The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction(HER) in alkaline media. However, it remains a challenge to...The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction(HER) in alkaline media. However, it remains a challenge to controllably create the high-density interface of double sites for optimal synergistic effect.Herein, we reported a simple chemical oxidation-induced surface reconfiguration strategy to obtain the interface-rich Fe_(3)O_(4)-FeS nanoarray supported on iron foam(Fe_(3)O_(4)-FeS/IF) using FeS nanosheets as precursors. The abundant Fe_(3)O_(4)-FeS interfaces could improve the dispersion of active sites and facilitate the electron transfer, leading to enhanced hydrogen evolution efficiency. And meanwhile, by altering the oxidation temperature, the content of S and O could be effectively controlled, further achieving the ratio optimization of Fe_(3)O_(4)to FeS. Synchrotron-based X-ray absorption near-edge structure, X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy consistently confirm the changes of electronic structure and d-band center of Fe_(3)O_(4)-FeS after chemical oxidation. Consequently, Fe_(3)O_(4)-FeS/IF exhibits excellent alkaline HER activity with a low overpotential of 120.8 mV to reach 20 mA cm^(-2),and remains stable ranging from 10, 20 to 50 mA cm^(-2) for each 20 h, respectively. Therefore, the facile and controllable chemical oxidation may be an effective strategy for designing high-density interfaces of transition metal-based sulfides towards alkaline HER.展开更多
We report an abnormal phenomenon that the source-drain current(I_(D))of AlGaN/GaN heterostructure devices decreases under visible light irradiation.When the incident light wavelength is 390 nm,the photon energy is les...We report an abnormal phenomenon that the source-drain current(I_(D))of AlGaN/GaN heterostructure devices decreases under visible light irradiation.When the incident light wavelength is 390 nm,the photon energy is less than the band gaps of GaN and AlGaN whereas it can causes an increase of ID.Based on the UV light irradiation,a decrease of I_(D) can still be observed when turning on the visible light.We speculate that this abnormal phenomenon is related to the surface barrier height,the unionized donor-like surface states below the surface Fermi level and the ionized donor-like surface states above the surface Fermi level.For visible light,its photon energy is less than the surface barrier height of the AlGaN layer.The electrons bound in the donor-like surface states below the Fermi level are excited and trapped by the ionized donor-like surface states between the Fermi level and the conduction band of AlGaN.The electrons trapped in ionized donor-like surface states show a long relaxation time,and the newly ionized donor-like surface states below the surface Fermi level are filled with electrons from the two-dimensional electron gas(2DEG)channel at AlGaN/GaN interface,which causes the decrease of ID.For the UV light,when its photon energy is larger than the surface barrier height of the AlGaN layer,electrons in the donor-like surface states below the Fermi level are excited to the conduction band and then drift into the 2DEG channel quickly,which cause the increase of ID.展开更多
The uniform distribution model of the surface donor states in AlGaN/GaN heterostructures has been widely used in the theoretical calculation.A common and a triple-channel AlGaN/GaN heterostructure Schottky barrier dio...The uniform distribution model of the surface donor states in AlGaN/GaN heterostructures has been widely used in the theoretical calculation.A common and a triple-channel AlGaN/GaN heterostructure Schottky barrier diodes have been fabricated to verify the models,but the calculation results show the uniform distribution model can not provide enough electrons to form three separate 2DEGs in the triple-channel Al GaN/GaN heterostructure.Our experiments indicate the uniform distribution model is not quite right,especially for the multiple-channel AlGaN/GaN heterostructures.Besides,it is found the exponential distribution model possibly matches the actual distribution of the surface donor states better,which allows the 2DEG to form in each channel structure during the calculation.The exponential distribution model would be helpful in the research field.展开更多
An Fe-doped NiO host in a well-defined nanorod assembly (Fe–NiMoO_(4)@NiO-30) with a large surface area is designed to achieve the triple capture of Fe via adjustable surface reconstruction and impregnation to optimi...An Fe-doped NiO host in a well-defined nanorod assembly (Fe–NiMoO_(4)@NiO-30) with a large surface area is designed to achieve the triple capture of Fe via adjustable surface reconstruction and impregnation to optimize the OER activity and durability of bimetallic NiFe hydroxides. The defective and robust NiO layer can not only ensure the first capture of Fe atoms through fast impregnation, but also prevent structural collapse and maintain large Fe adsorption layers. In addition, Fe is found to promote the reconstruction process, leading to more defects to facilitate the second capture. Moreover, the reconfiguration can be controlled by adjusting the ratio of Fe and Ni, obtaining appropriate and uniform dynamically stable Fe sites followed by the third trapping. This triple capture can maintain the dynamic balance of the dissolution and redeposition of active species. Thus, an elevated catalytic performance can be expected with an overpotential of 275 mV at 100 mA cm^(-2) and favorable durability.展开更多
The development of high-efficiency electrocatalysts for overall water splitting under large current density is significant and challenging.Herein,a high-performing Fe-doped MoNi alloy catalyst(M-H-MoNiFe-50)abundant w...The development of high-efficiency electrocatalysts for overall water splitting under large current density is significant and challenging.Herein,a high-performing Fe-doped MoNi alloy catalyst(M-H-MoNiFe-50)abundant with flower-like nanorods assemblies has been prepared by high-pressure microwave reaction and hydrogen reduction.Firstly,Fe doped NiMoO_(4) precursor(M-MoNiFe-50)was synthesized by microwave fast heating,ensuring the robustness of nanorods,which owns larger area and improved catalytic activity than that by conventional hydrothermal method.Secondly,M-MoNiFe-50 was reduced in H_(2)/Ar to fabricate Fe-incorporated MoNi_(4) alloys(M-H-MoNiFe-50),greatly enhancing the conductivity and facilitating hydrogen/oxygen spillover.The final M-H-MoNiFe-50 exhibits remarkable activity for alkaline/acidic hydrogen evolution reaction and oxygen evolution reaction with low overpotential of 208(alkaline),254(acid)and 347 mV at 1,000 mA·cm^(−2).Moreover,an alkaline water electrolyzer is established using M-H-MoNiFe-50 as anode and cathode,generating a current density of 100 mA·cm^(−2) at 1.58 V with encouraging durability of 50 h at 1,000 mA·cm^(−2).The extraordinary water splitting performance can be chalked up to the large surface area,favorable charge transfer,modified electron distribution,intrinsic robustness as well as an efficient gas spillover of M-H-MoNiFe-50.The final electrocatalyst has great prospects for practical application and confirms the significance of Fe doping,microwave method and spillover effect for catalytic performance improvement.展开更多
Electrocatalytic water splitting to produce hydrogen is an eco-friendly way to achieve sustainable utilization of renewable energy.The industrial application of water electrolysis, which is severely limited by slow ki...Electrocatalytic water splitting to produce hydrogen is an eco-friendly way to achieve sustainable utilization of renewable energy.The industrial application of water electrolysis, which is severely limited by slow kinetic reactions on electrode surfaces, requires the development of highly reactive, low-cost and stable electrocatalytic materials. Transition metal borides/borates have recently emerged as promising electrocatalytic materials for catalyzing hydrogen/oxygen evolution reactions(HER/OER) in inexpensive electrolyzers. However, so far, there has been little comprehensive summary of transition metal borides/borates. Here, this review provides the latest research progress on transition metal borides/borates for electrocatalytic water splitting. The structural characteristics of transition metal borides/borates and their synthesis methods in recent years are discussed. Then, the theoretical and experimental progress of transition metal borides including single-metal borides, multi-metal borides, borate derived and other nanocomposites containing boron(boron-doped nanocomposites/substrate with boron) in electrocatalytic reaction and the role of boron in regulating electrocatalytic performance are further emphasized. Finally, the potential challenges and future prospects of transition metal borides/borates in electrocatalysis are presented.展开更多
The correlation between crystal facets and electronic configurations of perovskite is closely related to the intrinsic activity for water splitting.Herein,we proposed a unique molten-salt method(MSM)to manipulate the ...The correlation between crystal facets and electronic configurations of perovskite is closely related to the intrinsic activity for water splitting.Herein,we proposed a unique molten-salt method(MSM)to manipulate the electronic properties of LaCoO_(3) by fine-tuning its crystal facet and atomic doping.LaCoO_(3) samples with oriented(110)(LCO(110))and(111)(LCO(111))facets were motivated by a capping agent(Sr^(2+)).Compared with the LCO(111)plane,the LCO(110)and Sr-doped LCO(111)(LSCO(111))planes possessed higher O 2p positions,stronger Co 3d-O 2p covalencies,and higher Co spin states by inducing CoO_(6) distortion,thus leading to superior oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performances.Specifically,the overpotentials at 10 mA cm^(−2) were 299,322,and 289 mV for LCO(110),LCO(111),and LSCO(111),respectively.In addition,the(110)crystal facet and Sr substitution bestowed enhanced stability on LaCoO_(3) due to the strengthened Co-O bonding.The present work enlightens new avenues of regulating electronic properties by crystal facet engineering and atom doping and provides a valuable reference for the electron structure-electrocatalytic activity connection for OER and HER.展开更多
Defense response genes in higher plant species are involved in a variety of signal transduction pathways and biochemical reactions to counterattack invading pathogens. In this study, a total of 366 non-redundant defen...Defense response genes in higher plant species are involved in a variety of signal transduction pathways and biochemical reactions to counterattack invading pathogens. In this study, a total of 366 non-redundant defense response gene homologs （DRHs）, including 124 unigenes/expressed sequence tags, 226 tentative consensuses, and 16 DRH contigs have been identified by mining the Maize Genetics and Genomics and The Institute for Genomic Research maize databases using 35 essential defense response genes. Of 366 DRHs, 202 are mapped to 152 loci across ten maize chromosomes via both the genetic and in silico mapping approaches. The mapped DRHs seem to cluster together rather than be evenly distributed along the maize genome. Approximately half of these DHRs are located in regions harboring either major resistance genes or quantitative trait loci （QTL）. Therefore, this comprehensive DRH linkage map will provide reference sequences to identify either positional candidate genes for resistance genes and/or QTLs or to develop makers for fine-mapping and marker-assisted selection of resistance genes and/or QTLs.展开更多
基金financially supported by National Natural Science Foundation of China (52174283)the Qingdao Science and Technology Benefiting People Special Project (20-3-4-8-nsh)+1 种基金the Fundamental Research Funds for the Central Universities(20CX02212A)the Development Fund of State Key Laboratory of Heavy Oil Processing and the Postgraduate Innovation Project of China University of Petroleum (YCX2020042)。
文摘The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction(HER) in alkaline media. However, it remains a challenge to controllably create the high-density interface of double sites for optimal synergistic effect.Herein, we reported a simple chemical oxidation-induced surface reconfiguration strategy to obtain the interface-rich Fe_(3)O_(4)-FeS nanoarray supported on iron foam(Fe_(3)O_(4)-FeS/IF) using FeS nanosheets as precursors. The abundant Fe_(3)O_(4)-FeS interfaces could improve the dispersion of active sites and facilitate the electron transfer, leading to enhanced hydrogen evolution efficiency. And meanwhile, by altering the oxidation temperature, the content of S and O could be effectively controlled, further achieving the ratio optimization of Fe_(3)O_(4)to FeS. Synchrotron-based X-ray absorption near-edge structure, X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy consistently confirm the changes of electronic structure and d-band center of Fe_(3)O_(4)-FeS after chemical oxidation. Consequently, Fe_(3)O_(4)-FeS/IF exhibits excellent alkaline HER activity with a low overpotential of 120.8 mV to reach 20 mA cm^(-2),and remains stable ranging from 10, 20 to 50 mA cm^(-2) for each 20 h, respectively. Therefore, the facile and controllable chemical oxidation may be an effective strategy for designing high-density interfaces of transition metal-based sulfides towards alkaline HER.
基金Project supported by Key-Area Research and Development Program of Guangdong Province,China(Grant Nos.2019B010132001 and 2019B010132003)the Joint Funding of the National Natural Science Foundation of China(NSFC)&the Macao Science and Technology Development Fund(FDCT)of China(Grant No.62061160368)+1 种基金the National Key Research and Development Program of China(Grant Nos.2016YFB0400105 and 2017YFB0403001)the Zhuhai Key Technology Laboratory of Wide Bandgap Semiconductor Power Electronics,Sun Yat-sen University,China(Grant No.20167612042080001).
文摘We report an abnormal phenomenon that the source-drain current(I_(D))of AlGaN/GaN heterostructure devices decreases under visible light irradiation.When the incident light wavelength is 390 nm,the photon energy is less than the band gaps of GaN and AlGaN whereas it can causes an increase of ID.Based on the UV light irradiation,a decrease of I_(D) can still be observed when turning on the visible light.We speculate that this abnormal phenomenon is related to the surface barrier height,the unionized donor-like surface states below the surface Fermi level and the ionized donor-like surface states above the surface Fermi level.For visible light,its photon energy is less than the surface barrier height of the AlGaN layer.The electrons bound in the donor-like surface states below the Fermi level are excited and trapped by the ionized donor-like surface states between the Fermi level and the conduction band of AlGaN.The electrons trapped in ionized donor-like surface states show a long relaxation time,and the newly ionized donor-like surface states below the surface Fermi level are filled with electrons from the two-dimensional electron gas(2DEG)channel at AlGaN/GaN interface,which causes the decrease of ID.For the UV light,when its photon energy is larger than the surface barrier height of the AlGaN layer,electrons in the donor-like surface states below the Fermi level are excited to the conduction band and then drift into the 2DEG channel quickly,which cause the increase of ID.
基金Project supported by the Science&Technology Plan of Guangdong Province,China(Grant Nos.2019B010132001 and 2019B010132003)the joint funding of the Nature Science Foundation of China(NSFC)&the Macao Science and Technology Development Fund(FDCT)of China(Grant No.62061160368)+1 种基金the National Key Research and Development Program of China(Grant Nos.2016YFB0400105 and 2017YFB0403001)the Zhuhai Key Technology Laboratory of Wide Bandgap Semiconductor Power Electronics,Sun Yat-sen University,China(Grant No.20167612042080001)。
文摘The uniform distribution model of the surface donor states in AlGaN/GaN heterostructures has been widely used in the theoretical calculation.A common and a triple-channel AlGaN/GaN heterostructure Schottky barrier diodes have been fabricated to verify the models,but the calculation results show the uniform distribution model can not provide enough electrons to form three separate 2DEGs in the triple-channel Al GaN/GaN heterostructure.Our experiments indicate the uniform distribution model is not quite right,especially for the multiple-channel AlGaN/GaN heterostructures.Besides,it is found the exponential distribution model possibly matches the actual distribution of the surface donor states better,which allows the 2DEG to form in each channel structure during the calculation.The exponential distribution model would be helpful in the research field.
基金supported by the National Natural Science Foundation of China(52174283)the Shandong Provincial Natural Science Foundation(ZR2020MB044)the Qingdao Science and Technology Benefiting People Special Project(20-3-4-8-nsh)。
文摘An Fe-doped NiO host in a well-defined nanorod assembly (Fe–NiMoO_(4)@NiO-30) with a large surface area is designed to achieve the triple capture of Fe via adjustable surface reconstruction and impregnation to optimize the OER activity and durability of bimetallic NiFe hydroxides. The defective and robust NiO layer can not only ensure the first capture of Fe atoms through fast impregnation, but also prevent structural collapse and maintain large Fe adsorption layers. In addition, Fe is found to promote the reconstruction process, leading to more defects to facilitate the second capture. Moreover, the reconfiguration can be controlled by adjusting the ratio of Fe and Ni, obtaining appropriate and uniform dynamically stable Fe sites followed by the third trapping. This triple capture can maintain the dynamic balance of the dissolution and redeposition of active species. Thus, an elevated catalytic performance can be expected with an overpotential of 275 mV at 100 mA cm^(-2) and favorable durability.
基金supported by the National Natural Science Foundation of China(No.52174283)Qingdao Science and Technology Benefiting People Special Project(No.20-3-4-8-nsh)+1 种基金the Fundamental Research Funds for the Central Universities(No.20CX02212A)the Development Fund of State Key Laboratory of Heavy Oil Processing and the Postgraduate Innovation Project of China University of Petroleum(No.YCX2020046).
文摘The development of high-efficiency electrocatalysts for overall water splitting under large current density is significant and challenging.Herein,a high-performing Fe-doped MoNi alloy catalyst(M-H-MoNiFe-50)abundant with flower-like nanorods assemblies has been prepared by high-pressure microwave reaction and hydrogen reduction.Firstly,Fe doped NiMoO_(4) precursor(M-MoNiFe-50)was synthesized by microwave fast heating,ensuring the robustness of nanorods,which owns larger area and improved catalytic activity than that by conventional hydrothermal method.Secondly,M-MoNiFe-50 was reduced in H_(2)/Ar to fabricate Fe-incorporated MoNi_(4) alloys(M-H-MoNiFe-50),greatly enhancing the conductivity and facilitating hydrogen/oxygen spillover.The final M-H-MoNiFe-50 exhibits remarkable activity for alkaline/acidic hydrogen evolution reaction and oxygen evolution reaction with low overpotential of 208(alkaline),254(acid)and 347 mV at 1,000 mA·cm^(−2).Moreover,an alkaline water electrolyzer is established using M-H-MoNiFe-50 as anode and cathode,generating a current density of 100 mA·cm^(−2) at 1.58 V with encouraging durability of 50 h at 1,000 mA·cm^(−2).The extraordinary water splitting performance can be chalked up to the large surface area,favorable charge transfer,modified electron distribution,intrinsic robustness as well as an efficient gas spillover of M-H-MoNiFe-50.The final electrocatalyst has great prospects for practical application and confirms the significance of Fe doping,microwave method and spillover effect for catalytic performance improvement.
基金financially supported by National Natural Science Foundation of China(Nos.22078362 and 21808243)the Postgraduate Innovation Engineering Project of China University of Petroleum(East China)(YCX2021063)。
文摘Electrocatalytic water splitting to produce hydrogen is an eco-friendly way to achieve sustainable utilization of renewable energy.The industrial application of water electrolysis, which is severely limited by slow kinetic reactions on electrode surfaces, requires the development of highly reactive, low-cost and stable electrocatalytic materials. Transition metal borides/borates have recently emerged as promising electrocatalytic materials for catalyzing hydrogen/oxygen evolution reactions(HER/OER) in inexpensive electrolyzers. However, so far, there has been little comprehensive summary of transition metal borides/borates. Here, this review provides the latest research progress on transition metal borides/borates for electrocatalytic water splitting. The structural characteristics of transition metal borides/borates and their synthesis methods in recent years are discussed. Then, the theoretical and experimental progress of transition metal borides including single-metal borides, multi-metal borides, borate derived and other nanocomposites containing boron(boron-doped nanocomposites/substrate with boron) in electrocatalytic reaction and the role of boron in regulating electrocatalytic performance are further emphasized. Finally, the potential challenges and future prospects of transition metal borides/borates in electrocatalysis are presented.
基金supported by the National Natural Science Foundation of China(52174283)。
文摘The correlation between crystal facets and electronic configurations of perovskite is closely related to the intrinsic activity for water splitting.Herein,we proposed a unique molten-salt method(MSM)to manipulate the electronic properties of LaCoO_(3) by fine-tuning its crystal facet and atomic doping.LaCoO_(3) samples with oriented(110)(LCO(110))and(111)(LCO(111))facets were motivated by a capping agent(Sr^(2+)).Compared with the LCO(111)plane,the LCO(110)and Sr-doped LCO(111)(LSCO(111))planes possessed higher O 2p positions,stronger Co 3d-O 2p covalencies,and higher Co spin states by inducing CoO_(6) distortion,thus leading to superior oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performances.Specifically,the overpotentials at 10 mA cm^(−2) were 299,322,and 289 mV for LCO(110),LCO(111),and LSCO(111),respectively.In addition,the(110)crystal facet and Sr substitution bestowed enhanced stability on LaCoO_(3) due to the strengthened Co-O bonding.The present work enlightens new avenues of regulating electronic properties by crystal facet engineering and atom doping and provides a valuable reference for the electron structure-electrocatalytic activity connection for OER and HER.
基金Supported by the National 0utstanding Youth Foundation of China(30525035)the High-Tech Research and Development(863)Program of China(2006AA10A107)+1 种基金the Natural Science Foundation of Beijing(5060001)the Beijing Agricultural Innovative Platform-Beijing Natural Science Fund Program(YZPT02-06).
文摘Defense response genes in higher plant species are involved in a variety of signal transduction pathways and biochemical reactions to counterattack invading pathogens. In this study, a total of 366 non-redundant defense response gene homologs （DRHs）, including 124 unigenes/expressed sequence tags, 226 tentative consensuses, and 16 DRH contigs have been identified by mining the Maize Genetics and Genomics and The Institute for Genomic Research maize databases using 35 essential defense response genes. Of 366 DRHs, 202 are mapped to 152 loci across ten maize chromosomes via both the genetic and in silico mapping approaches. The mapped DRHs seem to cluster together rather than be evenly distributed along the maize genome. Approximately half of these DHRs are located in regions harboring either major resistance genes or quantitative trait loci （QTL）. Therefore, this comprehensive DRH linkage map will provide reference sequences to identify either positional candidate genes for resistance genes and/or QTLs or to develop makers for fine-mapping and marker-assisted selection of resistance genes and/or QTLs.
