Designing new inorganic antimony(III) contained polyoxometalates for the oxidation of benzyl alcohol to benzaldehyde is of great significance. Two cases of Sb-bridged polyoxotungstate [H2N(CH3)2]10H2[(As2W19O67(H2O)(SbO)2]·13H2O (Sb − 1) and [H2N(CH3)2]14H4{[(As2W19O67(H2O)(SbO)2][P2W18O62]}·12H2O (Sb − 2), were synthesized by conventional aqueous method. Interestingly, the polyanion of [(As2W19O67(H2O)(SbO)2]12− consists of a [As2W19O67(H2O)]14− subunit with double {SbO} groups inserted in the vacant sites of it. Sb − 1 and Sb − 2 were applied in the thermal catalytic oxidation of benzyl alcohol to benzaldehyde with H2O2 as oxidant and displayed excellent catalytic performance with high conversion of 94.3 % and 99.6 % and selectivity of 91.5 % and 96.3 %, respectively. Notably, they exhibited advantages of high activity and selectivity, environmental friendliness and easy recycling in catalysis. Moreover, a reaction mechanism was proposed, which was further verified by free radical quenching experiments and EPR capture experiments, indicating that they can effectively activate H2O2 to produce active species 1O2 for selectively oxidation of benzyl alcohol to benzaldehyde.
{"title":"Designing Sb − bridged polyoxotungstates for efficiently catalytic oxidation of benzyl alcohol","authors":"Miao Zhang, Lihua Liu, Yizhen Song, Mengmeng Hou, Pengtao Ma, Qiuxia Han","doi":"10.1016/j.jcat.2025.115957","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115957","url":null,"abstract":"Designing new inorganic antimony(III) contained polyoxometalates for the oxidation of benzyl alcohol to benzaldehyde is of great significance. Two cases of Sb-bridged polyoxotungstate [H<sub>2</sub>N(CH<sub>3</sub>)<sub>2</sub>]<sub>10</sub>H<sub>2</sub>[(As<sub>2</sub>W<sub>19</sub>O<sub>67</sub>(H<sub>2</sub>O)(SbO)<sub>2</sub>]·13H<sub>2</sub>O (<strong>Sb − 1</strong>) and [H<sub>2</sub>N(CH<sub>3</sub>)<sub>2</sub>]<sub>14</sub>H<sub>4</sub>{[(As<sub>2</sub>W<sub>19</sub>O<sub>67</sub>(H<sub>2</sub>O)(SbO)<sub>2</sub>][P<sub>2</sub>W<sub>18</sub>O<sub>62</sub>]}·12H<sub>2</sub>O (<strong>Sb − 2</strong>), were synthesized by conventional aqueous method. Interestingly, the polyanion of [(As<sub>2</sub>W<sub>19</sub>O<sub>67</sub>(H<sub>2</sub>O)(SbO)<sub>2</sub>]<sup>12−</sup> consists of a [As<sub>2</sub>W<sub>19</sub>O<sub>67</sub>(H<sub>2</sub>O)]<sup>14−</sup> subunit with double {SbO} groups inserted in the vacant sites of it. <strong>Sb − 1</strong> and <strong>Sb − 2</strong> were applied in the thermal catalytic oxidation of benzyl alcohol to benzaldehyde with H<sub>2</sub>O<sub>2</sub> as oxidant and displayed excellent catalytic performance with high conversion of 94.3 % and 99.6 % and selectivity of 91.5 % and 96.3 %, respectively. Notably, they exhibited advantages of high activity and selectivity, environmental friendliness and easy recycling in catalysis. Moreover, a reaction mechanism was proposed, which was further verified by free radical quenching experiments and EPR capture experiments, indicating that they can effectively activate H<sub>2</sub>O<sub>2</sub> to produce active species <sup>1</sup>O<sub>2</sub> for selectively oxidation of benzyl alcohol to benzaldehyde.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"20 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940559","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 : 2025-01-09DOI: 10.1016/j.jcat.2025.115955
Fábio G. Delolo, Jesus A. Avendaño-Villarreal, Maíra dos Santos Costa, Eduardo N. dos Santos, Elena V. Gusevskaya
The chemical modification of naturally occurring compounds, e.g., terpenes, opens a path to new products potentially useful for the flavor & fragrance industry. Hydroformylation allows the introduction of the olfactorily relevant formyl group in a C–C double-bound, but its direct application to these substrates often is not straightforward because of the steric hinderance of the olefin moieties. In this work, we developed an efficient two-step one-pot protocol involving a Johnson-Claisen rearrangement followed by hydroformylation, which allowed transforming natural products containing an allyl alcohol moiety (linalool, nerol, cinnamyl alcohol, myrtenol, perillyl alcohol, and carveol) into derivatives containing an aldehyde and an ester functional group, both related to desirable olfactive properties in fragrances.
{"title":"Two-step one-pot Johnson-Claisen rearrangement/hydroformylation of renewable feedstocks","authors":"Fábio G. Delolo, Jesus A. Avendaño-Villarreal, Maíra dos Santos Costa, Eduardo N. dos Santos, Elena V. Gusevskaya","doi":"10.1016/j.jcat.2025.115955","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115955","url":null,"abstract":"The chemical modification of naturally occurring compounds, e.g., terpenes, opens a path to new products potentially useful for the flavor & fragrance industry. Hydroformylation allows the introduction of the olfactorily relevant formyl group in a C–C double-bound, but its direct application to these substrates often is not straightforward because of the steric hinderance of the olefin moieties. In this work, we developed an efficient two-step one-pot protocol involving a Johnson-Claisen rearrangement followed by hydroformylation, which allowed transforming natural products containing an allyl alcohol moiety (linalool, nerol, cinnamyl alcohol, myrtenol, perillyl alcohol, and carveol) into derivatives containing an aldehyde and an ester functional group, both related to desirable olfactive properties in fragrances.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"13 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940579","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}
Cycobutanecarboxylates are widely present in bioactive molecules and hold important application value. However, due to the significant strain energy associated with four-membered ring, their direct synthesis poses considerable challenges. Cyclobutanol, a readily synthesized four-membered ring compound, is a direct precursor for synthesizing cyclobutane derivatives. Nonetheless, traditional oxidative esterification between different alcohols leads to the ring-opening of cyclobutanol, resulting in the loss of the cyclobutane motif. Herein, we report a palladium-catalyzed selective alkoxycarbonylation between cyclobutanols and alcohols that directly produces cyclobutanecarboxylates while retaining the cyclobutane framework. This approach demonstrates excellent function group compatibility, enabling the successful conversion of primary, secondary, and tertiary alcohols, and phenols, and delivers the desired esters with outstanding selectivity.
{"title":"Palladium-catalyzed selective alkoxycarbonylation of different alcohols toward the direct synthesis of cyclobutanecarboxylates","authors":"Yu-Kun Liu, Xing-Wei Gu, Yan-Hua Zhao, Xiao-Feng Wu","doi":"10.1016/j.jcat.2025.115956","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115956","url":null,"abstract":"Cycobutanecarboxylates are widely present in bioactive molecules and hold important application value. However, due to the significant strain energy associated with four-membered ring, their direct synthesis poses considerable challenges. Cyclobutanol, a readily synthesized four-membered ring compound, is a direct precursor for synthesizing cyclobutane derivatives. Nonetheless, traditional oxidative esterification between different alcohols leads to the ring-opening of cyclobutanol, resulting in the loss of the cyclobutane motif. Herein, we report a palladium-catalyzed selective alkoxycarbonylation between cyclobutanols and alcohols that directly produces cyclobutanecarboxylates while retaining the cyclobutane framework. This approach demonstrates excellent function group compatibility, enabling the successful conversion of primary, secondary, and tertiary alcohols, and phenols, and delivers the desired esters with outstanding selectivity.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"71 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940580","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 : 2025-01-08DOI: 10.1016/j.jcat.2025.115946
Mónica Martínez-Aguirre, Janira Herce, Elena Serrano, Javier García-Martínez, Miguel A. Rodríguez, Jesús R. Berenguer
Visible light photocatalysis represents a powerful approach to advancing the principles of green chemistry. Consequently, there is considerable research interest in the development of novel photocatalysts that are not only highly active but also readily reusable. To this end, we report here the synthesis of a novel luminescent organometallo-ionosilica obtained by sol–gel reactions. This material consists of discrete nanoparticles composed entirely of cationic cyclometallated iridium(III) fragments and their corresponding PF6- counterions. This organometallo-ionosilica has been extensively tested as a photocatalyst under heterogeneous conditions in both reductive and oxidative single electron transfer deactivation reactions, achieving reaction yields of around 90% and retaining up to 80% of its efficiency after seven consecutive reuse cycles. These results demonstrate the potential of our self-condensation strategy to heterogenize photoactive complexes, while retaining their catalytic activity and showing excellent reusability.
{"title":"Self-condensed organometallo Ir(III) ionosilica for sustainable visible-light promoted electron-transfer photocatalysis","authors":"Mónica Martínez-Aguirre, Janira Herce, Elena Serrano, Javier García-Martínez, Miguel A. Rodríguez, Jesús R. Berenguer","doi":"10.1016/j.jcat.2025.115946","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115946","url":null,"abstract":"Visible light photocatalysis represents a powerful approach to advancing the principles of green chemistry. Consequently, there is considerable research interest in the development of novel photocatalysts that are not only highly active but also readily reusable. To this end, we report here the synthesis of a novel luminescent organometallo-ionosilica obtained by sol–gel reactions. This material consists of discrete nanoparticles composed entirely of cationic cyclometallated iridium(III) fragments and their corresponding PF<sub>6</sub><sup>-</sup> counterions. This organometallo-ionosilica has been extensively tested as a photocatalyst under heterogeneous conditions in both reductive and oxidative single electron transfer deactivation reactions, achieving reaction yields of around 90% and retaining up to 80% of its efficiency after seven consecutive reuse cycles. These results demonstrate the potential of our self-condensation strategy to heterogenize photoactive complexes, while retaining their catalytic activity and showing excellent reusability.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"14 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937428","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}
It remains great challenges to keep long-term photocatalytic performance of metal halide perovskites (MHPs) under oxygen-rich and moisture environments owing to their intrinsic lability to these conditions. Herein, we employed high oxyphilic trivalent ruthenium ions (Ru3+) as oxygen atom anchors to dope into the lattice of lead-free perovskite Cs3Bi2Br9 (CBB), aiming to enhance the structural stability by inhibiting the penetration of reactive oxygen species (ROS) and water (H2O) into CBB. Besides, the photocatalytic performance of Ru3+-doped CBB (Ru-CBB) for the selective oxidation of sulfides was evaluated in the presence of O2 and H2O. Series of sulfides (38 examples) were converted into corresponding sulfoxides with excellent yields and the Ru-CBB were recycled at least 5 times without the change of crystalline structure. The enhanced photocatalytic activity of Ru-CBB, compared to the pristine CBB, can be attributed to its more positive valence band position and more efficient formation of ROS. Mechanism studies revealed that two reaction pathways, predominated by H2O and ROS respectively, were involved in the titled transformation. In the former, H2O served as an essential oxygen source for the formation of sulfoxides as established by isotope labelling experiment.
{"title":"Ru3+-doped lead-free perovskite Cs3Bi2Br9 for photocatalytic selective oxidation of sulfides to sulfoxides using trace water as an oxygen source","authors":"Qiangwen Fan, Dawei Liu, Zhaohong Liao, Debo Wu, Zongbo Xie, Haibo Zhu, Zhanggao Le","doi":"10.1016/j.jcat.2025.115945","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115945","url":null,"abstract":"It remains great challenges to keep long-term photocatalytic performance of metal halide perovskites (MHPs) under oxygen-rich and moisture environments owing to their intrinsic lability to these conditions. Herein, we employed high oxyphilic trivalent ruthenium ions (Ru<sup>3+</sup>) as oxygen atom anchors to dope into the lattice of lead-free perovskite Cs<sub>3</sub>Bi<sub>2</sub>Br<sub>9</sub> (CBB), aiming to enhance the structural stability by inhibiting the penetration of reactive oxygen species (ROS) and water (H<sub>2</sub>O) into CBB. Besides, the photocatalytic performance of Ru<sup>3+</sup>-doped CBB (Ru-CBB) for the selective oxidation of sulfides was evaluated in the presence of O<sub>2</sub> and H<sub>2</sub>O. Series of sulfides (38 examples) were converted into corresponding sulfoxides with excellent yields and the Ru-CBB were recycled at least 5 times without the change of crystalline structure. The enhanced photocatalytic activity of Ru-CBB, compared to the pristine CBB, can be attributed to its more positive valence band position and more efficient formation of ROS. Mechanism studies revealed that two reaction pathways, predominated by H<sub>2</sub>O and ROS respectively, were involved in the titled transformation. In the former, H<sub>2</sub>O served as an essential oxygen source for the formation of sulfoxides as established by isotope labelling experiment.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"78 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936390","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 : 2025-01-06DOI: 10.1016/j.jcat.2025.115943
Lennert A. D’ooghe, Nadadur Veeraraghavan Srinath, Valentijn De Coster, Hilde Poelman, Jolien Dendooven, Marie-Françoise Reyniers, Kevin M. Van Geem, Vladimir.V. Galvita
Pt:Sn/MgAl2O4 and Pt:In/MgAl2O4 catalysts with 3 wt% Pt and 3 wt% Sn or In were tested for CO2-assisted propane dehydrogenation (CO2-PDH). This reaction was referenced against Reverse water–gas shift (RWGS) and non-oxidative PDH, while CO-DRIFTS detailed the nanoparticle (NP) surface. Results were connected to a preceding study, focused on NP material properties using Quick X-ray Absorption Spectroscopy and Temporal Analysis of Products. During CO2-PDH, CO2 was mainly consumed through RWGS. CO2 consumption beyond the RWGS equilibrium arose from carbon oxidation. Promoter oxidation by CO2 and the consequent loss of the Pt-based alloys induced carbon formation. This deactivation increased the in situ CO2:H2 ratio, further accelerating promoter oxidation and carbon formation. Repeated catalyst regeneration cycles increased the promoter concentration in the alloyed NPs. This occurred throughout the entire Pt:Sn NP, while for Pt:In, it was limited to the NP surface with concomitant NP bulk depletion. This promoter enrichment contributed to catalyst deactivation.
{"title":"Detailing the activity and deactivation of supported Pt-Sn and Pt-In catalysts for CO2-assisted PDH","authors":"Lennert A. D’ooghe, Nadadur Veeraraghavan Srinath, Valentijn De Coster, Hilde Poelman, Jolien Dendooven, Marie-Françoise Reyniers, Kevin M. Van Geem, Vladimir.V. Galvita","doi":"10.1016/j.jcat.2025.115943","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115943","url":null,"abstract":"Pt:Sn/MgAl<sub>2</sub>O<sub>4</sub> and Pt:In/MgAl<sub>2</sub>O<sub>4</sub> catalysts with 3 wt% Pt and 3 wt% Sn or In were tested for CO<sub>2</sub>-assisted propane dehydrogenation (CO<sub>2</sub>-PDH). This reaction was referenced against Reverse water–gas shift (RWGS) and non-oxidative PDH, while CO-DRIFTS detailed the nanoparticle (NP) surface. Results were connected to a preceding study, focused on NP material properties using Quick X-ray Absorption Spectroscopy and Temporal Analysis of Products. During CO<sub>2</sub>-PDH, CO<sub>2</sub> was mainly consumed through RWGS. CO<sub>2</sub> consumption beyond the RWGS equilibrium arose from carbon oxidation. Promoter oxidation by CO<sub>2</sub> and the consequent loss of the Pt-based alloys induced carbon formation. This deactivation increased the in situ CO<sub>2</sub>:H<sub>2</sub> ratio, further accelerating promoter oxidation and carbon formation. Repeated catalyst regeneration cycles increased the promoter concentration in the alloyed NPs. This occurred throughout the entire Pt:Sn NP, while for Pt:In, it was limited to the NP surface with concomitant NP bulk depletion. This promoter enrichment contributed to catalyst deactivation.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"36 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929568","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 : 2025-01-04DOI: 10.1016/j.jcat.2025.115942
Oluwatofunmi O. Akinsanya, Deep M. Patel, Christopher R. O’Connor, Marta Perxés Perich, Jessi E.S. van der Hoeven, Christian Reece, Luke T. Roling, Nathaniel M. Eagan
Oxidative coupling reactions enable biomass-derived oxygenates to serve as sustainable platform molecules for a wide range of high-value chemicals. These catalytic reactions can be selectively triggered over alloys wherein a highly active dopant metal such as Pd is diluted into a sea of highly selective host metal atoms such as Au. Here, a range of supported Pd1Aux (x = 5–200) alloy nanoparticles were synthesized using a sequential reduction method with colloidal Au to achieve a high degree of compositional control and particle size uniformity. The promotional role of Pd was examined in the oxidation of ethanol to yield acetaldehyde and the coupling product ethyl acetate. Reactivity trends indicate that both the overall rate of ethanol oxidation and the selectivity toward coupling increase with Pd doping. Rate order and activation energy trends further suggest that the promotional role of Pd does not likely originate from simple O2 dissociation and spillover but rather from the stabilization of alkoxides at Pd-Au interfaces, disproportionately increasing coupling vs simple oxidation. Infrared spectroscopy and density functional theory calculations offer further insights into Pd microstructures in the presence of various key adsorbates, suggesting that Pd can lend this promotion in an isolated state. While this state is generally unstable in the surface due to preferences for segregation into the bulk, oxygen and pathway intermediates may aid in stabilizing surface structures. These findings lay groundwork to explain selectivity and activity control in a much wider range of oxidative functionalizations and to guide further catalyst development.
{"title":"Understanding the promotional role of Pd in oxidative alcohol coupling reactions over dilute PdAu alloys","authors":"Oluwatofunmi O. Akinsanya, Deep M. Patel, Christopher R. O’Connor, Marta Perxés Perich, Jessi E.S. van der Hoeven, Christian Reece, Luke T. Roling, Nathaniel M. Eagan","doi":"10.1016/j.jcat.2025.115942","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115942","url":null,"abstract":"Oxidative coupling reactions enable biomass-derived oxygenates to serve as sustainable platform molecules for a wide range of high-value chemicals. These catalytic reactions can be selectively triggered over alloys wherein a highly active dopant metal such as Pd is diluted into a sea of highly selective host metal atoms such as Au. Here, a range of supported Pd<sub>1</sub>Au<sub>x</sub> (x = 5–200) alloy nanoparticles were synthesized using a sequential reduction method with colloidal Au to achieve a high degree of compositional control and particle size uniformity. The promotional role of Pd was examined in the oxidation of ethanol to yield acetaldehyde and the coupling product ethyl acetate. Reactivity trends indicate that both the overall rate of ethanol oxidation and the selectivity toward coupling increase with Pd doping. Rate order and activation energy trends further suggest that the promotional role of Pd does not likely originate from simple O<sub>2</sub> dissociation and spillover but rather from the stabilization of alkoxides at Pd-Au interfaces, disproportionately increasing coupling <em>vs</em> simple oxidation. Infrared spectroscopy and density functional theory calculations offer further insights into Pd microstructures in the presence of various key adsorbates, suggesting that Pd can lend this promotion in an isolated state. While this state is generally unstable in the surface due to preferences for segregation into the bulk, oxygen and pathway intermediates may aid in stabilizing surface structures. These findings lay groundwork to explain selectivity and activity control in a much wider range of oxidative functionalizations and to guide further catalyst development.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"76 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925242","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}
This study unravels gas-driven structural and chemical dynamics of Fe clusters in a Fe-Zn catalyst during the hydrogenation of CO2, using kinetics, chemical titration, and in-situ spectroscopic characterizations. The gas-driven dynamics of iron clusters lead to a promotion in formation rates of C2+ hydrocarbons and C2+ olefins by almost one magnitude, in response to the changes in reactants. These rates are single-valued functions of the ratio which determines the carbon chemical potential at the catalyst surface and influences the thermodynamic tendency for carbon deposition and carbonization of iron species. As the ratio increases, both the quantities of carbon species and iron carbides rise, however, crystalline graphite grows faster and covers part of iron carbide species at higher ratios. These gas-driven structural dynamics allow the maximum formation of exposed iron carbide species for the formation of C2+ hydrocarbons and result in a volcano-type relationship between these formation rates and the ratio.
{"title":"Reactant-driven structural and chemical dynamics of Fe clusters for promoting hydrocarbon formation over a Na/FeZn catalyst","authors":"Wenqi Liu, Longfei Yan, Xiaonan Zhang, Zhenzhou Zhang, Shanshan Dang, Yi-Fan Han, Weifeng Tu","doi":"10.1016/j.jcat.2025.115940","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115940","url":null,"abstract":"This study unravels gas-driven structural and chemical dynamics of Fe clusters in a Fe-Zn catalyst during the hydrogenation of CO<sub>2</sub>, using kinetics, chemical titration, and in-situ spectroscopic characterizations. The gas-driven dynamics of iron clusters lead to a promotion in formation rates of C<sub>2+</sub> hydrocarbons and C<sub>2+</sub> olefins by almost one magnitude, in response to the changes in reactants. These rates are single-valued functions of the <span><math><mrow is=\"true\"><msup is=\"true\"><mrow is=\"true\"><msub is=\"true\"><mi is=\"true\" mathvariant=\"normal\">P</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">C</mi><mi is=\"true\" mathvariant=\"normal\">O</mi></mrow></msub></mrow><mn is=\"true\">2</mn></msup><mo is=\"true\" stretchy=\"false\">/</mo><msub is=\"true\"><mi is=\"true\" mathvariant=\"normal\">P</mi><msub is=\"true\"><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">C</mi><mi is=\"true\" mathvariant=\"normal\">O</mi></mrow><mn is=\"true\">2</mn></msub></msub></mrow></math></span> ratio which determines the carbon chemical potential at the catalyst surface and influences the thermodynamic tendency for carbon deposition and carbonization of iron species. As the ratio increases, both the quantities of carbon species and iron carbides rise, however, crystalline graphite grows faster and covers part of iron carbide species at higher <span><math><mrow is=\"true\"><msup is=\"true\"><mrow is=\"true\"><msub is=\"true\"><mi is=\"true\" mathvariant=\"normal\">P</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">C</mi><mi is=\"true\" mathvariant=\"normal\">O</mi></mrow></msub></mrow><mn is=\"true\">2</mn></msup><mo is=\"true\" stretchy=\"false\">/</mo><msub is=\"true\"><mi is=\"true\" mathvariant=\"normal\">P</mi><msub is=\"true\"><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">C</mi><mi is=\"true\" mathvariant=\"normal\">O</mi></mrow><mn is=\"true\">2</mn></msub></msub></mrow></math></span> ratios. These gas-driven structural dynamics allow the maximum formation of exposed iron carbide species for the formation of C<sub>2+</sub> hydrocarbons and result in a volcano-type relationship between these formation rates and the <span><math><mrow is=\"true\"><msup is=\"true\"><mrow is=\"true\"><msub is=\"true\"><mi is=\"true\" mathvariant=\"normal\">P</mi><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">C</mi><mi is=\"true\" mathvariant=\"normal\">O</mi></mrow></msub></mrow><mn is=\"true\">2</mn></msup><mo is=\"true\" stretchy=\"false\">/</mo><msub is=\"true\"><mi is=\"true\" mathvariant=\"normal\">P</mi><msub is=\"true\"><mrow is=\"true\"><mi is=\"true\" mathvariant=\"normal\">C</mi><mi is=\"true\" mathvariant=\"normal\">O</mi></mrow><mn is=\"true\">2</mn></msub></msub></mrow></math></span> ratio.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"14 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924568","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 : 2025-01-04DOI: 10.1016/j.jcat.2025.115941
Jiaming Wang, Lei Wu, Siqin Liu, Shunan Liu, Hongwei Ji, Chuncheng Chen, Yuchao Zhang, Jincai Zhao
The anodic water oxidation reaction (WOR) is usually considered as the main hindrance due to its theoretically high redox potential and sluggish kinetics in an overall carbon dioxide reduction reaction (CO2RR) cell. However, the actual bias distribution between CO2RR and WOR half reactions in practice has not been systematically investigated. In this work, we find that in a photoelectrochemical (PEC) overall CO2RR cell with a hematite (α-Fe2O3) photoanode to catalyze WOR, although most of the applied bias is exerted on the Au cathode for satisfying the CO2RR thermodynamics, the cathode struggles to get sufficient voltage to drive CO production. Employing the value-added olefin epoxidation reaction to replace WOR and the introduction of Au plasmonic effect on the α-Fe2O3 photoanode allow for a controlled bias distribution between anode and cathode during the overall reaction process, enabling the cathode to reach the potential window for selective CO production under lower applied bias. Accordingly, the efficient oxygen atom utilization of CO2 is achieved and a model of oxygen atom transfer between the cathode and anode is proposed.
{"title":"Bias distribution and regulation for efficient oxygen atom transfer in photoelectrochemical cells coupled with styrene epoxidation and CO2 reduction","authors":"Jiaming Wang, Lei Wu, Siqin Liu, Shunan Liu, Hongwei Ji, Chuncheng Chen, Yuchao Zhang, Jincai Zhao","doi":"10.1016/j.jcat.2025.115941","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115941","url":null,"abstract":"The anodic water oxidation reaction (WOR) is usually considered as the main hindrance due to its theoretically high redox potential and sluggish kinetics in an overall carbon dioxide reduction reaction (CO<sub>2</sub>RR) cell. However, the actual bias distribution between CO<sub>2</sub>RR and WOR half reactions in practice has not been systematically investigated. In this work, we find that in a photoelectrochemical (PEC) overall CO<sub>2</sub>RR cell with a hematite (α-Fe<sub>2</sub>O<sub>3</sub>) photoanode to catalyze WOR, although most of the applied bias is exerted on the Au cathode for satisfying the CO<sub>2</sub>RR thermodynamics, the cathode struggles to get sufficient voltage to drive CO production. Employing the value-added olefin epoxidation reaction to replace WOR and the introduction of Au plasmonic effect on the α-Fe<sub>2</sub>O<sub>3</sub> photoanode allow for a controlled bias distribution between anode and cathode during the overall reaction process, enabling the cathode to reach the potential window for selective CO production under lower applied bias. Accordingly, the efficient oxygen atom utilization of CO<sub>2</sub> is achieved and a model of oxygen atom transfer between the cathode and anode is proposed.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"41 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925253","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 : 2025-01-03DOI: 10.1016/j.jcat.2025.115938
Yu Guang, Yan-Ling Ying, Bin Wang, Li-Ping Mo, Zhan-Hui Zhang
The chemoselective transformation of carbon dioxide into valuable chemicals is of great significance. A novel, sustainable, and straightforward approach has been developed for the preparation of carbamates via a three-component reaction of amines, alkyl halides, and carbon dioxide at atmospheric pressure and room temperature in the presence of choline hydroxide (ChOH). ChOH acts as both promoter and green solvent without any additives or organic solvents. This methodology can also be applied to a wide range of amines and a series of carbamates are synthesized with high to excellent yields.
{"title":"Choline hydroxide-promoted chemoselective transformation of carbon dioxide into carbamates under ambient conditions","authors":"Yu Guang, Yan-Ling Ying, Bin Wang, Li-Ping Mo, Zhan-Hui Zhang","doi":"10.1016/j.jcat.2025.115938","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.115938","url":null,"abstract":"The chemoselective transformation of carbon dioxide into valuable chemicals is of great significance. A novel, sustainable, and straightforward approach has been developed for the preparation of carbamates via a three-component reaction of amines, alkyl halides, and carbon dioxide at atmospheric pressure and room temperature in the presence of choline hydroxide (ChOH). ChOH acts as both promoter and green solvent without any additives or organic solvents. This methodology can also be applied to a wide range of amines and a series of carbamates are synthesized with high to excellent yields.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"5 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924798","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：