzoxazine derivatives proceeds via a hydrogen transfer mechanism. The key transition states in the corresponding processes have been studied in particular. The transition state structures have been located with relatively low energy barriers, which provide an important basis for understanding the reaction kinetics. In addition, in order to further explore the relationship between different spin multiplicities, the minimum energy crossing points (MECPs) were systematically investigated, which provided a theoretical basis for elucidating the possible spin state transition during the reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115027"},"PeriodicalIF":3.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643701","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

Modulating d‑Band center of iron oxide via interfacial oxygen vacancies engineering for boosting electrocatalytic nitrogen reduction

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-18 DOI: 10.1016/j.mcat.2025.115031

Sixia Liu , Xiaobo Zhang , Nidu Wang , Nagimovich Karimov , Yujie Wang , Zihan Gao , Dongguang Wang , Baikang Zhu , Shuying Gao , Fu Yang

{"title":"Modulating d‑Band center of iron oxide via interfacial oxygen vacancies engineering for boosting electrocatalytic nitrogen reduction","authors":"Sixia Liu , Xiaobo Zhang , Nidu Wang , Nagimovich Karimov , Yujie Wang , Zihan Gao , Dongguang Wang , Baikang Zhu , Shuying Gao , Fu Yang","doi":"10.1016/j.mcat.2025.115031","DOIUrl":"10.1016/j.mcat.2025.115031","url":null,"abstract":"<div><div>The electrochemical nitrogen reduction reaction (e-NRR) is a promising energy-efficient and low-emission alternative to the traditional Haber–Bosch process, but the sluggish kinetic and difficult activation of nitrogen impede the reaction activity. In particular, addressing the weak interaction of nitrogen with catalysts is very challenging in this field. Here, a surface oxygen vacancies tailored method was proposed to shift the <span>d</span>-band center of iron-based electrocatalysts to Femi energy level, by leveraging molecule self-assembly strategy to obtain Fe-base gels followed by ultrafast calcined process. The optimal electrocatalysts (Fe<sub>3</sub>O<sub>4</sub>-xGO) possess a hierarchical porous architecture (coral-like morphology), thereby endowed with outstanding structural properties (329.1 cm<sup>2</sup> g⁻<sup>1</sup>). Meanwhile, interfacial oxygen vacancies could be constructed during the ultrafast heat-pyrolysis process, and their concentration could be tailored with the assistance of graphene oxide (GO). Benefiting from these structure characters, the <span>d</span>-band center of Fe in coral-like iron oxide can be shifted to a higher energy level, which is conducive to trapping and activating the intermediate in the e-NRR process. The results of the electrocatalytic NRR test, as anticipated, indicated that Fe<sub>3</sub>O<sub>4</sub>–10GO achieved a high Faradaic efficiency of 28 % and an NH<sub>3</sub> production rate of 30.45 μg h⁻¹ mg<sub>cat</sub>⁻¹ at −0.3 V vs. RHE in a 0.1 M Na<sub>2</sub>SO<sub>4</sub>, positioning it comparably to most iron-based electrocatalytic materials used in e-NRR applications. This work could provide new insight for moldering the d band center of the electrocatalyst.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115031"},"PeriodicalIF":3.9,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643700","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

Promoting effect of alkaline earth metals on Ni/CeO2 catalysts for ammonia decomposition reaction

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-17 DOI: 10.1016/j.mcat.2025.115016

Zhen Zhang , Minghui Yu , Meiqing Shen , Wei Li , Gurong Shen

{"title":"Promoting effect of alkaline earth metals on Ni/CeO2 catalysts for ammonia decomposition reaction","authors":"Zhen Zhang , Minghui Yu , Meiqing Shen , Wei Li , Gurong Shen","doi":"10.1016/j.mcat.2025.115016","DOIUrl":"10.1016/j.mcat.2025.115016","url":null,"abstract":"<div><div>Ni-based catalysts, as non-noble metal alternatives, are widely regarded for their potential in ammonia decomposition for hydrogen production. However, their performance at low temperatures is suboptimal, necessitating the addition of promoters and a clear understanding of their mechanisms to enhance catalytic activity. In this study, we have successfully improved the low-temperature ammonia decomposition performance of Ni/CeO<sub>2</sub> by incorporating alkaline earth metals and conducted a comprehensive analysis of the underlying structural and electronic effects. The findings reveal that alkaline earth metals can enhance the basicity of the catalyst and increase electron density around the active metal sites, thereby facilitating the rate-determining step of recombination and desorption of N atom. Moreover, the presence of alkaline earth metals disrupts hydrogen adsorption stability on the catalysts, effectively mitigating the impact of hydrogen inhibition. Based on systematic kinetic experiments, a kinetic model was developed that accurately captures the hydrogen inhibition effect for Ni/CeO<sub>2</sub> catalysts. The insights into the promotional mechanisms of alkaline earth metals offer theoretical guidance for the development of highly active and cost-effective catalysts for ammonia decomposition.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115016"},"PeriodicalIF":3.9,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143631944","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

A combined DFT and kMC study of reaction kinetics for the acetoxylation of propylene to allyl acetate on PdCu catalysts

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-15 DOI: 10.1016/j.mcat.2025.115026

Weiwei Zhang , Liangfeng An , Yingzhe Yu , Minhua Zhang

{"title":"A combined DFT and kMC study of reaction kinetics for the acetoxylation of propylene to allyl acetate on PdCu catalysts","authors":"Weiwei Zhang , Liangfeng An , Yingzhe Yu , Minhua Zhang","doi":"10.1016/j.mcat.2025.115026","DOIUrl":"10.1016/j.mcat.2025.115026","url":null,"abstract":"<div><div>Allyl acetate is a vital intermediate in organic synthesis, which is produced by the acetoxylation of propylene on PdCu catalysts and mainly used for the synthesis of allyl alcohol and a range of derivatives, including 1,4-butanediol. Nevertheless, the absence of reaction kinetics in this process imposes limitations on the reactor design and process optimization. By combining Density Functional Theory and kinetic Monte Carlo simulations, the reaction kinetics were systematically studied. The critical oxygen concentration of the reaction system was calculated, and the feed molar ratio of oxygen was determined to be 8 %. The feed molar ratio of acetic acid was set to be 16 % to keep higher turnover frequency of allyl acetate and lower energy consumption. The preferential formation route of allyl acetate was obtained and the turnover frequency and space-time yield of allyl acetate were calculated. The apparent activation energy was determined to be 62.35 kJ⋅mol<sup>-1</sup>. Finally, the reaction kinetic equation was derived and the kinetic parameters were obtained by fitting the data of space-time yield. This work provides theoretical guidance for reactor design and technological process improvement on microscopic and mesoscopic scales. Of particular significance is the contribution of a novel approach to the acquisition of reaction kinetic equations, which has a good application prospect.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115026"},"PeriodicalIF":3.9,"publicationDate":"2025-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143629140","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

Swelling poly(ionic liquid)s supported silver N-heterocyclic carbene for efficient conversion of propargyl alcohols with CO2

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-14 DOI: 10.1016/j.mcat.2025.114999

Dandan Li , Tong Lai , Jingshun Zhang, Yang Hong, Ziwang Zhang, Guohua Gao

{"title":"Swelling poly(ionic liquid)s supported silver N-heterocyclic carbene for efficient conversion of propargyl alcohols with CO2","authors":"Dandan Li , Tong Lai , Jingshun Zhang, Yang Hong, Ziwang Zhang, Guohua Gao","doi":"10.1016/j.mcat.2025.114999","DOIUrl":"10.1016/j.mcat.2025.114999","url":null,"abstract":"<div><div>The conversion of propargyl alcohols and carbon dioxide (CO<sub>2</sub>) represents a hot spot in the field of CO<sub>2</sub> utilization. In this study, a novel type of swelling poly(ionic liquid)s supported silver N-heterocyclic carbene (Ag-NHC@P(VBImOAc)-n) was designed and successfully synthesized through the free-radical copolymerization of silver N-heterocyclic carbene (Ag-NHC), 1-vinyl-3-butylimidazolium acetate ([VBIm]OAc) and the cross-linker N, N'-methylene bisacrylamide (MBA). The swelling behavior of Ag-NHC@P(VBImOAc)-n in various solvents was investigated and the corresponding molar swelling ratios were determined as 314.6 mmol/g in water, 73.0 mmol/g in acetonitrile (CH<sub>3</sub>CN), and 56.8 mmol/g in 2-methyl-3-butyn-2-ol (1a). Notably, Ag-NHC@P(VBImOAc)-n exhibited a porous structure with a diameter of approximately ranging from 0.2 to 4 μm when swollen in CH<sub>3</sub>CN, effectively dispersing Ag-NHC moieties within the channels of the poly(ionic liquid) matrix. Ag-NHC@P(VBImOAc)-n were applied as catalysts for the carboxylative cyclization and hydration of propargylic alcohols in the absence of any homogeneous base additives. The catalysts achieved high yields (99 %) of 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one (2a) and 3‑hydroxy-3-methyl-2-butanone (3a) by synergistically utilizing active sites provided by both silver (Ag-NHC) and base ([VBIm]OAc) moieties under mild conditions. Moreover, the catalysts could be reused six times without obvious loss in catalytic activity and had good substrate generality.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 114999"},"PeriodicalIF":3.9,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143619572","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