Yulin Zhou, Jing Sun, Sébastien Gallet, Jesus Raya, Corinne Boudon, Antoine Bonnefont, Laurent Ruhlmann, V. Badets
We describe here an immobilization method of four Keggin‐type polyoxometalates (POMs) ([H2W12O40]6‐, [BW12O40]5‐ [SiW12O40]4‐, [PW12O40]3‐) by using the reaction with an ionic liquid, 1‐butyl‐3‐vinylimidazolium (BVIM) bromide. The reaction yields a hybrid material (BVIM‐POM) as a water‐insoluble salt. The chemical structure of both compounds is preserved, as indicated by infrared spectroscopy (FT‐IR), although with a reduced crystallinity (shown by X‐ray diffraction analysis) due to a decrease of water content (shown by thermogravimetric analysis). Cross polarization 1H‐31P NMR evidenced the presence of BVIM in the structure of (BVIM)3[PW12O40]. The salt is mixed with carbon powder and Nafion to prepare an ink and casted on glassy carbon electrodes. The electrochemical behavior of immobilized POMs material is preserved. The electrochemical activity for nitrite reduction is measured by cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). It was observed that the reduction current of 10 mM HNO2 at pH 1 in 0.5 M Na2SO4 is enhanced in the presence of these hybrid materials. DEMS has evidenced the formation of nitrous oxide (N2O) at potentials more positive compared to the use of parent POMs in solution.
{"title":"Nitrite electroreduction enhanced by hybrid compounds of Keggin polyoxometalates and 1‐butyl‐3‐vinylimidazolium","authors":"Yulin Zhou, Jing Sun, Sébastien Gallet, Jesus Raya, Corinne Boudon, Antoine Bonnefont, Laurent Ruhlmann, V. Badets","doi":"10.1002/cctc.202400226","DOIUrl":"https://doi.org/10.1002/cctc.202400226","url":null,"abstract":"We describe here an immobilization method of four Keggin‐type polyoxometalates (POMs) ([H2W12O40]6‐, [BW12O40]5‐ [SiW12O40]4‐, [PW12O40]3‐) by using the reaction with an ionic liquid, 1‐butyl‐3‐vinylimidazolium (BVIM) bromide. The reaction yields a hybrid material (BVIM‐POM) as a water‐insoluble salt. The chemical structure of both compounds is preserved, as indicated by infrared spectroscopy (FT‐IR), although with a reduced crystallinity (shown by X‐ray diffraction analysis) due to a decrease of water content (shown by thermogravimetric analysis). Cross polarization 1H‐31P NMR evidenced the presence of BVIM in the structure of (BVIM)3[PW12O40]. The salt is mixed with carbon powder and Nafion to prepare an ink and casted on glassy carbon electrodes. The electrochemical behavior of immobilized POMs material is preserved. The electrochemical activity for nitrite reduction is measured by cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). It was observed that the reduction current of 10 mM HNO2 at pH 1 in 0.5 M Na2SO4 is enhanced in the presence of these hybrid materials. DEMS has evidenced the formation of nitrous oxide (N2O) at potentials more positive compared to the use of parent POMs in solution.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141351738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Juan Chen, A. Zanina, Jianshuo Li, Kai Wu, Guiyuan Jiang, E. Kondratenko
The direct conversion of cheap and widely available C1‐C3 alkanes in natural gas/shale gas into building blocks for the chemical industry is highly attractive from an environmental perspective as a replacement for current oil‐based processes. Due to the high chemical inertness of these alkanes, but the high reactivity of the desired reaction products, which are easily involved in non‐selective sequential reactions, ongoing research activities are focused on controlling product selectivity through catalyst design and/or reactor operation. In this context, we have critically analyzed research studies dealing with the effect of steam or liquid water on catalyst activity and, in particular, on selectivity in the conversion of CH4, C2H6 and C3H8 to C2+‐hydrocarbons, formaldehyde, methanol, ethylene, acetic acid, and propene. In addition, our personal views on possible future developments are also given.
{"title":"Mechanistic and Kinetic Insights into H2O Effects in the Conversion of C1‐C3 Hydrocarbons to Value‐added Products","authors":"Juan Chen, A. Zanina, Jianshuo Li, Kai Wu, Guiyuan Jiang, E. Kondratenko","doi":"10.1002/cctc.202400571","DOIUrl":"https://doi.org/10.1002/cctc.202400571","url":null,"abstract":"The direct conversion of cheap and widely available C1‐C3 alkanes in natural gas/shale gas into building blocks for the chemical industry is highly attractive from an environmental perspective as a replacement for current oil‐based processes. Due to the high chemical inertness of these alkanes, but the high reactivity of the desired reaction products, which are easily involved in non‐selective sequential reactions, ongoing research activities are focused on controlling product selectivity through catalyst design and/or reactor operation. In this context, we have critically analyzed research studies dealing with the effect of steam or liquid water on catalyst activity and, in particular, on selectivity in the conversion of CH4, C2H6 and C3H8 to C2+‐hydrocarbons, formaldehyde, methanol, ethylene, acetic acid, and propene. In addition, our personal views on possible future developments are also given.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141383560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Eleni Papaplioura, Maëva Mercier, Soufyan Jerhaoui, M. Schnürch
Transition metal catalysis allows for the efficient and selective introduction of vinyl moieties onto organic molecules and offers a versatile approach to synthesizing complex organic molecules. Nonetheless, few transition‐metal free vinylation reactions have also been reported, exhibiting exceptional functional group tolerance and circumventing selectivity issues. This review provides an overview of carbon, nitrogen and oxygen vinylation, presenting innovative strategies and key advancements in the field. Hence, it will serve as a valuable resource for organic chemists who are interested in the synthesis of vinyl‐containing compounds. By understanding the diverse strategies involved in vinylation, readers will gain insights into harnessing this powerful synthetic methodology for the efficient construction of carbon‐carbon and carbon‐heteroatom bonds.
{"title":"The Vinyl Group: Small but Mighty ‐ Transition Metal Catalyzed and Non‐Catalyzed Vinylation Reactions","authors":"Eleni Papaplioura, Maëva Mercier, Soufyan Jerhaoui, M. Schnürch","doi":"10.1002/cctc.202400513","DOIUrl":"https://doi.org/10.1002/cctc.202400513","url":null,"abstract":"Transition metal catalysis allows for the efficient and selective introduction of vinyl moieties onto organic molecules and offers a versatile approach to synthesizing complex organic molecules. Nonetheless, few transition‐metal free vinylation reactions have also been reported, exhibiting exceptional functional group tolerance and circumventing selectivity issues. This review provides an overview of carbon, nitrogen and oxygen vinylation, presenting innovative strategies and key advancements in the field. Hence, it will serve as a valuable resource for organic chemists who are interested in the synthesis of vinyl‐containing compounds. By understanding the diverse strategies involved in vinylation, readers will gain insights into harnessing this powerful synthetic methodology for the efficient construction of carbon‐carbon and carbon‐heteroatom bonds.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141101933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of highly efficient and selective catalysts for carbonylation reactions represents a significant challenge in catalysis. Single‐atom catalysts (SACs) have postulated as promising candidates able to combine the strengths of both homogeneous and heterogeneous catalysts. In this paper, we review recent advances in tailoring solid supports for SACs to enhance their catalytic performance in carbonylation reactions. We first discuss the effect of supports on the hydroformylation reaction catalysed by SACs, followed by recent advances for methanol, ethanol, and dimethyl ether carbonylation reactions, focusing on the design of halide‐free catalysts with improved activity and stability. Overall, this review highlights the importance of tailoring solid supports for SACs to achieve highly active and selective catalysts in carbonylation reactions, paving the way for future developments in sustainable catalysis.
{"title":"Carbonylation Reactions Using Single Atom Catalysts","authors":"Lole Jurado, Sergio Posada-Pérez, M. Rosa Axet","doi":"10.1002/cctc.202400543","DOIUrl":"https://doi.org/10.1002/cctc.202400543","url":null,"abstract":"The development of highly efficient and selective catalysts for carbonylation reactions represents a significant challenge in catalysis. Single‐atom catalysts (SACs) have postulated as promising candidates able to combine the strengths of both homogeneous and heterogeneous catalysts. In this paper, we review recent advances in tailoring solid supports for SACs to enhance their catalytic performance in carbonylation reactions. We first discuss the effect of supports on the hydroformylation reaction catalysed by SACs, followed by recent advances for methanol, ethanol, and dimethyl ether carbonylation reactions, focusing on the design of halide‐free catalysts with improved activity and stability. Overall, this review highlights the importance of tailoring solid supports for SACs to achieve highly active and selective catalysts in carbonylation reactions, paving the way for future developments in sustainable catalysis.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141110571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fan Yang, Lucie Guillaume, Régis M. Gauvin, Christophe M. Thomas
One‐pot processes have emerged as a powerful strategy in (macro)molecular synthesis: integrating a multicatalytic process maximizes efficiency, reduces waste, improves profitability, and provides versatile tools for designing of more sustainable processes without compromising selectivity and activity. This review article provides a critical overview of the application of one‐pot transformations in polymerization, with the goal of synthesizing polymers with tailored structures and functions for a wide range of applications. Recent advances in one‐pot polymerization techniques are highlighted, including examples from controlled polymerization methods such as atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer (RAFT) polymerization, and ring‐opening polymerization (ROP), among others. Special emphasis is placed on the design and optimization of reaction conditions, catalyst systems, and monomer combinations to achieve precise control over polymer structure and functionality.
{"title":"One‐Pot Catalytic Approaches: Building a New Toolbox for Macromolecular Design","authors":"Fan Yang, Lucie Guillaume, Régis M. Gauvin, Christophe M. Thomas","doi":"10.1002/cctc.202400443","DOIUrl":"https://doi.org/10.1002/cctc.202400443","url":null,"abstract":"One‐pot processes have emerged as a powerful strategy in (macro)molecular synthesis: integrating a multicatalytic process maximizes efficiency, reduces waste, improves profitability, and provides versatile tools for designing of more sustainable processes without compromising selectivity and activity. This review article provides a critical overview of the application of one‐pot transformations in polymerization, with the goal of synthesizing polymers with tailored structures and functions for a wide range of applications. Recent advances in one‐pot polymerization techniques are highlighted, including examples from controlled polymerization methods such as atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer (RAFT) polymerization, and ring‐opening polymerization (ROP), among others. Special emphasis is placed on the design and optimization of reaction conditions, catalyst systems, and monomer combinations to achieve precise control over polymer structure and functionality.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141115892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The sustainable preparation of N‐heterocycles is one of the most active research areas owing to their predominance as synthetics building blocks with extensive applications in organic, pharmaceutical, and material chemistry fields. Among the various catalytic protocols, the C–H bond functionalization with the concomitant C–N bond formation, so‐called C–H bond annulation, has become one of the most sustainable routes to access N‐heterocycles because it starts from low‐functionalized materials and generates a limited amount of waste, all respecting the concept of atom economy. Rhodium complexes often catalyze these reactions. This review focuses on the synthesis of 5‐ and 6‐membered ring N‐containing heterocycles such as indoles, pyrroles, indolines, (iso)quinolinones, dihydroquinolines, and pyrrolidones from readily available starting materials, with an emphasis on the novel C–H bond cascade synthetic methodologies via C–N/C–C bond formation, as well as on the mechanisms of these reactions, especially the oxidation steps. We hope this review will help researchers looking to prepare N‐heterocycles in a minimum of steps and those who want to develop new methodologies based on C–H bond activation/functionalizations.
{"title":"Rhodium‐Catalyzed C–H Bond Annulation for the Synthesis of 5‐ and 6‐Membered N‐Heterocyclic Building Blocks","authors":"Marie Peng, Henri Doucet, Jean-François Soulé","doi":"10.1002/cctc.202400279","DOIUrl":"https://doi.org/10.1002/cctc.202400279","url":null,"abstract":"The sustainable preparation of N‐heterocycles is one of the most active research areas owing to their predominance as synthetics building blocks with extensive applications in organic, pharmaceutical, and material chemistry fields. Among the various catalytic protocols, the C–H bond functionalization with the concomitant C–N bond formation, so‐called C–H bond annulation, has become one of the most sustainable routes to access N‐heterocycles because it starts from low‐functionalized materials and generates a limited amount of waste, all respecting the concept of atom economy. Rhodium complexes often catalyze these reactions. This review focuses on the synthesis of 5‐ and 6‐membered ring N‐containing heterocycles such as indoles, pyrroles, indolines, (iso)quinolinones, dihydroquinolines, and pyrrolidones from readily available starting materials, with an emphasis on the novel C–H bond cascade synthetic methodologies via C–N/C–C bond formation, as well as on the mechanisms of these reactions, especially the oxidation steps. We hope this review will help researchers looking to prepare N‐heterocycles in a minimum of steps and those who want to develop new methodologies based on C–H bond activation/functionalizations.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-05-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140965821","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Paresh A. Kamble, C. P. Vinod, Virendra K. Rathod, Lakshmikantam Mannepalli
A series of nickel hydroxyapatite catalysts were synthesized by the co‐precipitation method followed by calcination and reduction. These catalysts were employed for the aqueous phase hydrogenation of glucose to sorbitol. The Ni‐HAP catalyst with comparatively high surface area and acid‐base strength gave high sorbitol selectivity in 1 h. Ni‐HAP‐4 catalyst with moderate Ni (3.5 wt.%) content having smaller and highly dispersed nickel particles gives an excellent yield of sorbitol, 97% in 1h. The Ni‐HAP‐4 catalyst works well with other polar protic solvents. Different characterization techniques like XRD, TEM, SEM‐EDS, BET, NH3‐TPD, and CO2‐TPD were employed to analyze the Ni‐HAP‐4 catalyst.
{"title":"Hydrogenation of Glucose to Sorbitol by Using Nickel Hydroxyapatite Catalyst","authors":"Paresh A. Kamble, C. P. Vinod, Virendra K. Rathod, Lakshmikantam Mannepalli","doi":"10.1002/cctc.202301590","DOIUrl":"https://doi.org/10.1002/cctc.202301590","url":null,"abstract":"A series of nickel hydroxyapatite catalysts were synthesized by the co‐precipitation method followed by calcination and reduction. These catalysts were employed for the aqueous phase hydrogenation of glucose to sorbitol. The Ni‐HAP catalyst with comparatively high surface area and acid‐base strength gave high sorbitol selectivity in 1 h. Ni‐HAP‐4 catalyst with moderate Ni (3.5 wt.%) content having smaller and highly dispersed nickel particles gives an excellent yield of sorbitol, 97% in 1h. The Ni‐HAP‐4 catalyst works well with other polar protic solvents. Different characterization techniques like XRD, TEM, SEM‐EDS, BET, NH3‐TPD, and CO2‐TPD were employed to analyze the Ni‐HAP‐4 catalyst.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139808205","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Layered double hydroxides (LDHs) is a category of 2D materials that possess excellent physicochemical properties for enhancing photocatalytic (PC), electrocatalytic (EC), and photoelectrochemical (PEC) performances. However, pristine LDH encounters challenges like sluggish charge‐carrier mobility, high rate of electron–hole recombination, low conductivity, and tendency to agglomerate, making them unsuitable for practical applications. Therefore, modifications such as composite preparations, co‐catalyst integration, semiconductor coupling, and ternary heterostructure engineering have been explored to disclose new possibilities for LDHs in PC, EC, and PEC applications. In the realm of semiconducting materials aimed at enhancing LDH productivity, quantum dots (QDs) i.e., 0D materials have proven to be effective due to their advantages, including abundant reserves, affordability, and environmental friendliness. This review explores the role of QDs as interlayer support, co‐catalyst, mediator, semiconductor, and sensitizer in QDs@LDH heterostructures to achieve superior photocatalytic activities. These QD‐infused heterostructures also deliver improved EC and PEC water‐splitting performance coupled with long‐term stabilities. Additionally, this review delves into characterization techniques, intrinsic structural features, and designing of the QD@LDH heterostructures. Future scopes and challenges in constructing and cutting‐edge theoretical anticipations of QD@LDH are also discussed. This review may be a guiding light to a sustainable approach to outperform QD‐modified LDH for versatile catalysts.
{"title":"Recent Advancement in Quantum Dot Modified Layered Double Hydroxide towards Photocatalytic, Electrocatalytic, and Photoelectrochemical Applications","authors":"Preeti Prabha Sarangi, D. Sahoo, Upali Aparajita Mohanty, Susanginee Nayak, Kulamani Parida","doi":"10.1002/cctc.202301533","DOIUrl":"https://doi.org/10.1002/cctc.202301533","url":null,"abstract":"Layered double hydroxides (LDHs) is a category of 2D materials that possess excellent physicochemical properties for enhancing photocatalytic (PC), electrocatalytic (EC), and photoelectrochemical (PEC) performances. However, pristine LDH encounters challenges like sluggish charge‐carrier mobility, high rate of electron–hole recombination, low conductivity, and tendency to agglomerate, making them unsuitable for practical applications. Therefore, modifications such as composite preparations, co‐catalyst integration, semiconductor coupling, and ternary heterostructure engineering have been explored to disclose new possibilities for LDHs in PC, EC, and PEC applications. In the realm of semiconducting materials aimed at enhancing LDH productivity, quantum dots (QDs) i.e., 0D materials have proven to be effective due to their advantages, including abundant reserves, affordability, and environmental friendliness. This review explores the role of QDs as interlayer support, co‐catalyst, mediator, semiconductor, and sensitizer in QDs@LDH heterostructures to achieve superior photocatalytic activities. These QD‐infused heterostructures also deliver improved EC and PEC water‐splitting performance coupled with long‐term stabilities. Additionally, this review delves into characterization techniques, intrinsic structural features, and designing of the QD@LDH heterostructures. Future scopes and challenges in constructing and cutting‐edge theoretical anticipations of QD@LDH are also discussed. This review may be a guiding light to a sustainable approach to outperform QD‐modified LDH for versatile catalysts.","PeriodicalId":503942,"journal":{"name":"ChemCatChem","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139807980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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