Pub Date : 2024-12-27DOI: 10.1021/acscatal.4c05717
Zengrong Li, Peng Wang, Chengzhi Ren, Linyi Wu, Yangtao Yao, Shuxian Zhong, Hongjun Lin, Leihong Zhao, Yijing Gao, Song Bai
Controlling product selectivity in CO2 photoreduction remains a grand challenge, particularly when CH3OH is the targeted product. Herein, we demonstrate a strategy for tuning the selectivity of core–shell-structured UiO-66@ZnIn2S4 (UiO/ZIS) in visible-light-driven catalytic reduction of CO2 by regulating the location of PtCu cocatalysts. The PtCu nanoparticles are confined within the inner UiO-66 core to afford PtCu/UiO/ZIS, incorporated at the UiO-66/ZnIn2S4 heterointerface to form UiO/PtCu/ZIS, and anchored on the outer ZnIn2S4 surface to fabricate UiO/ZIS/PtCu. The primary CO2 reduction products for PtCu/UiO/ZIS, UiO/PtCu/ZIS, and UiO/ZIS/PtCu are CO, CH3OH, and CH4, with selectivities of 52.1, 72.7, and 88.8%, respectively. Experimental and theoretical results demonstrate that the spatial position of PtCu affects both the charge separation efficiency and the H2O oxidation rate in the ternary photocatalysts. This, in turn, influences the supply of electrons and protons to the active sites, leading to varying degrees of CO2 hydrogenation and deoxygenation. Additionally, different PtCu positions also create distinct reactive sites and surrounding microenvironments, altering the energy barriers of key reaction steps and giving rise to diverse CO2 reduction pathways. This work provides fresh hints for rationally controlling product selectivity in artificial photosynthesis through the precise regulation of cocatalyst placement within heterostructured photocatalysts.
{"title":"Modulating the Selectivity of CO2 Photoreduction by Regulating the Location of PtCu in a UiO-66@ZnIn2S4 Core–Shell Nanoreactor","authors":"Zengrong Li, Peng Wang, Chengzhi Ren, Linyi Wu, Yangtao Yao, Shuxian Zhong, Hongjun Lin, Leihong Zhao, Yijing Gao, Song Bai","doi":"10.1021/acscatal.4c05717","DOIUrl":"https://doi.org/10.1021/acscatal.4c05717","url":null,"abstract":"Controlling product selectivity in CO<sub>2</sub> photoreduction remains a grand challenge, particularly when CH<sub>3</sub>OH is the targeted product. Herein, we demonstrate a strategy for tuning the selectivity of core–shell-structured UiO-66@ZnIn<sub>2</sub>S<sub>4</sub> (UiO/ZIS) in visible-light-driven catalytic reduction of CO<sub>2</sub> by regulating the location of PtCu cocatalysts. The PtCu nanoparticles are confined within the inner UiO-66 core to afford PtCu/UiO/ZIS, incorporated at the UiO-66/ZnIn<sub>2</sub>S<sub>4</sub> heterointerface to form UiO/PtCu/ZIS, and anchored on the outer ZnIn<sub>2</sub>S<sub>4</sub> surface to fabricate UiO/ZIS/PtCu. The primary CO<sub>2</sub> reduction products for PtCu/UiO/ZIS, UiO/PtCu/ZIS, and UiO/ZIS/PtCu are CO, CH<sub>3</sub>OH, and CH<sub>4</sub>, with selectivities of 52.1, 72.7, and 88.8%, respectively. Experimental and theoretical results demonstrate that the spatial position of PtCu affects both the charge separation efficiency and the H<sub>2</sub>O oxidation rate in the ternary photocatalysts. This, in turn, influences the supply of electrons and protons to the active sites, leading to varying degrees of CO<sub>2</sub> hydrogenation and deoxygenation. Additionally, different PtCu positions also create distinct reactive sites and surrounding microenvironments, altering the energy barriers of key reaction steps and giving rise to diverse CO<sub>2</sub> reduction pathways. This work provides fresh hints for rationally controlling product selectivity in artificial photosynthesis through the precise regulation of cocatalyst placement within heterostructured photocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888897","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}
Oxazolidinones are important heterocycles widely utilized in medicinal chemistry for the synthesis of antifungals, antibacterials, and other bioactive compounds and in organic chemistry as chiral auxiliaries for asymmetric synthesis. Herein, we report a biocatalytic strategy for the synthesis of enantioenriched oxazolidinones through the intramolecular C(sp3)–H amination of carbamate derivatives using engineered myoglobin-based catalysts. This method is applicable to a diverse range of substrates with high functional group tolerance to provide enantioenriched oxazolidinones in good yields with high enantioselectivity. The synthetic utility of this methodology is further highlighted by the development of enantiodivergent biocatalysts for this transformation and through the preparative-scale synthesis of key oxazolidinone intermediates for the production of cholesterol-lowering drugs ezetimibe and CJ-15-161. An outer sphere mutation, Y146F, was found to be beneficial in favoring the productive C–H amination reaction over an unproductive reductive pathway commonly observed in hemeprotein-catalyzed nitrene transfer reactions. This study demonstrates a biocatalytic, enantiodivergent synthesis of oxazolidinones via C–H amination of carbamate derivatives, which offers an attractive strategy for the synthesis of these valuable intermediates for applications in medicinal chemistry, target-directed synthesis, and asymmetric synthesis.
{"title":"Highly Enantioselective Construction of Oxazolidinone Rings via Enzymatic C(sp3)–H Amination","authors":"Jadab Majhi, Satyajit Roy, Anwita Chattopadhyay, Rudi Fasan","doi":"10.1021/acscatal.4c06066","DOIUrl":"https://doi.org/10.1021/acscatal.4c06066","url":null,"abstract":"Oxazolidinones are important heterocycles widely utilized in medicinal chemistry for the synthesis of antifungals, antibacterials, and other bioactive compounds and in organic chemistry as chiral auxiliaries for asymmetric synthesis. Herein, we report a biocatalytic strategy for the synthesis of enantioenriched oxazolidinones through the intramolecular C(sp<sup>3</sup>)–H amination of carbamate derivatives using engineered myoglobin-based catalysts. This method is applicable to a diverse range of substrates with high functional group tolerance to provide enantioenriched oxazolidinones in good yields with high enantioselectivity. The synthetic utility of this methodology is further highlighted by the development of enantiodivergent biocatalysts for this transformation and through the preparative-scale synthesis of key oxazolidinone intermediates for the production of cholesterol-lowering drugs ezetimibe and CJ-15-161. An outer sphere mutation, Y146F, was found to be beneficial in favoring the productive C–H amination reaction over an unproductive reductive pathway commonly observed in hemeprotein-catalyzed nitrene transfer reactions. This study demonstrates a biocatalytic, enantiodivergent synthesis of oxazolidinones via C–H amination of carbamate derivatives, which offers an attractive strategy for the synthesis of these valuable intermediates for applications in medicinal chemistry, target-directed synthesis, and asymmetric synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888899","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 hydrogenation of CO and CO2 to long-chain olefins presents a promising route for chemical production, but optimizing the reaction process requires a thorough understanding of the tail gas recycling process. The effects of cofeeding ethylene on the hydrogenation of CO and CO2 using a zinc- and sodium-promoted iron catalyst (FeZnNa catalyst) are carefully investigated in this work. For CO2 hydrogenation, ethylene showed negligible impact on CO2 conversion, CO selectivity, or CH4 selectivity but primarily served as a feedstock for the production of ethane and higher carbon number olefins. In contrast, during CO hydrogenation, CO conversion improved with ethylene cofeeding. Ethylene also contributed to chain growth, although a higher fraction was converted to ethane via hydrogenation compared to CO2 hydrogenation. Structural analysis using XRD and Mössbauer spectroscopy revealed that the catalyst in CO2 hydrogenation consisted exclusively of the Fe5C2 phase, whereas CO hydrogenation resulted in the formation of both Fe5C2 and Fe2C phases. XPS and TPO analyses indicated significantly lower carbon deposition on the catalyst during CO2 hydrogenation compared to that during CO hydrogenation.
{"title":"Comparative Study on the Effect of Ethylene Cofeeding in CO2 and CO Hydrogenation to Olefins over FeZnNa Catalyst","authors":"Kaiyu Zhu, Xingwu Liu, Haoyi Tang, Shuheng Tian, Junzhong Xie, Lingzhen Zeng, Tianye Wang, Hongwei Li, Meng Wang, Ding Ma","doi":"10.1021/acscatal.4c06550","DOIUrl":"https://doi.org/10.1021/acscatal.4c06550","url":null,"abstract":"The hydrogenation of CO and CO<sub>2</sub> to long-chain olefins presents a promising route for chemical production, but optimizing the reaction process requires a thorough understanding of the tail gas recycling process. The effects of cofeeding ethylene on the hydrogenation of CO and CO<sub>2</sub> using a zinc- and sodium-promoted iron catalyst (FeZnNa catalyst) are carefully investigated in this work. For CO<sub>2</sub> hydrogenation, ethylene showed negligible impact on CO<sub>2</sub> conversion, CO selectivity, or CH<sub>4</sub> selectivity but primarily served as a feedstock for the production of ethane and higher carbon number olefins. In contrast, during CO hydrogenation, CO conversion improved with ethylene cofeeding. Ethylene also contributed to chain growth, although a higher fraction was converted to ethane via hydrogenation compared to CO<sub>2</sub> hydrogenation. Structural analysis using XRD and Mössbauer spectroscopy revealed that the catalyst in CO<sub>2</sub> hydrogenation consisted exclusively of the Fe<sub>5</sub>C<sub>2</sub> phase, whereas CO hydrogenation resulted in the formation of both Fe<sub>5</sub>C<sub>2</sub> and Fe<sub>2</sub>C phases. XPS and TPO analyses indicated significantly lower carbon deposition on the catalyst during CO<sub>2</sub> hydrogenation compared to that during CO hydrogenation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"20 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888898","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: 10.1021/acscatal.4c06344
Yawen Shi, Xinyong Diao, Na Ji, Hu Ding, Zongyang Ya, Dong Xu, Ruhan Wei, Kaihao Cao, Shengbo Zhang
Catalytic conversion of waste plastic has attracted widespread attention due to pressing environmental issues and energy crisis. Although some methods have been successful in converting single-component plastic waste, unfortunately, plastic waste in the real-world typically made up of a mixture of various plastics, which poses significant difficulties and challenges for catalyst selection and product distribution in the catalytic conversion of mixed plastic. Recently, a number of new technologies have been developed to address the catalytic conversion of mixed plastic, aiming to overcome the limitations of current methods and drive progress in this field. This review summarizes the progress in catalytic recycling and upgrading of mixed plastic into monomers or value-added chemicals by thermocatalysis, photocatalysis/photothermal catalysis, and tandem chemical-biocatalysis. The construction of efficient catalysts, understanding of reaction pathways, design of reaction systems, and practical applicability in each method are highlighted and discussed in detail. Our goal is to elucidate the catalytic mechanisms and principles of process design, providing guidance for the development, integration or optimization of new technologies that enhance catalytic efficiency and processing capabilities for mixed plastic waste. Furthermore, the economic feasibility and environmental impact of mixed plastic treatment were comprehensively evaluated by summarizing techno-economic analysis and life cycle assessment studies. Lastly, the remaining technological challenges and future directions for the industrial-scale conversion of real-world mixed plastic waste to generate value-added products are described.
{"title":"Advances and Challenges for Catalytic Recycling and Upgrading of Real-World Mixed Plastic Waste","authors":"Yawen Shi, Xinyong Diao, Na Ji, Hu Ding, Zongyang Ya, Dong Xu, Ruhan Wei, Kaihao Cao, Shengbo Zhang","doi":"10.1021/acscatal.4c06344","DOIUrl":"https://doi.org/10.1021/acscatal.4c06344","url":null,"abstract":"Catalytic conversion of waste plastic has attracted widespread attention due to pressing environmental issues and energy crisis. Although some methods have been successful in converting single-component plastic waste, unfortunately, plastic waste in the real-world typically made up of a mixture of various plastics, which poses significant difficulties and challenges for catalyst selection and product distribution in the catalytic conversion of mixed plastic. Recently, a number of new technologies have been developed to address the catalytic conversion of mixed plastic, aiming to overcome the limitations of current methods and drive progress in this field. This review summarizes the progress in catalytic recycling and upgrading of mixed plastic into monomers or value-added chemicals by thermocatalysis, photocatalysis/photothermal catalysis, and tandem chemical-biocatalysis. The construction of efficient catalysts, understanding of reaction pathways, design of reaction systems, and practical applicability in each method are highlighted and discussed in detail. Our goal is to elucidate the catalytic mechanisms and principles of process design, providing guidance for the development, integration or optimization of new technologies that enhance catalytic efficiency and processing capabilities for mixed plastic waste. Furthermore, the economic feasibility and environmental impact of mixed plastic treatment were comprehensively evaluated by summarizing techno-economic analysis and life cycle assessment studies. Lastly, the remaining technological challenges and future directions for the industrial-scale conversion of real-world mixed plastic waste to generate value-added products are described.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888896","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: 10.1021/acscatal.4c07185
Jonas Düker, Maximilian Philipp, Thomas Lentner, Jamie A. Cadge, João E. A. Lavarda, Ruth M. Gschwind, Matthew S. Sigman, Indrajit Ghosh, Burkhard König
Transition metal catalysis is crucial for the synthesis of complex molecules, with ligands and bases playing a pivotal role in optimizing cross-coupling reactions. Despite advancements in ligand design and base selection, achieving effective synergy between these components remains challenging. We present here a general approach to nickel-catalyzed photoredox reactions employing tert-butylamine as a cost-effective bifunctional additive, acting as the base and ligand. This method proves effective for C–O and C–N bond-forming reactions with a diverse array of nucleophiles, including phenols, aliphatic alcohols, anilines, sulfonamides, sulfoximines, and imines. Notably, the protocol demonstrates significant applicability in biomolecule derivatization and facilitates sequential one-pot functionalizations. Spectroscopic investigations revealed the robustness of the dynamic catalytic system, while elucidation of structure–reactivity relationships demonstrated how computed molecular properties of both the nucleophile and electrophile correlated to reaction performance, providing a foundation for effective reaction outcome prediction.
{"title":"Cross-Coupling Reactions with Nickel, Visible Light, and tert-Butylamine as a Bifunctional Additive","authors":"Jonas Düker, Maximilian Philipp, Thomas Lentner, Jamie A. Cadge, João E. A. Lavarda, Ruth M. Gschwind, Matthew S. Sigman, Indrajit Ghosh, Burkhard König","doi":"10.1021/acscatal.4c07185","DOIUrl":"https://doi.org/10.1021/acscatal.4c07185","url":null,"abstract":"Transition metal catalysis is crucial for the synthesis of complex molecules, with ligands and bases playing a pivotal role in optimizing cross-coupling reactions. Despite advancements in ligand design and base selection, achieving effective synergy between these components remains challenging. We present here a general approach to nickel-catalyzed photoredox reactions employing <i>tert</i>-butylamine as a cost-effective bifunctional additive, acting as the base and ligand. This method proves effective for C–O and C–N bond-forming reactions with a diverse array of nucleophiles, including phenols, aliphatic alcohols, anilines, sulfonamides, sulfoximines, and imines. Notably, the protocol demonstrates significant applicability in biomolecule derivatization and facilitates sequential one-pot functionalizations. Spectroscopic investigations revealed the robustness of the dynamic catalytic system, while elucidation of structure–reactivity relationships demonstrated how computed molecular properties of both the nucleophile and electrophile correlated to reaction performance, providing a foundation for effective reaction outcome prediction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"26 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142888900","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: 10.1021/acscatal.4c06289
Fan Fang, Fang Xu, Xue Li, Chong Chen, Nengjie Feng, Yijiao Jiang, Jun Huang
Soot catalytic combustion using single-crystalline perovskite-type materials holds great promise as an efficient non-noble metal catalyst, with K+-modified SrTiO3 emerging as one of the most desirable candidates. However, balancing the crystallinity and an optimized pore structure and revealing the mechanism underlying the K+ action remain challenges. Herein, by the electrospinning technique, we successfully self-assembled the K-doped single-crystalline SrTi0.95Al0.05O3 nanotubular webs with ordered mesopores. The good crystallinity and mesoporous structures contribute to the enhanced catalytic performance with desirable stability. Based on comprehensive characterizations and density functional theory (DFT) calculations, K+ ions effectively accumulate defect charges, facilitating the generation of additional oxygen vacancies and expediting oxygen activation during the reaction. Additionally, the presence of K+ ions prefers to preserve O2 bond integrity during activation, significantly increasing NO adsorption capacity. Utilizing KNO3 as the medium, K+ effectively facilitates the storage and subsequent release of active oxygen species, leading to the promised catalytic performance (T50 = 368 °C, Ea = 64.97 kJ mol–1, TOFK = 0.017 h–1). This study provides mechanistic insights into developing advanced materials for thermal catalytic heterogeneous reactions.
{"title":"Mechanistic Insights into Potassium-Assistant Thermal-Catalytic Oxidation of Soot over Single-Crystalline SrTiO3 Nanotubes with Ordered Mesopores","authors":"Fan Fang, Fang Xu, Xue Li, Chong Chen, Nengjie Feng, Yijiao Jiang, Jun Huang","doi":"10.1021/acscatal.4c06289","DOIUrl":"https://doi.org/10.1021/acscatal.4c06289","url":null,"abstract":"Soot catalytic combustion using single-crystalline perovskite-type materials holds great promise as an efficient non-noble metal catalyst, with K<sup>+</sup>-modified SrTiO<sub>3</sub> emerging as one of the most desirable candidates. However, balancing the crystallinity and an optimized pore structure and revealing the mechanism underlying the K<sup>+</sup> action remain challenges. Herein, by the electrospinning technique, we successfully self-assembled the K-doped single-crystalline SrTi<sub>0.95</sub>Al<sub>0.05</sub>O<sub>3</sub> nanotubular webs with ordered mesopores. The good crystallinity and mesoporous structures contribute to the enhanced catalytic performance with desirable stability. Based on comprehensive characterizations and density functional theory (DFT) calculations, K<sup>+</sup> ions effectively accumulate defect charges, facilitating the generation of additional oxygen vacancies and expediting oxygen activation during the reaction. Additionally, the presence of K<sup>+</sup> ions prefers to preserve O<sub>2</sub> bond integrity during activation, significantly increasing NO adsorption capacity. Utilizing KNO<sub>3</sub> as the medium, K<sup>+</sup> effectively facilitates the storage and subsequent release of active oxygen species, leading to the promised catalytic performance (<i>T</i><sub>50</sub> = 368 °C, <i>E</i><sub>a</sub> = 64.97 kJ mol<sup>–1</sup>, TOF<sub>K</sub> = 0.017 h<sup>–1</sup>). This study provides mechanistic insights into developing advanced materials for thermal catalytic heterogeneous reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886797","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: 10.1021/acscatal.4c05805
Ting C. Lin, Elizabeth E. Bickel Rogers, Aditya Bhan
<span><sup>a</sup></span>Stoichiometric amounts of H<sub>2</sub> and H<sub>2</sub>O were omitted. How can the reaction network connectivity between CO<sub>2</sub>, CO, and hydrocarbon/oxygenate products be determined to assess pathway-specific rates? How can thermodynamic contributions to observed trends in rates and selectivity be identified and decoupled from kinetic contributions? How can relationships between and constraints imposed by thermodynamic driving forces be illustrated in energy diagrams? Figure 1. (a) Hypothetical reaction networks where <i>A</i> converts to <i>B</i>, <i>C</i>, <i>D</i>, and <i>E</i> following two cases: (i) <i>C</i> is a secondary product with no product inhibition present, and (ii) all species are primary products with <i>E</i> inhibiting the formation rates of <i>B</i> and <i>D</i>. Here, <i>C</i><sub><i>E</i></sub> denotes the concentration of species <i>E</i>. (b, c) Simulated first rank delplots and (d, e) yields as a function of contact time for the two cases. Inset in (c) shows the selectivity to product <i>C</i> over the 0–3% conversion region of the first rank plot for case (ii). (f) Simulated TOFs as a function of contact time for case (i). Values of rate and equilibrium constants were chosen for illustrative purposes and do not impact the general trends shown. Arbitrary units are abbreviated as a.u. Simulation details are provided in section S1 (Supporting Information (SI)). Figure 2. Simulated (a) overall reversibility and (b) carbon selectivity as a function of contact time during CO<sub>2</sub> hydrogenation to methanol, CO, and ethanol on a hypothetical catalyst kinetically selective toward methanol (30 bar; 503 K; 1 a.u. total inlet flow rate; H<sub>2</sub>:CO<sub>2</sub> = 3). (c) Calculated equilibrium carbon selectivity (30 bar; H<sub>2</sub>:CO<sub>2</sub> = 3) as a function of temperature, where the methanol selectivity is too low to be observed in the figure. The result at 503 K is highlighted and expectedly consistent with selectivity from (b) in the limit of infinite contact time. Simulation details are provided in section S3 (SI). Figure 3. (a) Free energy diagrams at the standard state (<i>C</i><sub>0</sub> = 1 a.u.) and under reaction conditions (initial <i>C</i><sub><i>A</i>,0</sub> = 10 a.u.; <i>X</i><sub><i>A</i></sub> = 0.23) for single-path reaction sequence <i>A</i> ⇄ <i>B</i> ⇄ <i>C</i> ⇄ <i>D</i>. (b) Free energy diagrams for CO<sub>2</sub> hydrogenation at 523 K referenced to CO<sub>2</sub> + 3H<sub>2</sub> at the standard state (<i>P</i><sub>0</sub> = 1 bar), hypothetical reaction condition 1 (<i>P</i><sub>tot</sub> = 10 bar; inlet CO<sub>2</sub>:H<sub>2</sub> = 1:3; <i>X</i><sub>CO<sub>2</sub></sub> = 0.03; <i>S</i><sub>CH<sub>3</sub>OH</sub> = 0.5), and hypothetical reaction condition 2 (<i>P</i><sub>tot</sub> = 10 bar; inlet CO<sub>2</sub>:H<sub>2</sub> = 1:3; <i>X</i><sub>CO<sub>2</sub></sub> = 0.03; <i>S</i><sub>CH<sub>3</sub>OH</sub> = 0.05) calculated based on values fro
{"title":"Kinetic and Thermodynamic Considerations in Thermocatalytic CO2 Hydrogenation","authors":"Ting C. Lin, Elizabeth E. Bickel Rogers, Aditya Bhan","doi":"10.1021/acscatal.4c05805","DOIUrl":"https://doi.org/10.1021/acscatal.4c05805","url":null,"abstract":"<span><sup>a</sup></span>Stoichiometric amounts of H<sub>2</sub> and H<sub>2</sub>O were omitted. How can the reaction network connectivity between CO<sub>2</sub>, CO, and hydrocarbon/oxygenate products be determined to assess pathway-specific rates? How can thermodynamic contributions to observed trends in rates and selectivity be identified and decoupled from kinetic contributions? How can relationships between and constraints imposed by thermodynamic driving forces be illustrated in energy diagrams? Figure 1. (a) Hypothetical reaction networks where <i>A</i> converts to <i>B</i>, <i>C</i>, <i>D</i>, and <i>E</i> following two cases: (i) <i>C</i> is a secondary product with no product inhibition present, and (ii) all species are primary products with <i>E</i> inhibiting the formation rates of <i>B</i> and <i>D</i>. Here, <i>C</i><sub><i>E</i></sub> denotes the concentration of species <i>E</i>. (b, c) Simulated first rank delplots and (d, e) yields as a function of contact time for the two cases. Inset in (c) shows the selectivity to product <i>C</i> over the 0–3% conversion region of the first rank plot for case (ii). (f) Simulated TOFs as a function of contact time for case (i). Values of rate and equilibrium constants were chosen for illustrative purposes and do not impact the general trends shown. Arbitrary units are abbreviated as a.u. Simulation details are provided in section S1 (Supporting Information (SI)). Figure 2. Simulated (a) overall reversibility and (b) carbon selectivity as a function of contact time during CO<sub>2</sub> hydrogenation to methanol, CO, and ethanol on a hypothetical catalyst kinetically selective toward methanol (30 bar; 503 K; 1 a.u. total inlet flow rate; H<sub>2</sub>:CO<sub>2</sub> = 3). (c) Calculated equilibrium carbon selectivity (30 bar; H<sub>2</sub>:CO<sub>2</sub> = 3) as a function of temperature, where the methanol selectivity is too low to be observed in the figure. The result at 503 K is highlighted and expectedly consistent with selectivity from (b) in the limit of infinite contact time. Simulation details are provided in section S3 (SI). Figure 3. (a) Free energy diagrams at the standard state (<i>C</i><sub>0</sub> = 1 a.u.) and under reaction conditions (initial <i>C</i><sub><i>A</i>,0</sub> = 10 a.u.; <i>X</i><sub><i>A</i></sub> = 0.23) for single-path reaction sequence <i>A</i> ⇄ <i>B</i> ⇄ <i>C</i> ⇄ <i>D</i>. (b) Free energy diagrams for CO<sub>2</sub> hydrogenation at 523 K referenced to CO<sub>2</sub> + 3H<sub>2</sub> at the standard state (<i>P</i><sub>0</sub> = 1 bar), hypothetical reaction condition 1 (<i>P</i><sub>tot</sub> = 10 bar; inlet CO<sub>2</sub>:H<sub>2</sub> = 1:3; <i>X</i><sub>CO<sub>2</sub></sub> = 0.03; <i>S</i><sub>CH<sub>3</sub>OH</sub> = 0.5), and hypothetical reaction condition 2 (<i>P</i><sub>tot</sub> = 10 bar; inlet CO<sub>2</sub>:H<sub>2</sub> = 1:3; <i>X</i><sub>CO<sub>2</sub></sub> = 0.03; <i>S</i><sub>CH<sub>3</sub>OH</sub> = 0.05) calculated based on values fro","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886798","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}
Effective local electron regulation in ruthenium-based catalysts in acidic oxygen evolution reactions (OER) remains a key challenge. The lack of a unified understanding of catalyst activity and stability based on electron regulation limits the further development of proton exchange membrane water electrolysis (PEMWE). In this study, we develop the concept of oxygen coordination unsaturated Ti (TiOCU) sites. Based on the constructed local dual-oxide heterojunction interface in the Ru/TiOx catalyst, we achieve precise modulation of the d-electron orbitals of Ru sites. The charge redistribution between the Ru–Obridge–TiOCU local coordination units and the strengthened Ru–O bonds suppresses the formation of high-valence species and deactivation of catalyst. Combined with density functional theory (DFT) calculations and in situ spectroscopic experiments, we confirm that the modulation of the dz2 orbital charge significantly optimizes the deprotonation process of interfacial water and the formation of a hydroxyl-rich interface, thereby enhancing the OER kinetics and the dominance of the adsorbed evolution mechanism (AEM). Consequently, the Ru/TiOx catalyst exhibits superior OER performance, achieving a current density of 10 mA/cm2 at an overpotential of only 237 mV in 0.5 M H2SO4, and demonstrates stability for over 160 h. This work reveals the application of interfacial TiOCU, providing a perspective for the development of transition metal defect materials in water electrolysis.
{"title":"Enhancing Acidic Water Electrolysis via Local Electronic Regulation of Ru/TiOx Catalyst with Oxygen Coordination Unsaturated Ti Sites","authors":"Wei Xia, Kangnan Yuan, Xuejie Cao, Hongye Qin, Guangliang Lin, Jinyang Zhang, Ting Jin, Qinglun Wang, Lifang Jiao","doi":"10.1021/acscatal.4c06836","DOIUrl":"https://doi.org/10.1021/acscatal.4c06836","url":null,"abstract":"Effective local electron regulation in ruthenium-based catalysts in acidic oxygen evolution reactions (OER) remains a key challenge. The lack of a unified understanding of catalyst activity and stability based on electron regulation limits the further development of proton exchange membrane water electrolysis (PEMWE). In this study, we develop the concept of oxygen coordination unsaturated Ti (Ti<sub>OCU</sub>) sites. Based on the constructed local dual-oxide heterojunction interface in the Ru/TiO<sub><i>x</i></sub> catalyst, we achieve precise modulation of the d-electron orbitals of Ru sites. The charge redistribution between the Ru–O<sub>bridge</sub>–Ti<sub>OCU</sub> local coordination units and the strengthened Ru–O bonds suppresses the formation of high-valence species and deactivation of catalyst. Combined with density functional theory (DFT) calculations and in situ spectroscopic experiments, we confirm that the modulation of the d<sub><i>z</i><sup>2</sup></sub> orbital charge significantly optimizes the deprotonation process of interfacial water and the formation of a hydroxyl-rich interface, thereby enhancing the OER kinetics and the dominance of the adsorbed evolution mechanism (AEM). Consequently, the Ru/TiO<sub><i>x</i></sub> catalyst exhibits superior OER performance, achieving a current density of 10 mA/cm<sup>2</sup> at an overpotential of only 237 mV in 0.5 M H<sub>2</sub>SO<sub>4</sub>, and demonstrates stability for over 160 h. This work reveals the application of interfacial Ti<sub>OCU</sub>, providing a perspective for the development of transition metal defect materials in water electrolysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"303 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886799","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: 10.1021/acscatal.4c07209
Hang Wang, Yuxuan Duan, Baiquan Wang, Bin Li
A synthetic strategy for the catalytic cycloaddition of α-trifluoromethyl-α-diazoketones with nitriles has been achieved based on cobalt(II) metalloradical catalysis. The easily accessible starting materials, cost-effective catalyst, and experimental simplicity rendered this protocol a robust and practical approach to construct diverse functionalized 4-CF3-substituted oxazoles with high efficiency. A wide substrate scope of both α-trifluoromethylated diazoketones and nitriles is amenable to this catalytic system. The high level of functional group tolerance of this protocol provides several opportunities for precise late-stage modifications of bioactive and drug-like molecules. Mechanistic experiments and spectroscopic investigations confirm the radical nature of the reaction and reveal the involvement of both monocarbene and biscarbene radical intermediates during the catalytic process.
{"title":"Expeditious Synthesis of Highly Functional 4-Trifluoromethyl-Substituted Oxazoles Enabled by Cobalt(II) Metalloradical Catalysis","authors":"Hang Wang, Yuxuan Duan, Baiquan Wang, Bin Li","doi":"10.1021/acscatal.4c07209","DOIUrl":"https://doi.org/10.1021/acscatal.4c07209","url":null,"abstract":"A synthetic strategy for the catalytic cycloaddition of α-trifluoromethyl-α-diazoketones with nitriles has been achieved based on cobalt(II) metalloradical catalysis. The easily accessible starting materials, cost-effective catalyst, and experimental simplicity rendered this protocol a robust and practical approach to construct diverse functionalized 4-CF<sub>3</sub>-substituted oxazoles with high efficiency. A wide substrate scope of both α-trifluoromethylated diazoketones and nitriles is amenable to this catalytic system. The high level of functional group tolerance of this protocol provides several opportunities for precise late-stage modifications of bioactive and drug-like molecules. Mechanistic experiments and spectroscopic investigations confirm the radical nature of the reaction and reveal the involvement of both monocarbene and biscarbene radical intermediates during the catalytic process.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"58 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886800","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}
In the present study, 76 different metal-oxide-supported-transition-metal catalysts were prepared using 11 different metal oxides (MgO, Al2O3, SiO2, TiO2, V2O5, ZrO2, Nb2O5, MoO3, Ta2O5, WO3, and La2O3) and seven 3d metals (V, Mn, Fe, Co, Ni, Cu, and Zn). The 76 supported catalysts, along with 11 single metal oxides, were screened to identify catalytically active lattice oxygen structures for the partial oxidation of CH4 to formaldehyde and methanol. Fe/MoO3, Fe/V2O5, and particularly Fe/Nb2O5 were found to be highly effective. Structural analysis of the active Fe sites in the 11 supported Fe catalysts was performed using high-energy-resolution-fluorescence-detected Fe K-edge X-ray absorption near-edge structure spectroscopy, revealing that FeNbO4, FeMoO4, and FeVO4 species in Fe/Nb2O5, Fe/MoO3, and Fe/V2O5, respectively, are responsible for their partial-oxidation activities. In contrast, Fe2O3 species formed in Fe/Al2O3, Fe/SiO2, Fe/Ta2O5, and Fe/WO3 were found to be active for complete oxidation to CO2 than partial oxidation, as were the MgFe2O4, LaFeO3, and TiFe2O5 species formed in Fe/MgO, Fe/La2O3, and Fe/TiO2, respectively, and the interstitial solid solution of Fe3+ in ZrO2 generated in Fe/ZrO2. Furthermore, while the Fe2O3 species in Fe/WO4 are ineffective for partial oxidation, FeWO4 prepared by a hydrothermal method exhibits high selectivity for partial oxidation. Additionally, previous studies have shown that CuWO4 and CuMoO4 are active for partial CH4 oxidation. Accordingly, the ABO4 structure (where A is a 3d metal and B is a group 5 or 6 metal) is indicated as a viable design basis for the development of catalysts for partial CH4 oxidation.
{"title":"ABO4 as an Active Catalyst Structure for Direct Partial CH4 Oxidation as Identified through Screening of Supported Catalysts","authors":"Junya Ohyama, Yuriko Yoshioka, Momoka Tsukamoto, Rina Kuroki, Daichi Takahashi, Keisuke Awaya, Masato Machida, Kotaro Higashi, Tomoya Uruga, Naomi Kawamura, Shun Nishimura, Keisuke Takahashi","doi":"10.1021/acscatal.4c06376","DOIUrl":"https://doi.org/10.1021/acscatal.4c06376","url":null,"abstract":"In the present study, 76 different metal-oxide-supported-transition-metal catalysts were prepared using 11 different metal oxides (MgO, Al<sub>2</sub>O<sub>3</sub>, SiO<sub>2</sub>, TiO<sub>2</sub>, V<sub>2</sub>O<sub>5</sub>, ZrO<sub>2</sub>, Nb<sub>2</sub>O<sub>5</sub>, MoO<sub>3</sub>, Ta<sub>2</sub>O<sub>5</sub>, WO<sub>3</sub>, and La<sub>2</sub>O<sub>3</sub>) and seven 3d metals (V, Mn, Fe, Co, Ni, Cu, and Zn). The 76 supported catalysts, along with 11 single metal oxides, were screened to identify catalytically active lattice oxygen structures for the partial oxidation of CH<sub>4</sub> to formaldehyde and methanol. Fe/MoO<sub>3</sub>, Fe/V<sub>2</sub>O<sub>5</sub>, and particularly Fe/Nb<sub>2</sub>O<sub>5</sub> were found to be highly effective. Structural analysis of the active Fe sites in the 11 supported Fe catalysts was performed using high-energy-resolution-fluorescence-detected Fe K-edge X-ray absorption near-edge structure spectroscopy, revealing that FeNbO<sub>4</sub>, FeMoO<sub>4</sub>, and FeVO<sub>4</sub> species in Fe/Nb<sub>2</sub>O<sub>5</sub>, Fe/MoO<sub>3</sub>, and Fe/V<sub>2</sub>O<sub>5</sub>, respectively, are responsible for their partial-oxidation activities. In contrast, Fe<sub>2</sub>O<sub>3</sub> species formed in Fe/Al<sub>2</sub>O<sub>3</sub>, Fe/SiO<sub>2</sub>, Fe/Ta<sub>2</sub>O<sub>5</sub>, and Fe/WO<sub>3</sub> were found to be active for complete oxidation to CO<sub>2</sub> than partial oxidation, as were the MgFe<sub>2</sub>O<sub>4</sub>, LaFeO<sub>3</sub>, and TiFe<sub>2</sub>O<sub>5</sub> species formed in Fe/MgO, Fe/La<sub>2</sub>O<sub>3</sub>, and Fe/TiO<sub>2</sub>, respectively, and the interstitial solid solution of Fe<sup>3+</sup> in ZrO<sub>2</sub> generated in Fe/ZrO<sub>2</sub>. Furthermore, while the Fe<sub>2</sub>O<sub>3</sub> species in Fe/WO<sub>4</sub> are ineffective for partial oxidation, FeWO<sub>4</sub> prepared by a hydrothermal method exhibits high selectivity for partial oxidation. Additionally, previous studies have shown that CuWO<sub>4</sub> and CuMoO<sub>4</sub> are active for partial CH<sub>4</sub> oxidation. Accordingly, the ABO<sub>4</sub> structure (where A is a 3d metal and B is a group 5 or 6 metal) is indicated as a viable design basis for the development of catalysts for partial CH<sub>4</sub> oxidation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884504","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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