Herein,a cross-linked porous Ta3N5 film was prepared via a simple solution combustion route followed by a high-temperature nitridation process for photoelectrochemical(PEC) water oxidation.Meanwhile,the metal cations(...Herein,a cross-linked porous Ta3N5 film was prepared via a simple solution combustion route followed by a high-temperature nitridation process for photoelectrochemical(PEC) water oxidation.Meanwhile,the metal cations(Mg2+ and Zr4+) were incorporated into the porous Ta3N5 to enhance the PEC performance.The porous Mg/Zr co-doped Ta3N5 photoanode yielded a photocurrent density of 1.40 mA cm^(-2) at 1.23 V vs RHE,which is 5.6 times higher than that of the dense Ta3N5 photoanode.The enhanced performance should be ascribed to the synergistic effect of porous structure and cation doping,which can enlarge the electrochemical active surface area and accelerate the charge transfer by introducing ON substitution defects.Subsequently,Co(OH)2 cocatalyst was loaded on the Mg/Zr-Ta3N5 photoanode to negatively shift the onset potential to 0.45 V vs RHE and further improve the photocurrent density to 3.5 mA cm^(-2)at 1.23 V vs.RHE,with a maximum half-cell solar to hydrogen efficiency of 0.45%.The present study provides a new strategy to design efficient Ta3N5 photoelectrodes via the simultaneous control of the morphology and composition.展开更多
利用一种新的原位水解沉积方法,以在高湿度空气中老化的甲醇中作为溶剂,通过乙醇钽水解而成前驱体微球颗粒沉积,制备出了高效的Ta_3N_5微球光电极,其1.6 V(vs RHE)电极电位下的光电流值达到了6.6 m A·cm^(-2)。相反地,在新鲜的甲...利用一种新的原位水解沉积方法,以在高湿度空气中老化的甲醇中作为溶剂,通过乙醇钽水解而成前驱体微球颗粒沉积,制备出了高效的Ta_3N_5微球光电极,其1.6 V(vs RHE)电极电位下的光电流值达到了6.6 m A·cm^(-2)。相反地,在新鲜的甲醇溶液中没有钽前驱体微球颗粒沉积。这表明甲醇中水的含量对Ta_3N_5微球光电极的形成十分重要。另外,本制备方法也能方便地在其他透明导电衬底上制备出Ta_3N_5。展开更多
The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta_(3)N_(5) single cry...The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta_(3)N_(5) single crystals grown on the surface of KTaO_(3) can accomplish photocatalytic overall water splitting for the first time.In order to comprehend the underlying mechanism of this photocatalytic system,we have performed a systematic study based on density functional theory first-principles calculations.Ta_(3)N_(5)(010)/KTaO_(3)(110)slab models have been built according to experimental observations by considering two common terminations of KTaO_(3)(110)surface,named as Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO.The formations of interfacial bonds are thermodynamically stable,showing a covalent interaction between two components of a heterostructure.Ta_(3)N_(5)/O_(2) has a higher mobility of photogenerated charge carriers and lower recombination rate of charge carriers than Ta_(3)N_(5)/KTaO.The light absorption of heterostructures displays the feature of KTaO_(3) in the short wavelength region and the characteristic of Ta_(3)N_(5) in the long wavelength region.The calculated band offsets show that Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO have distinct Type-II band alignments,with Ta_(3)N_(5) as the accumulator of photoinduced electrons in the former and the collector of photogenerated holes in the latter,respectively.The difference in charge density and electrostatic potential between two components acts as a driving force to promote the transfer of electrons and holes to different domains of the interface,which is beneficial to extend the lifetime of photoinduced carriers.Our results demonstrate that the function of Ta_(3)N_(5) in Ta_(3)N_(5)/KTaO_(3) photocatalytic system is determined by the termination property of KTaO_(3)(110)surface,which provides a likely reason of the observed photocatalytic activity of overall water splitting achieved by Ta_(3)N_(5) synthesized by using KTaO_(3) as a precursor for the nitridation reaction.展开更多
Ta3N5 is regarded as a promising photocatalyst for solar water splitting because of its excellent visible light absorption characteristics and simple composition.Conventional Ta3N5 photocatalysts prepared from oxide p...Ta3N5 is regarded as a promising photocatalyst for solar water splitting because of its excellent visible light absorption characteristics and simple composition.Conventional Ta3N5 photocatalysts prepared from oxide precursors typically comprise aggregated polycrystalline particles with defects and grain boundaries that reduce the water oxidation activity of the material.In the present work,well-dispersed Ta3N5 nanoparticulate single crystals were synthesized via a mild nitridation process using pure Ta metal nanopowder or Ta nanopowder mixed with NaCl.The resulting high-quality Ta3N5 nanoparticles,after loading with an oxygen evolution cocatalyst,exhibited impressively high photocatalytic performance during O_(2)evolution from a sacrificial AgNO3 solution,with an apparent quantum yield of 9.4%at 420 nm.Our findings suggest a new approach to the facile fabrication of nanostructured single-crystal photocatalysts for efficient solar water splitting,based on the use of metal nanopowders.展开更多
Metal nitrides are widely studied due to their outstanding physical properties, including high hardness,high thermal and chemical stability, low electrical resistivity etc. Generally, metal nitrides can be obtained fr...Metal nitrides are widely studied due to their outstanding physical properties, including high hardness,high thermal and chemical stability, low electrical resistivity etc. Generally, metal nitrides can be obtained from the direct reaction of metal and ammonia/nitrogen. However, some of the metal nitrides,such as Ta_3N_5, cannot be synthesized by direct nitridation of metals. To achieve Ta_3N_5, high-oxidationstate Ta precursors like Ta_2O_5, NaTaO_3, TaS_3, K_6Ta_(10.8)O_(30), Ta(N(CH_3)_2)_5 and TaCl_5 have to be employed,which is a time-consuming and laborious process with the possibility of introducing undesirable impurities. Here taking Ta_3N_5 as an example, a facile carbonate-assisted one-step nitridation method is proposed, which enables the direct synthesis of high-oxidation-state metal nitride films from metal precursors under ammonia flow. The mechanism of the nitridation process has been studied, which carbon dioxide released from carbonates decomposition reacts with metallic Ta and assists the one-step conversion of metallic Ta to Ta_3N_5. The as-prepared Ta_3N_5 film, after modified with NiFe layered double hydroxide, exhibits promising water splitting performance and stability. This method avoids the preoxidation process of metal precursors in high-oxidation-state metal nitride synthesis, and may facilitate the direct fabrication of other important metal nitrides besides Ta_3N_5.展开更多
Solar-driven photoelectrochemical(PEC) water splitting is a promising technology for sustainable hydrogen production, which relies on the development of efficient and stable photoanodes for water oxidation reaction. T...Solar-driven photoelectrochemical(PEC) water splitting is a promising technology for sustainable hydrogen production, which relies on the development of efficient and stable photoanodes for water oxidation reaction. The thickness and microstructure of semiconductor films are generally crucial to their PEC properties. Herein, three-dimensional(3D) interconnected nanoporous Ta3N5 film photoanodes with controlled thickness were successfully fabricated via galvanostatic anodization and NH3 nitridation. The porous Ta3N5 nanoarchitectures(NAs) of 900 nm in thickness showed the highest PEC performance due to the optimal lightharvesting and charge separation. Compared with the holeinduced photocorrosion, the electrochemical oxidation at high anodic potentials resulted in severer performance degradation of Ta3N5. Although the surface oxide layer on deteriorated Ta3N5 photoanodes could be removed by NH3 re-treatment,the PEC performance was only partially recovered. As an alternative, anchoring a dual-layer Co(OH)x/Co OOH co-catalyst shell on the porous Ta3N5 NAs demonstrated substantially enhanced PEC performance and stability. Overall, this work provides reference to controllably fabricate 3D nanoporous Ta3N5-based photoanodes for efficient and stable PEC water splitting via optimizing the light absorption, hole extraction,charge separation and utilization.展开更多
基金the financial support from the China National Key Research and Development Plan Project (No. 2018YFB1502003)the National Natural Science Foundation of China (No. 21606175)the Shaanxi Technical Innovation Guidance Project (Grant no. 2018HJCG-14)。
文摘Herein,a cross-linked porous Ta3N5 film was prepared via a simple solution combustion route followed by a high-temperature nitridation process for photoelectrochemical(PEC) water oxidation.Meanwhile,the metal cations(Mg2+ and Zr4+) were incorporated into the porous Ta3N5 to enhance the PEC performance.The porous Mg/Zr co-doped Ta3N5 photoanode yielded a photocurrent density of 1.40 mA cm^(-2) at 1.23 V vs RHE,which is 5.6 times higher than that of the dense Ta3N5 photoanode.The enhanced performance should be ascribed to the synergistic effect of porous structure and cation doping,which can enlarge the electrochemical active surface area and accelerate the charge transfer by introducing ON substitution defects.Subsequently,Co(OH)2 cocatalyst was loaded on the Mg/Zr-Ta3N5 photoanode to negatively shift the onset potential to 0.45 V vs RHE and further improve the photocurrent density to 3.5 mA cm^(-2)at 1.23 V vs.RHE,with a maximum half-cell solar to hydrogen efficiency of 0.45%.The present study provides a new strategy to design efficient Ta3N5 photoelectrodes via the simultaneous control of the morphology and composition.
文摘利用一种新的原位水解沉积方法,以在高湿度空气中老化的甲醇中作为溶剂,通过乙醇钽水解而成前驱体微球颗粒沉积,制备出了高效的Ta_3N_5微球光电极,其1.6 V(vs RHE)电极电位下的光电流值达到了6.6 m A·cm^(-2)。相反地,在新鲜的甲醇溶液中没有钽前驱体微球颗粒沉积。这表明甲醇中水的含量对Ta_3N_5微球光电极的形成十分重要。另外,本制备方法也能方便地在其他透明导电衬底上制备出Ta_3N_5。
基金financially supported by the Natural Science Foundation of Liaoning Province(Grant No.2019-ZD-0304)the Educational Department of Liaoning Province(Grant No.LJ2019009)+1 种基金Liaoning BaiQianWan Talents Program,Doctoral Start-up Foundation of Liaoning Province(Grant No.20170520231)the open fund of the State Key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics(Grant No.SKLMRDK202001),Chinese Academy of Sciences。
文摘The rational fabrication of heterostructures is one of efficient strategies for improving photocatalytic performance of semiconductor photocatalysts.Very recently,Domen and co-workers found that Ta_(3)N_(5) single crystals grown on the surface of KTaO_(3) can accomplish photocatalytic overall water splitting for the first time.In order to comprehend the underlying mechanism of this photocatalytic system,we have performed a systematic study based on density functional theory first-principles calculations.Ta_(3)N_(5)(010)/KTaO_(3)(110)slab models have been built according to experimental observations by considering two common terminations of KTaO_(3)(110)surface,named as Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO.The formations of interfacial bonds are thermodynamically stable,showing a covalent interaction between two components of a heterostructure.Ta_(3)N_(5)/O_(2) has a higher mobility of photogenerated charge carriers and lower recombination rate of charge carriers than Ta_(3)N_(5)/KTaO.The light absorption of heterostructures displays the feature of KTaO_(3) in the short wavelength region and the characteristic of Ta_(3)N_(5) in the long wavelength region.The calculated band offsets show that Ta_(3)N_(5)/O_(2) and Ta_(3)N_(5)/KTaO have distinct Type-II band alignments,with Ta_(3)N_(5) as the accumulator of photoinduced electrons in the former and the collector of photogenerated holes in the latter,respectively.The difference in charge density and electrostatic potential between two components acts as a driving force to promote the transfer of electrons and holes to different domains of the interface,which is beneficial to extend the lifetime of photoinduced carriers.Our results demonstrate that the function of Ta_(3)N_(5) in Ta_(3)N_(5)/KTaO_(3) photocatalytic system is determined by the termination property of KTaO_(3)(110)surface,which provides a likely reason of the observed photocatalytic activity of overall water splitting achieved by Ta_(3)N_(5) synthesized by using KTaO_(3) as a precursor for the nitridation reaction.
基金supported by the Artificial Photosynthesis Project of the New Energy and Industrial Technology Development Organization(NEDO).Part of this work was conducted at the Advanced Characterization Nanotechnology Platform of the University of Tokyo,supported by the“Nanotechnology Platform”of the Ministry of Education,Culture,Sports,Science and Technology(MEXT),Japan(No.JPMXP09A-19-UT-0023).
文摘Ta3N5 is regarded as a promising photocatalyst for solar water splitting because of its excellent visible light absorption characteristics and simple composition.Conventional Ta3N5 photocatalysts prepared from oxide precursors typically comprise aggregated polycrystalline particles with defects and grain boundaries that reduce the water oxidation activity of the material.In the present work,well-dispersed Ta3N5 nanoparticulate single crystals were synthesized via a mild nitridation process using pure Ta metal nanopowder or Ta nanopowder mixed with NaCl.The resulting high-quality Ta3N5 nanoparticles,after loading with an oxygen evolution cocatalyst,exhibited impressively high photocatalytic performance during O_(2)evolution from a sacrificial AgNO3 solution,with an apparent quantum yield of 9.4%at 420 nm.Our findings suggest a new approach to the facile fabrication of nanostructured single-crystal photocatalysts for efficient solar water splitting,based on the use of metal nanopowders.
基金supported by the National Natural Science Foundation of China (U1663228 and 21473090)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘Metal nitrides are widely studied due to their outstanding physical properties, including high hardness,high thermal and chemical stability, low electrical resistivity etc. Generally, metal nitrides can be obtained from the direct reaction of metal and ammonia/nitrogen. However, some of the metal nitrides,such as Ta_3N_5, cannot be synthesized by direct nitridation of metals. To achieve Ta_3N_5, high-oxidationstate Ta precursors like Ta_2O_5, NaTaO_3, TaS_3, K_6Ta_(10.8)O_(30), Ta(N(CH_3)_2)_5 and TaCl_5 have to be employed,which is a time-consuming and laborious process with the possibility of introducing undesirable impurities. Here taking Ta_3N_5 as an example, a facile carbonate-assisted one-step nitridation method is proposed, which enables the direct synthesis of high-oxidation-state metal nitride films from metal precursors under ammonia flow. The mechanism of the nitridation process has been studied, which carbon dioxide released from carbonates decomposition reacts with metallic Ta and assists the one-step conversion of metallic Ta to Ta_3N_5. The as-prepared Ta_3N_5 film, after modified with NiFe layered double hydroxide, exhibits promising water splitting performance and stability. This method avoids the preoxidation process of metal precursors in high-oxidation-state metal nitride synthesis, and may facilitate the direct fabrication of other important metal nitrides besides Ta_3N_5.
基金financially supported by the National Natural Science Foundation of China (51774145,51872317 and 21835007)China Postdoctoral Science Foundation (2019M661644)China Scholarship Council (CSC) for financial support。
文摘Solar-driven photoelectrochemical(PEC) water splitting is a promising technology for sustainable hydrogen production, which relies on the development of efficient and stable photoanodes for water oxidation reaction. The thickness and microstructure of semiconductor films are generally crucial to their PEC properties. Herein, three-dimensional(3D) interconnected nanoporous Ta3N5 film photoanodes with controlled thickness were successfully fabricated via galvanostatic anodization and NH3 nitridation. The porous Ta3N5 nanoarchitectures(NAs) of 900 nm in thickness showed the highest PEC performance due to the optimal lightharvesting and charge separation. Compared with the holeinduced photocorrosion, the electrochemical oxidation at high anodic potentials resulted in severer performance degradation of Ta3N5. Although the surface oxide layer on deteriorated Ta3N5 photoanodes could be removed by NH3 re-treatment,the PEC performance was only partially recovered. As an alternative, anchoring a dual-layer Co(OH)x/Co OOH co-catalyst shell on the porous Ta3N5 NAs demonstrated substantially enhanced PEC performance and stability. Overall, this work provides reference to controllably fabricate 3D nanoporous Ta3N5-based photoanodes for efficient and stable PEC water splitting via optimizing the light absorption, hole extraction,charge separation and utilization.
