Effect of Cu loading on Cu/ZnO water–gas shift catalysts for shut-down/start-up operation

Cu/ZnO catalysts with Cu loadings of 44–5 wt% were prepared by coprecipitation and evaluated in temperature-dependant and shut-down/start-up water–gas shift (WGS) reactions using realistic reformate. These catalysts had similar Cu crystallite sizes, and the metallic Cu surface area and surface Cu content increased with the Cu loading. In temperature-dependent reactions, the CO conversion on the 25wt%Cu/ZnO catalyst slightly exceeded that on 44wt%Cu/ZnO. In shut-down/start-up operation, which is imperative for mobile and residential fuel cell applications, the catalysts with Cu loadings higher than 5 wt% suffered slight activity loss. Among them, the 15wt%Cu/ZnO catalyst deactivated the most reluctantly. As a result, after three shut-down/start-up cycles the CO conversion on 15wt%Cu/ZnO, 25wt%Cu/ZnO, and 44wt%Cu/ZnO became comparable. These results demonstrate the feasibility to lower the Cu loading without degrading the WGS performance of the Cu/ZnO catalyst in shut-down/start-up operation, which will guarantee the operation safety when the catalyst will be operated unattended for domestic small-scale fuel cell applications. Unexpectedly, the CO conversion was doubled on 5wt%Cu/ZnO after one shut-down/start-up cycle, which is interpreted as the redispersion of Cu nanoparticles based on transmission electron microscopy (TEM) and temperature-programmed reduction (TPR).