Yang Miaosen, Meng Ge, Li Hongyi, Wei Tianran, Liu Qian, He Jia, Feng Ligang, Sun Xuping, Liu Xijun
School of Chemical Engineering, Northeast Electric Power University, Jilin 132012, China; Nanchang Institute of Technology, Nanchang 330044, China.
Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.
J Colloid Interface Sci. 2023 Dec 15;652(Pt A):155-163. doi: 10.1016/j.jcis.2023.08.079. Epub 2023 Aug 12.
It is an appealing avenue for electrosyntheis of high-valued chemicals at both anode and cathode by coupling 5-hydroxymethylfurfural (HMF) oxidation and nitrate reduction reactions simultaneously, while the development such bifunctional electrocatalysts is still in its infancy with dissatisfied selectivity and low yield rate. Here, we first report that Zn-doped CoO nanowires array can be served as an efficient and robust dual-functional catalyst for HMF oxidation and nitrate reduction at ambient conditions. Specifically, the catalyst shows a faradaic efficiency of 91 % and a yield rate of 241.2 μmol h cm for 2,5-furandicarboxylic acid formation together with a high conversion of nearly 100 % at a potential of 1.40 V. It also displays good cycling stability. Besides, the catalyst is capable of catalyzing the reduction of nitrate to NH, giving a maximal faradaic efficiency of 92 % and a peak NH yield rate of 4.65 mg h cm at a potential of -0.70 V. These results surpass those obtained using pristine CoO and are comparable to those of state-of-the-art electrocatalysts. Moreover, the catalyst is further employed as the cathode catalyst to assemble a Zn-nitrate battery, giving a peak power density of 5.24 mW cm and a high yield rate of 0.72 mg h cm. Theoretical simulations further reveal that Zn-doping favors the adsorption and dissociation of nitrate and HMF species and reduces the energy barrier as well. Our work demonstrates the potential interest of CoO-based materials for the highly selective production of valuable feedstocks via ambient electrolysis.
通过同时耦合5-羟甲基糠醛(HMF)氧化和硝酸盐还原反应,在阳极和阴极进行高价值化学品的电合成是一条很有吸引力的途径,然而,这种双功能电催化剂的开发仍处于起步阶段,选择性不尽人意且产率较低。在此,我们首次报道了锌掺杂的CoO纳米线阵列可作为一种高效且稳定的双功能催化剂,用于在环境条件下氧化HMF和还原硝酸盐。具体而言,该催化剂在1.40 V的电位下,对于2,5-呋喃二甲酸的生成,法拉第效率为91%,产率为241.2 μmol h cm,同时转化率接近100%。它还表现出良好的循环稳定性。此外,该催化剂能够催化硝酸盐还原为NH,在-0.70 V的电位下,最大法拉第效率为92%,NH的峰值产率为4.65 mg h cm。这些结果超过了使用原始CoO所获得的结果,并且与最先进的电催化剂相当。此外,该催化剂还被用作阴极催化剂来组装锌-硝酸盐电池,峰值功率密度为5.24 mW cm,产率为0.72 mg h cm。理论模拟进一步表明,锌掺杂有利于硝酸盐和HMF物种的吸附和解离,同时也降低了能垒。我们的工作证明了基于CoO的材料在通过环境电解高选择性生产有价值原料方面的潜在价值。