Harada Jaye K, Charles Nenian, Poeppelmeier Kenneth R, Rondinelli James M
Department of Materials Science and Engineering, Northwestern University, Evanston, IL, 60208, USA.
Department of Chemistry, Northwestern University, Evanston, IL, 60208, USA.
Adv Mater. 2019 May;31(19):e1805295. doi: 10.1002/adma.201805295. Epub 2019 Mar 12.
The burgeoning field of anion engineering in oxide-based compounds aims to tune physical properties by incorporating additional anions of different size, electronegativity, and charge. For example, oxychalcogenides, oxynitrides, oxypnictides, and oxyhalides may display new or enhanced responses not readily predicted from or even absent in the simpler homoanionic (oxide) compounds because of their proximity to the ionocovalent-bonding boundary provided by contrasting polarizabilities of the anions. In addition, multiple anions allow heteroanionic materials to span a more complex atomic structure design palette and interaction space than the homoanionic oxide-only analogs. Here, established atomic and electronic principles for the rational design of properties in heteroanionic materials are contextualized. Also described are synergistic quantum mechanical methods and laboratory experiments guided by these principles to achieve superior properties. Lastly, open challenges in both the synthesis and the understanding and prediction of the electronic, optical, and magnetic properties afforded by anion-engineering principles in heteroanionic materials are reviewed.
氧化物基化合物中新兴的阴离子工程领域旨在通过引入具有不同尺寸、电负性和电荷的额外阴离子来调节物理性质。例如，氧硫属化物、氧氮化物、氧磷化物和氧卤化物可能会表现出一些新的或增强的响应，而这些响应在更简单的同阴离子（氧化物）化合物中是难以预测甚至不存在的，这是因为它们接近由阴离子极化率差异所提供的离子共价键边界。此外，与仅含同阴离子氧化物的类似物相比，多种阴离子使杂阴离子材料能够跨越更复杂的原子结构设计范围和相互作用空间。在此，将杂阴离子材料性能合理设计的既定原子和电子原理置于具体情境中进行阐述。还介绍了受这些原理指导的协同量子力学方法和实验室实验，以实现优异性能。最后，综述了杂阴离子材料中阴离子工程原理在合成以及电子、光学和磁性能的理解与预测方面所面临的开放性挑战。
