Unveiling the effect of intermolecular interactions on metal-to-metal electron transfer(MMET)is challenging,but preferentially essential for the engineering of magnetically switchable crystalline materials and devices...Unveiling the effect of intermolecular interactions on metal-to-metal electron transfer(MMET)is challenging,but preferentially essential for the engineering of magnetically switchable crystalline materials and devices.Herein,we reported a family of[Fe_(4)Co_(4)]cubes sharing the identically cyanide-bridged cubic octanuclear architecture{[Fe(pzTp)(CN)_(3)]_(4)[Co(ddpd)]_(4)}4+(pzTp−=tetrakis(pyrazolyl)borate,ddpd=N,N’-dimethyl-N,N’-dipyridin-2-ylpyridine-2,6-diamine)but different counterions with tunable sizes,including BF_(4)^(−)(1·BF_(4)),ClO_(4)−(2·ClO_(4)),PF_(6)^(−)(3·PF_(6)),AsF_(6)^(−()4·AsF_(6))and SbF_(6)^(−)(5·SbF_(6)).All compounds were isomorphic and crystallized in the tetragonal P[4 with combining macron]21c space group.Magnetic susceptibility measurements revealed that compound 1·BF4 with the smallest counterion exhibited the most pronounced MMET behavior,while 5·SbF_(6)with the largest counterion completely lost the MMET behavior.By employing both experimental and computational approaches,we demonstrated that the number and strength of intermolecular interactions depend highly on the counterion size.The enhanced interactions impose a strong limiting effect on the octahedral coordination geometry of the cobalt centers,which consequently have a non-negligible influence on the orbital overlap,electrostatic potential,and redox potentials,thereby modulating MMET behavior.展开更多
All-inorganic heterostructures have attracted intense interest for new energy and environmental applications recently,especially in photoelectronic devices.Herein,we firstly obtain a novel CoIn_(2)S_(4) thiospinel oct...All-inorganic heterostructures have attracted intense interest for new energy and environmental applications recently,especially in photoelectronic devices.Herein,we firstly obtain a novel CoIn_(2)S_(4) thiospinel octahedron through a simple one-step hydrothermal synthesis method.On this basis we further propose a strategy to prepare all-inorganic heterostructures(NH_(4))4Co^(Ⅱ)[Co^(Ⅱ)W_(12)O_(40)]·20H_(2)O/CoIn_(2)S_(4)(CoW_(12)-n/CoIn_(2)S_(4),where n represents the molar number of CoW_(12))through doping Keggin-type polyoxometalates(POMs).The addition of POMs can alleviate the cross-growth of the CoIn_(2)S_(4) octahedron and increase the specific surface area and the number of exposed active sites of the heterostructures.What’s more,we investigate the electrocatalytic triiodide reduction properties of the heterostructures.Electrochemical measurements show that POM contents have an obvious influence on the catalytic activity of this heterostructure catalyst.The CoW_(12)-0.3/CoIn_(2)S_(4) heterostructures present the best catalytic performance and the lowest charge transfer resistance.Consequently,the dye-sensitized solar cells(DSSCs)with CoW_(12)-0.3/CoIn_(2)S_(4) heterostructures as a counter electrode(CE)show the highest photovoltaic conversion efficiency(PCE)of up to 6.79%,superior to that of the Pt CE(5.83%).This work not only provides an approach for designing composites for efficient electrocatalytic triiodide reduction,but also represents a further step towards the application of all-inorganic heterostructures in photoelectronic devices.展开更多
Heterogeneous metal atom doping is considered as an effective strategy to boost catalytic activity through the coordinated modulation of metal active sites and the electronic structure,which is also beneficial for est...Heterogeneous metal atom doping is considered as an effective strategy to boost catalytic activity through the coordinated modulation of metal active sites and the electronic structure,which is also beneficial for establishing the relationship between structure and performance in energy conversion devices.Herein,we developed Mo-doped NiSe hierarchical microspheres with different Mo doping amounts by a simple solvothermal method.DFT calculation results including the more appropriate adsorption energy for adsorption of I_(3)^(-),the further elongated I_(1)-I_(2)bond length of I_(3)^(-),and efficient interaction between metal 3d and I 5p states collectively indicated that the catalytic activity for the IRR can be significantly enhanced by doping molybdenum in NiSe.Subsequently,dye-sensitized solar cells(DSSCs)fabricated with the optimized Mo_(0.10)-NiSe display a remarkable power conversion efficiency of 8.92%,superior to that of the Mo_(0.05)-NiSe(8.40%),Mo_(0.15)-NiSe(8.62%),NiSe(7.51%),and Pt-based devices(7.74%)in comparison.The impressive performance endows Mo_(0.10)-NiSe with a new opportunity to achieve the substitution of noble Pt in low-cost DSSCs.展开更多
基金supported by the National Natural Science Foundation of China(Grants 22222103,22025101,22173015,and 22103009)the Fundamental Research Funds for the Central Universities(DUT22LAB606)the Liaoning Binhai Laboratory(LBLE-2023-02),and the“Excellence Co-innovation Program”International Exchange Fund Project(DUTIO-ZG-202505).
文摘Unveiling the effect of intermolecular interactions on metal-to-metal electron transfer(MMET)is challenging,but preferentially essential for the engineering of magnetically switchable crystalline materials and devices.Herein,we reported a family of[Fe_(4)Co_(4)]cubes sharing the identically cyanide-bridged cubic octanuclear architecture{[Fe(pzTp)(CN)_(3)]_(4)[Co(ddpd)]_(4)}4+(pzTp−=tetrakis(pyrazolyl)borate,ddpd=N,N’-dimethyl-N,N’-dipyridin-2-ylpyridine-2,6-diamine)but different counterions with tunable sizes,including BF_(4)^(−)(1·BF_(4)),ClO_(4)−(2·ClO_(4)),PF_(6)^(−)(3·PF_(6)),AsF_(6)^(−()4·AsF_(6))and SbF_(6)^(−)(5·SbF_(6)).All compounds were isomorphic and crystallized in the tetragonal P[4 with combining macron]21c space group.Magnetic susceptibility measurements revealed that compound 1·BF4 with the smallest counterion exhibited the most pronounced MMET behavior,while 5·SbF_(6)with the largest counterion completely lost the MMET behavior.By employing both experimental and computational approaches,we demonstrated that the number and strength of intermolecular interactions depend highly on the counterion size.The enhanced interactions impose a strong limiting effect on the octahedral coordination geometry of the cobalt centers,which consequently have a non-negligible influence on the orbital overlap,electrostatic potential,and redox potentials,thereby modulating MMET behavior.
基金financially supported by the National Natural Science Foundation of China(No.21871041 and 21801038)the Natural Science Foundation of Jilin Province(No.20180101298JC)+1 种基金the Technology Foundation for Selected Overseas Chinese Scholars of Personnel Ministry of ChinaScience and Technology Activities Project Preferential Funding for Selected Overseas Chinese Scholars of Jilin Province Human Resources and Social Bureau.
文摘All-inorganic heterostructures have attracted intense interest for new energy and environmental applications recently,especially in photoelectronic devices.Herein,we firstly obtain a novel CoIn_(2)S_(4) thiospinel octahedron through a simple one-step hydrothermal synthesis method.On this basis we further propose a strategy to prepare all-inorganic heterostructures(NH_(4))4Co^(Ⅱ)[Co^(Ⅱ)W_(12)O_(40)]·20H_(2)O/CoIn_(2)S_(4)(CoW_(12)-n/CoIn_(2)S_(4),where n represents the molar number of CoW_(12))through doping Keggin-type polyoxometalates(POMs).The addition of POMs can alleviate the cross-growth of the CoIn_(2)S_(4) octahedron and increase the specific surface area and the number of exposed active sites of the heterostructures.What’s more,we investigate the electrocatalytic triiodide reduction properties of the heterostructures.Electrochemical measurements show that POM contents have an obvious influence on the catalytic activity of this heterostructure catalyst.The CoW_(12)-0.3/CoIn_(2)S_(4) heterostructures present the best catalytic performance and the lowest charge transfer resistance.Consequently,the dye-sensitized solar cells(DSSCs)with CoW_(12)-0.3/CoIn_(2)S_(4) heterostructures as a counter electrode(CE)show the highest photovoltaic conversion efficiency(PCE)of up to 6.79%,superior to that of the Pt CE(5.83%).This work not only provides an approach for designing composites for efficient electrocatalytic triiodide reduction,but also represents a further step towards the application of all-inorganic heterostructures in photoelectronic devices.
基金support of the National Natural Science Foundation of China(22005161)the Fundamental Research Funds in Heilongjiang Provincial Universities of China(145109209)the Heilongjiang Provincial Key Laboratory of Surface Active Agent and Auxiliary(BMHXJKF006).
文摘Heterogeneous metal atom doping is considered as an effective strategy to boost catalytic activity through the coordinated modulation of metal active sites and the electronic structure,which is also beneficial for establishing the relationship between structure and performance in energy conversion devices.Herein,we developed Mo-doped NiSe hierarchical microspheres with different Mo doping amounts by a simple solvothermal method.DFT calculation results including the more appropriate adsorption energy for adsorption of I_(3)^(-),the further elongated I_(1)-I_(2)bond length of I_(3)^(-),and efficient interaction between metal 3d and I 5p states collectively indicated that the catalytic activity for the IRR can be significantly enhanced by doping molybdenum in NiSe.Subsequently,dye-sensitized solar cells(DSSCs)fabricated with the optimized Mo_(0.10)-NiSe display a remarkable power conversion efficiency of 8.92%,superior to that of the Mo_(0.05)-NiSe(8.40%),Mo_(0.15)-NiSe(8.62%),NiSe(7.51%),and Pt-based devices(7.74%)in comparison.The impressive performance endows Mo_(0.10)-NiSe with a new opportunity to achieve the substitution of noble Pt in low-cost DSSCs.
