IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and character...IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and characterized by means of structural,surface analytical and electrochemical techniques.Nb doping of titania significantly increased the surface area of the support from 145(TNTs)to 260 m2g-1(Nb-TNTs),which was significantly higher than those of the Nb-doped titania supports previously reported in the literature.The surface analytical techniques showed good dispersion of the catalysts onto the supports.The X-ray photoelectron spectroscopy analyses showed that Nb was mainly in the form of Nb(IV)species,the suitable form to behave as a donor introducing free electrons to the conduction band of titania.The redox transitions of the cyclic voltammograms,in agreement with the XPS results,were found to be reversible.Despite the supported materials presented bigger crystallite sizes than the unsupported ones,the total number of active sites of the former was also higher due to their better catalyst dispersion.Considering the outer and the total charges of the cyclic voltammograms in the range 0.1–1.4 V,stability and electrode potentials at given current densities,the preferred catalyst was Ir O2 supported on the Nb-TNTs.The electrode potentials corresponding to given current densities were between the smallest ones given in the literature despite the small oxide loading used in this work and its Nb doping,thus making the Nb-TNTs-supported IrO2 catalyst a promising candidate for the OER.The good dispersion of IrO2,high specific surface area of the Nb-doped supports,accessibility of the electroactive centers,increased stability due to Nb doping and electron donor properties of the Nb(IV)oxide species were considered the main reasons for its good performance.展开更多
Perovskite solar cells are one of the most promising alternatives to conventional photovoltaic devices, and extensive studies are focused on device optimization to further improve their performance. A compact layer of...Perovskite solar cells are one of the most promising alternatives to conventional photovoltaic devices, and extensive studies are focused on device optimization to further improve their performance. A compact layer of TiO2 is generally used in perovskite solar cells to block holes from reaching the fluorine-doped tin oxide electrode. In this contribution, we engineered a TiO2 compact layer using Nb doping, which resulted in solar cells with a power conversion efficiency （PCE） of 10.26%, which was higher than that of devices with the same configuration but containing a pristine TiO2 compact layer （PCE = 9.22%）. The device performance enhancement was attributed to the decreased selective contact resistance and increased charge recombination resistance resulting from Nb doping, which was revealed by the impedance spectroscopy measurements. The developed strategy highlights the importance of interface optimization for perovskite solar cells.展开更多
This paper investigates the effect of Nb doping on the electronic structure and optical properties of Sr2TiO4 by the first-principles calculation of plane wave ultra-soft pseudo-potential based on density functional t...This paper investigates the effect of Nb doping on the electronic structure and optical properties of Sr2TiO4 by the first-principles calculation of plane wave ultra-soft pseudo-potential based on density functional theory （DFT）.The calculated results reveal that due to the electron doping,the Fermi level shifts into conduction bands（CBs） for Sr2NbxTi1-xO4 with x=0.125 and the system shows n-type degenerate semiconductor features. Sr2TiO4 exhibits optical anisotropy in its main crystal axes,and the c-axis shows the most suitable crystal growth direction for obtaining a wide transparent region.The optical transmittance is higher than 90% in the visible range for Sr2Nb0.125Ti0.875O4.展开更多
The influence of oxygen defects upon the electronic properties of Nb-doped TiO2 has been studied by using the general gradient approximation （GGA）＋U method. Four independent models （i.e., an undoped anatase cell, ...The influence of oxygen defects upon the electronic properties of Nb-doped TiO2 has been studied by using the general gradient approximation （GGA）＋U method. Four independent models （i.e., an undoped anatase cell, an anatase cell with a Nb dopant at Ti site （NbTi）, an anatase cell with a Nb-dopant and an oxygen vacancy （NbTi＋Vo）, and an anatase cell with a Nb-dopant and an interstitial oxygen （NbTi＋Oi）） were considered. The density of states, effective mass, Bader charge, charge density, and electron localization function were calcul^ited. The results show that in the NbTi＋Vo cell both eg and t2g levels of Ti 3d orbits make contributions to the electronic conductivity, and the oxygen vacancies （Vo） collaborate with Nb-dopants to favor the high electrical conductivity by inducing the Nb-dopants to release more excess charges. In NbTi＋Oi, an unoccupied impurity level appears in the band gap, which served as an acceptor level and suppressed the electronic conductivity. The results qualitatively coincide with experimental results and possibly provide insights into the preparation of TCOs with desirable conductivity.展开更多
Nb-doped TiO2 nanoparticles were prepared by hydrothermal treatment of titanate nanotubes in niobium oxalate aqueous solution.The effect of Nb doping and rutile content on the photoelectrochemical performance based on...Nb-doped TiO2 nanoparticles were prepared by hydrothermal treatment of titanate nanotubes in niobium oxalate aqueous solution.The effect of Nb doping and rutile content on the photoelectrochemical performance based on TiO2 powder electrodes was investigated.The results show that Nb-doped TiO2 with a small amount of rutile exhibits the enhanced photoelectric conversion efficiency for dye-sensitized solar cell.The highest photoelectric conversion efficiency of 8.53%is obtained for 1%Nb—TiO2 containing a small amount of rutile.When a small amount of rutile contained in 2%Nb—TiO2,a higher photoelectric conversion efficiency of8.77%is achieved.展开更多
All-inorganic CsPbBr_(3)-based perovskite solar cells(PSCs)have attracted great attention because of their high chemical and thermal stabilities in ambient air.However,the short-circuit current density(J_(sc))of CsPbB...All-inorganic CsPbBr_(3)-based perovskite solar cells(PSCs)have attracted great attention because of their high chemical and thermal stabilities in ambient air.However,the short-circuit current density(J_(sc))of CsPbBr_(3)-based PSCs is inadequate under solar illumination because of the wide bandgap,inefficient charge extraction and recombination loss,leading to lower power-conversion efficiencies(PCEs).It is envisaged that in addition to narrowing the bandgap by alloying,J_(sc)of the PSCs could be enhanced by effective improvement of electron transportation,suppression of charge recombination at the interface between the perovskite and electron transporting layer(ETL),and tuning of the space charge field in the device.In this work,Nb-doped SnO_(2)films as ETLs in the CsPbBr_(3)-based PSCs have been deposited at room temperature by high target utilization sputtering(Hi TUS).Through optimizing the Nb doping level alone,the J_(sc)was increased by nearly 19%,from 7.51 to 8.92 mA·cm^(-2)and the PCE was enhanced by 27%from 6.73%to 8.54%.The overall benefit by replacing the spin-coated SnO_(2)with sputtered SnO_(2)with Nb doping was up to 39%increase in J_(sc)and 62%increase in PCE.Moreover,the PCE of the optimized device showed negligible degradation over exposure to ambient environment(T~25°C,RH~45%),with 95.4%of the original PCE being maintained after storing the device for 1200 h.展开更多
Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolu...Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.展开更多
We prepared TiO 2(anatase) and Sn doped TiO 2 nanoparticlate film by Plasma enhanced Chemical Vapor Deposition(PECVD) method. XRD and XPS experiments showed that Sn was doped into the lattice of TiO 2 with a ratio of ...We prepared TiO 2(anatase) and Sn doped TiO 2 nanoparticlate film by Plasma enhanced Chemical Vapor Deposition(PECVD) method. XRD and XPS experiments showed that Sn was doped into the lattice of TiO 2 with a ratio of n (Sn)∶ n (Ti)=1∶10 . Sn doping largely enhanced the photocatalytic activity of TiO 2 film for phenol degradation. The enhancement in photoactivity by doping was discussed, based on the characterization with AFM, FTIR and EFISPS. Sn doping produced localized level of Sn 4+ in the band gap of TiO 2, about 0.4 eV below the conduction band, which could capture photogenerated electrons and reduce O 2 adsorbed on the surface of TiO 2 film, thus accelerated the photocatalytic reaction.展开更多
The transition metal ion doped TiO 2 nanoparticles were prepared with hydrothermal method, and the effects of doping different metal ions on the ability of TiO 2 in photocatalyzing degradation of rhodamine B(RB) were ...The transition metal ion doped TiO 2 nanoparticles were prepared with hydrothermal method, and the effects of doping different metal ions on the ability of TiO 2 in photocatalyzing degradation of rhodamine B(RB) were studied. The results showed that the doping of Fe 3+ , Co 2+ , Ni 2+ and Cr 3+ in TiO 2 nanoparticles made the photocatalytic efficiency of the TiO 2 particles reduce and the higher the initial content of Fe 3+ , the lower the ability of TiO 2 in photocatalyzing the degradation of RB. But the doping of Zn 2+ and Cd 2+ , especially Zn 2+ , made the photocatalytic efficiency of the TiO 2 particles enhance, showing a great increase of the rate constant( k ) and the initial reaction rate( r ini ).展开更多
文摘IrO2 and IrRuOx(Ir:Ru 60:40 at%),supported by 50 wt%onto titania nanotubes(TNTs)and(3 at%Nb)Nb-doped titania nanotubes(Nb-TNTs),as electrocatalysts for the oxygen evolution reaction(OER),were synthesized and characterized by means of structural,surface analytical and electrochemical techniques.Nb doping of titania significantly increased the surface area of the support from 145(TNTs)to 260 m2g-1(Nb-TNTs),which was significantly higher than those of the Nb-doped titania supports previously reported in the literature.The surface analytical techniques showed good dispersion of the catalysts onto the supports.The X-ray photoelectron spectroscopy analyses showed that Nb was mainly in the form of Nb(IV)species,the suitable form to behave as a donor introducing free electrons to the conduction band of titania.The redox transitions of the cyclic voltammograms,in agreement with the XPS results,were found to be reversible.Despite the supported materials presented bigger crystallite sizes than the unsupported ones,the total number of active sites of the former was also higher due to their better catalyst dispersion.Considering the outer and the total charges of the cyclic voltammograms in the range 0.1–1.4 V,stability and electrode potentials at given current densities,the preferred catalyst was Ir O2 supported on the Nb-TNTs.The electrode potentials corresponding to given current densities were between the smallest ones given in the literature despite the small oxide loading used in this work and its Nb doping,thus making the Nb-TNTs-supported IrO2 catalyst a promising candidate for the OER.The good dispersion of IrO2,high specific surface area of the Nb-doped supports,accessibility of the electroactive centers,increased stability due to Nb doping and electron donor properties of the Nb(IV)oxide species were considered the main reasons for its good performance.
基金This work was financially supported by the National Natural Science Foundation of China （Grant Nos. 21103032 and 51272049）, the National Basic Research Program of China （973 Program） （No. 2011CB932702）, and SInberise R279-000-393-592. Dr. X. Yin thanks Mr. Jin Fang for help on IPCE measurements and Au evaporation.
文摘Perovskite solar cells are one of the most promising alternatives to conventional photovoltaic devices, and extensive studies are focused on device optimization to further improve their performance. A compact layer of TiO2 is generally used in perovskite solar cells to block holes from reaching the fluorine-doped tin oxide electrode. In this contribution, we engineered a TiO2 compact layer using Nb doping, which resulted in solar cells with a power conversion efficiency （PCE） of 10.26%, which was higher than that of devices with the same configuration but containing a pristine TiO2 compact layer （PCE = 9.22%）. The device performance enhancement was attributed to the decreased selective contact resistance and increased charge recombination resistance resulting from Nb doping, which was revealed by the impedance spectroscopy measurements. The developed strategy highlights the importance of interface optimization for perovskite solar cells.
基金Project supported by the Natural Science Foundation of ShaanXi Province of China (Grant No 2005F06)Northwest University(NWU) Graduate Innovation and Creativity Funds (Grant No 08YZZ47)
文摘This paper investigates the effect of Nb doping on the electronic structure and optical properties of Sr2TiO4 by the first-principles calculation of plane wave ultra-soft pseudo-potential based on density functional theory （DFT）.The calculated results reveal that due to the electron doping,the Fermi level shifts into conduction bands（CBs） for Sr2NbxTi1-xO4 with x=0.125 and the system shows n-type degenerate semiconductor features. Sr2TiO4 exhibits optical anisotropy in its main crystal axes,and the c-axis shows the most suitable crystal growth direction for obtaining a wide transparent region.The optical transmittance is higher than 90% in the visible range for Sr2Nb0.125Ti0.875O4.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51002135 and 51172200)the Fundamental Research Funds for the Central Universities of Ministry of Education of China(Grant No.2013QNA4011)
文摘The influence of oxygen defects upon the electronic properties of Nb-doped TiO2 has been studied by using the general gradient approximation （GGA）＋U method. Four independent models （i.e., an undoped anatase cell, an anatase cell with a Nb dopant at Ti site （NbTi）, an anatase cell with a Nb-dopant and an oxygen vacancy （NbTi＋Vo）, and an anatase cell with a Nb-dopant and an interstitial oxygen （NbTi＋Oi）） were considered. The density of states, effective mass, Bader charge, charge density, and electron localization function were calcul^ited. The results show that in the NbTi＋Vo cell both eg and t2g levels of Ti 3d orbits make contributions to the electronic conductivity, and the oxygen vacancies （Vo） collaborate with Nb-dopants to favor the high electrical conductivity by inducing the Nb-dopants to release more excess charges. In NbTi＋Oi, an unoccupied impurity level appears in the band gap, which served as an acceptor level and suppressed the electronic conductivity. The results qualitatively coincide with experimental results and possibly provide insights into the preparation of TCOs with desirable conductivity.
基金supported by the National Natural Science Foundation of China(No.51172233)the Major State Basic Research Development Program of China("973 Program",No. 2009CB220002)the Key Laboratory of Water and Air Pollution Control of Guandong Province,China(GD2012A05)
文摘Nb-doped TiO2 nanoparticles were prepared by hydrothermal treatment of titanate nanotubes in niobium oxalate aqueous solution.The effect of Nb doping and rutile content on the photoelectrochemical performance based on TiO2 powder electrodes was investigated.The results show that Nb-doped TiO2 with a small amount of rutile exhibits the enhanced photoelectric conversion efficiency for dye-sensitized solar cell.The highest photoelectric conversion efficiency of 8.53%is obtained for 1%Nb—TiO2 containing a small amount of rutile.When a small amount of rutile contained in 2%Nb—TiO2,a higher photoelectric conversion efficiency of8.77%is achieved.
基金supported by the National Natural Science Foundation of China(Nos.51602290,91233101,11174256)the Fundamental Research Program from the Ministry of Science and Technology of China(No.2014CB31704)+4 种基金Project funded by China Postdoctoral Science Foundation(No.2016M592310)the financial support from EPSRC New Investigator Award(2018EP/R043272/1)H2020-EU grant(2018CORNET 760949)
文摘All-inorganic CsPbBr_(3)-based perovskite solar cells(PSCs)have attracted great attention because of their high chemical and thermal stabilities in ambient air.However,the short-circuit current density(J_(sc))of CsPbBr_(3)-based PSCs is inadequate under solar illumination because of the wide bandgap,inefficient charge extraction and recombination loss,leading to lower power-conversion efficiencies(PCEs).It is envisaged that in addition to narrowing the bandgap by alloying,J_(sc)of the PSCs could be enhanced by effective improvement of electron transportation,suppression of charge recombination at the interface between the perovskite and electron transporting layer(ETL),and tuning of the space charge field in the device.In this work,Nb-doped SnO_(2)films as ETLs in the CsPbBr_(3)-based PSCs have been deposited at room temperature by high target utilization sputtering(Hi TUS).Through optimizing the Nb doping level alone,the J_(sc)was increased by nearly 19%,from 7.51 to 8.92 mA·cm^(-2)and the PCE was enhanced by 27%from 6.73%to 8.54%.The overall benefit by replacing the spin-coated SnO_(2)with sputtered SnO_(2)with Nb doping was up to 39%increase in J_(sc)and 62%increase in PCE.Moreover,the PCE of the optimized device showed negligible degradation over exposure to ambient environment(T~25°C,RH~45%),with 95.4%of the original PCE being maintained after storing the device for 1200 h.
基金support from the European Union Horizon 2020 program(project HERMES,nr.952184)the Ministry of Education,Youth and Sports of the Czech Republic for supporting CEMNAT(LM2023037)+1 种基金Czech-NanoLab(LM2023051)infrastructures for providing ALD,SEM,EDX,XPS,TEM,and XRDCzech Science Foundation(project 23-08019X,EXPRO).
文摘Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.
文摘We prepared TiO 2(anatase) and Sn doped TiO 2 nanoparticlate film by Plasma enhanced Chemical Vapor Deposition(PECVD) method. XRD and XPS experiments showed that Sn was doped into the lattice of TiO 2 with a ratio of n (Sn)∶ n (Ti)=1∶10 . Sn doping largely enhanced the photocatalytic activity of TiO 2 film for phenol degradation. The enhancement in photoactivity by doping was discussed, based on the characterization with AFM, FTIR and EFISPS. Sn doping produced localized level of Sn 4+ in the band gap of TiO 2, about 0.4 eV below the conduction band, which could capture photogenerated electrons and reduce O 2 adsorbed on the surface of TiO 2 film, thus accelerated the photocatalytic reaction.
文摘The transition metal ion doped TiO 2 nanoparticles were prepared with hydrothermal method, and the effects of doping different metal ions on the ability of TiO 2 in photocatalyzing degradation of rhodamine B(RB) were studied. The results showed that the doping of Fe 3+ , Co 2+ , Ni 2+ and Cr 3+ in TiO 2 nanoparticles made the photocatalytic efficiency of the TiO 2 particles reduce and the higher the initial content of Fe 3+ , the lower the ability of TiO 2 in photocatalyzing the degradation of RB. But the doping of Zn 2+ and Cd 2+ , especially Zn 2+ , made the photocatalytic efficiency of the TiO 2 particles enhance, showing a great increase of the rate constant( k ) and the initial reaction rate( r ini ).
