通过强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术研究在光电分解水制氢体系中碳点光阳极与KOH电解液界面的动力学行为。结果表明,光强在30–90 m W·cm^(-2)范围内,界面的电子传输时间(τ_d)、电子寿命(τ_n)、电子扩散系...通过强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术研究在光电分解水制氢体系中碳点光阳极与KOH电解液界面的动力学行为。结果表明,光强在30–90 m W·cm^(-2)范围内,界面的电子传输时间(τ_d)、电子寿命(τ_n)、电子扩散系数(D_n)、电子扩散长度(L_n)均没有变化;当光强增加到110和130 m W·cm^(-2)时,τ_d和τ_n延长,而D_n减小。实验表明,不同于Ti O_2/电解液等界面,碳点光电极/电解液界面中碳点电极存在的缺陷少,因此电子主要以无陷阱限制扩散方式传输为主。且在30–130 m W·cm^(-2)的光强范围内,与τ_d和τ_n相关的载流子收集效率(η_(cc))相近。展开更多
Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen ...Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.展开更多
Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a st...Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.展开更多
Rapid industrialization has accordingly increased the demand for energy.This has resulted in the increasingly severe energy and environmental crises.Hydrogen production,based on the photocatalytic water splitting driv...Rapid industrialization has accordingly increased the demand for energy.This has resulted in the increasingly severe energy and environmental crises.Hydrogen production,based on the photocatalytic water splitting driven by sunlight,is able to directly convert solar energy into a usable or storable energy resource,which is considered to be an ideal alternative energy source to assist in solving the energy crisis and environmental pollution.Unfortunately,the hydrogen production efficiency of single phase photocatalysts is too low to meet the practical requirements.The construction of heterostructured photocatalyst systems,which are comprised of multiple components or multiple phases,is an efficient method to facilitate the separation of electron‐hole pairs to minimize the energy‐waste,provide more electrons,enhance their redox ability,and hence improve the photocatalytic activity.We summarize the recent progress in the rational design and fabrication of nanoheterostructured photocatalysts.The heterojunction photocatalytic hydrogen generation systems can be divided into type‐I,type‐II,pn‐junction and Z‐scheme junction,according to the differences in the transfer of the photogenerated electrons and holes.Finally,a summary and some of the challenges and prospects for the future development of heterojunction photocatalytic systems are discussed.展开更多
Photoelectrochemical(PEC)water splitting process is regarded as a promising route to generate hydrogen by solar energy and at the heart of PEC is efficient electrode design.Great progress has been achieved in the aspe...Photoelectrochemical(PEC)water splitting process is regarded as a promising route to generate hydrogen by solar energy and at the heart of PEC is efficient electrode design.Great progress has been achieved in the aspects of material design,cocatalyst study,and electrode fabrication over the past decades.However,some key challenges remain unsolved,including the most demanded conversion efficiency issue.As three critical steps,i.e.light harvesting,charge transfer and surface reaction of the PEC process,occur in a huge range of time scale(from10-12s to100s),how to manage these subsequent steps to facilitate the seamless cooperation between each step to realize efficient PEC process is essentially important.This review focuses on an integral consideration of the three key criteria based on the recent progress on high efficient and stable photoelectrode design in PEC.The basic principles and potential strategies are summarized.Moreover,the challenge and perspective are also discussed.展开更多
Searching for low-cost widely applicable electrocatalysts for hydrogen production is very important. Here, 3D self-supported NiS2/MoS2 heterostructures were synthesized via a one-step millisecond- laser-direct-writing...Searching for low-cost widely applicable electrocatalysts for hydrogen production is very important. Here, 3D self-supported NiS2/MoS2 heterostructures were synthesized via a one-step millisecond- laser-direct-writing method;these structures exhibited excellent hydrogen evolution reaction activities over a wide pH range. The current density of 10 mA cm^-2 could be reached at low overpotentials of 98 and 159 mV in alkaline and neutral electrolytes, respectively. Such an outstanding electrocatalytic performance should be attributed to the integration of the 3D self-supported nanostructures, the high conductivity of the framework, and particularly, the incalculable heterointerfaces formed between NiS2 and MoS2. This work provides a new strategy to study interfacial engineering and the mechanism of interface enhancement.展开更多
Hydrogen production via solar water splitting is regarded as one of the most promising ways to utilize solar energy and has attracted more and more attention. Great progress has been made on photocatalytic water split...Hydrogen production via solar water splitting is regarded as one of the most promising ways to utilize solar energy and has attracted more and more attention. Great progress has been made on photocatalytic water splitting for hydrogen production in the past few years. This review summarizesthe very recent progress (mainly in the last 2–3 years) on three major types of solar hydrogenproduction systems: particulate photocatalysis (PC) systems, photoelectrochemical (PEC) systems,and photovoltaic‐photoelectrochemical (PV‐PEC) hybrid systems. The solar‐to‐hydrogen (STH)conversion efficiency of PC systems has recently exceeded 1.0% using a SrTiO3:La,Rh/Au/BiVO4:Mophotocatalyst, 2.5% for PEC water splitting on a tantalum nitride photoanode, and reached 22.4%for PV‐PEC water splitting using a multi‐junction GaInP/GaAs/Ge cell and Ni electrode hybrid system.The advantages and disadvantages of these systems for hydrogen production via solar watersplitting, especially for their potential demonstration and application in the future, are briefly describedand discussed. Finally, the challenges and opportunities for solar water splitting solutions are also forecasted.展开更多
Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from ...Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from low efficiencies.In this article,we report a tractable approach to modifying g-C3N4 with vanadyl phthalocyanine(VOPc/CN)for efficient visible-light-driven hydrogen production.A non-covalent VOPc/CN hybrid photocatalyst formed viaπ-πstacking interactions between the two components,as confirmed by analysis of UV-vis absorption spectra.The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability.Under optimal conditions,the corresponding H2 evolution rate is nearly 6 times higher than that of pure g-C3N4.The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively.It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C3N4-based hybrid systems with strong light absorption and high-efficiency carrier separation.展开更多
Escalating apprehension about the harmful effects of widespread use of conventional fossil fuels in the marine field and in internal combustion engines in general, has led to a vast amount of efforts and the directing...Escalating apprehension about the harmful effects of widespread use of conventional fossil fuels in the marine field and in internal combustion engines in general, has led to a vast amount of efforts and the directing of large capital investment towards research and development of sustainable alternative energy sources. One of the most promising and abundant of these sources is hydrogen. Firstly, the use of current fossil fuels is. discussed focusing on the emissions and economic sides to emphasize the need for a new, cleaner and renewable fuel with particular reference to hydrogen as a suitable possible alternative. Hydrogen properties, production and storage methods are then reviewed along with its suitability from the economical point of view. Finally, a cost analysis for the use of hydrogen in internal combustion engines is carried out to illustrate the benefits of its use as a replacement for diesel. The outcome of this cost analysis shows that 98% of the capital expenditure is consumed by the equipment, and 68.3% of the total cost of the equipment is spent on the solar photovoltaic cells. The hydrogen plant is classified as a large investment project because of its high initial cost which is about 1 billion US$; but this is justified because hydrogen is produced in a totally green way. When hydrogen is used as a fuel, no harmful emissions are obtained.展开更多
In this manuscript, a series of catalyst SG n-[VVO2-PAMAM-MSA] (SG silica gel, PAMAM polyamidoamine, MSA 5-methyl salicylaldehyde, n=0, 1, 2, 3) was prepared and their structures were fully characterized by Fourier tr...In this manuscript, a series of catalyst SG n-[VVO2-PAMAM-MSA] (SG silica gel, PAMAM polyamidoamine, MSA 5-methyl salicylaldehyde, n=0, 1, 2, 3) was prepared and their structures were fully characterized by Fourier transform-infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and inductive coupled plasma emission spectrometer (ICP) etc. XPS revealed that the metal V and SG n-PAMAM-MSA combined more closely after the formation of Schiff base derivatives. Their catalytic activities for oxidation of dibenzothiophene were evaluated using tert-butyl hydroperoxide as oxidant. The results showed that the catalyst SG 2.0-[VVO2-PAMAM-MSA] presented good catalytic activity and recycling time. Meanwhile, the optimal condition for the catalytic oxidation of SG 2.0-[VVO2-PAMAM-MSA] was also investigated, which showed that when the oxidation temperature was 90 °C, time was 60 min, the O/S was 3:1, and the mass content of catalyst was 1%, the rate of desulfurization could reach 85.2%. Moreover, the catalyst can be recycled several times without significant decline in catalytic activity.展开更多
文摘通过强度调制光电流谱(IMPS)和强度调制光电压谱(IMVS)技术研究在光电分解水制氢体系中碳点光阳极与KOH电解液界面的动力学行为。结果表明,光强在30–90 m W·cm^(-2)范围内,界面的电子传输时间(τ_d)、电子寿命(τ_n)、电子扩散系数(D_n)、电子扩散长度(L_n)均没有变化;当光强增加到110和130 m W·cm^(-2)时,τ_d和τ_n延长,而D_n减小。实验表明,不同于Ti O_2/电解液等界面,碳点光电极/电解液界面中碳点电极存在的缺陷少,因此电子主要以无陷阱限制扩散方式传输为主。且在30–130 m W·cm^(-2)的光强范围内,与τ_d和τ_n相关的载流子收集效率(η_(cc))相近。
文摘Covalent organic frameworks(COFs)are promising materials for converting solar energy into green hydrogen.However,limited charge separation and transport in COFs impede their application in the photocatalytic hydrogen evolution reaction(HER).In this study,the intrinsically tunable internal bond electric field(IBEF)at the imine bonds of COFs was manipulated to cooperate with the internal molecular electric field(IMEF)induced by the donor-acceptor(D-A)structure for an efficient HER.The aligned orientation of IBEF and IMEF resulted in a remarkable H_(2) evolution rate of 57.3 mmol·g^(-1)·h^(-1)on TNCA,which was approximately 520 times higher than that of TCNA(0.11 mmol·g^(-1)·h^(-1))with the opposing electric field orientation.The superposition of the dual electric fields enables the IBEF to function as an accelerating field for electron transfer,kinetically facilitat-ing the migration of photogenerated electrons from D to A.Furthermore,theoretical calculations indicate that the inhomogeneous charge distribution at the C and N atoms in TNCA not only pro-vides a strong driving force for carrier transfer but also effectively hinders the return of free elec-trons to the valence band,improving the utilization of photoelectrons.This strategy of fabricating dual electric fields in COFs offers a novel approach to designing photocatalysts for clean energy synthesis.
基金the financial support from Australian Research Council through its DP and FF programsthe support from Australian Government Research Training Program and UQ Centennial Scholarships
基金supported by the National Natural Science Foundation of of China(51472191,21407115,21773179)the Natural Science Foundation of Hubei Province of China(2017CFA031)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education(JDGD-201509)~~
文摘Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.
基金supported by the National Natural Science Foundation of China (51572253,21271165)Scientific Research Grant of Hefei Science Center of CAS (2015SRG-HSC048)Cooperation between NSFC and Netherlands Organization for Scientific Research (51561135011)~~
文摘Rapid industrialization has accordingly increased the demand for energy.This has resulted in the increasingly severe energy and environmental crises.Hydrogen production,based on the photocatalytic water splitting driven by sunlight,is able to directly convert solar energy into a usable or storable energy resource,which is considered to be an ideal alternative energy source to assist in solving the energy crisis and environmental pollution.Unfortunately,the hydrogen production efficiency of single phase photocatalysts is too low to meet the practical requirements.The construction of heterostructured photocatalyst systems,which are comprised of multiple components or multiple phases,is an efficient method to facilitate the separation of electron‐hole pairs to minimize the energy‐waste,provide more electrons,enhance their redox ability,and hence improve the photocatalytic activity.We summarize the recent progress in the rational design and fabrication of nanoheterostructured photocatalysts.The heterojunction photocatalytic hydrogen generation systems can be divided into type‐I,type‐II,pn‐junction and Z‐scheme junction,according to the differences in the transfer of the photogenerated electrons and holes.Finally,a summary and some of the challenges and prospects for the future development of heterojunction photocatalytic systems are discussed.
文摘Photoelectrochemical(PEC)water splitting process is regarded as a promising route to generate hydrogen by solar energy and at the heart of PEC is efficient electrode design.Great progress has been achieved in the aspects of material design,cocatalyst study,and electrode fabrication over the past decades.However,some key challenges remain unsolved,including the most demanded conversion efficiency issue.As three critical steps,i.e.light harvesting,charge transfer and surface reaction of the PEC process,occur in a huge range of time scale(from10-12s to100s),how to manage these subsequent steps to facilitate the seamless cooperation between each step to realize efficient PEC process is essentially important.This review focuses on an integral consideration of the three key criteria based on the recent progress on high efficient and stable photoelectrode design in PEC.The basic principles and potential strategies are summarized.Moreover,the challenge and perspective are also discussed.
基金financially supported by the National Natural Science Foundation of China(51572188 and 51822106)~~
文摘Searching for low-cost widely applicable electrocatalysts for hydrogen production is very important. Here, 3D self-supported NiS2/MoS2 heterostructures were synthesized via a one-step millisecond- laser-direct-writing method;these structures exhibited excellent hydrogen evolution reaction activities over a wide pH range. The current density of 10 mA cm^-2 could be reached at low overpotentials of 98 and 159 mV in alkaline and neutral electrolytes, respectively. Such an outstanding electrocatalytic performance should be attributed to the integration of the 3D self-supported nanostructures, the high conductivity of the framework, and particularly, the incalculable heterointerfaces formed between NiS2 and MoS2. This work provides a new strategy to study interfacial engineering and the mechanism of interface enhancement.
基金supported by the National Basic Research Program of the Ministry of Science and Technology (973 Program, 2014CB239400)the National Natural Science Foundation of China (21501236, 21673230)Youth Innovation Promotion Association of Chinese Academy of Sciences (2016167)~~
文摘Hydrogen production via solar water splitting is regarded as one of the most promising ways to utilize solar energy and has attracted more and more attention. Great progress has been made on photocatalytic water splitting for hydrogen production in the past few years. This review summarizesthe very recent progress (mainly in the last 2–3 years) on three major types of solar hydrogenproduction systems: particulate photocatalysis (PC) systems, photoelectrochemical (PEC) systems,and photovoltaic‐photoelectrochemical (PV‐PEC) hybrid systems. The solar‐to‐hydrogen (STH)conversion efficiency of PC systems has recently exceeded 1.0% using a SrTiO3:La,Rh/Au/BiVO4:Mophotocatalyst, 2.5% for PEC water splitting on a tantalum nitride photoanode, and reached 22.4%for PV‐PEC water splitting using a multi‐junction GaInP/GaAs/Ge cell and Ni electrode hybrid system.The advantages and disadvantages of these systems for hydrogen production via solar watersplitting, especially for their potential demonstration and application in the future, are briefly describedand discussed. Finally, the challenges and opportunities for solar water splitting solutions are also forecasted.
基金supported by the National Natural Science Foundation of China(51572253,21771171)Scientific Research Grant of Hefei National Synchrotron Radiation Laboratory(UN2017LHJJ)+1 种基金the Fundamental Research Funds for the Central Universitiescooperation between NSFC and Netherlands Organization for Scientific Research(51561135011)~~
文摘Photocatalytic H2 evolution reactions on pristine graphitic carbon nitrides(g-C3N4),as a promising approach for converting solar energy to fuel,are attractive for tackling global energy concerns but still suffer from low efficiencies.In this article,we report a tractable approach to modifying g-C3N4 with vanadyl phthalocyanine(VOPc/CN)for efficient visible-light-driven hydrogen production.A non-covalent VOPc/CN hybrid photocatalyst formed viaπ-πstacking interactions between the two components,as confirmed by analysis of UV-vis absorption spectra.The VOPc/CN hybrid photocatalyst shows excellent visible-light-driven photocatalytic performance and good stability.Under optimal conditions,the corresponding H2 evolution rate is nearly 6 times higher than that of pure g-C3N4.The role of VOPc in promoting hydrogen evolution activity was to extend the visible light absorption range and prevent the recombination of photoexcited electron-hole pairs effectively.It is expected that this facile modification method could be a new inspiration for the rational design and exploration of g-C3N4-based hybrid systems with strong light absorption and high-efficiency carrier separation.
文摘Escalating apprehension about the harmful effects of widespread use of conventional fossil fuels in the marine field and in internal combustion engines in general, has led to a vast amount of efforts and the directing of large capital investment towards research and development of sustainable alternative energy sources. One of the most promising and abundant of these sources is hydrogen. Firstly, the use of current fossil fuels is. discussed focusing on the emissions and economic sides to emphasize the need for a new, cleaner and renewable fuel with particular reference to hydrogen as a suitable possible alternative. Hydrogen properties, production and storage methods are then reviewed along with its suitability from the economical point of view. Finally, a cost analysis for the use of hydrogen in internal combustion engines is carried out to illustrate the benefits of its use as a replacement for diesel. The outcome of this cost analysis shows that 98% of the capital expenditure is consumed by the equipment, and 68.3% of the total cost of the equipment is spent on the solar photovoltaic cells. The hydrogen plant is classified as a large investment project because of its high initial cost which is about 1 billion US$; but this is justified because hydrogen is produced in a totally green way. When hydrogen is used as a fuel, no harmful emissions are obtained.
基金Supported by the National Natural Science Foundation of China (20901063) the Natural Science Foundation of Hubei Province (2011CDB221)
文摘In this manuscript, a series of catalyst SG n-[VVO2-PAMAM-MSA] (SG silica gel, PAMAM polyamidoamine, MSA 5-methyl salicylaldehyde, n=0, 1, 2, 3) was prepared and their structures were fully characterized by Fourier transform-infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and inductive coupled plasma emission spectrometer (ICP) etc. XPS revealed that the metal V and SG n-PAMAM-MSA combined more closely after the formation of Schiff base derivatives. Their catalytic activities for oxidation of dibenzothiophene were evaluated using tert-butyl hydroperoxide as oxidant. The results showed that the catalyst SG 2.0-[VVO2-PAMAM-MSA] presented good catalytic activity and recycling time. Meanwhile, the optimal condition for the catalytic oxidation of SG 2.0-[VVO2-PAMAM-MSA] was also investigated, which showed that when the oxidation temperature was 90 °C, time was 60 min, the O/S was 3:1, and the mass content of catalyst was 1%, the rate of desulfurization could reach 85.2%. Moreover, the catalyst can be recycled several times without significant decline in catalytic activity.