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戊二醛废料的工业电氧化制戊二酸——调控*OH覆盖度

Industrial electrooxidation of glutaraldehyde waste to glutaric acid tailoring OH* coverage.

作者信息

Han Jiani, Yu Yaodong, Wei Yingying, Bagliuk G A, Chi Jingqi, Lai Jianping, Wang Lei

机构信息

State Key Laboratory Base 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

Chem Sci. 2025 May 26;16(26):11970-11978. doi: 10.1039/d5sc02658j. eCollection 2025 Jul 2.

Abstract

Glutaric acid (GA) is an important organic chemical raw material, but current industrialized production routes suffer from process complexity, low yield, and the use of high-polluting oxidants. Electrocatalytic synthesis of GA from glutaraldehyde waste provides a sustainable alternative to highly polluting conventional production methods. However, industrial production still faces challenges such as low energy efficiency (EE) and selectivity. Here, we present a commercially feasible GA electrosynthesis strategy with an EE of 55.4%, which significantly exceeds the 34.8% EE deemed economically viable based on a technical-economic analysis. We demonstrate that the high selectivity of glutaric acid (97%) is achieved through hydroxyl spillover from the introduction of Fe, which reduces the OH* coverage on the NiOOH site to inhibit the over-oxidation of glutaraldehyde. The bifunctional electrocatalyst-catalyzed HER-GOR system exhibits high Faraday efficiencies at both electrodes (99.8% for the HER and 92.7% for the GOR) and excellent stability after 24 hours of continuous operation at 500 mA cm, achieving an EE of 55.4%.

摘要

戊二酸(GA)是一种重要的有机化工原料,但目前的工业化生产路线存在工艺复杂、产率低以及使用高污染氧化剂等问题。从戊二醛废料中电催化合成GA为高污染的传统生产方法提供了一种可持续的替代方案。然而,工业生产仍面临着诸如能源效率(EE)低和选择性差等挑战。在此,我们提出了一种商业上可行的GA电合成策略,其EE为55.4%,显著超过了基于技术经济分析认为经济可行的34.8%的EE。我们证明,通过引入Fe产生的羟基溢流实现了戊二酸的高选择性(97%),这降低了NiOOH位点上OH*的覆盖度,从而抑制了戊二醛的过度氧化。双功能电催化剂催化的HER-GOR系统在两个电极上均表现出高法拉第效率(HER为99.8%,GOR为92.7%),并且在500 mA cm下连续运行24小时后具有出色的稳定性,实现了55.4%的EE。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8477/12217597/89f01da8fa1b/d5sc02658j-f1.jpg

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