Atomically mixed Fe-group nanoalloys: catalyst design for the selective electrooxidation of ethylene glycol to oxalic acid
Atomically mixed Fe-group nanoalloys: catalyst design for the selective electrooxidation of ethylene glycol to oxalic acid
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DOI：
10.1039/c5cp00954e
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发表时间：
2015-01-01
影响因子：
3.3
通讯作者：
Yamauchi, Miho
中科院分区：
文献类型：
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作者：
Matsumoto, Takeshi;Sadakiyo, Masaaki;Yamauchi, Miho
我们演示了在碱性介质中通过一系列铁基纳米合金（NA）催化剂上乙二醇（EG）的电氧化发电。合成了一系列以碳为载体的铁基二元NA催化剂（FeCo/C、FeNi/C和CoNi/C）和一元类似物（Fe/C、Co/C和Ni/C）。采用循环伏安法和计时电流法研究了所制备的Fe基NA催化剂在EG电氧化反应中的催化活性和产物分布，并与已报道的FeCoNi/C催化剂进行了比较，阐明了金属组分对EG电氧化活性、C-2产物选择性和催化剂耐久性的影响.含Co的催化剂，如Co/C、FeCo/C和FeCoNi/C，对EG的电氧化表现出较高的催化活性，而含Ni的催化剂的催化活性相对较低。然而，我们发现包含Ni是防止由于催化剂表面改性而导致快速降解的必要条件。值得注意的是，FeCoNi/C在0.4V下相对于可逆氢电极（RHE）显示出最高的草酸生产选择性而不产生CO2，这是由于所有组分元素的协同作用。最后，我们进行了发电使用的直接EG碱性燃料电池的存在下，铁族催化剂。在每种催化剂上获得的功率密度直接反映了相应催化剂在电化学实验中阐明的催化性能。本文公开的催化作用和合金化效应提供了关于设计含有Fe族金属的高效电催化剂的信息。
We demonstrate electric power generation via the electrooxidation of ethylene glycol (EG) on a series of Fe-group nanoalloy (NA) catalysts in alkaline media. A series of Fe-group binary NA catalysts supported on carbon (FeCo/C, FeNi/C, and CoNi/C) and monometallic analogues (Fe/C, Co/C, and Ni/C) were synthesized. Catalytic activities and product distributions on the prepared Fe-group NA catalysts in the EG electrooxidation were investigated by cyclic voltammetry and chronoamperometry, and compared with those of the previously reported FeCoNi/C, which clarified the contributory factors of the metal components for the EG electrooxidation activity, C-2 product selectivity, and catalyst durability. The Co-containing catalysts, such as Co/C, FeCo/C, and FeCoNi/C, exhibit relatively high catalytic activities for EG electrooxidation, whereas the catalytic performances of Ni-containing catalysts are relatively low. However, we found that the inclusion of Ni is a requisite for the prevention of rapid degradation due to surface modification of the catalyst. Notably, FeCoNi/C shows the highest selectivity for oxalic acid production without CO2 generation at 0.4 V vs. the reversible hydrogen electrode (RHE), resulting from the synergetic contribution of all of the component elements. Finally, we performed power generation using the direct EG alkaline fuel cell in the presence of the Fe-group catalysts. The power density obtained on each catalyst directly reflected the catalytic performances elucidated in the electrochemical experiments for the corresponding catalyst. The catalytic roles and alloying effects disclosed herein provide information on the design of highly efficient electrocatalysts containing Fe-group metals.