文献类型：期刊文献

英文题名：Dihydroxyacetone valorization with high atom efficiency via controlling radical oxidation pathways over natural mineral-inspired catalyst

作者：Wang, Jinling[1,2];Dai, Xingchao[3,4];Wang, Hualin[1];Liu, Honglai[2];Rabeah, Jabor[3];Bruckner, Angelika[3];Shi, Feng[4];Gong, Ming[5];Yang, Xuejing[1]

机构：[1]East China Univ Sci & Technol ECUST, Natl Engn Lab Ind Wastewater Treatment, Shanghai 200237, Peoples R China;[2]ECUST, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[3]Univ Rostock LIKAT, Leibniz Inst Katalyse eV, D-18059 Rostock, Germany;[4]Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China;[5]Fudan Univ, Dept Chem, Shanghai 200438, Peoples R China

年份：2021

卷号：12

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000722866700044)】；

基金：This work was supported by grants from the National Key Research and Development Program of China (2019YFC1906700), the National Natural Science Foundation of China (219611322025, 21876049, 91834301). We also thank mineral collector Qinglang Luo (Guilin Qinglang Mineral Specimens Co., Ltd.) for providing the natural minerals and his valuable discussion about the mineralogy, Dr. Casey Finnerty (University of California, Berkeley) for polishing the language of the manuscript, and Shiyanjia Lab (www.shiyanjia.com) for the assistance of HRTEM test.

语种：英文

摘要：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 MnO2/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 (center dot CH2OH) radicals, which are further oxidized into formic acid. The kinetic and isotopic labeling experiments reveal that the catalase-like activity of MnO2 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. Radicals-mediated Fenton chemistry has the potential for biomass valorization. Here, inspired from the natural goethite mineral, the authors develop a MnO2/goethite catalyst showing excellent yields of glycolic acid and formic acid from dihydroxyacetone, an important biomass-based platform molecule.