A new crown ether appended Fe（Ⅲ） porphyrin complex was prepared by sulfuryl chloride appended benzo-15-crown-5 to the meso position of meso-5,10,15,20-tetra（4-hydrophenyl）porphyrin,and it was applied to catalytic...A new crown ether appended Fe（Ⅲ） porphyrin complex was prepared by sulfuryl chloride appended benzo-15-crown-5 to the meso position of meso-5,10,15,20-tetra（4-hydrophenyl）porphyrin,and it was applied to catalytic oxidation of cyclohexene with molecular oxygen without reductant,showing a remarkable catalytic activity（conversion is up to 94%） and selectivity for 2-cyclohexen-1-ol（73%）.展开更多
Developing highly efficient electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR)has attracted increasing interest in the past decade.Herein,we report on the design and synthesis of Fe porphyrin 1 with an appen...Developing highly efficient electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR)has attracted increasing interest in the past decade.Herein,we report on the design and synthesis of Fe porphyrin 1 with an appended N,N-di(2-picolyl)ethylenediamine(DPEN)unit that boosts electrocatalytic activity for CO_(2)-to-CO conversion in acetonitrile with water as the proton source.By mimicking carbon monoxide dehydrogenase(CODH),1 has poly-pyridine/amine units located at the active site to form hydrogen-bonded water-containing networks that enable fast proton transfer.The protonated and positively charged DPEN unit can also stabilize CO_(2) reduction intermediates through electrostatic and hydrogen-bonding interactions.These factors make 1 a highly active electrocatalyst for the CO_(2)RR by achieving a TOFmax of 5.0×10^(4)s^(−1) with water providing the protons.These critical roles of the DPEN unit in the CO_(2)RR are further supported by theoretical studies.This work is significant to highlight the benefits of using molecular catalysts to elucidate structural effects.展开更多
基金the National Natural Science Foundation of China(No51063006)the Key Subject Foundation of Tianshui Normal University(NoTSA0818)for providing financial support for this project
文摘A new crown ether appended Fe（Ⅲ） porphyrin complex was prepared by sulfuryl chloride appended benzo-15-crown-5 to the meso position of meso-5,10,15,20-tetra（4-hydrophenyl）porphyrin,and it was applied to catalytic oxidation of cyclohexene with molecular oxygen without reductant,showing a remarkable catalytic activity（conversion is up to 94%） and selectivity for 2-cyclohexen-1-ol（73%）.
基金We are grateful for support from National Natural Science Foundation of China(21773146,22003036 and 22171176)Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University,Fundamental Research Funds for the Central Universities(GK202103045 and GK202103033)Research Funds of Shaanxi Normal University,and the open fund of State Key Laboratory of Structural Chemistry.U.-P.A.thanks for the support by the Fraunhofer Internal Programs under Grant No.Attract 097-602175 and the DFG under Germany's Excellence Strategy-EXC-2033-Projektnummer 390677874“RESOLV”.
文摘Developing highly efficient electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR)has attracted increasing interest in the past decade.Herein,we report on the design and synthesis of Fe porphyrin 1 with an appended N,N-di(2-picolyl)ethylenediamine(DPEN)unit that boosts electrocatalytic activity for CO_(2)-to-CO conversion in acetonitrile with water as the proton source.By mimicking carbon monoxide dehydrogenase(CODH),1 has poly-pyridine/amine units located at the active site to form hydrogen-bonded water-containing networks that enable fast proton transfer.The protonated and positively charged DPEN unit can also stabilize CO_(2) reduction intermediates through electrostatic and hydrogen-bonding interactions.These factors make 1 a highly active electrocatalyst for the CO_(2)RR by achieving a TOFmax of 5.0×10^(4)s^(−1) with water providing the protons.These critical roles of the DPEN unit in the CO_(2)RR are further supported by theoretical studies.This work is significant to highlight the benefits of using molecular catalysts to elucidate structural effects.
