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The effects of three different mixing methods of CuO/ZnO/Al2O3 (CZA) and HZSM-5 bifunctional catalyst on the stability for dimethyl ether (DME) synthesis from carbon dioxide (CO2) hydrogenation were investigated. When the bifunctional catalyst was prepared by method A (mixing powder without pelletization), there was no significant change in DME production and catalyst stability when the HZSM-5 loading was varied between 0.1 g and 0.5 g with a fixed CZA loading of 0.5 g,. When the bifunctional catalysts were prepared by method B (pressed into pellets of CZA and pellets of HZSM-5 and then mixed) and method C (mixed CZA and HZSM-5 powders, then pressed into pellets), the mixing methods did not initially impact CO2 conversion and had a minor effect on DME yield. However, long-term tests (100 h) indicated that the mixing method had a significant influence on the catalyst stability. Method B showed the best stability and the extent of catalyst deactivation followed the sequence of method B < method A < method C. Characterizations of spent catalysts indicated that method B could reduce the extent of copper (Cu) oxidation, which due to the relatively low surface contact between Cu active sites and HZSM-5. Large amounts of water generated in CO2 hydrogenation to synthesize DME and intimate contact between CZA and HZSM-5 catalyst could induce severe oxidation of Cu and metal ions migration from hydrogenation catalyst to HZSM-5, which can result in the number reduction of acidic sites. Keywords: Dimethyl ether (DME), CO2 hydrogenation, Bifunctional catalyst, Mixing method