Boosting CO₂ Hydrogenation to Formic Acid Through Secondary Metal Promotion in Fe₃O-Based MOF Catalysts.

Authors

Pavee Apilardmongkol, Manussada Ratanasak, Sirilak Kongkaew, Wilasinee Santiwarodom, Thanawit Kuamit, Tatiya Chokbunpiam, Fadjar Mulya, Thanyada Rungrotmongkol, Jun-Ya Hasegawa, Yasuteru Shigeta, Vudhichai Parasuk

Published in

Journal of computational chemistry. Volume 47. Issue 24. Pages e70509. Sep 15, 2026.

Abstract

Metal-organic framework (MOF) catalysts are promising platforms for hydrogen energy systems, enabling CO₂ conversion to formic acid (HCOOH), a liquid organic hydrogen carrier (LOHC) for hydrogen storage and release. Density functional theory (DFT) calculations (M06-2X/6-31G(d)/LANL2DZ) are performed to investigate CO₂ hydrogenation on PCN-250(Fe) clusters featuring frustrated Lewis pair (FLP) sites formed by linker removal. The full hydrogenation pathway, including H₂ adsorption, activation, and HCOOH formation, is explored, with HCOOH formation identified as the rate-determining step. Activation barriers from large and small cluster models are consistent (10.0 and 9.4 kcal mol^-1). Secondary metal substitution at the Fe₂MO node is screened using first- and second-row transition metals (Mn-Zn and Tc-Cd). Results show electronic effects dominate first-row metals, whereas steric effects govern second-row systems. Kinetic volcano analysis identifies Cu(II) and Ru(III) as optimal catalysts for efficient CO₂ hydrogenation, supporting rational design of MOF-based hydrogen storage and conversion systems for sustainable energy applications.

PMID:
42728064
Bibliographic data and abstract were imported from PubMed on 12 Sep 2026.

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