Lee Wooseok, Kim Jongseung, Kim Heejin, Back Seoin
Department of Chemical and Biomolecular Engineering, Institute of Emergent Materials, Sogang University, Seoul, 04107, Republic of Korea.
Division of Analytical Science, Korea Basic Science Institute (KBSI), Yuseong-gu, Daejon, 34133, Republic of Korea.
Phys Chem Chem Phys. 2022 Aug 24;24(33):19911-19918. doi: 10.1039/d2cp01518h.
Transition metal dichalcogenides (TMDs) have been considered as promising materials for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysis. While there have been numerous studies focusing on layered TMDs, the ORR and OER catalytic activity trends of various cubic pyrite TMDs have not been systematically explored yet. Herein, we investigated 12 earth abundant element-based pyrite TMDs (MX, where M = Mn, Fe, Co, Ni and X = S, Se, Te) using density functional theory (DFT) calculations. We initially constructed surface Pourbaix diagrams to determine the most stable surface coverages under the reaction conditions and found that the oxidized surfaces are most energetically preferred in all cases. We then calculated the binding free energies of reaction intermediates (O*, OH* and OOH*) and established their scaling relations. The electrochemical ORR and OER performances were then displayed on two-dimensional volcano plots, which suggest MnS, FeS, NiTe and CoSe to be ORR active, and CoTe and CoSe to be OER active. In addition, we built multivariate linear regression models to predict Δ and Δ using only atomic and bulk properties to readily estimate the catalytic activities of pyrite TMDs and to explore correlations between those properties. Particularly, we found that the electron affinity and bulk Bader charges of metal atoms are critical in determining the ORR and OER catalytic activities, which could be used as a guidance for future catalyst design.
过渡金属二硫属化物（TMDs）被认为是用于氧还原反应（ORR）和析氧反应（OER）电催化的有前景的材料。虽然已经有许多研究聚焦于层状TMDs，但各种立方黄铁矿TMDs的ORR和OER催化活性趋势尚未得到系统探索。在此，我们使用密度泛函理论（DFT）计算研究了12种基于地球丰富元素的黄铁矿TMDs（MX，其中M = Mn、Fe、Co、Ni，X = S、Se、Te）。我们首先构建了表面Pourbaix图，以确定反应条件下最稳定的表面覆盖情况，发现氧化表面在所有情况下在能量上都是最有利的。然后我们计算了反应中间体（O*、OH和OOH）的结合自由能，并建立了它们的标度关系。然后在二维火山图上展示了电化学ORR和OER性能，这表明MnS、FeS、NiTe和CoSe具有ORR活性，而CoTe和CoSe具有OER活性。此外，我们建立了多元线性回归模型，仅使用原子和体相性质来预测Δ和Δ，以便轻松估计黄铁矿TMDs的催化活性，并探索这些性质之间的相关性。特别地，我们发现金属原子的电子亲和能和体相巴德电荷在决定ORR和OER催化活性方面至关重要，这可为未来的催化剂设计提供指导。
