Pub Date : 2026-02-02DOI: 10.1016/j.jcat.2026.116729
Yongkun Zheng, Nacho Solá-Ferrer, Lluís Martínez-Belenguer, Belén Lerma-Berlanga, Antonio Leyva-Pérez
Ethyl methyl carbonate (EMC), as the simplest asymmetric carbonate, is considered a unique green liquid organic compound for lithium batteries (electrolyte) and gasoline blending (octane enhancer additive), with properties between dimethyl and diethyl carbonate. In accordance, its chemical production is expected to boost during the coming years, despite green chemical syntheses for EMC are still to be developed. Here we show the selective synthesis of EMC from DMC and ethanol with one of the cheapest commercially available solids, i.e. zeolites, as a heterogeneous catalyst for the reaction, surpassing most of the current soluble catalysts employed for this reaction. While a pristine commercial zeolite such as NaX already shows a significant catalytic activity (65% conversion, 91% selectivity to EMC) without any pre-activation treatment, is recoverable and reusable, and can be implemented in batch and in flow, the incorporation of alkaline oxide clusters inside the zeolitic framework, i.e. K2O, boosts the catalytic activity not only for the NaX zeolite but also for the parent H-USY and NaY zeolites, otherwise barely catalytically active for the reaction, to give yields up to >99% and ≈80% selectivity to EMC. These results bring a sustainable and cheap catalytic system for the production of EMC.
{"title":"Alkaline oxide clusters inside zeolites catalyze the selective synthesis of ethyl methyl carbonate","authors":"Yongkun Zheng, Nacho Solá-Ferrer, Lluís Martínez-Belenguer, Belén Lerma-Berlanga, Antonio Leyva-Pérez","doi":"10.1016/j.jcat.2026.116729","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116729","url":null,"abstract":"Ethyl methyl carbonate (EMC), as the simplest asymmetric carbonate, is considered a unique green liquid organic compound for lithium batteries (electrolyte) and gasoline blending (octane enhancer additive), with properties between dimethyl and diethyl carbonate. In accordance, its chemical production is expected to boost during the coming years, despite green chemical syntheses for EMC are still to be developed. Here we show the selective synthesis of EMC from DMC and ethanol with one of the cheapest commercially available solids, i.e. zeolites, as a heterogeneous catalyst for the reaction, surpassing most of the current soluble catalysts employed for this reaction. While a pristine commercial zeolite such as NaX already shows a significant catalytic activity (65% conversion, 91% selectivity to EMC) without any pre-activation treatment, is recoverable and reusable, and can be implemented in batch and in flow, the incorporation of alkaline oxide clusters inside the zeolitic framework, i.e. K<sub>2</sub>O, boosts the catalytic activity not only for the NaX zeolite but also for the parent H-USY and NaY zeolites, otherwise barely catalytically active for the reaction, to give yields up to >99% and ≈80% selectivity to EMC. These results bring a sustainable and cheap catalytic system for the production of EMC.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"58 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098234","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.jcat.2026.116720
Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He
Piperidine derivatives serve as crucial synthetic building blocks for pharmaceuticals and agrochemicals. With breakthroughs in the production capacity of diamines (such as 2-methylpentanediamine and 1,5-pentanediamine), employing cyclization strategies to access piperidine frameworks has garnered increasing attention. Herein, we report an efficient strategy to rapidly access piperidines via a “hydrogen-borrowing” mechanism over Shvo Ru catalysis without any additives. Firstly, the interaction between the Shvo Ru complex and diamines was investigated by 1H NMR, FT-IR, mass spectrometry, and DFT calculations, revealing the role of diamines in dissociating the Shvo pre-catalyst and facilitating the formation of reactive intermediates. Based on this observation, Shvo-based catalysts with efficient activity for the solvent/promoter-free cyclization of diamines to piperidines were developed. This catalytic system is applicable not only to 100-gram scale-up synthesis with a record-high turnover number (TON) of 8645 and excellent selectivity (>99%), but also remains stable for over 4 cycles without significant loss of activity. Finally, the catalytic mechanism of the Shvo Ru-mediated, solvent/promoter-free cyclization of diamines to piperidines was proposed by DFT calculations and control experiments.
{"title":"Substrate-activated Shvo catalyst for the solvent/promoter-free cyclization of diamines to piperidines and analogues","authors":"Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He","doi":"10.1016/j.jcat.2026.116720","DOIUrl":"10.1016/j.jcat.2026.116720","url":null,"abstract":"<div><div>Piperidine derivatives serve as crucial synthetic building blocks for pharmaceuticals and agrochemicals. With breakthroughs in the production capacity of diamines (such as 2-methylpentanediamine and 1,5-pentanediamine), employing cyclization strategies to access piperidine frameworks has garnered increasing attention. Herein, we report an efficient strategy to rapidly access piperidines via a “hydrogen-borrowing” mechanism over Shvo Ru catalysis without any additives. Firstly, the interaction between the Shvo Ru complex and diamines was investigated by <sup>1</sup>H NMR, FT-IR, mass spectrometry, and DFT calculations, revealing the role of diamines in dissociating the Shvo pre-catalyst and facilitating the formation of reactive intermediates. Based on this observation, Shvo-based catalysts with efficient activity for the solvent/promoter-free cyclization of diamines to piperidines were developed. This catalytic system is applicable not only to 100-gram scale-up synthesis with a record-high turnover number (TON) of 8645 and excellent selectivity (>99%), but also remains stable for over 4 cycles without significant loss of activity. Finally, the catalytic mechanism of the Shvo Ru-mediated, solvent/promoter-free cyclization of diamines to piperidines was proposed by DFT calculations and control experiments.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116720"},"PeriodicalIF":6.5,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.jcat.2026.116716
Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei
{"title":"Influence of tailoring acidic sites and silicon distribution of SAPO-11 zeolite via in-situ Zn modification for superior hydroisomerization of Fischer-Tropsch wax","authors":"Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei","doi":"10.1016/j.jcat.2026.116716","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116716","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"94 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.jcat.2026.116721
Isabel Poves-Ruiz, Beatriz Sánchez-Page, M.Victoria Jiménez, Miguel Gallegos, Julen Munarriz, Vincenzo Passarelli, Jesús J. Pérez-Torrente
In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI{(MeIm)2CH2}]+, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI2(IMe)] (IMe = 1,3-dimethylimidozolin-2-ylidene). It This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η4-Cp*H], formed through protonation of the Cp* moiety.
{"title":"Mechanistic Insights on the β-(Z) alkyne hydrosilylation by a NHC-based Cp*Rh(III) catalyst: from catalyst design to an alternative model for H-Si activation","authors":"Isabel Poves-Ruiz, Beatriz Sánchez-Page, M.Victoria Jiménez, Miguel Gallegos, Julen Munarriz, Vincenzo Passarelli, Jesús J. Pérez-Torrente","doi":"10.1016/j.jcat.2026.116721","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116721","url":null,"abstract":"In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI{(MeIm)<sub>2</sub>CH<sub>2</sub>}]<sup>+</sup>, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI<sub>2</sub>(IMe)] (IMe = 1,3-dimethylimidozolin-2-ylidene). <del>It</del> This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η<sup>4</sup>-Cp*H], formed through protonation of the Cp* moiety.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"140 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.jcat.2026.116728
Yiyuan Zhang, Xianhong Wu, Jinjie Lin, Hanyang Chen, Run-Cang Sun
The electrochemical oxidative cleavage of C(OH)-C bonds facilitates the conversion of lignin-derived secondary alcohols and ketones into valuable carboxylates in a mild and environmentally friendly manner. In this study, we present efficient and cost-effective FeNi layered double-hydroxide (LDH) nanosheets created through a one-step galvanostatic electrodeposition on nickel foam (NF). The FeNi-LDH/NF shows a high activity for α-phenethyl alcohol (α-PEA) electrooxidation reaction leading to low potential 1.489 V vs. RHE to reach a current density of 100 mA cm−2, α-PEA was almost completely transformed, and the yield of benzoic acid (BA) was high (> 95%). Both theory and experiments show that α-PEA is first oxidized to acetophenone and then to benzoic acid. The dehydrogenation and oxygenation of the C–H bond is the rate-limiting step of the reaction. In addition, an energy-saving and multifunctional flow electrolytic cell has been developed successfully, througn coupling α-PEA electrooxidation reaction with hydrogen evolution reaction, with FeNi-LDH/NF as dual-functional electrocatalyst. The flow electrolytic cell can operate stably for 200 h.
C(OH)-C键的电化学氧化裂解有助于木质素衍生的仲醇和酮以温和和环保的方式转化为有价值的羧酸盐。在这项研究中，我们通过一步恒流电沉积在泡沫镍（NF）上制备了高效且具有成本效益的FeNi层状双氢氧化物（LDH）纳米片。FeNi-LDH/NF对α-苯乙醇（α-PEA）具有较高的电氧化反应活性，相对于RHE电位为1.489 V，电流密度为100 mA cm−2，α-PEA几乎完全转化，苯甲酸（BA）收率高（95%）。理论和实验都表明，α-PEA首先被氧化为苯乙酮，然后被氧化为苯甲酸。C-H键的脱氢和氧化是反应的限速步骤。此外，通过α-PEA电氧化反应与析氢反应耦合，以FeNi-LDH/NF为双功能电催化剂，成功研制出节能多功能流动电解槽。流动电解槽可稳定运行200 h。
{"title":"Layered double hydroxides enabled efficient electrocatalytic oxidative cleavage of C(OH)−C bonds","authors":"Yiyuan Zhang, Xianhong Wu, Jinjie Lin, Hanyang Chen, Run-Cang Sun","doi":"10.1016/j.jcat.2026.116728","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116728","url":null,"abstract":"The electrochemical oxidative cleavage of C(OH)-C bonds facilitates the conversion of lignin-derived secondary alcohols and ketones into valuable carboxylates in a mild and environmentally friendly manner. In this study, we present efficient and cost-effective FeNi layered double-hydroxide (LDH) nanosheets created through a one-step galvanostatic electrodeposition on nickel foam (NF). The FeNi-LDH/NF shows a high activity for α-phenethyl alcohol (α-PEA) electrooxidation reaction leading to low potential 1.489 V vs. RHE to reach a current density of 100 mA cm<sup>−2</sup>, α-PEA was almost completely transformed, and the yield of benzoic acid (BA) was high (> 95%). Both theory and experiments show that α-PEA is first oxidized to acetophenone and then to benzoic acid. The dehydrogenation and oxygenation of the C–H bond is the rate-limiting step of the reaction. In addition, an energy-saving and multifunctional flow electrolytic cell has been developed successfully, througn coupling α-PEA electrooxidation reaction with hydrogen evolution reaction, with FeNi-LDH/NF as dual-functional electrocatalyst. The flow electrolytic cell can operate stably for 200 h.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"4 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095952","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.jcat.2026.116723
Manish Maurya, Hannah Fejzić, Xavier C. Krull, Huy Nguyen, Matthew Neurock, Joseph T. Hupp, Chibueze V. Amanchukwu, Rachel B. Getman
{"title":"Modulating Cu electrode microenvironments with MOF coatings: insights from molecular dynamics and electrochemical experiments of CO reduction","authors":"Manish Maurya, Hannah Fejzić, Xavier C. Krull, Huy Nguyen, Matthew Neurock, Joseph T. Hupp, Chibueze V. Amanchukwu, Rachel B. Getman","doi":"10.1016/j.jcat.2026.116723","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116723","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"8 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1016/j.jcat.2026.116726
Zhe Wang, Jie Huang, Min Zhou, Lin Ma, Min Zhang
{"title":"A tandem visible-light/heterogeneous-alumina catalytic platform for sustainable transition-metal-free cyclobutene synthesis","authors":"Zhe Wang, Jie Huang, Min Zhou, Lin Ma, Min Zhang","doi":"10.1016/j.jcat.2026.116726","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116726","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"78 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1016/j.jcat.2026.116722
Jiwoo Kim, Dong Hwan Kim, Seungki Hong, Tae Hoon Seo, Jaegeun Lee
{"title":"Understanding metal-support interaction for single-walled carbon nanotube synthesis: a comparative study of Co on MgO and Al2O3","authors":"Jiwoo Kim, Dong Hwan Kim, Seungki Hong, Tae Hoon Seo, Jaegeun Lee","doi":"10.1016/j.jcat.2026.116722","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116722","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"8 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1016/j.jcat.2026.116715
Jinwon Choi, Mireu Kim, Yeonsu Kwak, Amol Pophali, Gary Halada, Huiting Luo, Gihan Kwon, Insoo Ro, Jaewoo Kim, Miriam Rafailovich, Taejin Kim
{"title":"Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides","authors":"Jinwon Choi, Mireu Kim, Yeonsu Kwak, Amol Pophali, Gary Halada, Huiting Luo, Gihan Kwon, Insoo Ro, Jaewoo Kim, Miriam Rafailovich, Taejin Kim","doi":"10.1016/j.jcat.2026.116715","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116715","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"75 1","pages":"116715"},"PeriodicalIF":7.3,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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