Antimony orthophosphate explained
Antimony phosphate, (also called antimony orthophosphate, or antimonous phosphate) is a chemical compound of antimony and phosphate with formula . Antimony is in the form Sb(III) with +3 oxidation state. Antimony atoms have a lone pair of electrons.
Layered form
occurs as a layered compound. Two-dimensional layers are weakly held together by electrostatic forces. is one of the most compressible materials, and under pressure compresses more perpendicular to the layers. At standard conditions crystallises in a monoclinic form[1] with space group P21/m. Antimony phosphate has been investigated for use in lithium ion and sodium ion batteries.[2] [3]
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.[1] 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°.[1] The structure of differs from two forms of BiPO4, where bismuth associates with five or eight phosphate groups.[1]
In 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.[4]
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 P.[5] 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.
Antimony(V) phosphate
Antimony(V) phosphate 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 and . At 1218 K it loses oxygen to become antimony(III) phosphate.[6]
Formation
may be formed by soaking antimonous oxide in pure phosphoric acid and then filtering the solid, and heating to 600 °C.
A related method involves heating a water solution of phosphoric acid with antimonous oxide at about 120 °C.
Yet another procedure involves heating diammonium phosphate with antimonous oxide at 600 °C.
Reactions
reacts with bases such as ammonia, hydrazine and ethylenediamine to form and hydrogenphosphate salts.[7]
However intercalation is also claimed with amines.[8] 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.[8]
There are also double salts where phosphate groups are joined to antimony.
List
| 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 | | |
| Sb5PO10 | | orthorhombic | P212121 | a=6.8373 b=7.0932 c=19.873 Z=8 | 963.8 | | layered, SbPO4 and Sb4O6 | [9] |
| 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 | [10] |
| β-SbIIISbV(P2O7)2 | | orthorhombic | Pna21 | a = 8.018 b = 16.134 c = 8.029 Z = 4 | 1038.6 | 3.78 | colourless | |
| SbIIISbV3(PO4)6 | | trigonal | R | a = 16.880 c = 21.196 Z=12 | 5230 | | | [11] |
| [H<sub>3</sub>N(CH<sub>2</sub>)<sub>2</sub>NH<sub>3</sub>]0.5SbF(PO4) | | monoclinic | P21/c | a=6.5417 b=14.9877 c=9.2193 β=134.7698° | | | | [12] |
| (NH4)2Sb4O2(H2O)(PO4)2[PO<small><sub>3</sub></small>(OH)]2 | 955.00 | triclinic | P | 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 | [13] |
| [H<sub>3</sub>N(CH<sub>2</sub>)<sub>2</sub>NH<sub>3</sub>]1.5[(SbO)<sub>2</sub>(SbF)<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>] | 935.09 | monoclinic | P21/c | a=14.822 b=13.766, c=9.3022 β =105.341° Z=2 | 1830.4 | 3.393 | | |
| (H3O)Sb2(SO4)2(PO4) | | triclinic | P | a=5.134 b=7.908Å c=12.855 α=81.401° β=87.253° γ=86.49° | | | | [14] |
| NaSb3O2(PO4)2 | | orthorhombic | Pca21 | a=13.944 b=6.682 c=20.886 | 1946.1 | | | [15] |
| 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 | [16] |
| 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 | | |
| KSb2(SO4)2(PO4) | | triclinic | P | a=5.1453 b=7.9149 c=12.6146 α=82.054° β=87.715° γ=86.655° | | | | |
| RbSb2(SO4)2(PO4) | | triclinic | P | a=5.1531 b=7.957 c=12.845 α=81.801° β=87.676° γ=86.703° | | | | |
| 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 | | |
| Rb3(SbO2)3(PO4)2 | 907.60 | trigonal | Rm | a=7.1423 c=31.826 Z=3 | 1406.0 | 3.216 | | |
| 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 | [17] |
| Cs2Sb3O(PO4)3 | 931.98 | triclinic | P | 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 | |
| Cs3(SbO2)3(PO4)2(H2O)1.32 | 1093.49 | trigonal | Rm | a=7.1486 c=32.7496 Z=3 | 1449.37 | 3.758 | | |
| 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 | | |
Notes and References
- Kinberger . Bengt . Danielsen . Jacob . Haaland . Arne . Jerslev . Bodil . Schäffer . Claus Erik . Sunde . Erling . Sørensen . Nils Andreas . The Crystal Structure of SbPO4. . Acta Chemica Scandinavica . 1970 . 24 . 320–328 . 10.3891/acta.chem.scand.24-0320.
- Diwakar . K. . Rajkumar . P. . Subadevi . R. . Arjunan . P. . Sivakumar . M. . Electrospun assisted antimony phosphate (SbPO4) anode for elevated performance in sodium and lithium ion charge storage application . Journal of Alloys and Compounds . July 2021 . 870 . 159317 . 10.1016/j.jallcom.2021.159317.
- Zhou . Xiaozhong . Deng . Hongling . Wang . Aixia . Song . Jinxu . Lei . Ziqiang . Xu . Yuxi . Antimony Oxides-Based Anode Materials for Alkali Metal-Ion Storage . Chemistry – A European Journal . 19 June 2023 . 29 . 34 . e202300506 . 10.1002/chem.202300506. 36988079 .
- Sudarsan . V . Muthe . K.P . Vyas . J.C . Kulshreshtha . S.K . PO43− tetrahedra in SbPO4 and SbOPO4: a 31P NMR and XPS study . Journal of Alloys and Compounds . April 2002 . 336 . 1–2 . 119–123 . 10.1016/S0925-8388(01)01888-6.
- 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 . Experimental and Theoretical Study of SbPO 4 under Compression . Inorganic Chemistry . 6 January 2020 . 59 . 1 . 287–307 . 10.1021/acs.inorgchem.9b02268. 10234/186679 . 2102.10111 .
- Piffard . Y. . Oyetola . S. . Verbaere . A. . Tournoux . M. . Synthesis, thermal stability, and crystal structure of antimony(V) phosphate SbOPO4 . Journal of Solid State Chemistry . June 1986 . 63 . 1 . 81–85 . 10.1016/0022-4596(86)90155-6.
- Alonzo . G. . Bertazzi . N. . Galli . P. . Massucci . M.A. . Patrono . P. . Saiano . F. . On the synthesis and characterization of layered antimony(III) phosphate and its interaction with moist ammonia and amines . Materials Research Bulletin . August 1998 . 33 . 8 . 1221–1231 . 10.1016/S0025-5408(98)00094-4.
- Saadaoui . H. . Boukhari . A. . Flandrois . S. . Aride . J. . Intercalation of Hydrazine and Amines in Antimony Phosphate . Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals . April 1994 . 244 . 1 . 173–178 . 10.1080/10587259408050100 . 1994MCLCA.244..173S . en . 1058-725X.
- Adair . Brian A. . Cheetham . Anthony K. . December 2000 . Synthesis and Structure of Sb5PO10, a New Phosphate of Antimony(III) . Journal of Solid State Chemistry . en . 155 . 2 . 451–454 . 10.1006/jssc.2000.8948.
- 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 . en . 75 . 2 . 217–224 . 10.1016/0022-4596(88)90161-2.
- 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 . en . 118 . 1 . 104–111 . 10.1006/jssc.1995.1317.
- 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 . de . 112 . 4 . 761–763 . 10.1002/(SICI)1521-3757(20000218)112:4<761::AID-ANGE761>3.0.CO;2-B . 2000AngCh.112..761A . 0044-8249.
- 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 . en . 29 . 34 . 10.1002/chem.202300626 . 0947-6539.
- 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 . en . 642 . 4 . 343–349 . 10.1002/zaac.201500743 . 0044-2313.
- 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 . en . 151 . 1 . 21–24 . 10.1006/jssc.1999.8606.
- 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 . en . 59 . 47 . 21151–21156 . 10.1002/anie.202009441 . 32745331 . 1433-7851.
- 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. en. 60. 3. 1957–1964. 10.1021/acs.inorgchem.0c03419. 33434013 . 0020-1669.
