A Computational Framework to Accelerate the Discovery of Perovskites for Solar Thermochemical Hydrogen Production: Identification of Gd Perovskite Oxide Redox Mediators
A Computational Framework to Accelerate the Discovery of Perovskites for Solar Thermochemical Hydrogen Production: Identification of Gd Perovskite Oxide Redox Mediators
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DOI：
10.1002/adfm.202200201
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发表时间：
2022-03-20
影响因子：
19
通讯作者：
Musgrave, Charles B.
中科院分区：
文献类型：
--
作者：
Bare, Zachary-L;Morelock, Ryan N.;Musgrave, Charles B.
提出了一种识别新型多元钙钛矿氧化还原介体的高通量计算框架，并应用该框架发现了能分解水的含Gd钙钛矿氧化物组合物Gd2BB'O-6、O-GdA'B2O6和GdA'BB'O-6。该计算方案使用一系列经验方法来评估这些材料的稳定性、电子特性和氧空位热力学，包括对还原熵、Delta H-TR 和 Delta S-TR 的贡献。该方案使用机器学习描述符 tau 来识别可能作为钙钛矿稳定的成分，使用键价方法来估计 BO6 八面体倾斜的幅度和相位，并提供钙钛矿几何形状的准确初始估计，并使用包括磁和缺陷采样在内的密度泛函理论来预测 STCH 相关特性。报道了从 4392 含 Gd 组合物中向下选择的 83 种有前途的 STCH 候选钙钛矿氧化物，其中三种被提交给实验合作者进行表征并表现出 STCH 活性。结果表明，本文描述的高通量计算方案——用于评估含Gd组合物，但可以应用于任何感兴趣的多元钙钛矿氧化物组合空间——以合理的计算费用加速新型STCH活性氧化还原介体的发现。
A high-throughput computational framework to identify novel multinary perovskite redox mediators is presented, and this framework is applied to discover the Gd-containing perovskite oxide compositions Gd2BB ' O-6,O- GdA ' B2O6, and GdA ' BB ' O-6 that split water. The computational scheme uses a sequence of empirical approaches to evaluate the stabilities, electronic properties, and oxygen vacancy thermodynamics of these materials, including contributions to the enthalpies and entropies of reduction, Delta H-TR and Delta S-TR. This scheme uses the machine-learned descriptor tau to identify compositions that are likely stable as perovskites, the bond valence method to estimate the magnitude and phase of BO6 octahedral tilting and provide accurate initial estimates of perovskite geometries, and density functional theory including magnetic- and defect-sampling to predict STCH-relevant properties. Eighty-three promising STCH candidate perovskite oxides down-selected from 4392 Gd-containing compositions are reported, three of which are referred to experimental collaborators for characterization and exhibit STCH activity. The results demonstrate that the high-throughput computational scheme described herein-which is used to evaluate Gd-containing compositions but can be applied to any multinary perovskite oxide compositional space(s) of interest-accelerates the discovery of novel STCH active redox mediators with reasonable computational expense.