We report the detailed crystal structures and physical properties of Ru_(1-x)Mo_(x)alloys in the solid solution range of x=0.1-0.9.Structure characterizations indicate that the crystal structure changes from the hcp-M...We report the detailed crystal structures and physical properties of Ru_(1-x)Mo_(x)alloys in the solid solution range of x=0.1-0.9.Structure characterizations indicate that the crystal structure changes from the hcp-Mg-type,toβ-CrFe-type,and then bcc-W-type.The measurements of physical properties show that the Ru_(1-x)Mo_(x)samples with x≥0.2are superconductors and the superconducting transition temperature T_c as a function of Mo content exhibits a dome-like behavior.展开更多
A novel compound(H_(2)L)SCN(5⁃methyl⁃3⁃phenyl⁃2H⁃pyrazol⁃1⁃ium thiocyanate)has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol.Two zinccomplexes[Zn(HL)_(2)(NCS)(CH_(3)COO)](1)and[Zn_(...A novel compound(H_(2)L)SCN(5⁃methyl⁃3⁃phenyl⁃2H⁃pyrazol⁃1⁃ium thiocyanate)has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol.Two zinccomplexes[Zn(HL)_(2)(NCS)(CH_(3)COO)](1)and[Zn_(2)(L)_(2)(HL)_(2)(NCS)_(2)]_(2)·2CH_(3)OH(2)have been synthesized by the coordination reactions of Zn(OAc)_(2)·2H_(2)O or ZnCl_(2)with(H_(2)L)SCN under reflux conditions.Elemental analyses and single⁃crystal X⁃ray diffraction have con⁃firmed the structures of the synthesized compounds.The(H_(2)L)SCN ligand and complex 1 pertain to the triclinic sys⁃tem with space group P1,while complex 2 belongs to the monoclinic system with space group P2_(1)/n.Additionally,the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bac⁃terial strains(Candida albicans,Staphylococcus aureus,and Escherichia coli).The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria,and the complexes possessed stronger antibac⁃terial activities against the same bacteria than the free ligand.CCDC:2190252,(H2L)SCN;2190253,1;2190256,2.展开更多
Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars wi...Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars with concurrent production of H_(2),which remains challenging.Here,the photo-catalytic activity for glucose decomposition to HCOOH,CO(C_(1) chemicals),and H_(2) on Cu/TiO_(2)was enhanced by nitrogen doping.Owing to nitrogen doping,atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO_(2).The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2p orbit,distinct from undoped Cu/TiO_(2).Therefore,the lifetime of charge carriers is prolonged,resulting in the pro-duction of C_(1) chemicals and H_(2) with productivities 1.7 and 2.1 folds that of Cu/TiO_(2).This work pro-vides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.展开更多
The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction...The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.展开更多
In this work,we report the preparation of 1T'-MoS_(2)/g-C_(3)N_(4) nanocage(NC)heterostructure by loading 2D semi-metal noble-metal-free 1T'-MoS_(2) on the g-C_(3)N_(4) nanocages(NCs).DFT calculation and exper...In this work,we report the preparation of 1T'-MoS_(2)/g-C_(3)N_(4) nanocage(NC)heterostructure by loading 2D semi-metal noble-metal-free 1T'-MoS_(2) on the g-C_(3)N_(4) nanocages(NCs).DFT calculation and experimental data have shown that the 1T'-MoS_(2)/g-C_(3)N_(4) NC heterostructure has a stronger light absorption capacity and larger specific surface area than pure g-C_(3)N_(4) NCs and g-C_(3)N_(4) nanosheets(NSs),and the presence of the co-catalysts 1T'-MoS_(2) can effectively inhibit the photoinduced carrier recombination.As a result,the 1T'-MoS_(2)/g-C_(3)N_(4) NC heterostructure with an optimum 1T'-MoS_(2) loading of 9 wt%displays a hydrogen evolution rate of 1949 mmol h^(-1) g^(-1),162.4,1.2,1.5,1.6 and 1.2 times than pure g-C_(3)N_(4) NCs(12 mmol h^(-1) g^(-1)),Pt/g-C_(3)N_(4) NCs(1615 mmol h^(-1) g^(-1))and Pt/g-C_(3)N_(4) nanosheets(NSs,1297 mmol h^(-1) g^(-1)),1T'-MoS_(2)/g-C_(3)N_(4) nanosheets(1216 mmol h^(-1) g^(-1))and 2H-MoS_(2)/g-C_(3)N_(4) nanocages(1573 mmol h^(-1) g^(-1)),respectively,and exhibits excellent cycle stability.Therefore,1T'-MoS_(2)/g-C_(3)N_(4) NC heterostructure is a suitable photocatalyst for green H_(2) production.展开更多
A novel heterometallic complex,[Zn4Ni（OH）2（btec）2（titb）2（H2O）2]·2H2O（1）（H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris（imidazol-1-ylmethyl）-2,4,6-trime-thylbenzene）,has been hydrothermal...A novel heterometallic complex,[Zn4Ni（OH）2（btec）2（titb）2（H2O）2]·2H2O（1）（H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris（imidazol-1-ylmethyl）-2,4,6-trime-thylbenzene）,has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817（10）,b=11.878（11）,c=14.569（14）,α=71.762（12）,β=76.122（13）,γ=71.493（13）°,V=1665（3）3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F（000）=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections（Ⅰ 2σ（Ⅰ））.In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.展开更多
The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H1...The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?展开更多
Eighteen novel triazole compounds containing 1,3,4-oxadiazole groups were synthesized from 2-（1H-1,2,4-triazol-1-yl）acetohydrazide and carbon disulfide by several step reactions. The target compounds were characteri...Eighteen novel triazole compounds containing 1,3,4-oxadiazole groups were synthesized from 2-（1H-1,2,4-triazol-1-yl）acetohydrazide and carbon disulfide by several step reactions. The target compounds were characterized by elemental analysis, 1H NMR, 13C NMR, IR, MS, and X-ray crystallography. The results of preliminary biological tests show that all the compounds exhibit certain fungicidal activities.展开更多
The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its...The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.展开更多
As typical quarternary copper-based chalcogenides,Cu–Zn–Sn–S nanocrystals(CZTS NCs)have emerged as a newfashioned electrocatalyst in hydrogen evolution reactions(HERs).Oleylamine(OM),a reducing surfactant and solve...As typical quarternary copper-based chalcogenides,Cu–Zn–Sn–S nanocrystals(CZTS NCs)have emerged as a newfashioned electrocatalyst in hydrogen evolution reactions(HERs).Oleylamine(OM),a reducing surfactant and solvent,plays a significant role in the assisting synthesis of CZTS NCs due to the ligand effect.Herein,we adopted a facile one-pot colloidal method for achieving the structure evolution of CZTS NCs from 2D nanosheets to 1D nanorods assisted through the continuous addition of OM.During the process,the mechanism of OM-induced morphology evolution was further discussed.When merely adding pure 1-dodecanethiol(DDT)as the solvent,the CZTS nanosheets were obtained.As OM was gradually added to the reaction,the CZTS NCs began to grow along the sides of the nanosheets and gradually shrink at the top,followed by the formation of stable nanorods.In acidic electrolytic conditions,the CZTS NCs with 1.0 OM addition display the optimal HER activity with a low overpotential of 561 m V at 10 m A/cm^(2) and a small Tafel slope of 157.6 m V/dec compared with other CZTS samples.The enhancement of HER activity could be attributed to the contribution of the synergistic effect of the diverse crystal facets to the reaction.展开更多
The title compound 5,5-dimethyl-2-（4-chlorophenyl）（3-hydroxy-5,5-dimethyl- 2-cyclohexen-1-one-2-yl）methyl-3-（4-methoxyphenylamino）-2-cyclohexen-1-one has been synthesized, and its crystal structure was character...The title compound 5,5-dimethyl-2-（4-chlorophenyl）（3-hydroxy-5,5-dimethyl- 2-cyclohexen-1-one-2-yl）methyl-3-（4-methoxyphenylamino）-2-cyclohexen-1-one has been synthesized, and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/c with a = 9.4193（13）, b = 26.915（4）, c= 21.188（3） A, β = 101.906（3）°, V = 5256.2（13） A3, Z = 4, C60H68C12N2O8, Mr =1016.06, Dc = 1.284 g/cm3, F（000） = 2160, λ（MoKα） = 0.71073 A, μ = 0.182 mm^-1, R = 0.0530 and wR = 0.1131 for 4128 observed reflections （1 〉 2α（Ⅰ））. X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition, there are four intramolecular hydrogen bonds in the title molecule.展开更多
The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with eq...The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with equal amount of K_2CO_3 as acid acceptor. The structure of compound 3 was characterized by ~1H NMR, 13 C NMR, HRMS and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n with a = 5.7227（8）, b = 27.924（4）, c = 6.2282（7） ？, β = 101.892（11）°, V = 973.9（2） ？~3, Z = 4, T = 180.00（10） K, μ（MoKα） = 0.087 mm^（-1）, Dc = 1.243 g/cm^3, 3832 reflections measured（3.648≤θ≤26.022°）, 1916 unique reflections（Rint = 0.0359, Rsigma = 0.0572） used in all calculations. The final R = 0.0557（I 〉 2σ（I）） and w R = 0.1276（all data）. Bioassay showed that 3 displayed excellent activity as plant growth regulator with inducing lateral root formation and enhancing primary root elongation at 0.27 mmol/L（50 ppm） in soybeen（He Feng-50）. Good water solubility was found with 50 mg in 1 m L of water. Therefore, application of 3 in agriculture is more environmentally friendly due to cosolvent-free condition, and results in improved abiotic-stress tolerance by affecting the root growth. And furthermore, it can be used as a precursor to investigate the function of regulating plant root growth.展开更多
The title compound [HphenNO2]+NO3- has been prepared and characterized by elemental analysis, electronic absorption spectroscopy, TG/DTA, IR, 1H and 13C NMR spectro- scopy. Single-crystal X-ray structure determination...The title compound [HphenNO2]+NO3- has been prepared and characterized by elemental analysis, electronic absorption spectroscopy, TG/DTA, IR, 1H and 13C NMR spectro- scopy. Single-crystal X-ray structure determination of the title compound was also carried out. It crystallizes in monoclinic, space group Cc with a = 13.861(3), b = 10.142(2), c = 8.7320(17) ? b = 103.70(3)? C12H8N4O5, Mr = 288.22, V = 1192.6(4) 3, Z = 4, Dc = 1.605 g/cm3 , F(000) = 592, (MoK) = 0.129 mm-1, R = 0.0439, wR = 0.1125 and GOF =1.114. In the crystal lattice, the molecules create a network structure through hydrogen bonds. The second order optical non- linearity was performed by quantum chemical method, showing the title compound has higher molecular hyper polarizability value (?= 24.66×10-30 esu).展开更多
The measurement on radial profile of electrostatic Reynolds stress, plasma poloidal rotations, radial and poloidal electric field have been performed in the plasma boundary region of the HL-IM Tokamak using a multi-ar...The measurement on radial profile of electrostatic Reynolds stress, plasma poloidal rotations, radial and poloidal electric field have been performed in the plasma boundary region of the HL-IM Tokamak using a multi-array of Mach/Langmuir probes. In the experiments of Lower Hybrid Current Drive (LHCD), Supersonic Molecular Beam injection (SMBI), Multi-shot Pellet Injection (MPI) and Neutral Beam injection (NBI), the correlation between the Reynolds stress and poloidal flow in the edge plasma is presented. The results indicate that a sheared poloidal flow can be generated in Tokamak plasma due to radially varying Reynolds stress.展开更多
One novel 1-D copper（Ⅱ）-organic compound,namely {[Cu2（PP）2（CBPC）]2·7H2O}n（1,H2CBPC=1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-（2-pyridyl）pyrazole）,was synthesized ...One novel 1-D copper（Ⅱ）-organic compound,namely {[Cu2（PP）2（CBPC）]2·7H2O}n（1,H2CBPC=1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-（2-pyridyl）pyrazole）,was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu（Ⅱ） ions in the distorted dimer [Cu2（PP）2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656（8）,b=12.715（3）,c=22.405（5）,β=122.758（3）°,V=7344（3）3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F（000）=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ（Ⅰ）.展开更多
The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the tric...The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a = 6.018（3）, b = 9.832（5）, c = 9.921（5）A, a = 78.270（8）, β = 74.550（8）, γ = 83.807（8）°, V = 553.1（5）A^3, Z = 1, C14H16Cl4CoN10O2, Mr = 557.10, Dc = 1.673 g/cm^3, F（000） = 281,μ（MoKα） = 1.293 mm^-1, the final R = 0.0453 and wR = 0.1181 for 1539 observed reflections with I 〉 2σ（I）. The Co（II） ion is in a distorted centrosymmetric six-coordinate octahedral environment with two Ntriazole, two Omethanol and two Cl atoms. Via hydrogen bonds the configuration of 1 has been extended into 1D chains which are developed to 2D layers via π-π sticking action, and these layers are further extended into a 3D network by hydrogen bonds. The antibacterial activity of the title compound has been detected, and the results show that the ligands and cobalt（II） complex exhibit certain fungicidal activity against several bacteria. Furthermore, the spectral properties of the title compound have been also studied and discussed.展开更多
基金Project supported by Beijing Natural Science Foundation (Grant No.Z200005)the National Key R&D Program of China (Grant Nos.2018YFE0202600 and 2022YFA1403800)+1 种基金the National Natural Science Foundation of China (Grant No.12274459)Beijing National Laboratory for Condensed Matter Physics,and Collaborative Research Project of Laboratory for Materials and Structures,Institute of Innovative Research,Tokyo Institute of Technology。
文摘We report the detailed crystal structures and physical properties of Ru_(1-x)Mo_(x)alloys in the solid solution range of x=0.1-0.9.Structure characterizations indicate that the crystal structure changes from the hcp-Mg-type,toβ-CrFe-type,and then bcc-W-type.The measurements of physical properties show that the Ru_(1-x)Mo_(x)samples with x≥0.2are superconductors and the superconducting transition temperature T_c as a function of Mo content exhibits a dome-like behavior.
文摘A novel compound(H_(2)L)SCN(5⁃methyl⁃3⁃phenyl⁃2H⁃pyrazol⁃1⁃ium thiocyanate)has been obtained by the reaction of thiosemicarbazide with benzoylacetone in ethanol.Two zinccomplexes[Zn(HL)_(2)(NCS)(CH_(3)COO)](1)and[Zn_(2)(L)_(2)(HL)_(2)(NCS)_(2)]_(2)·2CH_(3)OH(2)have been synthesized by the coordination reactions of Zn(OAc)_(2)·2H_(2)O or ZnCl_(2)with(H_(2)L)SCN under reflux conditions.Elemental analyses and single⁃crystal X⁃ray diffraction have con⁃firmed the structures of the synthesized compounds.The(H_(2)L)SCN ligand and complex 1 pertain to the triclinic sys⁃tem with space group P1,while complex 2 belongs to the monoclinic system with space group P2_(1)/n.Additionally,the antibacterial activities of the compounds were evaluated in vitro using the agar diffusion method against the bac⁃terial strains(Candida albicans,Staphylococcus aureus,and Escherichia coli).The results showed that the ligand exhibited relatively good antibacterial activities against the bacteria,and the complexes possessed stronger antibac⁃terial activities against the same bacteria than the free ligand.CCDC:2190252,(H2L)SCN;2190253,1;2190256,2.
文摘Photocatalytic decomposition of sugars is a promising way of providing H_(2),CO,and HCOOH as sus-tainable energy vectors.However,the production of C_(1) chemicals requires the cleavage of robust C−C bonds in sugars with concurrent production of H_(2),which remains challenging.Here,the photo-catalytic activity for glucose decomposition to HCOOH,CO(C_(1) chemicals),and H_(2) on Cu/TiO_(2)was enhanced by nitrogen doping.Owing to nitrogen doping,atomically dispersed and stable Cu sites resistant to light irradiation are formed on Cu/TiO_(2).The electronic interaction between Cu and nitrogen ions originates valence band structure and defect levels composed of N 2p orbit,distinct from undoped Cu/TiO_(2).Therefore,the lifetime of charge carriers is prolonged,resulting in the pro-duction of C_(1) chemicals and H_(2) with productivities 1.7 and 2.1 folds that of Cu/TiO_(2).This work pro-vides a strategy to design coordinatively stable Cu ions for photocatalytic biomass conversion.
基金supported by the National Key Research and Development Program of China(2021YFB4001301)the Science and Technology Commission of Shanghai Municipality(21DZ1208600)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2021ZD105)。
文摘The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.
基金funding from the National Natural Science Foundation of China (No.51872173)Taishan Scholar Foundation of Shandong Province (No.tsqn201812068)+2 种基金Youth Innovation Technology Project of Higher School in Shandong Province (No.2019KJA013)Science and Technology Special Project of Qingdao City (No.20-3-4-3-nsh)the Opening Fund of State Key Laboratory of Heavy Oil Processing (No.SKLOP202002006)。
文摘In this work,we report the preparation of 1T'-MoS_(2)/g-C_(3)N_(4) nanocage(NC)heterostructure by loading 2D semi-metal noble-metal-free 1T'-MoS_(2) on the g-C_(3)N_(4) nanocages(NCs).DFT calculation and experimental data have shown that the 1T'-MoS_(2)/g-C_(3)N_(4) NC heterostructure has a stronger light absorption capacity and larger specific surface area than pure g-C_(3)N_(4) NCs and g-C_(3)N_(4) nanosheets(NSs),and the presence of the co-catalysts 1T'-MoS_(2) can effectively inhibit the photoinduced carrier recombination.As a result,the 1T'-MoS_(2)/g-C_(3)N_(4) NC heterostructure with an optimum 1T'-MoS_(2) loading of 9 wt%displays a hydrogen evolution rate of 1949 mmol h^(-1) g^(-1),162.4,1.2,1.5,1.6 and 1.2 times than pure g-C_(3)N_(4) NCs(12 mmol h^(-1) g^(-1)),Pt/g-C_(3)N_(4) NCs(1615 mmol h^(-1) g^(-1))and Pt/g-C_(3)N_(4) nanosheets(NSs,1297 mmol h^(-1) g^(-1)),1T'-MoS_(2)/g-C_(3)N_(4) nanosheets(1216 mmol h^(-1) g^(-1))and 2H-MoS_(2)/g-C_(3)N_(4) nanocages(1573 mmol h^(-1) g^(-1)),respectively,and exhibits excellent cycle stability.Therefore,1T'-MoS_(2)/g-C_(3)N_(4) NC heterostructure is a suitable photocatalyst for green H_(2) production.
基金supported by the National Natural Science Foundation of China (No. 20971004)the Key Project of Chinese Ministry of Education (No. 210102)
文摘A novel heterometallic complex,[Zn4Ni（OH）2（btec）2（titb）2（H2O）2]·2H2O（1）（H4btec=1,2,4,5-benzenetetracarboxylic acid,titb=1,3,5-tris（imidazol-1-ylmethyl）-2,4,6-trime-thylbenzene）,has been hydrothermally prepared and characterized by IR spectroscopy,elemental analysis and single-crystal X-ray diffraction.The crystal is of triclinic system,space group P1 with a=10.817（10）,b=11.878（11）,c=14.569（14）,α=71.762（12）,β=76.122（13）,γ=71.493（13）°,V=1665（3）3,C62H62N12O22Zn4Ni,Mr=1647.43,Dc=1.643 g/cm3,F（000）=842,μ=1.784 mm-1 and Z=1.The final R=0.0531 and wR=0.0890 for 3545 observed reflections（Ⅰ 2σ（Ⅰ））.In the title complex,the btec ligand acts as a five-dentate bridging ligand to link up zinc and nickel atoms into a lamellar framework,which are further interlinked into a 3-D framework via the titb ligands.
基金This work was supported by the foundation of Natural Science Research of Jiangsu Education Department (02KJB150007)
文摘The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?
基金the National Natural Science Foundation of China(Nos.20771030 and 20671025)
文摘Eighteen novel triazole compounds containing 1,3,4-oxadiazole groups were synthesized from 2-（1H-1,2,4-triazol-1-yl）acetohydrazide and carbon disulfide by several step reactions. The target compounds were characterized by elemental analysis, 1H NMR, 13C NMR, IR, MS, and X-ray crystallography. The results of preliminary biological tests show that all the compounds exhibit certain fungicidal activities.
基金the Science Research Foundation of Henan Institute of Science and Technology (No. 06036)
文摘The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.
基金partially supported by National Natural Science Foundation of China (12274021 and 62075005)。
文摘As typical quarternary copper-based chalcogenides,Cu–Zn–Sn–S nanocrystals(CZTS NCs)have emerged as a newfashioned electrocatalyst in hydrogen evolution reactions(HERs).Oleylamine(OM),a reducing surfactant and solvent,plays a significant role in the assisting synthesis of CZTS NCs due to the ligand effect.Herein,we adopted a facile one-pot colloidal method for achieving the structure evolution of CZTS NCs from 2D nanosheets to 1D nanorods assisted through the continuous addition of OM.During the process,the mechanism of OM-induced morphology evolution was further discussed.When merely adding pure 1-dodecanethiol(DDT)as the solvent,the CZTS nanosheets were obtained.As OM was gradually added to the reaction,the CZTS NCs began to grow along the sides of the nanosheets and gradually shrink at the top,followed by the formation of stable nanorods.In acidic electrolytic conditions,the CZTS NCs with 1.0 OM addition display the optimal HER activity with a low overpotential of 561 m V at 10 m A/cm^(2) and a small Tafel slope of 157.6 m V/dec compared with other CZTS samples.The enhancement of HER activity could be attributed to the contribution of the synergistic effect of the diverse crystal facets to the reaction.
基金the Foundation of the Key Laboratory of Biotechnology for Medical Plants of Jiangsu Province (No. 02AXL13)
文摘The title compound 5,5-dimethyl-2-（4-chlorophenyl）（3-hydroxy-5,5-dimethyl- 2-cyclohexen-1-one-2-yl）methyl-3-（4-methoxyphenylamino）-2-cyclohexen-1-one has been synthesized, and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/c with a = 9.4193（13）, b = 26.915（4）, c= 21.188（3） A, β = 101.906（3）°, V = 5256.2（13） A3, Z = 4, C60H68C12N2O8, Mr =1016.06, Dc = 1.284 g/cm3, F（000） = 2160, λ（MoKα） = 0.71073 A, μ = 0.182 mm^-1, R = 0.0530 and wR = 0.1131 for 4128 observed reflections （1 〉 2α（Ⅰ））. X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition, there are four intramolecular hydrogen bonds in the title molecule.
基金supported by the National Natural Science Foundation of China(No.2012BAD20B04)
文摘The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with equal amount of K_2CO_3 as acid acceptor. The structure of compound 3 was characterized by ~1H NMR, 13 C NMR, HRMS and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n with a = 5.7227（8）, b = 27.924（4）, c = 6.2282（7） ？, β = 101.892（11）°, V = 973.9（2） ？~3, Z = 4, T = 180.00（10） K, μ（MoKα） = 0.087 mm^（-1）, Dc = 1.243 g/cm^3, 3832 reflections measured（3.648≤θ≤26.022°）, 1916 unique reflections（Rint = 0.0359, Rsigma = 0.0572） used in all calculations. The final R = 0.0557（I 〉 2σ（I）） and w R = 0.1276（all data）. Bioassay showed that 3 displayed excellent activity as plant growth regulator with inducing lateral root formation and enhancing primary root elongation at 0.27 mmol/L（50 ppm） in soybeen（He Feng-50）. Good water solubility was found with 50 mg in 1 m L of water. Therefore, application of 3 in agriculture is more environmentally friendly due to cosolvent-free condition, and results in improved abiotic-stress tolerance by affecting the root growth. And furthermore, it can be used as a precursor to investigate the function of regulating plant root growth.
文摘The title compound [HphenNO2]+NO3- has been prepared and characterized by elemental analysis, electronic absorption spectroscopy, TG/DTA, IR, 1H and 13C NMR spectro- scopy. Single-crystal X-ray structure determination of the title compound was also carried out. It crystallizes in monoclinic, space group Cc with a = 13.861(3), b = 10.142(2), c = 8.7320(17) ? b = 103.70(3)? C12H8N4O5, Mr = 288.22, V = 1192.6(4) 3, Z = 4, Dc = 1.605 g/cm3 , F(000) = 592, (MoK) = 0.129 mm-1, R = 0.0439, wR = 0.1125 and GOF =1.114. In the crystal lattice, the molecules create a network structure through hydrogen bonds. The second order optical non- linearity was performed by quantum chemical method, showing the title compound has higher molecular hyper polarizability value (?= 24.66×10-30 esu).
文摘The measurement on radial profile of electrostatic Reynolds stress, plasma poloidal rotations, radial and poloidal electric field have been performed in the plasma boundary region of the HL-IM Tokamak using a multi-array of Mach/Langmuir probes. In the experiments of Lower Hybrid Current Drive (LHCD), Supersonic Molecular Beam injection (SMBI), Multi-shot Pellet Injection (MPI) and Neutral Beam injection (NBI), the correlation between the Reynolds stress and poloidal flow in the edge plasma is presented. The results indicate that a sheared poloidal flow can be generated in Tokamak plasma due to radially varying Reynolds stress.
基金supported by the Chinese Academy of Sciences (KJCX2-YW-M05,KJCX2-YW-319)the Natural Science Foundation of Fujian Province (2007HZ0001-1,2009HZ0004-1)
文摘One novel 1-D copper（Ⅱ）-organic compound,namely {[Cu2（PP）2（CBPC）]2·7H2O}n（1,H2CBPC=1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-（2-pyridyl）pyrazole）,was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu（Ⅱ） ions in the distorted dimer [Cu2（PP）2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656（8）,b=12.715（3）,c=22.405（5）,β=122.758（3）°,V=7344（3）3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F（000）=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ（Ⅰ）.
文摘The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a = 6.018（3）, b = 9.832（5）, c = 9.921（5）A, a = 78.270（8）, β = 74.550（8）, γ = 83.807（8）°, V = 553.1（5）A^3, Z = 1, C14H16Cl4CoN10O2, Mr = 557.10, Dc = 1.673 g/cm^3, F（000） = 281,μ（MoKα） = 1.293 mm^-1, the final R = 0.0453 and wR = 0.1181 for 1539 observed reflections with I 〉 2σ（I）. The Co（II） ion is in a distorted centrosymmetric six-coordinate octahedral environment with two Ntriazole, two Omethanol and two Cl atoms. Via hydrogen bonds the configuration of 1 has been extended into 1D chains which are developed to 2D layers via π-π sticking action, and these layers are further extended into a 3D network by hydrogen bonds. The antibacterial activity of the title compound has been detected, and the results show that the ligands and cobalt（II） complex exhibit certain fungicidal activity against several bacteria. Furthermore, the spectral properties of the title compound have been also studied and discussed.
