Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous pol...Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous polyoxometalate-pillared metal-organic frameworks,formulated as H_(3n)[Cu_(3)(pidc)_(2)(H_(2)O)_(2.5)]_(2)[PW_(12)O_(40)]_n·x H_(2)O (n=1.5,x=6 for 1,n=1,x=12 for 2;and H_(3)pidc=2-(3-pyridinyl)-1H-imidazole-4,5-dicarboxylic acid),were consciously manufacture and employed for heterogeneously catalyzed sulfide-sulfoxide transformation.Structural analysis shows that 1 and 2 exhibit similar porous frameworks with nearly identical two-dimensional metal-organic layers further pillared by tetradentate POM ligands with different coordination modes,which also result in the porosity of 1 being almost twice that of 2.In catalyzing the conversion of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO),1 can convert nearly 100%of MPS into MPSO within 30 min,while 2 achieved the similar results requires 50 min.The higher activity of 1 may be attributed to its larger channel that can provide more active sites and more efficient mass transfer process.Systematic structure-activity analyses and mechanistic studies revealed dual-reaction pathways driven by POM sites and metal sites assisted by the structural microenvironment.展开更多
The development of new strategy for environmentally friendly,cost-effective and large-scale electro-synthesis of anticancer drugs is highly desirable to replace high-cost traditional methods and realize high atomic ec...The development of new strategy for environmentally friendly,cost-effective and large-scale electro-synthesis of anticancer drugs is highly desirable to replace high-cost traditional methods and realize high atomic economy.GW 610,an antitumor agent with potent and selective anticancer activity against lung,colon,and breast cancer cell lines in real medical treatment processes,has a market price of~10……(7) USD/kg and calls for novel methods like electro-synthesis to reduce the cost.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of microwave-synthesized polyoxometalate-based metal-organic framework(MW-POMOF)that can converse S-S bond substrates into valuable C-S bond products like anticancer drug molecules(e.g.,GW 610).Specifically,the solid-phase MW-POMOF as heterogeneous redox mediator exhibits the excellent electrocatalytic efficiency for the formation of liquid-phase C-S bond products(yields up to 95%)coupling with the generation of gas-phase H_(2) product(~402μmol·g^(-1)·h^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the kilo-scale production(~1 kg in a batch experiment)of GW 610 at one thousandth of the market price(from~10^(7) to~3200 USD/kg).This work may inaugurate a new electrocatalytic avenue to explore porous crystalline materials in electrocatalysis field.展开更多
The conception and production of nitrogen-fixing photocatalysts with efficient charge separation rates and multiple active sites have been the focus of research.In this paper,we prepared Cu/WO_(2) nanoparticles by hig...The conception and production of nitrogen-fixing photocatalysts with efficient charge separation rates and multiple active sites have been the focus of research.In this paper,we prepared Cu/WO_(2) nanoparticles by high-temperature calcination of polyoxometalate based open frameworks(POMOFs)and then anchored them in interstitial carbon-doped BiOBr using a one-step hydrothermal method to obtain a novel Z-scheme Cu/WO_(2)/C-BOB ternary heterostructure.The ammonia generation rate over the Cu/WO_(2)/C-BOB heterojunction is 477.5μmol g^(−1) h^(−1) in deionized water without any sacrificial reagents under the full solar spectrum,which is nearly 6.1 times greater than that of pure BiOBr.The synergistic effect of heteroatom doping,Z-scheme heterojunction and oxygen vacancies inhibits the recombination of photogenerated carriers and maintains their maximum redox capacity,providing more reaction sites and significantly improving the photocatalytic performance.In addition,the localized surface plasmon resonance(LSPR)effect of Cu NPs enhances light absorption and induces high-energy hot electrons to produce additional oxygen vacancies.Meanwhile,we explored the charge transfer pathways and possible reaction mechanisms of the heterojunctions through experimental characterization and DFT calculations,which provided a new idea to synergistically utilize the LSPR effect and Z-scheme heterostructures for the design of efficient photocatalysts.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 21371027, 20901013)Natural Science Foundation of Liaoning Province (No. 2015020232)Fundamental Research Funds for the Central Universities (Nos. DUT19LK01, DUT15LN18)。
文摘Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge.In this work,two porous polyoxometalate-pillared metal-organic frameworks,formulated as H_(3n)[Cu_(3)(pidc)_(2)(H_(2)O)_(2.5)]_(2)[PW_(12)O_(40)]_n·x H_(2)O (n=1.5,x=6 for 1,n=1,x=12 for 2;and H_(3)pidc=2-(3-pyridinyl)-1H-imidazole-4,5-dicarboxylic acid),were consciously manufacture and employed for heterogeneously catalyzed sulfide-sulfoxide transformation.Structural analysis shows that 1 and 2 exhibit similar porous frameworks with nearly identical two-dimensional metal-organic layers further pillared by tetradentate POM ligands with different coordination modes,which also result in the porosity of 1 being almost twice that of 2.In catalyzing the conversion of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO),1 can convert nearly 100%of MPS into MPSO within 30 min,while 2 achieved the similar results requires 50 min.The higher activity of 1 may be attributed to its larger channel that can provide more active sites and more efficient mass transfer process.Systematic structure-activity analyses and mechanistic studies revealed dual-reaction pathways driven by POM sites and metal sites assisted by the structural microenvironment.
基金supported by the National Natural Science Foundation of China(Nos.21871125,22475057,22171139 and 22201116)Natural Science Foundation of Guangdong Province(No.2023B1515020076)+1 种基金Natural Science Foundation of Shandong Province(No.ZR2022QB066 and ZR2023MB018)Foundation of State Key Laboratory of Coal Conversion(No.J24-25-902).
文摘The development of new strategy for environmentally friendly,cost-effective and large-scale electro-synthesis of anticancer drugs is highly desirable to replace high-cost traditional methods and realize high atomic economy.GW 610,an antitumor agent with potent and selective anticancer activity against lung,colon,and breast cancer cell lines in real medical treatment processes,has a market price of~10……(7) USD/kg and calls for novel methods like electro-synthesis to reduce the cost.Here,for the first time,we design a solid-liquid-gas three-phase indirect electrolysis system based on a kind of microwave-synthesized polyoxometalate-based metal-organic framework(MW-POMOF)that can converse S-S bond substrates into valuable C-S bond products like anticancer drug molecules(e.g.,GW 610).Specifically,the solid-phase MW-POMOF as heterogeneous redox mediator exhibits the excellent electrocatalytic efficiency for the formation of liquid-phase C-S bond products(yields up to 95%)coupling with the generation of gas-phase H_(2) product(~402μmol·g^(-1)·h^(-1)),resulting in an interesting three-phase indirect electrolysis system.Remarkably,it enables the kilo-scale production(~1 kg in a batch experiment)of GW 610 at one thousandth of the market price(from~10^(7) to~3200 USD/kg).This work may inaugurate a new electrocatalytic avenue to explore porous crystalline materials in electrocatalysis field.
基金supported by the Natural Science Foundation of China(Grant No.22071018)the Natural Science Foundation of Jilin Province(No.20220101069JC)。
文摘The conception and production of nitrogen-fixing photocatalysts with efficient charge separation rates and multiple active sites have been the focus of research.In this paper,we prepared Cu/WO_(2) nanoparticles by high-temperature calcination of polyoxometalate based open frameworks(POMOFs)and then anchored them in interstitial carbon-doped BiOBr using a one-step hydrothermal method to obtain a novel Z-scheme Cu/WO_(2)/C-BOB ternary heterostructure.The ammonia generation rate over the Cu/WO_(2)/C-BOB heterojunction is 477.5μmol g^(−1) h^(−1) in deionized water without any sacrificial reagents under the full solar spectrum,which is nearly 6.1 times greater than that of pure BiOBr.The synergistic effect of heteroatom doping,Z-scheme heterojunction and oxygen vacancies inhibits the recombination of photogenerated carriers and maintains their maximum redox capacity,providing more reaction sites and significantly improving the photocatalytic performance.In addition,the localized surface plasmon resonance(LSPR)effect of Cu NPs enhances light absorption and induces high-energy hot electrons to produce additional oxygen vacancies.Meanwhile,we explored the charge transfer pathways and possible reaction mechanisms of the heterojunctions through experimental characterization and DFT calculations,which provided a new idea to synergistically utilize the LSPR effect and Z-scheme heterostructures for the design of efficient photocatalysts.
