For Ti-doped hematite photoanodes, high temperature annealing drastically increases the water oxidation plateau photocurrent, but also induces an anodic shift of onset potential by about 100 m V, thus hindering the pe...For Ti-doped hematite photoanodes, high temperature annealing drastically increases the water oxidation plateau photocurrent, but also induces an anodic shift of onset potential by about 100 m V, thus hindering the performance under low applied bias. To the best of our knowledge, the effects of high temperature annealing on the onset potential have been rarely studied. Herein, both X-ray photoelectron spectroscopy（XPS） measurements and theoretical calculations indicated that the increase of surface Ti/Fe atomic ratio after high temperature annealing decreased the adsorption capacity of hydroxide ions on the hematite surface. Subsequently, the flatband potential（i.e., the theoretical onset potential） of Ti doped hematite photoanodes positively shifted, which was supported by the Mott-Schottky measurements.展开更多
Combining a progressive tandem junction design with a unique Si nanowire(SiNW)framework paves the way for the development of high‐onset‐potential photocathodes and enhancement of solar hydrogen production.Herein,a r...Combining a progressive tandem junction design with a unique Si nanowire(SiNW)framework paves the way for the development of high‐onset‐potential photocathodes and enhancement of solar hydrogen production.Herein,a radial tandem junction(RTJ)thin film water‐splitting photo‐cathode has been demonstrated experimentally for the first time.The photocathode is directly fab‐ricated on vapor‐liquid‐solid‐grown SiNWs and consists of two radially stacked p‐i‐n junctions,featuring hydrogenated amorphous silicon(a‐Si:H)as the outer absorber layer,which absorbs short wavelengths,and hydrogenated amorphous silicon germanium(a‐SiGe:H)as the inner layer,which absorbs long wavelengths.The randomly distributed SiNW framework enables highly efficient light‐trapping,which facilitates the use of very thin absorber layers of a‐Si:H(~50 nm)and a‐SiGe:H(~40 nm).In a neutral electrolyte(pH=7),the three‐dimensional(3D)RTJ photocathode delivers a high photocurrent onset of 1.15 V vs.the reversible hydrogen electrode(RHE),accompanied by a photocurrent of 2.98 mA/cm^(2) at 0 V vs.RHE,and an overall applied‐bias photon‐to‐current effi‐ciency of 1.72%.These results emphasize the promising role of 3D radial tandem technology in developing a new generation of durable,low‐cost,high‐onset‐potential photocathodes capable of large‐scale implementation。展开更多
Photoelectrochemical(PEC)water splitting for solar energy conversion into chemical fuels has attracted intense research attention.The semiconductor hematite(α-Fe_(2)O_(3)),with its earth abundance,chemical stability,...Photoelectrochemical(PEC)water splitting for solar energy conversion into chemical fuels has attracted intense research attention.The semiconductor hematite(α-Fe_(2)O_(3)),with its earth abundance,chemical stability,and efficient light harvesting,stands out as a promising photoanode material.Unfortunately,its electron affinity is too deep for overall water splitting,requiring additional bias.Interface engineering has been used to reduce the onset potential of hematite photoelectrode.Here we focus instead on energy band engineering hematite by shrinking the crystal lattice,and the water-splitting onset potential can be decreased from 1.14 to 0.61 V vs.the reversible hydrogen electrode.It is the lowest record reported for a pristine hematite photoanode without surface modification.X-ray absorption spectroscopy and magnetic properties suggest the redistribution of 3d electrons in the as-synthesized grey hematite electrode.Density function theory studies herein show that the smaller-lattice-constant hematite benefits from raised energy bands,which accounts for the reduced onset potential.展开更多
Electrochemical nitrate(NO_(3)^(-))reduction offers a promising route for ammonia(NH_(3))synthesis from industrial wastewater using renewable energy.However,achieving selective and active NO_(3)^(-)to NH_(3)conversion...Electrochemical nitrate(NO_(3)^(-))reduction offers a promising route for ammonia(NH_(3))synthesis from industrial wastewater using renewable energy.However,achieving selective and active NO_(3)^(-)to NH_(3)conversion at low potentials remains challenging due to complex multi-electron transfer processes and competing reactions.Herein,we tackle this challenge by developing a cascade catalysis approach using synergistic active sites at Cu-Fe_(2)O_(3)interfaces,significantly reducing the NO_(3)^(-)to NH_(3)at a low onset potential to about+0.4 V_(RHE).Specifically,Cu optimizes^(*)NO_(3)adsorption,facilitating NO_(3)^(-)to nitrite(NO_(2)-)conversion,while adjacent Fe species in Fe_(2)O_(3)promote the subsequent NO_(2)-reduction to NH_(3)with favorable^(*)NO_(2)adsorption.Electrochemical operating experiments,in situ Raman spectroscopy,and in situ infrared spectroscopy consolidate this improved onset potential and reduction kinetics via cascade catalysis.An NH_(3)partial current density of~423 mA cm^(-2)and an NH_(3)Faradaic efficiency(FENH_(3))of 99.4%were achieved at-0.6 V_(RHE),with a maximum NH_(3)production rate of 2.71 mmol h^(-1)cm^(-2)at-0.8 V_(RHE).Remarkably,the half-cell energy efficiency exceeded 35%at-0.27 V_(RHE)(80%iR corrected),maintaining an FENH_(3)above 90%across a wide range of NO_(3)^(-)concentrations(0.05^(-1)mol L^(-1)).Using 15N isotopic tracing,we confirmed NO_(3)^(-)as the sole nitrogen source and attained a 98%NO_(3)^(-)removal efficiency.The catalyst exhibit stability over 106-h of continuous operation without noticeable degradation.This work highlights distinctive active sites in Cu-Fe_(2)O_(3)for promoting the cascade NO_(3)^(-)to NO_(2)^(-)and NO_(2)^(-)to NH_(3)electrolysis at industrial relevant current densities.展开更多
The establishment of multi-component catalytic systems on Fe2O3 photoanodes presents considerable potential for significantly enhancing the performance of photoelectrochemical water splitting systems. In this study, w...The establishment of multi-component catalytic systems on Fe2O3 photoanodes presents considerable potential for significantly enhancing the performance of photoelectrochemical water splitting systems. In this study, we hydrothermally synthesized a Fe2O3 photoanode. In addition, d-Fe OOH synthesized via dip-coating and hydrothermally prepared h-FeOOH were used as cocatalysts and their synergistic combinations with cobalt phosphate(Co-Pi) were investigated. The synergy between h-FeOOH and Co-Pi was remarkable, whereas that between d-Fe OOH and Co-Pi was negligible. For example, the onset potentials of the Co-Pi/h-FeOOH and Co-Pi/d-FeOOH dual catalysts, were cathodically shifted by 270 and 170 m V, respectively. Moreover, the photocurrent density of the Co-Pi/h-FeOOH/Fe2O3 anode was significantly higher than that of the Co-Pi/d-FeOOH/Fe2O3 one. The synergistic effect of Co-Pi and h-FeOOH could be attributed to the significantly inhibited recombination of surface charges owing to the formation of a p-n junction between β-FeOOH and Fe2O3 and the large contact area between the granular h-FeOOH and Co-Pi. However, the thin amorphous FeOOH layer of the Co-Pi/d-FeOOH/Fe2O3 anode acted as a hole-transfer medium, and weakly promoted the kinetics of the charge transfer process.展开更多
The earth-abundant and robust aluminum ferrite,AlFeO_(3)(AFO),is mainly studied in the context of ferroelectrics.Herein,we demonstrate that AFO can be used as a stable solar absorber in photoelectrochemical cells for ...The earth-abundant and robust aluminum ferrite,AlFeO_(3)(AFO),is mainly studied in the context of ferroelectrics.Herein,we demonstrate that AFO can be used as a stable solar absorber in photoelectrochemical cells for solar water splitting,exhibiting attractive performance.This is the first report on the photoelectrochemical activity of AFO.AFO thin-film photoelectrodes prepared by solution-processing methods are composed of vertically oriented thin nanosheets,featuring the rhombohedral symmetry(R3c)and n-type conductivity.The as-prepared AFO photoanodes generate a photocurrent density of+0.78 mA·cm^(-2) at 1.23 V vs.reversible hydrogen electrode(RHE)with the photocurrent _(onset) potential(U_(onset))close to the flat band potential of 0.5 V vs.RHE in the presence of hole scavengers.Remarkably,the U_(onset) of AFO for solar water splitting coincides with the flat band potential as well,which is rare in n-type inorganic absorbers.We also report other properties of AFO associated with photoelectrochemical performance.AFO films exhibit a band gap energy of 2.31 eV and positive band edges with low dispersion.Moreover,the carrier lifetimes in AFO films are up to millisecond timescales under the mediation of defect traps.Based on the photoelectrochemical behavior and optoelectronic properties,we believe that AFO has great potential for application in photoelectrochemical cells.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 21473090, U1663228)
文摘For Ti-doped hematite photoanodes, high temperature annealing drastically increases the water oxidation plateau photocurrent, but also induces an anodic shift of onset potential by about 100 m V, thus hindering the performance under low applied bias. To the best of our knowledge, the effects of high temperature annealing on the onset potential have been rarely studied. Herein, both X-ray photoelectron spectroscopy（XPS） measurements and theoretical calculations indicated that the increase of surface Ti/Fe atomic ratio after high temperature annealing decreased the adsorption capacity of hydroxide ions on the hematite surface. Subsequently, the flatband potential（i.e., the theoretical onset potential） of Ti doped hematite photoanodes positively shifted, which was supported by the Mott-Schottky measurements.
文摘Combining a progressive tandem junction design with a unique Si nanowire(SiNW)framework paves the way for the development of high‐onset‐potential photocathodes and enhancement of solar hydrogen production.Herein,a radial tandem junction(RTJ)thin film water‐splitting photo‐cathode has been demonstrated experimentally for the first time.The photocathode is directly fab‐ricated on vapor‐liquid‐solid‐grown SiNWs and consists of two radially stacked p‐i‐n junctions,featuring hydrogenated amorphous silicon(a‐Si:H)as the outer absorber layer,which absorbs short wavelengths,and hydrogenated amorphous silicon germanium(a‐SiGe:H)as the inner layer,which absorbs long wavelengths.The randomly distributed SiNW framework enables highly efficient light‐trapping,which facilitates the use of very thin absorber layers of a‐Si:H(~50 nm)and a‐SiGe:H(~40 nm).In a neutral electrolyte(pH=7),the three‐dimensional(3D)RTJ photocathode delivers a high photocurrent onset of 1.15 V vs.the reversible hydrogen electrode(RHE),accompanied by a photocurrent of 2.98 mA/cm^(2) at 0 V vs.RHE,and an overall applied‐bias photon‐to‐current effi‐ciency of 1.72%.These results emphasize the promising role of 3D radial tandem technology in developing a new generation of durable,low‐cost,high‐onset‐potential photocathodes capable of large‐scale implementation。
基金financially supported by the National Natural Science Funds for Distinguished Young Scholars (51725201)the International (Regional) Cooperation and Exchange Projects of the National Natural Science Foundation of China (51920105003)+3 种基金the Innovation Program of Shanghai Municipal Education Commission (E00014)the National Natural Science Foundation of China (51902105)the Shanghai Engineering Research Center of Hierarchical Nanomaterials (18DZ2252400)the Shanghai Sailing Program (19YF1411600)
文摘Photoelectrochemical(PEC)water splitting for solar energy conversion into chemical fuels has attracted intense research attention.The semiconductor hematite(α-Fe_(2)O_(3)),with its earth abundance,chemical stability,and efficient light harvesting,stands out as a promising photoanode material.Unfortunately,its electron affinity is too deep for overall water splitting,requiring additional bias.Interface engineering has been used to reduce the onset potential of hematite photoelectrode.Here we focus instead on energy band engineering hematite by shrinking the crystal lattice,and the water-splitting onset potential can be decreased from 1.14 to 0.61 V vs.the reversible hydrogen electrode.It is the lowest record reported for a pristine hematite photoanode without surface modification.X-ray absorption spectroscopy and magnetic properties suggest the redistribution of 3d electrons in the as-synthesized grey hematite electrode.Density function theory studies herein show that the smaller-lattice-constant hematite benefits from raised energy bands,which accounts for the reduced onset potential.
文摘Electrochemical nitrate(NO_(3)^(-))reduction offers a promising route for ammonia(NH_(3))synthesis from industrial wastewater using renewable energy.However,achieving selective and active NO_(3)^(-)to NH_(3)conversion at low potentials remains challenging due to complex multi-electron transfer processes and competing reactions.Herein,we tackle this challenge by developing a cascade catalysis approach using synergistic active sites at Cu-Fe_(2)O_(3)interfaces,significantly reducing the NO_(3)^(-)to NH_(3)at a low onset potential to about+0.4 V_(RHE).Specifically,Cu optimizes^(*)NO_(3)adsorption,facilitating NO_(3)^(-)to nitrite(NO_(2)-)conversion,while adjacent Fe species in Fe_(2)O_(3)promote the subsequent NO_(2)-reduction to NH_(3)with favorable^(*)NO_(2)adsorption.Electrochemical operating experiments,in situ Raman spectroscopy,and in situ infrared spectroscopy consolidate this improved onset potential and reduction kinetics via cascade catalysis.An NH_(3)partial current density of~423 mA cm^(-2)and an NH_(3)Faradaic efficiency(FENH_(3))of 99.4%were achieved at-0.6 V_(RHE),with a maximum NH_(3)production rate of 2.71 mmol h^(-1)cm^(-2)at-0.8 V_(RHE).Remarkably,the half-cell energy efficiency exceeded 35%at-0.27 V_(RHE)(80%iR corrected),maintaining an FENH_(3)above 90%across a wide range of NO_(3)^(-)concentrations(0.05^(-1)mol L^(-1)).Using 15N isotopic tracing,we confirmed NO_(3)^(-)as the sole nitrogen source and attained a 98%NO_(3)^(-)removal efficiency.The catalyst exhibit stability over 106-h of continuous operation without noticeable degradation.This work highlights distinctive active sites in Cu-Fe_(2)O_(3)for promoting the cascade NO_(3)^(-)to NO_(2)^(-)and NO_(2)^(-)to NH_(3)electrolysis at industrial relevant current densities.
文摘The establishment of multi-component catalytic systems on Fe2O3 photoanodes presents considerable potential for significantly enhancing the performance of photoelectrochemical water splitting systems. In this study, we hydrothermally synthesized a Fe2O3 photoanode. In addition, d-Fe OOH synthesized via dip-coating and hydrothermally prepared h-FeOOH were used as cocatalysts and their synergistic combinations with cobalt phosphate(Co-Pi) were investigated. The synergy between h-FeOOH and Co-Pi was remarkable, whereas that between d-Fe OOH and Co-Pi was negligible. For example, the onset potentials of the Co-Pi/h-FeOOH and Co-Pi/d-FeOOH dual catalysts, were cathodically shifted by 270 and 170 m V, respectively. Moreover, the photocurrent density of the Co-Pi/h-FeOOH/Fe2O3 anode was significantly higher than that of the Co-Pi/d-FeOOH/Fe2O3 one. The synergistic effect of Co-Pi and h-FeOOH could be attributed to the significantly inhibited recombination of surface charges owing to the formation of a p-n junction between β-FeOOH and Fe2O3 and the large contact area between the granular h-FeOOH and Co-Pi. However, the thin amorphous FeOOH layer of the Co-Pi/d-FeOOH/Fe2O3 anode acted as a hole-transfer medium, and weakly promoted the kinetics of the charge transfer process.
基金support from the project of State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(Nos.LAPS21004 and LAPS202114)the National Natural Science Foundation of China(Nos.52272200,51972110,52102245,52102203,and 52072121)+6 种基金China Postdoctoral Science Foundation(No.2022M721129)Beijing Science and Technology Project(No.Z211100004621010)Beijing Natural Science Foundation(Nos.2222076 and 2222077)Hebei Natural Science Foundation(No.E2022502022)Huaneng Group Headquarters Science and Technology Project(No.HNKJ20-H88)2022 Strategic Research Key Project of Science and Technology Commission of the Ministry of Education,the Fundamental Research Funds for the Central Universities(Nos.2022MS030,2021MS028,2020MS023,and 2020MS028)the NCEPU“Double First-Class”Program.
文摘The earth-abundant and robust aluminum ferrite,AlFeO_(3)(AFO),is mainly studied in the context of ferroelectrics.Herein,we demonstrate that AFO can be used as a stable solar absorber in photoelectrochemical cells for solar water splitting,exhibiting attractive performance.This is the first report on the photoelectrochemical activity of AFO.AFO thin-film photoelectrodes prepared by solution-processing methods are composed of vertically oriented thin nanosheets,featuring the rhombohedral symmetry(R3c)and n-type conductivity.The as-prepared AFO photoanodes generate a photocurrent density of+0.78 mA·cm^(-2) at 1.23 V vs.reversible hydrogen electrode(RHE)with the photocurrent _(onset) potential(U_(onset))close to the flat band potential of 0.5 V vs.RHE in the presence of hole scavengers.Remarkably,the U_(onset) of AFO for solar water splitting coincides with the flat band potential as well,which is rare in n-type inorganic absorbers.We also report other properties of AFO associated with photoelectrochemical performance.AFO films exhibit a band gap energy of 2.31 eV and positive band edges with low dispersion.Moreover,the carrier lifetimes in AFO films are up to millisecond timescales under the mediation of defect traps.Based on the photoelectrochemical behavior and optoelectronic properties,we believe that AFO has great potential for application in photoelectrochemical cells.
