Fractions of various heavy metals in a sulfidic minespoil were investigated. Column leaching experimentwas also conducted to simulate 'acid mine drainage' (AMD) from the minespoil. The results show thatleachin...Fractions of various heavy metals in a sulfidic minespoil were investigated. Column leaching experimentwas also conducted to simulate 'acid mine drainage' (AMD) from the minespoil. The results show thatleaching of heavy metals from the minespoil was extremely significant during the initial water flushing.The amounts of heavy metals leached out dramatically reduced after leaching twice. It is worthwhile tonote that in this study, Zn, Mn, Fe, As and Ni in the first leachate exceeded the total amount of eachcorresponding water-extractable (1:5, soil:water) metal contained in the minespoil sample. This appears tosuggest that 1:5 water extraction did not allow accurate estimation of water-leachable concentrations of theabove heavy metals. This work has implications for the management of sulfidic minespoils. Acid drainageof great environmental concerns is likely to occur only during heavy rainfall events after substantial solubleand readily exchangeable acid and metals are accumulated in the minespoils. The slow-reacting fractionsother than water-soluble and readily exchangeable fractions may pose little environmental hazards. This isparticularly true for Pb, As and Ni.展开更多
Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increa...Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increasing attention as active OER catalysts due to their excellent physical and chemical characters,and massive efforts have been devoted to improving the phosphide and sulfide‐based materials with better activity and stability in recent years.In this review,the recent progress on phosphide and sulfide‐based OER electrocatalysts in terms of chemical properties,synthetic methodologies,catalytic performances evaluation and improvement strategy is reviewed.The most accepted reaction pathways as well as the thermodynamics and electrochemistry of the OER are firstly introduced in brief,followed by a summary of the recent research and optimization strategy of phosphide and sulfide‐based OER electrocatalysts.Finally,some mechanistic studies of the active phase of phosphide and sulfide‐based compounds are discussed to give insight into the nature of active catalytic sites.It is expected to indicate guidance for further improving the performances of phosphide and sulfide‐based OER electrocatalysts.展开更多
Metal-rich transition metal sulfides recently gained increasing attention as electrocatalysts for the hydrogen evolution reaction(HER),as they are capable to overcome major challenges faced by sulfide-rich metal catal...Metal-rich transition metal sulfides recently gained increasing attention as electrocatalysts for the hydrogen evolution reaction(HER),as they are capable to overcome major challenges faced by sulfide-rich metal catalysts such as limited conductivity and the necessity of nanostructuring.Herein,we present the synthesis,characterization and electrocatalytic investigation of ternary metal-rich sulfide composites FexCo9-xS8 as well as Ni_(y)Co_(9-y)S_(8)(x=y=0-4.5),which possess pentlandite-type structures.In this study,we show a stepwise alteration of the binary cobalt pentlandite Co9S8 and report on the replacement of cobalt with up to 4.5 equivalents of either iron or nickel.These altered pentlandite composites facilitate the proton reduction in acidic media at different temperatures.We furthermore show that the stoichiometric variation has a decisive influence on the electrochemical activation/deactivation behavior of the catalysts under reductive electrocatalytic conditions.Here,Co-deficient composites display an improved HER performance in contrast to Co_(9)S_(8).Notably,Ni/Co compounds generally tend to show higher catalytic activities towards HER than their respective Fe/Co compounds.展开更多
The title compound Cu3PSe4 was synthesized by the reaction of CuCl, P2Se5 and Se in a molar ratio of 1:1:1 at 500 C and structurally characterized by X-ray crystallography. The crystal belongs to orthorhombic, space g...The title compound Cu3PSe4 was synthesized by the reaction of CuCl, P2Se5 and Se in a molar ratio of 1:1:1 at 500 C and structurally characterized by X-ray crystallography. The crystal belongs to orthorhombic, space group Pmn21 with cell parameters: a = 7.685(2), b = 6.656(1), c = 6.377(1) , V = 326.2(1) 3, Z = 2, Dc = 5.472 g/cm3, Mr = 537.43, F(000) = 476, m = 32.12 mm-1, R = 0.0642, wR = 0.1481 and S = 1.037. The 3-D structure can be regarded as constructed from the alternately stacking of [Cu(2)Se4] tetrahedral layers and Cu(1)PSe tetrahedral layers along the b direction, in which the Cu(2)Se layer is comprised of corner-sharing [Cu(2)Se4] tetrahedra along the a and c directions, and the Cu(1)PSe layer is consisted of alternately corner-sharing [Cu(1)Se4] tetrahedra and [PSe4] tetrahedra along the a and c directions.展开更多
Recently, the photocatalysts have attracted lots of attention and efforts due to their great potential for environmental remediation application. Toxic ions in water are an increasing environmental pollutant with the ...Recently, the photocatalysts have attracted lots of attention and efforts due to their great potential for environmental remediation application. Toxic ions in water are an increasing environmental pollutant with the fast development. Numerous researches have been made to develop photocatalysts to treat ionic pollutants under the illumination of ultraviolet light and visible light. Here, photocatalytic remediation of toxic ionic pollutants has been reviewed. This review summarized and discussed various photocatalysts including TiO〉 modified TiO2, metal oxides, metalsulfides, and nitrides and their recent progress in removing ionic pollutants such as heavy metal ion. The latest achievements and their future prospects of photocatalytic remediation of ion pollutant have also been reviewed.展开更多
Two-dimensional(2D)transition metal chalcogenides(TMCs)are promising for nanoelectronics and energy applications.Among them,the emerging non-layered TMCs are unique due to their unsaturated dangling bonds on the surfa...Two-dimensional(2D)transition metal chalcogenides(TMCs)are promising for nanoelectronics and energy applications.Among them,the emerging non-layered TMCs are unique due to their unsaturated dangling bonds on the surface and strong intralayer and interlayer bonding.However,the synthesis of non-layered 2D TMCs is challenging and this has made it difficult to study their structures and properties at thin thickness limit.Here,we develop a universal dual-metal precursors method to grow non-layered TMCs in which a mixture of a metal and its chloride serves as the metal source.Taking hexagonal Fe_(1-x)S as an example,the thickness of the Fe_(1-x)S flakes is down to 3 nm with a lateral size of over 100 μm.Importantly,we find ordered cation Fe vacancies in Fe_(1-x)S,which is distinct from layered TMCs like MoS_(2) where anion vacancies are commonly observed.Low-temperature transport measurements and theoretical calculations show that 2D Fe_(1-x)S is a stable semiconductor with a narrow bandgap of60 meV.In addition to Fe_(1-x)S,the method is universal in growing various non-layered 2D TMCs containing ordered cation vacancies,including Fe_(1-x)Se,Co_(1-x)S,Cr_(1-x)S,and V_(1-x)S.This work paves the way to grow and exploit properties of non-layered materials at 2D thickness limit.展开更多
Aqueous precursors provide an alluring approach for low-cost and environmentally friendly production of earth-abundant Cu2ZnSn(S,Se)4(CZTSSe)solar cells.The key is to find an appropriate molecular agent to prepare a s...Aqueous precursors provide an alluring approach for low-cost and environmentally friendly production of earth-abundant Cu2ZnSn(S,Se)4(CZTSSe)solar cells.The key is to find an appropriate molecular agent to prepare a stable solution and optimize the coordination structure to facilitate the subsequent crystallization process.Herein,we introduce thioglycolic acid(TGA),which possesses strong coordination(SH)and hydrophilic(COOH)groups,as the agent and use deprotonation to regulate the coordination competition within the aqueous solution.Ultimately,metal cations are adequately coordinated with thiolate anions,and carboxylate anions are released to become hydrated to form an ultrastable aqueous solution.These factors have contributed to achieving CZTSSe solar cells with an efficiency as high as 12.3%(a certified efficiency of 12.0%)and providing an extremely wide time window for precursor storage and usage.This work represents significant progress in the non-toxic solution fabrication of CZTSSe solar cells and holds great potential for the development of CZTSSe and other metal sulfide solar cells.展开更多
基金Project partly supported by an internal grant of Southern Cross University,Australia(Project No.305093).
文摘Fractions of various heavy metals in a sulfidic minespoil were investigated. Column leaching experimentwas also conducted to simulate 'acid mine drainage' (AMD) from the minespoil. The results show thatleaching of heavy metals from the minespoil was extremely significant during the initial water flushing.The amounts of heavy metals leached out dramatically reduced after leaching twice. It is worthwhile tonote that in this study, Zn, Mn, Fe, As and Ni in the first leachate exceeded the total amount of eachcorresponding water-extractable (1:5, soil:water) metal contained in the minespoil sample. This appears tosuggest that 1:5 water extraction did not allow accurate estimation of water-leachable concentrations of theabove heavy metals. This work has implications for the management of sulfidic minespoils. Acid drainageof great environmental concerns is likely to occur only during heavy rainfall events after substantial solubleand readily exchangeable acid and metals are accumulated in the minespoils. The slow-reacting fractionsother than water-soluble and readily exchangeable fractions may pose little environmental hazards. This isparticularly true for Pb, As and Ni.
文摘Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increasing attention as active OER catalysts due to their excellent physical and chemical characters,and massive efforts have been devoted to improving the phosphide and sulfide‐based materials with better activity and stability in recent years.In this review,the recent progress on phosphide and sulfide‐based OER electrocatalysts in terms of chemical properties,synthetic methodologies,catalytic performances evaluation and improvement strategy is reviewed.The most accepted reaction pathways as well as the thermodynamics and electrochemistry of the OER are firstly introduced in brief,followed by a summary of the recent research and optimization strategy of phosphide and sulfide‐based OER electrocatalysts.Finally,some mechanistic studies of the active phase of phosphide and sulfide‐based compounds are discussed to give insight into the nature of active catalytic sites.It is expected to indicate guidance for further improving the performances of phosphide and sulfide‐based OER electrocatalysts.
文摘Metal-rich transition metal sulfides recently gained increasing attention as electrocatalysts for the hydrogen evolution reaction(HER),as they are capable to overcome major challenges faced by sulfide-rich metal catalysts such as limited conductivity and the necessity of nanostructuring.Herein,we present the synthesis,characterization and electrocatalytic investigation of ternary metal-rich sulfide composites FexCo9-xS8 as well as Ni_(y)Co_(9-y)S_(8)(x=y=0-4.5),which possess pentlandite-type structures.In this study,we show a stepwise alteration of the binary cobalt pentlandite Co9S8 and report on the replacement of cobalt with up to 4.5 equivalents of either iron or nickel.These altered pentlandite composites facilitate the proton reduction in acidic media at different temperatures.We furthermore show that the stoichiometric variation has a decisive influence on the electrochemical activation/deactivation behavior of the catalysts under reductive electrocatalytic conditions.Here,Co-deficient composites display an improved HER performance in contrast to Co_(9)S_(8).Notably,Ni/Co compounds generally tend to show higher catalytic activities towards HER than their respective Fe/Co compounds.
基金This work was supported by the National Natural Science Foundation of China (20001007 20131020) Natural Science Foundation of the Chinese Academy of Sciences (KJCX2-H3) and Fujian Province (2000F006)
文摘The title compound Cu3PSe4 was synthesized by the reaction of CuCl, P2Se5 and Se in a molar ratio of 1:1:1 at 500 C and structurally characterized by X-ray crystallography. The crystal belongs to orthorhombic, space group Pmn21 with cell parameters: a = 7.685(2), b = 6.656(1), c = 6.377(1) , V = 326.2(1) 3, Z = 2, Dc = 5.472 g/cm3, Mr = 537.43, F(000) = 476, m = 32.12 mm-1, R = 0.0642, wR = 0.1481 and S = 1.037. The 3-D structure can be regarded as constructed from the alternately stacking of [Cu(2)Se4] tetrahedral layers and Cu(1)PSe tetrahedral layers along the b direction, in which the Cu(2)Se layer is comprised of corner-sharing [Cu(2)Se4] tetrahedra along the a and c directions, and the Cu(1)PSe layer is consisted of alternately corner-sharing [Cu(1)Se4] tetrahedra and [PSe4] tetrahedra along the a and c directions.
基金supported by Recruitment Program of Global Experts in Chinathe Start-up Funds from Shanghai Jiao Tong University+1 种基金the National Natural Science Foundation of China(51372151,21303103)the Foundation of Shanghai Government(15PJ1404000)
文摘Recently, the photocatalysts have attracted lots of attention and efforts due to their great potential for environmental remediation application. Toxic ions in water are an increasing environmental pollutant with the fast development. Numerous researches have been made to develop photocatalysts to treat ionic pollutants under the illumination of ultraviolet light and visible light. Here, photocatalytic remediation of toxic ionic pollutants has been reviewed. This review summarized and discussed various photocatalysts including TiO〉 modified TiO2, metal oxides, metalsulfides, and nitrides and their recent progress in removing ionic pollutants such as heavy metal ion. The latest achievements and their future prospects of photocatalytic remediation of ion pollutant have also been reviewed.
基金supported by the National Science Fund for Distinguished Young Scholars(52125309)the National Natural Science Foundation of China(51991343,51920105002,51991340,52188101,and 11974156)+3 种基金Guangdong Innovative and Entrepreneurial Research Team Program(2017ZT07C341 and 2019ZT08C044)the Bureau of Industry and Information Technology of Shenzhen for the “2017 Graphene Manufacturing Innovation Center Project”(201901171523)Shenzhen Basic Research Project(JCYJ20200109144616617 and JCYJ20190809180605522)Shenzhen Science and Technology Program(KQTD20190929173815000 and 20200925161102001)。
文摘Two-dimensional(2D)transition metal chalcogenides(TMCs)are promising for nanoelectronics and energy applications.Among them,the emerging non-layered TMCs are unique due to their unsaturated dangling bonds on the surface and strong intralayer and interlayer bonding.However,the synthesis of non-layered 2D TMCs is challenging and this has made it difficult to study their structures and properties at thin thickness limit.Here,we develop a universal dual-metal precursors method to grow non-layered TMCs in which a mixture of a metal and its chloride serves as the metal source.Taking hexagonal Fe_(1-x)S as an example,the thickness of the Fe_(1-x)S flakes is down to 3 nm with a lateral size of over 100 μm.Importantly,we find ordered cation Fe vacancies in Fe_(1-x)S,which is distinct from layered TMCs like MoS_(2) where anion vacancies are commonly observed.Low-temperature transport measurements and theoretical calculations show that 2D Fe_(1-x)S is a stable semiconductor with a narrow bandgap of60 meV.In addition to Fe_(1-x)S,the method is universal in growing various non-layered 2D TMCs containing ordered cation vacancies,including Fe_(1-x)Se,Co_(1-x)S,Cr_(1-x)S,and V_(1-x)S.This work paves the way to grow and exploit properties of non-layered materials at 2D thickness limit.
基金supported by the National Natural Science Foundation of China(51961165108,51421002,51972332 and 51627803)。
文摘Aqueous precursors provide an alluring approach for low-cost and environmentally friendly production of earth-abundant Cu2ZnSn(S,Se)4(CZTSSe)solar cells.The key is to find an appropriate molecular agent to prepare a stable solution and optimize the coordination structure to facilitate the subsequent crystallization process.Herein,we introduce thioglycolic acid(TGA),which possesses strong coordination(SH)and hydrophilic(COOH)groups,as the agent and use deprotonation to regulate the coordination competition within the aqueous solution.Ultimately,metal cations are adequately coordinated with thiolate anions,and carboxylate anions are released to become hydrated to form an ultrastable aqueous solution.These factors have contributed to achieving CZTSSe solar cells with an efficiency as high as 12.3%(a certified efficiency of 12.0%)and providing an extremely wide time window for precursor storage and usage.This work represents significant progress in the non-toxic solution fabrication of CZTSSe solar cells and holds great potential for the development of CZTSSe and other metal sulfide solar cells.
