Zhou Fu-Qiang, Xu Wen-Hua, Li Jin-Feng, Zhao Ru-Fang, Yin Bing
MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, College of Chemistry and Materials Science, Northwest University , Xi'an 710069, China.
Inorg Chem. 2017 Oct 2;56(19):11787-11797. doi: 10.1021/acs.inorgchem.7b01754. Epub 2017 Sep 11.
A series of 27 composite structures, consisting of superhalogen and Brønsted acid, is designed and systematically studied based on combined ab initio and DFT calculations focusing on their potentials as novel superacids. As indicated by high-level CCSD(T) results, all the composites here fulfill the theoretical criterion for superacid and the acidities of two of them are close to the strongest superacid ever reported. The influences of various factors on the superacid properties of these composites were analyzed in detail. Our results demonstrate that the acidity of these superacids is mainly determined by the superhalogen components while the effect of Brønsted acids, irrespective of their number or type, is relatively mild. Therefore, it is probable to design novel composite superacid with enhanced property through the regulation of the superhalogen component. It is encouraging that MP2 and DFT could also provide reliable results when compared with the high-level CCSD(T) method. The reliability of these low-cost methods implies the capability of theoretical calculations for future composite superacid of enlarged size, and thus it is highly probable that an effective guide to the related experimental research could be provided by the theory.
基于量子化学从头算和密度泛函理论（DFT）计算，设计并系统研究了一系列由超卤素和布朗斯特酸组成的27种复合结构，重点关注它们作为新型超强酸的潜力。高水平耦合簇单双激发（CCSD(T)）计算结果表明，这里所有的复合材料都符合超强酸的理论标准，其中两种复合材料的酸度接近有史以来报道的最强超强酸。详细分析了各种因素对这些复合材料超强酸性质的影响。我们的结果表明，这些超强酸的酸度主要由超卤素成分决定，而布朗斯特酸的影响相对较小，无论其数量或类型如何。因此，通过调节超卤素成分来设计具有增强性能的新型复合超强酸是可能的。令人鼓舞的是，与高水平CCSD(T)方法相比，MP2和DFT也能提供可靠的结果。这些低成本方法的可靠性意味着理论计算有能力处理未来更大尺寸的复合超强酸，因此理论很有可能为相关实验研究提供有效的指导。
