The rapid recombination of photoinduced electron-hole pairs as well as the deficiency of high-energy carriers restricted the redox ability and products selectivity.Herein,the heterojunction of SnS_(2)-deco rated three...The rapid recombination of photoinduced electron-hole pairs as well as the deficiency of high-energy carriers restricted the redox ability and products selectivity.Herein,the heterojunction of SnS_(2)-deco rated three-dimensional ordered macropores(3DOM)-SrTiO_(3) catalysts were in-situ constructed to provide transmit channel for high-energy electron transmission.The suitable band edges of SnS_(2) and SrTiO_(3) contribute to the Z-scheme transfer of photogenerated carrier.The 3DOM structure of SrTiO_(3)-based catalyst possesses the slow light effect for enhancing light adsorption efficiency,and the surface alkalis strontium is benefit to the boosting adsorption for CO_(2).The in-situ introduced SnS_(2) decorated on the macroporous wall surface of 3DOM-SrTiO_(3) altered the primary product from CO to CH4.The Z-scheme electron transfer from SnS_(2) combining with the holes in SrTiO_(3) occurred under full spectrum photoexcitation,which improved the excitation and utilization of photogene rated electrons for C02 multi-electrons reduction.As a result,(SnS_(2))3/3 DOM-SrTiO_(3) catalyst exhibits higher activity for photocatalytic CO_(2) reduction to CH4 compared with single SnS_(2) or 3 DOM-SrTiO_(3),i.e.,its yield and selectivity of CH4 are 12.5μmol g^(-1) h^(-1) and 74.9%,re spectively.The present work proposed the theoretical foundation of Z-scheme heterojunction construction for enhancing photocatalytic activity and selectivity for CO_(2) conversion.展开更多
In order to satisfy the growing global demand for lithium, selective extraction of lithium from brine has attracted extensive attention. LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the best c...In order to satisfy the growing global demand for lithium, selective extraction of lithium from brine has attracted extensive attention. LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the best choices for commercial applications because of its high selectivity and low energy consumption.However, the low ion diffusion coefficient of lithium manganate limits the further development of electrochemical lithium recovery system. In this work, a novel porous disc-like LiMn_(2)O_(4) was successfully synthesized for the first time via two-step annealing manganese(Ⅱ) precursors. The as-prepared LiMn_(2)O_(4) exhibits porous disc-like morphology, excellent crystallinity, high Li^(+)diffusion coefficient(average 7.6×10^(-9)cm^(2)·s^(-1)), high cycle stability(after 30 uninterrupted extraction and release cycles, the crystal structure hardly changed) and superior rate capacity(93.5% retention from 10-120 mA·g^(-1)). The porous structure and disc-like morphology further promote the contact between lithium ions and electrode materials. Therefore, the assembled electrochemical lithium extraction device with LiMn_(2)O_(4) as positive electrode and silver as negative electrode can realize the rapid and selective extraction of lithium in simulated brine(adsorption capacity of lithium can reach 4.85 mg·g^(-1) in 1 h). The mechanism of disc-like LiMn_(2)O_(4) in electrochemical lithium extraction was proposed based on the analysis of electrochemical characterization and quasi in situ XRD. This novel structure may further promote the practical application of electrochemical lithium extraction from brine.展开更多
High-rate CO_(2)-to-CH_(4)photoreduction with high selectivity is highly attractive,which is a win-win strategy for mitigating the greenhouse effect and the energy crisis.However,the poor photocatalytic activity and l...High-rate CO_(2)-to-CH_(4)photoreduction with high selectivity is highly attractive,which is a win-win strategy for mitigating the greenhouse effect and the energy crisis.However,the poor photocatalytic activity and low product selectivity hinder the practical application.To precisely tailor the product selectivity and realize high-rate CO_(2)photoreduction,we design atomically precise Pd species supported on In_(2)O_(3)nanosheets.Taking the synthetic 1.30Pd/In_(2)O_(3)nanosheets as an example,the aberration-correction high-angle annular dark-field scanning transmission electron microscopy image displayed the Pd species atomically dispersed on the In_(2)O_(3)nanosheets.Raman spectra and X-ray photoelectron spectra established that the strong interaction between the Pd species and the In_(2)O_(3)substrate drove electron transfer from In to Pd species,resulting in electron-enriched Pd sites for CO_(2)activation.Synchrotronradiation photoemission spectroscopy demonstrated that the Pd species can tailor the conduction band edge of In_(2)O_(3)nanosheets to match the CO_(2)-to-CH_(4)pathway,instead of the CO_(2)-to-CO pathway,which theoretically accounts for the high CH_(4)selectivity.Moreover,in situ X-ray photoelectron spectroscopy unveiled that the catalytically active sites had a change from In species to Pd species over the 1.30Pd/In_(2)O_(3)nanosheets.In situ FTIR and EPR spectra reveal the atomically precise Pd species with rich electrons prefer to adsorb the electrophilic protons for accelerating the*COOH intermediates hydrogenation into CH_(4).Consequently,the 1.30Pd/In_(2)O_(3)nanosheets reached CO_(2)-to-CH_(4)photoconversion with 100%selectivity and 81.2μmol g^(−1)h^(−1)productivity.展开更多
Organo-halide perovskites in planar heterojunction architecture have shown considerable promise as efficient light harvesters in solar cells. We carry out a numerical modeling of a planar lead based perovskite solar c...Organo-halide perovskites in planar heterojunction architecture have shown considerable promise as efficient light harvesters in solar cells. We carry out a numerical modeling of a planar lead based perovskite solar cell(PSC) with Cu2ZnSnS4(CZTS) as the hole transporting material(HTM) using the one-dimensional solar cell capacitance simulator(SCAPS-1 D). The effects of numerous parameters such as defect density, thickness, and doping density of the absorber layer on the device performance are investigated. The doping densities and electron affinities of the electron transporting material(ETM) and the HTM are also varied to optimize the PSC performance. It has been observed that a thinner absorber layer of220 nm with a defect density of 1014 cm-3 compared to the reference structure improves the device performance. When doping density of the absorber layer increases beyond 2×1016 cm-3, the power conversion efficiency(PCE) reduces due to enhanced recombination rate. The defect density at the absorber/ETM interface reduces the PCE as well. Considering a series resistance of 5 ?·cm2 and all the optimum parameters of absorber, ETM and HTM layers simultaneously, the overall PCE of the device increases significantly. In comparison with the reference structure, the PCE of the optimized device has been increased from 12.76% to 22.7%, and hence the optimized CZTS based PSC is highly efficient.展开更多
基金the National Natural Science Foundation of China(Nos.21673142,21972166)Beijing Natural Science Foundation(No.2202045)+1 种基金Petro China Innovation Foundation(No.2018D-5007-0505)Science Foundation of China University of Petroleum,Beijing(Nos.242017QNXZ02,2462018BJC005)。
文摘The rapid recombination of photoinduced electron-hole pairs as well as the deficiency of high-energy carriers restricted the redox ability and products selectivity.Herein,the heterojunction of SnS_(2)-deco rated three-dimensional ordered macropores(3DOM)-SrTiO_(3) catalysts were in-situ constructed to provide transmit channel for high-energy electron transmission.The suitable band edges of SnS_(2) and SrTiO_(3) contribute to the Z-scheme transfer of photogenerated carrier.The 3DOM structure of SrTiO_(3)-based catalyst possesses the slow light effect for enhancing light adsorption efficiency,and the surface alkalis strontium is benefit to the boosting adsorption for CO_(2).The in-situ introduced SnS_(2) decorated on the macroporous wall surface of 3DOM-SrTiO_(3) altered the primary product from CO to CH4.The Z-scheme electron transfer from SnS_(2) combining with the holes in SrTiO_(3) occurred under full spectrum photoexcitation,which improved the excitation and utilization of photogene rated electrons for C02 multi-electrons reduction.As a result,(SnS_(2))3/3 DOM-SrTiO_(3) catalyst exhibits higher activity for photocatalytic CO_(2) reduction to CH4 compared with single SnS_(2) or 3 DOM-SrTiO_(3),i.e.,its yield and selectivity of CH4 are 12.5μmol g^(-1) h^(-1) and 74.9%,re spectively.The present work proposed the theoretical foundation of Z-scheme heterojunction construction for enhancing photocatalytic activity and selectivity for CO_(2) conversion.
基金supported by the National Natural Science Foundation of China (21878133, 21908082, 22178154)the Natural Science Foundation of Jiangsu Province (BK20190854)+1 种基金the China Postdoctoral Science Foundation (2020 M671364, 2021 M701472)the Science & Technology Foundation of Zhenjiang (GY2020027)。
文摘In order to satisfy the growing global demand for lithium, selective extraction of lithium from brine has attracted extensive attention. LiMn_(2)O_(4)-based electrochemical lithium recovery system is one of the best choices for commercial applications because of its high selectivity and low energy consumption.However, the low ion diffusion coefficient of lithium manganate limits the further development of electrochemical lithium recovery system. In this work, a novel porous disc-like LiMn_(2)O_(4) was successfully synthesized for the first time via two-step annealing manganese(Ⅱ) precursors. The as-prepared LiMn_(2)O_(4) exhibits porous disc-like morphology, excellent crystallinity, high Li^(+)diffusion coefficient(average 7.6×10^(-9)cm^(2)·s^(-1)), high cycle stability(after 30 uninterrupted extraction and release cycles, the crystal structure hardly changed) and superior rate capacity(93.5% retention from 10-120 mA·g^(-1)). The porous structure and disc-like morphology further promote the contact between lithium ions and electrode materials. Therefore, the assembled electrochemical lithium extraction device with LiMn_(2)O_(4) as positive electrode and silver as negative electrode can realize the rapid and selective extraction of lithium in simulated brine(adsorption capacity of lithium can reach 4.85 mg·g^(-1) in 1 h). The mechanism of disc-like LiMn_(2)O_(4) in electrochemical lithium extraction was proposed based on the analysis of electrochemical characterization and quasi in situ XRD. This novel structure may further promote the practical application of electrochemical lithium extraction from brine.
基金the National Key R&D Program of China(2022YFA1502904,2019YFA0210004,2021YFA1501502)National Natural Science Foundation of China(22125503,21975242,U2032212,21890754)+1 种基金Youth Innovation Promotion Association of CAS(CX2340007003)Technical Talent Promotion Plan(TS2021002).
文摘High-rate CO_(2)-to-CH_(4)photoreduction with high selectivity is highly attractive,which is a win-win strategy for mitigating the greenhouse effect and the energy crisis.However,the poor photocatalytic activity and low product selectivity hinder the practical application.To precisely tailor the product selectivity and realize high-rate CO_(2)photoreduction,we design atomically precise Pd species supported on In_(2)O_(3)nanosheets.Taking the synthetic 1.30Pd/In_(2)O_(3)nanosheets as an example,the aberration-correction high-angle annular dark-field scanning transmission electron microscopy image displayed the Pd species atomically dispersed on the In_(2)O_(3)nanosheets.Raman spectra and X-ray photoelectron spectra established that the strong interaction between the Pd species and the In_(2)O_(3)substrate drove electron transfer from In to Pd species,resulting in electron-enriched Pd sites for CO_(2)activation.Synchrotronradiation photoemission spectroscopy demonstrated that the Pd species can tailor the conduction band edge of In_(2)O_(3)nanosheets to match the CO_(2)-to-CH_(4)pathway,instead of the CO_(2)-to-CO pathway,which theoretically accounts for the high CH_(4)selectivity.Moreover,in situ X-ray photoelectron spectroscopy unveiled that the catalytically active sites had a change from In species to Pd species over the 1.30Pd/In_(2)O_(3)nanosheets.In situ FTIR and EPR spectra reveal the atomically precise Pd species with rich electrons prefer to adsorb the electrophilic protons for accelerating the*COOH intermediates hydrogenation into CH_(4).Consequently,the 1.30Pd/In_(2)O_(3)nanosheets reached CO_(2)-to-CH_(4)photoconversion with 100%selectivity and 81.2μmol g^(−1)h^(−1)productivity.
文摘Organo-halide perovskites in planar heterojunction architecture have shown considerable promise as efficient light harvesters in solar cells. We carry out a numerical modeling of a planar lead based perovskite solar cell(PSC) with Cu2ZnSnS4(CZTS) as the hole transporting material(HTM) using the one-dimensional solar cell capacitance simulator(SCAPS-1 D). The effects of numerous parameters such as defect density, thickness, and doping density of the absorber layer on the device performance are investigated. The doping densities and electron affinities of the electron transporting material(ETM) and the HTM are also varied to optimize the PSC performance. It has been observed that a thinner absorber layer of220 nm with a defect density of 1014 cm-3 compared to the reference structure improves the device performance. When doping density of the absorber layer increases beyond 2×1016 cm-3, the power conversion efficiency(PCE) reduces due to enhanced recombination rate. The defect density at the absorber/ETM interface reduces the PCE as well. Considering a series resistance of 5 ?·cm2 and all the optimum parameters of absorber, ETM and HTM layers simultaneously, the overall PCE of the device increases significantly. In comparison with the reference structure, the PCE of the optimized device has been increased from 12.76% to 22.7%, and hence the optimized CZTS based PSC is highly efficient.
