Transition metal chalcogenides have nowadays garnered burgeoning interest owing to their fascinating electronic and catalytic properties,thus possessing great implications for energy conversion and storage application...Transition metal chalcogenides have nowadays garnered burgeoning interest owing to their fascinating electronic and catalytic properties,thus possessing great implications for energy conversion and storage applications.In this regard,their controllable synthesis in a large scale at low cost has readily become a focus of research.Herein we report diatomite-template generic and scalable production of VS2 and other transition metal sulfides targeting emerging energy conversion and storage applications.The conformal growth of VS2over diatomite template would endow them with defect-abundant features.Throughout detailed experimental investigation in combination with theoretical simulation,we reveal that the enriched active sites/sulfur vacancies of thus-derived VS2 architectures would pose positive impacts on the catalytic performance such in electrocatalytic hydrogen evolution reactions.We further show that the favorable electrical conductivity and highly exposed sites of VS2 hold promise for serving as sulfur host in the realm of Li-S batteries.Our work offers new insights into the templated and customized synthesis of defect-rich sulfides in a scalable fashion to benefit multifunctional energy applications.展开更多
Defect engineering has been used to develop low-cost and effective catalysts to boost oxygen reduction reactions.However,the development of catalysts that use metal cation vacancies as the active sites for oxygen redu...Defect engineering has been used to develop low-cost and effective catalysts to boost oxygen reduction reactions.However,the development of catalysts that use metal cation vacancies as the active sites for oxygen reduction reaction is lacking.In this study,ZnS nanoparticles on N-doped carbon serve as an oxygen reduction reaction catalyst.These catalysts were prepared via a one-step method at 900℃.Amazingly,the high-resolution transmission electron microscope image revealed obvious defects in the ZnS nanoparticles.These facilitated the catalyst synthesis,and the product displayed good electrocatalytic performance for the oxygen reduction reaction in an alkaline medium,including a lower onset potential,lower mid-wave potential,four electron transfer process,and better durability compared with 20 wt%Pt/C.More importantly,the density functional theory results indicated that using the Zn vacancies in the prepared catalyst as active sites required a lower reaction energy to produce OOH*from*OO toward oxygen reduction reaction.Therefore,the proposed catalyst with Zn vacancies can be used as a potential electrocatalyst and may be substitutes for Pt-based catalysts in fuel cells,given the novel catalyst’s resulting performance.展开更多
According to the fact that the abnormalities of visual pigment genes were always involved in the changing of the exon 5, two oligonucleotide primers were designed to amplify the exon 5 of red pigment gene and green pi...According to the fact that the abnormalities of visual pigment genes were always involved in the changing of the exon 5, two oligonucleotide primers were designed to amplify the exon 5 of red pigment gene and green pigment gene. After electrophoresis of the PCR products digested with Rsal or Sau3A, the DNA fragments from the exon 5 of red pigment gene (RPG) and green pigment gene (GPG) were separated since there are different restriction endonuclease sites. On the other hand, we analyzed the exon 5 rela...展开更多
The positron annihilation lifetimes and the Doppler broadening by slow positron beam are measured in thin Fe films with thickness 500 nm, a thin Hf film with thickness 100 nm, and the bilayer Fe (50 nm)/Hf (50 nm) on ...The positron annihilation lifetimes and the Doppler broadening by slow positron beam are measured in thin Fe films with thickness 500 nm, a thin Hf film with thickness 100 nm, and the bilayer Fe (50 nm)/Hf (50 nm) on quartz glass substrate. We have analyzed the behavior in vacancy-type defects in each layer through some deposition temperatures and annealing. It is observed that the thin Fe film, the thin Hf film, and the bilayer Fe (50 nm)/Hf (50 nm) already contain many vacancy-type defects. We have investigated the change of densities of the vacancy-carbon complex and the small vacancy-cluster with carbons, through solid-state amorphization of Fe (50 nm)/Hf (50 nm) bilayer.展开更多
利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO_(2)RR)是一项具有革命性潜力的技术,因而备受关注.其中,一氧化碳被视为CO_(2)RR中最具经济效益的产物之一,可直接利用费托合成工艺将其用于合成醛、酮、烃类等...利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO_(2)RR)是一项具有革命性潜力的技术,因而备受关注.其中,一氧化碳被视为CO_(2)RR中最具经济效益的产物之一,可直接利用费托合成工艺将其用于合成醛、酮、烃类等产品.酞菁钴(CoPc)作为单位点催化剂,因其高原子利用率和高催化选择性能,在二氧化碳转化为一氧化碳过程中具有很大优势.然而,CoPc无法为CO_(2)RR中的质子化过程提供足够质子,导致其在工业大电流密度下的效率较低.因此,探索一种能够解决CO_(2)RR中质子供给不足问题的高效电催化剂对于提升CO_(2)RR的性能至关重要.本文设计了具有增强质子供给作用的缺陷碳纳米管(d-CNT),将其作为导电载体分散CoPc,用于制备CoPc/d-CNT电催化剂.通过引入富缺陷的碳纳米管(d-CNT),加速水解离进而增加CO_(2)RR的质子供给量.X射线光电子能谱、X射线吸收近边光谱和扩展X射线吸收精细结构谱结果表明,CoPc/d-CNT成功合成,同时保留了CoPc完整的Co-N4配位结构.透射电镜、粉末X射线衍射谱和拉曼光谱共同表明,d-CNT表面缺陷相对于商用CNT明显增加.动力学实验和原位衰减全反射表面增强红外吸收光谱研究表明,含大量缺陷的d-CNT具有加速水解离的能力,显著提高了二氧化碳还原反应过程中的质子供给,从而促进了CoPc_上CO_(2)活化生成*COOH.同时,密度泛函理论计算结果表明,d-CNT表面缺陷位点上从吸附水(*H2O)到质子水(H3O+)的吉布斯自由能为0.74 eV,远低于CNT(超过2 eV),表明d-CNT促进了水解过程和质子传递,再次证实了d-CNT降低了水分子解离的势垒.通过实验和理论的共同验证,阐明了d-CNT中的缺陷能够促进水解离,改善CO_(2)RR反应过程中质子供给,增强CoPc高效催化CO_(2)RR的能力.因此,CoPc/d-CNT混合材料表现出较好的催化性能.在电流密度为500 mA cm^(-2)的流动电池中,CoPc/d-CNT的CO法拉第效率(FECO)高达96%.相对而言,CoPc/CNT在200 mA cm^(-2)时FECO已经下降到90%以下.此外,在150 mA cm^(-2)的电流密度下,CoPc/d-CNT能够在20 h内维持FECO超过90%.综上,本文通过引入具有水解离能力的缺陷碳位点,解决了单位点催化剂CoPc在CO_(2)RR中质子供给不足的问题,为设计高性能催化剂提供了新见解.展开更多
The Global Reaction Model describes a set of chemical reactions that can potentially occur during the process of obtaining silicon rich oxide (SRO) films, regardless of the technique used to grow such films which are ...The Global Reaction Model describes a set of chemical reactions that can potentially occur during the process of obtaining silicon rich oxide (SRO) films, regardless of the technique used to grow such films which are an outside stoichiometry material. Particularly, chemical reactions that occur during the process of growing of SRO films by LPCVD technique are highlighted in this model. We suggest and evaluate either some types of molecules or resulting nanostructures and we predict theoretically, by applying the density functional theory, the contribution that they may have to the phenomenon of luminescence which is measured in SRO films. Also, we have calculated the opto-electronic properties of SRO films. The suggested model provides enough information required to identify the molecular structures resulting from the presence of defects in SRO films and also those corresponding to charged structures. It is also possible to detect the molecular structures which are modified due to the effect of heat treatment, and identify the presence of different oxidation states inclusive the formation of siloxanes.展开更多
基金financially supported by the National Natural Science Foundation of China(nos.51702225,21671059,51702218)Jiangsu Youth Science Foundation(no.BK20170336)Program for Changjiang Scholars and Innovative Research Team in University(IRT-17R36).
文摘Transition metal chalcogenides have nowadays garnered burgeoning interest owing to their fascinating electronic and catalytic properties,thus possessing great implications for energy conversion and storage applications.In this regard,their controllable synthesis in a large scale at low cost has readily become a focus of research.Herein we report diatomite-template generic and scalable production of VS2 and other transition metal sulfides targeting emerging energy conversion and storage applications.The conformal growth of VS2over diatomite template would endow them with defect-abundant features.Throughout detailed experimental investigation in combination with theoretical simulation,we reveal that the enriched active sites/sulfur vacancies of thus-derived VS2 architectures would pose positive impacts on the catalytic performance such in electrocatalytic hydrogen evolution reactions.We further show that the favorable electrical conductivity and highly exposed sites of VS2 hold promise for serving as sulfur host in the realm of Li-S batteries.Our work offers new insights into the templated and customized synthesis of defect-rich sulfides in a scalable fashion to benefit multifunctional energy applications.
基金supported by the National Natural Science Foundation of China(21865025)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT_15R46)
文摘Defect engineering has been used to develop low-cost and effective catalysts to boost oxygen reduction reactions.However,the development of catalysts that use metal cation vacancies as the active sites for oxygen reduction reaction is lacking.In this study,ZnS nanoparticles on N-doped carbon serve as an oxygen reduction reaction catalyst.These catalysts were prepared via a one-step method at 900℃.Amazingly,the high-resolution transmission electron microscope image revealed obvious defects in the ZnS nanoparticles.These facilitated the catalyst synthesis,and the product displayed good electrocatalytic performance for the oxygen reduction reaction in an alkaline medium,including a lower onset potential,lower mid-wave potential,four electron transfer process,and better durability compared with 20 wt%Pt/C.More importantly,the density functional theory results indicated that using the Zn vacancies in the prepared catalyst as active sites required a lower reaction energy to produce OOH*from*OO toward oxygen reduction reaction.Therefore,the proposed catalyst with Zn vacancies can be used as a potential electrocatalyst and may be substitutes for Pt-based catalysts in fuel cells,given the novel catalyst’s resulting performance.
文摘According to the fact that the abnormalities of visual pigment genes were always involved in the changing of the exon 5, two oligonucleotide primers were designed to amplify the exon 5 of red pigment gene and green pigment gene. After electrophoresis of the PCR products digested with Rsal or Sau3A, the DNA fragments from the exon 5 of red pigment gene (RPG) and green pigment gene (GPG) were separated since there are different restriction endonuclease sites. On the other hand, we analyzed the exon 5 rela...
文摘The positron annihilation lifetimes and the Doppler broadening by slow positron beam are measured in thin Fe films with thickness 500 nm, a thin Hf film with thickness 100 nm, and the bilayer Fe (50 nm)/Hf (50 nm) on quartz glass substrate. We have analyzed the behavior in vacancy-type defects in each layer through some deposition temperatures and annealing. It is observed that the thin Fe film, the thin Hf film, and the bilayer Fe (50 nm)/Hf (50 nm) already contain many vacancy-type defects. We have investigated the change of densities of the vacancy-carbon complex and the small vacancy-cluster with carbons, through solid-state amorphization of Fe (50 nm)/Hf (50 nm) bilayer.
文摘利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO_(2)RR)是一项具有革命性潜力的技术,因而备受关注.其中,一氧化碳被视为CO_(2)RR中最具经济效益的产物之一,可直接利用费托合成工艺将其用于合成醛、酮、烃类等产品.酞菁钴(CoPc)作为单位点催化剂,因其高原子利用率和高催化选择性能,在二氧化碳转化为一氧化碳过程中具有很大优势.然而,CoPc无法为CO_(2)RR中的质子化过程提供足够质子,导致其在工业大电流密度下的效率较低.因此,探索一种能够解决CO_(2)RR中质子供给不足问题的高效电催化剂对于提升CO_(2)RR的性能至关重要.本文设计了具有增强质子供给作用的缺陷碳纳米管(d-CNT),将其作为导电载体分散CoPc,用于制备CoPc/d-CNT电催化剂.通过引入富缺陷的碳纳米管(d-CNT),加速水解离进而增加CO_(2)RR的质子供给量.X射线光电子能谱、X射线吸收近边光谱和扩展X射线吸收精细结构谱结果表明,CoPc/d-CNT成功合成,同时保留了CoPc完整的Co-N4配位结构.透射电镜、粉末X射线衍射谱和拉曼光谱共同表明,d-CNT表面缺陷相对于商用CNT明显增加.动力学实验和原位衰减全反射表面增强红外吸收光谱研究表明,含大量缺陷的d-CNT具有加速水解离的能力,显著提高了二氧化碳还原反应过程中的质子供给,从而促进了CoPc_上CO_(2)活化生成*COOH.同时,密度泛函理论计算结果表明,d-CNT表面缺陷位点上从吸附水(*H2O)到质子水(H3O+)的吉布斯自由能为0.74 eV,远低于CNT(超过2 eV),表明d-CNT促进了水解过程和质子传递,再次证实了d-CNT降低了水分子解离的势垒.通过实验和理论的共同验证,阐明了d-CNT中的缺陷能够促进水解离,改善CO_(2)RR反应过程中质子供给,增强CoPc高效催化CO_(2)RR的能力.因此,CoPc/d-CNT混合材料表现出较好的催化性能.在电流密度为500 mA cm^(-2)的流动电池中,CoPc/d-CNT的CO法拉第效率(FECO)高达96%.相对而言,CoPc/CNT在200 mA cm^(-2)时FECO已经下降到90%以下.此外,在150 mA cm^(-2)的电流密度下,CoPc/d-CNT能够在20 h内维持FECO超过90%.综上,本文通过引入具有水解离能力的缺陷碳位点,解决了单位点催化剂CoPc在CO_(2)RR中质子供给不足的问题,为设计高性能催化剂提供了新见解.
文摘The Global Reaction Model describes a set of chemical reactions that can potentially occur during the process of obtaining silicon rich oxide (SRO) films, regardless of the technique used to grow such films which are an outside stoichiometry material. Particularly, chemical reactions that occur during the process of growing of SRO films by LPCVD technique are highlighted in this model. We suggest and evaluate either some types of molecules or resulting nanostructures and we predict theoretically, by applying the density functional theory, the contribution that they may have to the phenomenon of luminescence which is measured in SRO films. Also, we have calculated the opto-electronic properties of SRO films. The suggested model provides enough information required to identify the molecular structures resulting from the presence of defects in SRO films and also those corresponding to charged structures. It is also possible to detect the molecular structures which are modified due to the effect of heat treatment, and identify the presence of different oxidation states inclusive the formation of siloxanes.
基金supported by the National Natural Science Foundation of China (52172110)the “Scientific and Technical Innovation Action Plan” China Science&Technology Cooperation Project of Shanghai Science and Technology Committee (21520760500)+1 种基金the “Super Postdoctoral Incentive Program” of Shanghai Municipal Human Resources and Social Security Bureau (2021411)Special Research Assistant Grant Project from Chinese Academy of Sciences
