Unlocking a Dual‐channel Pathway in CO2 Hydrogenation to Methanol over Single‐site Zirconium on Amorphous Silica

Converting CO2 into methanol on a large scale is of great significance in the sustainable methanol economy. Zirconia are considered to be an essential support in Cu‐based catalysts due to its excellent properties on CO2 adsorption and activation. However, the evolution of Zr species during the reaction and the effect of their structure on the reaction pathways remain unclear. Herein, single‐site Zr species in amorphous SiO2 matrix are created by enhancing Zr‐Si interaction in Cu/ZrO2‐SiO2 catalysts. In situ X‐ray absorption spectroscopy (XAS) reveals that the coordination environment of single‐site Zr is sensitive to the atmosphere and reaction conditions. We demonstrate that the CO2 adsorption prefers on the interface of Cu and single‐site Zr rather than ZrO2 nanoparticles. Methanol synthesis in reverse water‐gas‐shift (RWGS)+CO‐hydro pathway is verified only over single‐dispersed Zr site, while ordinary formate pathway occurs on ZrO2 nanoparticles. Thus, it expands a non‐competitive parallel pathway as a supplement to the dominant formate pathway, resulting in the enhancement of Cu activity sixfold and twofold based on Cu/SiO2 and Cu/ZrO2 catalysts, respectively. The establishment of this dual‐channel pathway by single‐site Zr species in this work open new horizons for understanding atomically dispersed oxides in catalysis science.