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<p>To develop photocatalysts that function as metalloenzymes with high activity and/or selectivity, it is an essential prerequisite to precisely control spin state of the active centers. In this study, we report on the self-assembly ultrathin nanolayers of Fe<sub>4</sub> metalloclusters through intercluster <i>π</i>⋯<i>π</i> stacking interactions, where the spin transition of Fe<sup>3+</sup> active center from low-spin (LS, <i>S</i> = 1/2) to high-spin (HS, <i>S</i> = 5/2) occurs due to the substitution of only a bridging atom in the ligand. Concomitant with spin transition is a shift in redox potential by ∼210 mV and a 2.2-fold increase in current density. As a result, the photocatalytic CO<sub>2</sub> reduction performance over HS-Fe<sub>4</sub> catalyst is substantially enhanced with regard to production and selectivity (∼100%) in relative to its LS-Fe<sub>4</sub> counterpart. Density functional theory (DFT) calculations revealed that spin transition at the catalytic site switches on the increasing orbital interaction with CO<sub>2</sub> and the reduction in the Gibbs free energy for the formation of key intermediates. Hence, our findings provide an ideal model for comprehending the spin-state effect on electron transfer through preparing the self-assembly supercluster nanolayers for artificial photosynthesis.</p>

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Self-assembly ultrathin nanolayers of π-stacked Fe4 clusters boost CO2 photoreduction via spin-state-dependent electron transfer

  • 期刊论文

  • 发表日期：

    2026年2月24日

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  • Zhuofei Li,
  • Mengkai Zuo,
  • Jing Wu,
  • Hao Sun,
  • Wei Huang,
  • Dayu Wu

摘要

To develop photocatalysts that function as metalloenzymes with high activity and/or selectivity, it is an essential prerequisite to precisely control spin state of the active centers. In this study, we report on the self-assembly ultrathin nanolayers of Fe4 metalloclusters through intercluster π⋯π stacking interactions, where the spin transition of Fe3+ active center from low-spin (LS, S = 1/2) to high-spin (HS, S = 5/2) occurs due to the substitution of only a bridging atom in the ligand. Concomitant with spin transition is a shift in redox potential by ∼210 mV and a 2.2-fold increase in current density. As a result, the photocatalytic CO2 reduction performance over HS-Fe4 catalyst is substantially enhanced with regard to production and selectivity (∼100%) in relative to its LS-Fe4 counterpart. Density functional theory (DFT) calculations revealed that spin transition at the catalytic site switches on the increasing orbital interaction with CO2 and the reduction in the Gibbs free energy for the formation of key intermediates. Hence, our findings provide an ideal model for comprehending the spin-state effect on electron transfer through preparing the self-assembly supercluster nanolayers for artificial photosynthesis.