The first asymmetric Mannich reaction of α-aminomaleimides with N-Boc imines was successfully performed using 5 mol% of a urea-type organocatalyst derived from quinine to afford the corresponding Mannich adducts in high yields with high enantioselectivities. This protocol has a simple experimental procedure, good functional group tolerance, broad substrate scope, and high enantioselectivities.
{"title":"Organocatalyzed asymmetric Mannich reaction of α-aminomaleimides with N-Boc imines","authors":"Shun Suzuki, Kodai Kimura, Wei Han, T. Oriyama*","doi":"10.1093/bulcsj/uoae051","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae051","url":null,"abstract":"\u0000 The first asymmetric Mannich reaction of α-aminomaleimides with N-Boc imines was successfully performed using 5 mol% of a urea-type organocatalyst derived from quinine to afford the corresponding Mannich adducts in high yields with high enantioselectivities. This protocol has a simple experimental procedure, good functional group tolerance, broad substrate scope, and high enantioselectivities.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141036794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Akinari Chiba, Kan Hatakeyama‐Sato, Kenichi Oyaizu
Solid polymer electrolytes have been intensively studied to improve the safety and energy density of lithium-ion batteries (LiBs). Although high-rate performance of LiBs has been reported in electrolytes under polymer-in-salt conditions with an excess of lithium salts and polymers, effective conditions for achieving high ionic conductivity have been unresolved. In this study, we elucidated the mechanism and high Li-ion transportability of poly(sulfone-thioether) under polymer-in-salt conditions. In particular, the composition of the polymer with an asymmetric Li salt, lithium(fluorosulfonyl)(trifluoromethane sulfonyl)imide (LiFTFSI), induced a high ionic conductivity above 10−5 S/cm, which was higher than that of the poly(ethylene oxide) (PEO)-Li salt system. Under polymer-in-salt conditions, the enhanced conductivity of poly(sulfone-thioether) contrasts with the conductivity drop observed in the conventional PEO system. These results showed the superiority of polymers with soft Lewis bases, such as sulfur donor atoms, for Li-ion transport under polymer-in-salt conditions.
{"title":"Sulfur-containing Soft Lewis Base Polymers for Improved Lithium-ion Conductivity under Polymer-in-salt Conditions","authors":"Akinari Chiba, Kan Hatakeyama‐Sato, Kenichi Oyaizu","doi":"10.1093/bulcsj/uoae048","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae048","url":null,"abstract":"\u0000 Solid polymer electrolytes have been intensively studied to improve the safety and energy density of lithium-ion batteries (LiBs). Although high-rate performance of LiBs has been reported in electrolytes under polymer-in-salt conditions with an excess of lithium salts and polymers, effective conditions for achieving high ionic conductivity have been unresolved. In this study, we elucidated the mechanism and high Li-ion transportability of poly(sulfone-thioether) under polymer-in-salt conditions. In particular, the composition of the polymer with an asymmetric Li salt, lithium(fluorosulfonyl)(trifluoromethane sulfonyl)imide (LiFTFSI), induced a high ionic conductivity above 10−5 S/cm, which was higher than that of the poly(ethylene oxide) (PEO)-Li salt system. Under polymer-in-salt conditions, the enhanced conductivity of poly(sulfone-thioether) contrasts with the conductivity drop observed in the conventional PEO system. These results showed the superiority of polymers with soft Lewis bases, such as sulfur donor atoms, for Li-ion transport under polymer-in-salt conditions.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140681772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Computational screening of N-heterocyclic carbene-based PCP-type pincer ligands has been performed for the design of molybdenum-based molecular catalysts for nitrogen fixation. Previously, we theoretically and experimentally demonstrated that the introduction of electron-donating/withdrawing substituents to the original PCP ligand is a promising way to control the catalytic activity [Nat. Synth. 2023, 2, 635]. Here, we investigate electronic and energetic properties of nitrogenous Mo intermediates bearing 38 substituted PCP ligands [MoI(NHx)(R-PCP)] (x = 1-3) that are involved in the rate-determining step in our proposed catalytic mechanism. Electron-withdrawing substituents enhance the π-accepting ability of R-PCP and effectively stabilize the LUMO of the corresponding Mo-nitride (Mo≡N) complexes, which is expected to be advantageous for the transformation of the nitride N atom via proton-coupled electron transfer (PCET). The introduction of strong electron-withdrawing substituents to the PCP ligand also increases the N–H bond energy of [MoI(NHx)(R-PCP)] evaluated with the bond dissociation free energy (BDFE) and the bond dissociation enthalpy (BDE). As a result of the computational screening, we newly propose an alternative strategy for designing PCP ligands with high π-accepting ability, the extension of the π-conjugated system of the PCP ligand by introducing fused benzene rings.
{"title":"Computational Screening of PCP-Type Pincer Ligands for Mo-Catalyzed Nitrogen Fixation","authors":"Akihito Egi, Hiromasa Tanaka, Taiji Nakamura, Kazuya Arashiba, Y. Nishibayashi, Kazunari Yoshizawa","doi":"10.1093/bulcsj/uoae041","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae041","url":null,"abstract":"\u0000 Computational screening of N-heterocyclic carbene-based PCP-type pincer ligands has been performed for the design of molybdenum-based molecular catalysts for nitrogen fixation. Previously, we theoretically and experimentally demonstrated that the introduction of electron-donating/withdrawing substituents to the original PCP ligand is a promising way to control the catalytic activity [Nat. Synth. 2023, 2, 635]. Here, we investigate electronic and energetic properties of nitrogenous Mo intermediates bearing 38 substituted PCP ligands [MoI(NHx)(R-PCP)] (x = 1-3) that are involved in the rate-determining step in our proposed catalytic mechanism. Electron-withdrawing substituents enhance the π-accepting ability of R-PCP and effectively stabilize the LUMO of the corresponding Mo-nitride (Mo≡N) complexes, which is expected to be advantageous for the transformation of the nitride N atom via proton-coupled electron transfer (PCET). The introduction of strong electron-withdrawing substituents to the PCP ligand also increases the N–H bond energy of [MoI(NHx)(R-PCP)] evaluated with the bond dissociation free energy (BDFE) and the bond dissociation enthalpy (BDE). As a result of the computational screening, we newly propose an alternative strategy for designing PCP ligands with high π-accepting ability, the extension of the π-conjugated system of the PCP ligand by introducing fused benzene rings.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140689337","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We proposed a model for ionization–induced reactions between N2 and CH4, the main components of Titan’s atmosphere, and examined their mechanism using quantum mechanical and molecular dynamics methods. Bimolecular CH4—N2 clusters form through collision, and their conformation depends on the encounter cross section due to weak intermolecular interaction. These clusters acquire a driving force through vertical ionization because the vertically ionized structure is not situated at the minimum of the potential energy surface in the ionized state. This leads to multiple reactions, overcoming energy barriers in the process. In the divalent state, a robust attractive interaction occurs between CH4 and N2 through charge transfer. Subsequently, the H4C–N2 covalent bond forms prior to reactions, resulting in the production of N2H+, CH3+, CH3N2+, and CH2N2+; otherwise only N2H+, CH3+, and CH2+ are generated. In contrast, when ionized to monovalent state, although dissociation of N2H+ and isomerization to CH3NHN+ and CH3NNH+ occurs, a significant portion dissociates into CH4+ and N2 without undergoing further reactions. Additionally, the generation of N2H+ and CH3+ is limited in the monovalent state, primarily due to a lower driving force and the absence of Coulombic explosion. Our computational results highlight the pivotal role of divalent reactions within Titan’s atmosphere, which are more efficient than monovalent reactions.
{"title":"A Model of Ionization–Induced Reactions in CH4/N2 Clusters in Titan’s Atmosphere: Theoretical Insights into Mono– and Divalent States","authors":"Toshiaki Matsubara","doi":"10.1093/bulcsj/uoae047","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae047","url":null,"abstract":"\u0000 We proposed a model for ionization–induced reactions between N2 and CH4, the main components of Titan’s atmosphere, and examined their mechanism using quantum mechanical and molecular dynamics methods. Bimolecular CH4—N2 clusters form through collision, and their conformation depends on the encounter cross section due to weak intermolecular interaction. These clusters acquire a driving force through vertical ionization because the vertically ionized structure is not situated at the minimum of the potential energy surface in the ionized state. This leads to multiple reactions, overcoming energy barriers in the process. In the divalent state, a robust attractive interaction occurs between CH4 and N2 through charge transfer. Subsequently, the H4C–N2 covalent bond forms prior to reactions, resulting in the production of N2H+, CH3+, CH3N2+, and CH2N2+; otherwise only N2H+, CH3+, and CH2+ are generated. In contrast, when ionized to monovalent state, although dissociation of N2H+ and isomerization to CH3NHN+ and CH3NNH+ occurs, a significant portion dissociates into CH4+ and N2 without undergoing further reactions. Additionally, the generation of N2H+ and CH3+ is limited in the monovalent state, primarily due to a lower driving force and the absence of Coulombic explosion. Our computational results highlight the pivotal role of divalent reactions within Titan’s atmosphere, which are more efficient than monovalent reactions.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140692887","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polymer electrolyte fuel cells (PEFCs) offer promising alternatives to conventional gasoline engines in automobiles and have been commercialized over the past decade. This progress can be attributed to state-of-the-art materials with high performance, long-term durability, and robust manufacturing technologies. The multiscale hierarchical structure inherent in PEFCs facilitates the transfer of protons, electrons, oxygen, and water. As various phenomena in PEFCs occur at different scales, multiscale analysis, including quantum beam analysis, is of great interest for materials development and for understanding the processes that take place in PEFCs. In particular, advancements in this field have enabled the further tailoring of properties in a controlled manner and the design of nanostructures processing superior material properties. Additionally, the expansion of quantum beam sources has facilitated the study of manufacturing protocols. This review presents the achievements in the use of synchrotron X-ray and neutron sources in the field of PEFCs, while also addressing remaining issues for the widespread commercialization of fuel cell electric vehicles.
聚合物电解质燃料电池（PEFCs）是汽车中传统汽油发动机的理想替代品，在过去十年中已经实现了商业化。这一进步归功于具有高性能、长期耐久性和强大制造技术的最先进材料。PEFC 固有的多尺度分层结构有利于质子、电子、氧气和水的转移。由于 PEFC 中的各种现象发生在不同尺度上，因此多尺度分析（包括量子束分析）对于材料开发和了解 PEFC 中发生的过程具有重大意义。特别是，该领域的进步使得人们能够以可控方式进一步调整材料特性，并设计出具有优异材料特性的纳米结构。此外，量子束源的扩展也促进了对制造协议的研究。本综述介绍了同步辐射 X 射线源和中子源在 PEFC 领域的应用成果，同时还讨论了燃料电池电动汽车广泛商业化的其余问题。
{"title":"Multiscale Characterization of Polymer Electrolyte Fuel Cells Elucidated by Quantum Beam Analysis","authors":"Wataru Yoshimiune","doi":"10.1093/bulcsj/uoae046","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae046","url":null,"abstract":"\u0000 Polymer electrolyte fuel cells (PEFCs) offer promising alternatives to conventional gasoline engines in automobiles and have been commercialized over the past decade. This progress can be attributed to state-of-the-art materials with high performance, long-term durability, and robust manufacturing technologies. The multiscale hierarchical structure inherent in PEFCs facilitates the transfer of protons, electrons, oxygen, and water. As various phenomena in PEFCs occur at different scales, multiscale analysis, including quantum beam analysis, is of great interest for materials development and for understanding the processes that take place in PEFCs. In particular, advancements in this field have enabled the further tailoring of properties in a controlled manner and the design of nanostructures processing superior material properties. Additionally, the expansion of quantum beam sources has facilitated the study of manufacturing protocols. This review presents the achievements in the use of synchrotron X-ray and neutron sources in the field of PEFCs, while also addressing remaining issues for the widespread commercialization of fuel cell electric vehicles.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140691137","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Takami Inaba, Enggah Kurniawan, Takayoshi Hara, Yasuhiro Yamada, Satoshi Sato
Silica-supported alkali metal phosphate catalysts were investigated for the vapor-phase dehydration of 1,2-butanediol (1,2-BDO) to produce 1,3-butadiene (BD). Among the alkali metal phosphates explored, a silica-supported CsH2PO4 (CsH2PO4/SiO2) was found to be the most efficient catalyst. Several parameters, such as the Cs/P ratio, reaction temperature, and contact time, significantly affected the BD formation. The highest BD yield of 59.6% was achieved over 10CsH2PO4/SiO2 at 411 °C, with butanal and butanone as the main side products. Based on the conversion-selectivity plots at 411 °C, a possible reaction pathway for BD formation was proposed. In addition, the dehydrations of 1,2-epoxybutane and 2-buten-1-ol were also performed to verify the reaction sequence. The epoxidation of 1,2-BDO to 1,2-epoxybutane, which is one of the initial steps of the stepwise formation of BD, proceeded via an acid-base concerted mechanism. This work is the first report on the dehydration of 1,2-BDO to produce BD efficiently.
{"title":"Catalytic dehydration of 1,2-butanediol to 1,3-butadiene over CsH2PO4/SiO2","authors":"Takami Inaba, Enggah Kurniawan, Takayoshi Hara, Yasuhiro Yamada, Satoshi Sato","doi":"10.1093/bulcsj/uoae049","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae049","url":null,"abstract":"\u0000 Silica-supported alkali metal phosphate catalysts were investigated for the vapor-phase dehydration of 1,2-butanediol (1,2-BDO) to produce 1,3-butadiene (BD). Among the alkali metal phosphates explored, a silica-supported CsH2PO4 (CsH2PO4/SiO2) was found to be the most efficient catalyst. Several parameters, such as the Cs/P ratio, reaction temperature, and contact time, significantly affected the BD formation. The highest BD yield of 59.6% was achieved over 10CsH2PO4/SiO2 at 411 °C, with butanal and butanone as the main side products. Based on the conversion-selectivity plots at 411 °C, a possible reaction pathway for BD formation was proposed. In addition, the dehydrations of 1,2-epoxybutane and 2-buten-1-ol were also performed to verify the reaction sequence. The epoxidation of 1,2-BDO to 1,2-epoxybutane, which is one of the initial steps of the stepwise formation of BD, proceeded via an acid-base concerted mechanism. This work is the first report on the dehydration of 1,2-BDO to produce BD efficiently.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140690539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two tris(2,4,6-trichlorophenyl)methyl (TTM)-type luminescent radicals TTM-(3PCz)2 and TTM-(3PCz)3 bearing two and three 9-phenylcarbazol-3-yl (3PCz) substituents, respectively, were synthesized and characterized. The photo-bleaching of these radicals was suppressed compared with that of previously reported TTM-type luminescent radicals, suggesting a favorable effect of the multiple electron-donating 3PCz groups on the photostability of the TTM-type radicals.
{"title":"Synthesis and Optical Properties of Tris(2,4,6-trichlorophenyl)methyl-Type Luminescent Radicals Bearing Multiple Carbazole Substituents","authors":"Peiyuan Yang, Masakazu Nagata, Hiroki Fukumoto, Kouichi Nakashima, Takuma Yasuda, T. Agou","doi":"10.1093/bulcsj/uoae045","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae045","url":null,"abstract":"\u0000 Two tris(2,4,6-trichlorophenyl)methyl (TTM)-type luminescent radicals TTM-(3PCz)2 and TTM-(3PCz)3 bearing two and three 9-phenylcarbazol-3-yl (3PCz) substituents, respectively, were synthesized and characterized. The photo-bleaching of these radicals was suppressed compared with that of previously reported TTM-type luminescent radicals, suggesting a favorable effect of the multiple electron-donating 3PCz groups on the photostability of the TTM-type radicals.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140699253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Prostaglandins are a family of molecules that possess important biological properties, and some of the analogues are used as medicines. Many synthetic methods have been developed for the efficient synthesis of prostaglandins. In this review, we will describe recent advances in the synthesis of prostaglandins and our endeavors in the effective synthesis of prostaglandins. Our group has developed three [3 + 2] cycloaddition reactions catalyzed by diphenylprolinol silyl ether, affording chiral substituted cyclopentane frameworks with excellent diastereo- and enantioselectivities. By using these cyclopentanes as key intermediates and applying the pot reactions, several prostaglandins were synthesized efficiently in a small number of pots.
{"title":"Pot-economical total synthesis of prostaglandins via organocatalyst-mediated asymmetric reactions","authors":"Yujiro Hayashi","doi":"10.1093/bulcsj/uoae039","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae039","url":null,"abstract":"\u0000 Prostaglandins are a family of molecules that possess important biological properties, and some of the analogues are used as medicines. Many synthetic methods have been developed for the efficient synthesis of prostaglandins. In this review, we will describe recent advances in the synthesis of prostaglandins and our endeavors in the effective synthesis of prostaglandins. Our group has developed three [3 + 2] cycloaddition reactions catalyzed by diphenylprolinol silyl ether, affording chiral substituted cyclopentane frameworks with excellent diastereo- and enantioselectivities. By using these cyclopentanes as key intermediates and applying the pot reactions, several prostaglandins were synthesized efficiently in a small number of pots.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140364015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nali Chen, Mengyu Hu, Lulu Gou, Lin Tan, Dan Zhao, Huixia Feng
In this paper, carbon-doped Bi2MoO6 (C-Bi2MoO6) nanosheets self-assembled microspheres were prepared by solvothermal-calcination route to improve the photocatalytic activity of Bi2MoO6. The characterization results of XRD, FTIR, Raman, SEM, TEM, BET and XPS indicated that C replaced the O2- anion in Bi2MoO6 lattice, thinning the nanosheets, decreasing the size of microspheres, and increasing the specific surface area of Bi2MoO6. UV-Vis DRS, PL, EIS, transient photocurrent and LSV spectra demonstrated that the carbon doping reduced the band gap energy, raised the conduction band and enhanced the photogenerated electron-hole pairs separation efficiency of Bi2MoO6. Benefiting from these favorable changes, the C-Bi2MoO6 microspheres prepared at a molar ratio of C to Bi of 4 (4C-Bi2MoO6) exhibited the highest photocatalytic activity, and the photocatalytic degradation rate constant of rhodamine B by 4C-Bi2MoO6 microspheres was almost 2.26 times that by pristine Bi2MoO6 under simulated solar light. 4C-Bi2MoO6 microspheres (0.2 g/L) presented excellent photocatalytic performance toward RhB (20 mg/L) at pH value 1 and could remove 98.31% of RhB within 120 min. In addition, 4C-Bi2MoO6 microspheres also possessed a high photocatalytic activity toward methylene blue and tetracycline. 4C-Bi2MoO6 microspheres assembled from thin nanosheets can be used as effective photocatalysts to degrade toxic organic molecules from wastewater.
{"title":"Carbon-Doped Bi2MoO6 Nanosheets Self-Assembled Microspheres for Photocatalytic Degradation of Organic Dyes","authors":"Nali Chen, Mengyu Hu, Lulu Gou, Lin Tan, Dan Zhao, Huixia Feng","doi":"10.1093/bulcsj/uoae030","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae030","url":null,"abstract":"\u0000 In this paper, carbon-doped Bi2MoO6 (C-Bi2MoO6) nanosheets self-assembled microspheres were prepared by solvothermal-calcination route to improve the photocatalytic activity of Bi2MoO6. The characterization results of XRD, FTIR, Raman, SEM, TEM, BET and XPS indicated that C replaced the O2- anion in Bi2MoO6 lattice, thinning the nanosheets, decreasing the size of microspheres, and increasing the specific surface area of Bi2MoO6. UV-Vis DRS, PL, EIS, transient photocurrent and LSV spectra demonstrated that the carbon doping reduced the band gap energy, raised the conduction band and enhanced the photogenerated electron-hole pairs separation efficiency of Bi2MoO6. Benefiting from these favorable changes, the C-Bi2MoO6 microspheres prepared at a molar ratio of C to Bi of 4 (4C-Bi2MoO6) exhibited the highest photocatalytic activity, and the photocatalytic degradation rate constant of rhodamine B by 4C-Bi2MoO6 microspheres was almost 2.26 times that by pristine Bi2MoO6 under simulated solar light. 4C-Bi2MoO6 microspheres (0.2 g/L) presented excellent photocatalytic performance toward RhB (20 mg/L) at pH value 1 and could remove 98.31% of RhB within 120 min. In addition, 4C-Bi2MoO6 microspheres also possessed a high photocatalytic activity toward methylene blue and tetracycline. 4C-Bi2MoO6 microspheres assembled from thin nanosheets can be used as effective photocatalysts to degrade toxic organic molecules from wastewater.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140366173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ban Kinoshita, Saki Maejima, Yuta Niki, K. Mitsudo, Seiji Suga, Hideki Yorimitsu
Electrochemical reduction of the trimethylsilyl enolates of alkyl aryl ketones induces retro-Brook rearrangement to provide 1-aryl-1-trimethylsilylalkan-1-ols. The transformation proceeds through a sequence of 1) single-electron reduction of the silyl enolate, 2) protonation with a phenol, 3) another single-electron reduction to form siloxy-substituted benzylic anion, and 4) the pivotal retro-Brook rearrangement.
{"title":"[1,2]-Retro-Brook Rearrangement Induced by Electrochemical Reduction of Silyl Enolates","authors":"Ban Kinoshita, Saki Maejima, Yuta Niki, K. Mitsudo, Seiji Suga, Hideki Yorimitsu","doi":"10.1093/bulcsj/uoae038","DOIUrl":"https://doi.org/10.1093/bulcsj/uoae038","url":null,"abstract":"\u0000 Electrochemical reduction of the trimethylsilyl enolates of alkyl aryl ketones induces retro-Brook rearrangement to provide 1-aryl-1-trimethylsilylalkan-1-ols. The transformation proceeds through a sequence of 1) single-electron reduction of the silyl enolate, 2) protonation with a phenol, 3) another single-electron reduction to form siloxy-substituted benzylic anion, and 4) the pivotal retro-Brook rearrangement.","PeriodicalId":9511,"journal":{"name":"Bulletin of the Chemical Society of Japan","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140368633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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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