National Engineering Laboratory for Industrial Wastewater Treatment, East China University of Science and Technology (ECUST), Shanghai, 200237, China.
State Key Laboratory of Chemical Engineering, ECUST, Shanghai, 200237, China.
Nat Commun. 2021 Nov 25;12(1):6840. doi: 10.1038/s41467-021-27240-5.
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/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 (·CHOH) radicals, which are further oxidized into formic acid. The kinetic and isotopic labeling experiments reveal that the catalase-like activity of MnO 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.
化石燃料资源的减少和对可持续性的呼吁，促使人们迫切需要高效利用具有高原子经济性的可再生资源。受天然针铁矿与锰共生的启发，我们开发了具有成本效益的 MnO/针铁矿催化剂，用于高效转化重要的生物质基平台分子二羟丙酮为附加值较高的乙二醇酸和甲酸，产率分别达到 83.2%和 93.4%。DHA 底物首先经历 C-C 断裂，选择性地生成乙二醇酸和羟甲基（·CHOH）自由基，然后进一步氧化为甲酸。动力学和同位素标记实验表明，MnO 的过氧化氢酶样活性将氧化自由基转化为氧气，然后转而通过羟甲基过氧化物（HMOO）途径生成甲酸，并防止甲酸过度氧化。这种受自然启发的催化剂设计不仅将碳效率显著提高到 86.6%，还将氧原子利用率从 11.2%提高到 46.6%，表明这是一种很有前途的生物质转化过程。
