H2 production via water-gas shift reaction (WGS) is an important process and applied widely. Cobalt-modified CeO2 are promising catalysts for WGS reaction. Herein, a series of Co/Nb-CeO2 catalysts were prepared by varying the rate of precipitant addition during the coprecipitation method and examined for hydrogen generation through WGS reaction. The rates of precipitant addition were 1, 5, 15, and 25 mL/min. We obtained ceria supported cobalt catalysts with different sizes and morphology such as 3, 8 nm nanoclusters, 30 nm cubic nanoparticles, and 50 nm hexagonal nanoparticles. The well dispersed small cobalt particles in Co/Nb-CeO2 that was prepared at 5 mL/min titration rate exhibit strong interaction between cobalt oxide and CeO2 that retards the reduction of CoOx producing Co-CoOx pairs. In contrast, 1-Co/Nb-CeO2 and 25-Co/Nb-CeO2 result in bigger and aggregated Co particles, resulting in fewer interfaces with CeO2. The Co0, Coδ+, Ce3+, and Ov species are responsible for improved reducibility in Co/Nb-CeO2 catalysts and were quantitively measured using XPS, XAS, and Raman spectroscopy. The Co-CoOx interface assists dissociation of the H2O molecule; CO oxidation requires low activation energy and realizes a high turnover frequency of 9.8 s-1. The 5-Co/Nb-CeO2 catalyst achieved thermodynamic equilibrium equivalent CO conversion with efficient H2 production during WGS reaction at a gas hourly space velocity of 315,282 h-1. Successively, the 5-Co/Nb-CeO2 catalyst exhibited stable performance for straight 168 h attributed to stable CO-Coδ+ intermediate formation, achieving efficient inhibition of typical CO chemistry over the Co metal, suitable for hydrogen generation from waste derived synthesis gas.
Keywords: Co−CoOx pairs; high-temperature water−gas shift; hydrogen production; metal−support interactions; waste-derived syngas.