Bykov Alexey V, Demidenko Galina N, Nikoshvili Linda Zh, Kiwi-Minsker Lioubov
Department of Biotechnology, Chemistry and Standardization, Tver State Technical University, A. Nikitina str. 22, 170026 Tver, Russia.
Regional Technological Centre, Tver State University, Zhelyabova str. 33, 170100 Tver, Russia.
Molecules. 2021 Aug 31;26(17):5294. doi: 10.3390/molecules26175294.
Among different polymers nanostructured cross-linked aromatics have the greatest potential as catalytic supports due to their exceptional thermal and chemical stability and preservation of the active phase morphology. This work studies the ability of hyper-cross-linked polystyrene (HPS) to stabilize small Pd and Pt ( = 4 or 9) clusters. Unrestricted DFT calculations were carried out for benzene (BZ) adsorption at the BP level of theory using triple-zeta basis sets. The adsorption of BZ rings (stepwise from one to four) was found to result in noticeable gain in energy and stabilization of resulting adsorption complexes. Moreover, the interaction of metal clusters with HPS micropores was also addressed. For the first time, the incorporation of small clusters in the HPS structure was shown to influences its geometry resulting in the stabilization of polymer due to its partial relaxation.
在不同的聚合物中，纳米结构的交联芳烃因其卓越的热稳定性和化学稳定性以及活性相形态的保持，作为催化载体具有最大的潜力。这项工作研究了超交联聚苯乙烯（HPS）稳定小尺寸钯和铂（= 4或9）团簇的能力。使用三重ζ基组在BP理论水平上对苯（BZ）吸附进行了无限制密度泛函理论计算。发现BZ环的吸附（从一个逐步增加到四个）会导致能量显著增加以及所得吸附复合物的稳定。此外，还探讨了金属团簇与HPS微孔的相互作用。首次表明，小团簇在HPS结构中的掺入影响其几何形状，由于聚合物的部分弛豫导致聚合物稳定。
