Probing Photocatalytic Reduction Pathways of CO<sub>2</sub> by Catalyst PbBiO<sub>2</sub>Br Using In-Situ Raman Spectroscopy
Kang-Yu Hsiao, Fuyu Liu, Chiing‐Chang Chen, I‐Chia Chen
Abstract
High Resolution Image Download MS PowerPoint Slide PbBiO 2 Br is an emerging semiconductor material with great potential for visible light driven photocatalysis of CO 2 reduction. In-situ Raman spectroscopy combined with density functional theory (DFT) calculations was employed to clarify the reaction mechanism of CO 2 reduction on PbBiO 2 Br. By varying the excitation light intensity and using the activated catalyst, we observed the emergence of intermediates. In total, vibrational bands of seven key intermediates were identified as follows: the C–O stretch of H*COH at the Raman band of 1266 cm –1; the asymmetric stretch of O═C–O in *O*CO – at 1548 cm –1; the C═O stretch of bridge*CO at 1980 cm –1; the C≡O stretch of atop*CO at 2059 cm –1; the C≡O stretch of OC*C*O at 2115 cm –1; the C–H stretch of O*CCHO at 2644 cm –1; and several bands in the 2786–2901 cm –1 range, attributed to C–H stretches of alkyl groups. This study provides the spectroscopic evidence of H*COH intermediate formation. Under our experimental conditions, more H*COH than the other reactive intermediate, H*C*O, likely accumulated on the catalyst surfaces and thus had a higher probability of being detected. Methane was the primary product, and small amounts of C n hydrocarbons were detected by gas chromatography. The Raman spectra confirmed some C 2 intermediates, such as OC*C*O and O*CCHO. The DFT simulations showed the active catalytic sites on the PbBiO 2 Br surface to be associated with surface oxygen atoms binding to the carbon sites of adsorbates, resulting in more favorable production of hydrocarbons than of alcohols.