TY - JOUR

T1 - Double oxalates of Rh(III) with Cu(II) and Zn(II) – Effective precursors of nanoalloys for hydrogen production by steam reforming of propane

AU - Garkul, Ilia A.

AU - Zadesenets, Andrey V.

AU - Filatov, Evgeny Yu

AU - Байдина, Ираида Афанасьевна

AU - Plusnin, Pavel E.

AU - Urlukov, Artem S.

AU - Potemkin, Dmitriy I.

AU - Korenev, Sergey V.

N1 - This research was funded by the Russian Science Foundation, grant number 21-73-20203 (in part of synthesis and catalytic activity investigation of nanopowders), project number FWUR-2024-0033 (in part of analysis of correlations between catalysts structure and catalytic properties).

PY - 2024/9/11

Y1 - 2024/9/11

N2 - Heteronuclear coordination compounds of d-metals are effective precursors for the production of bimetallic nanoalloys (Plyusnin et al., 2022) [1], which, in turn, are widely used in catalysis. Catalysts based on Rh and Cu, as well as Rh and Zn, are highly active in the process of steam reforming of hydrocarbons. Double oxalates of Rh with Cu and Rh with Zn with the general formula [(C2O4)(H2O)2Rh−(μ-C2O4)−M(H2O)2−(μ-C2O4)–Rh(H2O)2(C2O4)]·6H2O (M = Cu, Zn) are synthesized and structurally characterized. According to thermogravimetric analysis, the complexes completely decompose in He and H2 atmospheres already at 300 °C with the formation of the corresponding nanoalloys in the Cu–Rh and Zn–Rh systems. Calcination in an O2 atmosphere leads to the formation of a mixed oxide with a spinel structure. The Cu–Rh/Ce0.75Zr0.25O2 and Zn–Rh/Ce0.75Zr0.25O2 catalysts were prepared by impregnation by moisture capacity on a porous support followed by calcination in a hydrogen atmosphere. The obtained catalysts were tested in propane steam reforming for hydrogen production at 300–480 °C and WHSV = 10 000–40 000 cm3 h−1∙gcat−1. At these conditions the Cu–Rh/Ce0.75Zr0.25O2 and Zn–Rh/Ce0.75Zr0.25O2 catalysts demonstrated high selectivity for hydrogen (more than 70 %) compared to the monometallic catalyst Rh/Ce0.75Zr0.25O2 (less than 60%). Bimetallic catalysts make it possible to increase hydrogen productivity by reducing the reaction rate of methanation of carbon oxides, which is achieved due to the presence of Cu and Zn in the catalyst structure.

AB - Heteronuclear coordination compounds of d-metals are effective precursors for the production of bimetallic nanoalloys (Plyusnin et al., 2022) [1], which, in turn, are widely used in catalysis. Catalysts based on Rh and Cu, as well as Rh and Zn, are highly active in the process of steam reforming of hydrocarbons. Double oxalates of Rh with Cu and Rh with Zn with the general formula [(C2O4)(H2O)2Rh−(μ-C2O4)−M(H2O)2−(μ-C2O4)–Rh(H2O)2(C2O4)]·6H2O (M = Cu, Zn) are synthesized and structurally characterized. According to thermogravimetric analysis, the complexes completely decompose in He and H2 atmospheres already at 300 °C with the formation of the corresponding nanoalloys in the Cu–Rh and Zn–Rh systems. Calcination in an O2 atmosphere leads to the formation of a mixed oxide with a spinel structure. The Cu–Rh/Ce0.75Zr0.25O2 and Zn–Rh/Ce0.75Zr0.25O2 catalysts were prepared by impregnation by moisture capacity on a porous support followed by calcination in a hydrogen atmosphere. The obtained catalysts were tested in propane steam reforming for hydrogen production at 300–480 °C and WHSV = 10 000–40 000 cm3 h−1∙gcat−1. At these conditions the Cu–Rh/Ce0.75Zr0.25O2 and Zn–Rh/Ce0.75Zr0.25O2 catalysts demonstrated high selectivity for hydrogen (more than 70 %) compared to the monometallic catalyst Rh/Ce0.75Zr0.25O2 (less than 60%). Bimetallic catalysts make it possible to increase hydrogen productivity by reducing the reaction rate of methanation of carbon oxides, which is achieved due to the presence of Cu and Zn in the catalyst structure.

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85200245563&origin=inward&txGid=4442087a63f825e22b32e1797a98e709

U2 - 10.1016/j.ijhydene.2024.07.446

DO - 10.1016/j.ijhydene.2024.07.446

M3 - Article

VL - 82

SP - 611

EP - 623

JO - International Journal of Hydrogen Energy

JF - International Journal of Hydrogen Energy

SN - 0360-3199

ER -