TY - JOUR

T1 - Bimetallic Rh/Ir–Cu Metastable Nanoalloys as Promising Catalysts for Propane Prereforming

AU - Sinitsa, Varvara

AU - Urlukov, Artem

AU - Filatov, Evgeny

AU - Plyusnin, Pavel

AU - Kuratieva, Natalia

AU - Raikov, Dmitry

AU - Ishchenko, Arcady

AU - Potemkin, Dmitriy

AU - Korenev, Sergey

N1 - The authors (V. Sinitsa, E. Filatov, P. Plyusnin, N. Kuratieva, S. Korenev) thank the Ministry of Science and Higher Education of the Russian Federation, project numbers 125021302133-1, 125021302132-4 (in the part of synthesis and thermal properties investigation of nanopowders). In the part of catalytic properties investigation, the work was supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental assignment for the Boreskov Institute of Catalysis under the project FWUR-2024-0033 (A. Urlukov, D. Raikov, A. Ishchenko, D. Potemkin). The in situ PXRD and HRTEM studies were carried out using facilities of the shared research center “National Center of Investigation of Catalysts” at the Boreskov Institute of Catalysis.

PY - 2025/12/22

Y1 - 2025/12/22

N2 - In the present work, we synthesized and characterized new complex compounds, [Rh(NH3)5Cl][Cu(H2O)(C2O4)2], [Ir(NH3)5Cl][Cu(H2O)(C2O4)2], and [RhxIr1–x(NH3)6]2[Cu(H2O)(C2O4)2]2[Cu(H2O)2(C2O4)2]·2H2O (x = 0, 0.25, 0.50, 0.75, 1). A detailed study of their thermal decomposition using ex situ and in situ PXRD allowed us to select the optimal conditions and synthesize a series of MxCu1–x (M = Rh, Ir) metastable nanoalloys. For the first time, single-phase metastable Ir0.50Cu0.50 and Ir0.40Cu0.60 nanoalloys were obtained. Nanoalloys were studied in the propane steam reforming reaction (prereforming) at WHSV = 4 000 mL·gcat–1·h–1, T = 300–500 °C, and p = 1 atm. The bimetallic Rh–Cu/Ce0.75Zr0.25O2 supported catalysts demonstrated high activity as well as greater hydrogen selectivity compared to the monometallic Rh sample, resulting in higher hydrogen productivity. Higher hydrogen productivity is achieved due to higher dispersion of the active component in bimetallic catalysts and due to inhibition of carbon monoxide methanation reactions in the overall rate of the steam reforming process.

AB - In the present work, we synthesized and characterized new complex compounds, [Rh(NH3)5Cl][Cu(H2O)(C2O4)2], [Ir(NH3)5Cl][Cu(H2O)(C2O4)2], and [RhxIr1–x(NH3)6]2[Cu(H2O)(C2O4)2]2[Cu(H2O)2(C2O4)2]·2H2O (x = 0, 0.25, 0.50, 0.75, 1). A detailed study of their thermal decomposition using ex situ and in situ PXRD allowed us to select the optimal conditions and synthesize a series of MxCu1–x (M = Rh, Ir) metastable nanoalloys. For the first time, single-phase metastable Ir0.50Cu0.50 and Ir0.40Cu0.60 nanoalloys were obtained. Nanoalloys were studied in the propane steam reforming reaction (prereforming) at WHSV = 4 000 mL·gcat–1·h–1, T = 300–500 °C, and p = 1 atm. The bimetallic Rh–Cu/Ce0.75Zr0.25O2 supported catalysts demonstrated high activity as well as greater hydrogen selectivity compared to the monometallic Rh sample, resulting in higher hydrogen productivity. Higher hydrogen productivity is achieved due to higher dispersion of the active component in bimetallic catalysts and due to inhibition of carbon monoxide methanation reactions in the overall rate of the steam reforming process.

UR - https://www.scopus.com/pages/publications/105025202279

UR - https://www.mendeley.com/catalogue/c281eea5-16ab-31b6-bf9d-9eab2f8de3a7/

U2 - 10.1021/acs.inorgchem.5c04567

DO - 10.1021/acs.inorgchem.5c04567

M3 - Article

VL - 64

SP - 24818

EP - 24833

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 50

ER -