Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of...Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.展开更多
The higher capacity of CO_(2)adsorption on the surface of magnesium oxide(MgO)with low-coordination O^(2-)sites would effectively enhance the catalytic reduction of CO_(2).Herein,a series of copper oxide(CuO)and MgO c...The higher capacity of CO_(2)adsorption on the surface of magnesium oxide(MgO)with low-coordination O^(2-)sites would effectively enhance the catalytic reduction of CO_(2).Herein,a series of copper oxide(CuO)and MgO composites with different mass ratios have been prepared by hydrothermal method and used for photothermal synergistic catalytic reduction of CO_(2)to ethanol.The catalyst with CuO mass ratio of 1.6% shows the best yield(15.17μmol·g^(-1)·h^(-1))under 3 h Xenon lamp illumination.The improved performance is attributable to the loose nano-sheet structure,uniform dispersion of active sites,the increased specific surface area,medium-strength basicity,the high separation efficiency of electrons and holes,and the formation of Mg-O-Cu species.The synthesized CuO and MgO composites with loose nano-sheet structure facilitate the diffusion of reactants CO_(2),so an excellent CO_(2)adsorption performance can be obtained.Meanwhile,the introduction of CuO in the form of bivalence provides higher specific surface area and porosity,thus obtaining more active sites.More importantly,the Mg-O-Cu species make the donation of electrons from MgO to CO_(2)easier,resulting in the breaking of the old Mg-O bond and the formation of C-O bond,thus promoting the adsorption and conversion of CO_(2)to ethanol.展开更多
The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosyn...The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.展开更多
Two new three-dimensional coordination polymers, namely [Mn(L)(bpdc)]n(1), [Mn(L)0.5(ndc)]n(2)(L = 1,4-bis(2-methylbenzimidazole)butane, H2 bpdc = 4,4?-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic a...Two new three-dimensional coordination polymers, namely [Mn(L)(bpdc)]n(1), [Mn(L)0.5(ndc)]n(2)(L = 1,4-bis(2-methylbenzimidazole)butane, H2 bpdc = 4,4?-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic acid) have been successfully synthesized under hydrothermal conditions. Two complexes were characterized by physico-chemical, spectroscopic methods and single-crystal X-ray diffraction. Complex 1 shows a 3D → 3D 5-fold interpenetrated network with a 4-connected uninodal dia topology. Complex 2 possesses a 3D → 3D 3-fold interpenetrating architecture with a binodal(4,5)-connected xah topology. The fluorescence and thermal properties of the title complexes were discussed.展开更多
The hydrothermal reactions of Cd(OAc)2·2H2O with 1,2,4,5-benzenetetracarboxylic acid(H4bta) and 1,4-bis(thiabendazolyl)butane(L1) or 1,6-bis(thiabendazolyl)hexane(L2) afforded two coordination polymers [Cd2(L1)(b...The hydrothermal reactions of Cd(OAc)2·2H2O with 1,2,4,5-benzenetetracarboxylic acid(H4bta) and 1,4-bis(thiabendazolyl)butane(L1) or 1,6-bis(thiabendazolyl)hexane(L2) afforded two coordination polymers [Cd2(L1)(bta)·2H2O]n(1) and [Cd2(L2)2(H2bta)2]n(2). Complex 1 holds a rare 3D binodal(4,6)-connected framework with fsh topology. Complex 2 features an infinite meandering chain structure, which is further extended via O–H···O hydrogen bonding into a 3D supramolecular network. The thermal and fluorescence proprieties of the two complexes were investigated.展开更多
基金support from the Tangshan Talent Funding Project(Grant No.A202202007)National Natural Science Foundation of China(Grant Nos.22102136 and 21703065)+2 种基金Natural Science Foundation of Hebei Province(Grant Nos.B2018209267 and E2022209039)Natural Science Foundation of Hubei Province(Grant No.2022CFB1001)Department of Education of Hubei Province(Grant No.Q20221701).
文摘Electrochemical C-C and C-N coupling reactions with the conversion of abundant and inexpensive small molecules,such as CO_(2) and nitrogencontaining species,are considered a promising route for increasing the value of CO_(2) reduction products.The development of high-performance catalysts is the key to the both electrocatalytic reactions.In this review,we present a systematic summary of the reaction systems for electrocatalytic CO_(2) reduction,along with the coupling mechanisms of C-C and C-N bonds over outstanding electrocatalytic materials recently developed.The key intermediate species and reaction pathways related to the coupling as well as the catalyst-structure relationship will be also discussed,aiming to provide insights and guidance for designing efficient CO_(2) reduction systems.
基金Financial supports by National Natural Science Foundation of China(21908052)the Key Program of Natural Science Foundation of Hebei Province(B2020209017)+1 种基金the Project of Science and Technology Innovation Team,Tang shan(20130203D)Youth Program of Natural Science of Hebei Province(B2020209065)。
文摘The higher capacity of CO_(2)adsorption on the surface of magnesium oxide(MgO)with low-coordination O^(2-)sites would effectively enhance the catalytic reduction of CO_(2).Herein,a series of copper oxide(CuO)and MgO composites with different mass ratios have been prepared by hydrothermal method and used for photothermal synergistic catalytic reduction of CO_(2)to ethanol.The catalyst with CuO mass ratio of 1.6% shows the best yield(15.17μmol·g^(-1)·h^(-1))under 3 h Xenon lamp illumination.The improved performance is attributable to the loose nano-sheet structure,uniform dispersion of active sites,the increased specific surface area,medium-strength basicity,the high separation efficiency of electrons and holes,and the formation of Mg-O-Cu species.The synthesized CuO and MgO composites with loose nano-sheet structure facilitate the diffusion of reactants CO_(2),so an excellent CO_(2)adsorption performance can be obtained.Meanwhile,the introduction of CuO in the form of bivalence provides higher specific surface area and porosity,thus obtaining more active sites.More importantly,the Mg-O-Cu species make the donation of electrons from MgO to CO_(2)easier,resulting in the breaking of the old Mg-O bond and the formation of C-O bond,thus promoting the adsorption and conversion of CO_(2)to ethanol.
基金supported by the National Natural Science Foundation of China(Grant Nos.21908052 and 22108200)the Key Program of the Natural Science Foundation of Hebei Province(Grant No.B2020209017)+2 种基金the Project of Science and Technology Innovation Team,Tangshan(Grant No.20130203D)the Natural Science Foundation of Zhejiang Province(Grant No.LQ22B060013)and the Science and Technology Project of Hebei Education Department(Grant No.QN2021113).
文摘The artificial photosynthesis technology has been recognized as a promising solution for CO_(2) utilization.Photothermal catalysis has been proposed as a novel strategy to promote the efficiency of artificial photosynthesis by coupling both photochemistry and thermochemistry.However,strategies for maximizing the use of solar spectra with different frequencies in photothermal catalysis are urgently needed.Here,a hierarchical full-spectrum solar light utilization strategy is proposed.Based on this strategy,a Cu@hollow titanium silicalite-1 zeolite(TS-1)nanoreactor with spatially separated photo/thermal catalytic sites is designed to realize high-efficiency photothermal catalytic artificial photosynthesis.The space-time yield of alcohol products over the optimal catalyst reached 64.4μmol g−1 h−1,with the selectivity of CH3CH2OH of 69.5%.This rationally designed hierarchical utilization strategy for solar light can be summarized as follows:(1)high-energy ultraviolet light is utilized to drive the initial and difficult CO_(2) activation step on the TS-1 shell;(2)visible light can induce the localized surface plasmon resonance effect on plasmonic Cu to generate hot electrons for H2O dissociation and subsequent reaction steps;and(3)low-energy near-infrared light is converted into heat by the simulated greenhouse effect by cavities to accelerate the carrier dynamics.This work provides some scientific and experimental bases for research on novel,highly efficient photothermal catalysts for artificial photosynthesis.
基金Project supported by the National Natural Science Foundation of China(No.51474086)Natural Science Foundation-Steel and Iron Foundation of Hebei Province(B2015209299)
文摘Two new three-dimensional coordination polymers, namely [Mn(L)(bpdc)]n(1), [Mn(L)0.5(ndc)]n(2)(L = 1,4-bis(2-methylbenzimidazole)butane, H2 bpdc = 4,4?-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic acid) have been successfully synthesized under hydrothermal conditions. Two complexes were characterized by physico-chemical, spectroscopic methods and single-crystal X-ray diffraction. Complex 1 shows a 3D → 3D 5-fold interpenetrated network with a 4-connected uninodal dia topology. Complex 2 possesses a 3D → 3D 3-fold interpenetrating architecture with a binodal(4,5)-connected xah topology. The fluorescence and thermal properties of the title complexes were discussed.
基金Project supported by the Natural Science Foundation-steel and Iron Foundation of Hebei Province(B2015209299 and E2016209304)
文摘The hydrothermal reactions of Cd(OAc)2·2H2O with 1,2,4,5-benzenetetracarboxylic acid(H4bta) and 1,4-bis(thiabendazolyl)butane(L1) or 1,6-bis(thiabendazolyl)hexane(L2) afforded two coordination polymers [Cd2(L1)(bta)·2H2O]n(1) and [Cd2(L2)2(H2bta)2]n(2). Complex 1 holds a rare 3D binodal(4,6)-connected framework with fsh topology. Complex 2 features an infinite meandering chain structure, which is further extended via O–H···O hydrogen bonding into a 3D supramolecular network. The thermal and fluorescence proprieties of the two complexes were investigated.