Pub Date : 2025-02-26DOI: 10.1016/j.checat.2025.101296
Matthew W. Coile, V. Sai Phani Kumar, Changxia Shi, Eugene Y.-X. Chen, Linda J. Broadbelt, Alexander Shaw
Most plastics recycled today are recycled mechanically, often referred to as downcycling due to the inevitable degradation of the polymer material. One alternative is to chemically recycle these materials back to a monomer, but this works most efficiently for intrinsically circular polymers (iCPs) that exhibit appropriate depolymerization thermodynamics and kinetics. In order to help design such iCP materials, modeling can provide insight into the effect of reaction conditions on their polymerization and depolymerization characteristics. Most iCPs reported are linear polymers, so architecturally complex hyperbranched polymers that exhibit complete chemical circularity are rare, and modeling on hyperbranched iCPs has not been reported. Here, we report a mechanistic model that incorporates chain-length-dependent transport phenomena and tracks the full polymer structure during the reversible polymerization of a hydroxyl-functionalized lactone leading to this hyperbranched polyester. This lays the groundwork for future modeling of this material’s depolymerization behavior and provides a framework that can be employed to study other iCPs.
{"title":"Mechanistic kinetic Monte Carlo modeling of the synthesis of hyperbranched polyesters","authors":"Matthew W. Coile, V. Sai Phani Kumar, Changxia Shi, Eugene Y.-X. Chen, Linda J. Broadbelt, Alexander Shaw","doi":"10.1016/j.checat.2025.101296","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101296","url":null,"abstract":"Most plastics recycled today are recycled mechanically, often referred to as downcycling due to the inevitable degradation of the polymer material. One alternative is to chemically recycle these materials back to a monomer, but this works most efficiently for intrinsically circular polymers (iCPs) that exhibit appropriate depolymerization thermodynamics and kinetics. In order to help design such iCP materials, modeling can provide insight into the effect of reaction conditions on their polymerization and depolymerization characteristics. Most iCPs reported are linear polymers, so architecturally complex hyperbranched polymers that exhibit complete chemical circularity are rare, and modeling on hyperbranched iCPs has not been reported. Here, we report a mechanistic model that incorporates chain-length-dependent transport phenomena and tracks the full polymer structure during the reversible polymerization of a hydroxyl-functionalized lactone leading to this hyperbranched polyester. This lays the groundwork for future modeling of this material’s depolymerization behavior and provides a framework that can be employed to study other iCPs.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"4 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143495761","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}
Pub Date : 2025-02-24DOI: 10.1016/j.checat.2024.101254
Yongqiang Wang, Jining Guo, Longbing Qu, Paul Webley, Hui Ding, Gang Kevin Li
Syngas, a mixture of hydrogen and carbon monoxide, is a crucial building block in various chemical processes and is primarily produced from fossil fuels. Exploring sustainable carbon and hydrogen sources for syngas production presents a promising avenue for reducing the carbon footprint in the chemical industry. Here, we demonstrate the production of syngas from atmospheric carbon dioxide and moisture by integrating adsorption-based CO2/H2O capture with electrochemical CO2 reduction. The water captured from the air not only was employed for the in situ generation of vapors at 60°C to effectively release CO2 adsorbed on amine-functionalized materials but also served as the hydrogen source in the subsequent electrolysis. The product CO2 and water were converted into syngas using a gallium-based electrolyzer, with an overall energy requirement of 56.4 MJ/kgsyngas. This air-to-syngas technology enables the production of carbon-neutral chemicals from the atmosphere, offering significant potential to reduce carbon emissions from industries.
{"title":"Syngas production from the air","authors":"Yongqiang Wang, Jining Guo, Longbing Qu, Paul Webley, Hui Ding, Gang Kevin Li","doi":"10.1016/j.checat.2024.101254","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101254","url":null,"abstract":"Syngas, a mixture of hydrogen and carbon monoxide, is a crucial building block in various chemical processes and is primarily produced from fossil fuels. Exploring sustainable carbon and hydrogen sources for syngas production presents a promising avenue for reducing the carbon footprint in the chemical industry. Here, we demonstrate the production of syngas from atmospheric carbon dioxide and moisture by integrating adsorption-based CO<sub>2</sub>/H<sub>2</sub>O capture with electrochemical CO<sub>2</sub> reduction. The water captured from the air not only was employed for the <em>in situ</em> generation of vapors at 60°C to effectively release CO<sub>2</sub> adsorbed on amine-functionalized materials but also served as the hydrogen source in the subsequent electrolysis. The product CO<sub>2</sub> and water were converted into syngas using a gallium-based electrolyzer, with an overall energy requirement of 56.4 MJ/kg<sub>syngas</sub>. This air-to-syngas technology enables the production of carbon-neutral chemicals from the atmosphere, offering significant potential to reduce carbon emissions from industries.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"128 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477764","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}
Pub Date : 2025-02-24DOI: 10.1016/j.checat.2025.101264
Xinxin Lu, Kok Bing Tan, Jun Zhao, Guowu Zhan
Recently, there has been growing interest in using green hydrogen (H2) to convert CO2 into multicarbon products (C2+) directly. This review highlights recent advancements in integrated catalysts featuring multiple components and complementary properties designed for the one-step synthesis of C2+ products via CO2 hydrogenation. The discussion particularly focuses on how chemical compositions (metals, metal oxides, zeolites, etc.) and spatial arrangement (proximity) affect their catalytic performance. Additionally, it explores various integration methods (physical, chemical, and bio-template assembly methods) for combining multiple active sites to overcome selectivity limitations. The review covers four key types of multicarbon products: (1) light olefins, (2) gasoline (C5–C11) or diesel fuel (C10–C20), (3) aromatics, and (4) C2+ oxygenates. Finally, it outlines future research directions by identifying the challenges and opportunities in CO2 hydrogenation to C2+ products. This review aims to foster greater interest among both academic and industrial researchers in advancing CO2 hydrogenation technologies by using integrated nanocatalysts.
{"title":"Advances in integrated catalysts for CO2 thermal hydrogenation to multicarbon products","authors":"Xinxin Lu, Kok Bing Tan, Jun Zhao, Guowu Zhan","doi":"10.1016/j.checat.2025.101264","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101264","url":null,"abstract":"Recently, there has been growing interest in using green hydrogen (H<sub>2</sub>) to convert CO<sub>2</sub> into multicarbon products (C<sub>2+</sub>) directly. This review highlights recent advancements in integrated catalysts featuring multiple components and complementary properties designed for the one-step synthesis of C<sub>2+</sub> products via CO<sub>2</sub> hydrogenation. The discussion particularly focuses on how chemical compositions (metals, metal oxides, zeolites, etc.) and spatial arrangement (proximity) affect their catalytic performance. Additionally, it explores various integration methods (physical, chemical, and bio-template assembly methods) for combining multiple active sites to overcome selectivity limitations. The review covers four key types of multicarbon products: (1) light olefins, (2) gasoline (C<sub>5</sub>–C<sub>11</sub>) or diesel fuel (C<sub>10</sub>–C<sub>20</sub>), (3) aromatics, and (4) C<sub>2+</sub> oxygenates. Finally, it outlines future research directions by identifying the challenges and opportunities in CO<sub>2</sub> hydrogenation to C<sub>2+</sub> products. This review aims to foster greater interest among both academic and industrial researchers in advancing CO<sub>2</sub> hydrogenation technologies by using integrated nanocatalysts.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"30 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477767","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}
Pub Date : 2025-02-24DOI: 10.1016/j.checat.2025.101294
Steven Chavez, Anubhab Acharya, Zhila Dehghan
Photon-driven catalytic reactions have long been explored as a way to reduce emissions by replacing fossil-fuel-derived process heat with solar energy. Light-harvesting plasmonic metal nanoparticles are promising photocatalysts because they can drive kinetically unfavorable reactions through combined non-thermal (hot charge carrier) and photothermal effects under illumination. Understanding the interplay between these effects is critical for optimizing these materials for sustainable photochemical production processes. Unfortunately, the simultaneous presence of these two mechanisms under relevant photocatalytic operating conditions has led to fierce debate in the plasmonic catalysis community about the relative contributions of each. This perspective examines frequently overlooked concepts when attempting to disentangle thermal and non-thermal effects in plasmon-driven, gas-phase heterogeneous photocatalysis. We focus on the rising use of hybrid plasmonic (antenna-reactor) materials, which combine light harvesting and catalytically active metal components. We postulate that the addition of second metal sites further complicates the distinction between thermal vs. non-thermal effects. Specifically, changes in light absorption, the energy and lifetime of charge carriers, nanoscale heating, and dynamic catalyst restructuring upon the creation of multicomponent systems need to be considered. Throughout this perspective, we highlight key questions that must be resolved to address these issues. We conclude by proposing pathways to bridge the fundamental and applied research gap to accelerate the potential integration of plasmonic catalysis into large-scale chemical processes.
{"title":"Revisiting thermal and non-thermal effects in hybrid plasmonic antenna reactor photocatalysts","authors":"Steven Chavez, Anubhab Acharya, Zhila Dehghan","doi":"10.1016/j.checat.2025.101294","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101294","url":null,"abstract":"Photon-driven catalytic reactions have long been explored as a way to reduce emissions by replacing fossil-fuel-derived process heat with solar energy. Light-harvesting plasmonic metal nanoparticles are promising photocatalysts because they can drive kinetically unfavorable reactions through combined non-thermal (hot charge carrier) and photothermal effects under illumination. Understanding the interplay between these effects is critical for optimizing these materials for sustainable photochemical production processes. Unfortunately, the simultaneous presence of these two mechanisms under relevant photocatalytic operating conditions has led to fierce debate in the plasmonic catalysis community about the relative contributions of each. This perspective examines frequently overlooked concepts when attempting to disentangle thermal and non-thermal effects in plasmon-driven, gas-phase heterogeneous photocatalysis. We focus on the rising use of hybrid plasmonic (antenna-reactor) materials, which combine light harvesting and catalytically active metal components. We postulate that the addition of second metal sites further complicates the distinction between thermal vs. non-thermal effects. Specifically, changes in light absorption, the energy and lifetime of charge carriers, nanoscale heating, and dynamic catalyst restructuring upon the creation of multicomponent systems need to be considered. Throughout this perspective, we highlight key questions that must be resolved to address these issues. We conclude by proposing pathways to bridge the fundamental and applied research gap to accelerate the potential integration of plasmonic catalysis into large-scale chemical processes.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"30 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143477766","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}
Pub Date : 2025-02-20DOI: 10.1016/j.checat.2025.101292
Paweł Krzesiński, Chiara Dinoi, Iker del Rosal, Laure Vendier, Pavel Kumandin, Adrian Sytniczuk, Stéphanie Bastin, Vincent César, Anna Kajetanowicz, Karol Grela
Olefin metathesis methods for preparing sterically hindered alkenes remain scarce. They are commonly based on specialized ruthenium catalysts with sterically reduced N-heterocyclic carbene (NHC) ligands, which are able to accommodate large olefinic substrates during the catalytic steps. Yet, these complexes easily undergo intramolecular C–H activation at the ortho position of the N-aryl group of the NHC, which leads to their decomposition. Considering that this deleterious process requires the rotation of one of the NHC’s N-aryl arms, we introduced a second decker of aromatic groups into this ligand. Such steric blockade led to more stable and highly efficient catalysts for challenging metathesis reactions of sterically crowded olefins. The beneficial effect of these upper aromatic “wings” is rationalized through experimental determination of the stereoelectronic properties of the resulting NHC ligands, complemented by density functional theory (DFT) calculations on the nature of the through-space interactions between the “wings” and on the decomposition pathway of these complexes.
{"title":"Biplane-like small N-heterocyclic carbenes as effective ligands in challenging Ru-catalyzed metathesis of sterically crowded olefins","authors":"Paweł Krzesiński, Chiara Dinoi, Iker del Rosal, Laure Vendier, Pavel Kumandin, Adrian Sytniczuk, Stéphanie Bastin, Vincent César, Anna Kajetanowicz, Karol Grela","doi":"10.1016/j.checat.2025.101292","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101292","url":null,"abstract":"Olefin metathesis methods for preparing sterically hindered alkenes remain scarce. They are commonly based on specialized ruthenium catalysts with sterically reduced N-heterocyclic carbene (NHC) ligands, which are able to accommodate large olefinic substrates during the catalytic steps. Yet, these complexes easily undergo intramolecular C–H activation at the <em>ortho</em> position of the <em>N</em>-aryl group of the NHC, which leads to their decomposition. Considering that this deleterious process requires the rotation of one of the NHC’s <em>N</em>-aryl arms, we introduced a second decker of aromatic groups into this ligand. Such steric blockade led to more stable and highly efficient catalysts for challenging metathesis reactions of sterically crowded olefins. The beneficial effect of these upper aromatic “wings” is rationalized through experimental determination of the stereoelectronic properties of the resulting NHC ligands, complemented by density functional theory (DFT) calculations on the nature of the through-space interactions between the “wings” and on the decomposition pathway of these complexes.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"6 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451520","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}
Pub Date : 2025-02-20DOI: 10.1016/j.checat.2025.101265
Liyuan Zhou, Liucheng Cao, Bao Yu Xia
As reported recently in Nature Synthesis, Sargent and co-workers have developed tandem electrocatalysts for CO2 reduction by combining planar Cu (which converts CO2 to CO) and dual-atomic-site catalysts (which produce hydrocarbons, such as ethylene and ethanol). This system achieves 46% ethanol Faradaic efficiency and 91% C2+ efficiency at 150 mA cm−2 under acidic conditions, advancing sustainable CO2 conversion.
{"title":"Dual atomic Cu sites enable CO2-to-C2+ conversion in strong acid","authors":"Liyuan Zhou, Liucheng Cao, Bao Yu Xia","doi":"10.1016/j.checat.2025.101265","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101265","url":null,"abstract":"As reported recently in <em>Nature Synthesis</em>, Sargent and co-workers have developed tandem electrocatalysts for CO<sub>2</sub> reduction by combining planar Cu (which converts CO<sub>2</sub> to CO) and dual-atomic-site catalysts (which produce hydrocarbons, such as ethylene and ethanol). This system achieves 46% ethanol Faradaic efficiency and 91% C<sub>2+</sub> efficiency at 150 mA cm<sup>−2</sup> under acidic conditions, advancing sustainable CO<sub>2</sub> conversion.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"31 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451521","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}
Pub Date : 2025-02-20DOI: 10.1016/j.checat.2025.101300
Tanja Junkers
In a recent Journal of the American Chemical Society article, Stache and co-workers developed a smart cobyrinate catalyst system that is able to mediate the atom-transfer radical polymerization of an acrylate with high efficiency to high conversions under red-light and near-infrared irradiation without the need for co-catalysts to keep the reaction proceeding.
{"title":"Red-light-induced reversible deactivation radical photopolymerizations mediated by a single catalyst","authors":"Tanja Junkers","doi":"10.1016/j.checat.2025.101300","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101300","url":null,"abstract":"In a recent <em>Journal of the American Chemical Society</em> article, Stache and co-workers developed a smart cobyrinate catalyst system that is able to mediate the atom-transfer radical polymerization of an acrylate with high efficiency to high conversions under red-light and near-infrared irradiation without the need for co-catalysts to keep the reaction proceeding.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"23 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451523","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}
This work presents a Cu single-atom catalyst (SAC)-catalyzed Sonogashira coupling reaction of lodine benzene and phenylacetylene to manufacture diphenylacetylene, with a satisfactory yield employing Cu single atoms on N-doped carbon (CN) supported on TiO2 (Cu1/CN/TiO2). Cu1/CN/TiO2 SACs with a low Cu loading (0.81 wt %) and a Cu-N2 structure achieved ultra-high conversion efficiency (99%) and yield for the Sonogashira coupling reaction, outperforming conventional heterogeneous and homogeneous Cu catalysts. Characterizations and density functional theory (DFT) calculations indicate that the presence of TiO2 not only alters the coordination environment of Cu to form the Cu-N2 coordination structure, with charge accumulation lowering the barrier for the adsorption and activation of the substrate, but also speeds the charge transfer from Cu1/CN to TiO2, which is advantageous for the oxidation addition steps in the reaction process, substantially boosting the Sonogashira coupling reaction. This work significantly broadens the scope of Cu SAC-catalyzed Sonogashira coupling processes.
{"title":"Low-coordinated single-atom Cu and enhanced charge transfer from Cu-N to TiO2 on Cu1/CN/TiO2 for efficient Sonogashira cross-coupling","authors":"Shuo Zhang, Chao Shang, Chen Li, Dianxing Lian, Shuo Wang, Xuemin Hu, Yongjun Ji, Erhong Duan","doi":"10.1016/j.checat.2025.101290","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101290","url":null,"abstract":"This work presents a Cu single-atom catalyst (SAC)-catalyzed Sonogashira coupling reaction of lodine benzene and phenylacetylene to manufacture diphenylacetylene, with a satisfactory yield employing Cu single atoms on N-doped carbon (CN) supported on TiO<sub>2</sub> (Cu<sub>1</sub>/CN/TiO<sub>2</sub>). Cu<sub>1</sub>/CN/TiO<sub>2</sub> SACs with a low Cu loading (0.81 wt %) and a Cu-N<sub>2</sub> structure achieved ultra-high conversion efficiency (99%) and yield for the Sonogashira coupling reaction, outperforming conventional heterogeneous and homogeneous Cu catalysts. Characterizations and density functional theory (DFT) calculations indicate that the presence of TiO<sub>2</sub> not only alters the coordination environment of Cu to form the Cu-N<sub>2</sub> coordination structure, with charge accumulation lowering the barrier for the adsorption and activation of the substrate, but also speeds the charge transfer from Cu<sub>1</sub>/CN to TiO<sub>2</sub>, which is advantageous for the oxidation addition steps in the reaction process, substantially boosting the Sonogashira coupling reaction. This work significantly broadens the scope of Cu SAC-catalyzed Sonogashira coupling processes.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"51 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451524","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}
Pub Date : 2025-02-20DOI: 10.1016/j.checat.2025.101291
Kai Wang, Chen Han, Shaomin Liu
In a recent issue of Nature Nanotechnology, Li and coworkers presented a tandem catalyst design, constructing an atomically intimate assembly with dual interfaces for ethanol production. This approach leverages the synergy of distinct interfaces tailored to specific reactions, ensuring seamless coordination for cascade processes and achieving high activity and selectivity.
{"title":"A tandem catalyst with dual interfaces for direct syngas conversion to ethanol","authors":"Kai Wang, Chen Han, Shaomin Liu","doi":"10.1016/j.checat.2025.101291","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101291","url":null,"abstract":"In a recent issue of <em>Nature Nanotechnology</em>, Li and coworkers presented a tandem catalyst design, constructing an atomically intimate assembly with dual interfaces for ethanol production. This approach leverages the synergy of distinct interfaces tailored to specific reactions, ensuring seamless coordination for cascade processes and achieving high activity and selectivity.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"85 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143451522","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}
Pub Date : 2025-02-14DOI: 10.1016/j.checat.2025.101266
Shiming Li, Lin Li, Wei Du, Tao Jiang, Ming Gong, Jianping Xiao
Glycine is an important amino acid for daily life, but its conventional synthesis often involves the use of toxic chemicals or catalysts. The electrochemical co-reduction of oxalic acid and nitric acid under mild conditions offers a greener alternative but is challenging over a single catalyst. Herein, we have realized this glycine electrosynthesis on a single low-cost and nontoxic rutile TiO2/CNT (CNT = carbon nanotube). The high glycine yield of 57% was made possible by the uniqueness of rutile TiO2 in the appropriate proton environment. Oxalic acid and nitric acid were competitively adsorbed on rutile TiO2 and selectively converted into glyoxylic acid and NH2OH at identical potentials. Further solution-phase C–N coupling and oxime reduction on rutile TiO2 produced glycine in high yields. Density functional theory calculations revealed that the appropriate Ti–Ti distance on the reduced rutile TiO2 fadvored the desorption of glyoxylic acid and NH2OH, as well as the stabilization of N-containing species at early-stage nitrate reduction.
{"title":"Glycine electrosynthesis by the co-reduction of oxalic and nitric acids on rutile TiO2","authors":"Shiming Li, Lin Li, Wei Du, Tao Jiang, Ming Gong, Jianping Xiao","doi":"10.1016/j.checat.2025.101266","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101266","url":null,"abstract":"Glycine is an important amino acid for daily life, but its conventional synthesis often involves the use of toxic chemicals or catalysts. The electrochemical co-reduction of oxalic acid and nitric acid under mild conditions offers a greener alternative but is challenging over a single catalyst. Herein, we have realized this glycine electrosynthesis on a single low-cost and nontoxic rutile TiO<sub>2</sub>/CNT (CNT = carbon nanotube). The high glycine yield of 57% was made possible by the uniqueness of rutile TiO<sub>2</sub> in the appropriate proton environment. Oxalic acid and nitric acid were competitively adsorbed on rutile TiO<sub>2</sub> and selectively converted into glyoxylic acid and NH<sub>2</sub>OH at identical potentials. Further solution-phase C–N coupling and oxime reduction on rutile TiO<sub>2</sub> produced glycine in high yields. Density functional theory calculations revealed that the appropriate Ti–Ti distance on the reduced rutile TiO<sub>2</sub> fadvored the desorption of glyoxylic acid and NH<sub>2</sub>OH, as well as the stabilization of N-containing species at early-stage nitrate reduction.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"183 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418446","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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