Operando NMR spectroscopic analysis of proton transfer in heterogeneous photocatalytic reactions.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 27311326.
- Also identified by DOI 10.1038/ncomms11918 and PMC identifier 4915033.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Proton transfer (PT) processes in solid-liquid phases play central roles throughout chemistry, biology and materials science. Identification of PT routes deep into the realistic catalytic process is experimentally challenging, thus leaving a gap in our understanding. Here we demonstrate an approach using operando nuclear magnetic resonance (NMR) spectroscopy that allows to quantitatively describe the complex species dynamics of generated H2/HD gases and liquid intermediates in pmol resolution during photocatalytic hydrogen evolution reaction (HER). In this system, the effective protons for HER are mainly from H2O, and CH3OH evidently serves as an outstanding sacrificial agent reacting with holes, further supported by our density functional theory calculations. This results rule out controversy about the complicated proton sources for HER. The operando NMR method provides a direct molecular-level insight with the methodology offering exciting possibilities for the quantitative studies of mechanisms of proton-involved catalytic reactions in solid-liquid phases.