Dihydroxyacetone valorization with high atom efficiency via controlling radical oxidation pathways over natural mineral-inspired catalyst.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 34824262.
- Also identified by DOI 10.1038/s41467-021-27240-5 and PMC identifier 8617048.
- 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
Diminishing fossil fuel resources and calls for sustainability are driving the urgent need for efficient valorization of renewable resources with high atom efficiency. Inspired from the natural goethite mineral with Mn paragenesis, we develop cost-effective MnO<sub>2</sub>/goethite catalysts for the efficient valorization of dihydroxyacetone, an important biomass-based platform molecule, into value-added glycolic acid and formic acid with 83.2% and 93.4% yields. The DHA substrates first undergo C-C cleavage to selectively form glycolic acid and hydroxymethyl (·CH<sub>2</sub>OH) radicals, which are further oxidized into formic acid. The kinetic and isotopic labeling experiments reveal that the catalase-like activity of MnO<sub>2</sub> turns the oxidative radicals into oxygen, which then switches towards a hydroxymethyl peroxide (HMOO) pathway for formic acid generation and prevents formic acid over-oxidation. This nature-inspired catalyst design not only significantly improves the carbon efficiency to 86.6%, but also enhances the oxygen atom utilization efficiency from 11.2% to 46.6%, indicating a promising biomass valorization process.