In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 30902990.
- Also identified by DOI 10.1038/s41467-019-09188-9 and PMC identifier 6430772.
- 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
Single-atom catalysts have recently been applied in many applications such as CO oxidation. Experimental in situ investigations into this reaction, however, are limited. Hereby, we present a suite of operando/in situ spectroscopic experiments for structurally well-defined atomically dispersed Rh on phosphotungstic acid during CO oxidation. The identification of several key intermediates and the steady-state catalyst structure indicate that the reactions follow an unconventional Mars-van Krevelen mechanism and that the activation of O<sub>2</sub> is rate-limiting. In situ XPS confirms the contribution of the heteropoly acid support while in situ DRIFT spectroscopy consolidates the oxidation state and CO adsorption of Rh. As such, direct observation of three key components, i.e., metal center, support and substrate, is achieved, providing a clearer picture on CO oxidation on atomically dispersed Rh sites. The obtained information are used to engineer structurally similar catalysts that exhibit T<sub>20</sub> values up to 130 °C below the previously reported Rh<sub>1</sub>/NPTA.