Hess Peter
Institute of Physical Chemistry, INF 253, University of Heidelberg, 69120 Heidelberg, Germany.
Nanoscale Horiz. 2021 Oct 25;6(11):856-892. doi: 10.1039/d1nh00113b.
This tutorial review describes the ongoing effort to convert main-group elements of the periodic table and their combinations into stable 2D materials, which is sometimes called modern 'alchemy'. Theory is successfully approaching this goal, whereas experimental verification is lagging far behind in the synergistic interplay between theory and experiment. The data collected here gives a clear picture of the bonding, structure, and mechanical performance of the main-group elements and their binary compounds. This ranges from group II elements, with two valence electrons, to group VI elements with six valence electrons, which form not only 1D structures but also, owing to their variable oxidation states, low-symmetry 2D networks. Outside of these main groups reviewed here, predominantly ionic bonding may be observed, for example in group II-VII compounds. Besides high-symmetry graphene with its shortest and strongest bonds and outstanding mechanical properties, low-symmetry 2D structures such as various borophene and tellurene phases with intriguing properties are receiving increasing attention. The comprehensive discussion of data also includes bonding and structure of few-layer assemblies, because the electronic properties, , the band gap, of these heterostructures vary with interlayer layer separation and interaction energy. The available data allows the identification of general relationships between bonding, structure, and mechanical stability. This enables the extraction of periodic trends and fundamental rules governing the 2D world, which help to clear up deviating results and to estimate unknown properties. For example, the observed change of the bond length by a factor of two alters the cohesive energy by a factor of four and the extremely sensitive Young's modulus and ultimate strength by more than a factor of 60. Since the stiffness and strength decrease with increasing atom size on going down the columns of the periodic table, it is important to look for suitable allotropes of elements and binaries in the upper rows of the periodic table when mechanical stability and robustness are issues. On the other hand, the heavy compounds are of particular interest because of their low-symmetry structures with exotic electronic properties.
本教程综述描述了将元素周期表中的主族元素及其化合物转化为稳定二维材料的持续努力,这有时被称为现代“炼金术”。理论已成功朝着这一目标迈进,而在理论与实验的协同作用中,实验验证却远远滞后。此处收集的数据清晰地展现了主族元素及其二元化合物的键合、结构和力学性能。这涵盖了从具有两个价电子的第II族元素到具有六个价电子的第VI族元素,它们不仅形成一维结构,而且由于其可变的氧化态,还形成低对称性的二维网络。在本文所综述的这些主族之外,例如在第II - VII族化合物中,可能主要观察到离子键。除了具有最短和最强键以及出色力学性能的高对称性石墨烯外,具有有趣性质的低对称性二维结构,如各种硼烯和碲烯相,也受到越来越多的关注。对数据的全面讨论还包括少层组装体的键合和结构,因为这些异质结构的电子性质,即带隙,会随层间间距和相互作用能而变化。现有数据有助于确定键合、结构和力学稳定性之间的一般关系。这使得能够提取出支配二维世界的周期性趋势和基本规则,有助于厘清偏差结果并估计未知性质。例如,观察到键长变化两倍会使内聚能变化四倍,而杨氏模量和极限强度极其敏感,变化超过60倍。由于在元素周期表的列中,随着原子尺寸增大,刚度和强度会降低,因此当涉及力学稳定性和坚固性问题时,在元素周期表的上排寻找合适的元素和二元化合物的同素异形体很重要。另一方面,重化合物因其具有奇异电子性质的低对称性结构而特别受关注。