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Efficient and Selective Interplay Revealed: CO 2 Reduction to CO over ZrO 2 by Light with Further Reduction to Methane over Ni 0 by Heat Converted from Light
Author(s) -
Zhang Hongwei,
Itoi Takaomi,
Konishi Takehisa,
Izumi Yasuo
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202016346
Subject(s) - formate , fourier transform infrared spectroscopy , extended x ray absorption fine structure , chemistry , spectroscopy , absorption (acoustics) , analytical chemistry (journal) , methane , bicarbonate , transition metal , absorption spectroscopy , photochemistry , inorganic chemistry , catalysis , materials science , organic chemistry , physics , quantum mechanics , composite material
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 a rate of 0.98 mmol h −1 g cat −1 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. EXAFS confirmed exclusive presence of Ni 0 sites. Then, FTIR spectroscopy detected methyl species on Ni 0 , which was reversibly heated to 394 K owing to the heat converted from light. With D 2 O and H 2 , the H/D ratio in the formed methane agreed with reactant H/D ratio. This study paves the way for using first row transition metals for solar fuel generation using only UV/Vis light.