In view of the dearth of active components and the unsatisfactory dispersion of Cu-based catalysts,it is imperative to undertake a detailed investigation of catalysts with enhanced catalytic performance.In order to ac...In view of the dearth of active components and the unsatisfactory dispersion of Cu-based catalysts,it is imperative to undertake a detailed investigation of catalysts with enhanced catalytic performance.In order to achieve a balance between the catalytic activity and stability in the reaction process,a series of P-atom doped Cu^(0)/Cu^(δ+)binary Cu-based catalysts were prepared by means of heteroatom introduction and heat treatment.The introduction of P enhanced the stability of Cu during heat treatment,thereby inhibiting the excessive agglomeration of Cu.The structure of the Cu^(0)/Cu^(δ+)binary catalyst was modified through heat treatment and HCl activation,and the relationship between its structure and catalytic activity was subsequently investigated.The activation process of HCl facilitated the conversion of the Cu^(0)state to the Cu-Cl state and augmented the valence state of Cu.The valence modulation of the Cu site by HCl during the reaction prevented the over-reduction of the Cu site by acetylene and enhanced the stability of the catalyst.The 3Cu/5Cu P/AC-800 catalyst was operated for 50 h without significant deactivation under the reaction conditions of T=180°C,V(HCl)/V(C_(2)H_(2))=1.15 and GHSV(C_(2)H_(2))=180 h^(-1).This design strategy provides a novel reference point for further studies of Cu Cl_(2)based catalysts for acetylene hydrochlorination.展开更多
Hydrogen(H2)is considered to be a promising substitute for fossil fuels.Two-dimensional(2D)nanomaterials have exhibited an efficient electrocatalytic capacity to catalyze hydrogen evolution reaction(HER).Particularly,...Hydrogen(H2)is considered to be a promising substitute for fossil fuels.Two-dimensional(2D)nanomaterials have exhibited an efficient electrocatalytic capacity to catalyze hydrogen evolution reaction(HER).Particularly,phase engineering of 2D nanomaterials is opening a novel research direction to endow 2D nanostructures with fascinating properties for deep applications in catalyzing HER.In this review,we briefly summarize the research progress and present the current challenges on phase engineering of 2D nanomaterials for their applications in electrocatalytic HER.Our summary will be of significance to provide fundamental understanding for designing novel 2D nanomaterials with unconventional phases to electrochemically catalyze HER.展开更多
Carbon materials have been used as the support for catalysts in the field of acetylene hydrochlorination,the influence of inevitable oxygen-containing moieties on the reaction is often ignored and the mechanism of the...Carbon materials have been used as the support for catalysts in the field of acetylene hydrochlorination,the influence of inevitable oxygen-containing moieties on the reaction is often ignored and the mechanism of the oxygen-doping structure remains ambiguous.Herein,we explored the effect of the oxygen-containing group(C-O-C)in the support on the activity of single-atom dispersed Cu catalysts.By immersing the Cu single-atom catalyst in an alkaline solution,the epoxy species on the carbon support was cleaved to obtain a pure ether species while the Cu site was modified to a more electron-deficient state.The turnover frequency value of Cu/O-FLP catalyst with epoxy groups was 1.6-fold higher than that of alkaline treated catalyst.Our result indicated that the epoxy groups could assist adjacent single-atom Cu sites to synergistically promote the adsorption and cleavage of the reactant hydrogen chloride toward form C-OH and Cu-Cl bonds,and reduce the reaction energy barrier.The presence of electron deficient Cu sites and ether species could induce competitive adsorption of the acetylene and hydrogen chloride,thereby reducing the activity of the catalyst.This study highlights the influence of surface oxygen species and the tunability of the support,providing the foundation for the fabrication of higher-activity Cu catalysts for acetylene hydrochlorination.展开更多
Weather,climatic conditions and assessment of meteorological disaster risks are all important factors that restrict and affect the smooth holding of major events.It is crucial to accurately and promptly grasp the weat...Weather,climatic conditions and assessment of meteorological disaster risks are all important factors that restrict and affect the smooth holding of major events.It is crucial to accurately and promptly grasp the weather forecast at key nodes such as the start,critical period and end of major events to deal with the adverse effects caused by sudden weather.The intelligent grid forecast system has been gradually applied in meteorological service guarantee work,and effectively improved the accuracy and refinement level of weather forecast.It is needed to provide full-process and refined meteorological service guarantee,promote the standardization and normalization of meteorological services for major events,and enhance the level and efficiency of meteorological services.展开更多
Simultaneously boosting acetylene hydrochlorination activity and avoiding formation of explosive copper acetylide over Cu-based catalyst,which represented a promising alternative to Hg-based and noble metal catalysts,...Simultaneously boosting acetylene hydrochlorination activity and avoiding formation of explosive copper acetylide over Cu-based catalyst,which represented a promising alternative to Hg-based and noble metal catalysts,remained challenging.Herein,we fabricated a frustrated single-atom Cu/O Lewis pair catalyst(Cu/O-FLP)by coupling epoxide group(C-O-C)with atomdispersed Cu-cis-N_(2)C_(2)Cl center to address this challenge.The basic epoxy site modulated the electron-deficient state of Lewisacidic Cu center and paired with the Cu-cis-N_(2)C_(2)Cl moiety to preferentially break HCl into different electronegative Cu-Clδ-and C-O-H^(δ+)intermediates,which further induced both an extra localized electric field to polarize acetylene and a upshift of the dband center of catalyst,thereby promoting adsorption and enrichment of acetylene by enhancing the dipolar interaction between acetylene and active intermediates.Moreover,the generated Cu-Clδ-and C-O-H^(δ+)drastically reduced the energy barrier of ratelimiting step and made vinyl chloride easier to desorb from the Lewis-basic oxygen-atom site rather than traditional Lewis-acidic Cu center.These superiorities ensured a higher activity of Cu/O-FLP compared with its counterparts.Meanwhile,preferential dissociation of HCl endowed single-atom Cu with the coordination-saturated configuration,which impeded formation of explosive copper acetylide by avoiding the direct interaction between Cu and acetylene,ensuring the intrinsic safety during catalysis.展开更多
基金supported by the National Natural Science Foundation of China(No.22062021)the Science and Technology Project of Xinjiang supported by Central Government(No.2022BC001)+3 种基金Science and Technology Planning Project(No.2024AB048)Tianshan Talents Training Program of Xinjiang(Science and Technology Innovation Team,No.CZ002701)the Start-Up Foundation for high-level professionals of Shihezi University(No.RCZK201932)2024 Talent Development Fund-Tianchi Young Doctor of Excellence(No.CZ002744)。
文摘In view of the dearth of active components and the unsatisfactory dispersion of Cu-based catalysts,it is imperative to undertake a detailed investigation of catalysts with enhanced catalytic performance.In order to achieve a balance between the catalytic activity and stability in the reaction process,a series of P-atom doped Cu^(0)/Cu^(δ+)binary Cu-based catalysts were prepared by means of heteroatom introduction and heat treatment.The introduction of P enhanced the stability of Cu during heat treatment,thereby inhibiting the excessive agglomeration of Cu.The structure of the Cu^(0)/Cu^(δ+)binary catalyst was modified through heat treatment and HCl activation,and the relationship between its structure and catalytic activity was subsequently investigated.The activation process of HCl facilitated the conversion of the Cu^(0)state to the Cu-Cl state and augmented the valence state of Cu.The valence modulation of the Cu site by HCl during the reaction prevented the over-reduction of the Cu site by acetylene and enhanced the stability of the catalyst.The 3Cu/5Cu P/AC-800 catalyst was operated for 50 h without significant deactivation under the reaction conditions of T=180°C,V(HCl)/V(C_(2)H_(2))=1.15 and GHSV(C_(2)H_(2))=180 h^(-1).This design strategy provides a novel reference point for further studies of Cu Cl_(2)based catalysts for acetylene hydrochlorination.
基金financially supported by the Key Grant for Special Professors in Jiangsu Province(No.RK030STP18001)the Scientific Research Foundation of Nanjing University of Posts and Telecommunications(No.NY218150)“1311 Talents Program”of Nanjing University of Posts and Telecommunications and the National Postdoctoral Program for Innovative Talents(No.BX20190156)。
文摘Hydrogen(H2)is considered to be a promising substitute for fossil fuels.Two-dimensional(2D)nanomaterials have exhibited an efficient electrocatalytic capacity to catalyze hydrogen evolution reaction(HER).Particularly,phase engineering of 2D nanomaterials is opening a novel research direction to endow 2D nanostructures with fascinating properties for deep applications in catalyzing HER.In this review,we briefly summarize the research progress and present the current challenges on phase engineering of 2D nanomaterials for their applications in electrocatalytic HER.Our summary will be of significance to provide fundamental understanding for designing novel 2D nanomaterials with unconventional phases to electrochemically catalyze HER.
基金supported by the National Natural Science Foundation of China(No.22062021)the Science and Technology Project of Xinjiang supported by Central Government(No.2022BC001)+3 种基金Tianshan Talents Training Program of Xinjiang(Science and Technology Innovation Team,No.CZ002701)the Opening Project of Key Laboratory for Green Processing of Chemical Engineering of Xinjiang(No.KF2019010)the Start-Up Foundation for high-level professionals of Shihezi University(No.RCZK201932)research project of Shihezi University(No.CXFZ202205)。
文摘Carbon materials have been used as the support for catalysts in the field of acetylene hydrochlorination,the influence of inevitable oxygen-containing moieties on the reaction is often ignored and the mechanism of the oxygen-doping structure remains ambiguous.Herein,we explored the effect of the oxygen-containing group(C-O-C)in the support on the activity of single-atom dispersed Cu catalysts.By immersing the Cu single-atom catalyst in an alkaline solution,the epoxy species on the carbon support was cleaved to obtain a pure ether species while the Cu site was modified to a more electron-deficient state.The turnover frequency value of Cu/O-FLP catalyst with epoxy groups was 1.6-fold higher than that of alkaline treated catalyst.Our result indicated that the epoxy groups could assist adjacent single-atom Cu sites to synergistically promote the adsorption and cleavage of the reactant hydrogen chloride toward form C-OH and Cu-Cl bonds,and reduce the reaction energy barrier.The presence of electron deficient Cu sites and ether species could induce competitive adsorption of the acetylene and hydrogen chloride,thereby reducing the activity of the catalyst.This study highlights the influence of surface oxygen species and the tunability of the support,providing the foundation for the fabrication of higher-activity Cu catalysts for acetylene hydrochlorination.
文摘Weather,climatic conditions and assessment of meteorological disaster risks are all important factors that restrict and affect the smooth holding of major events.It is crucial to accurately and promptly grasp the weather forecast at key nodes such as the start,critical period and end of major events to deal with the adverse effects caused by sudden weather.The intelligent grid forecast system has been gradually applied in meteorological service guarantee work,and effectively improved the accuracy and refinement level of weather forecast.It is needed to provide full-process and refined meteorological service guarantee,promote the standardization and normalization of meteorological services for major events,and enhance the level and efficiency of meteorological services.
基金This work was supported by the National Natural Science Foundation of China(No.22062021)the Science and Technology Project of Xinjiang Bingtuan supported by Central government(No.2022BC001)+2 种基金the Opening Project of Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan(No.KF2019010)the Start-Up Foundation for high-level professionals of Shihezi University(No.RCZK201932)the research project of Shihezi University(No.CXFZ202205).
文摘Simultaneously boosting acetylene hydrochlorination activity and avoiding formation of explosive copper acetylide over Cu-based catalyst,which represented a promising alternative to Hg-based and noble metal catalysts,remained challenging.Herein,we fabricated a frustrated single-atom Cu/O Lewis pair catalyst(Cu/O-FLP)by coupling epoxide group(C-O-C)with atomdispersed Cu-cis-N_(2)C_(2)Cl center to address this challenge.The basic epoxy site modulated the electron-deficient state of Lewisacidic Cu center and paired with the Cu-cis-N_(2)C_(2)Cl moiety to preferentially break HCl into different electronegative Cu-Clδ-and C-O-H^(δ+)intermediates,which further induced both an extra localized electric field to polarize acetylene and a upshift of the dband center of catalyst,thereby promoting adsorption and enrichment of acetylene by enhancing the dipolar interaction between acetylene and active intermediates.Moreover,the generated Cu-Clδ-and C-O-H^(δ+)drastically reduced the energy barrier of ratelimiting step and made vinyl chloride easier to desorb from the Lewis-basic oxygen-atom site rather than traditional Lewis-acidic Cu center.These superiorities ensured a higher activity of Cu/O-FLP compared with its counterparts.Meanwhile,preferential dissociation of HCl endowed single-atom Cu with the coordination-saturated configuration,which impeded formation of explosive copper acetylide by avoiding the direct interaction between Cu and acetylene,ensuring the intrinsic safety during catalysis.
