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用于将甘油高效电重整为甲酸的臭氧辅助铜基催化剂。

Ozone-Assisted Cu-Based Catalysts for the Efficient Electro-Reforming Glycerol to Formic Acid.

作者信息

Liu Yan, Zhao Liang, Fei Jiawei, Zhou Jun, Li Hongdong, Lai Jianping, Wang Lei

机构信息

Key Laboratory of Eco-chemical Engineering, Ministry of Education, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P.R. China.

Shandong Engineering Research Center for Marine Environment Corrosion and Safety Protection, College of Environment and Safety Engineering, Qingdao University of Science and Technology, Qingdao, 266042, P. R. China.

出版信息

ChemSusChem. 2025 Jan 14;18(2):e202400149. doi: 10.1002/cssc.202400149. Epub 2024 Oct 18.

Abstract

Glycerol electrooxidation reaction (GOR) to produce value-added chemicals, such as formic acid, could make more efficient use of abundant glycerol and meet future demand for formic acid as a fuel for direct or indirect formic acid fuel cells. Non-noble metal Cu-based catalysts have great potential in electro-reforming glycerol to formic acid. However, the high activity, selectivity and stability of Cu based catalysts in GOR cannot be achieved simultaneously. Here, we used ozone-assisted electrocatalyst to convert glycerol to formic acid under alkaline conditions, the onset potential was reduced by 60 mV, the Faraday efficiency (FE) reached 95 %. The catalyst has excellent stability within 300 h at the current density of 10 mA cm. The electron spin resonance proved that ozone produced superoxide anion during the GOR. In situ Raman spectroscopy, electrochemical studies showed that glycerol can be activated with ozone in GOR, and the C-C bond can be broken to reduce the polymerization of glycerol on the catalyst surface, so as to produce more formic acid at a lower voltage. Moreover, the removal of dissolved O from water can be up to 100 % after 30 minutes of GOR reaction at a solubility of 50 mg L as measured by UV-VIS spectrophotometry.

摘要

甘油电氧化反应(GOR)用于生产增值化学品,如甲酸,可更高效地利用丰富的甘油,并满足未来对甲酸作为直接或间接甲酸燃料电池燃料的需求。非贵金属铜基催化剂在将甘油电重整为甲酸方面具有巨大潜力。然而,铜基催化剂在GOR中无法同时实现高活性、高选择性和高稳定性。在此,我们使用臭氧辅助电催化剂在碱性条件下将甘油转化为甲酸,起始电位降低了60 mV,法拉第效率(FE)达到95%。该催化剂在10 mA cm的电流密度下300 h内具有优异的稳定性。电子自旋共振证明臭氧在GOR过程中产生超氧阴离子。原位拉曼光谱、电化学研究表明,甘油在GOR中可被臭氧活化,C-C键可被打破以减少甘油在催化剂表面的聚合,从而在较低电压下产生更多甲酸。此外,通过紫外可见分光光度法测量,在50 mg L的溶解度下进行30分钟的GOR反应后,水中溶解氧的去除率可达100%。

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