Citation: YIN Yazhi, HU Bing, LIU Guoliang, ZHOU Xiaohai, HONG Xinlin. ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO₂ to Methanol[J]. Acta Physico-Chimica Sinica, ;2019, 35(3): 327-336. doi: 10.3866/PKU.WHXB201803212 shu

ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO₂ to Methanol

College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, P. R. China

Corresponding author: ZHOU Xiaohai, zxh7954@hotmail.com HONG Xinlin, hongxl@whu.edu.cn
Received Date: 26 February 2018
Revised Date: 12 March 2018
Accepted Date: 19 March 2018
Available Online: 21 March 2018
Fund Project: the National Science Foundation of China 21373153The project was supported by the National Science Foundation of China (21373153)

Catalytic CO₂ hydrogenation to methanol is a promising route to mitigate the negative effects of anthropogenic CO₂. To develop an efficient Pd/ZnO catalyst, increasing the contact between Pd and ZnO is of the utmost importance, because "naked" Pd favors CO production via the reverse water-gas shift path. Here, we have utilized a ZnO@ZIF-8 core-shell structure to synthesize Pd/ZnO catalysts via Pd immobilization and calcination. The merit of this method is that the porous outer layer can offer abundant "guest rooms" for Pd, ensuring intimate contact between Pd and the post-generated ZnO. The synthesized Pd/ZnO catalysts (PZZ8-T, T denotes the temperature of calcination in degree Celsius) is compared with a ZnO nanorod-immobilized Pd catalyst (PZ). When the catalytic reaction was performed at lower reaction temperatures (250, 270, and 290 ℃), the highest methanol space time yield (STY) and highest STY per Pd achieved by PZ at 290 ℃ were 0.465 g g_cat^-1 h^-1 and 13.0 g g_Pd^-1 h^-1, respectively. However, all the PZZ8-T catalysts exhibited methanol selectivity values greater than 67.0% at 290 ℃, in sharp contrast to a methanol selectivity value of 32.8% for PZ at the same temperature. Thus, we performed additional investigations of the PZZ8-T catalysts at 310 and 360 ℃, which are unusually high temperatures for CO₂ hydrogenation to methanol because the required endothermic reaction is expected to be severely inhibited at such high temperatures. Interestingly, the PZZ8-T catalysts were observed to achieve a methanol selectivity value of approximately 60% at 310 ℃, and PZZ8-400 was observed to maintain a methanol selectivity value of 51.9% even at a temperature of 360 ℃. Thus, PZZ8-400 attains the highest methanol STY of 0.571 g g_cat^-1 h^-1at 310 ℃. For a better understanding of the structure-performance relationship, we characterized the catalysts using different techniques, focusing especially on the surface properties. X-ray photoelectron spectroscopy (XPS) results indicated a linear relationship between the methanol selectivity and the surface PdZn : Pd ratio, proving that the surface PdZn phase is the active site for CO₂ hydrogenation to methanol. Furthermore, analysis of the XPS O 1s spectrum together with the electronic paramagnetic resonance results revealed that both, the oxygen vacancy as well as the ZnO polar surface, played important roles in CO₂ activation. Chemisorption techniques provided further quantitative and qualitative information regarding the Pd-ZnO interface that is closely related to the CO₂ conversion rate. We believe that our results can provide insight into the catalytic reaction of CO₂ hydrogenation from the perspective of surface science. In addition, this work is an illustrative example of the use of novel chemical structures in the fabrication of superior catalysts using a traditional formula.
- ZnO@ZIF-8,
- PdZn alloy,
- Methanol synthesis,
- CO₂ hydrogenation,
- Surface oxygen vacancy
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ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO2 to Methanol

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通讯作者: 陈斌, bchen63@163.com

ZnO@ZIF-8 Core-Shell Structure as Host for Highly Selective and Stable Pd/ZnO Catalysts for Hydrogenation of CO₂ to Methanol