Breaking steric hindrance restriction: compressed metal bonds realizing deep-level orbital delocalization
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ID: 319813
2026
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Abstract
Abstract The introduction of large functional groups is a well-established strategy to enhance the stability and value of chemicals. However, the accompanying steric hindrance effects can significantly impede reaction progress, presenting a critical dilemma in synthetic design. Herein, a vacancy-constrained strategy was proposed to breaking steric hindrance restriction by realizing the deep-level delocalization of catalyst with compressed metal bonds. In detail, the delocalized deep-level orbit exhibits strong penetrating capability to overcome the steric hindrance effect of large functional groups by enhancing the charge-transfer process between the active sites and substrates. By taking bismuth atoms supported on defective CeO2 as an example, an ‘O4-Bi-Bi-O4’ ensemble was constructed by confining two adjacent Bi atoms in the vacancy of CeO2 nanosheets, where the Bi–Bi bond was strongly constrained from 3.10 Å to 3.05 Å. Such a functional Bi2/CeO2 catalyst exhibits enhanced photocatalytic efficiency in overcoming the steric hindrance from large functional groups, which is three times and two times higher than that of Bi single-atom catalyst and Bi clusters catalyst. This work proposed an applicable way in overcoming steric hindrance effects during high value-added chemical synthesis.
| Reference Key |
openalex_W7167470616
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|---|---|
| Authors | Hanghao Ying, Lei Xu, Xia Zhong, Yi Liu, Xi Zhang, Y D Xie |
| Journal | national science review |
| Year | 2026 |
| DOI |
10.1093/nsr/nwag388
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| URL | |
| Keywords | Keywords not found |
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