# Transition Metal Chelation Effect in MOF-253 Materials: Guest Molecule Adsorption Dynamics and Proposed Formic Acid Synthesis Investigated by Atomistic Simulations

## TL;DR

This paper uses simulations to study how guest molecules interact with MOF-253 materials, focusing on the role of transition metal chelation and its potential for CO2 reduction.

## Contribution

The study introduces a new mechanism for formic acid synthesis from CO2 and H2 using binuclear TM catalytic sites in MOF-253.

## Key findings

- Linker orientation in MOF-253 affects guest molecule adsorption and is hard to distinguish via PXRD.
- Short inter-TM structures may form binuclear catalytic sites for CO2 reduction.
- A formic acid generation mechanism is proposed using DFT calculations.

## Abstract

The dynamic characterization of guest molecules in the metal–organic frameworks (MOFs) can always provide the insightful and inspiring information to facilitate the synthetic design of MOF materials from the bottom-up design of perspective. Herein, we present a series of atomistic molecular dynamics simulation for investigating the bipyridine dicarboxylate (bpydc) linker rotation effect on guest molecule adsorption with and without considering the transition metal (TM) chelation in MOF-253 materials. The simulated PXRD patterns of the various linker orientations present the challenge of distinguishing these structural varieties by the conventional crystalline spectroscopic measurements. The observed short inter-TM stable structure may subsequently lead to the formation of a binuclear TM catalytic site, and a proposed formic acid generation mechanism from CO2 and H2 is derived based upon the density functional theory calculations for the application of CO2 reduction.