Xu Wenfan, Zhou Limei, Liu Lining, Duan Huimei, Ben Haoxi, Chen Sheng, Li Xingyun
State Key Laboratory of BioFibers and Eco-Textiles, Institute of Materials for Energy and Environment, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, China.
Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province, China West Normal University, Nanchong 637002, China.
Nanomaterials (Basel). 2024 May 22;14(11):907. doi: 10.3390/nano14110907.
Defect manipulation in metal oxide is of great importance in boosting catalytic performance for propane oxidation. Herein, a selective atom removal strategy was developed to construct a defective manganese oxide catalyst, which involved the partial etching of a Mg dopant in MnO. The resulting MgMnO-H catalysts exhibited superior low-temperature catalytic activity (T = 185 °C, T = 226 °C) with a propane conversion rate of 0.29 μmol·g·h for the propane oxidation reaction, which is 4.8 times that of pristine MnO. Meanwhile, a robust hydrothermal stability was guaranteed at 250 °C for 30 h of reaction time. The comprehensive experimental characterizations revealed that the catalytic performance improvement was closely related to the defective structures including the abundant (metal and oxygen) vacancies, distorted crystals, valence imbalance, etc., which prominently weakened the Mn-O bond and stimulated the mobility of surface lattice oxygen, leading to the elevation in the intrinsic oxidation activity. This work exemplifies the significance of defect engineering for the promotion of the oxidation ability of metal oxide, which will be valuable for the further development of efficient non-noble metal catalysts for propane oxidation.
金属氧化物中的缺陷调控对于提升丙烷氧化的催化性能至关重要。在此,我们开发了一种选择性原子去除策略来构建有缺陷的氧化锰催化剂,该策略涉及对MnO中Mg掺杂剂的部分蚀刻。所得的MgMnO-H催化剂在丙烷氧化反应中表现出优异的低温催化活性(T = 185 °C,T = 226 °C),丙烷转化率为0.29 μmol·g·h,是原始MnO的4.8倍。同时,在250 °C下反应30小时可确保其具有强大的水热稳定性。综合实验表征表明,催化性能的提升与包括大量(金属和氧)空位、晶体畸变、价态失衡等在内的缺陷结构密切相关,这些缺陷显著削弱了Mn-O键并促进了表面晶格氧的迁移,从而导致本征氧化活性的提高。这项工作例证了缺陷工程对于提升金属氧化物氧化能力的重要性,这对于丙烷氧化高效非贵金属催化剂的进一步开发具有重要价值。