Wikipedia

Antimony orthophosphate

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.

Antimony orthophosphate
Names
IUPAC name
Antimony(3+) phosphate
Other names
Antimony phosphate; Antimonous phosphate
Identifiers
3D model (JSmol)
ChemSpider
  • 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).

Layered form

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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

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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

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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

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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

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formula mw crystal system space group unit cell Å volume density comment references
SbPO4 monoclinic P21/m a=5.088 b=6.762 c=4.724 β=94.64° 4.45 [9]
Sb5PO10 orthorhombic P212121 a=6.8373 b=7.0932 c=19.873 Z=8 963.8 layered, SbPO4 and Sb4O6 [10]
α-SbIIISbV(P2O7)2 monoclinic P21/c a = 8.088 b = 16.015 c = 8.135 β = 90.17° Z = 4 1053.8 3.73 colourless [11]
β-SbIIISbV(P2O7)2 orthorhombic Pna21 a = 8.018 b = 16.134 c = 8.029 Z = 4 1038.6 3.78 colourless [11]
SbIIISbV3(PO4)6 trigonal R3 a = 16.880 c = 21.196 Z=12 5230 [12]
[H3N(CH2)2NH3]0.5SbF(PO4) monoclinic P21/c a=6.5417 b=14.9877 c=9.2193 ˆβ=134.7698° [13]
(NH4)2Sb4O2(H2O)(PO4)2[PO3(OH)]2 955.00 triclinic P1 a=7.2569 b=7.3904 c=18.905 α=85.297° β=81.574° γ=70.609° Z=2 945.5 3.354 band gap 5.30 eV; birefringence 0.045@1064 nm [14]
[H3N(CH2)2NH3]1.5[(SbO)2(SbF)2(PO4)3] 935.09 monoclinic P21/c a=14.822 b=13.766, c=9.3022 ⠈=105.341° Z=2ˆ 1830.4 3.393 [13]
(H3O)Sb2(SO4)2(PO4) triclinic P1 a=5.134 b=7.908Å c=12.855 α=81.401° β=87.253° γ=86.49° [15]
NaSb3O2(PO4)2 orthorhombic Pca21 a=13.944 b=6.682 c=20.886 1946.1 [16]
K2Sb(P2O7)F 392.89 tetragonal P4bm a=8.5239 c=5.572 Z=2 404.86 3.223 SHG 4.0×KH2PO4; birefringence 0.157@546 nm [17]
K4(SbO2)5(PO4)3 1210.06 monoclinic P21/c a=11.1084 b=14.9138 c=12.7957 β=112.907° Z=4 1952.7 4.116 [14]
KSb2(SO4)2(PO4) triclinic P1 a=5.1453 b=7.9149 c=12.6146 α=82.054° β=87.715° γ=86.655° [15]
RbSb2(SO4)2(PO4) triclinic P1 a=5.1531 b=7.957 c=12.845 α=81.801° β=87.676° γ=86.703° [15]
Rb(SbO2)2PO4 487.94 monoclinic C2/c a=12.4487 b=7.1018 c=15.0153 β=96.561° Z=8 1320.5 4.909 [14]
Rb3(SbO2)3(PO4)2 907.60 trigonal R3m a=7.1423 c=31.826 Z=3 1406.0 3.216 [14]
Cd3Sb2(PO4)4(H2O)2 996.61 monoclinic P21/c a=9.829 b=9.3437 c=8.6265 β=111.41° Z=2 737.6 4.487 colourless [18]
Cs2Sb3O(PO4)3 931.98 triclinic P1 a=7.2896 b=9.6583 c=11.5880 α=98.748° β=104.706° γ=109.279° Z=2 719.58 4.301 UV edge 213 nm; band gap 5.02 eV; birefringence 0.034@1064 [14]
Cs3(SbO2)3(PO4)2(H2O)1.32 1093.49 trigonal R3m a=7.1486 c=32.7496 Z=3 1449.37 3.758 [14]
Ba3Sb2(PO4)4 1035.4 monoclinic C2/c a=20.383 b=8.5292 c=8.9072 β=108.247° Z=4 1470.6 4.676 colourless [18]

References

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  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. ^ a b c d 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. ^ a b c 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. ^ a b c d e 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. ^ a b 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. ^ a b 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. ^ a b c d e f 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. ^ a b c 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. ^ a b 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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