TY - JOUR

T1 - Structural insights into thermal behavior and vibrational properties of Ni5P4

AU - Vereshchagin, Oleg S.

AU - Pankin, Dmitrii V.

AU - Gorelova, Liudmila A.

AU - Sagatov, Nursultan

AU - Khmelnitskaya, Maya O.

AU - Vlasenko, Natalia S.

AU - Gavryushkin, Pavel N.

AU - Britvin, Sergey N.

N1 - The authors are grateful to three anonymous reviewers for a careful examination of the manuscript that substantially improved the final version of the article. The authors express their gratitude to Editor Mario Aparicio for editorial handing of this contribution. The authors thank Center for Optical and Laser Materials Research, the Resource Center of X-ray diffraction studies and Geomodel Resource Centre of Saint-Petersburg State University for providing instrumental and computational resources. EMPA, SCXRD and Raman studies were supported by the Russian Science Foundation (grant 23-77-10025). DFT calculations were supported by the state assignment of IGM SB RAS (No 122041400157–9).

PY - 2026/1/15

Y1 - 2026/1/15

N2 - First-row transition metal (Me) phosphides are the cost-effective materials in sustainable chemistry, including applications in hydrogen evolution reaction and the development of alkaline-metal-ion batteries. However, thermal behavior and vibrational properties of transition metal phosphides have been poorly studied. We report data on Ni5P4, one of the technologically demanded nickel phosphides, which was investigated by means of scanning electron microscopy, electron microprobe analyses, electron backscatter diffraction, Raman spectroscopy combined with Density Functional Theory and single-crystal X-ray diffraction (over the temperature range of 163–773 K). For the first time we determine its thermal expansion coefficient (αV = 19 × 10−6 K−1) based on single crystal data, and showed that the crystal structure of Ni5P4 undergoes maximum expansion perpendicular to the c axis, and minimum expansion along the c axis. Ni5P4 has clear Raman spectrum (18 peaks, the most intense and best resolved peaks are 143, 203, 238, 314, 414, 425 and 476 cm−1). Our results evidence that quasi-metallic transition metal phosphides having Me/P ratio >1 can produce the quality Raman spectra applicable for their characterization.

AB - First-row transition metal (Me) phosphides are the cost-effective materials in sustainable chemistry, including applications in hydrogen evolution reaction and the development of alkaline-metal-ion batteries. However, thermal behavior and vibrational properties of transition metal phosphides have been poorly studied. We report data on Ni5P4, one of the technologically demanded nickel phosphides, which was investigated by means of scanning electron microscopy, electron microprobe analyses, electron backscatter diffraction, Raman spectroscopy combined with Density Functional Theory and single-crystal X-ray diffraction (over the temperature range of 163–773 K). For the first time we determine its thermal expansion coefficient (αV = 19 × 10−6 K−1) based on single crystal data, and showed that the crystal structure of Ni5P4 undergoes maximum expansion perpendicular to the c axis, and minimum expansion along the c axis. Ni5P4 has clear Raman spectrum (18 peaks, the most intense and best resolved peaks are 143, 203, 238, 314, 414, 425 and 476 cm−1). Our results evidence that quasi-metallic transition metal phosphides having Me/P ratio >1 can produce the quality Raman spectra applicable for their characterization.

KW - Halamishite

KW - Ni5P4

KW - Raman

KW - Thermal expansion

KW - X-ray diffraction

UR - https://www.scopus.com/inward/record.uri?partnerID=HzOxMe3b&scp=105017657666&origin=inward

UR - https://www.mendeley.com/catalogue/f1f29d8b-034b-3d8a-bbcb-9387ba0f6450/

U2 - 10.1016/j.matchemphys.2025.131642

DO - 10.1016/j.matchemphys.2025.131642

M3 - Article

VL - 348

JO - Materials Chemistry and Physics

JF - Materials Chemistry and Physics

SN - 0254-0584

IS - Part 2

M1 - 131642

ER -