使用密度泛函理论研究了Pd掺杂的Ni(111),Ni(100)和Ni(211)表面最稳定的结构,同时考察了干净的和Pd掺杂的Ni表面催化CH4解离反应的活性.结果表明,由Pd原子取代最外层Ni原子而形成的表面Pd掺杂的Ni表面在热力学上最为稳定,亚表面Pd掺杂的Ni表面在热力学上都不稳定;而对于表面Pd吸附的Ni表面,只有Pd/Ni(211)表面是稳定的,表面掺杂的Pd/Ni表面上CH4解离中间体(CH4,CH3,CH,C,H)吸附能的计算结果表明,Pd的掺杂在不同程度上减弱了除CH4之外各解离中间体的吸附能.另外,CH4和CH均优先在Ni(211)和Pd/Ni(211)台阶面上解离,其次是在比较开阔的Ni(100)和Pd/Ni(100)表面上.Pd的掺杂不同程度上提高了CH4和CH解离的能垒,对于活性最高的Ni(211)面,Pd的掺杂使得CH脱氢的能垒较CH4脱氢的高,改变了其速率控制步骤,从而抑制了积碳的生成.
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