Fulai Liu, Xutao Gao, Rui Shi, Jinfan Xiong, Zhengxiao Guo, Edmund C. M. Tse, Yong Chen
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引用次数: 0
Abstract
Adipic acid (AA) is a crucial feedstock for nylon polymers, and is industrially produced by thermal oxidation of cyclohexanone/cyclohexanol mixture (KA oil). However, this process consumes large quantities of corrosive nitric acid as oxidants, while emits ozone-depleting greenhouse gas N2O. Here, an electrocatalytic strategy for selective oxidation of KA oil to AA coupled with H2 evolution over a Co3O4/graphdiyne cooperative catalyst (Co3O4/GDY) is reported. The Co3O4/GDY displays high electrooxidation activity of KA oil to AA (100 mA cm−2 at ≈1.5 V vs RHE), outperforming all the reported findings. Detailed ex situ and in situ experimental studies, theoretical calculations, and molecular dynamic simulations reveal that GDY not only facilitates the enrichment of cyclohexanone on the catalyst surface in aqueous medium, but also upshifts the d-band center of Co sites, strengthening the adsorption/activation of cyclohexanone. This study offers a green route for AA synthesis and proposes a GDY interface engineering strategy for efficient electrooxidation.
己二酸(AA)是尼龙聚合物的重要原料,其工业化生产是通过对环己酮/环己醇混合物(KA 油)进行热氧化来实现的。然而,这一过程需要消耗大量具有腐蚀性的硝酸作为氧化剂,同时还会排放出破坏臭氧层的温室气体 N2O。本文报告了一种在 Co3O4/石墨二炔协同催化剂(Co3O4/GDY)上将 KA 油选择性氧化为 AA 并产生 H2 的电催化策略。Co3O4/GDY 将 KA 油电解氧化成 AA 的活性很高(100 mA cm-2,相对于 RHE ≈1.5 V),优于所有已报道的研究结果。详细的原位和原位实验研究、理论计算和分子动力学模拟表明,在水介质中,GDY 不仅能促进催化剂表面环己酮的富集,还能使 Co 位点的 d 带中心上移,从而增强对环己酮的吸附/活化。这项研究为 AA 的合成提供了一条绿色途径,并提出了一种实现高效电氧化的 GDY 界面工程策略。
期刊介绍:
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