Ding Peijia, Xue Yufeng, Chai Ziwei, Hu Qi, Tong Chuanjia, Teobaldi Gilberto, Liu Li-Min
School of Physics, Beihang University, Beijing 100191, People's Republic of China.
Department of Chemistry, University of Zurich, CH-8057 Zurich, Switzerland.
J Phys Chem Lett. 2024 Mar 14;15(10):2859-2866. doi: 10.1021/acs.jpclett.4c00201. Epub 2024 Mar 6.
Transition metal hydr(oxy)oxides (TMHs) are considered efficient electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. Toward identification of potential descriptors to circumvent the scaling relation limit for the OER, first-principles calculations were used to quantify the effects on the overpotential of different s (Mg), p (Al), and d (Ti, V, Cr, Fe, Co, Sc, and Zn) electron dopants in Ni-based TMHs. Both the adsorbate evolution mechanism (AEM) and the lattice oxygen-mediated mechanism (LOM) were examined. The results demonstrate that the formation energy of oxygen vacancies () is strongly affected by the chemical nature of the dopants. A linear relationship is identified between and the free energy difference for the oxygen-oxygen coupling. A descriptor could be employed to discriminate whether the LOM is energetically favored over the AEM. These findings fill existing gaps in appropriate yet computationally light descriptors for direct identification between the AEM and LOM.
过渡金属氢（氧）氧化物（TMHs）被认为是碱性条件下析氧反应（OER）的高效电催化剂。为了确定潜在的描述符以规避OER的比例关系限制，采用第一性原理计算来量化不同s（Mg）、p（Al）和d（Ti、V、Cr、Fe、Co、Sc和Zn）电子掺杂剂对镍基TMHs过电位的影响。研究了吸附质演化机制（AEM）和晶格氧介导机制（LOM）。结果表明，氧空位的形成能（）受掺杂剂化学性质的强烈影响。在与氧-氧耦合的自由能差之间确定了线性关系。可以使用一个描述符来区分LOM在能量上是否比AEM更有利。这些发现填补了在合适但计算量小的描述符方面的现有空白，以便直接识别AEM和LOM。
