Rely on the density functional theory(DFT)calculation,the catalytic performance of Pd_(x)Cu_(y)/GDY(x=1,2,3,4;x+y≤4)for CO oxidative coupling reaction was obtained.The Pdx/GDY(x=1,2,3,4)are not ideal catalyst for dim...Rely on the density functional theory(DFT)calculation,the catalytic performance of Pd_(x)Cu_(y)/GDY(x=1,2,3,4;x+y≤4)for CO oxidative coupling reaction was obtained.The Pdx/GDY(x=1,2,3,4)are not ideal catalyst for dimethyl oxalate(DMO)formation because byproduct dimethyl carbonate(DMC)is easily formed on Pd_(1)/GDY and Pd_(2)/GDY,and high activation energies are needed on Pd_(3)/GDY and Pd_(4)/GDY.Therefore the second metal Cu is doped to regulate the performance of Pdx/GDY(x=1,2,3,4).Doping Cu not only improve the activity of DMO formation,but more importantly,controlling the ratio of Cu:Pd can effectively regulate the selectivity of DMO.Thus taking into account the activity and selectivity of the reaction for the preparation of DMO by CO oxidative coupling,the Pd_(1)Cu_(1)/GDY and Pd_(1)Cu_(2)/GDY with the activation energies of 105.2 and 99.2 kJ mol^(-1)to generate DMO show excellent catalytic activity and high DMO selectivity,which are considered as good catalysts for CO oxidative coupling.The differential charge density analysis shows the decrease in the charge density of metal clusters is an important reason for improving the selectivity of the catalyst.展开更多
Lithium-sulfur batteries are considered important devices for the power of movable equipment,but there are still some challenges that limit their applications,such as how to obtain a cathode for high sulfide adsorptio...Lithium-sulfur batteries are considered important devices for the power of movable equipment,but there are still some challenges that limit their applications,such as how to obtain a cathode for high sulfide adsorption and rapid conversion.Here,a new strategy is proposed to enhance the performance of lithium-sulfur batteries by growing 3-dimensional hydrogen-substituted graphdiyne(HsGDY)layers on Ni foam via Glaser cross-coupling reaction to anchor MoS_(2)/Ni_(3)S_(2),enhancing the conductivity of host material of S.The results show that the 3-dimensional HsGDY framework enables the fast adsorption of lithium polysulfides and the Ni_(3)S_(2)/MoS_(2) performs as the reaction center with a low charge transfer resistance.The charge capacity of Ni@HsGDY/MoS_(2)/Ni_(3)S_(2) cell is up to 1,234.7 mAh·g^(−1) at the first circle,and the specific capacity keeps 486 mAh·g^(−1) after 500 cycles at a current density of 2 C.The incorporation of HsGDY into the cathode promotes the adsorption and the conversion of polysulfides,paving a path to obtain lithium-sulfur batteries with high energy density.展开更多
Inosine monophosphate(IMP),as a critical umami substance,is one of the most important indicators for evaluating the quality of meat products.Here,a sensitive electrochemiluminescence(ECL)biosensor based on graphdiyne(...Inosine monophosphate(IMP),as a critical umami substance,is one of the most important indicators for evaluating the quality of meat products.Here,a sensitive electrochemiluminescence(ECL)biosensor based on graphdiyne(GDY)/AuNPs/luminol nanocomposites was constructed to detect IMP.The GDY/AuNPs/luminol nanocomposites were synthesized by using simple one-pot method.GDY utilized its 2D framework to disperse and fix gold nanoparticles,which inhibited the agglomeration of gold nanoparticles and greatly improved its stability and catalytic properties.Importantly,GDY/AuNPs/luminol nanocomposites showed excellent catalytic ability and superior ECL activity towards luminol-H_(2)O_(2) systems due to the synergistic effect of GDY and AuNPs.Under optimal conditions,the prepared biosensor exhibited a wide linear range from 0.01 g/L to 20 g/L,a satisfactory limit detection of 0.0013 g/L,as well as an excellent specificity.Moreover,we carried out the precise analysis of IMP in actual meat samples with acceptable results compared to the liquid chromatography.We believe that this work could offer an efficient ECL platform for accurate and reliable report of IMP levels,which is significant for maintaining food quality and safety.展开更多
制备高效的OER电催化剂对水裂解制氢至关重要.具有丰富配位构型的MOFs可以衍生出各种优良的电催化材料.由于石墨炔(GDY)具有独特的可控合成特性,我们将其原位复合在MOF衍生的Co_(3)S_(4)/NF材料上,获得了自支撑电极GDY/Co_(3)S_(4)/NF,...制备高效的OER电催化剂对水裂解制氢至关重要.具有丰富配位构型的MOFs可以衍生出各种优良的电催化材料.由于石墨炔(GDY)具有独特的可控合成特性,我们将其原位复合在MOF衍生的Co_(3)S_(4)/NF材料上,获得了自支撑电极GDY/Co_(3)S_(4)/NF,大大提高了其OER催化性能.研究表明,GDY/Co_(3)S_(4)/NF在10 mA cm^(-2)电流密度下表现出223 mV的低过电位,在100 mA cm^(-2)的大电流密度下,能够稳定电解45小时左右,该材料显示出了巨大的实际应用潜力.结果表明,由于GDY独特的炔键和大孔结构,它可以通过强电子相互作用与Co_(3)S_(4)相互作用,从而调节电子结构并提供有效的电荷转移通道,从而大大提高了其电催化OER的性能.展开更多
The development of highly active and low-cost catalysts for electrochemical reactions is one of the most attractive topics in the renewable energy technology.Herein,the site-specific nitrogen doping of graphdiyne(GDY)...The development of highly active and low-cost catalysts for electrochemical reactions is one of the most attractive topics in the renewable energy technology.Herein,the site-specific nitrogen doping of graphdiyne(GDY)including grap-N,sp-N(Ⅰ)and sp-N(Ⅱ)GDY is systematically investigated as metal-free oxygen reduction electrocatalysts via density functional theory(DFT).Our results indicate that the doped nitrogen atom can significantly improve the oxygen(O2)adsorption activity of GDY through activating its neighboring carbon atoms.The free-energy landscape is employed to describe the electrochemical oxygen reduction reaction(ORR)in both O2 dissociation and association mechanisms.It is revealed that the association mechanism can provide higher ORR onset potential than dissociation mechanism on most of the substrates.Especially,sp-N(Ⅱ)GDY exhibits the highest ORR electrocatalytic activity through increasing the theoretical onset potential to 0.76 V.This work provides an atomic-level insight for the electrochemical ORR mechanism on metal-free N-doped GDY.展开更多
基金financially supported by the Key projects of National Natural Science Foundation of China(No.21736007)the National Natural Science Foundation of China(Grant Nos.21576178 and 21476155)Research Project Supported by Shanxi Scholarship Council of China(No.2016-030)。
文摘Rely on the density functional theory(DFT)calculation,the catalytic performance of Pd_(x)Cu_(y)/GDY(x=1,2,3,4;x+y≤4)for CO oxidative coupling reaction was obtained.The Pdx/GDY(x=1,2,3,4)are not ideal catalyst for dimethyl oxalate(DMO)formation because byproduct dimethyl carbonate(DMC)is easily formed on Pd_(1)/GDY and Pd_(2)/GDY,and high activation energies are needed on Pd_(3)/GDY and Pd_(4)/GDY.Therefore the second metal Cu is doped to regulate the performance of Pdx/GDY(x=1,2,3,4).Doping Cu not only improve the activity of DMO formation,but more importantly,controlling the ratio of Cu:Pd can effectively regulate the selectivity of DMO.Thus taking into account the activity and selectivity of the reaction for the preparation of DMO by CO oxidative coupling,the Pd_(1)Cu_(1)/GDY and Pd_(1)Cu_(2)/GDY with the activation energies of 105.2 and 99.2 kJ mol^(-1)to generate DMO show excellent catalytic activity and high DMO selectivity,which are considered as good catalysts for CO oxidative coupling.The differential charge density analysis shows the decrease in the charge density of metal clusters is an important reason for improving the selectivity of the catalyst.
基金Guangdong Basic and Applied Basic Research Foundation(2021A1515110152,2022A1515240007,and 2023A1515010562)Special Fund for the Sci-tech Innovation Strategy of Guangdong Province(STKJ202209083,STKJ202209066,2020ST006,and 210719165864287)+3 种基金Characteristic Innovation Project of Colleges and Universities in Guangdong(2021KTSCX030)Scientific Research Foundation of Shantou University(NTF20005 and NTF22018)Scientific Research Foundation of Guangdong Laboratory of Chemistry and Fine Chemical Industry Jieyang Center(QD2221007)2020 Li Ka Shing Foundation Cross-Disciplinary Research Grant(2020LKSFG01A).
文摘Lithium-sulfur batteries are considered important devices for the power of movable equipment,but there are still some challenges that limit their applications,such as how to obtain a cathode for high sulfide adsorption and rapid conversion.Here,a new strategy is proposed to enhance the performance of lithium-sulfur batteries by growing 3-dimensional hydrogen-substituted graphdiyne(HsGDY)layers on Ni foam via Glaser cross-coupling reaction to anchor MoS_(2)/Ni_(3)S_(2),enhancing the conductivity of host material of S.The results show that the 3-dimensional HsGDY framework enables the fast adsorption of lithium polysulfides and the Ni_(3)S_(2)/MoS_(2) performs as the reaction center with a low charge transfer resistance.The charge capacity of Ni@HsGDY/MoS_(2)/Ni_(3)S_(2) cell is up to 1,234.7 mAh·g^(−1) at the first circle,and the specific capacity keeps 486 mAh·g^(−1) after 500 cycles at a current density of 2 C.The incorporation of HsGDY into the cathode promotes the adsorption and the conversion of polysulfides,paving a path to obtain lithium-sulfur batteries with high energy density.
基金supported by The National Natural Science Foundation of China(31972198,31622042)The National Key R&D Program of China(2016YFD0400803,2016YFD0401501).
文摘Inosine monophosphate(IMP),as a critical umami substance,is one of the most important indicators for evaluating the quality of meat products.Here,a sensitive electrochemiluminescence(ECL)biosensor based on graphdiyne(GDY)/AuNPs/luminol nanocomposites was constructed to detect IMP.The GDY/AuNPs/luminol nanocomposites were synthesized by using simple one-pot method.GDY utilized its 2D framework to disperse and fix gold nanoparticles,which inhibited the agglomeration of gold nanoparticles and greatly improved its stability and catalytic properties.Importantly,GDY/AuNPs/luminol nanocomposites showed excellent catalytic ability and superior ECL activity towards luminol-H_(2)O_(2) systems due to the synergistic effect of GDY and AuNPs.Under optimal conditions,the prepared biosensor exhibited a wide linear range from 0.01 g/L to 20 g/L,a satisfactory limit detection of 0.0013 g/L,as well as an excellent specificity.Moreover,we carried out the precise analysis of IMP in actual meat samples with acceptable results compared to the liquid chromatography.We believe that this work could offer an efficient ECL platform for accurate and reliable report of IMP levels,which is significant for maintaining food quality and safety.
基金supported by the National Natural Science Foundation of China (22375148)the National Key R&D Program of China (2022YFA1502902)。
文摘制备高效的OER电催化剂对水裂解制氢至关重要.具有丰富配位构型的MOFs可以衍生出各种优良的电催化材料.由于石墨炔(GDY)具有独特的可控合成特性,我们将其原位复合在MOF衍生的Co_(3)S_(4)/NF材料上,获得了自支撑电极GDY/Co_(3)S_(4)/NF,大大提高了其OER催化性能.研究表明,GDY/Co_(3)S_(4)/NF在10 mA cm^(-2)电流密度下表现出223 mV的低过电位,在100 mA cm^(-2)的大电流密度下,能够稳定电解45小时左右,该材料显示出了巨大的实际应用潜力.结果表明,由于GDY独特的炔键和大孔结构,它可以通过强电子相互作用与Co_(3)S_(4)相互作用,从而调节电子结构并提供有效的电荷转移通道,从而大大提高了其电催化OER的性能.
基金financial supports by the Young Scientists Fund of the National Natural Science Foundation of China (11604249)the Fok Ying-Tong Education Foundation for Young Teachers in the Higher Education Institutions of China (161008)+3 种基金the Foundation of the State Key Laboratory of Optical Fiber and Cable Manufacture Technology (SKLD1602)the State Key Laboratory of Refractors and Metallurgy (G201605), the Fundamental Research Funds for the Central Universities (2019-III-034)the Research Board of the State Key Laboratory of Silicate Materials for Architecturesfinancial supports and grants from Xiamen University Malaysia,the Xiamen University Malaysia Research Fund (XMUMRF/2019-C3/ IENG/0013)
文摘The development of highly active and low-cost catalysts for electrochemical reactions is one of the most attractive topics in the renewable energy technology.Herein,the site-specific nitrogen doping of graphdiyne(GDY)including grap-N,sp-N(Ⅰ)and sp-N(Ⅱ)GDY is systematically investigated as metal-free oxygen reduction electrocatalysts via density functional theory(DFT).Our results indicate that the doped nitrogen atom can significantly improve the oxygen(O2)adsorption activity of GDY through activating its neighboring carbon atoms.The free-energy landscape is employed to describe the electrochemical oxygen reduction reaction(ORR)in both O2 dissociation and association mechanisms.It is revealed that the association mechanism can provide higher ORR onset potential than dissociation mechanism on most of the substrates.Especially,sp-N(Ⅱ)GDY exhibits the highest ORR electrocatalytic activity through increasing the theoretical onset potential to 0.76 V.This work provides an atomic-level insight for the electrochemical ORR mechanism on metal-free N-doped GDY.
