Wu Shipeng, Ruan Dinghua, Huang Zhen, Xu Hualong, Shen Wei
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Collaborative Innovation Center of Chemistry for Energy Materials, Fudan University, 220 Handan Road, 200433 Shanghai, China.
Inorg Chem. 2024 Jun 3;63(22):10264-10277. doi: 10.1021/acs.inorgchem.4c00715. Epub 2024 May 18.
Exploring highly efficient and robust non-noble metal catalysts for VOC abatement is crucial but challenging. Mn-based perovskites are a class of redox catalysts with good thermal stability, but their activity in the catalytic combustion of light alkanes is insufficient. In this work, we modulated the Mn-O bond strength in a Mn-based perovskite via defect engineering, over which the catalytic activity of propane combustion was significantly enhanced. It demonstrates that the oxygen vacancy concentration and the Mn-O bond strength can be efficiently modulated by finely tuning the Ni content in SmNiMnO perovskite catalysts (SNM), which in turn can enhance the redox ability and generate more active oxygen species. The SNM catalyst with the lowest Mn-O bond strength exhibits the lowest apparent activation energy, over which the propane conversion rate increases by 3.6 times compared to that on the SmMnO perovskite catalyst (SM). In addition, a SNM/cordierite monolithic catalyst can also exhibit a remarkable catalytic performance and deliver excellent long-term durability (1000 h), indicating broad prospects in industrial applications. Moreover, the promotional effect of Ni substitution was further unveiled by density functional theory (DFT) calculations. This work brings a favorable guidance for the exploration of highly efficient perovskite catalysts for light alkane elimination.
探索用于挥发性有机化合物(VOC)消除的高效且稳健的非贵金属催化剂至关重要但具有挑战性。锰基钙钛矿是一类具有良好热稳定性的氧化还原催化剂,但其在轻质烷烃催化燃烧中的活性不足。在这项工作中,我们通过缺陷工程调节了锰基钙钛矿中的Mn - O键强度,在此基础上丙烷燃烧的催化活性显著提高。结果表明,通过精细调节SmNiMnO钙钛矿催化剂(SNM)中的镍含量,可以有效调节氧空位浓度和Mn - O键强度,进而增强氧化还原能力并产生更多活性氧物种。具有最低Mn - O键强度的SNM催化剂表现出最低的表观活化能,在此条件下丙烷转化率比SmMnO钙钛矿催化剂(SM)提高了3.6倍。此外,SNM/堇青石整体式催化剂也能表现出卓越的催化性能并具有出色的长期耐久性(1000小时),表明其在工业应用中具有广阔前景。此外,通过密度泛函理论(DFT)计算进一步揭示了镍取代的促进作用。这项工作为探索用于轻质烷烃消除的高效钙钛矿催化剂提供了有益的指导。