Antimony orthophosphate

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Antimony orthophosphate
Names
IUPAC name
Antimony(3+) phosphate
Other names
Antimony phosphate; Antimonous phosphate
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/H3O4P.Sb/c1-5(2,3)4;/h(H3,1,2,3,4);/q;+3/p-3
    Key: KIQKNTIOWITBBA-UHFFFAOYSA-K
  • [O-]P(=O)([O-])[O-].[Sb+3]
Properties
O4PSb
Molar mass 216.730 g·mol−1
Melting point 877 °C (1,611 °F; 1,150 K) [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Antimony phosphate, (also called antimony orthophosphate, or antimonous phosphate) is a chemical compound of antimony and phosphate with formula SbPO4. Antimony is in the form Sb(III) with +3 oxidation state. Antimony atoms have a lone pair of electrons.

Contents

Layered form

SbPO4 occurs as a layered compound. Two-dimensional layers are weakly held together by electrostatic forces. SbPO4 is one of the most compressible materials, and under pressure compresses more perpendicular to the layers. At standard conditions SbPO4 crystallises in a monoclinic form [2] with space group P21/m. Antimony phosphate has been investigated for use in lithium ion and sodium ion batteries. [3] [4]

Antimony atoms are attached to four oxygen atoms. These atoms are arranged as a squarish pyramid with antimony at the apex. Antimony atoms form the top and bottom of the layers. Four oxygen atoms are arranged tetrahedrally around phosphorus. [2] Antimony to oxygen bond lengths are 1.98 2.04 2.18 and 2.93 Å. the O-Sb-O angles are 87.9 164.8 84.1 and 85.0°. [2] The structure of SbPO4 differs from two forms of BiPO4, where bismuth associates with five or eight phosphate groups. [2]

In SbPO4 the 31P chemical shift is −18 ppm. The binding energy of the 2p electrons of phosphorus atom as determined by XPS is 133.9 eV. [5]

When the pressure exceeds 3 GPa, bonds form between the layers, but it retains the monoclinic system. But when the pressure is between 9 and 20 GPa, it transitions to a triclinic form with space group P1. [6] 10.1021/acs.inorgchem.9b02268

The infrared spectrum shows absorption bands at 1145, 1052, and 973, 664, 590, 500, 475, and 372 cm−1. These are due to vibrations in P-O and Sb-O bonds and also bending in O-P-O bonds. [7]

Antimony(V) phosphate

Antimony(V) phosphate SbOPO4 has monoclinic crystals. It has space group C2c. The unit cell has dimensions a = 6.791 Å, b = 8.033 Å, c = 7.046 Å, and β = 115.90°, with number of formula per unit cell of Z = 4. It is formed by heating Sb2O5·xH2O and (NH4)H2PO4. At 1218 K it loses oxygen to become antimony(III) phosphate. [8]

Formation

SbPO4 may be formed by soaking antimonous oxide in pure phosphoric acid and then filtering the solid, and heating to 600°C. [7]

Sb2O3 + 2H3PO4 → 2SbPO4 + 3H2O

A related method involves heating a water solution of phosphoric acid with antimonous oxide at about 120°C. [9]

Yet another procedure involves heating diammonium phosphate with antimonous oxide at 600°C. [9]

Reactions

SbPO4 reacts with bases such as ammonia, hydrazine and ethylenediamine to form Sb2O3 and hydrogenphosphate salts. [7]

However intercalation is also claimed with amines. [9] Intercalation of amines expands the a axis of the crystals, but leaves c, and c dimensions unaltered. The β angle is reduced. This is due to a bilayer of molecules inserting between each layer in the original crystal. [9]

There are also double salts where phosphate groups are joined to antimony.

List

formulamwcrystal systemspace groupunit cell Åvolumedensitycommentreferences
SbPO4monoclinicP21/ma=5.088 b=6.762 c=4.724 β=94.64°4.45 [9]
Sb5PO10orthorhombicP212121a=6.8373 b=7.0932 c=19.873 Z=8963.8layered, SbPO4 and Sb4O6 [10]
α-SbIIISbV(P2O7)2monoclinicP21/ca = 8.088 b = 16.015 c = 8.135 β = 90.17° Z = 41053.83.73colourless [11]
β-SbIIISbV(P2O7)2orthorhombicPna21a = 8.018 b = 16.134 c = 8.029 Z = 41038.63.78colourless [11]
SbIIISbV3(PO4)6trigonalR3a = 16.880 c = 21.196 Z=125230 [12]
[H3N(CH2)2NH3]0.5SbF(PO4)monoclinicP21/ca=6.5417 b=14.9877 c=9.2193 ˆβ=134.7698° [13]
(NH4)2Sb4O2(H2O)(PO4)2[PO3(OH)]2955.00triclinicP1a=7.2569 b=7.3904 c=18.905 α=85.297° β=81.574° γ=70.609° Z=2945.53.354band gap 5.30 eV; birefringence 0.045@1064 nm [14]
[H3N(CH2)2NH3]1.5[(SbO)2(SbF)2(PO4)3]935.09monoclinicP21/ca=14.822 b=13.766, c=9.3022 β ˆ=105.341° Z=2ˆ1830.43.393 [13]
(H3O)Sb2(SO4)2(PO4)triclinicP1a=5.134 b=7.908Å c=12.855 α=81.401° β=87.253° γ=86.49° [15]
NaSb3O2(PO4)2orthorhombicPca21a=13.944 b=6.682 c=20.8861946.1 [16]
K2Sb(P2O7)F392.89tetragonalP4bma=8.5239 c=5.572 Z=2404.863.223SHG 4.0×KH2PO4; birefringence 0.157@546 nm [17]
K4(SbO2)5(PO4)31210.06monoclinicP21/ca=11.1084 b=14.9138 c=12.7957 β=112.907° Z=41952.74.116 [14]
KSb2(SO4)2(PO4)triclinicP1a=5.1453 b=7.9149 c=12.6146 α=82.054° β=87.715° γ=86.655° [15]
RbSb2(SO4)2(PO4)triclinicP1a=5.1531 b=7.957 c=12.845 α=81.801° β=87.676° γ=86.703° [15]
Rb(SbO2)2PO4487.94monoclinicC2/ca=12.4487 b=7.1018 c=15.0153 β=96.561° Z=81320.54.909 [14]
Rb3(SbO2)3(PO4)2907.60trigonalR3ma=7.1423 c=31.826 Z=31406.03.216 [14]
Cd3Sb2(PO4)4(H2O)2996.61monoclinicP21/ca=9.829 b=9.3437 c=8.6265 β=111.41° Z=2737.64.487colourless [18]
Cs2Sb3O(PO4)3931.98triclinicP1a=7.2896 b=9.6583 c=11.5880 α=98.748° β=104.706° γ=109.279° Z=2719.584.301UV edge 213 nm; band gap 5.02 eV; birefringence 0.034@1064 [14]
Cs3(SbO2)3(PO4)2(H2O)1.321093.49trigonalR3ma=7.1486 c=32.7496 Z=31449.373.758 [14]
Ba3Sb2(PO4)41035.4monoclinicC2/ca=20.383 b=8.5292 c=8.9072 β=108.247° Z=41470.64.676colourless [18]

Related Research Articles

Zirconium phosphates (zirconium hydrogen phosphate) are acidic, inorganic cation exchange materials that have a layered structure with formula Zr(HPO4)2∙nH2O. These salts have high thermal and chemical stability, solid state ion conductivity, resistance to ionizing radiation, and the capacity to incorporate different types of molecules with different sizes between their layers. There are various phases of zirconium phosphate which vary in their interlaminar spaces and their crystalline structure. Among all the Zirconium phosphate phases the most widely used are the alpha (Zr(HPO4)2∙H2O) and the gamma (Zr(PO4)(H2PO4)∙2H2O) phase. The salts have been widely used in several applications such as: drug delivery, catalysis, nanocomposite, nuclear waste management, clinical dialyzer, among others.

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<span class="mw-page-title-main">Cobalt(II) phosphate</span> Chemical compound

Cobalt phosphate is the inorganic compound with the formula Co3(PO4)2. It is a commercial inorganic pigment known as cobalt violet. Thin films of this material are water oxidation catalysts.

Vanadium phosphates are inorganic compounds with the formula VOxPO4 as well related hydrates with the formula VOxPO4(H2O)n. Some of these compounds are used commercially as catalysts for oxidation reactions.

The phosphidosilicates or phosphosilicides are inorganic compounds containing silicon bonded to phosphorus and one or more other kinds of elements. In the phosphosilicates each silicon atom is surrounded by four phosphorus atoms in a tetrahedron. The triphosphosilicates have a SiP3 unit, that can be a planar triangle like carbonate CO3. The phosphorus atoms can be shared to form different patterns e.g. [Si2P6]10− which forms pairs, and [Si3P7]3− which contains two-dimensional double layer sheets. [SiP4]8− with isolated tetrahedra, and [SiP2]2− with a three dimensional network with shared tetrahedron corners. SiP clusters can be joined, not only by sharing a P atom, but also by way of a P-P bond. This does not happen with nitridosilicates or plain silicates.

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<span class="mw-page-title-main">Nickel oxyacid salts</span>

The Nickel oxyacid salts are a class of chemical compounds of nickel with an oxyacid. The compounds include a number of minerals and industrially important nickel compounds.

The fluoride phosphates or phosphate fluorides are inorganic double salts that contain both fluoride and phosphate anions. In mineralogy, Hey's Chemical Index of Minerals groups these as 22.1. The Nickel-Strunz grouping is 8.BN.

An oxyhydride is a mixed anion compound containing both oxide O2− and hydride ions H−. These compounds may be unexpected as the hydrogen and oxygen could be expected to react to form water. But if the metals making up the cations are electropositive enough, and the conditions are reducing enough, solid materials can be made that combine hydrogen and oxygen in the negative ion role.

The telluride oxides or oxytellurides are double salts that contain both telluride and oxide anions. They are in the class of mixed anion compounds.

The borophosphates are mixed anion compounds containing borate and phosphate anions, which may be joined together by a common oxygen atom. Compounds that contain water or hydroxy groups can also be included in the class of compounds.

Borate phosphates are mixed anion compounds containing separate borate and phosphate anions. They are distinct from the borophosphates where the borate is linked to a phosphate via a common oxygen atom. The borate phosphates have a higher ratio of cations to number of borates and phosphates, as compared to the borophosphates.

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<span class="mw-page-title-main">Oxalate phosphate</span> Chemical compound containing oxalate and phosphate anions

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<span class="mw-page-title-main">Terbium compounds</span> Chemical compounds with at least one terbium atom

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<span class="mw-page-title-main">Praseodymium(III) phosphate</span> Chemical compound

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<span class="mw-page-title-main">Dysprosium(III) phosphate</span> Chemical compound

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Phosphatoantimonates are compounds that contain anions that contain phosphorus and antimony in the +5 oxidation state, along with oxygen. Thus they are a compound of phosphate and antimonate, bound together by oxygen.

References

  1. ↑ Melnikov, P.; Secco, M. A. C.; Guimarães, W. R.; dos Santos, H. W. L. (May 2008). "Thermochemistry of vitreous antimony orthophosphate". Journal of Thermal Analysis and Calorimetry. 92 (2): 579–582. doi:10.1007/s10973-007-8379-y.
  2. 1 2 3 4 Kinberger, Bengt; Danielsen, Jacob; Haaland, Arne; Jerslev, Bodil; Schäffer, Claus Erik; Sunde, Erling; Sørensen, Nils Andreas (1970). "The Crystal Structure of SbPO4". Acta Chemica Scandinavica. 24: 320–328. doi:10.3891/acta.chem.scand.24-0320.
  3. ↑ Diwakar, K.; Rajkumar, P.; Subadevi, R.; Arjunan, P.; Sivakumar, M. (July 2021). "Electrospun assisted antimony phosphate (SbPO4) anode for elevated performance in sodium and lithium ion charge storage application". Journal of Alloys and Compounds. 870: 159317. doi:10.1016/j.jallcom.2021.159317.
  4. ↑ Zhou, Xiaozhong; Deng, Hongling; Wang, Aixia; Song, Jinxu; Lei, Ziqiang; Xu, Yuxi (19 June 2023). "Antimony Oxides-Based Anode Materials for Alkali Metal-Ion Storage". Chemistry – A European Journal. 29 (34): e202300506. doi:10.1002/chem.202300506. PMID   36988079.
  5. ↑ Sudarsan, V; Muthe, K.P; Vyas, J.C; Kulshreshtha, S.K (April 2002). "PO43− tetrahedra in SbPO4 and SbOPO4: a 31P NMR and XPS study". Journal of Alloys and Compounds. 336 (1–2): 119–123. doi:10.1016/S0925-8388(01)01888-6.
  6. ↑ Pereira, André Luis de Jesus; Santamaría-Pérez, David; Vilaplana, Rosário; Errandonea, Daniel; Popescu, Catalin; da Silva, Estelina Lora; Sans, Juan Angel; Rodríguez-Carvajal, Juan; Muñoz, Alfonso; Rodríguez-Hernández, Plácida; Mujica, Andres; Radescu, Silvana Elena; Beltrán, Armando; Otero-de-la-Roza, Alberto; Nalin, Marcelo; Mollar, Miguel; Manjón, Francisco Javier (6 January 2020). "Experimental and Theoretical Study of SbPO 4 under Compression". Inorganic Chemistry. 59 (1): 287–307. arXiv: 2102.10111 . doi:10.1021/acs.inorgchem.9b02268. hdl:10234/186679.
  7. 1 2 3 Alonzo, G.; Bertazzi, N.; Galli, P.; Massucci, M.A.; Patrono, P.; Saiano, F. (August 1998). "On the synthesis and characterization of layered antimony(III) phosphate and its interaction with moist ammonia and amines". Materials Research Bulletin. 33 (8): 1221–1231. doi:10.1016/S0025-5408(98)00094-4.
  8. ↑ Piffard, Y.; Oyetola, S.; Verbaere, A.; Tournoux, M. (June 1986). "Synthesis, thermal stability, and crystal structure of antimony(V) phosphate SbOPO4". Journal of Solid State Chemistry. 63 (1): 81–85. doi:10.1016/0022-4596(86)90155-6.
  9. 1 2 3 4 5 Saadaoui, H.; Boukhari, A.; Flandrois, S.; Aride, J. (April 1994). "Intercalation of Hydrazine and Amines in Antimony Phosphate". Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals. 244 (1): 173–178. Bibcode:1994MCLCA.244..173S. doi:10.1080/10587259408050100. ISSN   1058-725X.
  10. ↑ Adair, Brian A.; Cheetham, Anthony K. (December 2000). "Synthesis and Structure of Sb5PO10, a New Phosphate of Antimony(III)". Journal of Solid State Chemistry. 155 (2): 451–454. doi:10.1006/jssc.2000.8948.
  11. 1 2 Verbaere, A.; Oyetola, S.; Guyomard, D.; Piffard, Y. (August 1988). "New mixed-valence antimony phosphates: α- and β-SbIIISbV(P2O7)2". Journal of Solid State Chemistry. 75 (2): 217–224. doi:10.1016/0022-4596(88)90161-2.
  12. ↑ Kasahara, Kenzo; Imoto, Hideo; Saito, Taro (August 1995). "Preparation and Crystal Structure of a New Form of Sb2(PO4)3 and M1/2SbV3/2(PO4)3 (M = Y, In, and Sc)". Journal of Solid State Chemistry. 118 (1): 104–111. doi:10.1006/jssc.1995.1317.
  13. 1 2 Adair, Brian A.; Díaz de Delgado, Graciela; Delgado, J. Miguel; Cheetham, Anthony K. (2000-02-18). "Synthesis and Characterization of an Open-Framework Antimony(III) Phosphate: [H3N(CH2)2NH3]1.5[(SbO)2(SbF)2(PO4)3]". Angewandte Chemie (in German). 112 (4): 761–763. Bibcode:2000AngCh.112..761A. doi:10.1002/(SICI)1521-3757(20000218)112:4<761::AID-ANGE761>3.0.CO;2-B. ISSN   0044-8249.
  14. 1 2 3 4 5 6 Huang, Hongyu; Li, Na; Zhang, Ruixin; Wang, Xinmei; He, Xianmeng; Wu, Lei; Liu, Lili; Jing, Qun; Chen, Zhaohui (2023-06-19). "Four New Sb-based Orthophosphates: Cation Regulation to Investigate Diversified Structural Architecture". Chemistry – A European Journal. 29 (34). doi:10.1002/chem.202300626. ISSN   0947-6539.
  15. 1 2 3 Zhao, Xiao; Mei, Dajiang; Xu, Jingli; Wu, Yuandong (February 2016). "A Sb 2 (SO 4 ) 2 (PO 4 ) ( A = H 3 O + , K, Rb): Layered Structure Containing Ordered Sulfate and Phosphate Anions". Zeitschrift für anorganische und allgemeine Chemie. 642 (4): 343–349. doi:10.1002/zaac.201500743. ISSN   0044-2313.
  16. ↑ Adair, Brian A.; de Delgado, Graciela Díaz; Miguel Delgado, J.; Cheetham, Anthony K. (April 2000). "A Novel Framework Antimony (III) Phosphate: Synthesis and Structure of NaSb3O2(PO4)2". Journal of Solid State Chemistry. 151 (1): 21–24. doi:10.1006/jssc.1999.8606.
  17. ↑ Deng, Yalan; Huang, Ling; Dong, Xuehua; Wang, Lei; Ok, Kang Min; Zeng, Hongmei; Lin, Zhien; Zou, Guohong (2020-11-16). "K 2 Sb(P 2 O 7 )F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance". Angewandte Chemie International Edition. 59 (47): 21151–21156. doi:10.1002/anie.202009441. ISSN   1433-7851. PMID   32745331.
  18. 1 2 Li, Xiao-Bao; Hu, Chun-Li; Kong, Fang; Mao, Jiang-Gao (2021-02-01). "Ba 3 Sb 2 (PO 4 ) 4 and Cd 3 Sb 2 (PO 4 ) 4 (H 2 O) 2 : Two New Antimonous Phosphates with Distinct [Sb(PO 4 ) 2 ] Structure Types and Enhanced Birefringence". Inorganic Chemistry. 60 (3): 1957–1964. doi:10.1021/acs.inorgchem.0c03419. ISSN   0020-1669. PMID   33434013.
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