Аннотация:Development of stable Ni-based catalysts with highresistance to sintering and carbon deposition is a challenge in thecatalytic ethanol dry reforming (EDR) process. An effective andpractical strategy is to introduce a second metal to obtain Ni-basedbimetallic catalysts. In this study, bimetallic Cu−Ni nanoparticlessupported on Al−Zr−Ce (ACZ) complex oxides were successfullydeveloped as a multifunctional catalyst for syngas production viaEDR and were compared with monometallic Ni and Cu catalystssupported on ACZ oxides. The addition of a small amount ofcopper (1%) to the catalyst resulted in the formation of a Cu−Nialloy with crystallite sizes ranging from 10 to 30 nm, exhibiting ahigh metal−support interaction and resistance to sintering.However, a high Cu content limited the activity of the catalystsdue to side reactions of ethanol decomposition, which led to catalyst deactivation. The catalyst 1Cu−9Ni/50ACZ exhibited thehighest H2 and CO yields (78% and 70%, respectively, at T = 750 °C) at H2/CO = 1.1. The addition of Cu enhanced the H2/COratio by shifting the water−gas shift (WGS) reaction pathway and increasing the reducibility and dispersibility of Ni, which isattributed to the formation of a Cu−Ni alloy. The Cu−Ni alloy is active in the WGS reaction and has a synergistic effect with Ni indehydration and dehydrogenation of ethanol, which affects the product distribution. Furthermore, copper plays a role in thereduction of carbide forms of nickel, which are precursors of graphitized coke. The support composition was also found to have asignificant effect on the activity and stability of the bimetallic catalysts. It was demonstrated that the Al/Zr ratio in the supportenables tuning the crystallite size of the active phase, which affects the surface concentrations of nickel and copper and their ratio anddetermines the ratio of reactive oxygen species that contribute to the gasification of the formed coke. This work provides a strategyto design highly selective catalysts with functional metal sites for hydrogen or syngas production with a regulated H2/CO ratio.
