TY - JOUR

T1 - Co and Co3O4 in the Hydrolysis of Boron-Containing Hydrides: H2O Activation on the Metal and Oxide Active Centers

AU - Butenko, Vladislav R.

AU - Komova, Oksana V.

AU - Simagina, Valentina I.

AU - Lipatnikova, Inna L.

AU - Ozerova, Anna M.

AU - Danilova, Natalya A.

AU - Rogov, Vladimir A.

AU - Odegova, Galina V.

AU - Bulavchenko, Olga A.

AU - Chesalov, Yuriy A.

AU - Netskina, Olga V.

N1 - This work was supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental order for Boreskov Institute of Catalysis (project FWUR-2024-0034).

PY - 2024/4

Y1 - 2024/4

N2 - This work focuses on the comparison of H2 evolution in the hydrolysis of boron-containing hydrides (NaBH4, NH3BH3, and (CH2NH2BH3)2) over the Co metal catalyst and the Co3O4-based catalysts. The Co3O4 catalysts were activated in the reaction medium, and a small amount of CuO was added to activate Co3O4 under the action of weaker reducers (NH3BH3, (CH2NH2BH3)2). The high activity of Co3O4 has been previously associated with its reduced states (nanosized CoBn). The performed DFT modeling shows that activating water on the metal-like surface requires overcoming a higher energy barrier compared to hydride activation. The novelty of this study lies in its focus on understanding the impact of the remaining cobalt oxide phase. The XRD, TPR H2, TEM, Raman, and ATR FTIR confirm the formation of oxygen vacancies in the Co3O4 structure in the reaction medium, which increases the amount of adsorbed water. The kinetic isotopic effect measurements in D2O, as well as DFT modeling, reveal differences in water activation between Co and Co3O4-based catalysts. It can be assumed that the oxide phase serves not only as a precursor and support for the reduced nanosized cobalt active component but also as a key catalyst component that improves water activation.

AB - This work focuses on the comparison of H2 evolution in the hydrolysis of boron-containing hydrides (NaBH4, NH3BH3, and (CH2NH2BH3)2) over the Co metal catalyst and the Co3O4-based catalysts. The Co3O4 catalysts were activated in the reaction medium, and a small amount of CuO was added to activate Co3O4 under the action of weaker reducers (NH3BH3, (CH2NH2BH3)2). The high activity of Co3O4 has been previously associated with its reduced states (nanosized CoBn). The performed DFT modeling shows that activating water on the metal-like surface requires overcoming a higher energy barrier compared to hydride activation. The novelty of this study lies in its focus on understanding the impact of the remaining cobalt oxide phase. The XRD, TPR H2, TEM, Raman, and ATR FTIR confirm the formation of oxygen vacancies in the Co3O4 structure in the reaction medium, which increases the amount of adsorbed water. The kinetic isotopic effect measurements in D2O, as well as DFT modeling, reveal differences in water activation between Co and Co3O4-based catalysts. It can be assumed that the oxide phase serves not only as a precursor and support for the reduced nanosized cobalt active component but also as a key catalyst component that improves water activation.

KW - DFT

KW - activation

KW - ammonia borane

KW - cobalt

KW - cobalt oxide

KW - ethylenediamine bisborane

KW - hydrogen production

KW - hydrolysis

KW - rate-determining step

KW - sodium borohydride

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85191382187&origin=inward&txGid=4463498e1b189ee842a24726b8ae4fb6

UR - https://www.mendeley.com/catalogue/9a440a3e-a505-3af9-bc25-915e27b73cb0/

U2 - 10.3390/ma17081794

DO - 10.3390/ma17081794

M3 - Article

C2 - 38673151

VL - 17

JO - Materials

JF - Materials

SN - 1996-1944

IS - 8

M1 - 1794

ER -