Pub Date : 2025-01-13DOI: 10.1016/j.checat.2024.101232
Jiarui Li, Xingbo Shi, Mei-Qi Zhang, Meng Wang, Ding Ma
The growing plastic pollution crisis calls for a greater focus on catalytic waste transformation. Among the plethora of plastics, polyethylene terephthalate (PET) is the most prevalent polyester, while polyoxymethylene (POM) is gaining traction as a widely utilized engineering plastic. In this study, we present a one-pot process for the simultaneous conversion of PET and POM plastic wastes with the use of a conventional acid catalyst. This process involves the condensation reaction of ethylene glycol (derived from PET) and formaldehyde (derived from POM), coupled with the prior depolymerization of PET and POM, resulting in the formation of 1,3-dioxolane and terephthalic acid as the major products. Notably, the catalytic reactions occur under mild conditions (no higher than 120°C) without the need for expensive catalysts or extreme environments, and all catalysts and solvents employed are recyclable. The proposed process could expand the application of waste PET and POM and inspire more upcycling strategies for plastic mixtures.
{"title":"Co-upcycling of polyethylene terephthalate and polyoxymethylene into valuable chemicals","authors":"Jiarui Li, Xingbo Shi, Mei-Qi Zhang, Meng Wang, Ding Ma","doi":"10.1016/j.checat.2024.101232","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101232","url":null,"abstract":"The growing plastic pollution crisis calls for a greater focus on catalytic waste transformation. Among the plethora of plastics, polyethylene terephthalate (PET) is the most prevalent polyester, while polyoxymethylene (POM) is gaining traction as a widely utilized engineering plastic. In this study, we present a one-pot process for the simultaneous conversion of PET and POM plastic wastes with the use of a conventional acid catalyst. This process involves the condensation reaction of ethylene glycol (derived from PET) and formaldehyde (derived from POM), coupled with the prior depolymerization of PET and POM, resulting in the formation of 1,3-dioxolane and terephthalic acid as the major products. Notably, the catalytic reactions occur under mild conditions (no higher than 120°C) without the need for expensive catalysts or extreme environments, and all catalysts and solvents employed are recyclable. The proposed process could expand the application of waste PET and POM and inspire more upcycling strategies for plastic mixtures.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"6 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142967977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sustainable hydrogen production through the photoconversion of water represents one of the leading-edge approaches for generating green energy to achieve carbon neutrality. However, most of the outstanding photocatalytic systems capable of effectively splitting pure water rely on expensive noble-metal co-catalysts. In this work, we incorporate low-cost Ni-hybrid co-catalysts onto sulfur-vacant hollow green ZnIn2S4 (NNOgZIS) through the co-deposition of Ni and NiOx onto the reductive and oxidative sites from self-generative electron-hole pairs. NNOgZIS demonstrates exceptional solar-driven pure water splitting and achieves a solar-to-hydrogen conversion efficiency exceeding that of most noble-metal-loaded single-sulfide-based systems. Additionally, it facilitates the photo-oxidative production of high-energy hydrogen peroxide. The diverse applications of NNOgZIS are positively presented through simulated seawater splitting and coupled oxidative reactions as well as a demonstration of workability in a film-based system. This study presents the potential of integrating low-cost metals into augmenting photocatalytic efficiency, establishing a foundation for cost-effective and sustainable photocatalytic-fuel-forming innovation.
{"title":"Unleashing the solar-driven overall water-splitting potential for green ZnIn2S4","authors":"Wei-Kean Chong, Boon-Junn Ng, Xin Ying Kong, Jingxiang Low, Hing Wah Lee, Lling-Lling Tan, Siang-Piao Chai","doi":"10.1016/j.checat.2024.101227","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101227","url":null,"abstract":"Sustainable hydrogen production through the photoconversion of water represents one of the leading-edge approaches for generating green energy to achieve carbon neutrality. However, most of the outstanding photocatalytic systems capable of effectively splitting pure water rely on expensive noble-metal co-catalysts. In this work, we incorporate low-cost Ni-hybrid co-catalysts onto sulfur-vacant hollow green ZnIn<sub>2</sub>S<sub>4</sub> (NNOgZIS) through the co-deposition of Ni and NiO<sub><em>x</em></sub> onto the reductive and oxidative sites from self-generative electron-hole pairs. NNOgZIS demonstrates exceptional solar-driven pure water splitting and achieves a solar-to-hydrogen conversion efficiency exceeding that of most noble-metal-loaded single-sulfide-based systems. Additionally, it facilitates the photo-oxidative production of high-energy hydrogen peroxide. The diverse applications of NNOgZIS are positively presented through simulated seawater splitting and coupled oxidative reactions as well as a demonstration of workability in a film-based system. This study presents the potential of integrating low-cost metals into augmenting photocatalytic efficiency, establishing a foundation for cost-effective and sustainable photocatalytic-fuel-forming innovation.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"12 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-20DOI: 10.1016/j.checat.2024.101229
Jianhua Liu, Diru Liu, Qi An, Tingxu Chen, Yunbo Yu, Guangyan Xu, Hong He
Ammonia emissions from vehicles and power plants cause significant environmental concerns. Here, a range of platinum and iridium catalysts supported on oxides with various levels of reducibility were investigated in ammonia selective catalytic oxidation. Weak metal-support interaction (MSI) led to the formation of metal nanoparticles on irreducible Al2O3, whereas strong MSI (SMSI) induced the generation of single-atom metals on reducible CeO2. Notably, MSI demonstrated opposite effects on the catalytic performance of Pt-based catalysts (Pt/Al2O3 ≫ Pt/TiO2 > Pt/CeO2) and Ir-based catalysts (Ir/CeO2 > Ir/TiO2 ≫ Ir/Al2O3). Metallic Pt nanoparticles on Pt/Al2O3 activated gaseous O2 and promoted the low-temperature NH3 oxidation. Conversely, on Ir/CeO2 catalysts, the single-atom Ir-O-Ce site demonstrated high reactivity for NH3 cleavage with an extremely low energy barrier, contributing to the superior low-temperature activity. This study provides insights into governing the MSI effect to regulate the structure on active sites of supported catalysts, thereby enhancing their catalytic performance.
汽车和发电厂排放的氨引起了严重的环境问题。本文研究了不同还原性氧化物负载的铂和铱催化剂在氨选择性催化氧化中的作用。弱金属-载体相互作用（MSI）导致不可还原Al2O3上形成金属纳米颗粒，而强金属-载体相互作用（SMSI）诱导可还原CeO2上形成单原子金属。值得注意的是，MSI对Pt基催化剂(Pt/Al2O3∶Pt/TiO2 >；Pt/CeO2)和Ir基催化剂(Ir/CeO2 >；Ir/TiO2 > Ir/Al2O3)。Pt/Al2O3表面的金属Pt纳米粒子活化了气态O2，促进了低温NH3氧化。相反，在Ir/CeO2催化剂上，单原子Ir- o - ce位点以极低的能垒对NH3裂解表现出很高的反应活性，从而具有优异的低温活性。本研究提供了控制MSI效应来调节负载型催化剂活性位点的结构，从而提高其催化性能的见解。
{"title":"Reverse effect of metal-support interaction on platinum and iridium catalysts in ammonia selective oxidation","authors":"Jianhua Liu, Diru Liu, Qi An, Tingxu Chen, Yunbo Yu, Guangyan Xu, Hong He","doi":"10.1016/j.checat.2024.101229","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101229","url":null,"abstract":"Ammonia emissions from vehicles and power plants cause significant environmental concerns. Here, a range of platinum and iridium catalysts supported on oxides with various levels of reducibility were investigated in ammonia selective catalytic oxidation. Weak metal-support interaction (MSI) led to the formation of metal nanoparticles on irreducible Al<sub>2</sub>O<sub>3</sub>, whereas strong MSI (SMSI) induced the generation of single-atom metals on reducible CeO<sub>2</sub>. Notably, MSI demonstrated opposite effects on the catalytic performance of Pt-based catalysts (Pt/Al<sub>2</sub>O<sub>3</sub> ≫ Pt/TiO<sub>2</sub> > Pt/CeO<sub>2</sub>) and Ir-based catalysts (Ir/CeO<sub>2</sub> > Ir/TiO<sub>2</sub> ≫ Ir/Al<sub>2</sub>O<sub>3</sub>). Metallic Pt nanoparticles on Pt/Al<sub>2</sub>O<sub>3</sub> activated gaseous O<sub>2</sub> and promoted the low-temperature NH<sub>3</sub> oxidation. Conversely, on Ir/CeO<sub>2</sub> catalysts, the single-atom Ir-O-Ce site demonstrated high reactivity for NH<sub>3</sub> cleavage with an extremely low energy barrier, contributing to the superior low-temperature activity. This study provides insights into governing the MSI effect to regulate the structure on active sites of supported catalysts, thereby enhancing their catalytic performance.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"11 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-19DOI: 10.1016/j.checat.2024.101218
Kai Zhang, Xiaohang Du, Jingde Li
In a recent issue of Cell Reports Physical Science, Bent and co-workers studied the electrochemical conversion of four typical nickel-based precatalysts toward alkaline oxygen evolution reaction and the effect of iron impurities on their conversion and catalytic activity. This is undoubtedly a key guide for designing alkaline oxygen evolution precatalysts.
{"title":"Key role of precatalyst composition and iron impurities in oxygen evolution reaction","authors":"Kai Zhang, Xiaohang Du, Jingde Li","doi":"10.1016/j.checat.2024.101218","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101218","url":null,"abstract":"In a recent issue of <em>Cell Reports Physical Science</em>, Bent and co-workers studied the electrochemical conversion of four typical nickel-based precatalysts toward alkaline oxygen evolution reaction and the effect of iron impurities on their conversion and catalytic activity. This is undoubtedly a key guide for designing alkaline oxygen evolution precatalysts.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"48 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849807","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-19DOI: 10.1016/j.checat.2024.101226
Yohei Katsuyama
In a recent issue of Nature Chemistry, Zhang and coworkers showed that the ATP-dependent N-nitrosylase Tri17 can catalyze azide synthesis. Tri17 is a promiscuous enzyme that can catalyze N-nitrosylation of various substrates. When specific substrates were used, it also catalyzed the dehydration of the N-nitroso moiety to synthesize an azide moiety.
{"title":"Enzymatic azide synthesis by ATP-dependent synthetase","authors":"Yohei Katsuyama","doi":"10.1016/j.checat.2024.101226","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101226","url":null,"abstract":"In a recent issue of <em>Nature Chemistry</em>, Zhang and coworkers showed that the ATP-dependent <em>N</em>-nitrosylase Tri17 can catalyze azide synthesis. Tri17 is a promiscuous enzyme that can catalyze <em>N</em>-nitrosylation of various substrates. When specific substrates were used, it also catalyzed the dehydration of the <em>N</em>-nitroso moiety to synthesize an azide moiety.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"12 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849831","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-19DOI: 10.1016/j.checat.2024.101228
Zihao Zhang, Jing Guo
In a recent issue of Nature Catalysis, Rost et al. directly visualized the step bunching on flame-annealed Pt(111)-vicinal surfaces at high step densities using in situ electrochemical scanning tunneling microscopy (EC-STM). This phenomenon originates from the increased step-step repulsive interaction between closely distanced steps, and the surface-free energy will be lowered when forming bunched steps with wider terraces. This work challenges the common assumption that all stepped surfaces present homogeneously spaced steps of monoatomic height and provides a convincing explanation at atomic level for the anomalous electrochemical behavior of the platinum surface at high step densities, including the activity and potential of zero total charge.
{"title":"Visualizing the step bunching on Pt surfaces and its effect in electrocatalysis with EC-STM","authors":"Zihao Zhang, Jing Guo","doi":"10.1016/j.checat.2024.101228","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101228","url":null,"abstract":"In a recent issue of <em>Nature Catalysis</em>, Rost et al. directly visualized the step bunching on flame-annealed Pt(111)-vicinal surfaces at high step densities using <em>in situ</em> electrochemical scanning tunneling microscopy (EC-STM). This phenomenon originates from the increased step-step repulsive interaction between closely distanced steps, and the surface-free energy will be lowered when forming bunched steps with wider terraces. This work challenges the common assumption that all stepped surfaces present homogeneously spaced steps of monoatomic height and provides a convincing explanation at atomic level for the anomalous electrochemical behavior of the platinum surface at high step densities, including the activity and potential of zero total charge.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"1 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849833","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-19DOI: 10.1016/j.checat.2024.101230
Yu Yang, Yaohui Shi, Fengwang Li
Understanding the evolution of Cu-based catalysts during electrochemical CO2 reduction (ECR) remains challenging. The study by Lim et al. in Joule devises an operando scanning transmission X-ray microscopy to investigate the dynamic phase transformations of Cu catalysts and reveals that Cu2+ species play a crucial role in enhancing C–C coupling. The findings inform the authors of an approach to dynamically redirect the oxidation state of Cu, achieving, as a result, higher selectivity and efficiency for ECR catalysis.
{"title":"Visualizing active species in CO2 electroreduction","authors":"Yu Yang, Yaohui Shi, Fengwang Li","doi":"10.1016/j.checat.2024.101230","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101230","url":null,"abstract":"Understanding the evolution of Cu-based catalysts during electrochemical CO<sub>2</sub> reduction (ECR) remains challenging. The study by Lim et al. in <em>Joule</em> devises an <em>operando</em> scanning transmission X-ray microscopy to investigate the dynamic phase transformations of Cu catalysts and reveals that Cu<sup>2+</sup> species play a crucial role in enhancing C–C coupling. The findings inform the authors of an approach to dynamically redirect the oxidation state of Cu, achieving, as a result, higher selectivity and efficiency for ECR catalysis.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"31 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-12-18DOI: 10.1016/j.checat.2024.101220
Aditya Prajapati, Alexandra Zagalskaya, Natalie Hwee, Jonathan T. Davis, Hui-Yun Jeong, Jennifer Moreno, Jenna Ynzunza, Sneha A. Akhade, Jeremy T. Feaster
Nitric acid is an important commodity chemical in agriculture and industry, yet its conventional production through the Haber-Bosch and Ostwald processes is energy and carbon-emission intensive. An electrochemical nitrogen oxidation reaction (NOR) to produce nitrates shows great potential as an environmentally friendly method of producing fertilizers under mild conditions. Progress in this field requires fundamental mechanistic understanding and establishing robust experimental methods, which is essential for the efficient design and synthesis of electrocatalysts for the NOR. We present a synergistic computational and experimental approach to exploring NOR pathways on a PtO<sub>2</sub> catalyst to gain mechanistic insights into the NOR. This study marks the first attempt to perform the NOR in a vapor-fed reactor designed through advanced (additive) manufacturing. The vapor-fed reactor significantly improved the N<sub>2</sub> mass transport to the catalyst, allowing us to report the highest rate for nitrate production to date at <span><span style=""></span><span data-mathml='<math xmlns="http://www.w3.org/1998/Math/MathML"><mrow is="true"><mn is="true">3.3</mn><mspace width="0.25em" is="true" /><mi is="true">μ</mi><mtext is="true">mol</mtext><mspace width="0.25em" is="true" /><mi mathvariant="normal" is="true">c</mi><msup is="true"><mi mathvariant="normal" is="true">m</mi><mrow is="true"><mo is="true">−</mo><mn is="true">2</mn></mrow></msup><msup is="true"><mi mathvariant="normal" is="true">h</mi><mrow is="true"><mo is="true">−</mo><mn is="true">1</mn></mrow></msup></mrow></math>' role="presentation" style="font-size: 90%; display: inline-block; position: relative;" tabindex="0"><svg aria-hidden="true" focusable="false" height="2.779ex" role="img" style="vertical-align: -0.697ex;" viewbox="0 -896.2 7838.8 1196.3" width="18.206ex" 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"><g is="true"><use xlink:href="#MJMAIN-33"></use><use x="500" xlink:href="#MJMAIN-2E" y="0"></use><use x="779" xlink:href="#MJMAIN-33" y="0"></use></g><g is="true"></g><g is="true" transform="translate(1529,0)"><use xlink:href="#MJMATHI-3BC"></use></g><g is="true" transform="translate(2133,0)"><use xlink:href="#MJMAIN-6D"></use><use x="833" xlink:href="#MJMAIN-6F" y="0"></use><use x="1334" xlink:href="#MJMAIN-6C" y="0"></use></g><g is="true"></g><g is="true" transform="translate(3995,0)"><use xlink:href="#MJMAIN-63"></use></g><g is="true" transform="translate(4440,0)"><g is="true"><use xlink:href="#MJMAIN-6D"></use></g><g is="true" transform="translate(833,362)"><g is="true"><use transform="scale(0.707)" xlink:href="#MJMAIN-2212"></use></g><g
{"title":"Decarbonizing nitrogen fertilizer production via the electrochemical nitrogen oxidation reaction","authors":"Aditya Prajapati, Alexandra Zagalskaya, Natalie Hwee, Jonathan T. Davis, Hui-Yun Jeong, Jennifer Moreno, Jenna Ynzunza, Sneha A. Akhade, Jeremy T. Feaster","doi":"10.1016/j.checat.2024.101220","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101220","url":null,"abstract":"Nitric acid is an important commodity chemical in agriculture and industry, yet its conventional production through the Haber-Bosch and Ostwald processes is energy and carbon-emission intensive. An electrochemical nitrogen oxidation reaction (NOR) to produce nitrates shows great potential as an environmentally friendly method of producing fertilizers under mild conditions. Progress in this field requires fundamental mechanistic understanding and establishing robust experimental methods, which is essential for the efficient design and synthesis of electrocatalysts for the NOR. We present a synergistic computational and experimental approach to exploring NOR pathways on a PtO<sub>2</sub> catalyst to gain mechanistic insights into the NOR. This study marks the first attempt to perform the NOR in a vapor-fed reactor designed through advanced (additive) manufacturing. The vapor-fed reactor significantly improved the N<sub>2</sub> mass transport to the catalyst, allowing us to report the highest rate for nitrate production to date at <span><span style=\"\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\"><mrow is=\"true\"><mn is=\"true\">3.3</mn><mspace width=\"0.25em\" is=\"true\" /><mi is=\"true\">&#x3BC;</mi><mtext is=\"true\">mol</mtext><mspace width=\"0.25em\" is=\"true\" /><mi mathvariant=\"normal\" is=\"true\">c</mi><msup is=\"true\"><mi mathvariant=\"normal\" is=\"true\">m</mi><mrow is=\"true\"><mo is=\"true\">&#x2212;</mo><mn is=\"true\">2</mn></mrow></msup><msup is=\"true\"><mi mathvariant=\"normal\" is=\"true\">h</mi><mrow is=\"true\"><mo is=\"true\">&#x2212;</mo><mn is=\"true\">1</mn></mrow></msup></mrow></math>' role=\"presentation\" style=\"font-size: 90%; display: inline-block; position: relative;\" tabindex=\"0\"><svg aria-hidden=\"true\" focusable=\"false\" height=\"2.779ex\" role=\"img\" style=\"vertical-align: -0.697ex;\" viewbox=\"0 -896.2 7838.8 1196.3\" width=\"18.206ex\" 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\"><g is=\"true\"><use xlink:href=\"#MJMAIN-33\"></use><use x=\"500\" xlink:href=\"#MJMAIN-2E\" y=\"0\"></use><use x=\"779\" xlink:href=\"#MJMAIN-33\" y=\"0\"></use></g><g is=\"true\"></g><g is=\"true\" transform=\"translate(1529,0)\"><use xlink:href=\"#MJMATHI-3BC\"></use></g><g is=\"true\" transform=\"translate(2133,0)\"><use xlink:href=\"#MJMAIN-6D\"></use><use x=\"833\" xlink:href=\"#MJMAIN-6F\" y=\"0\"></use><use x=\"1334\" xlink:href=\"#MJMAIN-6C\" y=\"0\"></use></g><g is=\"true\"></g><g is=\"true\" transform=\"translate(3995,0)\"><use xlink:href=\"#MJMAIN-63\"></use></g><g is=\"true\" transform=\"translate(4440,0)\"><g is=\"true\"><use xlink:href=\"#MJMAIN-6D\"></use></g><g is=\"true\" transform=\"translate(833,362)\"><g is=\"true\"><use transform=\"scale(0.707)\" xlink:href=\"#MJMAIN-2212\"></use></g><g ","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"18 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dearomative cycloaddition is a crucial method for constructing three-dimensional (3D) complex molecules from simple precursors, but the difficulty in exciting many arenes limits the application of this method. Herein, we report a photocatalytic intermolecular dearomative [2 + 2]/[4 + 2] cycloaddition of phenanthrenes and naphthalenes with excited gem-difluoroalkenes for the synthesis of fused gem-difluorocyclobutanes and gem-difluorocyclohexanes. Previous dearomative cycloaddition reactions involving excited phenanthrenes and naphthalenes required electron-deficient substituents to lower their excited-state energies, allowing for energy-transfer catalysis to occur. Our strategy involves excited-state gem-difluoroalkenes undergoing dearomative cycloaddition reactions with ground-state phenanthrenes and naphthalenes, enabling it to tolerate not only electron-deficient arenes but also electron-neutral and electron-rich arenes.
{"title":"Photocatalytic intermolecular dearomative cycloaddition of phenanthrenes and naphthalenes with excited gem-difluoroalkenes","authors":"Yunxiao Zhang, Youyuan Guo, Yizhi Zhang, Shanshan Liu, Xiao Shen","doi":"10.1016/j.checat.2024.101200","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101200","url":null,"abstract":"Dearomative cycloaddition is a crucial method for constructing three-dimensional (3D) complex molecules from simple precursors, but the difficulty in exciting many arenes limits the application of this method. Herein, we report a photocatalytic intermolecular dearomative [2 + 2]/[4 + 2] cycloaddition of phenanthrenes and naphthalenes with excited <em>gem</em>-difluoroalkenes for the synthesis of fused <em>gem</em>-difluorocyclobutanes and <em>gem</em>-difluorocyclohexanes. Previous dearomative cycloaddition reactions involving excited phenanthrenes and naphthalenes required electron-deficient substituents to lower their excited-state energies, allowing for energy-transfer catalysis to occur. Our strategy involves excited-state <em>gem</em>-difluoroalkenes undergoing dearomative cycloaddition reactions with ground-state phenanthrenes and naphthalenes, enabling it to tolerate not only electron-deficient arenes but also electron-neutral and electron-rich arenes.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"30 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142833048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Phosphonium salts are widely applied in organic synthesis, catalysis, materials science, and medicinal chemistry. Hydro-phosphoniumylation of alkene is one of the most powerful and straightforward methodologies for phosphonium salt synthesis. However, the established phospha-Michael reaction is limited to electronically activated olefins, and unactivated alkenes are not reactive. Herein, we report a photocatalytic and redox-neutral protocol for the efficient addition of phosphines and CF3COOH to various unactivated olefins, which would be thermodynamically unfavorable under thermochemical conditions. The reaction commences with the generation of a phosphine radical cation (PRC) through the single-electron oxidation of phosphine by an excited photocatalyst. PRC adds to alkene in a kinetically barrierless manner. The method exhibits a broad substrate scope for both phosphines and alkenes. β-Deuterated phosphonium salts, whose synthesis is difficult by other methods, could also be accessed by this reaction with CF3COOD/D2O. Mechanistic and density functional theory (DFT) studies support a radical addition mechanism for P–C bond formation.
{"title":"Photon-driven radical hydro-phosphoniumylation of unactivated olefins","authors":"Kaihui Liu, Chang Liu, Guangqi Hu, Tianqi Wang, Zhiyong He, Juntao Pu, Ziliang Yuan, Jing Hou, Lewu Zhan, Bindong Li, Dinghai Wang","doi":"10.1016/j.checat.2024.101219","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101219","url":null,"abstract":"Phosphonium salts are widely applied in organic synthesis, catalysis, materials science, and medicinal chemistry. Hydro-phosphoniumylation of alkene is one of the most powerful and straightforward methodologies for phosphonium salt synthesis. However, the established phospha-Michael reaction is limited to electronically activated olefins, and unactivated alkenes are not reactive. Herein, we report a photocatalytic and redox-neutral protocol for the efficient addition of phosphines and CF<sub>3</sub>COOH to various unactivated olefins, which would be thermodynamically unfavorable under thermochemical conditions. The reaction commences with the generation of a phosphine radical cation (PRC) through the single-electron oxidation of phosphine by an excited photocatalyst. PRC adds to alkene in a kinetically barrierless manner. The method exhibits a broad substrate scope for both phosphines and alkenes. β-Deuterated phosphonium salts, whose synthesis is difficult by other methods, could also be accessed by this reaction with CF<sub>3</sub>COOD/D<sub>2</sub>O. Mechanistic and density functional theory (DFT) studies support a radical addition mechanism for P–C bond formation.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"41 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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