The_Catalyst_Review_December_2023 - 16

converted into CH3CHO* with O-terminal adsorption on the Ag site, which is further protonated into CH3
on the bridge In-Ag site. At this point, CH3
CH2O* is hydrogenated to ethanol. imultaneously, H2
CH2O* with O-terminal adsorption
dissociated to provide protons for the protonation of carbonaceous intermediates. The reduction pathway for CO2
Figure 2 . Gibbs free-energy profiles for CO2
H: white; O: red.
O molecules adsorbed on Se sites can be
ER to ethanol on Agx
nanosheets is summarized in Figure 2. Xiangyu , Zhiwei J, Peng , et al. (2023) Angew. Chem. Int. Ed., doi.org/10.1002/anie.202313646
and b) Ag+-doped InSe. c) Gibbs free-energy profiles for the reduction of CO to ethanol on InSe (in green) and Ag+
Schematic illustration for the catalytic mechanism of ethanol production in CO2
ER to formate (in purple) and CO (in red), and the activation of *CO to *CHO* (in blue) on a) InSe
-doped InSe (in purple). d)
ER on Ag+-doped InSe. In: orange; Se: yellow; Ag: blue; C: gray;
In1- x
Sey
Carborane-based Three-dimensional Covalent Organic Frameworks
Covalent organic frameworks (COFs) are
of particular interest due to their potential
use in gas adsorption separation and other
processes. When heteroatoms are introduced
into the pore walls of COFs, new physical
and chemical characteristics emerge that can
interact with guest molecules, influencing key
processes such as adsorption, separation,
and catalysis. However, exact control over
composition, topology, porosity, and stability
to realize tailored functioning remains a
significant challenge. Herein, the authors
describe a new kind of three-dimensional
carborane-based COF with a 7-fold
interpenetrating diatopological structure.
These COFs exhibited high crystallinity,
exceptional porosity, and strong robustness.
More significantly, the slightly lower
electronegativity of boron (2.04) than that of
hydrogen (2.20) can lead to the polarization
of the B−H bond into a Bδ+
−Hδ−
mode, which
renders these COFs as high-performance
materials for the adsorption and separation
of hexane isomers through the B−Hδ−
···Hδ+
interaction.
16
The Catalyst Review
December 2023
−C
Figure 1. Design and synthesis of 3D carborane-based COFs. (a) Schematic diagrams for
the synthesis of TAA-DFCB-COF and TAPM-DFCB-COF under solvothermal conditions. Top
views of a structural representation of (b) TAA-DFCB-COF and (c) TAPM-DFCB-COF (C,
blue spot; N, yellow spot; B, pink spot; H, white spot).
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