Heterogeneous catalysts have attracted wide attention due to their remarkable oxygen evolution reaction(OER)capabilities.Herein,a one-step strategy involving the coupling of NixSeywith CeO_(2)is proposed to concurrent...Heterogeneous catalysts have attracted wide attention due to their remarkable oxygen evolution reaction(OER)capabilities.Herein,a one-step strategy involving the coupling of NixSeywith CeO_(2)is proposed to concurrently construct heterogeneous interfaces,adjust phase structure,and regulate electronic configuration,thereby enhancing OER performance.Thanks to the role of CeO_(2)coupling in reducing the activation-energy and accelerating the reaction kinetics,the heterogeneous NixSey/CeO_(2)catalyst exhibits a low overpotential of 218 mV at 10 mA/cm2and long-term stability(>400 h)in 1.0 mol/L KOH for OER.Moreover,the post-OER characterization reveals that the NixSeymatrix is reconstructed into NiOOH,while the incorporated CeO_(2)nanocrystals self-assemble into larger polycrystalline particles.Theoretical analysis further demonstrates that the optimized electronic states at NiOOH/CeO_(2)interfaces can modulate intermediate chemisorption toward favorable OER kinetics.This study offers fresh perspectives on the synthesis and structure-activity relationship of CeO_(2)-coupled electrocatalysts.展开更多
Recently,metal selenides have obtained widespread attention as electrode materials for alkali(Li^(+)/Na^(+)/K^(+))batteries due to their promising theoretical capacity and mechanism.Nevertheless,metal selenides,simila...Recently,metal selenides have obtained widespread attention as electrode materials for alkali(Li^(+)/Na^(+)/K^(+))batteries due to their promising theoretical capacity and mechanism.Nevertheless,metal selenides,similar to metal oxides and sulfides,also suffer from severe volume explosion during repeated charge/discharge processes,which results in the structure collapse and the following pulverization of electrode materials.Hence,it leads to poor cycle stability and influencing their further application.In order to solve these issues,some special strategies,including elemental doping,coupling with carbon materials,synthesis of the bimetal selenides with heterostructure,etc.,have been gradually applied to design novel electrode materials with outstanding electrochemical performance.Herein,the recent research progress on metal selenides as anodes for alkali ion batteries is summarized,including the regulation of crystal structure,synthesis strategies,modification methods,and electrochemical mechanisms and kinetics.Besides,the challenges of metal selenides and the perspective for future electrode material design are proposed.It is hoped to pave a way for the development of metal selenide electrode materials for the potential applications for alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries.展开更多
Lithium-sulfur batteries(LSBs)have attracted the attention of more and more researchers due to the advantages of high energy density,environmental friendliness,and low production cost.However,the low electronic conduc...Lithium-sulfur batteries(LSBs)have attracted the attention of more and more researchers due to the advantages of high energy density,environmental friendliness,and low production cost.However,the low electronic conductivity of active material and shuttling effect of lithium polysulfides(LiPSs)limit the commercial development of LSBs.To solve these problems,we design a core-shell composite with nitrogen-doped carbon(NC)and two types of selenides(FeSe_(2)-NC@ZnSe-NC).The FeSe_(2)-NC@ZnSe-NC has a strong adsorption capacity,and can effectively adsorb LiPSs.At the same time,it also effectively alleviates the shuttling effect of LiPSs,and improves the utilization of the active substance during the charge/discharge reaction processes.The mechanism involved in FeSe_(2)-NC@ZnSe-NC is demonstrated by both experiments and density-functional theory(DFT)calculations.The electrochemical test results indicate that LSB with S/FeSe_(2)-NC@ZnSe-NC delivers an initial discharge capacity of 1260 mAh·g^(-1)at 0.2C.And after 500 cycles at 1C,the capacity decay rate per cycle is 0.031%,and the capacity retention rate is 85%.The FeSe_(2)-NC@ZnSe-NC core-shell structure verifies a rational strategy to construct an electrode material for high-performance LSBs.展开更多
Alkynyl selenides were prepared under very mild conditions by reacting terminal alkynes with respective diorganic diselenides in the presence of potassium t-butoxide. The advantages of this protocol include the use of...Alkynyl selenides were prepared under very mild conditions by reacting terminal alkynes with respective diorganic diselenides in the presence of potassium t-butoxide. The advantages of this protocol include the use of readily available substrates and reagent and good yield of the products.展开更多
Reduction of diaryldiselenides by the system of Cp2TiCl2/Bu'MgBr/THF gave the nucleophilic arylselenium complex. They reacted with diaryl iodonium salts to afford unsymmetrical diaryl selenides in high yields.
A simple and convenient procedure for stercoselective synthesis of （Z）-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethyls...A simple and convenient procedure for stercoselective synthesis of （Z）-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCI system to form selemde anions, which then undergo SN2＇ substitution of Baylis-Hillman adducts to produce the （Z）-allyl selenides.展开更多
The shell structure design has been recognized as a highly efficient strategy to buffer the severe volume expansion and consecutive pulverization of conversion-type anodes.Nevertheless,construction of a functional she...The shell structure design has been recognized as a highly efficient strategy to buffer the severe volume expansion and consecutive pulverization of conversion-type anodes.Nevertheless,construction of a functional shell with a stabilized structure that meets the demands of both high electronic conductivity and feasible pathways for Na^(+)ions has been a challenge so far.Herein,we design a two-in-one shell configuration for bimetal selenides to achieve fast sodium storage within broadened voltage windows.The hybridized shell,which benefits from the combination of titanium dioxide quantum dots and amorphous carbon,can not only effectively buffer the strain and maintain structural integrity but also allow facile and reversible transport of electrons and Na^(+)uptake for electrode materials during sodiation/desodiation processes,resulting in increased reaction kinetics and diffusion of sodium ions,conferring many benefits to the functionality of conversion-type electrode materials.As a representative material,Ni-CoSe_(2) with such structural engineering shows a reversible capacity of 515 mAh g^(−1)at 0.1 A g^(−1)and a stable capacity of 416 mAh g^(−1)even at 6.4 A g^(−1);more than 80%of the capacity at 0.1 A g^(−1)could be preserved,so that this strategy holds great promise for designing fast-charging conversion-type anodes in the future.展开更多
Bimetallic selenide with core-shell structure(CoSe_(2)/ZnSe/NC@ZnSe/NC)has been successfully prepared through facile carbonization and selenization processes of its core-shell metal-organic framework precursors,in whi...Bimetallic selenide with core-shell structure(CoSe_(2)/ZnSe/NC@ZnSe/NC)has been successfully prepared through facile carbonization and selenization processes of its core-shell metal-organic framework precursors,in which the precursor is synthesized by epitaxial growth of zinc-based zeolite imidazolate framework(ZIF-8)on the surface of cobalt-based and zinc-based zeolite imidazolate framework(ZIF-67@ZIF-8).The coreshell structure has the advantage of alleviating the volume expansion during repeated insertion and extraction of sodium ions which can effectively avoid structural collapse.Additionally,bimetallic selenides and heterostructure are effective strategies to greatly improve the rate capability of the material.Therefore,the core-shell structural CoSe2/ZnSe/NC@ZnSe/NC material can maintain the original dodecahedron structure and delivers a specific capacity of 308.6 mAh·g^(-1)at 1.0 A·g^(-1)after 300 cycles with the desirable capacity retention of 90%.With the synergistic effects of heterostructure and core-shell structure,CoSe_(2)/ZnSe/NC@ZnSe/NC exhibits better electrochemical performance than CoSe_(2)/ZnSe/NC and CoSe_(2)/NC.These prove that both core-shell structure and heterostructure have positive effects on improving the electrochemical properties of materials.展开更多
In the presence of catalytic amount of cesium hydroxide the hydrothiolation of alkynyl selenides occurred at room temperature in DMF under nitrogen atmosphere to give exclusive（Z）-1-organoseleno-2-arylthio-1-alkene ...In the presence of catalytic amount of cesium hydroxide the hydrothiolation of alkynyl selenides occurred at room temperature in DMF under nitrogen atmosphere to give exclusive（Z）-1-organoseleno-2-arylthio-1-alkene in excellent yields.It could provide a new and expedient way for the preparation of（Z）-1-arylseleno-2-arylthio-1-alkene.展开更多
In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respective...In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respectively in moderate to good yields.展开更多
A mild, one-pot procedure for the synthesis of vinyl ethers in good yields from 2-hydroxyalkyl phenyl selenides with primary or secondary organic halides has been developed.
The insertion of elemental selenium into the Csp(2)-Zr bond of alkenylchloro-zirconocenes affords (E)-vinylseleno zirconocenes, which were trapped by alkyl halides giving (E)-vinylic selenides in moderate to good yields.
Several polystyrene-supported selenides and selenoxide have been prepared firstly. These novel reagents were treated with LDA to produce selenium stabilized carbanions, which reacted with aldehydes and alkyl halides, ...Several polystyrene-supported selenides and selenoxide have been prepared firstly. These novel reagents were treated with LDA to produce selenium stabilized carbanions, which reacted with aldehydes and alkyl halides, followed by selenoxide syn-elimination and [2,3] sigmatropic rearrangement respectively to give Z-allylic alcohols stereoselectively.展开更多
Cost-effective and stable electrocatalysts with ultra-high current densities for electrochemical oxygen evolution reaction(OER)are critical to the energy crisis and environmental pollution.Herein,we report a superaero...Cost-effective and stable electrocatalysts with ultra-high current densities for electrochemical oxygen evolution reaction(OER)are critical to the energy crisis and environmental pollution.Herein,we report a superaerophobic three dimensional(3D)heterostructured nanowrinkles of bimetallic selenides consisting of crystalline NiSe2 and NiFe2Se4 grown on NiFe alloy(NiSe2/NiFe2Se4@NiFe)prepared by a thermal selenization procedure.In this unique 3D heterostructure,numerous nanowrinkles of NiSe2/NiFe2Se4 hybrid with a thickness of ~100 nm are grown on NiFe alloy in a uniform manner.Profiting by the large active surface area and high electronic conductivity,the superaerophobic NiSe2/NiFe2Se4@NiFe heterostructure exhibits excellent electrocatalytic activity and durability towards OER in alkaline media,outputting the low potentials of 1.53 and 1.54 V to achieve ultra-high current densities of 500 and 1000 mA cm^−2,respectively,which is among the most active Ni/Fe-based selenides,and even superior to the benchmark Ir/C catalyst.The in-situ derived FeOOH and NiOOH species from NiSe2/NiFe2Se4@NiFe are deemed to be efficient active sites for OER.展开更多
Exploration of novel narrow bandgap semiconductors for overall water splitting is vital for the realization of practical solar H2 production.In the work,solid solutions of zinc selenide and copper gallium selenide wit...Exploration of novel narrow bandgap semiconductors for overall water splitting is vital for the realization of practical solar H2 production.In the work,solid solutions of zinc selenide and copper gallium selenide with absorption edge wavelengths ranging from 480 to 730 nm were developed.Using these metal selenides as H2-evolving photocatalysts,CoOx/BiVO4 as the O2-evolving photocatalyst,and reduced graphene oxide as the electron mediator,all-solid-state Z-scheme overall pure water splitting systems were constructed.The rate of photocatalytic H2 evolution from aqueous solutions containing Na2S and Na2SO3 as the electron donors was evaluated while employing these selenide photocatalysts at various Zn/(Zn+Cu)and Ga/Cu molar ratios.The data demonstrate that efficient Z-scheme overall water splitting was significantly correlated to the photoelectrochemical performance of the selenide photocatalysts acting as photocathodes,rather than the photocatalytic activities of these materials during the sacrificial H2 evolution.展开更多
基金supported by the grants from the National Natural Science Foundation of China(No.22202098)the Natural Science Foundation of Henan Province(No.242300420199)。
文摘Heterogeneous catalysts have attracted wide attention due to their remarkable oxygen evolution reaction(OER)capabilities.Herein,a one-step strategy involving the coupling of NixSeywith CeO_(2)is proposed to concurrently construct heterogeneous interfaces,adjust phase structure,and regulate electronic configuration,thereby enhancing OER performance.Thanks to the role of CeO_(2)coupling in reducing the activation-energy and accelerating the reaction kinetics,the heterogeneous NixSey/CeO_(2)catalyst exhibits a low overpotential of 218 mV at 10 mA/cm2and long-term stability(>400 h)in 1.0 mol/L KOH for OER.Moreover,the post-OER characterization reveals that the NixSeymatrix is reconstructed into NiOOH,while the incorporated CeO_(2)nanocrystals self-assemble into larger polycrystalline particles.Theoretical analysis further demonstrates that the optimized electronic states at NiOOH/CeO_(2)interfaces can modulate intermediate chemisorption toward favorable OER kinetics.This study offers fresh perspectives on the synthesis and structure-activity relationship of CeO_(2)-coupled electrocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.51563002 and 52101243)the"100-level"Innovative Talents Project of Guizhou Province,China(No.[2016]5653)+1 种基金the Natural Science Foundation of Guangdong Province(No.2020A1515010886)the Science and Technology Planning Project of Guangzhou(No.202102010373)。
文摘Recently,metal selenides have obtained widespread attention as electrode materials for alkali(Li^(+)/Na^(+)/K^(+))batteries due to their promising theoretical capacity and mechanism.Nevertheless,metal selenides,similar to metal oxides and sulfides,also suffer from severe volume explosion during repeated charge/discharge processes,which results in the structure collapse and the following pulverization of electrode materials.Hence,it leads to poor cycle stability and influencing their further application.In order to solve these issues,some special strategies,including elemental doping,coupling with carbon materials,synthesis of the bimetal selenides with heterostructure,etc.,have been gradually applied to design novel electrode materials with outstanding electrochemical performance.Herein,the recent research progress on metal selenides as anodes for alkali ion batteries is summarized,including the regulation of crystal structure,synthesis strategies,modification methods,and electrochemical mechanisms and kinetics.Besides,the challenges of metal selenides and the perspective for future electrode material design are proposed.It is hoped to pave a way for the development of metal selenide electrode materials for the potential applications for alkali metal ion(Li^(+)/Na^(+)/K^(+))batteries.
基金financially supported by the National Natural Science Foundation of China(No.52130101)the Project of Science and Technology Development Plan of Jilin Province in China(Nos.20210402058GH and 20220201114GX)。
文摘Lithium-sulfur batteries(LSBs)have attracted the attention of more and more researchers due to the advantages of high energy density,environmental friendliness,and low production cost.However,the low electronic conductivity of active material and shuttling effect of lithium polysulfides(LiPSs)limit the commercial development of LSBs.To solve these problems,we design a core-shell composite with nitrogen-doped carbon(NC)and two types of selenides(FeSe_(2)-NC@ZnSe-NC).The FeSe_(2)-NC@ZnSe-NC has a strong adsorption capacity,and can effectively adsorb LiPSs.At the same time,it also effectively alleviates the shuttling effect of LiPSs,and improves the utilization of the active substance during the charge/discharge reaction processes.The mechanism involved in FeSe_(2)-NC@ZnSe-NC is demonstrated by both experiments and density-functional theory(DFT)calculations.The electrochemical test results indicate that LSB with S/FeSe_(2)-NC@ZnSe-NC delivers an initial discharge capacity of 1260 mAh·g^(-1)at 0.2C.And after 500 cycles at 1C,the capacity decay rate per cycle is 0.031%,and the capacity retention rate is 85%.The FeSe_(2)-NC@ZnSe-NC core-shell structure verifies a rational strategy to construct an electrode material for high-performance LSBs.
基金the K.N.Toosi University of Technology Research Council for financial assistance
文摘Alkynyl selenides were prepared under very mild conditions by reacting terminal alkynes with respective diorganic diselenides in the presence of potassium t-butoxide. The advantages of this protocol include the use of readily available substrates and reagent and good yield of the products.
文摘Reduction of diaryldiselenides by the system of Cp2TiCl2/Bu'MgBr/THF gave the nucleophilic arylselenium complex. They reacted with diaryl iodonium salts to afford unsymmetrical diaryl selenides in high yields.
基金Project (No. 2004C21032) supported by the Key Technologies R &D Program of Zhejiang Province, China
文摘A simple and convenient procedure for stercoselective synthesis of （Z）-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCI system to form selemde anions, which then undergo SN2＇ substitution of Baylis-Hillman adducts to produce the （Z）-allyl selenides.
基金Fundamental Research Funds for the Central Universities,Grant/Award Numbers:531118010111,531118010633National Natural Science Foundation of China,Grant/Award Numbers:22109041,52103313。
文摘The shell structure design has been recognized as a highly efficient strategy to buffer the severe volume expansion and consecutive pulverization of conversion-type anodes.Nevertheless,construction of a functional shell with a stabilized structure that meets the demands of both high electronic conductivity and feasible pathways for Na^(+)ions has been a challenge so far.Herein,we design a two-in-one shell configuration for bimetal selenides to achieve fast sodium storage within broadened voltage windows.The hybridized shell,which benefits from the combination of titanium dioxide quantum dots and amorphous carbon,can not only effectively buffer the strain and maintain structural integrity but also allow facile and reversible transport of electrons and Na^(+)uptake for electrode materials during sodiation/desodiation processes,resulting in increased reaction kinetics and diffusion of sodium ions,conferring many benefits to the functionality of conversion-type electrode materials.As a representative material,Ni-CoSe_(2) with such structural engineering shows a reversible capacity of 515 mAh g^(−1)at 0.1 A g^(−1)and a stable capacity of 416 mAh g^(−1)even at 6.4 A g^(−1);more than 80%of the capacity at 0.1 A g^(−1)could be preserved,so that this strategy holds great promise for designing fast-charging conversion-type anodes in the future.
基金financially supported by the National Natural Science Foundation of China(Nos.52101243 and 51563002)the Natural Science Foundation of Guangdong Province(Nos.2020A1515010886 and 2021A1515010078)+1 种基金the Scientific and Technological Plan of Guangdong Province,China(No.2019B090905007)the Science and Technology Planning Project of Guangzhou(No.202102010373)。
文摘Bimetallic selenide with core-shell structure(CoSe_(2)/ZnSe/NC@ZnSe/NC)has been successfully prepared through facile carbonization and selenization processes of its core-shell metal-organic framework precursors,in which the precursor is synthesized by epitaxial growth of zinc-based zeolite imidazolate framework(ZIF-8)on the surface of cobalt-based and zinc-based zeolite imidazolate framework(ZIF-67@ZIF-8).The coreshell structure has the advantage of alleviating the volume expansion during repeated insertion and extraction of sodium ions which can effectively avoid structural collapse.Additionally,bimetallic selenides and heterostructure are effective strategies to greatly improve the rate capability of the material.Therefore,the core-shell structural CoSe2/ZnSe/NC@ZnSe/NC material can maintain the original dodecahedron structure and delivers a specific capacity of 308.6 mAh·g^(-1)at 1.0 A·g^(-1)after 300 cycles with the desirable capacity retention of 90%.With the synergistic effects of heterostructure and core-shell structure,CoSe_(2)/ZnSe/NC@ZnSe/NC exhibits better electrochemical performance than CoSe_(2)/ZnSe/NC and CoSe_(2)/NC.These prove that both core-shell structure and heterostructure have positive effects on improving the electrochemical properties of materials.
基金Natural Science Foundation of Hunan(No.2009NK3162)National Natural Science Foundation of China(No.21003040,20372020) for financial support
文摘In the presence of catalytic amount of cesium hydroxide the hydrothiolation of alkynyl selenides occurred at room temperature in DMF under nitrogen atmosphere to give exclusive（Z）-1-organoseleno-2-arylthio-1-alkene in excellent yields.It could provide a new and expedient way for the preparation of（Z）-1-arylseleno-2-arylthio-1-alkene.
基金the Natural Science Foundation of the Education Commission of Jiangsu Province
文摘In the presence of BiCl3/Al or BiCl3/Fe, in THF-H2O, allylic (benzylic) bromides or α-bromoketones react with diorganyl diselenides to give allylic (benzylic) selenides orα-organylselenocarbonyl compounds respectively in moderate to good yields.
基金the Natural Science Foundation of Jiangxi Province(No.0420017)for financial support
文摘A mild, one-pot procedure for the synthesis of vinyl ethers in good yields from 2-hydroxyalkyl phenyl selenides with primary or secondary organic halides has been developed.
文摘The insertion of elemental selenium into the Csp(2)-Zr bond of alkenylchloro-zirconocenes affords (E)-vinylseleno zirconocenes, which were trapped by alkyl halides giving (E)-vinylic selenides in moderate to good yields.
文摘Several polystyrene-supported selenides and selenoxide have been prepared firstly. These novel reagents were treated with LDA to produce selenium stabilized carbanions, which reacted with aldehydes and alkyl halides, followed by selenoxide syn-elimination and [2,3] sigmatropic rearrangement respectively to give Z-allylic alcohols stereoselectively.
基金financially supported by the National Natural Science Foundation of China(21922811,51702284,and 21878270)Zhejiang Provincial Natural Science Foundation of China(LR19B060002)the Startup Foundation for Hundred-Talent Program of Zhejiang University.
文摘Cost-effective and stable electrocatalysts with ultra-high current densities for electrochemical oxygen evolution reaction(OER)are critical to the energy crisis and environmental pollution.Herein,we report a superaerophobic three dimensional(3D)heterostructured nanowrinkles of bimetallic selenides consisting of crystalline NiSe2 and NiFe2Se4 grown on NiFe alloy(NiSe2/NiFe2Se4@NiFe)prepared by a thermal selenization procedure.In this unique 3D heterostructure,numerous nanowrinkles of NiSe2/NiFe2Se4 hybrid with a thickness of ~100 nm are grown on NiFe alloy in a uniform manner.Profiting by the large active surface area and high electronic conductivity,the superaerophobic NiSe2/NiFe2Se4@NiFe heterostructure exhibits excellent electrocatalytic activity and durability towards OER in alkaline media,outputting the low potentials of 1.53 and 1.54 V to achieve ultra-high current densities of 500 and 1000 mA cm^−2,respectively,which is among the most active Ni/Fe-based selenides,and even superior to the benchmark Ir/C catalyst.The in-situ derived FeOOH and NiOOH species from NiSe2/NiFe2Se4@NiFe are deemed to be efficient active sites for OER.
基金financially supported by the Artificial Photosynthesis Project of the New Energy and Industrial Technology Development Organization(NEDO)Grant-in-Aids for Scientific Research(A)(No.16H02417)Young Scientists(A)(No.15H05494)from the Japan Society for the Promotion of Science(JSPS)
文摘Exploration of novel narrow bandgap semiconductors for overall water splitting is vital for the realization of practical solar H2 production.In the work,solid solutions of zinc selenide and copper gallium selenide with absorption edge wavelengths ranging from 480 to 730 nm were developed.Using these metal selenides as H2-evolving photocatalysts,CoOx/BiVO4 as the O2-evolving photocatalyst,and reduced graphene oxide as the electron mediator,all-solid-state Z-scheme overall pure water splitting systems were constructed.The rate of photocatalytic H2 evolution from aqueous solutions containing Na2S and Na2SO3 as the electron donors was evaluated while employing these selenide photocatalysts at various Zn/(Zn+Cu)and Ga/Cu molar ratios.The data demonstrate that efficient Z-scheme overall water splitting was significantly correlated to the photoelectrochemical performance of the selenide photocatalysts acting as photocathodes,rather than the photocatalytic activities of these materials during the sacrificial H2 evolution.
