Citation: Xinmeng Xu, Zuoshuai Xi, Hongyi Gao, Jing Lin, Jingjing Wang, Xiao Chen, Ge Wang. Structural and electronic co-engineering of Ce-MOFs enables highly dispersed, electron-rich Ni sites for efficient, durable hydrogenation catalysis[J]. Chinese Chemical Letters, ;2026, 37(11): 112404. doi: 10.1016/j.cclet.2026.112404 shu

Structural and electronic co-engineering of Ce-MOFs enables highly dispersed, electron-rich Ni sites for efficient, durable hydrogenation catalysis

Xinmeng Xu ^{a, 1} ,
Zuoshuai Xi ^{a, 1} ,
Hongyi Gao ^{a, b, *,} ,
Jing Lin ^a ,
Jingjing Wang ^a ,
Xiao Chen ^{c, *,} ,
Ge Wang ^{a, *,}

a.
Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
b.
Shunde Innovation School, University of Science and Technology Beijing, Shunde 528399, China
c.
School of Physics and Astronomy, Beijing Normal University, Beijing 100875, China

hygao@ustb.edu.cn

xiaochen@bnu.edu.cn

gewang@ustb.edu.cn

Received Date: 6 October 2025
Revised Date: 29 December 2025
Accepted Date: 12 January 2026
Available Online: 12 January 2026

Figures(6)

The electronic structure and stability of active sites are crucial for catalytic activity in hydrogenation. Herein, we report a structural–electronic dual-engineering strategy for constructing highly dispersed, electron-rich Ni⁰ active sites within Ce-MOFs (Ce-TCPP-X_MAA), achieving high efficiency and durability. Structurally, in situ introduction of mercaptoacetic acid (MAA) in Ce-TCPP enhanced metal–support electronic interactions and, together with pore confinement, synergistically stabilized highly dispersed Ni sites. Electronically, in situ alloying of Ni and Cu fosters intimate Ni–Cu coupling, while the high reduction potential of Cu, together with the pronounced redox activity and 4f orbital features of Ce nodes, synergistically modulates the electronic structure of Ni to form electron-rich Ni⁰ centers. The optimized NiCu_0.1@Ce-TCPP-20_MAA catalyst achieves nearly 100% conversion and selectivity in dicyclopentadiene hydrogenation under mild conditions, maintaining activity over eight cycles. Comparative experimental and computational results demonstrated that thiol anchoring, pore confinement, Cu-induced lattice distortion, and electron transfer from Ce collectively preserved the dispersion and stability of Ni⁰ under reaction conditions. This work offers new insights into designing non-noble metal hydrogenation catalysts.
- Cerium-based MOFs,
- Hydrogenation catalysis,
- Structural–electronic dual engineering,
- Ni active sites,
- Thiol anchoring,
- Sintering stability
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