Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),...Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.展开更多
For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of e...For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of electrical conductivity and structural stability in the electrode materials during electrochemical cycling.We report the production of a novel flexible electrode material,by anchoring MnO_(2) nanosheets on a B,N co-doped carbon nanotube ar-ray(BNCNTs)grown on carbon cloth(BNCNTs@MnO_(2)),which was fabricated by in-situ pyrolysis and hydrothermal growth.The generated BNCNTs were strongly bonded to the surface of the car-bon fibers in the carbon cloth which provides both excellent elec-tron transport and ion diffusion,and improves the stability and dur-ability of the cathode.Importantly,the BNCNTs offer more active sites for the hydrothermal growth of MnO_(2),ensuring a uniform dis-tribution.Electrochemical tests show that BNCNTs@MnO_(2) delivers a high specific capacity of 310.7 mAh g^(−1) at 0.1 A g^(−1),along with excellent rate capability and outstanding cycling stability,with a 79.7% capacity retention after 8000 cycles at 3 A g^(−1).展开更多
The mechanism of stability of Co-doped spinel λ-MnO_2 that is referred to as spinel Li_xMn_2O_4 (x=0) was studied by using the first-principle calculation method. The total energy and formation enthalpy can be decrea...The mechanism of stability of Co-doped spinel λ-MnO_2 that is referred to as spinel Li_xMn_2O_4 (x=0) was studied by using the first-principle calculation method. The total energy and formation enthalpy can be decreased remarkably due to the Co substation, resulting in a more stable structure of λ-Mn_xCr_(2-x)O_4. The bond order and DOS analysis were given in detail to explain the nature of stability improvement. The calculated results show that as the content of Co dopant increases, the bond order of Mn—O becomes larger and the peak of density of states around Fermi level shifts toward lower energy. The charge density distribution illustrates that the Mn—O bonding is ionic and partially covalent, and the covalent Mn-O bonding becomes stronger with the increase of Co dopant content. The results confirm that the Codoping will enhance the stability of λ-MnO_2 and hence improve the electrochemistry performance of Li_xMn_2O_4.展开更多
Improving interfacial bonding and alloying design are effective strategies for enhancing mechanical properties of particle-reinforced steel matrix composites(SMCs).This study prepared SMCs with uniformly distributed T...Improving interfacial bonding and alloying design are effective strategies for enhancing mechanical properties of particle-reinforced steel matrix composites(SMCs).This study prepared SMCs with uniformly distributed TiC_(P)in matrix using master alloying method.The TiC(002)/Fe(011)interface model was established based on the orientation relationship of(011)_(Fe)//(002)_(TiC),and[100]_(Fe)//[100]_(TiC).The effects of single and co-doping of alloying elements(Mn,Cr,Mo,Ni,Cu and Si)on the interface bonding behavior of TiC/Fe in composites were investigated in conjunction with first principles.The results demonstrate that the interface between TiC and matrix is continuous and stable.Compared to the undoped TiC/Fe interface,single-doping Mn,Cr,and Mo can improve the stability of TiC/Fe interface and enhance tensile strength.Conversely,single-doping with Ni,Cu,and Si reduced the interface stability and marginally reduces tensile strength.Relative to the undoped and singly Ni-doped TiC/Fe interfaces,the co-doping Ni-Mo boosts binding energy and separation work at the TiC/Fe interface,which is conducive to the interface bonding between TiC_(P)and matrix,and thus improves the mechanical properties of composites.Thus,in the alloying design of TiC particle reinforced low-alloy SMCs,incorporating Mn,Cr,Mo,and Ni into matrix can enhance the overall mechanical properties of composites.展开更多
To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising no...To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising non-precious metal catalysts.We used Ketjenblack carbon as the precursor and mixed it with a polymeric ionic liquid(PIL)of[Hvim]NO_(3) and Fe(NO_(3))_(3),which was thermally calcined at 900℃ to produce a porous FeO_(x),N co-doped carbon material denoted FeO_(x)-N/C.Because the PIL of[Hvim]NO_(3) strongly combines with and disperses Fe^(3+)ions,and NO_(3)−is thermally pyrolyzed to form the porous structure,the FeO_(x)-N/C catalyst has a high electrocatalytic activity for the ORR in both 0.1 mol L^(−1) KOH and 0.5 mol L^(−1) H_(2)SO_(4) electrolytes.It was used as the catalyst to assemble a zinc-air battery,which had a peak power density of 185 mW·cm^(−2).Its superior electrocatalytic activity,wide pH range,and easy preparation make FeO_(x)-N/C a promising electrocatalyst for fuel cells and metal-air batteries.展开更多
Practical application of Na_(3)SbS_(4)(NSS)solid-state electrolyte in sodium metal batteries has been significantly hindered by poor interfacial stability and insufficient ionic conductivity.In this study,a series of ...Practical application of Na_(3)SbS_(4)(NSS)solid-state electrolyte in sodium metal batteries has been significantly hindered by poor interfacial stability and insufficient ionic conductivity.In this study,a series of dual-site doped Na_(3-2x)Sb_(1-x)W_(x)S_(4-x)F_(x)(x=0,0.12,0.24,0.36)electrolytes through high-energy ball milling followed by high-temperature sintering is prepared,where tungsten(W)substitutes for antimony(Sb)and fluorine(F)replaces sulfur(S)in the NSS lattice.The co-doping of W and F not only broadens the interplanar spacing of NSS but also promotes the stable formation of the cubic phase of NSS,thereby effectively enhancing the transport ability of sodium ions within NSS.Among them,Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24) exhibits the highest ionic conductivity of 4.45 mS·cm^(-1).Furthermore,F doping facilitates the in-situ formation of NaF between the electrolyte and metallic sodium,significantly improving interfacial stability.Electrochemical evaluation shows that the Na/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na symmetric cell achieves a high critical current density of 1.65 mA·cm^(-2) and maintains stable sodium plating/stripping cycling for 500 h at 0.1 mA·cm^(-2).Additionally,the TiS2/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na full cell exhibits outstanding cycling stability and rate capability.展开更多
基金National Natural Science Foundation of China(21806023)Natural Science Foundation of Hunan Province(2021JJ40199)+2 种基金Education Department Foundation of Hunan Province(20C0813)Hunan University of Science and Technology Fundamental Research FundsPostgraduate Scientific Research Innovation Project of Hunan Province(CX20240877)。
文摘Elemental doping is an effective strategy for tuning the band structure of graphite carbon nitride(CN)to enhance its photocatalytic performance.In this study,sodium(Na)and oxygen(O)co-doped carbon nitride(Na/O-CN_(x),x=1.0,2.0,3.0,4.0)was synthesized via solid-phase reaction of sodium citrate(NaCA)and pure CN powder in the Teflon-sealed autoclave under air conditions at 180℃.Surface area of Na/O-CN_(3.0) is measured to be 18.8 m^(2)/g,increasing by 60.7%compared to that of pure CN(11.7 m^(2)/g).Bandgap energy of Na/O-CN_(3.0) is determined to be 2.68 eV,marginally lower than that of pure CN(2.70 eV),thereby enhancing its capacity for sunlight absorption.Meanwhile,the incorporation of Na and O atoms into Na/O-CN_(x) is found to effectively reduce recombination rates of photogenerated electron-hole pairs.As a result,Na/O-CN_(x) samples exhibit markedly enhanced photocatalytic hydrogen evolution activity under visible light irradiation.Notably,the optimal Na/O-CN_(3.0) sample achieves a photocatalytic hydrogen production rate of 103.2μmol·g^(–1)·h^(–1),which is 8.2 times greater than that of pure CN(11.2μmol·g^(–1)·h^(–1)).Furthermore,a series of Na/O-CN_(x)-yO_(2)(y=0,20%,40%,60%,80%,100%)samples were prepared by modulating the oxygen content within reaction atmosphere.The catalytic performance evaluations reveal that the incorporation of both Na and O atoms in Na/O-CN_(3.0) enhances photocatalytic activity.This study also introduces novel methodologies for synthesis of metal atom-doped CN materials at lower temperature,highlighting the synergistic effect of Na and O atoms in photocatalytic hydrogen production of Na/O-CN_(x) samples.
基金financial support from projects funded by the National Natural Science Foundation of China(52172038,22179017)the National Key Research and Development Program of China(2022YFB4101600,2022YFB4101601)。
文摘For rechargeable aqueous zinc-ion batteries(ZIBs),the design of nanocomposites comprised of electrochemically active materials and carbon materials with novel structures has great prom-ise in addressing the issue of electrical conductivity and structural stability in the electrode materials during electrochemical cycling.We report the production of a novel flexible electrode material,by anchoring MnO_(2) nanosheets on a B,N co-doped carbon nanotube ar-ray(BNCNTs)grown on carbon cloth(BNCNTs@MnO_(2)),which was fabricated by in-situ pyrolysis and hydrothermal growth.The generated BNCNTs were strongly bonded to the surface of the car-bon fibers in the carbon cloth which provides both excellent elec-tron transport and ion diffusion,and improves the stability and dur-ability of the cathode.Importantly,the BNCNTs offer more active sites for the hydrothermal growth of MnO_(2),ensuring a uniform dis-tribution.Electrochemical tests show that BNCNTs@MnO_(2) delivers a high specific capacity of 310.7 mAh g^(−1) at 0.1 A g^(−1),along with excellent rate capability and outstanding cycling stability,with a 79.7% capacity retention after 8000 cycles at 3 A g^(−1).
基金Project(20376086) supported by National Natural Science Foundation of China
文摘The mechanism of stability of Co-doped spinel λ-MnO_2 that is referred to as spinel Li_xMn_2O_4 (x=0) was studied by using the first-principle calculation method. The total energy and formation enthalpy can be decreased remarkably due to the Co substation, resulting in a more stable structure of λ-Mn_xCr_(2-x)O_4. The bond order and DOS analysis were given in detail to explain the nature of stability improvement. The calculated results show that as the content of Co dopant increases, the bond order of Mn—O becomes larger and the peak of density of states around Fermi level shifts toward lower energy. The charge density distribution illustrates that the Mn—O bonding is ionic and partially covalent, and the covalent Mn-O bonding becomes stronger with the increase of Co dopant content. The results confirm that the Codoping will enhance the stability of λ-MnO_2 and hence improve the electrochemistry performance of Li_xMn_2O_4.
基金Project supported by the Special Funding Support for the Development of 1500 Meter Subsea Christmas Tree and Control System,China。
文摘Improving interfacial bonding and alloying design are effective strategies for enhancing mechanical properties of particle-reinforced steel matrix composites(SMCs).This study prepared SMCs with uniformly distributed TiC_(P)in matrix using master alloying method.The TiC(002)/Fe(011)interface model was established based on the orientation relationship of(011)_(Fe)//(002)_(TiC),and[100]_(Fe)//[100]_(TiC).The effects of single and co-doping of alloying elements(Mn,Cr,Mo,Ni,Cu and Si)on the interface bonding behavior of TiC/Fe in composites were investigated in conjunction with first principles.The results demonstrate that the interface between TiC and matrix is continuous and stable.Compared to the undoped TiC/Fe interface,single-doping Mn,Cr,and Mo can improve the stability of TiC/Fe interface and enhance tensile strength.Conversely,single-doping with Ni,Cu,and Si reduced the interface stability and marginally reduces tensile strength.Relative to the undoped and singly Ni-doped TiC/Fe interfaces,the co-doping Ni-Mo boosts binding energy and separation work at the TiC/Fe interface,which is conducive to the interface bonding between TiC_(P)and matrix,and thus improves the mechanical properties of composites.Thus,in the alloying design of TiC particle reinforced low-alloy SMCs,incorporating Mn,Cr,Mo,and Ni into matrix can enhance the overall mechanical properties of composites.
文摘To replace precious metal oxygen reduction reaction(ORR)electrocatalysts,many transition metals and N-doped car-bon composites have been proposed in the last decade resulting in their rapid development as promising non-precious metal catalysts.We used Ketjenblack carbon as the precursor and mixed it with a polymeric ionic liquid(PIL)of[Hvim]NO_(3) and Fe(NO_(3))_(3),which was thermally calcined at 900℃ to produce a porous FeO_(x),N co-doped carbon material denoted FeO_(x)-N/C.Because the PIL of[Hvim]NO_(3) strongly combines with and disperses Fe^(3+)ions,and NO_(3)−is thermally pyrolyzed to form the porous structure,the FeO_(x)-N/C catalyst has a high electrocatalytic activity for the ORR in both 0.1 mol L^(−1) KOH and 0.5 mol L^(−1) H_(2)SO_(4) electrolytes.It was used as the catalyst to assemble a zinc-air battery,which had a peak power density of 185 mW·cm^(−2).Its superior electrocatalytic activity,wide pH range,and easy preparation make FeO_(x)-N/C a promising electrocatalyst for fuel cells and metal-air batteries.
文摘Practical application of Na_(3)SbS_(4)(NSS)solid-state electrolyte in sodium metal batteries has been significantly hindered by poor interfacial stability and insufficient ionic conductivity.In this study,a series of dual-site doped Na_(3-2x)Sb_(1-x)W_(x)S_(4-x)F_(x)(x=0,0.12,0.24,0.36)electrolytes through high-energy ball milling followed by high-temperature sintering is prepared,where tungsten(W)substitutes for antimony(Sb)and fluorine(F)replaces sulfur(S)in the NSS lattice.The co-doping of W and F not only broadens the interplanar spacing of NSS but also promotes the stable formation of the cubic phase of NSS,thereby effectively enhancing the transport ability of sodium ions within NSS.Among them,Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24) exhibits the highest ionic conductivity of 4.45 mS·cm^(-1).Furthermore,F doping facilitates the in-situ formation of NaF between the electrolyte and metallic sodium,significantly improving interfacial stability.Electrochemical evaluation shows that the Na/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na symmetric cell achieves a high critical current density of 1.65 mA·cm^(-2) and maintains stable sodium plating/stripping cycling for 500 h at 0.1 mA·cm^(-2).Additionally,the TiS2/Na_(2.52)Sb_(0.76)W_(0.24)S_(3.76)F_(0.24)/Na full cell exhibits outstanding cycling stability and rate capability.
