Electronic Structure Of Cobalt Phosphates Co1-xmxpo4 Doped With Iron And Nickel Atoms

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Abstract

In this research, the electronic states, band structures, and bond properties of the framework compounds of CoPO4, Co1-xFexPO4, and Co1–xNixPO4 were investigated by the density functional theory calculations. The potential capabilities of these systems in the photocatalytic water splitting to produce hydrogen were analyzed. The spin-up electron densities of states for the CoPO4, Co1–xFexPO4, and Co1–xNixPO4 systems have band gaps of 2.7, 3.4, and 3.45 eV, respectively. The band of spin-down electron states has several energy gaps above the Fermi level. The density of states of electron with spin up near the Fermi level is obviously greater than that of electrons with spin down. In this case, localized states of electrons appear in the band gap of doped semiconductors due to impurity atoms. The calculated value of the energy at the lower edge of the conduction band for CoPO4 was –0.7 eV, which is more negative than the energy required for water splitting. Meanwhile, the calculated value of the energy at the upper edge of the valence band was 2.01 eV, which is more positive than the oxygen evolution energy of 1.23 eV.

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M. D. Pecherskaya

Institute of Materials Science, Uzbekistan Academy of Sciences

Author for correspondence.
Email: mariya.pecherskaya@yahoo.com
Uzbekistan, Tashkent, 100084

O. A. Galkina

Institute of Chemistry and Physics of Polymers, Uzbekistan Academy of Sciences

Email: mariya.pecherskaya@yahoo.com
Uzbekistan, Tashkent, 100128

O. N. Ruzimuradov

Turin Polytechnic University in Tashkent

Email: mariya.pecherskaya@yahoo.com
Uzbekistan, Tashkent, 100095

Sh. I. Mamatkulov

Institute of Materials Science, Uzbekistan Academy of Sciences

Email: mariya.pecherskaya@yahoo.com
Uzbekistan, Tashkent, 100084

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Supplementary files

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2. Fig. 1. The crystal structure of CoPO4 (a), Co1–xFexPO4 (b) and Co1–xNixPO4 (c) used in calculations. Oxygen atoms are indicated in red, phosphorus in yellow, and cobalt in dark green.

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3. Fig. 2. Density of electronic states (DOS) with spin up and down for pure CoPO4 (a, b), as well as CoPO4 doped with iron (c, d) and nickel (e, e). Zero energy is taken at the Fermi level, the left half of the figures shows the state with spin up, and The right one is a spin–down state.

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4. Fig. 3. The structure of energy zones and partial densities of states of the CoPO4 system for electrons with spins up (a) and for electrons with spins down (b). For this crystal, the band structures for electrons with different spin directions differ from each other, which leads to bandgap zones of unequal magnitude and amount to One = 2.7 eV and Egd = 1.1 eV.

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5. Fig. 4. The structure of energy zones and partial densities of states of the Co1–xFexPO4 system for electrons with spins up (a) and for electrons with spins down (b).

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6. Fig. 5. The structure of energy zones and partial densities of states of the Co1–xNixPO4 system for electrons with spins up (a) and for electrons with spins down (b).

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