Two New Adamite-Type Phases, CO2(OH)PO4 and Zn2(OH)PO4: Structure-Directing Effect of Organic Additives

doi:10.1006/jssc.1995.1022

Journal of Solid State Chemistry

Volume 114, Issue 1, January 1995, Pages 151-158

https://doi.org/10.1006/jssc.1995.1022 Get rights and content

Abstract

The hydrothermal syntheses, X-ray single crystal structures, and certain properties of cobalt hydroxyphosphate, Co₂(OH)PO₄, and zinc hydroxyphosphate, Zn₂(OH)PO₄, are described. Both materials are isomorphous with the adamite-type M₂ (OH)XO₄ structure, and consist of a condensed vertex- and edge-sharing network of MO₅, distorted M O₆(M = Co, Zn), and PO₄ subunits. Both snythetic procedures required the presence of organic reagents which are not incorporated into the crystalline reaction products. Crystal data: Co₂(OH)PO₄, M_r = 229.84, orthorhombic, space group Pnnm (No. 58), a = 8.042(3) Å, b = 8.369(2) Å, c = 5.940(2) Å, V = 399.80 Å³, Z = 4, R = 2.40%, and R_w = 2.71% (589 observed reflections with I > 3 σ(I)). Zn₂(OH)PO₄, M_r = 242.74, orthorhombic, space group Pnnm (No. 58), a = 8.103(2), Å, b = 8.3292(9) Å, c = 5.9659(8) Å, V = 402.65 Å, Z = 4, R = 3.58%, and R_w = 3.90% (708 data with I > 3σ(I)).

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The MWHT process by Jähne [200] delivered micrometer-sized (∼10 μm) crystals with an octahedra-like morphology, whereas the MWST process by Kreder [163] in a tetraethylene glycol (TTEG) solvent produced nanorods (∼200 nm × 1 μm), demonstrating that the product morphology is influenced by the synthesis conditions. The formation of Pna21-LiCoPO4 in the MWHT process [200] was found to compete with Pnma-LiCoPO4 [222], Co2(OH)PO4 [224], and Li3PO4 [225], the key parameters being the synthesis temperature, pH value, and precursor concentration [200]. As a result, the synthesis parameter region where pure Pna21-LiCoPO4 can be obtained was found to be rather small, the optimum being reached at T = 220 °C, pH = 9.0, and c(Co2+) = 0.04 mol/L.
This review summarizes the development, investigation, and optimization of polymorphic lithium cobalt phosphate LiCoPO₄. One of the three polymorphs known to date, olivine-type or Pnma-LiCoPO₄, shows intriguing electrochemical properties as a high-voltage cathode material, which are of interest for next-generation lithium-ion batteries with higher energy density. Hence, scientists have developed optimization strategies to improve its performance for commercial applications. Herein, a number of procedures for the synthesis of Pnma-LiCoPO₄ is presented, including thermodynamic as well as kinetically controlled approaches. The continuous improvement of its electrochemical performance is illustrated, which was realized by the development of solvothermal techniques that allow a precise particle size and morphology control. In the course of these investigations, two new polymorphs, Pna2₁-LiCoPO₄ and Cmcm-LiCoPO₄, have been discovered which show different physical and structural properties compared to Pnma-LiCoPO₄. Despite their significantly poorer electrochemical performance, these polymorphs allow interesting insights into the variable structure chemistry of transition-metal phosphates, which canalizes in intriguing magnetic and thermal properties. The similarities and differences in the chemical and physical properties of Pnma-LiCoPO₄, Pna2₁-LiCoPO₄, and Cmcm-LiCoPO₄ are discussed.
Solid state coordination chemistry of metal-azolate compounds: Structural consequences of incorporation of phosphate components in the Co(II)/4-pyridyltetrazolate/phosphate system
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Furthermore, the trinuclear {M3(μ3-Ophospahte)} core of complex 1 is a new variant of a common structural motif seen in similar systems with cobalt and other transition metals. These {M3(μ3-OH)} and {M3(μ3-O)} cores have been described for systems with azolate N,N′-bridging ligand types with examples including: {Cu(II)3}, {V(IV)3}, {Cr(III)3}, {Co(II)3)}, {Fe(III)3}, {Ni(III)3} and {Cr(III)2Fe(III)} [82–88] and entries of Table 3 [55,59,63,67,89–94]. A variety of additional potentially bridging coligands such as capping sulfato- or phosphato-groups may be accommodated, as shown in Fig. 3, which provide spatial expansion to generate extended architectures.
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Heat capacity and neutron diffraction studies on the frustrated magnetic Co <inf>2</inf>(OH)(PO <inf>4</inf>) <inf>1-x</inf>(AsO <inf>4</inf>) <inf>x</inf> [0≤x≤1] solid solution
2012, Journal of Solid State Chemistry
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The diffraction patterns were collected every 2 K and 25 min in the angular range 10≤2θ≤90. The Rietveld method [38] was used to refine the nuclear and magnetic structures. All the patterns were analyzed using the FULLPROF program suite [35].
The Co₂(OH)(PO₄)_1−x(AsO₄)_x [0≤x≤1] solid solution exhibits a complex magnetic behaviour due to the bond-frustration in its magnetic structure. Heat capacity measurements of the (x=0.1–0.5) phases show a three-dimensional magnetic ordering (λ anomaly) that shifts to lower temperatures and becomes broader as the AsO₄³⁻ content increases. For x=0.75, no significant feature was observed whereas for higher arsenate ion content, x=0.9 and 1, a small maximum was detected. The magnetic structures of solid solution are consistent with the existence of predominant antiferromagnetic superexchange interactions through the |OH| and |XO₄| (X=P and As) groups between the Co⁺² ions. The substitution of PO₄³⁻ by AsO₄³⁻ anions by more than 90% substantially modifies the magnetic exchange pathways in the solid solution, leading to an incommensurate antiferromagnetic structure in Co₂(OH)(PO₄)_1−x(AsO₄)_x [x=0.9 and 1] phases.
Magnetostructural correlations in the antiferromagnetic Co<inf>2-x</inf> Cu<inf>x</inf>(OH)AsO<inf>4</inf> (x=0 and 0.3) phases
2011, Journal of Solid State Chemistry
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At temperatures above 700 °C additional weight losses were not observed on the thermogravimetric curve. These results are in good agreement with those obtained for other hydroxi-phosphate and arsenate related compounds [23,25,30]. Spectroscopic measurements of Co2−x Cux(OH)AsO4 (x=0 and 0.3) were studied by both infrared and diffuse reflectance data.
The Co_2−xCu_x(OH)AsO₄ (x=0 and 0.3) compounds have been synthesized under mild hydrothermal conditions and characterized by X-ray single-crystal diffraction and spectroscopic data. The hydroxi-arsenate phases crystallize in the Pnnm orthorhombic space group with Z=4 and the unit-cell parameters are a=8.277(2) Å, b=8.559(2) Å, c=6.039(1) Å and a=8.316(1) Å, b=8.523(2) Å, c=6.047(1) Å for x=0 and 0.3, respectively. The crystal structure consists of a three-dimensional framework in which M(1)O₅-trigonal bipyramid dimers and M(2)O₆-octahedral chains (M=Co and Cu) are present. Co₂(OH)AsO₄ shows an anomalous three-dimensional antiferromagnetic ordering influenced by the magnetic field below 21 K within the presence of a ferromagnetic component below the ordering temperature. When Co²⁺ is partially substituted by Cu²⁺ions, Co_1.7Cu_0.3(OH)AsO₄, the ferromagnetic component observed in Co₂(OH)AsO₄ disappears and the antiferromagnetic order is maintained in the entire temperature range. Heat capacity measurements show an unusual magnetic field dependence of the antiferromagnetic transitions. This λ-type anomaly associated to the three-dimensional antiferromagnetic ordering grows with the magnetic field and becomes better defined as observed in the non-substituted phase. These results are attributed to the presence of the unpaired electron in the dx²−y² orbital and the absence of overlap between neighbour ions.
Synthesis and characterization of a new organically templated zincophosphate: (C<inf>2</inf>N<inf>2</inf>H<inf>10</inf>)<inf>2</inf>[Zn(PO<inf>4</inf>)<inf>2</inf>]
2008, Journal of Alloys and Compounds
A new open-framework zincophosphate, (C₂N₂H₁₀)₂[Zn(PO₄)₂], has been synthesized hydrothermally from a mixture of zinc chloride, phosphoric acid, ethylenediamine and deionized water. It has the following crystal data: orthorhombic space group Pccn, a = 17.056(3) Å, b = 8.4219(17) Å, c = 8.7260(18) Å, V = 1253.4(4) Å³, Z = 4. The crystal structure of the title compound is characterized by corner-sharing PO₄ and ZnO₄ tetrahedra, leading to infinite corner-shared four-membered ring chains. There is extensive Zn–O–P bonding in the structure in the form of infinite chains. The structure is stabilized by template-to-framework hydrogen bonding. The title compound was also characterized by IR spectroscopy and TG–DTA. Luminescent measurement of (C₂N₂H₁₀)₂[Zn(PO₄)₂] shows an emission band between 665 nm and 688 nm when excited with 451 nm UV light.
Hydrothermal synthesis and structure of an open framework Co<inf>0.7</inf>Zn<inf>1.3</inf>(PO<inf>4</inf>)<inf>2</inf> (NH<inf>3</inf>-CH<inf>2</inf>CH<inf>2</inf>NH<inf>3</inf>) and Co<inf>6.2</inf>(OH)<inf>4</inf>(PO<inf>4</inf>)<inf>4</inf>Zn <inf>1.80</inf>, a new adamite type phase
2007, Inorganica Chimica Acta
The hydrothermal reaction of cobalt(II)oxalate di-hydrate, zinc oxide, and triethyl-orthophosphate, using 1,2-diaminoethane as structure directing template in water, produced two major crystal phases in almost equal amount: the purple crystals of [NH₃–CH₂CH₂NH₃][Co_0.7Zn_1.3(PO₄)₂] (1) and the red burgundy crystals of Co_6.2(OH)₄(PO₄)₄Zn_1.80 (2), a new adamite type phase. The structure of [NH₃–CH₂CH₂NH₃] [Co_0.7Zn_1.3(PO₄)₂] (1) exhibits a 3D open framework built from PO₄ and (Co/Zn)O₄ tetrahedra, and (Co/Zn)O₅ trigonal bipyramids, forming two major channels, an 8-membered ring channel and a 16-membered ring channel, that host the ethanediammonium ions. The Co_6.2(OH)₄(PO₄)₄Zn_1.80 (2) is isomorphous with adamite-type M₂(OH)XO₄ structure, with a condensed vertex and edge sharing network of (Co/Zn)O₅, and distorted CoO₆, and PO₄ subunits. The cobalt preference for higher coordination numbers is displayed in this structure, where the octahedral sites are wholly occupied by cobalt. Thermal analysis confirmed that these compounds display high thermal stability.

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Regular ArticleTwo New Adamite-Type Phases, CO2(OH)PO4 and Zn2(OH)PO4: Structure-Directing Effect of Organic Additives

Abstract

Regular Article
Two New Adamite-Type Phases, CO₂(OH)PO₄ and Zn₂(OH)PO₄: Structure-Directing Effect of Organic Additives