Molecular Catalysis最新文献

{"title":"Harnessing visible light for alkenylation reactions: A promising strategy in organic synthesis","authors":"M Manod ,&nbsp;Archana Vijayakumar ,&nbsp;TS Abhinav ,&nbsp;R Bharath Krishna ,&nbsp;Chithra Mohan","doi":"10.1016/j.mcat.2025.115028","DOIUrl":"10.1016/j.mcat.2025.115028","url":null,"abstract":"<div><div>The development of green and streamlined methods for alkenylation reactions has long been a longstanding challenge in organic synthesis. Recently, visible light-mediated alkenylation has emerged as a potent strategy for the efficient and sustainable synthesis of diverse carbon-carbon double bonds. This approach offers a more effective and environmentally friendly alternative to traditional synthetic approaches. This review highlights the latest advancements in visible light-mediated alkenylation reactions, with a focus on novel photocatalytic systems, alkene sources, and applications in complex molecule synthesis. Mechanistic insights into the role of visible light in facilitating efficient and selective alkenylation are also provided.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115028"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686352","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":"In-situ controlled synthesis of BiOI/Bi2S3 Z-scheme heterostructure with enriched oxygen vacancies for efficient photocatalytic removal of hexavalent chromium","authors":"Meng Lan,&nbsp;Xiaoli Dong,&nbsp;Nan Zheng,&nbsp;Yujun Liu","doi":"10.1016/j.mcat.2025.115023","DOIUrl":"10.1016/j.mcat.2025.115023","url":null,"abstract":"<div><div>The continuous increase of heavy metal pollution has seriously affected the ecological environment and human health, and photocatalysis technology is considered to be one of the most effective and environmentally friendly treatment methods. Herein, BiOI/Bi₂S₃ Z-scheme heterostructure photocatalyst with abundant oxygen vacancies was fabricated and applied for the removal of hexavalent chromium (Cr(VI)). The tightly contact interface of in situ heterostructure and abundant oxygen vacancies can accelerate charge transport and improve the photogenerated carrier separation efficiency. The unique charge transmission path of the Z-scheme heterostructure endows the material with superior redox ability. BiOI/Bi₂S₃ with optimized ratio can achieve effective reduction of Cr(VI) with the efficiency of 95.6 % under 10 min visible light illumination This work offers a promising photocatalyst for promoting the disposal of chromium-containing wastewater.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115023"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686313","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":"One-step direct immobilization of engineered prenyltransferase on polystyrene for prenylated flavonoid production","authors":"Wenbo Li ,&nbsp;Xin Yan ,&nbsp;Wenli Xia ,&nbsp;Linguo Zhao ,&nbsp;Jianjun Pei","doi":"10.1016/j.mcat.2025.115047","DOIUrl":"10.1016/j.mcat.2025.115047","url":null,"abstract":"<div><div>Enzymes are highly efficient and specific biocatalysts. However, they are unstable and prone to deactivation, which limits their practical applications. To address these challenges, immobilization technology has been developed. Traditional immobilization methods typically require purified enzymes, but enzyme purification is often time-consuming and labor-intensive. Therefore, this study aims to develop a one-step method that directly purifies, adsorbs, and immobilizes enzymes from crude extracts, while simultaneously enhancing their activity. In this work, we examined the importance of the location of anchoring peptide (LCI) in fused enzyme functionality and binding affinity across various materials. LCI was fused with <em>Aspergillus fumigatiaffinis</em> prenyltransferase (AfPT) at the N-terminus to obtain the fusion enzyme LCI-AfPT, which displayed maximum load (38.9 mg/g) and highest activity recovery (92.7%) on polystyrene (PS). The free enzyme LCI-AfPT exhibited highest activity at pH 8.0 and 40°C. The highest activity of LCI-AfPT@PS was achieved at pH 7.5 and 55°C, with over 70% residual activity after 4 hours of incubation at 55°C. The tolerance of LCI-AfPT@PS to ethanol and methanol was significantly higher than that of LCI-AfPT. Immobilization significantly improved substrate affinity (<em>Km</em> reduced from 0.273 mM to 0.09 mM) and organic solvent tolerance, with no activity loss in ≤10% ethanol/methanol, highlighting its potential for industrial biocatalysis of hydrophobic flavonoids. The <em>Kcat/Km</em> value of LCI-AfPT@PS reached 0.072 s^-1· mM^-1, which was higher than that of LCI-AfPT and AfPT. LCI-AfPT was directly immobilized on PS from crude enzymes without purification, with a high adsorption selectivity of 80.5%, which was about 8-fold higher than that of AfPT. LCI-AfPT@PS retained 70% of its original activity after 10 cycles of reuse, resulting in a total of 4.4 mM of 3’-C-prenylnaringenin. This study represents the first investigation on the one-step purification and immobilization of prenyltransferase using an anchoring peptide, and its application in the efficient production of prenylated flavonoids.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115047"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686304","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":"The ring-opening polymerization of cyclic ester and carbonate catalyzed by trimethyl glycine and catalyst design: A DFT study","authors":"Shuang Li ,&nbsp;Xiaowei Xu ,&nbsp;Ziqiang Li ,&nbsp;Lijuan Ding ,&nbsp;Ying Peng ,&nbsp;Xiaohui Kang ,&nbsp;Yi Luo","doi":"10.1016/j.mcat.2025.115050","DOIUrl":"10.1016/j.mcat.2025.115050","url":null,"abstract":"<div><div>Organic catalytic ring-opening polymerization (ROP) of cyclic esters and carbonates is an effective strategy for obtaining biodegradable and biocompatible aliphatic polyesters and polycarbonates. The challenge is to develop highly active and green organocatalysts in this domain. Herein, the zwitterionic carboxybetaine catalyzed the ROP mechanism of trimethylene carbonate (TMC) cyclic ester and lactide (LA) was investigated by density functional theory (DFT). By comparing the ROP of TMC catalyzed by natural trimethyl glycine (TMG) and unnatural tetramethylammonium acetate (TMAA), we found the proton-accepting ability of the anion part in zwitterionic carboxybetaine is the main influencing factor of polymerization activity. Based on this finding, it is proposed to enhance the proton-accepting ability of the anion part in TMG by extending carbon spacer lengths between CH₃COO^‒ and N(CH₃)₄⁺ of TMG. Among them zwitterionic carboxybetaine molecules ((CH₃)₃N⁺(CH₂)_nCOO^‒ (n = 1–5)), the (CH₃)₃N⁺(CH₂)₄COO^‒ shows the highest catalytic activity in the ROP of TMC. Moreover, the ROP of LA catalyzed by (CH₃)₃N⁺(CH₂)₄COO^‒ showed very high catalytic activity compared to the TMG in both theoretical calculation and experiment. This work will inspire the future development of natural organocatalysts with high catalytic performance.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115050"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686312","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":"Nickel phthalocyanine based porous bimetallic catalysts for high activity CO2 electroreduction over wide potential window","authors":"Liang Chen ,&nbsp;Ling Gao ,&nbsp;Xinai Zhang ,&nbsp;Xueling Liu ,&nbsp;Qin Chen ,&nbsp;Jinchao Li ,&nbsp;Yaping Zhang ,&nbsp;Tianxia Liu","doi":"10.1016/j.mcat.2025.115039","DOIUrl":"10.1016/j.mcat.2025.115039","url":null,"abstract":"<div><div>Robust electrocatalyst with high catalytic activity and high selectivity over wide potential window is a crucial element for CO₂ electroreduction. In this study, combining the advantages of metal-nitrogen-carbon catalyst and bimetallic atomic catalyst, nickel phthalocyanine based porous bimetallic catalyst was synthesized using various porous carbon supports. Benefit from the complementary and synergistic effect of dual active metals derived from nickel and copper, prepared bimetallic catalyst achieved high selectivity and CO Faradaic efficiency (FE_CO) exceeding 90% over a wide cathodic potential range (-0.57 V to -1.07 V), along with high current density and good long-term stability in CO₂ reduction (ECR) under low overpotential conditions of 464 millivolts. Besides, different carbon source carriers (citric acid, carbon, and ZIF-8) supported bimetallic catalyst were detailed, and the citric acid derived carbon source carrier fabricated bimetallic catalyst exhibited best performances with a highest current density (114.2 mA cm⁻² at -1.1 V) and a wide cathodic potential range (-0.57 V to -1.07 V) for FE_CO&gt;90%. This work provides a cost-effective, extendable, and efficient strategy to fabricate electrocatalyst for CO₂ reduction to CO, which can meaningfully extend the CO₂ electroreduction in practical application.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115039"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686308","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":"Engineered nanoporous HPM@NH2−MIL-101(Fe) catalyst for efficient oxidative desulfurization: Anchoring, electron channel, and valence state","authors":"Qinyi Li,&nbsp;Chunfeng Mao,&nbsp;Ziyi Wang,&nbsp;Haojie Sun,&nbsp;Jingxuan Xu,&nbsp;Menghua Li,&nbsp;Pengxu Yan","doi":"10.1016/j.mcat.2025.115046","DOIUrl":"10.1016/j.mcat.2025.115046","url":null,"abstract":"<div><div>Supported metal catalysts frequently experience diminished catalytic activity, attributed to the loss of active sites and impaired electron transport efficiency during reactions. From the perspective of structure-activity relationships, developing composite multivalent metal catalysts and elucidating the key role of synergistic effects are crucial for enhancing electron transport and ultimately improving oxidative desulfurization(ODS) performance. In this study, core-shell nanostructure based on Phosphomolybdic acid(HPM) and amino-functionalized MIL-101(Fe)(NH₂₋MIL-101(Fe)) was successfully synthesized through a facile and controllable impregnation method. The phosphate groups in HPM not only regulate the acidity of the catalytic environment but also maintain the overall structural stability. The enhanced mobility of lattice oxygen in HPM promotes the formation of oxygen vacancies during its interaction with NH₂₋MIL-101(Fe). The abundance of directional anchor sites for HPM can be provided by coordination via empty orbitals in Mo-O clusters with lone pairs of electrons on the nitrogen atoms in the amino group of NH₂₋MIL-101(Fe). The variable valence states of Fe and Mo efficiently activate hydrogen peroxide(H₂O₂). Furthermore, the mass transfer can be facilitated by carefully design pore windows, which matching the size of sulfur compounds. These synergistic effects collectively achieved 99.8 % ODS performance under optimal conditions(V(Ionic liquids, ILs)=1 mL, V(H₂O₂)=0.15 mL, catalyst: model oil (0.02:5, g/mL), 50 °C), while also demonstrating excellent recyclability. The reaction activation energy (45.25 kJ/mol) is calculated and the dual-pathway synergistic catalytic reaction mechanism was proposed by experiment and characterization. This study provides a promising design strategy for the research of advanced functional catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115046"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686315","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 ruthenium(II) bis(N-Heterocyclic Carbene) complexes for homogeneous catalysis","authors":"Filippo Campagnolo,&nbsp;Eleonora Aneggi,&nbsp;Walter Baratta,&nbsp;Daniele Zuccaccia","doi":"10.1016/j.mcat.2025.115032","DOIUrl":"10.1016/j.mcat.2025.115032","url":null,"abstract":"<div><div>A tetrakis(acetonitrile) complex bearing a bidentate bis(N-Heterocyclic Carbene) ligand was synthesized, and its formation was extensively studied. Triethylamine played a pivotal role in the reaction, initially forming a ruthenium(II)-triethylamino complex with the precursor. It then functioned as a base to produce the ruthenium(II) bis(NHC) complex, which was found to be very active in catalyzing the direct ortho-arylation of 2-phenylpyridine, with loadings as low as 2 % (a significant result considering that most reported examples in the literature require loadings as high as 10 % and are typically limited to monoarylations). Additionally, the reactive complex was successfully functionalized with various bidentate ligands of the amino, pyridine, and phosphine types, yielding a series of novel ruthenium(II) bis(NHC) dicationic organonitrile complexes. These complexes were evaluated in the catalytic transfer hydrogenation reaction, demonstrating notable activity (TOF of 50,000 h^-1). It is notable that within the pool of reported ruthenium(II) complexes featuring bidentate bis(NHC) ligands, cis- [Ru(CH₃CN)₂(1,1′-bis(3-methyl-imidazol-2-ylidene)methylene))(2–2′Bipyridine)](PF₆)₂ demonstrates exceptional high rate, marking it as one of the fastest known. Overall, the synthesized tetrakis(acetonitrile) complex proves to be a promising platform for the development of future catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115032"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143684659","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":"Ammonia decomposition using barrier discharge Ru/Fe bed reactor: plasma catalytic synergy effect study on all-metal catalyst","authors":"Zhijun Wang ,&nbsp;Jiyou Deng ,&nbsp;Guangjiu Lei ,&nbsp;Huilin He ,&nbsp;Yi Duan ,&nbsp;Guoyao Zheng ,&nbsp;Shaofei Geng ,&nbsp;Ke Zhang ,&nbsp;Xiayu Qiu ,&nbsp;Kun Zhang ,&nbsp;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 NH₃, 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}

{"title":"A comparative study of CeO2 and Nb2O5-based supports for ethanol steam reforming (ESR) catalysts","authors":"I. Dancini-Pontes ,&nbsp;M. de Souza ,&nbsp;R.M. Pontes ,&nbsp;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 CeO₂ and Nb₂O₅-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 CeO₂ support calcined at 800 °C and the Nb₂O₅-Na support calcined at 500 °C presented the best results in ESR, both in terms of acidity, conversion and selectivity. While CeO₂ gives predominantly hydrogen and acetone, Nb₂O₅ 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 Nb₂O₅ 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}

{"title":"Foamed copper-based three-dimensional monolithic Cu6Mo5O18-X/CuInS2 microreactor for photocatalytic nitrogen fixation","authors":"Xianxin Fang ,&nbsp;Rui Liu ,&nbsp;Chaojie Li ,&nbsp;Yunlong Qu ,&nbsp;Mengqi Bian ,&nbsp;Qinghai Zhang ,&nbsp;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 (CuInS₂/Cu₆Mo₅O_18-X@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_cat^-1·h^-1 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}