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Anthony K Cheetham

Publications and source records attributed to Anthony K Cheetham.

At least 19 recordsLinked to original sources
PubMed2007

Inorganic-organic framework structures; M(II) ethylenediphosphonates (M = Co, Ni, Mn) and a Mn(II) ethylenediphosphonato-phenanthroline.

The reaction of nickel, cobalt, and manganese with 1,2-ethylenediphosphonic acid or 1,2-ethylenediphosphonic acid and 1,10-phenanthroline under hydrothermal conditions resulted in the pillared layered structures Co2(H2O)2(O3PC2H4PO3) (I) and Ni2(H2O)2(O3PC2H4PO3) (II), which are isostructural to a zinc phase that has previously been characterized by X-ray powder methods. In addition, a 1D chain structure, Mn(HO3P(CH2)2PO3H)(H2O)2(C12H8N2) (III), and a pillared layered structure, Mn(HO3P(CH2)2PO3H) (IV), were obtained. The structures of these phases were solved by single-crystal X-ray diffraction methods. The crystallographic data are as follows: compound I P21/n (No. 14), a = 5.6500(11) A, b = 4.7800(10) A, c = 15.330(3) A, beta = 98.50(3) degrees, V = 409.47(14) A3, Z = 2; compound II P21/n (No. 14), a = 5.5807(11) A, b = 4.7205(9) A, c = 15.250(3) A, beta = 98.55(3) degrees, V = 397.28(13) A3, Z = 2; compound III C2/c (No. 15), a = 12.109(2) A, b = 15.328(3) A, c = 9.848(2) A, beta = 108.88(3) degrees, V = 1729.5(6) A3, Z = 4; compound IV P (No. 2), a = 5.498(5) A, b = 7.715(6) A, c = 8.093(7) A, alpha = 82.986(12) degrees, beta = 75.565(12) degrees, gamma = 80.582(12)degrees, V = 326.7(5) A3, Z = 2. Magnetic measurements show antiferromagnetic behavior below TN = 7 K for I and 13 K for II.

Journal Article↗
PubMed2006

Adsorption of molecular hydrogen on coordinatively unsaturated Ni(II) sites in a nanoporous hybrid material.

A porous hybrid inorganic/organic material, NaNi3(OH)(SIP)2 [SIP = 5-sulfoisophthalate][1], is shown to strongly bind molecular hydrogen at coordinatively unsaturated metal sites. A combination of H2 sorption isotherms, temperature programmed desorption, and inelastic neutron scattering spectroscopy show the existence of a considerable number of such strong binding sites in [1] along with other sites where hydrogen is more weakly physisorbed. The overall capacity for hydrogen of this material as well as the much stronger binding of hydrogen than in typical porous material represent an important step toward a possible utilization of porous media for hydrogen storage.

Adsorption↗
PubMed2006

Microwave synthesis of hybrid inorganic-organic porous materials: phase-selective and rapid crystallization.

Microwave synthesis of two porous nickel glutarates was compared with conventional hydrothermal synthesis. The cubic nickel glutarate, [Ni20(C5H6O4)20(H2O)8] x 40 H2O (1), was synthesized by conventional electrical heating in several hours or days, depending on synthesis temperature. Crystallization was greatly accelerated by microwave irradiation, in which more stable, tetragonal nickel glutarate, [Ni22(C5H6O4)20(OH)4(H2O)10] x 38 H2O (2), was formed within a few minutes, suggesting the efficiency of the microwave technique in the synthesis of porous hybrid materials. The cubic phase 1 is formed preferentially at low pH, low temperature, and especially under conventional electrical heating. In contrast, the tetragonal phase 2 is obtained favorably at high pH, high temperature, and especially with microwave irradiation. This work demonstrates that the microwave method provides not only the very fast synthesis of a hybrid material, but also the possibility to discover a new porous hybrid material not yet identified by conventional hydrothermal synthesis. The hydrothermal formation of metal-organic hybrid materials in a matter of minutes is an important step towards developing commercially viable routes for producing this valuable class of materials.

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PubMed2005

Pillared layered structures based upon M(III) ethylene diphosphonates: the synthesis and crystal structures of M(III)(H(2)O)(HO(3)P(CH(2))(2)PO(3)) (M = Fe, Al, Ga).

A three-dimensional iron(III) diphosphonate, Fe(III)(H(2)O)(HO(3)P(CH(2))(2)PO(3)), I, has been synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Pbca (no. 61) where a = 9.739(5) A, b = 9.498(5) A, c = 15.940(8) A, V = 1474.4(1) A(3), Z = 8, and R(1) = 0.0380. The structure consists of inorganic sheets pillared by the 1,2-ethylenediphosphonate groups. The sheets are composed of Fe(H(2)O)O(5) octahedra connected through PO(3)C tetrahedra. The corresponding isostructural aluminum (II) and gallium (III) compounds were also synthesized and indexed: II, a = 9.534(1) A, b = 9.255(2) A, c = 15.724(1) A, V = 1387.5(1) A(3); III, a = 9.670(1) A, b = 9.357(2) A, c = 15.862(4) A, V = 1435.4(1) A(3).

Aluminum↗
PubMed2005

Isomorphous substitution of transition-metal ions in the nanoporous nickel phosphate VSB-5.

The transition-metal-incorporated nickel phosphate molecular sieves (TMI-VSB-5) have been hydrothermally synthesized at 453 K in weak basic conditions under microwave irradiation. By means of X-ray diffraction, inductively coupled plasma (ICP), ultraviolet-visible (UV-vis) diffuse reflectance, and Mössbauer spectroscopies, successful isomorphous (at least partial) substitution of transition-metal ions in the VSB-5 framework has been verified. Characterization results show that the framework structure of nanoporous VSB-5 can accommodate a substantial level of isomorphous substitution of transition-metal ions up to about 10, 5, and 3 atom % for Fe, Mn, and V, respectively, in both octahedral nickel sites (Mn and Fe) and tetrahedral phosphorus sites (V). The isomorphous substitution including the replacement mechanism was studied by not only the change of unit cell parameters but also spectroscopic analysis. The unit cell parameters of TMI-VSB-5 including a unit cell volume and a-axis length relied on the ionic radii difference between the incorporated ion and the original framework ions such as Ni or P (RTMI - RNi or RTMI - RP).

Journal Article↗
PubMed2004

Alkalicyamelurates, M3[C6N7O3].xH2O, M = Li, Na, K, Rb, Cs: UV-luminescent and thermally very stable ionic tri-s-triazine derivatives.

Cyamelurates are salts of cyameluric acid, a derivative of tri-s-triazine (1,3,4,6,7,9-hexaazacyclo[3.3.3]azine or s-heptazine). These compounds are thermally very stable and possess interesting structural and optical properties. Only very few tri-s-triazine derivatives have been reported in the literature. The water-soluble alkali cyamelurates were extensively characterized using NMR, FTIR, Raman, UV, luminescence spectroscopy and elemental analysis. In addition, the single crystal X-ray structure analyses of the four hydrates of lithium, sodium, potassium and rubidium cyamelurates (Li(3)[C(6)N(7)O(3)].6H(2)O; Na(3)[C(6)N(7)O(3)].4.5H(2)O; K(3)[C(6)N(7)O(3)].3H(2)O; Rb(3)[C(6)N(7)O(3)].3H(2)O) are presented. Thermogravimetric analysis shows that the dehydrated salts start to decompose at temperatures above 500 degrees C. The thermal stability does not depend on the cations which is in contrast to the analogous s-triazine salts, i.e. the alkali cyanurates M(3)[C(3)N(3)O(3)]. The photoluminescence spectra indicate a very strong solid state UV-emission with maxima between 280 and 400 nm.

Journal Article↗
PubMed2004

Synchrotron X-ray powder diffraction and computational investigation of purely siliceous zeolite Y under pressure.

High-pressure synchrotron X-ray powder diffraction measurements of a sample of purely siliceous zeolite Y (faujasite) were carried out up to 8.0 GPa at room temperature using a diamond anvil cell. Measurements using silicone oil as the pressure-transmitting medium show compression of the zeolite followed by a loss of long-range ordering at 2.2 GPa. The experimentally determined bulk modulus, 38(2) GPa, is, within experimental error, identical to that of quartz. When using a methanol:ethanol:water mixture (16:3:1) as the pressure-transmitting medium, two distinct compressibility regions are observed with a dramatic change in the compression mechanism at 4 GPa. Rietveld refinement analysis of the powder patterns provides a detailed description of the underlying chemistry, with sequential pore filling the main response up to 4 GPa and framework distortions at higher pressures.

Journal Article↗
PubMed2004

Metal-oxygen-metal arrays in lamellar hybrid materials: cobalt and manganese 4-cyclohexene-1,2-dicarboxylates.

We have obtained three layered hybrid materials from the hydrothermal reaction of 4-cyclohexene-1,2-dicarboxylic acid with Co and Mn salts: Co(C(8)H(8)O(4))[1], Mn(H(2)O)(C(8)H(8)O(4))[2], and Mn(4)(H(2)O)(C(8)H(8)O(4))(4).0.3(H(2)O)[3]. The structures for all materials were solved by single-crystal XRD ([1]P1, a=4.805(2) A, b=6.650(3) A, c=12.960(6) A, alpha=98.285(7) degrees, beta=98.986(7) degrees, gamma=95.689(7) degrees, V= 401.6(3) A(3), R(1)= 0.0438; [2] P2(1)/c, a=11.151(2) A, b=11.330(2) A, c=7.6560(15) A, beta=108.813(3) degrees , V=915.6(3) A(3), R(1)=0.0412; [3] P1, a= 11.412(3) A, b=12.136(4) A, c=13.809(4) A, alpha=104.703(6) degrees, beta=103.207(6) degrees, gamma=92.468(5) degrees, V=1790.6(9) A(3), R(1)=0.1056). While all three structures are two-dimensional overall, the metal-oxygen-metal dimensionality within the layers varies from isolated metal atoms in the case of [1] to 1D ribbons of vertex sharing MnO(6) octahedra [2] and 2D arrays of edge- and vertex-sharing polyhedra in [3].

Journal Article↗
PubMed2003

Synthesis and characterization of two polymorphic crystalline phases and an amorphous powder of nickel(II) bisimidazolate.

Nickel(II) bisimidazolate is polymorphic. Depending on the synthetic strategy adopted, two crystalline phases (alpha- and beta-Ni(im)(2)) or an amorphous material of the same composition can be prepared. The thermodynamically stable alpha-Ni(im)(2) phase, which can be prepared in water at elevated temperatures, contains a two-dimensional polymer (of nearly square meshes) with square-planar NiN(4) chromophores and exo-bidentate imidazolate ligands bridging nickel atoms that are ca. 5.73 A apart. The beta-Ni(im)(2) phase can be kinetically stabilized at lower temperatures, but the structural complexity and the lack of single crystals prevented its full structural characterization, even in the presence of an indexed powder diffraction pattern. The spectroscopic features of these crystalline phases are compared with those of the amorphous material.

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PubMed2003

Phase separation in metal oxides.

A fascinating phenomenon, recently found to occur in certain transition-metal oxides, is phase separation wherein pure, nominally monophasic oxides of transition metals with well-defined compositions separate into two or more phases over a specific temperature range. Such phase separation is entirely reversible, and is generally the result of a competition between charge-localization and -delocalization, the two situations being associated with contrasting electronic and magnetic properties. Coexistence of more than one phase, therefore, gives rise to electronic inhomogeneity and a diverse variety of magnetic, transport, and other properties, not normally expected of the nominal monophasic composition. An interesting feature of phase separation is that it covers a wide range of length scales anywhere between 1-200 nm. While cuprates and manganates, especially the latter, provide excellent examples of phase separation, it is possible that many other transition-metal compounds with extended structures will be found to exhibit phase separation.

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PubMed2003

Hydrogen adsorption in nanoporous nickel(II) phosphates.

Hydrogen sorption in the nanoporous nickel phosphates VSB-1 and VSB-5 has been studied with a combination of BET, temperature programmed desorption (TPD), and inelastic neutron scattering (INS) measurements. H(2) BET isotherms for VSB-1 are similar to those seen in nanoporous zeolites, while VSB-5 adsorbs substantially more hydrogen due to a steep initial uptake at low partial pressures. TPD data show that hydrogen interacts strongly with VSB-5, with desorption peaks at 109 and 149 K in a nitrogen flow, whereas the absence of similar peaks for VSB-1 suggests a weaker interaction. INS spectra of the rotational tunnel transition of the adsorbed H(2) also reveal a strong interaction with the VSB-5 host. These data strongly suggest the existence of coordinatively unsaturated Ni(2+) sites accessible to H(2) molecules in the pores of VSB-5.

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PubMed2002

Incommensurate modulation in the microporous silica SSZ-24.

A detailed investigation of the structure of microporous silica, SSZ-24, is presented. It is shown by X-ray powder diffraction and (29)Si MAS NMR experiments that the structure deviates from the previously proposed AlPO(4)-5-type structure. At room temperature, electron diffraction (ED) patterns exhibit extra diffraction spots, which can be attributed to an incommensurate structural modulation along the c axis. This in turn results in a pleat pattern in real space with two different intervals arranged aperiodically along the c axis, as observed with high-resolution electron microscopy (HREM). The modulated structure may easily turn into a disordered one through excessive electron irradiation or heat-treatment. In order to understand the origin of the modulation, soft phonon-modes of the ideal premodulated structure were analyzed by the use of the rigid-unit-mode model. The distribution of soft modes in reciprocal space might correspond roughly to diffuse streaks that could be observed in the diffraction patterns at higher temperatures. It was found that several phonon branches soften at specific wave vectors, which are incommensurate with respect to the original period and might be responsible for the modulation. We present a simple analytic treatment to deduce the wave vectors and associated displacement eigenvectors for the incommensurate soft-modes.

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