A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temp...A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temperature via coordination modulation method.By adding different modulators（monocarboxylic acids） into the reaction system,the morphologies of HKUST-1 crystals were tuned from nano spheres to micro octahedrons at room temperature without any complex equipment.X-Ray diffractions and gas sorption measurements revealed highly crystalline particles with large Brunauer-Emmett-Teller（BET） surface areas（1116―1273 m^ 2 /g） and total pore volumes（0.62―0.73 cm^ 3 /g）.The significantly small particle sizes and high capacity of gas sorption are considered advantageous for envisaged application in practical industrial process.展开更多
The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in orde...The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in order to simultaneously promote the electrical conductivity and water stability of ZIF-67, an insitu monomer trapping strategy is deployed to synthesize polypyrrole(PPy)-reinforced ZIF-67 ensembles.Through coordination modulation, the incremental addition of pyrrole monomers enables to alter the crystal morphology of ZIF-67 from rhombic dodecahedra to truncated rhombic dodecahedra, and further to cubes. Upon polymerization, the resulted composite, in comparison to ZIF-67, demonstrates a billionfold conductivity enhancement, much improved chemical stability in pronated solvents, as well as largely retained specific surface area and porosity, enabling it functioning as an outstanding co-catalyst for catalyzing robust photocatalytic CO_(2) reduction. Furthermore, a PPy-mediated electron harvest and relay mechanism is proposed for rationalizing the enhanced photocatalytic performance.展开更多
Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among va...Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among various catalysts,single atom catalysts(SACs)have attracted much attention due to their high atom utilization efficiency and expressive catalytic performances.Additionally,SACs serve as an ideal platform for the investigation of complex reaction pathways and mechanisms thanks to their explicit active sites.In this review,the possible re-action pathways for the generation of various products(mainly C1 products for SACs)were firstly summarized.Then,recent progress of SACs for electrochemical reduction of CO_(2)was discussed in aspect of different central metal sites.As the most popular and efficient coordination modulation strategy,introducing heteroatom was then reviewed.Moreover,as an extension of SACs,the development of dual atom catalysts was also briefly discussed.At last,some issues and challenges regarding the SACs for CO_(2)reduction reaction(CO_(2)RR)were listed,followed by corresponding suggestions.展开更多
The electrosynthesis of hydrogen peroxide is limited by the competitive four-electron oxygen reduction reaction(ORR)pathway.The modulation for the adsorption of OOH^(*)intermediate on active sites is considered as the...The electrosynthesis of hydrogen peroxide is limited by the competitive four-electron oxygen reduction reaction(ORR)pathway.The modulation for the adsorption of OOH^(*)intermediate on active sites is considered as the effective approach to tune the ORR selectivity,but it remains challenging.Herein,we report the neighboring phosphorus atom in the second coordination shell to regulate the electronic structure of the isolated Ni-N_(4) sites,leading to the favored OOH^(*)adsorption and thus boosting the electrocatalytic ORR to hydrogen peroxide through the two-electron pathway.Spectroscopy characterizations and density functional theory calculations indicate the neighboring phosphorus atom in the second coordination shell triggers the electron transfer to central Ni atom,strengthening the adsorption of OOH^(*)on Ni sites and thus increasing the catalytic performance for two-electron ORR,delivering a selectivity above 90%for production of hydrogen peroxide under the current density of 150 mA·cm^(−2).This work reveals tailoring second coordination shell of isolated metal sites could be as a precise and efficient way to engineer the catalytic performance,which thus provides a promising approach to the design of advanced catalysts.展开更多
基金Supported by the National Natural Science Foundation of China(Nos.21173034,20907006)
文摘A simple and fast route for the synthesis of metal-organic framework（MOF） particles was presented.Cu 3（BTC） 2（HKUST-1,BTC=1,3,5-benzenetricarboxylate）,one of the most well-known MOFs,was synthesized at room temperature via coordination modulation method.By adding different modulators（monocarboxylic acids） into the reaction system,the morphologies of HKUST-1 crystals were tuned from nano spheres to micro octahedrons at room temperature without any complex equipment.X-Ray diffractions and gas sorption measurements revealed highly crystalline particles with large Brunauer-Emmett-Teller（BET） surface areas（1116―1273 m^ 2 /g） and total pore volumes（0.62―0.73 cm^ 3 /g）.The significantly small particle sizes and high capacity of gas sorption are considered advantageous for envisaged application in practical industrial process.
基金supported by the National Natural Science Foundation of China (Nos. 22072101, 22075193, 51911540473)the Natural Science Research Project of Jiangsu Higher Education Institutions of China (18KJA480004)+2 种基金the Key Technology Initiative of Suzhou Municipal Science and Technology Bureau (SYG201934) Six Talent Peaks Project in Jiangsu Province (TD-XCL-006)the Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutionsthe support from the Honorary Professor Program of Jiangsu Province。
文摘The implementation of metal organic frameworks(MOFs) as the co-catalysts in hybrid photocatalytic systems puts requirements on both their charge-carrying capability and solvent stability. In the current study, in order to simultaneously promote the electrical conductivity and water stability of ZIF-67, an insitu monomer trapping strategy is deployed to synthesize polypyrrole(PPy)-reinforced ZIF-67 ensembles.Through coordination modulation, the incremental addition of pyrrole monomers enables to alter the crystal morphology of ZIF-67 from rhombic dodecahedra to truncated rhombic dodecahedra, and further to cubes. Upon polymerization, the resulted composite, in comparison to ZIF-67, demonstrates a billionfold conductivity enhancement, much improved chemical stability in pronated solvents, as well as largely retained specific surface area and porosity, enabling it functioning as an outstanding co-catalyst for catalyzing robust photocatalytic CO_(2) reduction. Furthermore, a PPy-mediated electron harvest and relay mechanism is proposed for rationalizing the enhanced photocatalytic performance.
文摘Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among various catalysts,single atom catalysts(SACs)have attracted much attention due to their high atom utilization efficiency and expressive catalytic performances.Additionally,SACs serve as an ideal platform for the investigation of complex reaction pathways and mechanisms thanks to their explicit active sites.In this review,the possible re-action pathways for the generation of various products(mainly C1 products for SACs)were firstly summarized.Then,recent progress of SACs for electrochemical reduction of CO_(2)was discussed in aspect of different central metal sites.As the most popular and efficient coordination modulation strategy,introducing heteroatom was then reviewed.Moreover,as an extension of SACs,the development of dual atom catalysts was also briefly discussed.At last,some issues and challenges regarding the SACs for CO_(2)reduction reaction(CO_(2)RR)were listed,followed by corresponding suggestions.
基金financially supported by the Taishan Scholar Project Foundation of Shandong Province(Nos.tsqn202211028 and tsqn202306080)the Natural Science Foundation of Shandong Province(Nos.ZR2022JQ08 and 2023HWYQ-028)the Instrument Improvement Founds of Shandong University Public Technology Platform(No.ts20230209).
文摘The electrosynthesis of hydrogen peroxide is limited by the competitive four-electron oxygen reduction reaction(ORR)pathway.The modulation for the adsorption of OOH^(*)intermediate on active sites is considered as the effective approach to tune the ORR selectivity,but it remains challenging.Herein,we report the neighboring phosphorus atom in the second coordination shell to regulate the electronic structure of the isolated Ni-N_(4) sites,leading to the favored OOH^(*)adsorption and thus boosting the electrocatalytic ORR to hydrogen peroxide through the two-electron pathway.Spectroscopy characterizations and density functional theory calculations indicate the neighboring phosphorus atom in the second coordination shell triggers the electron transfer to central Ni atom,strengthening the adsorption of OOH^(*)on Ni sites and thus increasing the catalytic performance for two-electron ORR,delivering a selectivity above 90%for production of hydrogen peroxide under the current density of 150 mA·cm^(−2).This work reveals tailoring second coordination shell of isolated metal sites could be as a precise and efficient way to engineer the catalytic performance,which thus provides a promising approach to the design of advanced catalysts.
