Water Reaction Mechanism in Metal Organic Frameworks with Coordinatively Unsaturated Metal Ions: MOF-74

TL;DR

This study uses in situ IR spectroscopy and first-principles calculations to investigate water dissociation mechanisms on MOF-74, revealing temperature-dependent reactions and spectroscopic signatures of dissociation, advancing understanding of water interactions with metal-organic frameworks.

Contribution

The paper demonstrates the use of combined spectroscopic and computational methods to elucidate water dissociation mechanisms on MOF-74, a model system for oxide surface reactions.

Findings

Water adsorption on MOF-74 is reversible below 19.7 Torr.

Water dissociation occurs at ~150°C even at low vapor pressures.

Distinct IR signature identified for D2O dissociation at high temperature.

Abstract

Water dissociation represents one of the most important reactions in catalysis, essential to the surface and nano sciences [e.g., Hass et al., Science, 1998, 282, 265-268; Brown et al., Science 2001, 294, 67-69; Bikondoa et al., Nature 2005, 5, 189-192]. However, the dissociation mechanism on most oxide surfaces is not well understood due to the experimental challenges of preparing surface structures and characterizing reaction pathways. To remedy this problem, we propose the metal organic framework MOF-74 as an ideal model system to study water reactions. Its crystalline structure is well characterized; the metal oxide node mimics surfaces with exposed cations; and it degrades in water. Combining in situ IR spectroscopy and first-principles calculations, we explored the MOF-74/water interaction as a function of vapor pressure and temperature. Here, we show that, while adsorption is reversible below the water condensation pressure (~19.7 Torr) at room temperature, a reaction takes place at ~150 centigrades even at low water vapor pressures. This important finding is unambiguously demonstrated by a clear spectroscopic signature for the direct reaction using D2O, which is not present using H2O due to strong phonon coupling. Specifically, a sharp absorption band appears at 970 cm-1 when D2O is introduced at above 150 centigrades, which we attribute to an O-D bending vibration on the phenolate linker. Although H2O undergoes a similar dissociation reaction, the corresponding O-H mode is too strongly coupled to MOF vibrations to detect. In contrast, the O-D mode falls in the phonon gap of the MOF and remains localized.