First-Principles Comparative Study on Electronic Structure Modulation and Photocatalytic Performance of Co/Fe/Ni-Doped LaTiO3

doi:10.16553/j.cnki.issn1000-985x.2026.0077

Abstract

Abstract: To overcome the bottlenecks of narrow photoresponse range and the thermodynamic limitations for photocatalytic water splitting in LaTiO₃， first-principles calculations were performed to compare the modulation mechanisms of Co， Fe， and Ni single-doping. The results show that all three doped systems exhibit negative formation energies， with Ni doping yielding the lowest value （-1.14 eV）. Phonon spectra display no imaginary frequencies， confirming the kinetic stability of all systems. The band gap of pristine LaTiO₃ is 2.299 eV， which decreases to 1.674 （indirect band gap）， 1.405， and 0.928 eV for Co， Fe， and Ni doping， respectively. Notably， the band gaps for Fe and Ni doping are too narrow to satisfy the thermodynamic requirement for overall water splitting （≥1.23 eV）. -COHP and Bader charge analyses confirm the enhanced M—O covalency after doping， with the net bonding strength from high to low following the order of Co， Fe， and Ni doping， while the charge transfer strength from high to low follows the order of Ni， Co， and Fe doping， with Ni doping exhibiting the largest charge transfer （electron loss of 1.15 e）. Co doping shifts the absorption edge to 520 nm， achieving a peak visible-light absorption coefficient of 2.0×10⁵ cm^-1， and increases the work function to 3.05 eV， which is attributed to the reconstruction of the electronic density of states near the Fermi level. Based on the comprehensive evaluation of band gap， optical absorption， and charge carrier separation performance， Co doping is identified as the optimal strategy for modifying LaTiO₃ for photocatalytic water splitting. This study provides theoretical support for the design and optimization of perovskite-based photocatalytic materials through doping.

Key words: LaTiO₃; perovskite; transition metal doping; electronic structure; first-principles calculation

CLC Number:

TB34

CHEN Meizhu, WANG Ao, ZHANG Guanlun, LI Jinying, YANG Chunwei. First-Principles Comparative Study on Electronic Structure Modulation and Photocatalytic Performance of Co/Fe/Ni-Doped LaTiO₃[J]. Journal of Synthetic Crystals, 2026, 55(9): 1481-1489.

Figures/Tables 12

Fig.1 Supercell models of pristine and Co/Fe/Ni doped LaTiO3

Table 1 Summary of lattice constants， total energies， and formation energies for pristine and doped LaTiO3 systems

System	Lattice constant， a/Å	Lattice constant， b/Å	Lattice constant， c/Å	Total energy/eV	Formation energy， $E f$ /eV	Average M—O bond length/Å	Effective coordination	Magnetic moment
Pristine LaTiO₃	5.560	5.560	7.830	-528.63	—	—	—	—
Co-doped LaTiO₃	5.542	5.542	7.815	-529.07	-0.96	2.18	8	2.1μ_B
Fe-doped LaTiO₃	5.531	5.531	7.808	-529.25	-0.79	2.14	7	4.3μ_B
Ni-doped LaTiO₃	5.523	5.523	7.802	-529.43	-1.14	2.12	6	1.2μ_B

Table 1 Summary of lattice constants， total energies， and formation energies for pristine and doped LaTiO3 systems

System	Lattice constant， a/Å	Lattice constant， b/Å	Lattice constant， c/Å	Total energy/eV	Formation energy， $E f$ /eV	Average M—O bond length/Å	Effective coordination	Magnetic moment
Pristine LaTiO₃	5.560	5.560	7.830	-528.63	—	—	—	—
Co-doped LaTiO₃	5.542	5.542	7.815	-529.07	-0.96	2.18	8	2.1μ_B
Fe-doped LaTiO₃	5.531	5.531	7.808	-529.25	-0.79	2.14	7	4.3μ_B
Ni-doped LaTiO₃	5.523	5.523	7.802	-529.43	-1.14	2.12	6	1.2μ_B

Fig.2 Phonon dispersion curves and phonon density of states （DOS） of pristine and doped LaTiO3 systems

Fig.3 Band structures of pristine and doped LaTiO3 systems

Fig.4 Charge density distribution maps of pristine and doped LaTiO3 systems

Fig.5 Comparison of partial density of states （PDOS） of pristine and doped LaTiO3 systems

Fig.6 Comparison of work functions of pristine and doped LaTiO3 systems

Fig.7 -COHP analysis of pristine and doped LaTiO3 systems

Fig.8 Charge density difference maps of doped LaTiO3 systems

Table 2 Optical absorption and charge transfer parameters of pristine and doped LaTiO3 systems

System	Absorption edge/nm	α_max/（10⁵ cm^-1）	Electron loss/e	Adjacent O electron gain/e
Pristine LaTiO₃	387	1.0	—	—
Fe-doped LaTiO₃	419	1.4	0.58	0.55
Co-doped LaTiO₃	520	2.0	0.72	0.68
Ni-doped LaTiO₃	1 336	1.0	1.15	1.09

Fig.9 Absorption coefficient spectra of pristine and doped LaTiO3 systems

Fig.10 Dielectric function spectra of pristine and doped LaTiO3 systems

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First-Principles Comparative Study on Electronic Structure Modulation and Photocatalytic Performance of Co/Fe/Ni-Doped LaTiO₃

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