Microscopic Insights into the Catalytic Activity–Stability Trade-Off on Copper Nanoclusters for CO2 Hydrogenation to HCOOH DOI
Zechen Ye, Kuiwei Yang, Kang Hui Lim

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: 129(9), P. 2247 - 2258

Published: Feb. 25, 2025

Lowly coordinated copper clusters are the most cost-effective benchmark catalysts for CO2 hydrogenation, but there is a meticulous balance between catalytic activity and stability. Herein, density functional theory (DFT) calculations implemented to examine performance of Cun nanoclusters (n = 4, 8, 16, 32) in CO2-to-HCOOH conversion. Facile activation H2 observed with significant electron transfer from antibonding orbitals H2; conversely, C–O bond poorly activated due low degree orbital overlap. During reaction, structural fluxionality occurs on Cu4 Cu8 because stability; however, negligible deformation Cu16 Cu32. In addition, achieves good kinetics each elementary which is, difficult be maintained Cu4, Cu8, Therefore, satisfies trade-off stability Energy decomposition analysis clarifies that barrier second hydrogenation originates energy hydride desorption, electronic repulsion hydroxyl group formation, as well local Cu–O cleavage. The high demand mainly sourced last term. From bottom up, this work provides microscopic insights into activity–stability HCOOH would facilitate rational design advanced high-value utilization exhaust gas.

Language: Английский

Microscopic Insights into the Catalytic Activity–Stability Trade-Off on Copper Nanoclusters for CO2 Hydrogenation to HCOOH DOI
Zechen Ye, Kuiwei Yang, Kang Hui Lim

et al.

The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: 129(9), P. 2247 - 2258

Published: Feb. 25, 2025

Lowly coordinated copper clusters are the most cost-effective benchmark catalysts for CO2 hydrogenation, but there is a meticulous balance between catalytic activity and stability. Herein, density functional theory (DFT) calculations implemented to examine performance of Cun nanoclusters (n = 4, 8, 16, 32) in CO2-to-HCOOH conversion. Facile activation H2 observed with significant electron transfer from antibonding orbitals H2; conversely, C–O bond poorly activated due low degree orbital overlap. During reaction, structural fluxionality occurs on Cu4 Cu8 because stability; however, negligible deformation Cu16 Cu32. In addition, achieves good kinetics each elementary which is, difficult be maintained Cu4, Cu8, Therefore, satisfies trade-off stability Energy decomposition analysis clarifies that barrier second hydrogenation originates energy hydride desorption, electronic repulsion hydroxyl group formation, as well local Cu–O cleavage. The high demand mainly sourced last term. From bottom up, this work provides microscopic insights into activity–stability HCOOH would facilitate rational design advanced high-value utilization exhaust gas.

Language: Английский

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