利用XPS鉴定硫化物和多硫化物<a href="#fn1" title="提供电子补充信息（ESI）。参见DOI：10.1039 / c5ra14915k">†</a>,RSC Advances

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利用XPS鉴定硫化物和多硫化物 †
RSC Advances ( IF 3.9 ) Pub Date : 2015-08-28 00:00:00 , DOI: 10.1039/c5ra14915k
Marzia Fantauzzi _{1,

2,

3,

4,

5} , Bernhard Elsener _{1,

2,

3,

4,

5} , Davide Atzei _{1,

2,

3,

4,

5} , Americo Rigoldi _{1,

2,

3,

4,

5} , Antonella Rossi _{1,

2,

3,

4,

5}

Affiliation

基于S2p光电子光谱以及首次通过X射线激发的S KLL Auger光谱的曲线拟合，鉴定了表面硫化物和多硫化物种类。表面上存在的不同硫化学状态（多硫化物链中的硫化物S ²⁻，中心S和末端S）可以在化学状态图中明确分配。中心或末端的硫原子分别位于斜率为ca的直线上。-3与指示相似的初始状态效应的阳离子无关。另一方面，对于给定的多硫化物，例如K ₂ S _n，在同一条直线上发现中心或末端位置的硫原子，斜率-1表示相似的最终状态效应。通过多硫化物链中的负电荷主要位于末端的硫原子上，可以使这种行为合理化。实际上，以中心S形式存在的硫相对于元素硫（S ₈）的结合能位移为-0.6 eV ，而在末端S处的硫的位移能为-2.4 eV。这种方法在商业碱多硫化物测试中的应用提供了一种用于SKLL信号和硫物种形成的曲线拟合的三种不同的硫化矿物硫砷铜矿（铜₃ ASS ₄），黄铜矿（CuFeS ₂）和毒砂（FeAsS）。同样对于矿物硫化物的表面，也可以成功地确定多硫化物链中的末端S原子和中心S原子。

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Exploiting XPS for the identification of sulfides and polysulfides†

The identification of surface sulfide and polysulfide species based on the curve fitting of S2p photoelectron spectra and, for the first time, of X-ray excited S KLL Auger spectra has been performed. The different sulfur chemical states present on the surface (sulfide S²⁻, central S and terminal S in polysulfide chains) could be unambiguously assigned in the chemical state plot. Sulfur atoms in the central or terminal position, respectively, are found on a line with slope ca. −3 irrespective of the cation indicating similar initial state effects. On the other hand, for a given polysulfide, e.g. K₂S_n, sulfur atoms both in central or terminal positions are found on the same line with slope −1 indicating similar final state effects. This behavior can be rationalized with the fact that the negative charge in polysulfide chains is located mainly on sulfur atoms in the terminal position; indeed, sulfur present as central S shows a binding energy shift of −0.6 eV with respect to elemental sulfur (S₈), and sulfur in terminal S a shift of −2.4 eV. An application of this approach tested on commercial alkali polysulfides is provided for the curve fitting of SKLL signals and sulfur speciation of three different sulfide minerals enargite (Cu₃AsS₄), chalcopyrite (CuFeS₂) and arsenopyrite (FeAsS). Also for the surface of mineral sulfides, terminal S atoms and central S atoms in the polysulfide chains can successfully be identified.

更新日期：2015-08-28

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