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加入优级纯 CsCl 作内标,用其中 Cs3d_(■/2)校正荷电效应,准确地测定了 HPW_nMo_(12-n)(n=0,3,6,9,12)及 HXM_(12)(X=P,As,Si,Ge;M=W,Mo)中 Ols 及 HPM_(12)中 P2p 的结合能,发现钨系中 Ols 的结合能比钼系中的高0.5eV;P2p 的结合能则相应地高0.8eV;同种金属的磷系杂多酸中 Ols 结合能比其他杂原子中的高约0.3eV.通过差热分析发现同类型杂多酸的热稳定性与阴离子中 Ols 结合能呈近似平行的关系.结果表明,跟钼系杂多酸相比,钨系杂多酸中氧原子有较低的电子云密度,钨氧之间有更多的轨道重叠;含磷杂多酸跟其他杂多酸相比,金属、氧之间有更强的相互作用.
CsHCl (12-n) (n = 0, 3, 6, 9, 12) and HXM_ (12) were accurately measured by using Cs3d_ (■ / (X = P, As, Si, Ge; M = W, Mo), and found that the binding energy of Ols in the tungsten system was higher than that in the molybdenum system by 0.5 eV; the binding of P2p The corresponding high 0.8eV; same metal phosphorus heteropoly acid Ols binding energy higher than other heteroatoms in about 0.3eV. Differential thermal analysis found that the same type of heteropoly acid thermal stability and anionic Ols The results show that compared with molybdenum-based heteropolyacids, oxygen atoms in tungsten-based heteropolyacids have lower electron cloud density and more orbital overlap between tungsten and oxygen; Polyacids have a stronger interaction with metals and oxygen than other heteropoly acids.