Wang Ju, Liu Yusheng, Zhuang Wenchang, Zhu Wenyou, Huang Ju, Tian Lin
School of Materials and Chemical Engineering, Xuzhou University of Technology, Xuzhou 221018, P.R. China.
ACS Omega. 2023 Jul 19;8(30):27293-27299. doi: 10.1021/acsomega.3c02667. eCollection 2023 Aug 1.
CoO, as the support of single-atom catalysts, is effective in electron-structure modulation to get distinct methanol adsorption behaviors and adjustable reaction pathways for the methanol oxidation reaction. Herein, we considered the facets that constitute a Co vacancy of the CoO(111) facet and a foreign metal atom M (M = Fe, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, Mn) leading to single-atom catalysts. The Mn@CoO(111) facet is the facet considered the most favorable among all of the possible terminations. Oxygen adsorption, decomposition, and its co-adsorption with methanol are the vital steps of methanol oxidation at the exposed Mn@CoO(111) facet, giving rise to the stable configuration: two O* and one CHOH* adsorbates. Then, the Mn@CoO(111) facet activates the O-H and C-H bonds within CHOH*, advances CHO* → HCO* → HCOO* → COO*, and releases the products H, HO, and CO consecutively.
作为单原子催化剂的载体，CoO在电子结构调制方面具有有效性，可实现不同的甲醇吸附行为以及甲醇氧化反应中可调节的反应路径。在此，我们考虑了构成CoO(111)晶面的Co空位和引入导致单原子催化剂的外来金属原子M（M = Fe、Ni、Cu、Ru、Rh、Pd、Ag、Os、Ir、Pt、Au、Mn）的晶面。在所有可能的晶面终止结构中，Mn@CoO(111)晶面被认为是最有利的晶面。氧吸附、分解及其与甲醇的共吸附是暴露的Mn@CoO(111)晶面上甲醇氧化的关键步骤，从而形成稳定构型：两个O和一个CHOH吸附质。然后，Mn@CoO(111)晶面激活CHOH中的O-H键和C-H键，推进CH0 → HCO* → HCOO* → COO*，并依次释放产物H、HO和CO。
