第一性原理研究
(1. 广西大学 资源与冶金学院，南宁530004；
2. 广西大学 化学化工学院，南宁 530004)
摘 要: 采用基于密度泛函理论的平面波赝势法对含铁杂质闪锌矿(110)表面电子结构及铜在闪锌矿表面的吸附进行模拟。计算结果表明：铁杂质与锌原子的替换能均为负值，说明铁很容易替换闪锌表面的锌，且该替换反应对位置不敏感；铁杂质的存在导致表面能带向溶部移动，且在禁带中出现由铁3d轨道的tg和e2g构成的杂质能级，以及硫3p轨道分裂形成的Tamm表面态能级；铁杂质还改变了闪锌矿表面d态和sp态电子的分布；铁杂质的存在有利于闪锌矿表面锌原子与铜发生交换反应，但闪锌矿表面的铁不能与铜发生置换反应，从而减小闪锌矿表面与铜发生交换的总锌位，降低铜对闪锌矿的活化效果。
关键字: 闪锌矿；铁杂质；密度泛出理论；铜活化
（1. College of Resources and Metallurgy, Guangxi University, Nanning 530004, China;
2. College of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China）
Abstract:The simulation of Fe doped sphalerite (110) surface and Cu adsorption on the sphalerite surface were performed by using plane wave-pseudopotential approach based on density-functional theory. The results show that the substitution energy for Fe substituted Zn atom are negative which indicate the Fe is easy to substitute Zn atom on sphalerite surface, and substitute reaction is insensitive to the site. The presence of Fe impurity shifts the energy band to deep part. Impurity level composed of tg and e2g of Fe 3d orbital and Tamm surface cased by the splitting of S 3p orbital occur in the band gap. Fe impurity changes the distribution of d state and sp state electrons. The calculation suggests that Fe doping sphalerite (110) surface is favorable for the exchange of Cu with Zn at the first layer, however, the Fe atom on the surface can not be replaced by Cu atom, which reduces the total Zn activation sites of sphalerite (110) surface, and the activation of copper on the sphalerite surface becomes poor.
Key words: sphalerite; iron impurity; density functional theory (DFT); copper activation
