Qiu Chenxi, Zhou Qiang, Gao Rui, Guo Yizheng, Qin Jiaqi, Wang Dongqi, Song Yujiang
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China.
Nanomaterials (Basel). 2023 Sep 28;13(19):2669. doi: 10.3390/nano13192669.
Direct ascorbic acid fuel cells (DAAFCs) employ biocompatible ascorbic acid (AA) as fuel, allowing convenient storage, transportation, and fueling as well as avoiding fuel crossover. The AA oxidation reaction (AAOR) largely governs the performance of DAAFCs. However, AAOR electrocatalysts currently have low activity, and state-of-the-art ones are limited to carbon black. Herein, we report the synthesis of an unprecedented AAOR electrocatalyst comprising 3.9 ± 1.1 nm CeO nanoparticles evenly distributed on carbon black simply by the wet chemical precipitation of Ce(OH) and a subsequent heat treatment. The resultant CeO/C shows a remarkable AAOR activity with a peak current density of 13.1 mA cm, which is 1.7 times of that of carbon black (7.67 mA cm). According to X-ray photoelectron spectroscopy (XPS), the surface Ce of CeO appears to contribute to the AAOR activity. Furthermore, our density functional theory (DFT) calculation reveals that that the proton of the hydroxyl group of AA can easily migrate to the bridging O sites of CeO, resulting in a faster AAOR with respect to the pristine carbon, -COOH, and -C=O sites of carbon. After an i-t test, CeO/C loses 17.8% of its initial current density, which is much superior to that of carbon black. CeO can capture the electrons generated by the AAOR to protect the -COOH and -C=O sites from being reduced. Finally, DAAFCs fabricated with CeO/C exhibit a remarkable power density of 41.3 mW cm, which is the highest among proton-exchange-membrane-based DAAFCs in the literature.
直接抗坏血酸燃料电池(DAAFCs)使用生物相容性抗坏血酸(AA)作为燃料,便于储存、运输和加注,同时避免了燃料交叉。抗坏血酸氧化反应(AAOR)在很大程度上决定了DAAFCs的性能。然而,目前AAOR电催化剂的活性较低,最先进的电催化剂仅限于炭黑。在此,我们报告了一种前所未有的AAOR电催化剂的合成,该催化剂由3.9±1.1nm的CeO纳米颗粒均匀分布在炭黑上,通过Ce(OH)的湿化学沉淀和随后的热处理即可实现。所得的CeO/C表现出显著的AAOR活性,峰值电流密度为13.1mA/cm²,是炭黑(7.67mA/cm²)的1.7倍。根据X射线光电子能谱(XPS),CeO的表面Ce似乎对AAOR活性有贡献。此外,我们的密度泛函理论(DFT)计算表明,AA羟基的质子可以很容易地迁移到CeO的桥连O位点,从而导致相对于原始碳、-COOH和碳的-C=O位点而言,AAOR更快。经过i-t测试后,CeO/C的初始电流密度损失了17.8%,这远优于炭黑。CeO可以捕获AAOR产生的电子,以保护-COOH和-C=O位点不被还原。最后,用CeO/C制备的DAAFCs表现出41.3mW/cm²的显著功率密度,这是文献中基于质子交换膜的DAAFCs中最高的。