排序方式: 共有19条查询结果,搜索用时 15 毫秒
1.
I. G. Filippova Yu. A. Simonov M. Gdanets V. Stavila 《Journal of Structural Chemistry》2005,46(6):1095-1098
The structure of tris(1,10-phenanthroline)iron(II) dinitrate dihydrate [Fe(phen)3](NO3)2·2H2O was established by X-ray diffraction analysis. The role of hydrogen bonds in crystal packing is discussed. 相似文献
2.
Stavila V. Gulya A. Shova S. Gdanec M. Simonov Yu. A. 《Russian Journal of Coordination Chemistry》2002,28(8):565-572
Compounds of the [Co(DH)2A2](BiEdta) · 6H2O type (where DH is the monodeprotonated dimethylglyoxime –ON=C(CH3)–(CH3)C=NOH; A is the o-, m-, or p-toluidine; and Edta is the ethylenediaminetetraacetate(4–) ion) were synthesized and studied. The composition and structures of the complexes were determined from their UV and 1H NMR spectra and from X-ray diffraction data. The isomer [Co(DH)2(o-NH2C6H4CH3)2]2[Bi2(μ-Edta)2(H2O)2] · 10H2O was structurally characterized using X-ray diffraction analysis. The crystals are triclinic: a = 12.153(2) Å, b = 12.824(3) Å, c = 16.215(3) Å, α = 67.73(3)°, β = 86.18(3)°, γ = 66.96(3)°, space group P $\overline 1$ , ρ(calcd) = 1.719 g/cm3, Z = 4. The structure is composed of complex binuclear [Bi2(μ-Edta)2(H2O)2]2– anions, [Co(DH)2(o-NH2C6H4CH3)2]+ cations, and molecules of crystallization water. The Edta4– anion chelates with the Bi atom in a hexadentate manner (N2O4); the fifth O atom functions as a bridging ligand. The bismuth coordination polyhedron can be regarded as a strongly distorted antiprism. In the octahedral cation, the Co(III) atom coordinates four N atoms of two DH ligands (average Co–N 1.897 Å) and two N atoms of two o-toluidine molecules (Co–N 2.023 Å). Thermolysis of the complexes studied was found to proceed in several successive steps, namely, the deaquation, deamination, and pyrolysis of the ligands. 相似文献
3.
Petrenko P. A. Gdaniec M. Simonov Yu. A. Stavila V. G. Gulea A. P. 《Russian Journal of Coordination Chemistry》2004,30(11):813-817
A Ni(II) complex of the composition Ni(HNta) · 4H2O (I) was synthesized. Its structure was found to consist of neutral mononuclear [Ni(HNta)(H2O)3] complexes and crystallization water molecules. The Ni atom has octahedral surrounding and is coordinated to tridentate-chelate HNta2– ligand through the N atom and O atoms of two deprotonated acetate groups and through the O atoms of three water molecules. The structure of I was compared with those of the Zn(HNta) · 4H2O and Co(HNta) · 4H2O complexes isostructural to I. Thermogravimetric method showed that the decomposition of compound I occurs through several successive stages of dehydration, deaquation, decarboxylation, and the formation of inorganic residue. 相似文献
4.
Ruven L. Davidovich Vitalie Stavila Kenton H. Whitmire 《Coordination chemistry reviews》2010,254(17-18):2193-2226
The stereochemistry of lead(II) complexes with S- and Se-donor atom ligands, including mixed ligand complexes is reviewed with respect to the geometry of the first coordination sphere of the Pb(II) atom in these compounds and rationalized in terms of the valence shell electron-pair repulsion (VSEPR) model. The most comprehensively structurally characterized classes of lead(II) thio and seleno complexes are discussed, including monothio-, dithio(seleno)-, trithio- and tetrathio-complexes, as well as Pb(II) dialkyldithio(seleno)carbamates, alkylxanthates and dialkyl(aryl) phosphorodithio(seleno)lates. Data about the polyhedral shape of the primary coordination sphere, coordination number (CN), bond lengths (primary and secondary) and bond angles of the Pb(II) atom in the compounds under investigation are systematized in comprehensive tables. The particularities of the stereochemistry of Pb(II) complexes with S(Se)-donor atom ligands are comparatively discussed with the stereochemistry of lead(II) complexes with oxygen donor ligands. 相似文献
5.
Vitalie Stavila Jae-Hyuk Her Wei Zhou Son-Jong Hwang Leigh Anna M. Ottley 《Journal of solid state chemistry》2010,183(5):1133-1140
Calcium borohydride can reversibly store up to 9.6 wt% hydrogen; however, the material displays poor cyclability, generally associated with the formation of stable intermediate species. In an effort to understand the role of such intermediates on the hydrogen storage properties of Ca(BH4)2, calcium dodecahydro-closo-dodecaborate was isolated and characterized by diffraction and spectroscopic techniques. The crystal structure of CaB12H12 was determined from powder XRD data and confirmed by DFT and neutron vibrational spectroscopy studies. Attempts to dehydrogenate/hydrogenate mixtures of CaB12H12 and CaH2 were made under conditions known to favor partial reversibility in calcium borohydride. However, up to 670 K no notable formation of Ca(BH4)2 (during hydrogenation) or CaB6 (during dehydrogenation) occurred. It was demonstrated that the stability of CaB12H12 can be significantly altered using CaH2 as a destabilizing agent to favor the hydrogen release. 相似文献
6.
Verdal N Udovic TJ Rush JJ Stavila V Wu H Zhou W Jenkins T 《The Journal of chemical physics》2011,135(9):094501
Low-temperature neutron scattering spectra of diammonium dodecahydro-closo-dodecaborate [(NH(4))(2)B(12)H(12)] reveal two NH(4)(+) rotational tunneling peaks (e.g., 18.5 μeV and 37 μeV at 4 K), consistent with the tetrahedral symmetry and environment of the cations. The tunneling peaks persist between 4 K and 40 K. An estimate was made for the tunnel splitting of the first NH(4)(+) librational state from a fit of the observed ground-state tunnel splitting as a function of temperature. At temperatures of 50 K-70 K, classical neutron quasi-elastic scattering appears to dominate the spectra and is attributed to NH(4)(+) cation jump reorientation about the four C(3) axes defined by the N-H bonds. A reorientational activation energy of 8.1 ± 0.6 meV (0.79 ± 0.06 kJ/mol) is determined from the behavior of the quasi-elastic linewidths in this temperature regime. This activation energy is in accord with a change in NH(4)(+) dynamical behavior above 70 K. A low-temperature inelastic neutron scattering feature at 7.8 meV is assigned to a NH(4)(+) librational mode. At increased temperatures, this feature drops in intensity, having shifted entirely to higher energies by 200 K, suggesting the onset of quasi-free NH(4)(+) rotation. This is consistent with neutron-diffraction-based model refinements, which derive very large thermal ellipsoids for the ammonium-ion hydrogen atoms at room temperature in the direction of reorientation. 相似文献
7.
Vitalie Stavila Ion Bulimestru Aurelian Gulea Adam C. Colson Kenton H. Whitmire 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(3):m65-m68
The title complexes, hexaaquacobalt(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Co(H2O)6][Bi2(C7H4NO4)4]·2H2O, (I), and hexaaquanickel(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Ni(H2O)6][Bi2(C7H4NO4)4]·2H2O, (II), are isomorphous and crystallize in the triclinic space group P. The transition metal ions are located on the inversion centre and adopt slightly distorted MO6 (M = Co or Ni) octahedral geometries. Two [Bi(pydc)2]− units (pydc is pyridine‐2,6‐dicarboxylate) are linked via bridging carboxylate groups into centrosymmetric [Bi2(pydc)4]2− dianions. The crystal packing reveals that the [M(H2O)6]2+ cations, [Bi2(pydc)4]2− anions and solvent water molecules form multiple hydrogen bonds to generate a supramolecular three‐dimensional network. The formation of secondary Bi...O bonds between adjacent [Bi2(pydc)4]2− dimers provides an additional supramolecular synthon that directs and facilitates the crystal packing of both (I) and (II). 相似文献
8.
Dr. Katherine E. Hurst Prof. Thomas Gennett Jesse Adams Dr. Mark D. Allendorf Dr. Rafael Balderas-Xicohténcatl Dr. Marek Bielewski Dr. Bryce Edwards Dr. L. Espinal Prof. Brent Fultz Dr. Michael Hirscher Dr. M. Sterlin L. Hudson Dr. Zeric Hulvey Dr. Michel Latroche Dr. Di-Jia Liu Dr. Matthew Kapelewski Dr. Emilio Napolitano Dr. Zachary T. Perry Dr. Justin Purewal Dr. Vitalie Stavila Mike Veenstra Dr. James L. White Yuping Yuan Prof. Hong-Cai Zhou Dr. Claudia Zlotea Philip Parilla 《Chemphyschem》2019,20(15):1997-2009
In order to determine a material's hydrogen storage potential, capacity measurements must be robust, reproducible, and accurate. Commonly, research reports focus on the gravimetric capacity, and often times the volumetric capacity is not reported. Determining volumetric capacities is not as straight-forward, especially for amorphous materials. This is the first study to compare measurement reproducibility across laboratories for excess and total volumetric hydrogen sorption capacities based on the packing volume. The use of consistent measurement protocols, common analysis, and figure of merits for reporting data in this study, enable the comparison of the results for two different materials. Importantly, the results show good agreement for excess gravimetric capacities amongst the laboratories. Irreproducibility for excess and total volumetric capacities is attributed to real differences in the measured packing volume of the material. 相似文献
9.
Klein MP Jacobs BW Ong MD Fares SJ Robinson DB Stavila V Wagner GJ Arslan I 《Journal of the American Chemical Society》2011,133(24):9144-9147
A well characterized and predictable aging pattern is necessary for practical energy storage applications of nanoporous particles that facilitate rapid transport of ions or redox species. Here we use STEM tomography with segmentation to show that surface diffusion and grain boundary diffusion are responsible for pore evolution at intermediate and higher temperatures, respectively. This unprecedented three dimensional understanding of pore behavior as a function of temperature suggests routes for optimizing pore stability in future energy storage materials. 相似文献
10.
Bhakta RK Maharrey S Stavila V Highley A Alam T Majzoub E Allendorf M 《Physical chemistry chemical physics : PCCP》2012,14(22):8160-8169
Reactive nanoparticles are of great interest for applications ranging from catalysis to energy storage. However, efforts to relate cluster size to thermodynamic stability and chemical reactivity are hampered by broad pore size distributions and poorly characterized chemical environments in many microporous templates. Metal hydrides are an important example of this problem. Theoretical calculations suggest that reducing their critical dimension to the nanoscale can in some cases considerably destabilize these materials and there is clear experimental evidence for accelerated kinetics, making hydrogen storage applications more attractive in some cases. However, quantitative measurements establishing the influence of size on thermodynamics are lacking, primarily because carbon aerogels often used as supports provide inadequate control over size and pore chemistry. Here, we employ the nanoporous metal-organic framework (MOF) Cu-BTC (also known as HKUST-1) as a template to synthesize and confine the complex hydride NaAlH(4). The well-defined crystalline structure and monodisperse pore dimensions of this MOF allow detailed, quantitative probing of the thermodynamics and kinetics of H(2) desorption from 1-nm NaAlH(4) clusters (NaAlH(4)@Cu-BTC) without the ambiguity associated with amorphous templates. Hydrogen evolution rates were measured as a function of time and temperature using the Simultaneous Thermogravimetric Modulated Beam Mass Spectrometry method, in which sample mass changes are correlated with a complete analysis of evolved gases. NaAlH(4)@Cu-BTC undergoes a single-step dehydrogenation reaction in which the Na(3)AlH(6) intermediate formed during decomposition of the bulk hydride is not observed. Comparison of the thermodynamically controlled quasi-equilibrium reaction pathways in the bulk and nanoscale materials shows that the nanoclusters are slightly stabilized by confinement, having an H(2) desorption enthalpy that is 7 kJ (mol H(2))(-1) higher than the bulk material. In addition, the activation energy for desorption is only 53 kJ (mol H(2))(-1), more than 60 kJ (mol H(2))(-1) lower than the bulk. When combined with first-principles calculations of cluster thermodynamics, these data suggest that although interactions with the pore walls play a role in stabilizing these particles, size exerts the greater influence on the thermodynamics and reaction rates. 相似文献