Heterojunction has been widely used in vibration-driven piezocatalysis for enhanced charges separation,while the weak interfaces seriously affect the efficiency during mechanical deformations due to prepared by tradit...Heterojunction has been widely used in vibration-driven piezocatalysis for enhanced charges separation,while the weak interfaces seriously affect the efficiency during mechanical deformations due to prepared by traditional step-by-step methods.Herein,the intimate contact interfaces with shared S atoms are ingeniously constructed in SnS_(2)/SnS anchored on porous carbon by effective interface engineering,which is in-situ derived from temperature-dependent self-transformation of SnS_(2).Benefiting from intimate contact interfaces,the piezoelectricity is remarkably improved due to the larger interfacial dipole moment caused by uneven distribution of charges.Importantly,vibration-induced piezoelectric polarization field strengthens the interfacial electric field to further promote the separation and migration of charges.The dynamic charges then transfer in porous carbon with high conductivity and adsorption for significantly improved piezocatalytic activity.The degradation efficiency of bisphenol A(BPA)is 6.3 times higher than SnS_(2) and H_(2) evolution rate is increased by 3.8 times.Compared with SnS_(2)/SnS prepared by two-step solvothermal method,the degradation efficiency of BPA and H2 evolution activity are increased by 3 and 2 times,respectively.It provides a theoretical guidance for developing various multiphase structural piezocatalyst with strong interface interactions to improve the piezocatalytic efficiency.展开更多
The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, l...The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.展开更多
Catechol adsorbed on TiO_(2)is one of the simplest models to explore the relevant properties of dye-sensitized solar cells.However,the effects of water and defects on the electronic levels and the excitonic properties...Catechol adsorbed on TiO_(2)is one of the simplest models to explore the relevant properties of dye-sensitized solar cells.However,the effects of water and defects on the electronic levels and the excitonic properties of the catechol/TiO_(2)interface have been rarely explored.Here,we investigate four catechol/TiO_(2)interfaces aiming to study the influence of coverage,water,and defects on the electronic levels and the excitonic properties of the catechol/TiO_(2)interface through the first-principles many-body Green’s function theory.We find that the adsorption of catechol on the rutile(110)surface increases the energies of both the TiO_(2)valence band maximum and conduction band minimum by approximately 0.7 eV.The increasing coverage and the presence of water can reduce the optical absorption of charge-transfer excitons with maximum oscillator strength.Regarding the reduced hydroxylated TiO_(2)substrate,the conduction band minimum decreases greatly,resulting in a sub-bandgap of 2.51 eV.The exciton distributions in the four investigated interfaces can spread across several unit cells,especially for the hydroxylated TiO2substrate.Although the hydroxylated TiO_(2)substrate leads to a lower open-circuit voltage,it may increase the separation between photogenerated electrons and holes and may therefore be beneficial for improving the photovoltaic efficiency by controlling its concentration.Our results may provide guidance for the design of highly efficient solar cells in future.展开更多
Device stability becomes one of the most crucial issues for the commercialization of organic solar cells(OSCs) after high power conversion efficiencies have been achieved. Besides the intrinsic stability of photoactiv...Device stability becomes one of the most crucial issues for the commercialization of organic solar cells(OSCs) after high power conversion efficiencies have been achieved. Besides the intrinsic stability of photoactive materials, the chemical/catalytic reaction between interfacial materials and photoactive materials is another critical factor that determines the stability of OSC devices. Herein, we design and synthesize a reaction-inert rylene diimide-embedded hyperbranched polymer named as PDIEIE, which effectively reduces the work function of indium tin oxide electrode from 4.62 to 3.65 eV. Meanwhile, PDIEIE shows negligible chemical reaction with high-performance photoactive materials and no catalytic effect under strong ultraviolet illumination, resulting in much better photo-stability of OSCs with PDIEIE cathode interlayer(CIL), relative to the traditional CILs, including most-widely used metal oxides and polyethyleneimine derivatives.展开更多
Rotational motion of fluorophores chemically attached to polystyrene chain-ends in ultra-thin films on solid substrates was studied by single-molecule fluorescence de-focus microscopy.The collective feature of the rot...Rotational motion of fluorophores chemically attached to polystyrene chain-ends in ultra-thin films on solid substrates was studied by single-molecule fluorescence de-focus microscopy.The collective feature of the rotational motion was found and evidenced by the sharp change of the population of fluorophores undergoing rotational motion within a very narrow temperature range(named as the changing temperature,T c).The T c value was found to depend on film thickness and interfacial chemistry and the variation of the T c value is also dependent on the molecular weight of the polymer.The results demonstrate that the spatial confinement effect enhances the segmental mobility near the polymer chain-ends while the interfacial attraction restricts the segmental motion inside the thin film.展开更多
Water electrolysis to produce H2 is a promising strategy for generating a renewable fuel.However,the sluggish-kinetics and low value-added anodic oxygen evolution reaction(OER)restricts the overall energy conversion e...Water electrolysis to produce H2 is a promising strategy for generating a renewable fuel.However,the sluggish-kinetics and low value-added anodic oxygen evolution reaction(OER)restricts the overall energy conversion efficiency.Herein we report a strategy of boosting H_(2)production at low voltages by replacing OER with a bioelectrochemical cascade reaction at a triphase bioanode.In the presence of oxygen,oxidase enzymes can convert biomass into valuable products,and concurrently generate H_(2)O_(2) that can be further electrooxidized at the bioanode.Benefiting from the efficient oxidase kinetics at an oxygen-rich triphase bioanode and the more favorable thermodynamics of H_(2)O_(2)oxidation than that of OER,the cell voltage and energy consumption are reduced by~0.70 V and~36%,respectively,relative to regular water electrolysis.This leads to an efficient H_(2)production at the cathode and valuable product generation at the bioanode.Integration of a bioelectrochemical cascade into the water splitting process provides an energy-efficient and promising pathway for achieving a renewable fuel.展开更多
文摘Heterojunction has been widely used in vibration-driven piezocatalysis for enhanced charges separation,while the weak interfaces seriously affect the efficiency during mechanical deformations due to prepared by traditional step-by-step methods.Herein,the intimate contact interfaces with shared S atoms are ingeniously constructed in SnS_(2)/SnS anchored on porous carbon by effective interface engineering,which is in-situ derived from temperature-dependent self-transformation of SnS_(2).Benefiting from intimate contact interfaces,the piezoelectricity is remarkably improved due to the larger interfacial dipole moment caused by uneven distribution of charges.Importantly,vibration-induced piezoelectric polarization field strengthens the interfacial electric field to further promote the separation and migration of charges.The dynamic charges then transfer in porous carbon with high conductivity and adsorption for significantly improved piezocatalytic activity.The degradation efficiency of bisphenol A(BPA)is 6.3 times higher than SnS_(2) and H_(2) evolution rate is increased by 3.8 times.Compared with SnS_(2)/SnS prepared by two-step solvothermal method,the degradation efficiency of BPA and H2 evolution activity are increased by 3 and 2 times,respectively.It provides a theoretical guidance for developing various multiphase structural piezocatalyst with strong interface interactions to improve the piezocatalytic efficiency.
基金supported by the National Natural Science Foundation of China(21477094)the Fundamental Research Funds for the Central Universities(WUT 2017IB002)~~
文摘The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.
基金supported by the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(No.2020L0609 and No.2020L0556)the Doctoral research funds of Jinzhong University(jzxybsjjxm2019005)the Basic Research Program in Shanxi Province under the Grant No.20210302124345。
文摘Catechol adsorbed on TiO_(2)is one of the simplest models to explore the relevant properties of dye-sensitized solar cells.However,the effects of water and defects on the electronic levels and the excitonic properties of the catechol/TiO_(2)interface have been rarely explored.Here,we investigate four catechol/TiO_(2)interfaces aiming to study the influence of coverage,water,and defects on the electronic levels and the excitonic properties of the catechol/TiO_(2)interface through the first-principles many-body Green’s function theory.We find that the adsorption of catechol on the rutile(110)surface increases the energies of both the TiO_(2)valence band maximum and conduction band minimum by approximately 0.7 eV.The increasing coverage and the presence of water can reduce the optical absorption of charge-transfer excitons with maximum oscillator strength.Regarding the reduced hydroxylated TiO_(2)substrate,the conduction band minimum decreases greatly,resulting in a sub-bandgap of 2.51 eV.The exciton distributions in the four investigated interfaces can spread across several unit cells,especially for the hydroxylated TiO2substrate.Although the hydroxylated TiO_(2)substrate leads to a lower open-circuit voltage,it may increase the separation between photogenerated electrons and holes and may therefore be beneficial for improving the photovoltaic efficiency by controlling its concentration.Our results may provide guidance for the design of highly efficient solar cells in future.
基金supported by the National Natural Science Foundation of China(52173189 and 22105208)。
文摘Device stability becomes one of the most crucial issues for the commercialization of organic solar cells(OSCs) after high power conversion efficiencies have been achieved. Besides the intrinsic stability of photoactive materials, the chemical/catalytic reaction between interfacial materials and photoactive materials is another critical factor that determines the stability of OSC devices. Herein, we design and synthesize a reaction-inert rylene diimide-embedded hyperbranched polymer named as PDIEIE, which effectively reduces the work function of indium tin oxide electrode from 4.62 to 3.65 eV. Meanwhile, PDIEIE shows negligible chemical reaction with high-performance photoactive materials and no catalytic effect under strong ultraviolet illumination, resulting in much better photo-stability of OSCs with PDIEIE cathode interlayer(CIL), relative to the traditional CILs, including most-widely used metal oxides and polyethyleneimine derivatives.
基金supported by the National Basic Research Program of China(2012CB821500)the National Natural Science Foundation of China(20925416)
文摘Rotational motion of fluorophores chemically attached to polystyrene chain-ends in ultra-thin films on solid substrates was studied by single-molecule fluorescence de-focus microscopy.The collective feature of the rotational motion was found and evidenced by the sharp change of the population of fluorophores undergoing rotational motion within a very narrow temperature range(named as the changing temperature,T c).The T c value was found to depend on film thickness and interfacial chemistry and the variation of the T c value is also dependent on the molecular weight of the polymer.The results demonstrate that the spatial confinement effect enhances the segmental mobility near the polymer chain-ends while the interfacial attraction restricts the segmental motion inside the thin film.
基金supported by the National Key R&D Program of China(2019YFA0709200)the National Natural Science Foundation of China(21988102,51772198 and 21975171)。
文摘Water electrolysis to produce H2 is a promising strategy for generating a renewable fuel.However,the sluggish-kinetics and low value-added anodic oxygen evolution reaction(OER)restricts the overall energy conversion efficiency.Herein we report a strategy of boosting H_(2)production at low voltages by replacing OER with a bioelectrochemical cascade reaction at a triphase bioanode.In the presence of oxygen,oxidase enzymes can convert biomass into valuable products,and concurrently generate H_(2)O_(2) that can be further electrooxidized at the bioanode.Benefiting from the efficient oxidase kinetics at an oxygen-rich triphase bioanode and the more favorable thermodynamics of H_(2)O_(2)oxidation than that of OER,the cell voltage and energy consumption are reduced by~0.70 V and~36%,respectively,relative to regular water electrolysis.This leads to an efficient H_(2)production at the cathode and valuable product generation at the bioanode.Integration of a bioelectrochemical cascade into the water splitting process provides an energy-efficient and promising pathway for achieving a renewable fuel.
