We demonstrate a molecular-level observation of controlling the structures of small molecules on the solid surface of metal nanoparticles (NP). This is achieved via the unique interface between a metal–organic framework (MOF) and a metal NP surface formed by coating NPs with a MOF. For example, using real-time surface-enhanced Raman scattering spectroscopy, a &gt;18-fold enhancement of surface coverage of CO2 is observed at the interface. The high surface concentration leads CO2 molecules to be in close proximity with the probe molecules on the metal surface (4-methylbenzenethiol), and transforms CO2 molecules into a bent conformation without the formation of chemical bonds. Such linear-to-bent transition of CO2 is unprecedented at ambient conditions in the absence of chemical bond formation, and is commonly observed only in pressurized systems (&gt;105 bar). The molecular-level observation of a quasi-condensed phase induced by MOF coating could impact the future design of hybrid materials in diverse applications, including catalytic CO2 conversion and ambient solid–gas operation.<br/>

Controlling the structures of small molecules at the interface between a nanoparticle surface and a metal–organic framework

256th National Meeting (2018)

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