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Solar driven CO hydrogenation to HCOOH on (TiO) ( = 1-6) atomic clusters
Artificial photosynthesis is a crucial reaction that addresses energy and environmental challenges by converting CO 2 into fuels and value-added chemicals. However, efficient catalytic activity using earth-abundant materials can be challenging due to intrinsic limitations. Herein, we explore neutral...
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Published in: | Physical chemistry chemical physics : PCCP 2023-10, Vol.25 (41), p.28533-2854 |
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Main Authors: | , , , , , , , |
Format: | Article |
Language: | |
Online Access: | Get full text |
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Summary: | Artificial photosynthesis is a crucial reaction that addresses energy and environmental challenges by converting CO
2
into fuels and value-added chemicals. However, efficient catalytic activity using earth-abundant materials can be challenging due to intrinsic limitations. Herein, we explore neutral (TiO
2
)
n
(
n
= 1-6) atomic clusters for CO
2
hydrogenation
via
comprehensive
ab initio
calculations combined with time-dependent functional theory. Our results show that these (TiO
2
)
n
clusters exhibit outstanding thermodynamic stabilities and decent surficial activities for CO
2
activation and H
2
dissociation, both of which possess kinetic barriers down to 0-0.74 eV. We establish a relationship between the binding strength of *CO
2
species and electron characterization for these (TiO
2
)
n
clusters. These clusters, which have a wide energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccpied molecular orbital (LUMO) that allows them to harvest the solar light in the ultraviolet regime, enabling efficient catalysis for driving the catalysis of CO
2
conversion. They provide exclusive reaction channels and high selectivity for yielding HCOOH products
via
the carboxyl mechanism, involving the kinetic barrier of the limiting step of 0.74-1.25 eV. We also investigated the substrate effect on supported (TiO
2
)
n
clusters, with non-metallic substrates featuring inert surfaces serving as suitable options for anchoring (TiO
2
)
n
clusters while preserving their intrinsic activity and selectivity. These computational results have significant implications not only for meeting energy demands but also for mitigating carbon emissions by utilizing CO
2
as an alternative feedstock rather than considering it solely as a greenhouse gas.
Artificial photosynthesis is a crucial reaction that addresses energy and environmental challenges by converting CO
2
into fuels and value-added chemicals. |
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ISSN: | 1463-9076 1463-9084 |
DOI: | 10.1039/d3cp03473a |