Cooperative Catalysis of Vibrationally Excited CO 2 and Alloy Catalyst Breaks the Thermodynamic Equilibrium Limitation

作者：Dae-Yeong Kim, Hyungwon Ham, Xiaozhong Chen, Shuai Liu, Haoran Xu, Bang Lu, Shinya Furukawa, Hyun‐Ha Kim, Satoru Takakusagi, Koichi Sasaki, Tomohiro Nozaki · 发表于：Journal of the American Chemical Society · 年份：2022 · DOI：10.1021/jacs.2c03764 · 被引用次数：89 · 研究领域：Catalytic Processes in Materials Science、CO2 Reduction Techniques and Catalysts、Catalysts for Methane Reforming

Using nonthermal plasma (NTP) to promote CO 2 hydrogenation is one of the most promising approaches that overcome the limitations of conventional thermal catalysis. However, the catalytic surface reaction dynamics of NTP-activated species are still under debate. The NTP-activated CO 2 hydrogenation was investigated in Pd 2 Ga/SiO 2 alloy catalysts and compared to thermal conditions. Although both thermal and NTP conditions showed close to 100% CO selectivity, it is worth emphasizing that when activated by NTP, CO 2 conversion not only improves more than 2-fold under thermal conditions but also breaks the thermodynamic equilibrium limitation. Mechanistic insights into NTP-activated species and alloy catalyst surface were investigated by using in situ transmission infrared spectroscopy, where catalyst surface species were identified during NTP irradiation. Moreover, in in situ X-ray absorption fine-structure analysis under reaction conditions, the catalyst under NTP conditions not only did not undergo restructuring affecting CO 2 hydrogenation but also could clearly rule out catalyst activation by heating. In situ characterizations of the catalysts during CO 2 hydrogenation depict that vibrationally excited CO 2 significantly enhances the catalytic reaction. The agreement of approaches combining experimental studies and density functional theory (DFT) calculations substantiates that vibrationally excited CO 2 reacts directly with hydrogen adsorbed on Pd sites while accelerating...