Biphasic Titania Derivatives of Titanium Metal‐Organic Framework Nanoplates for High‐Efficiency Photoreduction of Diluted CO2 to Methane

• Published in: ChemCatChem Vol. 13; no. 9; pp. 2215 - 2221
• Main Authors: Zheng, Ya‐Li, Ren, Jia‐Tong, Zhou, Liang, Yuan, Kun, Sun, Xiao‐Chen, Yin, Hai‐Jing, Zhang, Ya‐Wen
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 07.05.2021
• Subjects: 2D Ti-based MOF; Anatase; anatase/rutile interface; Carbon dioxide; CO2 photoreduction; defective engineering; Methane; Rutile; Selectivity; Titanium; Titanium dioxide
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202002005

Exploring earth‐abundant materials for low concentration CO2 photoreduction is the key in the energy related field. Here, we demonstrated biphasic titania (anatase and rutile) derived from Ti‐based metal‐organic framework (MOF) nanoplates exhibited excellent performance in CO2 photoreduction without any co‐catalysts and sacrificial agents under ambient condition, the maximum CH4 production rate was up to 65.39 μmol g−1 h−1 with near 100 % electron selectivity as well as great stability. The activity of the optimal derivative was maintained well even in 1 % CO2 (CH4: 45.59 μmol g−1 h−1) and much better than that of commercial P25. The upgraded performance originated from the synergism between local anatase/rutile interface and numerous defective sites (Ti3+ and Ov), by promoting the separation and migration of photogenerated carriers, CO2 adsorption and activation, and H2O dissociation. Besides, a possible fast hydrodeoxygenation mechanism for methane formation was proposed according to in situ DRIFTS characterization. Sun loving catalysis: Selective low concentration CO2 photoreduction: An excellent CH4 evolution rate (45.59 μmol g−1 h−1) with 96 % electron selectivity in diluted CO2 under light illumination was achieved by biphasic titania nanoplates derived from 2D Ti‐based MOF, benefiting from local anatase/rutile interface and numerous defective sites (Ti3+ and Ov) to boost separation and migration of photoinduced carriers, CO2 adsorption and activation, and H2O dissociation.