Efficient catalysis of unsaturated hydrocarbon hydrogenation/isomerization reactions is important for realizing sustainable chemical processes and enhancing the whole energy efficiency. However, the development of “one-pot” catalysts with high activity, excellent selectivity and outstanding stability remains a major challenge. This study presents a novel catalyst design that utilizes NU-1000 with open metal sites to enhance metal-molecule interactions and promote selective adsorption. By using a strategic multimetal doping technique Ti/Zr/Hf, homomeric high-density frustrated Lewis pairs (FLPs) architecture with different coordination metals namely M-NU-1000-X (M=Zr, Hf, Ti, X = 1~6 represented various metal combinations) were obtained. The strategic multimetal doping finely tune FLPs’ acidity/basicity and electron structure favorable for improve acid-base synergism effect and steric hindrance effect. DFT calculations reveal a mechanism that generated active hydrogen through cleaving H2 at the FLPs site then attack cycloolefin double bond selectively. The hydrogenation/isomerization mechanism was promoted greatly by catalysis effect induced by metals-based π anti-donation effect. Furthermore, we constructed a robust connection model between the calculated Gibbs free energy values of the transition state and some parameter and obtained activation energy barriers based on the descriptor model, thus significantly decreasing huge computational cost. Dynamic Time Warping (DTW) analysis reveals that the dynamic response of polarizability and LUMO energy levels is a key factor determining catalytic activity. The introduction of Ti significantly enhances these dynamic differences, while dynamic site regulation of the local coordination environment further amplifies the differentiation in catalytic performance. A novel approach has been established that integrates electronic structure properties, reaction path evolution, and energy descriptors. This opens a new gateway for developing highly efficient hydrogenation catalysts and provides innovative strategies for catalyst design.
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2025 The Author(s). Carbon Neutralization published by Wenzhou University and John Wiley & Sons Australia, Ltd.
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