The reduction of aromatic compounds is a stalwart transformation in modern organic synthesis since it allows the generation of novel complex three-dimensional (3D) chemical entities from two-dimensional precursors (2D), linking readily available aromatic feedstocks with unobtainable alicyclic structures. However, controlling the high level of selectivity of N-heteroarenes (quinolines and pyridines), particularly substituents positioned on the reducible quinoline ring, is both intriguing and challenging, and methods for selective saturation of structurally complex derivatives (multiple aromatic rings) are rarely unaddressed and need further improvements. Also, many approaches suffer from scalability problems, high cost, and low availability of catalysts and tailor-made ligands. To address this issue, we herein report the first example of commercially available titanocene dichloride (Cp2TiCl2)-catalyzed chemoselective reduction of structurally diverse nitrogen-based heteroarenes with ammonia borane as a reducing agent (>100 examples). The developed protocol features the advantage of chemoselectivity and wide functional group tolerance of quinolines. Meanwhile, the efficient reduction of challenging and unprotected functionalized pyridines, as well as pyrazines, are also furnished with remarkable functional group preservation and also with an improved F(sp3) carbon fraction. Additionally, a few selected furans and benzofuran derivatives were successfully demonstrated under synthetically relevant conditions, and gram-scale synthesis was effectively executed. The methodology can be extended to the saturation of complex N-heteroarenes with conserved selectivity. In addition, density functional theory (DFT) calculations were carried out to shed light on the mechanistic insights into the reduction of quinoline.
{"title":"Dearomative selective reduction of structurally diverse N-heteroarenes enabled by a homogeneous titanium catalyst","authors":"Tarun Bhatt, Vadithya Suman, Mridula Choudhary, Saurabh Kumar Singh, Kishore Natte","doi":"10.1016/j.jcat.2025.115937","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115937","url":null,"abstract":"The reduction of aromatic compounds is a stalwart transformation in modern organic synthesis since it allows the generation of novel complex three-dimensional (3D) chemical entities from two-dimensional precursors (2D), linking readily available aromatic feedstocks with unobtainable alicyclic structures. However, controlling the high level of selectivity of <em>N</em>-heteroarenes (quinolines and pyridines), particularly substituents positioned on the reducible quinoline ring, is both intriguing and challenging, and methods for selective saturation of structurally complex derivatives (multiple aromatic rings) are rarely unaddressed and need further improvements. Also, many approaches suffer from scalability problems, high cost, and low availability of catalysts and tailor-made ligands. To address this issue, we herein report the first example of commercially available titanocene dichloride (Cp<sub>2</sub>TiCl<sub>2</sub>)-catalyzed chemoselective reduction of structurally diverse nitrogen-based heteroarenes with ammonia borane as a reducing agent (>100 examples). The developed protocol features the advantage of chemoselectivity and wide functional group tolerance of quinolines. Meanwhile, the efficient reduction of challenging and unprotected functionalized pyridines, as well as pyrazines, are also furnished with remarkable functional group preservation and also with an improved F(sp<sup>3</sup>) carbon fraction. Additionally, a few selected furans and benzofuran derivatives were successfully demonstrated under synthetically relevant conditions, and gram-scale synthesis was effectively executed. The methodology can be extended to the saturation of complex <em>N</em>-heteroarenes with conserved selectivity. In addition, density functional theory (DFT) calculations were carried out to shed light on the mechanistic insights into the reduction of quinoline.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"41 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924569","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 : 2025-01-02DOI: 10.1016/j.jcat.2024.115936
Ting C. Lin, Michelle A. Nolen, Carrie A. Farberow, Stephanie Kwon, Aditya Bhan
We ally steady-state kinetics, kinetic isotope effects, and density functional theory (DFT) calculations to illustrate that Cu-based catalysts remain saturated by H-adatoms (H*) and molecular formic acid (HCOOH**) during CO<sub>2</sub> hydrogenation. High H* coverage under methanol synthesis conditions is evidenced by reverse water–gas shift (RWGS) rates that exhibit positive H<sub>2</sub> reaction orders only at P<sub>H2</sub> <span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML"><mo is="true">≲</mo></math>' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="2.548ex" role="img" style="vertical-align: -0.697ex;" viewbox="0 -796.9 778.5 1096.9" width="1.808ex" xmlns:xlink="http://www.w3.org/1999/xlink"><g fill="currentColor" stroke="currentColor" stroke-width="0" transform="matrix(1 0 0 -1 0 0)"><g is="true"><use xlink:href="#MJAMS-2272"></use></g></g></svg><span role="presentation"><math xmlns="http://www.w3.org/1998/Math/MathML"><mo is="true">≲</mo></math></span></span><script type="math/mml"><math><mo is="true">≲</mo></math></script></span> 0.5 bar, above which methanol synthesis and RWGS rates exhibit first and zeroth order dependence on P<sub>H2</sub>, respectively. HCOOH** also accumulates on the surface with increasing P<sub>CO2</sub> as informed by the Langmuir-type dependence on P<sub>CO2</sub> (0.25–23 bar) for both methanol synthesis and RWGS. As both HCOOH** and H* have one H-atom per site occupied, the two species share the same P<sub>H2</sub> dependence and give rise to CO<sub>2</sub> reaction orders that are independent of P<sub>H2</sub>. Surface coverages determined based on kinetic analyses are further corroborated with DFT-derived adsorption energies that show favorable HCOOH** adsorbate–adsorbate interactions as well as repulsive interactions for bidentate formate (HCOO**) on H*-saturated surfaces. Methanol selectivity remains invariant with P<sub>CO2</sub> and P<sub>CO</sub> despite CO inhibiting reaction rates, thereby demonstrating the two reactions occur on the same active site. In contrast, water preferentially inhibits methanol synthesis rates, increases methanol synthesis H<sub>2</sub> reaction order from 1.0 to 1.5, and alters the H<sub>2</sub>/D<sub>2</sub> kinetic isotope effect for methanol synthesis; the inhibitory effect of H<sub>2</sub>O thus cannot be attributed to competitive adsorption alone but rather a change in the rate-determining step for methanol synthesis. The disparate kinetics of methanol synthesis and RWGS evince a branching pathway where methanol is formed from formates and CO is formed from carboxylates. The presented work thus identifies the relevant surface species, underscores the distinct catalytic role of water in branching methanol synthesis and RWGS pathways, and, in doing so, details a mechanistic picture that yields pr
{"title":"Mechanistic and kinetic relevance of hydrogen and water in CO2 hydrogenation on Cu-based catalysts","authors":"Ting C. Lin, Michelle A. Nolen, Carrie A. Farberow, Stephanie Kwon, Aditya Bhan","doi":"10.1016/j.jcat.2024.115936","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115936","url":null,"abstract":"We ally steady-state kinetics, kinetic isotope effects, and density functional theory (DFT) calculations to illustrate that Cu-based catalysts remain saturated by H-adatoms (H*) and molecular formic acid (HCOOH**) during CO<sub>2</sub> hydrogenation. High H* coverage under methanol synthesis conditions is evidenced by reverse water–gas shift (RWGS) rates that exhibit positive H<sub>2</sub> reaction orders only at P<sub>H2</sub> <span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mo is=\"true\">&#x2272;</mo></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.548ex\" role=\"img\" style=\"vertical-align: -0.697ex;\" viewbox=\"0 -796.9 778.5 1096.9\" width=\"1.808ex\" xmlns:xlink=\"http://www.w3.org/1999/xlink\"><g fill=\"currentColor\" stroke=\"currentColor\" stroke-width=\"0\" transform=\"matrix(1 0 0 -1 0 0)\"><g is=\"true\"><use xlink:href=\"#MJAMS-2272\"></use></g></g></svg><span role=\"presentation\"><math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mo is=\"true\">≲</mo></math></span></span><script type=\"math/mml\"><math><mo is=\"true\">≲</mo></math></script></span> 0.5 bar, above which methanol synthesis and RWGS rates exhibit first and zeroth order dependence on P<sub>H2</sub>, respectively. HCOOH** also accumulates on the surface with increasing P<sub>CO2</sub> as informed by the Langmuir-type dependence on P<sub>CO2</sub> (0.25–23 bar) for both methanol synthesis and RWGS. As both HCOOH** and H* have one H-atom per site occupied, the two species share the same P<sub>H2</sub> dependence and give rise to CO<sub>2</sub> reaction orders that are independent of P<sub>H2</sub>. Surface coverages determined based on kinetic analyses are further corroborated with DFT-derived adsorption energies that show favorable HCOOH** adsorbate–adsorbate interactions as well as repulsive interactions for bidentate formate (HCOO**) on H*-saturated surfaces. Methanol selectivity remains invariant with P<sub>CO2</sub> and P<sub>CO</sub> despite CO inhibiting reaction rates, thereby demonstrating the two reactions occur on the same active site. In contrast, water preferentially inhibits methanol synthesis rates, increases methanol synthesis H<sub>2</sub> reaction order from 1.0 to 1.5, and alters the H<sub>2</sub>/D<sub>2</sub> kinetic isotope effect for methanol synthesis; the inhibitory effect of H<sub>2</sub>O thus cannot be attributed to competitive adsorption alone but rather a change in the rate-determining step for methanol synthesis. The disparate kinetics of methanol synthesis and RWGS evince a branching pathway where methanol is formed from formates and CO is formed from carboxylates. The presented work thus identifies the relevant surface species, underscores the distinct catalytic role of water in branching methanol synthesis and RWGS pathways, and, in doing so, details a mechanistic picture that yields pr","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"20 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917820","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 : 2025-01-02DOI: 10.1016/j.jcat.2024.115935
Qiangwei Li, Le-Cheng Wang, Xiao-Feng Wu
β-Aminoketones are widely employed skeletons that are broadly found in pharmaceuticals, modern materials, and bioactive molecules. Herein, we present a radical relay carbonylation access to β-aminoketones from bench-stable bifunctional reagents and styrenes through energy transfer photocatalysis with readily available carbon monoxide as a C1 source. This mild protocol is highly chemo- and regioselective, both acyl group and amine functionalities were installed into styrenes in a single-step.
{"title":"Photo-Promoted carbonylative Difunctionalization of alkenes toward β-Aminoketones","authors":"Qiangwei Li, Le-Cheng Wang, Xiao-Feng Wu","doi":"10.1016/j.jcat.2024.115935","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115935","url":null,"abstract":"β-Aminoketones are widely employed skeletons that are broadly found in pharmaceuticals, modern materials, and bioactive molecules. Herein, we present a radical relay carbonylation access to β-aminoketones from bench-stable bifunctional reagents and styrenes through energy transfer photocatalysis with readily available carbon monoxide as a C1 source. This mild protocol is highly chemo- and regioselective, both acyl group and amine functionalities were installed into styrenes in a single-step.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"160 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917795","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}
The GaZrOx solid solution has been recently employed in OX-ZEO bifunctional catalysts for efficient conversion of syngas to light olefins, but it remains challenging to identify the specific contributions of Zr and Ga and to understand the detailed reaction mechanisms due to the structural complexity. To address this complexity and elucidate the active sites over the Zr-Ga oxide system, this study presents a catalyst designed by physical mixing ZrO2 with different crystalline phases (m-ZrO2 & t-ZrO2) and α-Ga2O3. The physical mixture of m-ZrO2 and α-Ga2O3 achieves a high CO conversion of 39.1 %, with light olefins selectivity of 87.3% among hydrocarbons after combined with SAPO-34, surpassing the performance of physical mixture of t-ZrO2 and/or α-Ga2O3 with SAPO-34. Combining the various characterizations and DFT calculations, we have confirmed that m-ZrO2 site, enriched with oxygen vacancies and surface hydroxyl groups, is essential for CO adsorption and HCOO* intermediate formation, while the α-Ga2O3 site plays a key role in the dissociation of H2. Furthermore, the electron transfer from m-ZrO2 to α-Ga2O3 in their mixture is more efficient than in a physically mixed t-ZrO2 and α-Ga2O3. This accelerates the H2 dissociation and boosts the spillover of hydrogen from α-Ga2O3 to m-ZrO2, leading to the formation of more CH3O* intermediates and higher light olefins yield when combined with SAPO-34.
{"title":"Synergy induced by physical mixing m-ZrO2 and α-Ga2O3 for effective conversion of syngas to light olefins","authors":"Peng Zhang, Fangfang Li, Xuefang Yao, Pengze Zhang, Yukai Wu, Mengmeng Xi, Fanhui Meng, Lihua Kang, Mingyuan Zhu","doi":"10.1016/j.jcat.2024.115934","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115934","url":null,"abstract":"The GaZrO<em><sub>x</sub></em> solid solution has been recently employed in OX-ZEO bifunctional catalysts for efficient conversion of syngas to light olefins, but it remains challenging to identify the specific contributions of Zr and Ga and to understand the detailed reaction mechanisms due to the structural complexity. To address this complexity and elucidate the active sites over the Zr-Ga oxide system, this study presents a catalyst designed by physical mixing ZrO<sub>2</sub> with different crystalline phases (<em>m</em>-ZrO<sub>2</sub> & <em>t</em>-ZrO<sub>2</sub>) and <em>α</em>-Ga<sub>2</sub>O<sub>3</sub>. The physical mixture of <em>m</em>-ZrO<sub>2</sub> and <em>α</em>-Ga<sub>2</sub>O<sub>3</sub> achieves a high CO conversion of 39.1 %, with light olefins selectivity of 87.3% among hydrocarbons after combined with SAPO-34, surpassing the performance of physical mixture of <em>t</em>-ZrO<sub>2</sub> and/or <em>α</em>-Ga<sub>2</sub>O<sub>3</sub> with SAPO-34. Combining the various characterizations and DFT calculations, we have confirmed that <em>m</em>-ZrO<sub>2</sub> site, enriched with oxygen vacancies and surface hydroxyl groups, is essential for CO adsorption and HCOO* intermediate formation, while the <em>α</em>-Ga<sub>2</sub>O<sub>3</sub> site plays a key role in the dissociation of H<sub>2</sub>. Furthermore, the electron transfer from <em>m</em>-ZrO<sub>2</sub> to <em>α</em>-Ga<sub>2</sub>O<sub>3</sub> in their mixture is more efficient than in a physically mixed <em>t</em>-ZrO<sub>2</sub> and <em>α</em>-Ga<sub>2</sub>O<sub>3</sub>. This accelerates the H<sub>2</sub> dissociation and boosts the spillover of hydrogen from <em>α</em>-Ga<sub>2</sub>O<sub>3</sub> to <em>m</em>-ZrO<sub>2</sub>, leading to the formation of more CH<sub>3</sub>O* intermediates and higher light olefins yield when combined with SAPO-34.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"162 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142901947","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 : 2024-12-28DOI: 10.1016/j.jcat.2024.115933
Ren-Guan Miao, Yuanrui Wang, Xiao-Feng Wu
Phosphorus-containing compounds represent a class of chemicals of great significance. Therefore, it is of high value to develop efficient C-P bond formation methods. However, the activity of phosphoryl radicals results in the facile formation of hydrophosphination products when difunctionalized carbonylation was performed with the addition of alkenes. In this study, we presented a visible light-promoted phosphorylation carbonylation reaction of unactivated alkenes. Both visible light catalyst and oxidant-promoted generating phosphoryl radical from diarylphosphine oxide, which subsequently adding to unactivated alkenes and followed by intramolecular migration in the presence of carbon monoxide to yield the targeted phosphorus-containing carbonyl compounds.
{"title":"Visible-light-promoted phosphorylation carbonylation of unactivated alkenes","authors":"Ren-Guan Miao, Yuanrui Wang, Xiao-Feng Wu","doi":"10.1016/j.jcat.2024.115933","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115933","url":null,"abstract":"Phosphorus-containing compounds represent a class of chemicals of great significance. Therefore, it is of high value to develop efficient C-P bond formation methods. However, the activity of phosphoryl radicals results in the facile formation of hydrophosphination products when difunctionalized carbonylation was performed with the addition of alkenes. In this study, we presented a visible light-promoted phosphorylation carbonylation reaction of unactivated alkenes. Both visible light catalyst and oxidant-promoted generating phosphoryl radical from diarylphosphine oxide, which subsequently adding to unactivated alkenes and followed by intramolecular migration in the presence of carbon monoxide to yield the targeted phosphorus-containing carbonyl compounds.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"2 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888893","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 : 2024-12-27DOI: 10.1016/j.jcat.2024.115930
Wentao Du, Patchanee Chammingkwan, Keisuke Takahashi, Toshiaki Taniike
Traditional solid catalyst design is a highly labor-intensive and post hoc process, involving repeated experimental trials and errors based on hypotheses derived from prior knowledge. Recently, integrating high-throughput experimentation (HTE) with machine learning (ML) aims to achieve a more systematic catalyst design without relying on specific knowledge or assumptions about the target catalysis. As a first step, this study constructs an unbiased HTE dataset for dry reforming of methane (DRM) at 500 °C on 256 γ-Al2O3-supported multi-element catalysts, prepared by randomly combining 17 elements selected from the periodic table without any preconceptions. The obtained data and selected catalysts are analyzed in various ways to gain insights into catalyst design and catalysis. It is found that the inclusion of Ni or platinum group elements does not necessarily lead to DRM activity; rather, careful combinations of elements are crucial. Specifically, catalysts that exhibit the highest activities are not only based on Ni as the main active element but also frequently contain Li, Al, and Nb, with Al and Nb being elements that are seldom recognized as promoters in literature. Experimental validation of predictive ML models demonstrated that these frequent patterns were practically applicable for designing other high-performance catalysts. Studying the best-found Ni-based catalyst elucidates individual elements’ roles in improving activity and suppressing carbon deposition. In particular, the ternary combination of Al, Nb, and Hf reduces carbon deposition while enhancing activity. Overall, this study demonstrates the validity of unbiased exploration in providing a foundational dataset for ML and in discovering catalyst design guidelines.
{"title":"Unbiased dataset for methane dry reforming and catalyst design guidelines obtained by high-throughput experimentation and machine learning","authors":"Wentao Du, Patchanee Chammingkwan, Keisuke Takahashi, Toshiaki Taniike","doi":"10.1016/j.jcat.2024.115930","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115930","url":null,"abstract":"Traditional solid catalyst design is a highly labor-intensive and post hoc process, involving repeated experimental trials and errors based on hypotheses derived from prior knowledge. Recently, integrating high-throughput experimentation (HTE) with machine learning (ML) aims to achieve a more systematic catalyst design without relying on specific knowledge or assumptions about the target catalysis. As a first step, this study constructs an unbiased HTE dataset for dry reforming of methane (DRM) at 500 °C on 256 γ-Al<sub>2</sub>O<sub>3</sub>-supported multi-element catalysts, prepared by randomly combining 17 elements selected from the periodic table without any preconceptions. The obtained data and selected catalysts are analyzed in various ways to gain insights into catalyst design and catalysis. It is found that the inclusion of Ni or platinum group elements does not necessarily lead to DRM activity; rather, careful combinations of elements are crucial. Specifically, catalysts that exhibit the highest activities are not only based on Ni as the main active element but also frequently contain Li, Al, and Nb, with Al and Nb being elements that are seldom recognized as promoters in literature. Experimental validation of predictive ML models demonstrated that these frequent patterns were practically applicable for designing other high-performance catalysts. Studying the best-found Ni-based catalyst elucidates individual elements’ roles in improving activity and suppressing carbon deposition. In particular, the ternary combination of Al, Nb, and Hf reduces carbon deposition while enhancing activity. Overall, this study demonstrates the validity of unbiased exploration in providing a foundational dataset for ML and in discovering catalyst design guidelines.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"92 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888901","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 : 2024-12-26DOI: 10.1016/j.jcat.2024.115931
Zhi-Peng Tao, Chen-Ning Li, Lin Liu, Kechao Wang, Yun Jeong Hwang, Daqiang Yuan, Zheng-Bo Han
The regulation of active oxygen species (ROS) is a key step in the photocatalytic oxidation process, while the effect of catalyst surface structure on this process has rarely been explored. Herein, we modulate the catalyst surface structure by exposing different crystal facets and disclosing facet-dependent ROS generation mechanism over NH2-MIL-125(Ti). Under light irradiation, {110} facet exposed titanium clusters and {001} facet exposed ligands enrich photogenerated electrons and holes, respectively, while {111} facet exposed titanium clusters and ligands contain both. Accordingly, the {001}, {110} and {111} facet generate distinct ROS of •OH, O2•− and 1O2 through different pathways, respectively. Taking photocatalytic benzylamines oxidation as the model reaction, the O2•− and 1O2 produced on the {110} and {111} facets favor the oxidation benzylamine, while the •OH produced on the {001} facet exhibits catalytic inertia. The present work discloses a facet-dependent ROS generation mechanism and provides a new horizon to the design of photocatalytic systems.
{"title":"Facet-dependent reactive oxygen species generation regulates photocatalytic oxidation of benzylamines","authors":"Zhi-Peng Tao, Chen-Ning Li, Lin Liu, Kechao Wang, Yun Jeong Hwang, Daqiang Yuan, Zheng-Bo Han","doi":"10.1016/j.jcat.2024.115931","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115931","url":null,"abstract":"The regulation of active oxygen species (ROS) is a key step in the photocatalytic oxidation process, while the effect of catalyst surface structure on this process has rarely been explored. Herein, we modulate the catalyst surface structure by exposing different crystal facets and disclosing facet-dependent ROS generation mechanism over NH<sub>2</sub>-MIL-125(Ti). Under light irradiation, {110} facet exposed titanium clusters and {001} facet exposed ligands enrich photogenerated electrons and holes, respectively, while {111} facet exposed titanium clusters and ligands contain both. Accordingly, the {001}, {110} and {111} facet generate distinct ROS of •OH, O<sub>2</sub><sup>•−</sup> and <sup>1</sup>O<sub>2</sub> through different pathways, respectively. Taking photocatalytic benzylamines oxidation as the model reaction, the O<sub>2</sub><sup>•−</sup> and <sup>1</sup>O<sub>2</sub> produced on the {110} and {111} facets favor the oxidation benzylamine, while the •OH produced on the {001} facet exhibits catalytic inertia. The present work discloses a facet-dependent ROS generation mechanism and provides a new horizon to the design of photocatalytic systems.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"335 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888902","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 : 2024-12-26DOI: 10.1016/j.jcat.2024.115932
Chun-Xian Cai, Zi-Wen Zhou, Chun-Xiu Liu, Yun-Jie Wei, Xiao-Qi Yu, Li-Hong Zhou, Na Wang
Photo-enzyme catalysis featuring sustainability and selectivity is attractive, but remains challenges from efficiency and enzyme inactivation. This work provides a compatible and efficient photocatalyst-enzyme hybrid system for chiral alcohol synthesis. A covalent organic framework (COF) possessing broad visible light absorption edge to 554 nm was used for photocatalytic NADPH regeneration, achieving 82 % yield in 90 min. Then the influence of photocatalysis on coupled enzyme LbADH was unveiled by fluorescence spectra and circular dichroism. Further a facile and mild strategy of entrapping LbADH into Ca2+/Mn2+ doped alginate gel was carried out. Impressively, enzyme immobilized strategy not only enhances 3.2 times activity, but also protects LbADH from diverse harsh environments, thereby improving photo-enzyme catalytic yield from 26 % to 82 %. To our delight, this one-pot photo-enzyme catalytic system achieves highly yield (up to 99 %) with excellent enantioselectivity (90–99 ee%) for various chiral alcohols, and fulfills semipreparative scale preparation of (R)-1-[3,5-Bis(trifluoromethyl)phenyl] ethanol, prochiral intermediate of Aprepitant. This work sheds light on the new synthetic route of chiral compounds and development of photo-enzyme catalytic field.
{"title":"Development of compatible photocatalyst-enzyme hybrid system via Intensifying enzyme tolerance for enhanced chiral alcohol synthesis","authors":"Chun-Xian Cai, Zi-Wen Zhou, Chun-Xiu Liu, Yun-Jie Wei, Xiao-Qi Yu, Li-Hong Zhou, Na Wang","doi":"10.1016/j.jcat.2024.115932","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115932","url":null,"abstract":"Photo-enzyme catalysis featuring sustainability and selectivity is attractive, but remains challenges from efficiency and enzyme inactivation. This work provides a compatible and efficient photocatalyst-enzyme hybrid system for chiral alcohol synthesis. A covalent organic framework (COF) possessing broad visible light absorption edge to 554 nm was used for photocatalytic NADPH regeneration, achieving 82 % yield in 90 min. Then the influence of photocatalysis on coupled enzyme <em>Lb</em>ADH was unveiled by fluorescence spectra and circular dichroism. Further a facile and mild strategy of entrapping <em>Lb</em>ADH into Ca<sup>2+</sup>/Mn<sup>2+</sup> doped alginate gel was carried out. Impressively, enzyme immobilized strategy not only enhances 3.2 times activity, but also protects <em>Lb</em>ADH from diverse harsh environments, thereby improving photo-enzyme catalytic yield from 26 % to 82 %. To our delight, this one-pot photo-enzyme catalytic system achieves highly yield (up to 99 %) with excellent enantioselectivity (90–99 <em>ee</em>%) for various chiral alcohols, and fulfills semipreparative scale preparation of (<em>R</em>)-1-[3,5-Bis(trifluoromethyl)phenyl] ethanol, prochiral intermediate of Aprepitant. This work sheds light on the new synthetic route of chiral compounds and development of photo-enzyme catalytic field.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"114 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888894","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 : 2024-12-25DOI: 10.1016/j.jcat.2024.115928
Fanhao Kong, Hongru Zhou, Zhiwei Chen, Zhaolin Dou, Min Ji, Min Wang
Producing CO and H2 from renewable biomass represents a sustainable way, but is challenged to be rapidly produced with high yield at ambient condition. Herein, we report a stepwise electro-photocatalytic process for decomposition of biomass to produce CO and H2 that biomass carbohydrates are first electrocatalytic reformed to formic acid and H2, then the as-obtained formic acid electrolyte is directly dehydrated to CO via photocatalysis. MnO2 was prepared as the anode for the electrocatalytic oxidation, achieving up to 88 % yield of formic acid from sugars and polyols with a volcanic peak tendency. The hydroxyl radicals generated by water oxidation enable the oxidation of biomass to formic acid. The CdS nanorod shows the highest photocatalytic formic acid dehydration activity with CO yield of 70 %. The molecular formic acid instead of the dissociated formate is actively dehydrated to CO over CdS, and the C − H dissociation is a key initial step. Furthermore, one gram of primary biomass switchgrass is converted by stepwise processes with bringing out 7.7 m mol of CO and 14.7 m mol of H2 in the gas, 0.3 g of lignin solid. And the CO carbon yield is 31.5 %. This study provides a strategy to reform biomass to produce CO together with H2 under ambient conditions.
{"title":"Stepwise electro-photocatalytic decomposition of biomass to CO and H2 in acidic media","authors":"Fanhao Kong, Hongru Zhou, Zhiwei Chen, Zhaolin Dou, Min Ji, Min Wang","doi":"10.1016/j.jcat.2024.115928","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115928","url":null,"abstract":"Producing CO and H<sub>2</sub> from renewable biomass represents a sustainable way, but is challenged to be rapidly produced with high yield at ambient condition. Herein, we report a stepwise electro-photocatalytic process for decomposition of biomass to produce CO and H<sub>2</sub> that biomass carbohydrates are first electrocatalytic reformed to formic acid and H<sub>2</sub>, then the as-obtained formic acid electrolyte is directly dehydrated to CO via photocatalysis. MnO<sub>2</sub> was prepared as the anode for the electrocatalytic oxidation, achieving up to 88 % yield of formic acid from sugars and polyols with a volcanic peak tendency. The hydroxyl radicals generated by water oxidation enable the oxidation of biomass to formic acid. The CdS nanorod shows the highest photocatalytic formic acid dehydration activity with CO yield of 70 %. The molecular formic acid instead of the dissociated formate is actively dehydrated to CO over CdS, and the C − H dissociation is a key initial step. Furthermore, one gram of primary biomass switchgrass is converted by stepwise processes with bringing out 7.7 m mol of CO and 14.7 m mol of H<sub>2</sub> in the gas, 0.3 g of lignin solid. And the CO carbon yield is 31.5 %. This study provides a strategy to reform biomass to produce CO together with H<sub>2</sub> under ambient conditions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"2 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884506","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}
Bacterial infections pose a severe threat to human health and the living environment. Photodynamic antimicrobial strategies have attracted attention since they are not affected by the development of drug resistance by the organisms. Cuprous oxide (Cu2O) is a promising material for application in the photocatalytic antimicrobial field due to its excellent photo responsiveness. However, the fast recombination of photogenerated carriers and poor stability limit the application of Cu2O. This paper uses the advantages of the exceptional strength of copper oxide (CuO) and the photocatalytic potential of tungsten trioxide (WO3) to design a photocatalytic antimicrobial WO3/CuxO composite agent. The structure of the composite material reveals that CuO particles and WO3 nanosheets are grown in-situ on octahedral Cu2O crystals, with the outermost layer primarily consisting of WO3. Simultaneously, the ternary composite structure utilizes interfacial interactions to regulate the electronic structure, which acts as the conduit for electron transfer. The killing effect of WO3/CuxO on Escherichia coli (E. coli) after visible-light irradiation reaches 100.00%, which is 2.57 times higher than that of Cu2O and 34 times higher than that of WO3. The outstanding antimicrobial ability is attributed to the constructed stepped double Z-type heterojunction structure, which realizes multi-channel transfer of carriers and retains the carriers with superior redox capacity, increasing the quantum yield of reactive oxygen species (ROS). The ROS generated by photoexcitation of WO3/CuxO is the main reason for the superior antibacterial performance. The detection results indicate that ROS oxidizes the bacterial physiological structure, resulting in noticeable depressions, wrinkles, and ruptures in Escherichia coli. Meanwhile, during the mixing and collision process between bacteria and the material, metal ions can denature protein structures, and the bacterial cell surface can be punctured or even torn. These factors collectively affect bacterial activity. This work provides effective ways and methods for designing efficient antimicrobial agents.
{"title":"Enhanced photodynamic antimicrobial performance of WO3/CuxO double Z-type heterojunction using carrier multichannel conversion","authors":"Kangfu Wang, Meiru Lv, Tian Zhou, Zehuan Zhang, Xingkun Liang, Huaying Liu, Huan Li, Xiaoning Tang","doi":"10.1016/j.jcat.2024.115924","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115924","url":null,"abstract":"Bacterial infections pose a severe threat to human health and the living environment. Photodynamic antimicrobial strategies have attracted attention since they are not affected by the development of drug resistance by the organisms. Cuprous oxide (Cu<sub>2</sub>O) is a promising material for application in the photocatalytic antimicrobial field due to its excellent photo responsiveness. However, the fast recombination of photogenerated carriers and poor stability limit the application of Cu<sub>2</sub>O. This paper uses the advantages of the exceptional strength of copper oxide (CuO) and the photocatalytic potential of tungsten trioxide (WO<sub>3</sub>) to design a photocatalytic antimicrobial WO<sub>3</sub>/Cu<sub>x</sub>O composite agent. The structure of the composite material reveals that CuO particles and WO<sub>3</sub> nanosheets are grown in-situ on octahedral Cu<sub>2</sub>O crystals, with the outermost layer primarily consisting of WO<sub>3</sub>. Simultaneously, the ternary composite structure utilizes interfacial interactions to regulate the electronic structure, which acts as the conduit for electron transfer. The killing effect of WO<sub>3</sub>/Cu<sub>x</sub>O on <em>Escherichia coli</em> (<em>E. coli</em>) after visible-light irradiation reaches 100.00%, which is 2.57 times higher than that of Cu<sub>2</sub>O and 34 times higher than that of WO<sub>3</sub>. The outstanding antimicrobial ability is attributed to the constructed stepped double Z-type heterojunction structure, which realizes multi-channel transfer of carriers and retains the carriers with superior redox capacity, increasing the quantum yield of reactive oxygen species (ROS). The ROS generated by photoexcitation of WO<sub>3</sub>/Cu<sub>x</sub>O is the main reason for the superior antibacterial performance. The detection results indicate that ROS oxidizes the bacterial physiological structure, resulting in noticeable depressions, wrinkles, and ruptures in Escherichia coli. Meanwhile, during the mixing and collision process between bacteria and the material, metal ions can denature protein structures, and the bacterial cell surface can be punctured or even torn. These factors collectively affect bacterial activity. This work provides effective ways and methods for designing efficient antimicrobial agents.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"113 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884535","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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