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Updated: Jun 5, 2026

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance
Published on: September 5, 2018
Origin of enhanced dihydrogen-metal interaction in carboxylate bridged Cu2-paddle-wheel frameworks
Yong-Hyun Kim1, Joongoo Kang, Su-Huai Wei
1Graduate School of Nanoscience and Technology (WCU), KAIST, Daejeon 305-701, Korea. yong.hyun.kim@kaist.ac.kr
Abstract:
The experimentally observed enhancement of hydrogen adsorption in Cu2-tetracarboxylate paddle-wheel frameworks is investigated by ab initio density-functional theory calculations. We reveal that the puzzling enhancement is due to the effective orbital coupling between the occupied H2 σ and the unoccupied Cu 4s-derived states. The nontrivial dihydrogen-metal σ-s interaction is enabled by a strong localization of the Cu 4s orbital after hybridizing with the neighboring oxygen 2p orbitals. Based on this understanding, we predict that the dihydrogen-metal interaction can be further increased by alloying Cu with s-orbital element Zn or Mg.
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