On the luminescence of manganese(II) phosphates

doi:10.1016/0022-2313(84)90018-8

Journal of Luminescence

Volume 29, Issue 2, March–April 1984, Pages 199-204

https://doi.org/10.1016/0022-2313(84)90018-8 Get rights and content

Abstract

Luminescent properties of manganese(II) phosphates prepared by thermal dehydration of Mn(H₂PO₄)₂·2H₂O have been studied. The emission spectrum consists of two bands whose relative intensity and spectral position depend on the chemical and crystalline structure of phosphates. The different courses of temperature quenching of luminescence intensity and excitation spectra of each emission band of Mn(H₂PO₄)₂·2H₂O, Mn(H₂PO₄)₂, MnH₂P₂O₇ and c-Mn₂P₄O₁₂ are discussed.

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A single-phase white-emitting phosphor BaMg₂(PO₄)₂:Eu²⁺, Mn²⁺, Tb³⁺ is synthesized by a high temperature solid-state reaction. The luminescent properties and the efficient energy transfer from Eu²⁺ to Mn²⁺ and Tb³⁺ in BaMg₂(PO₄)₂ are investigated. The chromaticity coordinates of BaMg₂(PO₄)₂:Eu²⁺, Mn²⁺, Tb³⁺ can be tuned from (0.153, 0.056) (for BaMg₂(PO₄)₂:Eu²⁺) to (0.666, 0.261) (for BaMg₂(PO₄)₂:Mn²⁺), and eventually to (0.313, 0.562) (for BaMg₂(PO₄)₂:Tb³⁺) by the effective resonance type energy transfer. The warm white light can be realized with the superior chromaticity coordinates of (0.346, 0.299) and low correlated color temperature (CCT = 4464 K) by coupling the emission bands peaking at 447, 544 and 663 nm attributed to the contribution from Eu²⁺, Tb³⁺ and Mn²⁺, respectively.
Crystal structure, vibrational spectra and thermal analysis of a new centrosymmetric transition metal phosphate compound, Mn(H<inf>2</inf>PO <inf>4</inf>)<inf>2</inf>ṡ4H<inf>2</inf>O
2013, Journal of Molecular Structure
Citation Excerpt :
Among them, the tetrametaphosphates of general formula c-Mn2P4O12 can be prepared by thermal dehydration of dihydrogenphosphate of bivalent transition metal [14]. The cyclo-tetraphosphate have been tested by Trojan and Brandova [14] as microadditives to fertilizers with long-term action, and some of them have been used as special thermostable inorganic pigments: luminescent [9,15], anticorrosive [16,17] and coloured [18,19]. In this context, a great number of water containing manganese phosphate materials has been previously synthesized and studied [14,20–33].
The crystal of Manganese(II) bis(aqua) bis(dihydrogen phosphate) dihydrate, Mn(H₂O)₂(H₂PO₄)₂⋅2H₂O (Mn(H₂PO₄)₂⋅4H₂O), was obtained for the first time. Its structure was solved by the X-ray method at room temperature. The crystal belong to the $P \bar{1}$ space group of the triclinic system (a = 7.788(3) Å, b = 7.881(3) Å, c = 9.322(4) Å, α = 66.90(4)°, β = 84.75(2)°, γ = 72.71(3)°, V = 502.3(3) Å³ and Z = 2). The structure is composed of Mn(O)₄(Ow)₂ octahedra and $H_{2} {PO}_{4}^{2 -}$ tetrahedra, located at C₁ sites and forming octahedral-tetrahedral infinite chains which are linked by the oxygen atoms to layers and further to a three-dimensional framework. The proposed hydrogen-bonding scheme provides further linkage within the chains. IR, Raman, TGA and DSC results were interpreted on the basis of the formula of the title compound and its crystal structure.
Flower-like microparticles and novel superparamagnetic properties of new binary Co<inf>1/2</inf>Fe<inf>1/2</inf>(H<inf>2</inf>PO<inf>4</inf>) <inf>2</inf>·2H<inf>2</inf> O obtained by a rapid solid state route at ambient temperature
2009, Materials Research Bulletin
A new binary Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O was synthesized by a simple, rapid and cost-effective method using CoCO₃–Fe(c)–H₃PO₄ system at ambient temperature. Thermal treatment of the obtained Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O at 600 °C yielded as a binary cobalt iron cyclotetraphosphate CoFeP₄O₁₂. The FTIR and XRD results of the synthesized Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O and its final decomposed product CoFeP₄O₁₂ indicate the monoclinic phases with space group P2₁/n and C2/c, respectively. The particle morphologies of both binary metal compounds appear the flower-like microparticle shapes. Room temperature magnetization results show novel superparamagnetic behaviors of the Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O and its final decomposed product CoFeP₄O₁₂, having no hysteresis loops in the range of ±10,000 Oe with the specific magnetization values of 0.045 and 12.502 emu/g at 10 kOe, respectively. The dominant physical properties of the obtained binary metal compounds (Co_1/2Fe_1/2(H₂PO₄)₂·2H₂O and CoFeP₄O₁₂) are compared with the single compounds (M(H₂PO₄)₂·2H₂O and M₂P₄O₁₂; where M = Co, Fe), indicating the presence of Co ions in substitution position of Fe ions.
Synthesis of cyclo-tetraphosphates Ni<inf>2-x</inf>Mg<inf>x</inf>P<inf>4</inf>O<inf>12</inf>
1991, Materials Research Bulletin
The tetrametaphosphates of the type Ni_2−xMg_xP₄O₁₂, where x=0 to 2, have been synthesized as new binary compounds, and their existence has been proved. The synthesis is based on a thermal procedure making use of the reversible transformation of tetrametaphosphates to higher linear phosphates. Temperatures of formation of these products have been determined (i.e formation by thermal recrystallization from higher linear phosphates) which decrease with increasing magnesium content, x. The structure of the binary tetrametaphosphates belongs to the monoclinic system (over the whole range of x); the structural parameters determined slowly increase with increasing magnesium content. With respect to the proposed application of these products as inorganic pigments, the following properties have been determined experimentally: density, thermal stability and colour.
A study of the thermal preparation of c-Cd<inf>4/3</inf>Ca<inf>2/3</inf>P<inf>4</inf>O<inf>12</inf>
1990, Thermochimica Acta
The possibility of preparing binary cadmium-calcium cyclotetraphosphate (tetrametaphosphate) by means of thermal dehydration of the appropriate binary dihydrogen phosphate has been studied. The possible formation of this condensation product from the cadmium ions that are often present in the starting phosphoric compound used in the technological preparation of binary calcium cyclotetraphosphates (serving as new special pigments) would represent an important, hygienic method of binding them to an insoluble, less harmful cadmium compound. The maximum proportion of calcium in the binary product, as found by the authors of this paper, amounts to half of the cadmium constituent (in molar terms). That is why Cd_2/3Ca_1/3(H₂PO₄)₂·2H₂O was used as the starting material. Its dehydration was observed mainly by thermal analytical methods under quasi-isothermal-isobaric conditions. Isothermal calcination of the initial binary dihydrogenphosphate was carried out in an electric oven at various temperatures. The reaction products obtained were analysed by chromatography, IR spectroscopy, X-ray diffraction analysis, electron microscopy and AAS. The compositions of the calcinates were determined through extraction with solutions of inorganic compounds and with organic reagents.
A study of the reactions during formation of c-Ni<inf>2</inf>P<inf>4</inf>O<inf>12</inf>
1990, Thermochimica Acta
The reaction course of the calcination of Ni(H₂PO₄)₂-2H₂O to give nickel cyclo-tetraphosphate has been studied by thermogravimetry under quasi-isothermal-isobaric conditions. Isothermal calcination was also carried out in an electric furnace at various temperatures for 20 min. The reaction products were analysed by chromatography, IR and NMR spectroscopy and X-ray diffraction. The compositions of the calcinates were determined through extraction with various inorganic and organic solvents. It was found that the water-vapour pressure has a great influence on the course of these condensation reactions, as well as on the temperature and velocity of the reactions, and on their results. Depending on the vapour pressure, there is a partial splitting of the first condensation product, the dihydrogendiphosphate.

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Journal of Luminescence

Abstract

References (14)

Solid State Commun.

Some aspects of the luminescence of solids

J. Electrochem. Soc.

J. Chem. Soc. London

Izv. AN SSSR, Neorg. mater.

Sb. Věd. Pr., Vys. Sk. Chemickotechnol. Pardubice

Luminescence cristalline

Cited by (31)

A single-phased warm white-light-emitting phosphor BaMg<inf>2</inf>(PO <inf>4</inf>)<inf>2</inf>:Eu<sup>2+</sup>, Mn<sup>2+</sup>, Tb<sup>3+</sup> for white light emitting diodes

Crystal structure, vibrational spectra and thermal analysis of a new centrosymmetric transition metal phosphate compound, Mn(H<inf>2</inf>PO <inf>4</inf>)<inf>2</inf>ṡ4H<inf>2</inf>O

Flower-like microparticles and novel superparamagnetic properties of new binary Co<inf>1/2</inf>Fe<inf>1/2</inf>(H<inf>2</inf>PO<inf>4</inf>) <inf>2</inf>·2H<inf>2</inf> O obtained by a rapid solid state route at ambient temperature

Synthesis of cyclo-tetraphosphates Ni<inf>2-x</inf>Mg<inf>x</inf>P<inf>4</inf>O<inf>12</inf>

A study of the thermal preparation of c-Cd<inf>4/3</inf>Ca<inf>2/3</inf>P<inf>4</inf>O<inf>12</inf>

A study of the reactions during formation of c-Ni<inf>2</inf>P<inf>4</inf>O<inf>12</inf>