采用液相控制沉淀法制备了平均粒径约为10nm的C03O4/C催化剂,运用X射线衍射和透射电镜对催化剂进行了表征,通过循环伏安法和线性扫描伏安法测试了催化剂催化氧还原反应的性能.结果表明,在酸性条件下,C03O4/C对氧还原反应具有电催化活性.利用Koutecky-Levich理论计算得到了交换电流密度为1.1×10-9A/cm2,电子转移数为2.0569,表明氧还原过程是两电子还原过程.利用Materials Studio分子模拟软件对C03O4表面上氧吸附过程进行了模拟,计算得到了O和Co原子吸附前后的态密度、电子密度、键长和吸附能.结果表明,几何构型的限制使得O在Co活性点上只能发生端基吸附,吸附后O2p轨道和Co3d轨道重叠杂化,生成新的化学键.这主要是通过Co原子周围的电子向O原子周围富集来弱化O2中的π键,并活化未吸附端O原子,H+易从另一侧与未吸附端O原子形成新的化学键,发生二电子反应.
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