Electro-oxidation of furfural on gold is limited by furoate self-assembly
Electro-oxidation of furfural on gold is limited by furoate self-assembly
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DOI：
10.1016/j.jcat.2020.08.034
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发表时间：
2020-11-01
影响因子：
7.3
通讯作者：
Holewinski, Adam
中科院分区：
文献类型：
--
作者：
Roman, Alex M.;Agrawal, Naveen;Holewinski, Adam
利用电催化处理生物质衍生化合物已显示出将有价值原料的生产与可再生电力的储存直接结合起来的前景。电催化转化的一种潜在途径是将糠醛部分氧化为糠酸（FA），糠酸是 2,5-呋喃二甲酸（FDCA）的前体。我们利用微分电化学反应器研究以及红外光谱（ATR-SEIRAS）实验和密度泛函理论（DFT）计算来探讨酸性电解质中糠醛在金催化剂上的氧化反应途径。我们发现糠醛电氧化活性（类似于 1.0 V-RHE 下的 2 mA/cm(Au)(2)）比 Pt/C 上观察到的高一个数量级。 FA 的法拉第效率在 0.8 V-RHE 时达到 96 +/- 6%。产物解吸是速率限制的，光谱证据表明最丰富的中间体是表面糠酸盐。稀释糠醛时观察到的更深层次的氧化产物表明糠酸盐物质的自组装有助于选择性。 (C) 2020 Elsevier Inc. 保留所有权利。
Processing of biomass-derived compounds with electrocatalysis has shown promise to directly couple the production of valuable feedstocks with the storage of renewably produced electricity. One potential route of electrocatalytic conversion is the partial oxidation of furfural to furoic acid (FA), a precursor to 2,5-furandicarboxylic acid (FDCA). We have utilized differential electrochemical reactor studies along with infrared spectroscopy (ATR-SEIRAS) experiments and density functional theory (DFT) calculations to probe the oxidative reaction pathways of furfural on gold catalysts in acidic electrolyte. We find furfural electro-oxidation activity (similar to 2 mA/cm(Au)(2) at 1.0 V-RHE) to be an order of magnitude higher than that observed on Pt/C. 96 +/- 6% Faradaic efficiency to FA is achieved at 0.8 V-RHE. Product desorption is rate limiting, and spectroscopic evidence indicates that the most abundant intermediate is surface furoate. Deeper oxidation products observed with dilution of furfural suggest that self-assembly of the furoate species contributes to selectivity. (C) 2020 Elsevier Inc. All rights reserved.