Journal Article

PUBDB-2023-06068

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Developing post-modified Ce-MOF as a photocatalyst: a detail mechanistic insight into CO$_2$ reduction toward selective C2 product formation

Karmakar, S. ; Barman, S. ; Rahimi, F. A.Extern* ; Biswas, S.Extern* ; Nath, S. ; Maji, T. K. (Corresponding author)Extern*

2023
RSC Publ. Cambridge

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Please use a persistent id in citations: doi:10.1039/D2EE03755F  doi:10.3204/PUBDB-2023-06068

Abstract: Visible light-driven C–C bond formation to produce C2-based liquid fuel selectively from CO$_2$ is of great interest and remains a challenging task due to uphill electron transfer kinetics. Herein, we have developed [Ru(bpy)$_2$]$^{2+}$-grafted UiO-66-bpydc Ce-MOFvia post-synthetic modification to harvest visible light based on MLCT $(RU_{d\pi}^{II} \to \pi_{bpy}^*)$ transition. The employment of Ru-grafted Ce-MOF facilitates fast electron transfer due to the vacant low-lying 4f orbital of Ce$^{IV}$, which was realized from ultrafast transient absorption (TA) spectroscopy, XANES, and in situ UV-vis spectroscopy. The synergistic effect of facile electron transfer and concomitant accommodation of two CO$_2$ molecules in the proximal defect-site in Ce$^{IV}$ leads to facile C–C bond formation via COOH* coupling to yield acetic acid. The catalytic assembly produces 1133 μmol g$^{−1}$ of acetic acid with an impressive rate of 128 μmol g$^{−1}$ h$^{−1}$, suppressing the formation of other C1-based carbonaceous products in water (with selectivity 99.5%, apparent quantum yield (AQY) = 0.93%). A detailed DFT calculation has been performed to understand the mechanistic pathway of C–C bond formation, and the generation of different surface-adsorbed intermediates was further supported by in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy.

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Contributing Institute(s):

1. DOOR-User (DOOR ; HAS-User)

Research Program(s):

1. 6G3 - PETRA III (DESY) (POF4-6G3) (POF4-6G3)
2. INDIA-DESY - INDIA-DESY Collaboration (2020_Join2-INDIA-DESY) (2020_Join2-INDIA-DESY)

Experiment(s):

1. PETRA Beamline P64 (PETRA III)

Appears in the scientific report 2023

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Database coverage:
; ; Clarivate Analytics Master Journal List ; Current Contents - Agriculture, Biology and Environmental Sciences ; Current Contents - Engineering, Computing and Technology ; Current Contents - Physical, Chemical and Earth Sciences ; Essential Science Indicators ; IF >= 30 ; JCR ; National-Konsortium ; SCOPUS ; Science Citation Index Expanded ; Web of Science Core Collection

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