相對於貴金屬觸媒，鎳金屬觸媒是二氧化碳氫化非常好的選擇，因為其價格低廉與良好的活性，而鎳觸媒在二氧化碳氫化最主要的產物眾所周知是甲烷，並且有一氧化碳與水的副產物，但由於甲烷的使用多只用於燃料，想將甲烷轉化是非常的困難的，而一氧化碳能作為其他碳氫化合物的前驅物，可利用價值較高。因此如何去調控一氧化碳與甲烷的選擇性，是本研究主要的探討方向，本研究通過不同鎳擔載二氧化矽觸媒的反應性測試，發現透過Silicalite-1 分子篩限域鎳原子的方式，Ni0.2@S-1-red在二氧化碳氫化中，在常壓450℃與GHSV= 6000 mL/gCat/h反應條件時達到了>99％的一氧化碳選擇性及良好的一氧化碳空時產率(9.7 mol/gNi/h)，二氧化碳轉化率趨近於平衡轉化率，並且其選擇性不會受到氣體流速與溫度影響而改變，這由於Ni0.2@S-1-red 含有強Ni-O-Si作用與高分散的Niδ+和Ni0並且有著適洽的二氧化碳與一氧化碳吸附能力，使其有此反應性。而透過化學吸附性質與原味紅外線光譜鑑定，可得知HCO2 和 CO*為主要的反應中間產物，而不同觸媒對一氧化碳的吸附能力與CO* 是否會繼續氫化為反應產物選擇性的關鍵。本研究以XRD、BET、HRTEM、ICP、XAS、XPS、pyridine-IR、in-situ DRIFTS等鑑定方法進行觸媒探討與反應之可行性。

The catalytic hydrogenation of CO2 to CO via the reverse water-gas shift (RWGS) was investigated using Ni/SiO2-based catalysts. Among the array of catalysts tested, the Ni/SiO2 catalyst derived from the reduction of Silicalite-1-encapsulated, ligand-protected Ni2+ (Ni0.2@S-1-red) exhibited superior performance. This catalyst demonstrated a CO2 conversion rate approaching the equilibrium conversion of RWGS, a selectivity for CO exceeding 99%, and a high space time yield of CO (9.7 mol/gNi/h). The exceptional outcomes observed can be attributed to several factors, namely the highly dispersed Ni0 and Niδ+ species and the presence of bridging oxygen of the Ni-O-Si structure, of which CO2 can be adsorbed moderately. The moderately bonded CO2 on Ni0.2@S-1-red allows for the efficient desorption of its reduced intermediate, i.e. *CO, resulting in the generation of gaseous CO at a rapid rate, consequently preventing its deep hydrogenation to CH4.

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