Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides.
Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides.
复制标题
体相和表面对金属氧化物电离势的贡献。
DOI：
10.1002/anie.202308411
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Zhang X
中科院分区：
文献类型：
--
作者：
Zhang X
确定固体材料中的绝对能带边缘位置对于优化其在光催化和电子器件等广泛应用中的性能至关重要。然而，获得绝对能量是具有挑战性的，正如在CeO2中看到的那样，实验测量显示电离势（IP）存在很大差异。在这里，我们结合了几种理论方法，从经典静电学到量子力学，来阐明金属氧化物的体积和表面对IP的贡献。我们已经确定了化学计量ceo2的理论体积对IP的贡献仅为5.38 eV，而表面取向导致的本征IP变化范围为4.2 eV至8.2 eV。在TiO2， ZrO2和HfO2中也发现了高度可调谐的IPs，其中表面极化在远程能级转移中起关键作用。我们的分析，除了使实验结果的观察范围合理化之外，还为未来对氧化带结构的实验和计算研究的解释提供了坚实的基础。
Determining the absolute band edge positions in solid materials is crucial for optimising their performance in wide‐ranging applications including photocatalysis and electronic devices. However, obtaining absolute energies is challenging, as seen in CeO2, where experimental measurements show substantial discrepancies in the ionisation potential (IP). Here, we have combined several theoretical approaches, from classical electrostatics to quantum mechanics, to elucidate the bulk and surface contributions to the IP of metal oxides. We have determined a theoretical bulk contribution to the IP of stoichiometric CeO2of only 5.38 eV, while surface orientation results in intrinsic IP variations ranging from 4.2 eV to 8.2 eV. Highly tuneable IPs were also found in TiO2, ZrO2, and HfO2, in which surface polarisation plays a pivotal role in long‐range energy level shifting. Our analysis, in addition to rationalising the observed range of experimental results, provides a firm basis for future interpretations of experimental and computational studies of oxide band structures.