Molecular Catalysis最新文献_第3页

CdS quantum dots with sulfur defects for photoreforming plastics into valuable chemicals coupled with hydrogen production

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-24 DOI: 10.1016/j.mcat.2025.115049

Jiaxin Song , Cheng Rao , Zeshu Zhang , Xiangguang Yang , Yibo Zhang

{"title":"CdS quantum dots with sulfur defects for photoreforming plastics into valuable chemicals coupled with hydrogen production","authors":"Jiaxin Song , Cheng Rao , Zeshu Zhang , Xiangguang Yang , Yibo Zhang","doi":"10.1016/j.mcat.2025.115049","DOIUrl":"10.1016/j.mcat.2025.115049","url":null,"abstract":"<div><div>Photocatalytic reforming of plastics, involving converting plastics into valuable chemicals while producing hydrogen from water, is a promising green technology with sustainability potential. However, designing catalysts with optimized structures to further enhance efficiency remained a major challenge. In this study, a series of CdS Quantum dots (QDs) with different sulfur defect concentrations were synthesized by a one-step solvothermal method by adjusting the type of sulfur precursors. In the absence of co-catalysts, the optimal CdS-NS photocatalyst achieved reforming of polyethylene terephthalate (PET) into formate with 870 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup> and acetate esters with 90 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup>, while the hydrogen production rate reached 1771 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup>. EPR spectra and other analyses confirmed the presence of abundant sulfur defects in the prepared CdS QDs and further demonstrated that the concentration of sulfur defects was closely related to photocatalytic performance. Suitable sulfur defects effectively modulated the electronic and band structure of CdS QDs, enhanced the oxidation capacity of photogenerated holes, reduced the recombination rate of charge carriers, and ultimately improved photocatalytic activity. This work provided an effective approach for designing efficient photocatalysts for the high-value recycling of plastic waste to achieve carbon neutrality.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115049"},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686812","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

Zn-TiO2/AC photocatalysts for pollutants degradation from experimental and DFT studies

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-23 DOI: 10.1016/j.mcat.2025.115037

Xiao Chu, Chen Chen, Ying Liang, Yuliang Chen, Yuliang Wu, Yijiang Liu, Rui Meng, Wenmin Wang, Weiwei Huang, Fei Yang, Xuesong Yi, Jun Cheng

{"title":"Zn-TiO2/AC photocatalysts for pollutants degradation from experimental and DFT studies","authors":"Xiao Chu, Chen Chen, Ying Liang, Yuliang Chen, Yuliang Wu, Yijiang Liu, Rui Meng, Wenmin Wang, Weiwei Huang, Fei Yang, Xuesong Yi, Jun Cheng","doi":"10.1016/j.mcat.2025.115037","DOIUrl":"10.1016/j.mcat.2025.115037","url":null,"abstract":"<div><div>The massive emission of dye wastewater has caused significant environmental problems. In this study, zinc-doped titanium dioxide loaded on biochar was synthesized by a simple solvothermal method to investigate its ability of degradation for dyes in photocatalytic process. The discussion focused on the impact of unactivated, acid-activated, and alkali-activated biochar on the properties of composites. Additionally, the composite catalysts underwent comprehensive physical and chemical characterization. The results showed that the particle size of Zn-TiO<sub>2<img></sub>OHAC increased significantly, which improved the sedimentation performance. Zn-TiO<sub>2<img></sub>OHAC demonstrated exceptional photocatalytic efficiency in the degradation of various pollutants such as Rhodamine B, Congo Red, Methyl Orange, and Methylene Blue. The better performance of the alkali-treated biochar-loaded composite catalysts was attributed to the fact that the alkali-treated biochar changed the electronic structure of the loaded materials and contained more carbon-oxygen functional groups, which was favorable for the separation of electrons and holes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115037"},"PeriodicalIF":3.9,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686311","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

Construction of perylene diimide supramolecular polymers: Study of photocatalytic reduction conversion from sulfoxide to thioether

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-23 DOI: 10.1016/j.mcat.2025.115041

Yu-Song Bi , Cheng-Long Xin , Rong-Zhen Zhang , Hui Liu , Ling-Bao Xing

引用次数: 0

Morphology control of Ni(OH)2-TiO2 nanosheet array and its excellent electrochemical hydrogen evolution performance

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-23 DOI: 10.1016/j.mcat.2025.115042

Fen Qiao, Changshun Zheng, Jikang Zhao, Jiaxin Zhou, Genxiang Wang

{"title":"Morphology control of Ni(OH)2-TiO2 nanosheet array and its excellent electrochemical hydrogen evolution performance","authors":"Fen Qiao, Changshun Zheng, Jikang Zhao, Jiaxin Zhou, Genxiang Wang","doi":"10.1016/j.mcat.2025.115042","DOIUrl":"10.1016/j.mcat.2025.115042","url":null,"abstract":"<div><div>Aiming at the kinetic bottleneck of hydrogen evolution reaction in hydrogen production by electrolysis of water, Ni(OH)<sub>2</sub>-TiO<sub>2</sub> composites were successfully prepared on nickel foam (NF) substrate by two-step hydrothermal method. By adjusting the concentration of nickel source and reaction conditions, the composite catalysts with excellent morphology and structure were constructed. The Ni(OH)<sub>2</sub>-TiO<sub>2</sub> catalyst prepared under the optimized conditions has an overpotential of only 63 mV at the current density of 10 mA·cm<sup>−2</sup>, showing lower Tafel slope, higher double layer capacitance and excellent reaction kinetics. The results of density functional theory (DFT) revealed the phenomenon of charge transfer inside the composite and the influence of interface effect on the electron structure, and further confirmed that the electrons transfer from Ni(OH)<sub>2</sub> to TiO<sub>2</sub> optimized the charge distribution inside the composite, promoted the charge transfer at the interface, and reduced the activation energy of catalytic reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115042"},"PeriodicalIF":3.9,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686310","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

Bimetallic oxide catalysis meets silanol-enhanced synergy: A winning combination for efficient CO2 fixation by cycloaddition with styrene oxide

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-22 DOI: 10.1016/j.mcat.2025.115029

Chaitra N. Mallannavar , S. Sujith , Shrinidhi D. Patil , Sanjeev P. Maradur , Ganapati V. Shanbhag

{"title":"Bimetallic oxide catalysis meets silanol-enhanced synergy: A winning combination for efficient CO2 fixation by cycloaddition with styrene oxide","authors":"Chaitra N. Mallannavar , S. Sujith , Shrinidhi D. Patil , Sanjeev P. Maradur , Ganapati V. Shanbhag","doi":"10.1016/j.mcat.2025.115029","DOIUrl":"10.1016/j.mcat.2025.115029","url":null,"abstract":"<div><div>The bimetallic oxide dispersed on silanol rich SBA-15-OH was designed for the synthesis of cyclic carbonates from epoxides and CO<sub>2</sub>. The SBA-15-OH was synthesized via desilication and active metals were loaded by sol-gel method. Pure Sn-Ni oxide with a low surface area and lesser activity was modified by dispersing it on a high surface area SBA-15-OH. The different characterization techniques such as XRD, N<sub>2</sub>-sorption, CO<sub>2</sub> and NH<sub>3</sub>-TPD, H<sub>2</sub>-TPR, SEM-EDX, TEM and XPS confirmed that the surface silanol group acts as anchoring site for the enhanced metal oxide-support interaction. Supported Sn-Ni oxide exhibited 16-fold better activity than pure Sn-Ni oxide, due to improved dispersion, which enhances the accessibility of reactants to the catalytic sites. Under the optimized reaction conditions 10Sn5Ni/SBA-15-OH gave 92.9 % styrene oxide conversion and 84.3 % selectivity for styrene carbonate. The catalyst is recyclable and the flexibility of the catalyst is tested for different epoxides with CO<sub>2.</sub></div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115029"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686314","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

Bifunctional catalysts based on 2-amino-1,10-phenanthroline-containing podands for cyclic carbonates synthesis from CO2 and epoxides under mild conditions

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-22 DOI: 10.1016/j.mcat.2025.115019

Violetta A. Ionova , Artem N. Fakhrutdinov , Daniil I. Gusev , Anton S. Abel , Alexei D. Averin , Irina P. Beletskaya

{"title":"Bifunctional catalysts based on 2-amino-1,10-phenanthroline-containing podands for cyclic carbonates synthesis from CO2 and epoxides under mild conditions","authors":"Violetta A. Ionova , Artem N. Fakhrutdinov , Daniil I. Gusev , Anton S. Abel , Alexei D. Averin , Irina P. Beletskaya","doi":"10.1016/j.mcat.2025.115019","DOIUrl":"10.1016/j.mcat.2025.115019","url":null,"abstract":"<div><div>A new series of polytopic ligands based on 1,10-phenanthroline and polyoxadiamines has been synthesized through S<sub>N</sub>Ar amination between 2-chloro-1,10-phenanthroline and diamines of various structures. The obtained podands were investigated as polytopic ligands for potassium and zinc ions in the industrially important reaction of cyclic carbonates synthesis from CO<sub>2</sub> and epoxides under mild conditions (p(CO<sub>2</sub>) = 1 atm., T = 60–80 °C). The advantage of 1,11-diamino-3,6,9-trioxaundecane functionalized by 1,10-phenanthroline units compared to the diamine itself is demonstrated. It is revealed that heteroarylated 1,11-diamino-3,6,9-trioxaundecane can be used as a catalyst in the presence of KI (2 mol.%) with a low loading of the ligand (0.2 mol.%) instead of the usually employed 5–10 mol.% for unfunctionalized podands. Under these reaction conditions mono-substituted cyclic carbonates of various structures have been synthesized in excellent preparative yields ranging from 87 to 99%. Coordination of two Zn(II) ions to both 1,10-phenanthroline moieties has been shown to provide additional enhancement of catalytic activity. The catalysts demonstrate excellent stability and can be reused at least in 6 cycles.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115019"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686306","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

Fabrication of excellent bifunctional electrocatalyst FeNi-LDH@L-NiCoP using ZIF as a sacrifice template for alkaline electrolysis of water

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-22 DOI: 10.1016/j.mcat.2025.115052

Boxuan Zhang , Jinxing Cui , Zhifang Li , Changlong Yang , Weiwei Dong , Ke Li

引用次数: 0

Efficient biosynthesis of Pro-Xylane through semi-rational engineering of carbonyl reductase from Canariomyces notabilis

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-22 DOI: 10.1016/j.mcat.2025.115020

Jian Lu , Zhentao Jiang , Xiubing Xie , Zhiwen Xi , Wenchi Zhang , Rongzhen Zhang

{"title":"Efficient biosynthesis of Pro-Xylane through semi-rational engineering of carbonyl reductase from Canariomyces notabilis","authors":"Jian Lu , Zhentao Jiang , Xiubing Xie , Zhiwen Xi , Wenchi Zhang , Rongzhen Zhang","doi":"10.1016/j.mcat.2025.115020","DOIUrl":"10.1016/j.mcat.2025.115020","url":null,"abstract":"<div><div>Pro-Xylane (boseine), a key cosmetic ingredient renowned for its anti-wrinkle effects and bioaffinity, has drawn considerable attention for its efficient biosynthesis. In this study, a NADP(H)-dependent carbonyl reductase from <em>Canariomyces notabilis</em> (<em>Cn</em>CR) was identified through <em>in silico</em> screening. Using alanine scanning and semi-saturation mutagenesis, the double mutant Y98K/N208Q was obtained, exhibiting a 15.8-fold increase in specific activity (60.11 U mg⁻¹) and an 11.5-fold improvement in catalytic efficiency (<em>k</em><sub>cat</sub>/<em>K</em><sub>m</sub> = 0.25 mM⁻¹ s⁻¹) compared to the wild-type enzyme. Mechanistic insights into the improved performance of Y98K/N208Q were revealed through molecular docking. In the enzyme-β-acetone xyloside complex, Y98K/N208Q showed enhanced hydrogen bonding and a refined active site, which improving substrate binding and anchoring. The shorter distance to NADPH and stronger interactions with the substrate boosted the mutant's catalytic efficiency compared to the wild-type. To enable efficient cofactor regeneration, glucose dehydrogenase from <em>Bacillus amyloliquefaciens</em> was integrated into the Y98K/N208Q-mediated Pro-Xylane biosynthetic pathway. Under optimized conditions (30 °C, pH 7.5, 40 g L⁻¹ cells, and a co-substrate-to-substrate ratio of 1.5 : 1), the coupled system produced Pro-Xylane at a titer of 160 g L⁻¹ within 10 h, achieving a conversion rate and diastereomeric excess (<em>S</em>-enantiomer) of ≥99 %. To our knowledge, this is the highest reported Pro-Xylane production to date. This study highlights the discovery and semi-rational engineering of a novel enzyme for efficient Pro-Xylane biosynthesis, offering a robust platform for industrial-scale production of this valuable compound.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115020"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686307","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

Green and efficient epoxide fixation and CO2 separation using halogen-decorated Zr-based UiO-67 MOFs

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-22 DOI: 10.1016/j.mcat.2025.115045

Majed S. AlFayi , Farag M.A. Altalbawy , Viralkumar Mandaliya , Suhas Ballal , Jameel M.A. Sulaiman , Deepak Bhanot , Girish Chandra Sharma , Subhash Chandra , Iskandar Shernazarov , Fadhel F. Sead

{"title":"Green and efficient epoxide fixation and CO2 separation using halogen-decorated Zr-based UiO-67 MOFs","authors":"Majed S. AlFayi , Farag M.A. Altalbawy , Viralkumar Mandaliya , Suhas Ballal , Jameel M.A. Sulaiman , Deepak Bhanot , Girish Chandra Sharma , Subhash Chandra , Iskandar Shernazarov , Fadhel F. Sead","doi":"10.1016/j.mcat.2025.115045","DOIUrl":"10.1016/j.mcat.2025.115045","url":null,"abstract":"<div><div>This study reports the synthesis and characterization of novel halogen-functionalized UiO-67 MOFs for CO₂ capture and conversion. Three mixed-linker Zr-UiO-67 MOFs, [Zr₆O₄(OH)₄(L₁L₂)₁₂], were synthesized, incorporating 2,2′-bipyridine-5,5′-dicarboxylic acid (L₁) and halogen-substituted 4,4′-biphenyl dicarboxylic acids (L₂) with chlorine (<strong>MOF-1</strong>), bromine (<strong>MOF-2</strong>), or iodine (<strong>MOF-3</strong>). Comprehensive characterization confirmed successful MOF synthesis and halogen incorporation. Gas adsorption studies showed selective CO₂ adsorption over N₂ and CH₄. Critically, these MOFs exhibited exceptional catalytic activity for solvent-free CO₂ conversion to cyclic carbonates at ambient temperature and pressure. The Lewis acidic Zr centers facilitated heterogeneous catalysis of CO₂ fixation with epoxides, yielding cyclic carbonates with TBAB as a cocatalyst. High conversion (91–99 %) of epichlorohydrin to 4-(chloromethyl)-1,3-dioxolan-2-one was achieved within 12 h at room temperature and 1 bar CO₂ pressure. A structure-activity relationship was established, revealing a direct correlation between halogen electronegativity and catalytic performance. CO₂ uptake and epoxide conversion rates increased across the halogen series from chlorine to iodine, attributed to the synergistic effect of the Lewis acidic Zr centers and the increasing polarizability of the halogen substituents. Moreover, the MOFs demonstrated robust recyclability, retaining substantial catalytic activity for at least five cycles. These findings underscore the potential of halogen-functionalized UiO-67 MOFs as promising candidates for sustainable CO₂ capture and utilization strategies.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115045"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686828","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

Engineering mandelate dehydrogenase for the efficient biosynthesis of salvianic acid A

IF 3.9 2区化学

Molecular Catalysis Pub Date : 2025-03-22 DOI: 10.1016/j.mcat.2025.115051

Kangping Huang , Wei Song , Wanqing Wei , Guipeng Hu , Xiaomin Li , Cong Gao , Jing Wu

{"title":"Engineering mandelate dehydrogenase for the efficient biosynthesis of salvianic acid A","authors":"Kangping Huang , Wei Song , Wanqing Wei , Guipeng Hu , Xiaomin Li , Cong Gao , Jing Wu","doi":"10.1016/j.mcat.2025.115051","DOIUrl":"10.1016/j.mcat.2025.115051","url":null,"abstract":"<div><div>Salvianic acid A (SAA), a bioactive compound from <em>Salvia miltiorrhiza</em>, has attracted significant attention for its therapeutic properties, including antitumor and antioxidant activities. However, its large-scale application is limited by the conventional production methods, which rely primarily on physical extraction and chemical synthesis. In this study, we constructed a de novo biosynthetic pathway for SAA by integrating two key modules: the HPPA hydroxylation module HpaBC (4-hydroxyphenylacetate 3-monooxygenase from <em>Escherichia coli</em>) and the DHPPA reductase module <em>Rg</em>MDH (D-mandelic acid dehydrogenase from <em>Rhodotorula graminis</em>) into a high-yield tyrosine-producing strain, <em>Tyr0</em>, generating the engineered strain Dps01. Metabolic analysis identified the low catalytic efficiency of <em>Rg</em>MDH as the critical bottleneck. To address this, structure-guided protein engineering of <em>Rg</em>MDH was performed. Molecular dynamics (MD) simulations revealed that the optimal mutant <em>Rg</em>MDH<sup>M4</sup> (T312A/F316S/T255I/A59H) exhibited a 10.3-fold increase in catalytic conformation occupancy compared to the wild-type (4.74% vs 0.46%), indicating enhanced substrate channel dynamics. This mutant exhibited a 295% increase in activity toward DHPPA, with enhanced substrate affinity and a 5.76-fold improvement in catalytic efficiency (<em>k<sub>cat</sub></em>/<em>K</em><sub>m</sub>). When integrated into strain Dps02, the engineered system achieved a maximum SAA production of 6.82 g/L within 34 hours, with a productivity of 0.21 g/L·h⁻¹ in a 5 L fed-batch fermentation. These results represent a significant advancement in the biosynthesis of SAA.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115051"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686811","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