Pub Date : 2024-12-01DOI: 10.1016/j.mcat.2024.114725
Jinglin Ma , Fengxi Li , Hanqing Xie , Chunyu Wang , Wenhan Shi , Lei Wang , Peng Chen , Zhi Wang
A lipase-catalyzed, mild and environmentally friendly synthesis of polyhydroxyalkyl pyrroles from various unprotected sugars, benzoylacetonitriles and NH4OAc/benzylamine in water was reported for the first time in this work. Moreover, the synthetic potentiality of this enzymatic method was demonstrated by easy isolation of the final products using filtration. This green synthesis and purification approach not only enriches the strategies for synthesis of polyhydroxyalkyl pyrroles, but also expands the application of lipase in organic synthesis.
{"title":"Enzymatic and convenient synthesis of polyhydroxyalkyl pyrroles from unprotected sugars, benzoylacetonitriles, and NH4OAc/Benzylamines in water","authors":"Jinglin Ma , Fengxi Li , Hanqing Xie , Chunyu Wang , Wenhan Shi , Lei Wang , Peng Chen , Zhi Wang","doi":"10.1016/j.mcat.2024.114725","DOIUrl":"10.1016/j.mcat.2024.114725","url":null,"abstract":"<div><div>A lipase-catalyzed, mild and environmentally friendly synthesis of polyhydroxyalkyl pyrroles from various unprotected sugars, benzoylacetonitriles and NH<sub>4</sub>OAc/benzylamine in water was reported for the first time in this work. Moreover, the synthetic potentiality of this enzymatic method was demonstrated by easy isolation of the final products using filtration. This green synthesis and purification approach not only enriches the strategies for synthesis of polyhydroxyalkyl pyrroles, but also expands the application of lipase in organic synthesis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114725"},"PeriodicalIF":3.9,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142757604","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}
10-Camphor sulfonic acid (10-CSA) has gained popularity as an organocatalyst due to its broad range of solubility and user-friendliness. Affordable multicomponent reactions (MCRs) for the preparation of benzoxanthenes (4a-4 h) (5a-5i) are presented in this work. Extensive investigations and records have been conducted on the diverse biological features exhibited by xanthenes and benzoxanthenones, such as their antiviral, antibacterial, and anti-inflammatory capabilities.Using β-naphthol, dimedone, and aldehydes, we demonstrate a cost-effective and environmentally friendly catalytic method. Under ideal circumstances, the 10-CSA catalyzes one-pot reaction, procuring impressive amounts of benzoanthenes (85–95 %). All the synthesized compounds were characterized by 1H NMR and 13C NMR. A wide variety of suitable chemicals, simple work-up procedures, and solvent-free synthesis outperforms numerous existing methods for procuring biologically relevant benzoxanthene derivatives are some of the interesting features of this organocatalyzed bronsted acid process. Therefore this synthesis is industrially inevitable. Furthermore, computational studies such as molecular docking and ADMET data analysis were performed on a number of the synthesized benzoxanthene molecules. This has led to the identification of the most potent synthetic against the SARS-CoV-2 spike protein. Additionally, to mimic how medicinal compounds interact to target proteins, computational docking and dynamics techniques were used. These studies showed that, in terms of binding affinity and other crucial traits, 4a, 4b, and 5a are potential possibilities. Overall, the current study should be of great help in the development of benzoxanthene analogs which can be potential drugs for treatment of COVID-19.
{"title":"10-camphor sulfonic acid: A simple and efficient organocatalyst to access anti-SARS-COV-2 Benzoxanthene derivatives","authors":"Jayalakshmi M , Jyothis Devasia , Sampath Chinnam , Aatika Nizam , Ganga Periyasamy , Pankaj Wadhwa , Suresh Babu Naidu Krishna","doi":"10.1016/j.mcat.2024.114691","DOIUrl":"10.1016/j.mcat.2024.114691","url":null,"abstract":"<div><div>10-Camphor sulfonic acid (10-CSA) has gained popularity as an organocatalyst due to its broad range of solubility and user-friendliness. Affordable multicomponent reactions (MCRs) for the preparation of benzoxanthenes (4a-4 h) (5a-5i) are presented in this work. Extensive investigations and records have been conducted on the diverse biological features exhibited by xanthenes and benzoxanthenones, such as their antiviral, antibacterial, and anti-inflammatory capabilities.Using β-naphthol, dimedone, and aldehydes, we demonstrate a cost-effective and environmentally friendly catalytic method. Under ideal circumstances, the 10-CSA catalyzes one-pot reaction, procuring impressive amounts of benzoanthenes (85–95 %). All the synthesized compounds were characterized by <sup>1</sup>H NMR and <sup>13</sup>C NMR. A wide variety of suitable chemicals, simple work-up procedures, and solvent-free synthesis outperforms numerous existing methods for procuring biologically relevant benzoxanthene derivatives are some of the interesting features of this organocatalyzed bronsted acid process. Therefore this synthesis is industrially inevitable. Furthermore, computational studies such as molecular docking and ADMET data analysis were performed on a number of the synthesized benzoxanthene molecules. This has led to the identification of the most potent synthetic against the SARS-CoV-2 spike protein. Additionally, to mimic how medicinal compounds interact to target proteins, computational docking and dynamics techniques were used. These studies showed that, in terms of binding affinity and other crucial traits, 4a, 4b, and 5a are potential possibilities. Overall, the current study should be of great help in the development of benzoxanthene analogs which can be potential drugs for treatment of COVID-19.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114691"},"PeriodicalIF":3.9,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748005","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 : 2024-11-30DOI: 10.1016/j.mcat.2024.114741
Xiaofeng Wei, Jiaxin Su, Yuyin Ji, Hongyang Huang, Dalin Li, Huihuang Fang, Chongqi Chen, Yu Luo, Lilong Jiang
Ammonia is a carbon-free hydrogen carrier, and development of non-noble metal catalyst to decompose ammonia into hydrogen is desirable for practical applications. However, the metal catalyst is challenged by the sintering of metal particles under high-temperature reaction conditions. In this study, a series of Li-, Al-, and Co-containing hydrotalcite-like compounds (HTlc) were synthesized by co-precipitation and used as precursors to prepare well-dispersed and thermally stable Co nanoparticle catalysts for ammonia decomposition. The obtained precursors and catalysts were characterized by means of X-ray powder diffraction (XRD), temperature-programmed reduction (H2-TPR), X-ray photoelectron spectroscopy (XPS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and so on. All of the precursors formed hydrotalcite-like phase, which consisted of Li–Al–(Co) HTlc and/or Co–Al HTlc dependent on the Co content. Upon calcination at 500 °C, HTlc decomposed into an Al-substituted Co3O4 spinel oxide, as confirmed by two distinctly separated reduction steps in H2-TPR. Following reduction at 700 °C, well-dispersed Co metal nanoparticles with an average particle size of ∼9.2–12.4 nm were obtained. It was suggested that the incorporation of Al3+ into Co3O4 led to a strong interaction between cobalt and aluminum, which suppressed the crystal growth of Co3O4 and the sintering of Co metal during the thermal treatments, resulting in good Co dispersion. The optimal LiAlCo(1.5) catalyst showed superior activity than that prepared by impregnation method, giving almost complete conversion of ammonia at 575 °C under a space velocity of 5,000 mL gcat–1 h–1. More importantly, this catalyst maintained stable activity at 625 °C for 100 h, exhibiting high stability and sintering resistance. The good catalytic performance was attributed to the high Co metal dispersion and strong metal–support interaction benefiting from the uniform distribution of cobalt in the HTlc precursor. These results demonstrate the applicability of HTlc to the preparation of metal catalysts with improved dispersion and thermal stability.
氨是一种无碳氢载体，因此开发非贵金属催化剂将氨分解成氢气是实际应用的理想选择。然而，金属催化剂在高温反应条件下面临金属颗粒烧结的挑战。本研究采用共沉淀法合成了一系列含锂、铝和钴的类水滑石化合物 (HTlc)，并以此为前驱体制备了分散良好、热稳定的 Co 纳米粒子催化剂，用于氨分解。通过 X 射线粉末衍射 (XRD)、温度编程还原 (H2-TPR)、X 射线光电子能谱 (XPS)、高角度环形暗场扫描透射电子显微镜 (HAADF-STEM) 等方法对得到的前驱体和催化剂进行了表征。所有前驱体都形成了类似水滑石的相，根据 Co 含量的不同，由 Li-Al-(Co) HTlc 和/或 Co-Al HTlc 组成。在 500 °C 煅烧时，HTlc 分解成 Al 取代的 Co3O4 尖晶石氧化物，这一点在 H2-TPR 中两个明显分开的还原步骤中得到了证实。在 700 °C 下还原后，得到了分散良好的 Co 金属纳米颗粒，平均粒径为 9.2-12.4 nm。研究表明，在 Co3O4 中加入 Al3+ 会导致钴和铝之间产生强烈的相互作用，从而在热处理过程中抑制了 Co3O4 的晶体生长和 Co 金属的烧结，使 Co 得到良好的分散。最佳的 LiAlCo(1.5) 催化剂比浸渍法制备的催化剂具有更高的活性，在 575 °C 下，空间速度为 5,000 mL gcat-1 h-1 时，氨几乎完全转化。更重要的是，这种催化剂能在 625 °C 下保持 100 小时的稳定活性，表现出很高的稳定性和抗烧结性。良好的催化性能归功于 HTlc 前驱体中钴的均匀分布所带来的高钴金属分散性和强金属-支撑相互作用。这些结果表明 HTlc 适用于制备具有更好分散性和热稳定性的金属催化剂。
{"title":"Hydrotalcite-derived well-dispersed and thermally stable cobalt nanoparticle catalyst for ammonia decomposition","authors":"Xiaofeng Wei, Jiaxin Su, Yuyin Ji, Hongyang Huang, Dalin Li, Huihuang Fang, Chongqi Chen, Yu Luo, Lilong Jiang","doi":"10.1016/j.mcat.2024.114741","DOIUrl":"10.1016/j.mcat.2024.114741","url":null,"abstract":"<div><div>Ammonia is a carbon-free hydrogen carrier, and development of non-noble metal catalyst to decompose ammonia into hydrogen is desirable for practical applications. However, the metal catalyst is challenged by the sintering of metal particles under high-temperature reaction conditions. In this study, a series of Li-, Al-, and Co-containing hydrotalcite-like compounds (HTlc) were synthesized by co-precipitation and used as precursors to prepare well-dispersed and thermally stable Co nanoparticle catalysts for ammonia decomposition. The obtained precursors and catalysts were characterized by means of X-ray powder diffraction (XRD), temperature-programmed reduction (H<sub>2</sub>-TPR), X-ray photoelectron spectroscopy (XPS), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and so on. All of the precursors formed hydrotalcite-like phase, which consisted of Li–Al–(Co) HTlc and/or Co–Al HTlc dependent on the Co content. Upon calcination at 500 °C, HTlc decomposed into an Al-substituted Co<sub>3</sub>O<sub>4</sub> spinel oxide, as confirmed by two distinctly separated reduction steps in H<sub>2</sub>-TPR. Following reduction at 700 °C, well-dispersed Co metal nanoparticles with an average particle size of ∼9.2–12.4 nm were obtained. It was suggested that the incorporation of Al<sup>3+</sup> into Co<sub>3</sub>O<sub>4</sub> led to a strong interaction between cobalt and aluminum, which suppressed the crystal growth of Co<sub>3</sub>O<sub>4</sub> and the sintering of Co metal during the thermal treatments, resulting in good Co dispersion. The optimal LiAlCo(1.5) catalyst showed superior activity than that prepared by impregnation method, giving almost complete conversion of ammonia at 575 °C under a space velocity of 5,000 mL g<sub>cat</sub><sup>–1</sup> h<sup>–1</sup>. More importantly, this catalyst maintained stable activity at 625 °C for 100 h, exhibiting high stability and sintering resistance. The good catalytic performance was attributed to the high Co metal dispersion and strong metal–support interaction benefiting from the uniform distribution of cobalt in the HTlc precursor. These results demonstrate the applicability of HTlc to the preparation of metal catalysts with improved dispersion and thermal stability.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114741"},"PeriodicalIF":3.9,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747912","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 : 2024-11-30DOI: 10.1016/j.mcat.2024.114723
Satoshi Ishikawa , Hirokazu Nito , Wataru Ueda
ε-Keggin polyoxometalate based complex metal oxides are composed of the structural arrangement of ε-Keggin [Mo12O40], which connects with octahedral linker, {MO6}, to form a microporous structure that localizes counter cations X similar to FAU-type zeolites. In the present study, O2 adsorption properties of these materials (ε-[X]MoMO) are investigated. ε-[X]MoCoO with X = Fe and Cu showed significant O2 adsorption in an irreversible manner and the adsorption amount was saturated when 1.0 of O2 was adsorbed in the unit cell. The ε-Keggin unit of these materials were oxidized after the O2 adsorption at room temperature, resulting in the shrinkage of their lattice. Based on the characterization results and adsorption behavior, we suggest the O2 adsorption behavior as follows; O2 can freely access the whole ε-Keggin unit in ε-[Fe or Cu]MoCoO through the micropores involving redox between O2 and the ε-Keggin unit. The oxidation of this unit reduces the lattice size, which slows down the migration of O2 and results in the quasi-equilibrium adsorption near the surface. The selection of M element in ε-[Fe]MoMO was also crucial for the O2 adsorption.
{"title":"Molecular oxygen uptake behavior of crystalline porous complex metal oxide based on ε-Keggin polyoxometalate unit framework","authors":"Satoshi Ishikawa , Hirokazu Nito , Wataru Ueda","doi":"10.1016/j.mcat.2024.114723","DOIUrl":"10.1016/j.mcat.2024.114723","url":null,"abstract":"<div><div>ε-Keggin polyoxometalate based complex metal oxides are composed of the structural arrangement of ε-Keggin [Mo<sub>12</sub>O<sub>40</sub>], which connects with octahedral linker, {MO<sub>6</sub>}, to form a microporous structure that localizes counter cations X similar to FAU-type zeolites. In the present study, O<sub>2</sub> adsorption properties of these materials (ε-[X]MoMO) are investigated. ε-[X]MoCoO with X = Fe and Cu showed significant O<sub>2</sub> adsorption in an irreversible manner and the adsorption amount was saturated when 1.0 of O<sub>2</sub> was adsorbed in the unit cell. The ε-Keggin unit of these materials were oxidized after the O<sub>2</sub> adsorption at room temperature, resulting in the shrinkage of their lattice. Based on the characterization results and adsorption behavior, we suggest the O<sub>2</sub> adsorption behavior as follows; O<sub>2</sub> can freely access the whole ε-Keggin unit in ε-[Fe or Cu]MoCoO through the micropores involving redox between O<sub>2</sub> and the ε-Keggin unit. The oxidation of this unit reduces the lattice size, which slows down the migration of O<sub>2</sub> and results in the quasi-equilibrium adsorption near the surface. The selection of M element in ε-[Fe]MoMO was also crucial for the O<sub>2</sub> adsorption.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114723"},"PeriodicalIF":3.9,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747911","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 : 2024-11-30DOI: 10.1016/j.mcat.2024.114711
Nicholas L. Gadinas, Emily A. Anderson, Konstantinos A. Goulas
The coupling of furfural with aliphatic alcohols can yield precursor molecules for the production of high-performance detergents. In the present work, we use Ni-based homogeneous catalysts for this transformation and specifically examine ligand, solvent and base effects. We show that chloride and phosphine-ligated Ni catalysts exhibit long induction periods, while Ni catalysts with O ligands do not. We use operando X-ray absorption spectroscopy to attribute this induction to the requirement for the P and Cl ligand substitution during reaction. Solvent effect experiments demonstrate that hydrocarbon solvents, such as toluene and cyclohexane show the highest performance, while tert‑butanol is least optimal. Potassium carbonate as a base shows highest rates, while amine bases require higher temperatures and excess furfural to achieve equivalent product yields.
{"title":"When less is more: Ligand and solvent effects in Ni2+ Lewis acid transfer hydrogenation coupled with aldol condensation","authors":"Nicholas L. Gadinas, Emily A. Anderson, Konstantinos A. Goulas","doi":"10.1016/j.mcat.2024.114711","DOIUrl":"10.1016/j.mcat.2024.114711","url":null,"abstract":"<div><div>The coupling of furfural with aliphatic alcohols can yield precursor molecules for the production of high-performance detergents. In the present work, we use Ni-based homogeneous catalysts for this transformation and specifically examine ligand, solvent and base effects. We show that chloride and phosphine-ligated Ni catalysts exhibit long induction periods, while Ni catalysts with O ligands do not. We use operando X-ray absorption spectroscopy to attribute this induction to the requirement for the P and Cl ligand substitution during reaction. Solvent effect experiments demonstrate that hydrocarbon solvents, such as toluene and cyclohexane show the highest performance, while tert‑butanol is least optimal. Potassium carbonate as a base shows highest rates, while amine bases require higher temperatures and excess furfural to achieve equivalent product yields.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114711"},"PeriodicalIF":3.9,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142757407","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 : 2024-11-30DOI: 10.1016/j.mcat.2024.114740
Meng Xu , Xiaoling Liu , Zhuo Xiong , Yue Wu , Zhen Meng , Yu Zhou , Jun Wang
Furfural is an abundant biomass-derived building block that can be converted into furan-based N-containing compounds through direct reductive amination by using dihydrogen (H2). Nonetheless, the synthesis of furan-based tertiary amines is highly limited via this route. Herein, we reported the straightforward synthesis of MFI zeolite encapsulated Pt nanoparticles and finely modulated the surface electronic state by facilely controlling the reduction process. The constructed catalyst Pt@Z5 effectively catalyzed the amination of furfural with diethylamine for the synthesis of N-ethyl-N-(furan-2-ylmethyl)ethanamine, affording the high yield (>95 %), large turnover number (TON) of 2058, turnover frequency (TOF) of 1029 h−1, and stable recyclability. Systematic investigations comprising in-situ Fourier transform infrared spectroscopy (FTIR) spectra and kinetic isotope effect (KIE) unraveled that the mild reduction condition allowed the catalyst with a superior affinity towards H atom and beneficial furfural adsorption behavior, accelerating the H2 activation in the rate-determining step for the conversion of furfural into furan-based amine.
{"title":"Regulating the electronic state of MFI zeolite encapsulated Pt nanoparticles to boost the atom efficiency in reductive amination of biomass-derived furfural","authors":"Meng Xu , Xiaoling Liu , Zhuo Xiong , Yue Wu , Zhen Meng , Yu Zhou , Jun Wang","doi":"10.1016/j.mcat.2024.114740","DOIUrl":"10.1016/j.mcat.2024.114740","url":null,"abstract":"<div><div>Furfural is an abundant biomass-derived building block that can be converted into furan-based N-containing compounds through direct reductive amination by using dihydrogen (H<sub>2</sub>). Nonetheless, the synthesis of furan-based tertiary amines is highly limited <em>via</em> this route. Herein, we reported the straightforward synthesis of MFI zeolite encapsulated Pt nanoparticles and finely modulated the surface electronic state by facilely controlling the reduction process. The constructed catalyst Pt@Z5 effectively catalyzed the amination of furfural with diethylamine for the synthesis of N-ethyl-N-(furan-2-ylmethyl)ethanamine, affording the high yield (>95 %), large turnover number (TON) of 2058, turnover frequency (TOF) of 1029 <em>h</em><sup>−1</sup>, and stable recyclability. Systematic investigations comprising <em>in-situ</em> Fourier transform infrared spectroscopy (FTIR) spectra and kinetic isotope effect (KIE) unraveled that the mild reduction condition allowed the catalyst with a superior affinity towards H atom and beneficial furfural adsorption behavior, accelerating the H<sub>2</sub> activation in the rate-determining step for the conversion of furfural into furan-based amine.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114740"},"PeriodicalIF":3.9,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747910","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 : 2024-11-30DOI: 10.1016/j.mcat.2024.114737
Shide Wu , Yapeng Li , Dan Ping , Weitao Liu , Yichen Feng , Qingshuo Zhang , Mengjin Gao , Shuqing Liu , Di Wu , Shiwen Wang , Jianqiang Zhang , Shaoming Fang
Developing low-cost and efficient catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) still remains a challenge in water electrolysis. Herein, FeNi alloy encapsulated within boron and nitrogen co-doped carbon (FeNi@BNC) nanotubes are synthesized through a simple one-step pyrolysis method using FeCl3·6H2O, NiCl2·6H2O, H3BO3, urea and PEG-2000 as precursors. The BNC nanotubes are quite requisite for dispersing and stabilizing FeNi alloy nanoparticles (NPs) during pyrolysis. Benefiting from the synergistic catalytic effect of Fe and Ni, as well as the confinement effect of BNC nanotubes, such FeNi@BNC catalyst demonstrates impressive activities for both HER and OER, much superior to pristine Fe@BNC and Ni@BNC. Notably, the overpotentials needed to achieve a current density of 10 mA·cm−2 are just 230 mV for HER and 280 mV for OER. Moreover, the FeNi@BNC catalyst demonstrates significant stability, showing no noticeable degradation during potentiostatic electrolysis or repeated CV tests. Furthermore, FeNi@BNC exhibits remarkable activity for overall water splitting, requiring cell voltages of just 1.24 V and 1.60 V vs. RHE to achieve current densities of 10 mA·cm−2 and 20 mA·cm−2, respectively. This study introduces a novel strategy for developing bifunctional electrocatalysts with high-efficiency water splitting performance.
{"title":"In-situ confinement growth of FeNi alloy within B/N co-doped carbon nanotubes as efficient electrocatalyst for water splitting","authors":"Shide Wu , Yapeng Li , Dan Ping , Weitao Liu , Yichen Feng , Qingshuo Zhang , Mengjin Gao , Shuqing Liu , Di Wu , Shiwen Wang , Jianqiang Zhang , Shaoming Fang","doi":"10.1016/j.mcat.2024.114737","DOIUrl":"10.1016/j.mcat.2024.114737","url":null,"abstract":"<div><div>Developing low-cost and efficient catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) still remains a challenge in water electrolysis. Herein, FeNi alloy encapsulated within boron and nitrogen co-doped carbon (FeNi@BNC) nanotubes are synthesized through a simple one-step pyrolysis method using FeCl<sub>3</sub>·6H<sub>2</sub>O, NiCl<sub>2</sub>·6H<sub>2</sub>O, H<sub>3</sub>BO<sub>3</sub>, urea and PEG-2000 as precursors. The BNC nanotubes are quite requisite for dispersing and stabilizing FeNi alloy nanoparticles (NPs) during pyrolysis. Benefiting from the synergistic catalytic effect of Fe and Ni, as well as the confinement effect of BNC nanotubes, such FeNi@BNC catalyst demonstrates impressive activities for both HER and OER, much superior to pristine Fe@BNC and Ni@BNC. Notably, the overpotentials needed to achieve a current density of 10 mA·cm<sup>−2</sup> are just 230 mV for HER and 280 mV for OER. Moreover, the FeNi@BNC catalyst demonstrates significant stability, showing no noticeable degradation during potentiostatic electrolysis or repeated CV tests. Furthermore, FeNi@BNC exhibits remarkable activity for overall water splitting, requiring cell voltages of just 1.24 V and 1.60 V vs. RHE to achieve current densities of 10 mA·cm<sup>−2</sup> and 20 mA·cm<sup>−2</sup>, respectively. This study introduces a novel strategy for developing bifunctional electrocatalysts with high-efficiency water splitting performance.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114737"},"PeriodicalIF":3.9,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748004","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 : 2024-11-29DOI: 10.1016/j.mcat.2024.114706
Yaqian Li, Xiuhui Zheng, Jie Li, Jiarong Lu, Rong Fan, Mengnan Ma, Yibin Liu, Hao Yan, Xiang Feng, Chaohe Yang
Catalytic oxidation of low-carbon polyols to primary carboxylic acids is regarded as an important technology for sustainable traditional oxidation processes in industry. Despite decades of research and several breakthroughs in catalyst design, the precise reaction mechanism underlying the formation of specific carboxylic acids remains elusive. In this review, the oxidation of low-carbon polyols to primary carboxylic acids over metallic catalysts is systematically summarized with a focus on surface reaction mechanisms and catalyst design strategies. Essentially, the activation of C-H bond and the competitive adsorption/desorption of oxygen-containing intermediates serve as critical issues in determining the reaction mechanism. Insights into the reaction mechanism, the structure-performance relationships of oxophilic metal-based catalysts in various low-carbon polyol oxidation reactions lay the groundwork for rational catalyst design and manufacturing: (I) well-dispersed acidic sites can enhance the electronic density of oxophilic metals, thereby improving the H abstraction efficiency, while an adequate number of weak basic sites on the surface is beneficial for the adsorption of oxygen-containing intermediates; (II) the downshifted d-band center of oxophilic metal sites results in greater catalytic efficiency for C-H bond activation. This review aims to provide a comprehensive understanding of oxidation mechanisms and guide the rational design of efficient catalysts.
{"title":"Catalytic oxidation of low-carbon polyols to primary carboxylic acids: Advances on catalyst design and mechanistic studies","authors":"Yaqian Li, Xiuhui Zheng, Jie Li, Jiarong Lu, Rong Fan, Mengnan Ma, Yibin Liu, Hao Yan, Xiang Feng, Chaohe Yang","doi":"10.1016/j.mcat.2024.114706","DOIUrl":"10.1016/j.mcat.2024.114706","url":null,"abstract":"<div><div>Catalytic oxidation of low-carbon polyols to primary carboxylic acids is regarded as an important technology for sustainable traditional oxidation processes in industry. Despite decades of research and several breakthroughs in catalyst design, the precise reaction mechanism underlying the formation of specific carboxylic acids remains elusive. In this review, the oxidation of low-carbon polyols to primary carboxylic acids over metallic catalysts is systematically summarized with a focus on surface reaction mechanisms and catalyst design strategies. Essentially, the activation of C-H bond and the competitive adsorption/desorption of oxygen-containing intermediates serve as critical issues in determining the reaction mechanism. Insights into the reaction mechanism, the structure-performance relationships of oxophilic metal-based catalysts in various low-carbon polyol oxidation reactions lay the groundwork for rational catalyst design and manufacturing: (I) well-dispersed acidic sites can enhance the electronic density of oxophilic metals, thereby improving the H abstraction efficiency, while an adequate number of weak basic sites on the surface is beneficial for the adsorption of oxygen-containing intermediates; (II) the downshifted d-band center of oxophilic metal sites results in greater catalytic efficiency for C-H bond activation. This review aims to provide a comprehensive understanding of oxidation mechanisms and guide the rational design of efficient catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114706"},"PeriodicalIF":3.9,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747913","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 supported Pt/CeO2 catalysts are widely used for the catalytic oxidation of CO at ambient conditions. Herein, we reported a new strategy for modifying the interaction between Pt and CeO2 support via pulsed steam treatment, which significantly optimized the catalytic performance of Pt/CeO2 for CO oxidation. Specifically, the hollow CeO2 nanospheres were prepared by using carbon spheres as sacrificial templates and then subjected to pulsed steam treatment at 150 °C for different times to obtain the CeO2-xH support (x means the time of pulsed steam treatment, min). It was found that the complete oxidation of CO can be achieved at 90 °C over the Pt/CeO2–50H sample, which was much lower than that (130 °C) on Pt/CeO2 without pulsed steam treatment. The XPS and in-situ DRIFTS characterizations were conducted to reveal the high performance of the Pt/CeO2–50H catalyst for CO oxidation. It was found that the valence state of Pt significantly controlled by pulsed steam treatment was critical to the catalytic activity, whereby the presence of two types of active sites (Pt0-CO and Ptδ+-CO) over Pt/CeO2–50H greatly promoted the combination of adsorbed CO and O2 to generate CO2. Accordingly, this study provides a facile method to regulate the Pt valence state by pulsed steam treatment for CeO2 support, which is critical to the CO oxidation activity.
{"title":"Hollow Pt/CeO2 nanocatalysts pretreated with pulsed steam for enhanced CO oxidation performance","authors":"Mingzhen Huang, Jinxin He, Kaiji Xu, Dongren Cai, Guowu Zhan","doi":"10.1016/j.mcat.2024.114720","DOIUrl":"10.1016/j.mcat.2024.114720","url":null,"abstract":"<div><div>The supported Pt/CeO<sub>2</sub> catalysts are widely used for the catalytic oxidation of CO at ambient conditions. Herein, we reported a new strategy for modifying the interaction between Pt and CeO<sub>2</sub> support via pulsed steam treatment, which significantly optimized the catalytic performance of Pt/CeO<sub>2</sub> for CO oxidation. Specifically, the hollow CeO<sub>2</sub> nanospheres were prepared by using carbon spheres as sacrificial templates and then subjected to pulsed steam treatment at 150 °C for different times to obtain the CeO<sub>2</sub>-xH support (x means the time of pulsed steam treatment, min). It was found that the complete oxidation of CO can be achieved at 90 °C over the Pt/CeO<sub>2</sub>–50H sample, which was much lower than that (130 °C) on Pt/CeO<sub>2</sub> without pulsed steam treatment. The XPS and <em>in-situ</em> DRIFTS characterizations were conducted to reveal the high performance of the Pt/CeO<sub>2</sub>–50H catalyst for CO oxidation. It was found that the valence state of Pt significantly controlled by pulsed steam treatment was critical to the catalytic activity, whereby the presence of two types of active sites (Pt<sup>0</sup>-CO and Pt<sup>δ+</sup>-CO) over Pt/CeO<sub>2</sub>–50H greatly promoted the combination of adsorbed CO and O<sub>2</sub> to generate CO<sub>2</sub>. Accordingly, this study provides a facile method to regulate the Pt valence state by pulsed steam treatment for CeO<sub>2</sub> support, which is critical to the CO oxidation activity.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114720"},"PeriodicalIF":3.9,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748007","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 : 2024-11-29DOI: 10.1016/j.mcat.2024.114724
Chaokun Yang , Xin Wang , Xin Zhao
Designing efficient catalysts for CO2 cycloaddition to reduce CO2 emission is one of crucial for environmental issues technology. Herein, the multiple-amino functionalized triazine-based polymer (MAFTP) was prepared through the nucleophilic reaction of cyanuric chloride with melamine and ethylenediamine by a conventional heating method, which are favorable for CO2 adsorption due to their nitrogen-rich structure. MAFTP was characterized entirely, the CO2 adsorption capacity of MAFTP showed the CO2 uptake performance with the values of 5.73 cm3g−1 at 273 K and 1 bar. MAFTP/KI catalyst exhibited efficient catalytic activity for CO2 fixation to epoxides. 99 % propylene carbonate yield and 99 % selectivity were obtained under 120 °C, 2.0 MPa for 2.0 h without organic solvent. Additionally, the catalysts could be recycled easily from the products after reaction by centrifugation and then reused 5 times efficiently. Meanwhile, the catalytic activity of MAFTP/KI to other substituted epoxides was discussed. Moreover, DFT calculation was adopted to analyze the possible cycloaddition reaction mechanism. The MAFTP/KI system is a promising candidate for CO2 chemical fixation attributing to the low cost, abundant availability, easy separation and high catalytic activity for CO2 chemical fixation.
{"title":"Multi-amino functionalized triazine-based polymers as the catalyst for cycloaddition of CO2 to epoxides","authors":"Chaokun Yang , Xin Wang , Xin Zhao","doi":"10.1016/j.mcat.2024.114724","DOIUrl":"10.1016/j.mcat.2024.114724","url":null,"abstract":"<div><div>Designing efficient catalysts for CO<sub>2</sub> cycloaddition to reduce CO<sub>2</sub> emission is one of crucial for environmental issues technology. Herein, the multiple-amino functionalized triazine-based polymer (MAFTP) was prepared through the nucleophilic reaction of cyanuric chloride with melamine and ethylenediamine by a conventional heating method, which are favorable for CO<sub>2</sub> adsorption due to their nitrogen-rich structure. MAFTP was characterized entirely, the CO<sub>2</sub> adsorption capacity of MAFTP showed the CO<sub>2</sub> uptake performance with the values of 5.73 cm<sup>3</sup> <em>g</em><sup>−1</sup> at 273 K and 1 bar. MAFTP/KI catalyst exhibited efficient catalytic activity for CO<sub>2</sub> fixation to epoxides. 99 % propylene carbonate yield and 99 % selectivity were obtained under 120 °C, 2.0 MPa for 2.0 h without organic solvent. Additionally, the catalysts could be recycled easily from the products after reaction by centrifugation and then reused 5 times efficiently. Meanwhile, the catalytic activity of MAFTP/KI to other substituted epoxides was discussed. Moreover, DFT calculation was adopted to analyze the possible cycloaddition reaction mechanism. The MAFTP/KI system is a promising candidate for CO2 chemical fixation attributing to the low cost, abundant availability, easy separation and high catalytic activity for CO<sub>2</sub> chemical fixation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"572 ","pages":"Article 114724"},"PeriodicalIF":3.9,"publicationDate":"2024-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142747906","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}
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