Photocatalytic nitrogen fixation as a green, environmentally friendly, mild and low energy-consuming nitrogen fixation is considered as an ideal way to produce ammonia. Herein, inspired by nitrogen-fixing enzymes, the MOF materials Fe-sdc and Ti-sdc were synthesized by a simple solvothermal synthesis method using Fe and Ti as metal nodes and 4,4′-stilbenedicarboxylic acid (H2sdc) as a ligand. The ammonia production rates of Fe-sdc and Ti-sdc were 61.01 μmol g−1 h−1 and 46.84 μmol g−1 h−1. The 15N2 isotope experiments were utilized to determine the nitrogen source for ammonia synthesis during the nitrogen fixation process of Fe-sdc. Various characterization analyses were also utilized to analyze the reasons for the better nitrogen fixation performance of the two catalysts.
{"title":"Bio-inspired Fe/Ti-MOF photocatalysts for efficient nitrogen fixation under mild conditions","authors":"Can Sun , Runze Guo , Zhexiao Zhu , Shouxin Zhu , Jingyi Qu , Zijie Fang , Xiaolu Xu , Jiahui Lin , Yangben Chen , Shijie Zhang , Hui Zheng","doi":"10.1016/j.mcat.2025.115063","DOIUrl":"10.1016/j.mcat.2025.115063","url":null,"abstract":"<div><div>Photocatalytic nitrogen fixation as a green, environmentally friendly, mild and low energy-consuming nitrogen fixation is considered as an ideal way to produce ammonia. Herein, inspired by nitrogen-fixing enzymes, the MOF materials Fe-sdc and Ti-sdc were synthesized by a simple solvothermal synthesis method using Fe and Ti as metal nodes and 4,4′-stilbenedicarboxylic acid (H<sub>2</sub>sdc) as a ligand. The ammonia production rates of Fe-sdc and Ti-sdc were 61.01 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup> and 46.84 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup>. The <sup>15</sup>N<sub>2</sub> isotope experiments were utilized to determine the nitrogen source for ammonia synthesis during the nitrogen fixation process of Fe-sdc. Various characterization analyses were also utilized to analyze the reasons for the better nitrogen fixation performance of the two catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115063"},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746391","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}
Pub Date : 2025-04-01DOI: 10.1016/j.mcat.2025.115056
Li Xing , Yuhong Wang , Ke Lin , Wei Liu , Rui Cao , Lei Song
Electrocatalytic nitrate reduction reaction (NO3RR) offers a promising alternative to the Haber–Bosch process but requires efficient NH4+ electrocatalysts with enhanced performance and selectivity. Although copper-based catalysts have been extensively researched and employed in electrocatalytic NO3RR, the robust adsorption of intermediates and poor hydrolytic association activity of the catalysts result in reduced ammonia selectivity and interference of competing reactions. This study describes a nanoscale CuOx and CoOx coupling catalyst (CuOx/CoOx) with the most suitable ratio and tandem structure. Efficient and highly selective elimination of NO3− was accomplished through the tandem catalysis of two oxides. Efficient and notably selective elimination of NO3− was accomplished through the tandem catalysis of the two oxides. The CuOx/CoOx tandem catalyst achieved a NH4+ selectivity of 90.1 %, NH4+ Faraday efficiency of 95.3 % at a NO3− concentration of 400 mg/L with a cathodic potential of −0.58 V vs. RHE, and showed desirable stability, attributed to the twin lively website synergy and oxygen vacancy defects of the catalyst.
{"title":"CuOx/CoOx tandem catalyst for effectively reducing nitrate to ammonia","authors":"Li Xing , Yuhong Wang , Ke Lin , Wei Liu , Rui Cao , Lei Song","doi":"10.1016/j.mcat.2025.115056","DOIUrl":"10.1016/j.mcat.2025.115056","url":null,"abstract":"<div><div>Electrocatalytic nitrate reduction reaction (NO<sub>3</sub>RR) offers a promising alternative to the Haber–Bosch process but requires efficient NH<sub>4</sub><sup>+</sup> electrocatalysts with enhanced performance and selectivity. Although copper-based catalysts have been extensively researched and employed in electrocatalytic NO<sub>3</sub>RR, the robust adsorption of intermediates and poor hydrolytic association activity of the catalysts result in reduced ammonia selectivity and interference of competing reactions. This study describes a nanoscale CuOx and CoOx coupling catalyst (CuOx/CoOx) with the most suitable ratio and tandem structure. Efficient and highly selective elimination of NO<sub>3</sub><sup>−</sup> was accomplished through the tandem catalysis of two oxides. Efficient and notably selective elimination of NO<sub>3</sub><sup>−</sup> was accomplished through the tandem catalysis of the two oxides. The CuOx/CoOx tandem catalyst achieved a NH<sub>4</sub><sup>+</sup> selectivity of 90.1 %, NH<sub>4</sub><sup>+</sup> Faraday efficiency of 95.3 % at a NO<sub>3</sub><sup>−</sup> concentration of 400 mg/L with a cathodic potential of −0.58 V vs. RHE, and showed desirable stability, attributed to the twin lively website synergy and oxygen vacancy defects of the catalyst.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115056"},"PeriodicalIF":3.9,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746392","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}
Pub Date : 2025-03-31DOI: 10.1016/j.mcat.2025.115065
Faraz Ahmad , Yueli Wen , Muhammad Zeeshan , Bin Wang , Samia Kausar , El Gharrabi Mohamed , Wei Huang
Achieving an optimal acid-base synergy and uniform dispersion of active sites on catalyst surface is essential for high catalytic performance in the side chain alkylation of toluene with methanol (SATM). Herein, we report that ammonium (NH₃) treatment of Cu-modified NaX zeolite catalysts effectively modulates acid-base properties and enhances the dispersion of Cu active sites across the catalyst surface. A series of Cu-modified catalysts were prepared with and without NH₃ treatment and further modified with NaOH to evaluate their synergistic effects. Comprehensive characterization techniques, including Scanning Electron Microscopy (SEM), HAADF-STEM and EDS, Pyridine FTIR, Temperature-Programmed Desorption of NH₃ (TPD-NH₃), X-ray Photoelectron Spectroscopy (XPS O 1 s), and regression analysis, were used to correlate catalyst structure, and acid-base property and nature of acid sites with catalytic performance. Results reveal that NH₃ incorporation into the Cu-modified NaX framework significantly enhances catalytic efficiency by tuning acid-base properties and promoting a homogeneous distribution of Cu active sites. Notably, the 3Cu-4Na-N catalyst achieved a superior yield of ethylbenzene and styrene production, reaching 84.9 %, compared to 64.3 % for the 3Cu-4Na catalyst under identical conditions. Methanol conversion reached 97.7 %, with the catalyst demonstrating robust stability over 168 h of operation. Additionally, 3Cu-4Na-N catalyst exhibited the highest turnover frequency (TOF) reaching 27.3 h-1, confirming its superior intrinsic activity. This study highlights the critical role of NH₃ in advancing Cu-NaX catalysts for SATM and provides a promising strategy for optimizing catalytic performance through controlled acid-base interactions and active site dispersion.
{"title":"Effect of NH3-assisted Cu-modified NaX catalysts on acid-base property and their synergy in side chain alkylation of toluene with methanol","authors":"Faraz Ahmad , Yueli Wen , Muhammad Zeeshan , Bin Wang , Samia Kausar , El Gharrabi Mohamed , Wei Huang","doi":"10.1016/j.mcat.2025.115065","DOIUrl":"10.1016/j.mcat.2025.115065","url":null,"abstract":"<div><div>Achieving an optimal acid-base synergy and uniform dispersion of active sites on catalyst surface is essential for high catalytic performance in the side chain alkylation of toluene with methanol (SATM). Herein, we report that ammonium (NH₃) treatment of Cu-modified NaX zeolite catalysts effectively modulates acid-base properties and enhances the dispersion of Cu active sites across the catalyst surface. A series of Cu-modified catalysts were prepared with and without NH₃ treatment and further modified with NaOH to evaluate their synergistic effects. Comprehensive characterization techniques, including Scanning Electron Microscopy (SEM), HAADF-STEM and EDS, Pyridine FTIR, Temperature-Programmed Desorption of NH₃ (TPD-NH₃), X-ray Photoelectron Spectroscopy (XPS O <em>1</em> s), and regression analysis, were used to correlate catalyst structure, and acid-base property and nature of acid sites with catalytic performance. Results reveal that NH₃ incorporation into the Cu-modified NaX framework significantly enhances catalytic efficiency by tuning acid-base properties and promoting a homogeneous distribution of Cu active sites. Notably, the 3Cu-4Na-N catalyst achieved a superior yield of ethylbenzene and styrene production, reaching 84.9 %, compared to 64.3 % for the 3Cu-4Na catalyst under identical conditions. Methanol conversion reached 97.7 %, with the catalyst demonstrating robust stability over 168 h of operation. Additionally, 3Cu-4Na-N catalyst exhibited the highest turnover frequency (TOF) reaching 27.3 h<sup>-1</sup>, confirming its superior intrinsic activity. This study highlights the critical role of NH₃ in advancing Cu-NaX catalysts for SATM and provides a promising strategy for optimizing catalytic performance through controlled acid-base interactions and active site dispersion.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115065"},"PeriodicalIF":3.9,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746390","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}
Enhancing the catalytic performance of acetylene hydration catalysts remains a formidable challenge in current research. SiO2 was firstly employed as a support to synthesize Cu-based catalysts by dielectric barrier discharge plasma for the acetylene hydration reaction, achieving an impressive conversion of 95.9 % for acetylene and selectivity of 83.6 % for acetaldehyde within 8 h reaction time. The selectivity exhibits a relatively consistent stability within 30 h of reaction time. According to X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), plasma treatment promotes the interaction between the active component and the support, which can enhance the anti-reduction properties of active copper components. Transmission electron microscopy (TEM) and acetylene temperature-programmed desorption (C2H2-TPD) reveal that plasma treatment markedly improves the dispersion of Cu species and enhances the acetylene adsorption capacity, thereby leading to an improvement in catalytic performance.
{"title":"Effect of the dielectric barrier discharge plasma on Cu-based catalysts supported on SiO2 for acetylene hydration","authors":"Yi Cui, Xiejie Chen, Jiaxuan Gao, Shui Liu, Denghao Wang, Caixia Xu","doi":"10.1016/j.mcat.2025.115064","DOIUrl":"10.1016/j.mcat.2025.115064","url":null,"abstract":"<div><div>Enhancing the catalytic performance of acetylene hydration catalysts remains a formidable challenge in current research. SiO<sub>2</sub> was firstly employed as a support to synthesize Cu-based catalysts by dielectric barrier discharge plasma for the acetylene hydration reaction, achieving an impressive conversion of 95.9 % for acetylene and selectivity of 83.6 % for acetaldehyde within 8 h reaction time. The selectivity exhibits a relatively consistent stability within 30 h of reaction time. According to X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), plasma treatment promotes the interaction between the active component and the support, which can enhance the anti-reduction properties of active copper components. Transmission electron microscopy (TEM) and acetylene temperature-programmed desorption (C<sub>2</sub>H<sub>2</sub>-TPD) reveal that plasma treatment markedly improves the dispersion of Cu species and enhances the acetylene adsorption capacity, thereby leading to an improvement in catalytic performance.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115064"},"PeriodicalIF":3.9,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734977","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}
A pivotal aspect in advancing ZrZnOx catalysts for CO2 hydrogenation lies in the modulation of Zr-O-Zn active sites, with ZnO facets emerging as potential modulators of site activity. Whereas the beneficial influence of non-polar ZnO facets on ZrZnOx catalysts has been scarcely documented. Our investigation reveals that ZrZnOx catalysts exposed non-polar ZnO facets (ZrZnO-n) exhibit superior methanol selectivity (74 %) compared to those with randomly exposed ZnO facets (ZrZnO-r, 35 %). Characterization results demonstrate that it is ascribed to the formation of highly active Zr-O-Zn(2−δ)+ sites on ZrZnO-n, which facilitate H2 adsorption and dissociation. In situ spectroscopic studies and DFT calculations further substantiate this finding, demonstrating enhanced intermediates formation and more efficient hydrogenation processes. This research underscores the significance of ZnO facet engineering in the purposeful creation of efficient ZrZnOx catalysts for CO2 hydrogenation.
{"title":"Unlocking the positive effect of non-polar ZnO facets in ZrZnOx catalysts for CO2 hydrogenation","authors":"Xiaohong Guo, Liqiang Deng, Xiaoyue Wang, Yongjie Zhao, Zhifan Cao, Pengwei Li, Congming Li","doi":"10.1016/j.mcat.2025.115059","DOIUrl":"10.1016/j.mcat.2025.115059","url":null,"abstract":"<div><div>A pivotal aspect in advancing ZrZnO<sub>x</sub> catalysts for CO<sub>2</sub> hydrogenation lies in the modulation of Zr-O-Zn active sites, with ZnO facets emerging as potential modulators of site activity. Whereas the beneficial influence of non-polar ZnO facets on ZrZnO<sub>x</sub> catalysts has been scarcely documented. Our investigation reveals that ZrZnO<sub>x</sub> catalysts exposed non-polar ZnO facets (ZrZnO-n) exhibit superior methanol selectivity (74 %) compared to those with randomly exposed ZnO facets (ZrZnO-r, 35 %). Characterization results demonstrate that it is ascribed to the formation of highly active Zr-O-Zn<sup>(2−δ)+</sup> sites on ZrZnO-n, which facilitate H<sub>2</sub> adsorption and dissociation. In situ spectroscopic studies and DFT calculations further substantiate this finding, demonstrating enhanced intermediates formation and more efficient hydrogenation processes. This research underscores the significance of ZnO facet engineering in the purposeful creation of efficient ZrZnO<sub>x</sub> catalysts for CO<sub>2</sub> hydrogenation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115059"},"PeriodicalIF":3.9,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715533","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}
Pub Date : 2025-03-28DOI: 10.1016/j.mcat.2025.115078
Shujin Liu , Jingang Wang , Bo Yuan , Xin Meng , Ge Qu , Zhoutong Sun
With the rapid development of genomics and high-throughput sequencing technologies, massive amounts of genetic sequence data have become available. However, identifying functional sequences with desired properties from these datasets remains a significant challenge. In biocatalysis, discovering catalysts with suitable stereoselectivity is crucial for asymmetric synthesis. In this study, we developed a streamlined method for the rational design of (R)-ω-transaminases ((R)-ω-TA) sequences. A library of 1620 candidate (R)-ω-TA sequences was generated by in silico DNA shuffling and ancestral sequence reconstruction techniques. After four rounds of machine learning-guided functional prediction and virtually screening, 85 novel TAs were annotated, with a sequence identity varying from 27.1 % to 69.7 %. In the examination of the substrate spectrum, each of the 85 novel TAs was able to catalyze at least three substrates among the tested ketones. Eventually, preparative-scale synthesis of (R)-N-Boc-3-piperidine was performed on a gram-scale. The newly designed TA G6-L164V exhibited a conversion of 98.1 % with a specific activity of 3.9 U/mg, and an enantiomeric excess (ee) > 99 % after 7 h in a 10 mL system containing 50 mM substrate. Our study provides a promising framework for protein sequence design and expands the toolbox of (R)-ω-TA in the synthesis of chiral amines.
{"title":"Integration of Computational Tools for Rational Design of (R)-ω-Transaminases with Enhanced Asymmetric Catalysis","authors":"Shujin Liu , Jingang Wang , Bo Yuan , Xin Meng , Ge Qu , Zhoutong Sun","doi":"10.1016/j.mcat.2025.115078","DOIUrl":"10.1016/j.mcat.2025.115078","url":null,"abstract":"<div><div>With the rapid development of genomics and high-throughput sequencing technologies, massive amounts of genetic sequence data have become available. However, identifying functional sequences with desired properties from these datasets remains a significant challenge. In biocatalysis, discovering catalysts with suitable stereoselectivity is crucial for asymmetric synthesis. In this study, we developed a streamlined method for the rational design of (<em>R</em>)-ω-transaminases ((<em>R</em>)-ω-TA) sequences. A library of 1620 candidate (<em>R</em>)-ω-TA sequences was generated by <em>in silico</em> DNA shuffling and ancestral sequence reconstruction techniques. After four rounds of machine learning-guided functional prediction and virtually screening, 85 novel TAs were annotated, with a sequence identity varying from 27.1 % to 69.7 %. In the examination of the substrate spectrum, each of the 85 novel TAs was able to catalyze at least three substrates among the tested ketones. Eventually, preparative-scale synthesis of (<em>R</em>)-N-Boc-3-piperidine was performed on a gram-scale. The newly designed TA G6-L164V exhibited a conversion of 98.1 % with a specific activity of 3.9 U/mg, and an enantiomeric excess (<em>ee</em>) > 99 % after 7 h in a 10 mL system containing 50 mM substrate. Our study provides a promising framework for protein sequence design and expands the toolbox of (<em>R</em>)-ω-TA in the synthesis of chiral amines.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115078"},"PeriodicalIF":3.9,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715534","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}
Pub Date : 2025-03-27DOI: 10.1016/j.mcat.2025.115057
Andrew Nosakhare Amenaghawon , Ubani Oluwaseun Amune , Joshua Efosa Ayere , Ifechukwude Christopher Otuya , Stanley Aimhanesi Eshiemogie , Esther Imhande Ehiawaguan , Gabriel Diemesor , Emmanuel Christopher Abuga , Osamudiamhen Oiwoh , Olusola Tijani , Peter Kayode Oyefolu , Oseweuba Valentine Okoro , Amin Shavandi , Chinedu Lewis Anyalewechi , Ehiaghe Agbovhimen Elimian , Maxwell Ogaga Okedi , Ibhadebhunuele Gabriel Okoduwa , Steve Oshiokhai Eshiemogie , Osarieme Osazuwa , Handoko Darmokoesoemo , Heri Septya Kusuma
The over-reliance on fossil fuels has led to significant environmental and climatic challenges, emphasizing the urgent need for sustainable energy alternatives. Biodiesel, which is traditionally produced through the transesterification of vegetable oils and animal fats, provides a low-carbon alternative to fossil fuels. However, for catalytic systems, the efficiency of biodiesel synthesis is significantly dependent on the nature of the catalysts used. Conventional homogeneous catalysts, although effective, face challenges such as high energy consumption, soap formation, non-recoverability, and corrosion issues. In contrast, heterogeneous catalysts, especially those derived from biogenic waste, offer cost, reusability, and environmental impact advantages. This review provides a comprehensive examination of the synthesis methods and performance of heterogeneous catalysts derived from waste materials for biodiesel production, representing an elucidation of the role of synthesis methods on the properties of these catalysts. Understanding this relationship is important for optimizing biodiesel production efficiency as global efforts intensify to transition away from fossil fuels. This review analyzes the properties of these catalysts, such as surface area, pore structure, morphology, metal dispersion, chemical composition, and thermal stability, using fit-for-purpose characterization techniques. By focusing on the synthesis-property-performance nexus, this review highlights the importance of selecting and optimizing synthesis methods to achieve high-performance catalysts for efficient biodiesel production. The review also addresses challenges in heterogeneous catalyst synthesis, providing a balanced perspective on the current state of the art. Importantly, this work establishes a new framework for understanding and optimizing bio-derived catalyst synthesis, paving the way for more efficient and sustainable biodiesel production methods. This review contributes new knowledge to the field of renewable energy, aligning with global sustainability goals.
{"title":"A comprehensive insight into the role of synthesis methods on the properties and performance of bio-derived heterogeneous catalysts for biodiesel production","authors":"Andrew Nosakhare Amenaghawon , Ubani Oluwaseun Amune , Joshua Efosa Ayere , Ifechukwude Christopher Otuya , Stanley Aimhanesi Eshiemogie , Esther Imhande Ehiawaguan , Gabriel Diemesor , Emmanuel Christopher Abuga , Osamudiamhen Oiwoh , Olusola Tijani , Peter Kayode Oyefolu , Oseweuba Valentine Okoro , Amin Shavandi , Chinedu Lewis Anyalewechi , Ehiaghe Agbovhimen Elimian , Maxwell Ogaga Okedi , Ibhadebhunuele Gabriel Okoduwa , Steve Oshiokhai Eshiemogie , Osarieme Osazuwa , Handoko Darmokoesoemo , Heri Septya Kusuma","doi":"10.1016/j.mcat.2025.115057","DOIUrl":"10.1016/j.mcat.2025.115057","url":null,"abstract":"<div><div>The over-reliance on fossil fuels has led to significant environmental and climatic challenges, emphasizing the urgent need for sustainable energy alternatives. Biodiesel, which is traditionally produced through the transesterification of vegetable oils and animal fats, provides a low-carbon alternative to fossil fuels. However, for catalytic systems, the efficiency of biodiesel synthesis is significantly dependent on the nature of the catalysts used. Conventional homogeneous catalysts, although effective, face challenges such as high energy consumption, soap formation, non-recoverability, and corrosion issues. In contrast, heterogeneous catalysts, especially those derived from biogenic waste, offer cost, reusability, and environmental impact advantages. This review provides a comprehensive examination of the synthesis methods and performance of heterogeneous catalysts derived from waste materials for biodiesel production, representing an elucidation of the role of synthesis methods on the properties of these catalysts. Understanding this relationship is important for optimizing biodiesel production efficiency as global efforts intensify to transition away from fossil fuels. This review analyzes the properties of these catalysts, such as surface area, pore structure, morphology, metal dispersion, chemical composition, and thermal stability, using fit-for-purpose characterization techniques. By focusing on the synthesis-property-performance nexus, this review highlights the importance of selecting and optimizing synthesis methods to achieve high-performance catalysts for efficient biodiesel production. The review also addresses challenges in heterogeneous catalyst synthesis, providing a balanced perspective on the current state of the art. Importantly, this work establishes a new framework for understanding and optimizing bio-derived catalyst synthesis, paving the way for more efficient and sustainable biodiesel production methods. This review contributes new knowledge to the field of renewable energy, aligning with global sustainability goals.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115057"},"PeriodicalIF":3.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143715535","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}
Pub Date : 2025-03-27DOI: 10.1016/j.mcat.2025.115038
Xiao-Ting Zhao , Wen-Dian Li , Yao Yao , Ming-Liang Shi , Yun-Jie Wei , Ru-De Lin , Fei-Yan Tao , Na Wang
One-pot chemoenzymatic cascade process integrating the merits of biocatalysis and chemical catalysis has become a promising method for the efficient synthesis of complex chiral compounds. Herein, we designed a chemoenzymatic one-pot cascade system in water, involving UiO-67 catalyzed Michael addition and ketoreductases catalyzed CO asymmetric reduction with stereocomplementary selectivity. After studying experimental conditions systematically, a series of chiral indole derivatives with complementary (R)- or (S)-configurations were successfully synthesized with high yields (up to 92 %) and excellent stereoselectivity (up to 99 % ee). The strategy is environmentally friendly, mild and highly stereoselective, demonstrating the significant potential of one-pot chemoenzymatic cascade reaction in green synthetic chemistry and sustainable development.
{"title":"Efficient chemoenzymatic cascade reaction for one-pot enantioselective synthesis of chiral indole derivatives in water","authors":"Xiao-Ting Zhao , Wen-Dian Li , Yao Yao , Ming-Liang Shi , Yun-Jie Wei , Ru-De Lin , Fei-Yan Tao , Na Wang","doi":"10.1016/j.mcat.2025.115038","DOIUrl":"10.1016/j.mcat.2025.115038","url":null,"abstract":"<div><div>One-pot chemoenzymatic cascade process integrating the merits of biocatalysis and chemical catalysis has become a promising method for the efficient synthesis of complex chiral compounds. Herein, we designed a chemoenzymatic one-pot cascade system in water, involving UiO-67 catalyzed Michael addition and ketoreductases catalyzed <em>C<img>O</em> asymmetric reduction with stereocomplementary selectivity. After studying experimental conditions systematically, a series of chiral indole derivatives with complementary (<em>R</em>)- or (<em>S</em>)-configurations were successfully synthesized with high yields (up to 92 %) and excellent stereoselectivity (up to 99 % <em>ee</em>). The strategy is environmentally friendly, mild and highly stereoselective, demonstrating the significant potential of one-pot chemoenzymatic cascade reaction in green synthetic chemistry and sustainable development.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115038"},"PeriodicalIF":3.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143706144","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}
The detailed reaction mechanism of Rh-catalyzed [(3+2+2)] cycloisomerization reactions of dienophile-substituted alkylidenecyclopropanes to construct the bridged tricyclic products with DFT calculations has been investigated. The catalytic cycle primarily comprises four steps: oxidative addition, proximal alkene insertion, distal alkene insertion, and reductive elimination. The reactions initiate with Rh-mediated the cleavage of cyclopropane distal C−C bond to give the key η4-TMM Rh(III) intermediate, which undergoes the proximal alkene insertion step to dictate the stereochemical outcome. The subsequent competing the 1,2-insertion and 2,1-insertion of the distal alkene moiety has also been discussed for comparison. The calculations reproduce quite well diastereoselectivity observed experimentally, demonstrating that the cis coordination pathway has high diastereocontrol. For comparison, various C−C coupling reaction pathways and substrate scopes have been examined.
{"title":"Theoretical studies on the mechanism of Rh-catalyzed [(3+2+2)] cycloisomerization reactions of dienophile-substituted alkylidenecyclopropanes","authors":"Wanjun Zhao, Huimin Xu, Ying Ren, Tingting Zhang, Jianfeng Jia, Hai-Shun Wu","doi":"10.1016/j.mcat.2025.115055","DOIUrl":"10.1016/j.mcat.2025.115055","url":null,"abstract":"<div><div>The detailed reaction mechanism of Rh-catalyzed [(3+2+2)] cycloisomerization reactions of dienophile-substituted alkylidenecyclopropanes to construct the bridged tricyclic products with DFT calculations has been investigated. The catalytic cycle primarily comprises four steps: oxidative addition, proximal alkene insertion, distal alkene insertion, and reductive elimination. The reactions initiate with Rh-mediated the cleavage of cyclopropane distal C−C bond to give the key <em>η</em><sup>4</sup>-TMM Rh(III) intermediate, which undergoes the proximal alkene insertion step to dictate the stereochemical outcome. The subsequent competing the 1,2-insertion and 2,1-insertion of the distal alkene moiety has also been discussed for comparison. The calculations reproduce quite well diastereoselectivity observed experimentally, demonstrating that the <em>cis</em> coordination pathway has high diastereocontrol. For comparison, various C−C coupling reaction pathways and substrate scopes have been examined.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115055"},"PeriodicalIF":3.9,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143706243","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}
Pub Date : 2025-03-27DOI: 10.1016/j.mcat.2025.115062
Minghui Liu , Huanling Zhang , Shipeng Song , Rong Fan , Mengqi Wang , Zhengchao Wang , Hao Yan , Guowei Wang , Xiang Feng , Chunyi Li , Chaohe Yang , Xiaolin Zhu
The methylation of phenol with methanol is an environment-friendly and simple method for cresol production. In this work, the direct and selective production of p/m-cresol from phenol methylation was realized over the MCM-22 zeolite catalyst by sensitive regulation of the reaction temperature. On the one hand, the effect of zeolite acidity was investigated by varying SiO2/Al2O3 ratio, and the strong Bronsted acid sites were indicated to be crucial for phenol methylation reaction. The MCM-22 zeolite with strong acidity and moderate porosity exhibited outstanding and stable catalytic performance with high phenol conversion (∼40 %), excellent cresol selectivity (>95 %) and flexible product composition (p-cresol/cresols ∼40 % or m-cresol/cresols ∼50 %). On the other hand, the reaction network of phenol methylation was refined. It was demonstrated that, in addition to the direct production of cresols from C-alkylation of phenol, the cresols could also be produced by the transalkylation between phenol and anisole yield from phenol O-alkylation. This work not only develops a novel eco-friendly p/m-cresol production method, but also deepens people's knowledge of the reaction mechanism of phenol methylation.
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