The initial field electron emission degradation behaviour of original nano-structured sp^2-bonded amorphous carbon films has been observed, which can be attributed to the increase of the work function of the film in t...The initial field electron emission degradation behaviour of original nano-structured sp^2-bonded amorphous carbon films has been observed, which can be attributed to the increase of the work function of the film in the field emission process analysed using a Fowler-Nordheim plot. The possible reason for the change of work function is suggested to be the desorption of hydrogen from the original hydrogen termination film surface due to field emission current-induced local heating. For the explanation of the emission degradation behaviour of the nano-structured sp2-bonded amorphous carbon film, a cluster model with a series of graphite （0001） basal surfaces has been presented, and the theoretical calculations have been performed to investigate work functions of graphite （0001） surfaces with different hydrogen atom and ion chemisorption sites by using first principles method based on density functional theory-local density approximation.展开更多
Polymer materials offer controllable structure-dependent performances in separation,catalysis and drug release.Their molecular structures can be precisely tailored to accept Li^(+)for energy storage applications.Here ...Polymer materials offer controllable structure-dependent performances in separation,catalysis and drug release.Their molecular structures can be precisely tailored to accept Li^(+)for energy storage applications.Here the design of sp^(2)carbon-based polyphenylene(PPH)with high lithium-ion uptakes and long-term stability is reported.Linear-PPH(L-PPH)exceeds the performance of crosslink-PPH(C-PPH),due to the fact that it has an ordered lamellar structure,promoting the Li^(+)intercalation/deintercalation channel.The L-PPH cell shows a clear charge and discharge plateau at 0.35 and 0.15 V vs.Li^(+)/Li,respectively,which is absent in the C-PPH cell.The Li^(+)storage capacity of L-PPH is five times that of the C-PPH.The reversible storage capacity is further improved to 261 m Ah g;by functionalizing the L-PPH with the–SO_(3)H groups.In addition,the Li-intercalated structures of C-PPH and L-PPH are investigated via near-edge X-ray absorption fine structure(NEXAFS),suggesting the high reversible Li^(+)–C=C bond interaction at L-PPH.This strategy,based on new insight into sp^(2)functional groups,is the first step toward a molecular understanding of the structure storage-capacity relationship in sp^(2)carbon-based polymer.展开更多
The integration of nano-semiconductors into electromagnetic wave absorption materials is a highly desirable strategy for intensifying dielectric polarization loss;achieving high-attenuation microwave absorption and re...The integration of nano-semiconductors into electromagnetic wave absorption materials is a highly desirable strategy for intensifying dielectric polarization loss;achieving high-attenuation microwave absorption and realizing in-depth comprehension of dielectric loss mechanisms remain challenges.Herein,ultrafine oxygen vacancy-rich Nb_(2)O_(5)semiconductors are confined in carbon nanosheets(ov-Nb_(2)O_(5)/CNS)to boost dielectric polarization and achieve high attenuation.The polarization relaxation,electromagnetic response,and impedance matching of the ov-Nb_(2)O_(5)/CNS are significantly facilitated by the Nb_(2)O_(5)semiconductors with rich oxygen vacancies,which consequently realizes an extremely high attenuation performance of-80.8 dB(>99.999999%wave absorption)at 2.76 mm.As a dielectric polarization center,abundant Nb_(2)O_(5)–carbon heterointerfaces can intensify interfacial polarization loss to strengthen dielectric polarization,and the presence of oxygen vacancies endows Nb_(2)O_(5)semiconductors with abundant charge separation sites to reinforce electric dipole polarization.Moreover,the three-dimensional reconstruction of the absorber using microcomputer tomography technology provides insight into the intensification of the unique lamellar morphology regarding multiple reflection and scattering dissipation characteristics.Additionally,ov-Nb_(2)O_(5)/CNS demonstrates excellent application potential by curing into a microwave-absorbing,machinable,and heat-dissipating plate.This work provides insight into the dielectric polarization loss mechanisms of nano-semiconductor/carbon composites and inspires the design of high-performance microwave absorption materials.展开更多
Native amino-directed palladium-catalyzed C(sp^(3))-H activation/functionalization has been developed for modification ofα-amino acids and peptides.Herein a palladium(Ⅱ)-catalyzed C(sp^(2))-H arylation ofα-amino-β...Native amino-directed palladium-catalyzed C(sp^(3))-H activation/functionalization has been developed for modification ofα-amino acids and peptides.Herein a palladium(Ⅱ)-catalyzed C(sp^(2))-H arylation ofα-amino-β-aryl esters has been disclosed,using the native amino as the directing group.A variety of chiralα-amino-β-aryl esters can be functionalized to give the corresponding ortho-substituted mono-and di-arylated products.展开更多
Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of...Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.展开更多
A new coordination polymer [Cd（bimc）2]n was obtained by the reaction of Hbimc with Cd（NO3） 2·4H2O in NaOH solution, and characterized by elemental analysis, IR and singlecrystal X-ray diffraction. The crystal...A new coordination polymer [Cd（bimc）2]n was obtained by the reaction of Hbimc with Cd（NO3） 2·4H2O in NaOH solution, and characterized by elemental analysis, IR and singlecrystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbcn with a = 12.533（4）, b = 15.705（5）, c = 15.200（5） A, V= 2991.8（15） A^3, Mr = 434.68, Z = 8, Dc = 1.930 g/cm^3, F（000） = 1712,μ（MoKa） = 1.492 mm^-1, the final R = 0.0410 and wR = 0.0804 for 1661 observed reflections （I 〉 2σ（I））. The Cd atom exhibits a distorted six-coordinate CdNzOa octahedral coordination geometry. The complex molecules are linked by both μ2-（η2-O, O^-）, NI and μ2-（η2-O, O^-）, N3 coordination modes of ligands to form cross-like wave （4, 4） layer structures which are further stacked through interlayer hydrogen bonds and π-π stacking interactions in an offset fashion to form a 3D supramolecular structure.展开更多
文摘The initial field electron emission degradation behaviour of original nano-structured sp^2-bonded amorphous carbon films has been observed, which can be attributed to the increase of the work function of the film in the field emission process analysed using a Fowler-Nordheim plot. The possible reason for the change of work function is suggested to be the desorption of hydrogen from the original hydrogen termination film surface due to field emission current-induced local heating. For the explanation of the emission degradation behaviour of the nano-structured sp2-bonded amorphous carbon film, a cluster model with a series of graphite （0001） basal surfaces has been presented, and the theoretical calculations have been performed to investigate work functions of graphite （0001） surfaces with different hydrogen atom and ion chemisorption sites by using first principles method based on density functional theory-local density approximation.
基金funded by the Engineering and Physical Sciences Research Council(EPSRC)(EP/P02467X/1 and EP/S018204/1)the Centre for Nature Inspired Chemical Engineering(EP K038656/1)。
文摘Polymer materials offer controllable structure-dependent performances in separation,catalysis and drug release.Their molecular structures can be precisely tailored to accept Li^(+)for energy storage applications.Here the design of sp^(2)carbon-based polyphenylene(PPH)with high lithium-ion uptakes and long-term stability is reported.Linear-PPH(L-PPH)exceeds the performance of crosslink-PPH(C-PPH),due to the fact that it has an ordered lamellar structure,promoting the Li^(+)intercalation/deintercalation channel.The L-PPH cell shows a clear charge and discharge plateau at 0.35 and 0.15 V vs.Li^(+)/Li,respectively,which is absent in the C-PPH cell.The Li^(+)storage capacity of L-PPH is five times that of the C-PPH.The reversible storage capacity is further improved to 261 m Ah g;by functionalizing the L-PPH with the–SO_(3)H groups.In addition,the Li-intercalated structures of C-PPH and L-PPH are investigated via near-edge X-ray absorption fine structure(NEXAFS),suggesting the high reversible Li^(+)–C=C bond interaction at L-PPH.This strategy,based on new insight into sp^(2)functional groups,is the first step toward a molecular understanding of the structure storage-capacity relationship in sp^(2)carbon-based polymer.
基金supported by National Natural Science Foundation of China(No.22078100,No.52102098,and No.22008073)Fundamental Research Funds for the Central Universities(No.222201718002)。
文摘The integration of nano-semiconductors into electromagnetic wave absorption materials is a highly desirable strategy for intensifying dielectric polarization loss;achieving high-attenuation microwave absorption and realizing in-depth comprehension of dielectric loss mechanisms remain challenges.Herein,ultrafine oxygen vacancy-rich Nb_(2)O_(5)semiconductors are confined in carbon nanosheets(ov-Nb_(2)O_(5)/CNS)to boost dielectric polarization and achieve high attenuation.The polarization relaxation,electromagnetic response,and impedance matching of the ov-Nb_(2)O_(5)/CNS are significantly facilitated by the Nb_(2)O_(5)semiconductors with rich oxygen vacancies,which consequently realizes an extremely high attenuation performance of-80.8 dB(>99.999999%wave absorption)at 2.76 mm.As a dielectric polarization center,abundant Nb_(2)O_(5)–carbon heterointerfaces can intensify interfacial polarization loss to strengthen dielectric polarization,and the presence of oxygen vacancies endows Nb_(2)O_(5)semiconductors with abundant charge separation sites to reinforce electric dipole polarization.Moreover,the three-dimensional reconstruction of the absorber using microcomputer tomography technology provides insight into the intensification of the unique lamellar morphology regarding multiple reflection and scattering dissipation characteristics.Additionally,ov-Nb_(2)O_(5)/CNS demonstrates excellent application potential by curing into a microwave-absorbing,machinable,and heat-dissipating plate.This work provides insight into the dielectric polarization loss mechanisms of nano-semiconductor/carbon composites and inspires the design of high-performance microwave absorption materials.
基金supported by the National Key Research and Development Program of China(No.2018YFA0704502)the National Natural Science Foundation of China(Nos.21871261,21931011)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZZ105).
文摘Native amino-directed palladium-catalyzed C(sp^(3))-H activation/functionalization has been developed for modification ofα-amino acids and peptides.Herein a palladium(Ⅱ)-catalyzed C(sp^(2))-H arylation ofα-amino-β-aryl esters has been disclosed,using the native amino as the directing group.A variety of chiralα-amino-β-aryl esters can be functionalized to give the corresponding ortho-substituted mono-and di-arylated products.
基金the National Natural Science Foundation of China(Nos.22025206,21991094)supported by the Ministry of ScienceTechnology of the People’s Republic of China(No.2018YFE0118100)+1 种基金the CAS-NSTDA Joint Research Project(No.GJHZ2075)Dalian Science and Technology Innovation Fund(No.2019J11CY009).
文摘Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.
基金This work was supported by the NNSFC (No. 30460153 20561001), NSF of Guangxi Province (No. 0447019), and the Teaching and Research Award Program for Outstanding Young Teachers in Higher Education Institutions of Chinese Ministry of Education
文摘A new coordination polymer [Cd（bimc）2]n was obtained by the reaction of Hbimc with Cd（NO3） 2·4H2O in NaOH solution, and characterized by elemental analysis, IR and singlecrystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbcn with a = 12.533（4）, b = 15.705（5）, c = 15.200（5） A, V= 2991.8（15） A^3, Mr = 434.68, Z = 8, Dc = 1.930 g/cm^3, F（000） = 1712,μ（MoKa） = 1.492 mm^-1, the final R = 0.0410 and wR = 0.0804 for 1661 observed reflections （I 〉 2σ（I））. The Cd atom exhibits a distorted six-coordinate CdNzOa octahedral coordination geometry. The complex molecules are linked by both μ2-（η2-O, O^-）, NI and μ2-（η2-O, O^-）, N3 coordination modes of ligands to form cross-like wave （4, 4） layer structures which are further stacked through interlayer hydrogen bonds and π-π stacking interactions in an offset fashion to form a 3D supramolecular structure.
