Direct Synthesis of Dimethyl Ether from CO2 Hydrogenation over Core-Shell Nanotube Bi-Functional Catalyst

Abstract

Directly synthesising dimethyl ether (DME) from CO2 hydrogenation is a promising technique for efficiently utilising CO2 as a feedstock to produce clean fuel. The main challenges in this process are the low CO2 conversion and DME selectivity of the catalyst and its deactivation over time due to sintering, aggregation, coke formation, and water adsorption. This study aimed to develop a dual-functional, halloysite nanotube-supported CuZnO-PTA catalyst with a core-shell structure and investigate the effects of the active site mass ratio CuZnO/PTA on CO2 conversion and DME selectivity. A dual-functional core-shell mesopores halloysite nanotube (HNT) catalyst was developed, and both active sites were co-hosted on one support. The co-impregnation method was used to synthesise CuZnO and 12-phosphotungstic acids (PTA) that were then supported by a mesoporous core-shell (HNT). BET surface area, N2 physisorption, FE-SEM, SEM, XRD, H2-TPR, and NH3-TPD of the core-shell catalyst characterised physio-chemical properties of the prepared hybrid catalyst. The experimental results showed that the synthesised CuZn-PTA@HNT core-shell bifunctional catalyst was promising; the CO2 conversion was almost the same for all four catalysts, with an average of 22.17%, while the DME selectivity reached 68.9%. Furthermore, the effect of both active sites on the hybrid catalyst was studied, and the metal Cu wt% mass ratio loading was not significant. In contrast, the PTA acid sites positively affected DME selectivity; they also showed an excellent tolerance towards the water generated in the methanol dehydration reaction. In addition, the effect of the temperature and reusability of the CZ-PTA@HNT catalyst has also been investigated, and the results show that increasing the temperature improves CO2 conversion but decreases DME selectivity. A temperature of less than 305 °C is a good compromise between CO2 conversion and DME selectivity, and the catalyst also showed good stability and continuous activity/stability over five consecutive cycles. In conclusion, this study presents a novel approach of using a core-shell halloysite nanotube-supported CuZnO-PTA catalyst to directly synthesise dimethyl ether (DME) from CO2 hydrogenation which exhibits promising results in terms of CO2 conversion and DME selectivity.

CO2 to dimethyl ether (DME): structural and functional insights of hybrid catalysts

“…158 In this perspective, Mohamud et al have designed halloysite nanotube (HNT) support where two active sites Cu/ZnO and phosphotungstic acids (PTA) are embedded via the co-impregnation method in the mesoporous core–shell of HNT. 159 Authors have stated that the bifunctional Cu/ZnO–PTA@HNT core–shell catalyst shows promising CO 2 conversion (22.17%) and DME selectivity (68.9%) where Cu particles control the methanol formation and PTA provides acidic sites from methanol dehydration to DME. On the other hand, HNT improves the surface area along with the stability and activity of Cu/ZnO by inhibiting the aggregation of Cu/ZnO particles.…”