Molecular Catalysis最新文献

{"title":"Oxygen vacancy activated inlaid Fe active sites in WO3 for sustainable and efficient photo-Fenton oxidation in a wide pH range","authors":"Zhimin Yuan ,&nbsp;Honghai Miao ,&nbsp;Zaiyong Jiang ,&nbsp;Xingling Zhao ,&nbsp;Shukui Shi ,&nbsp;Xianglin Zhu","doi":"10.1016/j.mcat.2025.114962","DOIUrl":"10.1016/j.mcat.2025.114962","url":null,"abstract":"<div><div>The efficient and sustaining activation of Fe sites is of great importance for the heterogeneous photo-Fenton system. Here, through a simple doping strategy, the active Fe centers have been introduced into oxygen vacancy-rich WO₃ nanoplates. The Fe sites were activated by the electron transferring from W atom to Fe sites because of oxygen vacancies association between W and Fe in the photo-excitation process. The directional transport of electrons not only promoted the regeneration of Fe²⁺ to continuously activate the photo-Fenton system, but also promoted the transfer of the photogenerated charge carriers. In addition, the results of the DFT calculations prove that the doping of Fe in turn helps the stability of the oxygen vacancy. As a result, the optimized Fe–WO₃–0.75 sample exhibited a kinetic rate of 0.0424 min^-1 in the degradation of tetracycline hydrochloride. This rate is more than three times higher than that of WO₃ (0.0137 min^-1). The Fe–WO₃ catalyst exhibited a good stability and a wide range of adaptability of pH values by taking advantage of the synergy of Fe sites and oxygen vacancy, which indicates the practical potentials for environmental applications.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114962"},"PeriodicalIF":3.9,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519357","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":"Non-binder synthesis of g-C3N4 decorated on TiO2 nanotube arrays toward photo/electrochemical water splitting","authors":"Thach Khac Bui ,&nbsp;Hai Viet Le ,&nbsp;Hoang Thai Nguyen ,&nbsp;Viet Van Pham","doi":"10.1016/j.mcat.2025.114960","DOIUrl":"10.1016/j.mcat.2025.114960","url":null,"abstract":"<div><div>Photoelectrodes based TiO₂ materials are widely used for photoelectrochemical water splitting because of their low cost, abundance, stability, nontoxicity, and appropriate energy potential. Titanium nanotube arrays (TNAs) and graphitic carbon nitride (gCN) were combined to create a water splitting photoelectrode that enhances solar energy spectrum utilization and facilitates carrier transport. In this study, the PEC electrodes based on gCN/TNAs were fabricated by dip coating of gCN solution on the TNAs electrodes from the acidic exfoliation method of bulk g-C₃N₄. When an appropriate concentration of gCN (0.10 g L⁻¹) is applied, it demonstrates favorable performance for HER with an overpotential of 0.9 V at a current density of 10 mA cm⁻². The 0.10 gCN/TNAs-5 sample showed a photo-transient current density about 2.1 times higher than the TNAs-5 sample. These results demonstrate that the non-binder photoelectrode gCN/TNAs, produced through simple fabrication techniques, has promise for hydrogen production.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114960"},"PeriodicalIF":3.9,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519418","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":"Error-prone PCR of the tryptophan synthase coding gene in Escherichia coli to enhance the affinity for indole under inhibitory concentrations","authors":"Wen-Long Liu,&nbsp;Shuo Wan,&nbsp;Rui-Nan Xu,&nbsp;Shu-Ping Tian,&nbsp;Jian-Zhong Xu","doi":"10.1016/j.mcat.2025.114958","DOIUrl":"10.1016/j.mcat.2025.114958","url":null,"abstract":"<div><div>Tryptophan synthase (TrpS), a key enzyme for <span>l</span>-tryptophan biosynthesis, catalyzes the conversion of indole and L‑serine into <span>l</span>-tryptophan via the synergistic action of its α subunits (encoded by <em>trpA</em>) and β subunits (encoded by <em>trpB</em>). However, the suboptimal catalytic efficiency of the wild-type enzyme poses a major bottleneck for industrial <span>l</span>-tryptophan production. In this study, we employed error-prone PCR to mutate the TrpS-coding gene and a mutant with enhanced affinity for indole was screened using an <span>l</span>-tryptophan fluorescence sensor. Sequencing and alignment revealed 23 mutated residues in this mutant. To identify the key amino acids that affect the affinity of TrpS for indole, these 23 mutated residues were individually mutated in TrpS-coding gene from <span>l</span>-tryptophan-producing strain JW-5 by site-directed mutagenesis. The experimental results demonstrate that the mutants TrpS(B)^K61A, TrpS(B)^G84S, TrpS(B)^Q114M, and TrpS(B)^F385V significantly enhance the production of <span>l</span>-tryptophan. Subsequently, these effective residues were combined, and the results indicated that the TrpS(B)^Q114M,G84S showed as the optimal mutant. TrpS(B)^Q114M,G84S exhibited the improved <em>k</em>_cat (s^-1) and the reduced <em>k</em>_m (μM) for indole compared to the wild-type, indicating significantly enhanced the affinity for indole. Molecular docking analyses revealed that the substitutions at positions 114 (glutamine to methionine) and 84 (glycine to serine) restructured the binding pocket of TrpS, resulting in stronger interactions with indole. Scale-up fermentation in a 5 L bioreactor confirmed the efficacy of the engineered strain. After 40 h of fed-batch fermentation, the mutant strain achieved an <span>l</span>-tryptophan titer of 34.43 g/L, a 61.03 % increase over the control strain JW-5 (21.38 g/L). In addition, the conversion yield improved from 14.8 % to 21.6 %. These findings demonstrated that the substitutions at positions 114 and 84 in the β-subunit of TrpS significantly enhance indole affinity, thereby boosting <span>l</span>-tryptophan production and conversion efficiency.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114958"},"PeriodicalIF":3.9,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519356","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":"Se doped boron carbonitride nanotubes as a metal-free catalyst for selective oxidation of lignin-derived vanillyl alcohol to vanillin with molecular oxygen","authors":"Weitao Wang ,&nbsp;Shuang Yue ,&nbsp;Huan Wang ,&nbsp;Jiaqi Zhu ,&nbsp;Zhen-Hong He ,&nbsp;Zhao-Tie Liu","doi":"10.1016/j.mcat.2025.114961","DOIUrl":"10.1016/j.mcat.2025.114961","url":null,"abstract":"<div><div>Selective oxidation of lignin-derived vanillyl alcohol to vanillin is a vital reaction due to the widely application of vanillin. From aspect of green catalysis and sustainability, metal-free based heterogeneous catalyst for the entitled reaction is promising. In the present work, Se doped boron carbonitride (Se-BCN) nanotubes catalyst was rationally prepared and employed as the metal-free catalyst for the entitled reaction. The conversion can achieve 94.4 % with the selectivity of 89.4 % at 120 °C for 4 h, which is higher than most reported metal-based catalytic system. The reasons for the enhanced activity and selectivity of Se doped BCN nanotubes catalyst were revealed from the kinetic investigation and adsorption of vanillyl alcohol and vanillin. Mechanism study reveals that radicals are involved in the entitled reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114961"},"PeriodicalIF":3.9,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511890","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":"Continuous methane selective oxidation to methanol over Cu-SAPO-34","authors":"Lanlan Sun ,&nbsp;Yu Wang ,&nbsp;Meng Zhao ,&nbsp;Xuesong Gu ,&nbsp;Qian Wang ,&nbsp;Junjie Guo","doi":"10.1016/j.mcat.2025.114954","DOIUrl":"10.1016/j.mcat.2025.114954","url":null,"abstract":"<div><div>A Cu-SAPO-34 catalyst synthesized via a one-pot method exhibits exceptional performance in the selective oxidation of methane to methanol. In this system, water serves as a key reactant, while trace oxygen acts as an oxidant to enhance catalytic activity by facilitating methane activation; Isotopic labeling experiments combined with temperature-programmed surface reaction analysis confirm that the oxygen in methanol originates predominantly from water, highlighting the critical role of water in the reaction pathway; In situ UV-Vis spectroscopy reveals the operation of a Cu²⁺-Cu⁺-Cu²⁺ redox cycle, which is indispensable for catalytic activity, with trace oxygen proving necessary to sustain the cycle. In situ FTIR spectroscopy identifies Cu-OH species located on the six-membered rings of Cu-SAPO-34 as potential initial active centers, with their consumption during methane activation accompanied by changes in Brønsted acid sites. NMR spectroscopy further demonstrates weak methane adsorption on the zeolite surface and the formation of CH₃O⁻ intermediates during the reaction. These findings provide a comprehensive mechanistic understanding of methane selective oxidation over Cu-SAPO-34, offering valuable insights for the development of efficient methane-to-methanol conversion technologies.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114954"},"PeriodicalIF":3.9,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511889","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":"Precise synthesis of γ-valerolactone via selective hydrogenation of levulinic acid catalyzed by NiCo/ZnO bimetallic catalysts","authors":"Wenpeng Han ,&nbsp;Fujiang Geng ,&nbsp;Shujuan Wang ,&nbsp;Ruidi Wei ,&nbsp;Jinlong Li ,&nbsp;Fang Tian ,&nbsp;Tingchun Zhu ,&nbsp;Yuqi Wang ,&nbsp;Mingxing Tang","doi":"10.1016/j.mcat.2025.114924","DOIUrl":"10.1016/j.mcat.2025.114924","url":null,"abstract":"<div><div>The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) represents a pivotal reaction, with its resultant product is widely used in solvents, fuels, pesticides, pharmaceuticals and other fields. The challenge associated with this process resides in achieving high selective generation of GVL. In this work, a spherical flower-like ZnO supported Ni-Co bimetallic catalyst (NiCo/ZnO) was prepared to facilitate the process of LA to GVL. The results showed that the NiCo alloy formed in the catalyst enhance both the hydrogenation activity of LA and the selectivity of GVL. Furthermore, the Lewis basic sites (SLB) in ZnO are instrumental in activating the C = O group. More importantly, it was found that the ethanol solvent can combine with LA to form ethyl levulinate (EL) which was more easily hydrogenated than LA. By regulating the appropriate calcination temperature, the proportions of NiCo alloy and SLB can be adjusted, and the NiCo/ZnO-400 catalyst with good performance was synthesized. Under the reaction condition of 100 °C and 2 MPa of H₂ for 5 h, the LA was completely converted, yielding a remarkable GVL production of 99 %. The catalyst displayed good recyclability, maintaining its activity after 6 times without loss of activity, highlighting its potential for practical application in biomass conversion.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"577 ","pages":"Article 114924"},"PeriodicalIF":3.9,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511888","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":"MOF-derived zinc and nickel bimetals grown on carbon fibers as efficient catalysts for synergistic photo-thermal catalytic CO2 cycloaddition","authors":"Xujie Hao ,&nbsp;Ying Li ,&nbsp;Yinghui Sun ,&nbsp;Tong Xu ,&nbsp;Jie Bai","doi":"10.1016/j.mcat.2025.114949","DOIUrl":"10.1016/j.mcat.2025.114949","url":null,"abstract":"<div><div>Carbon dioxide (CO₂), as an abundant and cost-effective C1 resource, holds significant potential for conversion into high-value chemicals such as alcohols, acids, cyclic carbonates, etc. Among them, cyclic carbonates have a wide range of applications in battery electrolytes, pharmaceuticals, and polymer synthesis. In this study, a bimetallic composite (Ni_0.4-Zn/C) featuring highly accessible Lewis acid-base sites was synthesized through electrospinning, in situ solvothermal growth, and calcination. Leveraging the adsorption properties of metal-organic frameworks (MOFs), Ni and Zn species could uniformly disperse onto carbon fibers. The material exhibited exceptional photothermal performance, achieving a high light absorption (&gt;93 %) and rapid surface heating to 90 °C within 10 min under visible light (0.3 W/cm²). Under mild conditions (55 °C, 0.3 W/cm², 0.1 MPa), the yield of cyclic carbonate reached 88 % after a continuous reaction for 10 h, significantly surpassing the yield of traditional thermal catalytic reactions (only 31 %). Furthermore, the catalyst demonstrated robust cycling stability, retaining 79 % efficiency over six consecutive runs, underscoring its practicality for industrial applications.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"576 ","pages":"Article 114949"},"PeriodicalIF":3.9,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143510477","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":"Enhanced nitrogen vacancy density induced by sulfur doping on carbon nitride facilitates selective lactic acid production","authors":"Fuxiu Cao,&nbsp;Yue Wang,&nbsp;Dingbin Zhu,&nbsp;Tianping Lv,&nbsp;Wenlong Jia,&nbsp;Huai Liu,&nbsp;Rui Zhang,&nbsp;Lincai Peng,&nbsp;Junhua Zhang","doi":"10.1016/j.mcat.2025.114957","DOIUrl":"10.1016/j.mcat.2025.114957","url":null,"abstract":"<div><div>The integration of biorefining and photocatalysis represents a highly promising approach for enabling the green and efficient synthesis of high-value chemicals derived from biomass. Herein, we successfully synthesized a metal-free carbon nitride photocatalyst doped with sulfur (S), which induced the formation of nitrogen vacancies (N_V). The optimized catalyst (S₂₀–CN–N_V) exhibits outstanding photocatalytic activity, achieving 95.5 % of glucose conversion and 95.1 % of lactic acid (LA) selectivity within 60 min under visible-light irradiation. Remarkably, the LA yield remains impressively high at the initial 97.5 % even after 6 cycles. Experimental studies and characterizations reveal that S doping significantly increased the concentration of N_V, and the synergistic effect of N_V and S doping enhanced the visible-light absorption and facilitated the separation of photogenerated carriers as well as the activation of oxygen, thereby promoting the generation of superoxide radicals. Density functional theory simulations further reveal that S₂₀–CN–N_V exhibits exceptional glucose adsorption capacity and requires low activation energy in the rate-limiting step. Consequently, S doping induced the formation of N_V thus boosted the photocatalytic oxidation process of glucose into LA. This study provides valuable insights for guiding the design of photocatalyst through nonmetal-doping and defect engineering strategies, facilitating the efficient valorization of biomass-derived platform chemicals.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"576 ","pages":"Article 114957"},"PeriodicalIF":3.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488080","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":"Artificial neural networks assisted by DFT for boosting ligand design in ethylene tri-/tetramerization using silicon-bridged diphosphine (SBDP) ligands","authors":"Yu Zhang ,&nbsp;Ruoxing Shao ,&nbsp;Yan Jiang ,&nbsp;Haonan Fan ,&nbsp;Zeyu Wang ,&nbsp;Huijuan Shao ,&nbsp;Hailiang Sun ,&nbsp;Xuzhi Zhang ,&nbsp;Yating Wang ,&nbsp;Tao Jiang","doi":"10.1016/j.mcat.2025.114952","DOIUrl":"10.1016/j.mcat.2025.114952","url":null,"abstract":"<div><div>The Cr(Ⅲ) complexes based on diphodphine ligands offer impressive performance for ethylene tri-/tetramerization to produce high-valued linear alpha-olefins (LAOs), such as 1-hexene and 1-octene. However, a deficiency remains in a universal approach for designing these diphosphine ligands. The current Artificial Neural Network (ANN) is a machine learning algorithm that boosts the innovation in ligand designing. In this paper, we outlined a method for the designing of silicon-bridged diphosphine (SBDP) ligands for ethylene tri-/tetramerization by ANN. Two models namely ANN-1 and ANN-2 have been presented to respectively predict the 1-hexene and 1-octene selectivity of SBDP-based ligands. The steric and electronic descriptors of ligands were extracted through Density functional theory (DFT) and fed into the ANN for training and weight optimization, leading to the creation of a highly accurate performance prediction model ANN-1 (<em>R²</em> =0.990) and ANN-2 (<em>R²</em> =0.990). Based on the predicted results of ANN models, novel and highly efficient SBDP ligands have been successfully designed and screened for ethylene oligomerization. We found that the experimentally obtained results for 1-hexene and 1-octene selectivities are closely in line with the predicted results extracted from the ANN models. The results of cumulative effect indicated that the steric descriptors have a greater influence on the selectivity of 1-hexene, while the electronic descriptors have a greater influence on the selectivity of 1-octene. This successful model establishment serves as a foundational guide for artificial intelligence to unlock new horizons in ligand designing.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"576 ","pages":"Article 114952"},"PeriodicalIF":3.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488081","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":"Recent advances in the application of contiguously functionalized aziridines for the synthesis of pharmaceutical precursors via regioselective ring-opening reactions","authors":"Huimyoung Byeon ,&nbsp;Hyun-Joon Ha ,&nbsp;Jung Woon Yang","doi":"10.1016/j.mcat.2025.114943","DOIUrl":"10.1016/j.mcat.2025.114943","url":null,"abstract":"<div><div>Contiguously functionalized aziridines, including epoxyaziridines, bisaziridines, and cyclopropylaziridines, are valuable intermediates in the synthesis of medicinally relevant compounds owing to their distinctive reactivity and structural versatility. This review explores strategic routes for the synthesis and application of these three-membered (hetero)cyclic systems, highlighting how their regioselective ring-opening reactions (RORs) facilitate the formation of diverse nitrogen-containing scaffolds. By focusing on the design and functionalization of contiguous aziridines, we demonstrated their utility in constructing complex chiral frameworks and bioactive moieties, such as those found in antibiotics, antifungal agents, and other pharmacologically significant molecules. The unique reactivity of aziridine-based systems enables selective transformations that enhance both synthetic efficiency and stereocontrol, offering flexible pathways for the development of therapeutically relevant compounds. This review emphasizes the recent advancements in the regioselective functionalization of aziridine-based (hetero)cycles, underscoring their potential to drive innovation in medicinal chemistry and drug discovery.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"576 ","pages":"Article 114943"},"PeriodicalIF":3.9,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488083","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}