Oxygen Transport in Pr Nickelates: Elucidation of Atomic-Scale Features | Sciact - CRIS-система Института катализа

Oxygen Transport in Pr Nickelates: Elucidation of Atomic-Scale Features Научная публикация

Конференция

22nd International Conference on Solid State Ionics
16-21 июн. 2019 , PyeongChang

Журнал

Solid State Ionics
ISSN: 0167-2738

Вых. Данные

Год: 2020, Том: 344, Номер статьи : 115155, Страниц : 9 DOI: 10.1016/j.ssi.2019.115155

Ключевые слова

Density functional theory calculations; Oxygen diffusion; Pr2−xCaxNiO4; X-ray photoelectron spectroscopy

Авторы

Sadykov Vladislav ^1,2 , Pikalova Elena ^3,4 , Eremeev Nikita ¹ , Shubin Aleksandr ^1,2 , Zilberberg Igor ^1,2 , Prosvirin Igor ^1,2 , Sadovskaya Ekaterina ^1,2 , Bukhtiyarov Andrey ¹

Организации

1	Federal Research Center Boreskov Institute of Catalysis, Lavrentiev Ave. 5, Novosibirsk 630090, Russia
2	Novosibirsk State University, Pirogova st. 2, Novosibirsk 630090, Russia
3	Institute of High Temperature Electrochemistry UB RAS, Akademicheskaya st. 20, Yekaterinburg 620137, Russia
4	Ural Federal University, Mira st. 19, Yekaterinburg 620002, Russia

Информация о финансировании (1)

Российский научный фонд

16-13-00112

Pr2NiO4+δ oxide with a layered Ruddlesden–Popper structure is a promising material for SOFC cathodes and oxygen separation membranes due to a high oxygen mobility provided by the cooperative mechanism of oxygen migration involving both interstitial oxygen species and apical oxygen of the NiO6 octahedra. Doping by Ca improves thermodynamic stability and increases electronic conductivity of Pr2 − xCaxNiO4+δ, but decreases oxygen mobility due to decreasing the oxygen excess and appearing of 1–2 additional slow diffusion channels at x ≥ 0.4, probably, due to hampering of cooperative mechanism of migration. However, atomic-scale features of these materials determining oxygen migration require further studies. In this work characteristics of oxygen diffusion in Pr2 − xCaxNiO4+δ (x = 0–0.6) are compared with results of the surface analysis by X-ray photoelectron spectroscopy and modeling of the interstitial oxygen migration by the plane-wave density functional theory calculations. According to the X-ray photoelectron spectroscopy data, the surface is enriched by Pr for undoped sample and by Ca for doped ones. The O1s peak at ~531 eV corresponding to a weakly bound form of surface oxygen located at Pr cations disappears at ~500 °C. Migration of interstitial oxygen was modeled for a I4/mmm phase of Pr2NiO4+δ. The interstitial oxygen anion repulses the apical one in the NiO6 octahedra pushing it into the tetrahedral site between Pr cations. The calculated activation barrier of this migration is equal to 0.585 eV, which reasonably agrees with the experimental value of 0.83 eV obtained by the oxygen isotope exchange method. At the same time, for the model compound Ca2NiO4+δ, obtained by isomorphic substitution of Pr by Ca in Pr2NiO4+δ, calculations implied formation of the peroxide ion comprised of interstitial and lattice oxygen species not revealed in the case of incomplete substitution (up to PrCaNiO4+δ composition). Hence, calculations in the framework of the plane-wave density functional theory provide a realistic estimation of specificity of oxygen migration features in Pr2NiO4+δ doped by alkaline-earth metals. © 2019 Elsevier B.V.

Sadykov V. , Pikalova E. , Eremeev N. , Shubin A. , Zilberberg I. , Prosvirin I. , Sadovskaya E. , Bukhtiyarov A.
Oxygen Transport in Pr Nickelates: Elucidation of Atomic-Scale Features

Solid State Ionics. 2020. V.344. 115155 :1-9. DOI: 10.1016/j.ssi.2019.115155 WOS Scopus РИНЦ CAPlus OpenAlex

Полный текст от издателя

Поступила в редакцию:	21 июл. 2019 г.
Принята к публикации:	14 нояб. 2019 г.
Опубликована online:	23 нояб. 2019 г.
Опубликована в печати:	1 янв. 2020 г.

Web of science:	WOS:000509787200023
Scopus:	2-s2.0-85075285872
РИНЦ:	41822816
Chemical Abstracts:	2019:2237248
OpenAlex:	W2991394666

БД	Цитирований
Scopus	10
Web of science	10
РИНЦ	11
OpenAlex	11