立方体咪唑骨架衍生CoFe合金纳米粒子嵌入N-掺杂石墨化碳中用于锌空气电池放电反应（英文）

目前,贵金属铂被认为是性能最优异的氧还原催化剂,但是其昂贵的价格、有限的储量制约了其大规模应用,因此制备具有高催化活性和稳定性的过渡金属基催化剂迫在眉睫.在本工作中,我们构筑了一种CoFe合金纳米颗粒嵌入到N-掺杂石墨化碳纳米结构中的复合材料(CoFe/NC)作为氧还原催化剂.我们首先制备了ZIF-67纳米立方体,再利用离子交换法在其骨架中引入Fe2+形成CoFe-ZIF前驱体.通过在惰性气氛下煅烧得到CoFe/NC催化剂.由于钴、铁及氮掺杂的协同作用,CoFe/NC-0.2-900催化剂(在900°C下煅烧掺杂0.2 mmol硫酸亚铁的CoFe/NC)表现出优异的氧还原性能,尤其是极限电流密度(6.4 mA cm^-2)远高于Pt/C(5.1 mA cm^-2).采用CoFe/NC-0.2-900和NiFeP/NF(负载在泡沫镍上的NiFeP)分别作为放电和充电反应催化剂组装的可充电锌空气电池,与传统的Pt/C+RuO2/C催化剂组装的电池相比,具有较低的充放电电压差、较大的功率密度和更优异的循环稳定性.

Cubic imidazolate frameworks-derived CoFe alloy nanoparticles-embedded N-doped graphitic carbon for discharging reaction of Zn-air battery

The construction of transition metal-based catalysts with high activity and stability has been widely regarded as a promising method to replace the precious metal Pt for oxygen reduction reaction(ORR).Herein,we synthesized CoFe alloy nanoparticle-embedded N-doped graphitic carbon(CoFe/NC)nanostructures as ORR electrocatalysts.The ZIF-67(zeolitic imidazolate framework,ZIF)nanocubes were first synthesized,followed by an introduction of Fe2+ions to form CoFe-ZIF precursors via a simple ion-exchange route.Subsequently,the CoFe/NC composites were synthesized through a facile pyrolysis strategy.The ORR activity and the contents of cobalt and iron could be effectively adjusted by controlling the solution concentration of Fe2+ions used for the ion exchange and the pyrolysis temperature.The CoFe/NC-0.2-900 composite(synthesized with 0.2 mmol of FeSO4·7H2O at a pyrolysis temperature of 900℃)exhibited ORR activity that was superior to the other samples owing to a synergistic effect of the bimetal,especially considering the extremely high limiting current density of 6.4 mA cm^-2 compared with that of Pt/C(5.1 mA cm^-2).Rechargeable Zn-air batteries were assembled employing CoFe/NC-0.2-900 and NiFeP/NF(NiFeP supported on nickel foam(NF))as the catalysts for the discharging and charging processes,respectively,The above materials achieved reduced discharging and charging platforms,high power density,and prolonged cycling stability compared with conventional Pt/C+RuO2/C catalysts.