La_(1-x)Ce_(x)MnO_(3)-Ba/Al_(2)O_(3)催化剂对NO选择性生成NH_(3)的影响

为了实现碳中和目标,降低内燃机碳排放,稀薄燃烧技术成为了当前重要的研究方向.该技术不仅能提高发动机燃油热效率,还能有效降低CO_(2)排放.但是稀薄燃烧往往会伴随着大量氮氧化物的产生,为了解决该问题,采用LNT-SCR耦合的NO_(x)净化技术,此时LNT的作用是将排气中部分NO_(x)转化为NH_(3),为下游的SCR提供还原剂.基于此,制备了LNT催化剂,研究催化剂对NO选择性生成NH_(3)的影响.采用溶胶-凝胶法制备了La_(1-x)Ce_(x)MnO_(3)系列钙钛矿氧化物,并通过分步浸渍法得到了La_(1-x)Ce_(x)MnO_(3)-Ba/Al_(2)O_(3)负载型催化剂.利用XRD、H_(2)-TPR、NO-TPD等表征手段研究了钙钛矿氧化物的晶相结构,以及负载型催化剂的还原特性、NO_(x)吸附-脱附性能等物化性质,并且通过H_(2)选择性催化还原NO实验探究了催化剂掺杂Ce对NO转化成NH_(3)的影响.结果表明,Ce掺杂催化剂具有良好的NH_(3)产物选择性,并且显著提高了NO转化率.温度是NO转化和NH_(3)产物选择性生成的决定性因素,而H_(2)和NO体积比是NO转化和NH_(3)产物选择性生成的关键性因素.其中,La_(0.95)Ce_(0.05)MnO_(3)-Ba/Al_(2)O_(3)在低温下催化活性表现最佳,在350℃、H_(2)和NO体积比为5.0时NH_(3)产物选择性为65%,NO转化率为100%.此外,所制备的La_(1-x)Ce_(x)MnO_(3)都形成了钙钛矿型结构,而且Ce掺杂催化剂的大部分Ce离子可以进入到LaMnO_(3)结构中.在催化剂适量掺杂Ce后,H_(2)消耗总面积增大、还原峰的峰值温度降低,表明掺杂Ce改善了催化剂的还原特性;同时NO吸附和脱附面积增大,表明Ce掺杂改变了催化剂的NO_(x)吸附-脱附性能.

Ultrafine ordered L1_(2)-Pt-Co-Mn ternary intermetallic nanoparticles as high-performance oxygen-reduction electrocatalysts for practical fuel cells

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.

Synthesis and Crystal Structure of a Novel Heterometallic Complex with 1,2,4,5-Benzenetetracarboxylic Acid and 1,3,5-Tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene

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.

Structure and Biological Activities of Novel Triazole Compounds Containing 1,3,4-Oxadiazole Ring

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.

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

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) ?

Synthesis and Crystal Structure of 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

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.

Structure and superconducting properties of Ru_(1-x)Mo_(x)(x=0.1-0.9)alloys

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.

Synthesis and Crystal Structure of 5,5-Dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexene-1-one

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.

Synthesis,crystal structures,and antibacterial activities of two zinc(Ⅱ) complexes bearing 5⁃phenyl⁃1H⁃pyrazole group

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.

Synthesis,Crystal Structure and Plant Growth Regulatory Activity of 1-(3-Amino-[1,2,4]triazol-1-yl)-3,3-dimethyl-butan-2-one

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.

Engineering the coordination structure of Cu for enhanced photocatalytic production of C_(1) chemicals from glucose

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.

Synthesis, Crystal Structure and Second-order Optical Nonlinearity of 6-Nitro-[1,10]phenanthroline-1-ium Nitrate, [HphenNO2]^+NO_3^-

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).

Edge Structure of Reynolds Stress and Poloidal Flow on the HL-1M Tokamak

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.

Synthesis,Crystal Structure and Biological Activity of a Novel Complex:Co(L)_2(CH_3OH)_2Cl_2 (L=3-(1,2,4-Triazole-yl)-6-chloro-pyridazine)

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.

Hydrothermal Synthesis and Crystal Structure of One Novel 1-D Copper(Ⅱ)-organic Framework:{[Cu_2(PP)_2(CBPC)]_2·7H_2O}_n

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）.

Synthesis and Crystal Structure of 1-H-Pyrrole-2-carboxylic Acid [2-(Naphthalen-1-ylamino)-ethyl]-amide

1-H-Pyrrole-2-carboxylic acid [2-（naphthalen-1-ylamino）-ethyl]-amide has been synthesized and characterized. Its crystal is of monoclinic, space group P2 1/n with a = 5.930（6）, b = 12.144（13）, c = 20.10（2） , A, β = 95.709（17）°, V= 1441（3） ,A, Z= 4, C17H17N3O, Mr= 279.34, Dc= 1.288 g/cm^3, F（000） = 592, μ（MoKa） = 0.083 mm^-1, S = 1.019, R = 0.0473 and wR = 0.1181 for 1713 observed reflections with I 〉 2 σ（I）. X-ray diffraction reveals that two molecules of the title compound form a dimer through a pair of N-H…O hydrogen bonds.

Synthesis, Crystal Structure and Antibacterial Activity of 1-((2-Chloroquinolin-3-yl)-methyl)-pyridin-2(1H)-one

On the basis of the interesting structures and biological activities exhibited by several heterocyclic systems possessing the pyridone nucleus such as mappcine and camptothecin, we have planed to design the synthesis, crystal studies and antibacterial activity of the new 1-（（2- chloroquinolin-3yl）-methyl）-pyridine-2（1H）-one building block. An X-ray analysis has provided valuable insight into the effect of steric factors on the three-dimensional shape of this compound which serves as a useful advanced intermediate in the synthesis of these biologically active molecules. A multistep synthesis of camptothecin （5） has been designed by retrosynthetic analysis as part of an ongoing program on lead anticancer drug.

Synthesis and Crystal Structure of Dibromo [1,1′- bis(diphenylphosphino)ferrocene]cadmium(II)

The title complex Cd(dppf)Br2 (dppf=1,1′-bis(diphenylphosphino)ferrocene) (C34H28Br2 P2CdFe, Mr=826.57) has been synthesized and characterized by X-ray diffraction. The crystal is in monoclinic, space group C2/c with cell parameters: a = 34.285(4), b = 10.050(1), c = 18.697(2) ? β= 98.843(3)? V = 6366(1)3, Z = 8, Dc = 1.725g/cm3, (MoKa) = 0.71073 ? =3.757mm-1, F(000)=3248. The final refinement with 4469 observed reflections and 361 parameters gave R=0.0584 and wR=0.1522. The 1,1′-bis(diphenylphosphino)ferrocene group is connected to the Cd atom as a bidentate ligand. The Cd atom has a distorted tetrahedral coordination.

Synthesis and Molecular Structure of (E)-1- (Morpholino)-2-(thiomethyl)-2-phenylvinylphosphonate

The title compound 2 (C15H22NO4PS, Mr = 343.38) was prepared by the reaction of α-benzoylthioformmorpholine 1 with trimethyl phosphite. The crystal is of monoclinic, space group P21/c with a = 14.906(2), b = 8.4711(12), c = 13.343(2) ?, β = 96.761(4)o, Z = 4, V = 1673.1(5) ?3, Dc = 1.363 g/cm3, μ(MoKα) = 3.06 cm-1, F(000) = 728, the final R = 0.0590 and wR = 0.1740 for 3036 observed reflections (I > 2σ(I)). X-ray analysis revealed that the interatomic distance of C(5)–C(6) is 1.353(4) ?, indicating it is a normal C=C double bond. The P(1) atom takes a distorted tetrahedral geometry, and the morpholine ring adopts a chair conformation. The morpholino group is located at the 1-position of vinylphosphonate, and the phenyl and thiomethyl groups at the 2-position.

Syntheses and Crystal Structures of Two New Complexes Generated from 2-（（Pyridin-3-ylmethyl）thio）-5-（6-quinolinyl）-1,3,4-oxadiazole and Ag~Ⅰ Salts

Two new Ag~Ⅰ-complexes have been synthesized based on the semi-rigid ligand 2-（（pyridin-3-ylmethyl）thio）-5-（6-quinolinyl）-1,3,4-oxadiazole（L）,obtained by the condensation reaction of 5-（6-quinolinyl）-1,3,4-oxadiazole-2-thiol and 3-chloromethyl pyridine hydrochloride. Crystallization of L with Ag OTf and Ag PF_6 in a CH_2Cl_2/MeO H mixed solvent system at room temperature affords a novel supramolecular [Ag_2L_2（CF_3SO_3）_2]（I） and a coordination polymer [Ag L（PF_6）]_n（Ⅱ）,respectively. Two complexes were characterized by TGA,X-ray powder and single-crystal diffraction.