The reaction mechanism of CO 2 photoreduction into methane was elucidated by time-course monitoring of the mass chromatogram, in situ FTIR spectroscopy, and in situ extended X-ray absorption fine structure (EXAFS). Under 13 CO 2 ,H 2 , and UV/Vis light, 13 CH 4 was formed at ar ate of 0.98 mmol h À1 g cat À1 using Ni (10 wt %)-ZrO 2 that was effective at 96 kPa. Under UV/Vis light irradiation, the 13 CO 2 exchange reaction and FTIR identified physisorbed/chemisorbed bicarbonate and the reduction because of charge separation in/on ZrO 2 ,followed by the transfer of formate and CO onto the Ni surface.E XAFS confirmed exclusive presence of Ni 0 sites. Then, FTIR spectroscopyd etected methyl species on Ni 0 , which was reversibly heated to 394 Ko wing to the heat converted from light. With D 2 Oa nd H 2 ,t he H/D ratio in the formed methane agreed with reactant H/D ratio.T his study paves the way for using first row transition metals for solar fuel generation using only UV/Vis light.
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