State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum (East China), Qingdao, 266580, China.
Center for Reliability Science and Technologies, Center for Green Technology, Chang Gung University, Taoyuan, 33302, Taiwan.
Small Methods. 2023 Jul;7(7):e2300121. doi: 10.1002/smtd.202300121. Epub 2023 Mar 31.
This study adopts a facile and effective in situ encapsulation-oxidation strategy for constructing a coupling catalyst composed of atomically dispersed Pt-doped Co O spinel nanoparticles (NPs) embedded in polyhedron frames (PFs) for robust propane total oxidation. Benefiting from the abundant oxygen vacancies and more highly valent active Co species caused by the doping of Pt atoms as well as the confinement effect, the optimized 0.2Pt-Co O NPs/PFs catalyst exhibits excellent propane catalytic activity with low T (184 °C), superior apparent reaction rate (21.62×10 (mol g s )), low apparent activation energy (E = 17.89 kJ mol ), high turnover frequency ( 811×10 (mol g s )) as well as good stability. In situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations indicate that the doping of Pt atoms enhances the oxygen activation ability, and decreases the energy barrier required for CH bond breaking, thus improving the deep oxidation process of the intermediate species. This study opens up new ideas for constructing coupling catalysts from atomic scale with low cost to enhance the activation of oxygen molecules and the deep oxidation of linear short chain alkanes at low temperature.
本研究采用简便有效的原位包裹-氧化策略,构建了由原子分散的 Pt 掺杂 CoO 尖晶石纳米颗粒(NPs)嵌入多面体框架(PFs)组成的耦合催化剂,用于稳定丙烷完全氧化。受益于掺杂 Pt 原子引起的丰富氧空位和更高价态的活性 Co 物种以及限域效应,优化的 0.2Pt-CoO NPs/PFs 催化剂表现出优异的丙烷催化活性,低温 T(184°C)、高表观反应速率(21.62×10(mol g s))、低表观活化能(E = 17.89 kJ mol)、高周转频率(811×10(mol g s))和良好的稳定性。原位漫反射红外傅里叶变换光谱和密度泛函理论计算表明,掺杂 Pt 原子增强了氧的活化能力,降低了 CH 键断裂所需的能垒,从而改善了中间物种的深度氧化过程。本研究为构建从原子尺度、低成本的耦合催化剂提供了新思路,以增强氧气分子的活化和低温下线性短链烷烃的深度氧化。