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@ARTICLE{Karmakar:596137,
author = {Karmakar, Sanchita and Barman, Soumitra and Rahimi, Faruk
Ahamed and Biswas, Sandip and Nath, Sukhendu and Maji, Tapas
Kumar},
title = {{D}eveloping post-modified {C}e-{MOF} as a photocatalyst: a
detail mechanistic insight into {CO}$_2$ reduction toward
selective {C}2 product formation},
journal = {Energy $\&$ environmental science},
volume = {16},
number = {5},
issn = {1754-5692},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {PUBDB-2023-06068},
pages = {2187 - 2198},
year = {2023},
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.},
cin = {DOOR ; HAS-User},
ddc = {690},
cid = {I:(DE-H253)HAS-User-20120731},
pnm = {6G3 - PETRA III (DESY) (POF4-6G3) / INDIA-DESY - INDIA-DESY
Collaboration $(2020_Join2-INDIA-DESY)$},
pid = {G:(DE-HGF)POF4-6G3 / $G:(DE-HGF)2020_Join2-INDIA-DESY$},
experiment = {EXP:(DE-H253)P-P64-20150101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000964676500001},
doi = {10.1039/D2EE03755F},
url = {https://bib-pubdb1.desy.de/record/596137},
}