It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced ...It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.展开更多
Sn was used to replace Al in Co38Ni34Al28 alloy. The microstructure and microhardness of Co38Ni34Al28-xSnx （x=0, 1, 2, 3） magnetic shape memory alloys were investigated at different heat treatment temperatures （137...Sn was used to replace Al in Co38Ni34Al28 alloy. The microstructure and microhardness of Co38Ni34Al28-xSnx （x=0, 1, 2, 3） magnetic shape memory alloys were investigated at different heat treatment temperatures （1373 K, 1473 K, and 1573 K） for 2 h. The results show that more Sn substitution reduces the content of γ-phase and a partial phase of martensite can be obtained in Co38Ni34Al28-xSnx （x=1, 2, 3） alloys after treatment at 1573 K for 2 h. The maximum martensite phase appears when 2% Al is substituted by Sn. The reverse martensitic transformation temperature of Co38Ni34Al28-xSnx alloys increases at x=1 and 2, then decreases as x=3. As the content of Sn and the temperature increase, the microhardness will increase.展开更多
The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open...The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage （Voc）, and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu2Zn（SnyGel_y）（SxSe~ x）4 （CZTGSSe） solar cells. By precisely adjusting the Ge content in a small range, the Voc and Jsc are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/（Ge＋Sn） content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.展开更多
The effects of substitution of Sn for Co on the microstructure, hydrogen storage and electrochemical discharge capacity of La0.7Mg0.3Al0.3Mn0.4Co0.5-xSnxNi3.8 （x=0, 0.1, 0.2, 0.3 and 0.5） alloys were investigated us...The effects of substitution of Sn for Co on the microstructure, hydrogen storage and electrochemical discharge capacity of La0.7Mg0.3Al0.3Mn0.4Co0.5-xSnxNi3.8 （x=0, 0.1, 0.2, 0.3 and 0.5） alloys were investigated using X-ray diffraction （XRD）, pressure composition isotherm （PCT） and electrochemical discharge cycle. XRD, scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS） tests showed that all of alloys are mainly composed of LaNi5 and MgNi2 phases, but when increasing the content of Sn in alloys, the LaNiSn phase appears and microstructure is refined. The PCT showed that increasing substitution of Sn for Co results in decrease of the maximum hydrogen storage capacity from 1.48% （x=0） to 0.85% （x=0.5）. The electrochemical tests indicated that the maximum discharge capacity decreases from 337.1 mA-h/g （x=0） to 239.8 mA.h/g （x=0.5）; however, the discharge capacity retention at the 100th cycle increases from 70.2% （x=0） to 78.0% （x=0.5）.展开更多
The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large ...The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.展开更多
Na-doped Li1.05Mn2O4 cathodes were synthesized using a sol-gel process.The samples were characterized by X-ray diffractometry(XRD),cyclic voltammetry(CV),electrochemical impedance spectroscopy(EIS)and charge-discharge...Na-doped Li1.05Mn2O4 cathodes were synthesized using a sol-gel process.The samples were characterized by X-ray diffractometry(XRD),cyclic voltammetry(CV),electrochemical impedance spectroscopy(EIS)and charge-discharge measurements. The results show that all the samples exhibit the same cubic spinel phase structure without impurity.The lattice constant and unit cell volume decrease with increasing the sodium dopant amount.As the molar ratio of sodium to manganese(x=n(Na)/n(Mn))increases from 0 to 0.03,the initial discharge capacity of the Li1.05Mn2O4 cathodes decreases from 119.2 to 107.9 mA·h/g,and the discharge capability at large current rate and the storage performance decline dramatically,while cycling performance at room temperature and 55℃are improved.The CV and EIS studies indicate that reversibility of Li1.05Mn2O4 cathodes decreases and the electrochemical impedance increases with increasing the sodium dopant amount.展开更多
Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still h...Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.展开更多
Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,...Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.展开更多
The magnetic properties of spinel ferrites Cu_（1-x）Zn_xFe_2O_4 are studied using high-temperature series expansions combined with the Padé approximates. The exchange interactions, inter and intra-sublattices J_...The magnetic properties of spinel ferrites Cu_（1-x）Zn_xFe_2O_4 are studied using high-temperature series expansions combined with the Padé approximates. The exchange interactions, inter and intra-sublattices J_（AA）, J_（BB） and J_（AB） are obtained using a probability distribution law. The critical exponent associated with the magnetic susceptibility is obtained.展开更多
基金the National Natural Science Foundation of China (22209091)the Natural Science Foundation of Shandong Province (ZR2020QB057)+1 种基金the Key Program of National Natural Science Foundation of China (22133006)the Yankuang Group 2019 Science and Technology Program (YKKJ2019AJ05JG-R60)。
文摘It is a challenge to coordinate carrier-kinetics performance and the redox capacity of photogenerated charges synchronously at the atomic level for boosting photocatalytic activity.Herein,the atomic Ni was introduced into the lattice of hexagonal ZnIn_(2)S_(4) nanosheets(Ni/ZnIn_(2)S_(4))via directionalsubstituting Zn atom with the facile hydrothermal method.The electronic structure calculations indicate that the introduction of Ni atom effectively extracts more electrons and acts as active site for subsequent reduction reaction.Besides the optimized light absorption range,the elevation of Efand ECBendows Ni/ZnIn_(2)S_(4) photocatalyst with the increased electron concentration and the enhanced reduction ability for surface reaction.Moreover,ultrafast transient absorption spectroscopy,as well as a series of electrochemical tests,demonstrates that Ni/ZnIn_(2)S_(4) possesses 2.15 times longer lifetime of the excited charge carriers and an order of magnitude increase for carrier mobility and separation efficiency compared with pristine ZnIn_(2)S_(4).These efficient kinetics performances of charge carriers and enhanced redox capacity synergistically boost photocatalytic activity,in which a 3-times higher conversion efficiency of nitrobenzene reduction was achieved upon Ni/ZnIn_(2)S_(4).Our study not only provides in-depth insights into the effect of atomic directional-substitution on the kinetic behavior of photogenerated charges,but also opens an avenue to the synchronous optimization of redox capacity and carrier-kinetics performance for efficient solar energy conversion.
基金Projects (50771037, 50371020) supported by the National Natural Science Foundation of ChinaProject (2011B090400485) supported by the Combination Project for Guangdong Province and the Ministry of Education, China
文摘Sn was used to replace Al in Co38Ni34Al28 alloy. The microstructure and microhardness of Co38Ni34Al28-xSnx （x=0, 1, 2, 3） magnetic shape memory alloys were investigated at different heat treatment temperatures （1373 K, 1473 K, and 1573 K） for 2 h. The results show that more Sn substitution reduces the content of γ-phase and a partial phase of martensite can be obtained in Co38Ni34Al28-xSnx （x=1, 2, 3） alloys after treatment at 1573 K for 2 h. The maximum martensite phase appears when 2% Al is substituted by Sn. The reverse martensitic transformation temperature of Co38Ni34Al28-xSnx alloys increases at x=1 and 2, then decreases as x=3. As the content of Sn and the temperature increase, the microhardness will increase.
基金Project supported by the Joint Talent Cultivation Funds of NSFC-HN(Grant No.U1604138)the National Natural Science Foundation of China(Grant Nos.21603058 and 51702085)+2 种基金the Innovation Research Team of Science and Technology in Henan Province,China(Grant No.17IRTSTHN028)the Science and Technology Innovation Talents in Universities of Henan Province,China(Grant No.18HASTIT016)the Young Key Teacher Foundation of Universities of Henan Province,China(Grant No.2015GGJS-022)
文摘The kesterite Cu2ZnSn（S,Se）4 （CZTSSe） solar cells have yielded a prospective conversion efficiency among all thin- film photovoltaic technology. However, its further development is still hindered by the lower open-circuit voltage （Voc）, and the non-ideal bandgap of the absorber is an important factor affecting this issue. The substitution of Sn with Ge provides a unique ability to engineer the bandgap of the absorber film. Herein, a simple precursor solution approach was successfully developed to fabricate Cu2Zn（SnyGel_y）（SxSe~ x）4 （CZTGSSe） solar cells. By precisely adjusting the Ge content in a small range, the Voc and Jsc are enhanced simultaneously. Benefitting from the optimized bandgap and the maintained spike structure and light absorption, the 10% Ge/（Ge＋Sn） content device with a bandgap of approximately 1.1 eV yields the highest efficiency of 9.36%. This further indicates that a precisely controlled Ge content could further improve the cell performance for efficient CZTGSSe solar cells.
基金Institute for Superconducting and Electronic Materials (ISEM)University of Wollongong and Institute Nuclear and Energy Research (IPEN)+2 种基金University of Sao Paulo for the financial supportNational Council for Scientific and Technological Development – CNPQ – Brazil for the scholarshipsfinancial support (CNPQ 472504/2010-0) granted to Julio Cesar Serafim CASINI
文摘The effects of substitution of Sn for Co on the microstructure, hydrogen storage and electrochemical discharge capacity of La0.7Mg0.3Al0.3Mn0.4Co0.5-xSnxNi3.8 （x=0, 0.1, 0.2, 0.3 and 0.5） alloys were investigated using X-ray diffraction （XRD）, pressure composition isotherm （PCT） and electrochemical discharge cycle. XRD, scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS） tests showed that all of alloys are mainly composed of LaNi5 and MgNi2 phases, but when increasing the content of Sn in alloys, the LaNiSn phase appears and microstructure is refined. The PCT showed that increasing substitution of Sn for Co results in decrease of the maximum hydrogen storage capacity from 1.48% （x=0） to 0.85% （x=0.5）. The electrochemical tests indicated that the maximum discharge capacity decreases from 337.1 mA-h/g （x=0） to 239.8 mA.h/g （x=0.5）; however, the discharge capacity retention at the 100th cycle increases from 70.2% （x=0） to 78.0% （x=0.5）.
基金supported by the National Natural Science Foundation of China(61874159,62074052,61974173,52072327,51702085 and 51802081)the Joint Talent Cultivation Funds of NSFC-HN(U1704151 and U1904192)+1 种基金the Zhongyuan Thousand Talents(Zhongyuan Scholars)Program of Henan Province(202101510004)the Science and Technology Innovation Talents in Universities of Henan Province(21HASTIT023)。
文摘The environmentally friendly Cu_(2)ZnSn(S,Se)_(4)(CZTSSe) compounds are promising direct bandgap materials for application in thin film solar cells, but the spontaneous surface defects disordering would lead to large open-circuit voltage deficit(V_(oc,deficit)) and significantly limit kesterite photovoltaics performance,primarily arising from the generated more recombination centers and insufficient p to n conversion at p-n junction. Herein, we establish a surface defects ordering structure in CZTSSe system via local substitution of Cu by Ag to suppress disordered Cu_(Zn) defects and generate benign n-type Zn_(Ag) donors. Taking advantage of the decreased annealing temperature of Ag F post deposition treatment(PDT), the high concentration of Ag incorporated into surface absorber facilitates the formation of surface ordered defect environment similar to that of efficient CIGS PV. The manipulation of highly doped surface structure could effectively reduce recombination centers, increase depletion region width and enlarge the band bending near p-n junction. As a result, the Ag F-PDT device finally achieves maximum efficiency of 12.34% with enhanced V_(oc) of 0.496 V. These results offer a new solution route in surface defects and energy-level engineering, and open the way to build up high quality p-n junction for future development of kesterite technology.
基金Project(2007CB613607) supported by the National Basic Research Program of ChinaProjects(2009FJ1002, 2009CK3062) supported by the Science and Technology Program of Hunan Province, China
文摘Na-doped Li1.05Mn2O4 cathodes were synthesized using a sol-gel process.The samples were characterized by X-ray diffractometry(XRD),cyclic voltammetry(CV),electrochemical impedance spectroscopy(EIS)and charge-discharge measurements. The results show that all the samples exhibit the same cubic spinel phase structure without impurity.The lattice constant and unit cell volume decrease with increasing the sodium dopant amount.As the molar ratio of sodium to manganese(x=n(Na)/n(Mn))increases from 0 to 0.03,the initial discharge capacity of the Li1.05Mn2O4 cathodes decreases from 119.2 to 107.9 mA·h/g,and the discharge capability at large current rate and the storage performance decline dramatically,while cycling performance at room temperature and 55℃are improved.The CV and EIS studies indicate that reversibility of Li1.05Mn2O4 cathodes decreases and the electrochemical impedance increases with increasing the sodium dopant amount.
基金the National Natural Science Foundation of China(61874159,61974173,51702085,51802081 and 21603058)the Joint Talent Cultivation Funds of NSFC-HN(U1704151)the Science and Technology Innovation Talents in Universities of Henan Province(18HASTIT016)。
文摘Although silver(Ag) substitution offers several benefits in eliminating bulk defects and facilitating interface type inversion for Cu2ZnSn(S,Se)4(CZTSSe) photovoltaic(PV) technology, its further development is still hindered by the fairly low electrical conductivity due to the significant decrease of acceptors amount.In this work, a versatile Li–Ag co-doping strategy is demonstrated to mitigate the poor electrical conductivity arising from Ag through direct incorporating Li via postdeposition treatment(PDT) on top of the Ag-substituted CZTSSe absorber. Depth characterizations demonstrate that Li incorporation increases ptype carrier concentration, improves the carrier collection within the bulk, reduces the defects energy level as well as inverts the electric field polarity at grain boundaries(GBs) for Ag-substituted CZTSSe system. Benefiting from this lithium-assisted complex engineering of electrical performance both in grain interior(GI) and GBs, the power conversion efficiency(PCE) is finally increased from 9.21% to 10.29%. This systematic study represents an effective way to overcome the challenges encountered in Ag substitution,and these findings support a new aspect that the synergistic effects of double cation dopant will further pave the way for the development of high efficiency kesterite PV technology.
文摘Our previous research showed that aliphatic amines were put in order of high reactivity as “ethylamine > ammonia > t-butylamine > diethylamine” on the aromatic nucleophilic substitution of 1-dimetylamino-2,4-bis(trifluoroacetyl)-naphthalene 1 in acetonitrile. The DFT calculation study (B3LYP/6-31G* with solvation model) for the reactions of 1 with above four amines rationally explained the difference of each amines reactivity based on the energies of their Meisenheimer complexes 3 which are assumed to formed as the reaction intermediates in the course of the reaction giving the corresponding N-N exchange products 2. Intramolecular hydrogen bond between amino proton in 1-amino group and carbonyl oxygen in 2-trifluoroacetyl group stabilizes Meisenheimer complexes 3 effectively, and accelerates the substitution reaction from 1 to 2. Our calculation results also predicted that the above order of amines is also true if less polar toluene is used as a solvent instead of acetonitrile even though more enhanced conditions are required.
文摘The magnetic properties of spinel ferrites Cu_（1-x）Zn_xFe_2O_4 are studied using high-temperature series expansions combined with the Padé approximates. The exchange interactions, inter and intra-sublattices J_（AA）, J_（BB） and J_（AB） are obtained using a probability distribution law. The critical exponent associated with the magnetic susceptibility is obtained.
