Gan Tao, Yang Jingxiu, Morris David, Chu Xuefeng, Zhang Peng, Zhang Wenxiang, Zou Yongcun, Yan Wenfu, Wei Su-Huai, Liu Gang
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Electron Microscopy Center, Jilin University, Changchun, China.
Key Laboratory for Comprehensive Energy Saving of Cold Regions Architecture of Ministry of Education, School of Materials Science and Engineering, Jilin Jianzhu University, Changchun, China.
Nat Commun. 2021 May 12;12(1):2741. doi: 10.1038/s41467-021-22946-y.
Activation of O is a critical step in heterogeneous catalytic oxidation. Here, the concept of increased electron donors induced by nitrogen vacancy is adopted to propose an efficient strategy to develop highly active and stable catalysts for molecular O activation. Carbon nitride with nitrogen vacancies is prepared to serve as a support as well as electron sink to construct a synergistic catalyst with Pt nanoparticles. Extensive characterizations combined with the first-principles calculations reveal that nitrogen vacancies with excess electrons could effectively stabilize metallic Pt nanoparticles by strong p-d coupling. The Pt atoms and the dangling carbon atoms surround the vacancy can synergistically donate electrons to the antibonding orbital of the adsorbed O. This synergistic catalyst shows great enhancement of catalytic performance and durability in toluene oxidation. The introduction of electron-rich non-oxide substrate is an innovative strategy to develop active Pt-based oxidation catalysts, which could be conceivably extended to a variety of metal-based catalysts for catalytic oxidation.
氧的活化是多相催化氧化中的关键步骤。在此，采用由氮空位诱导的电子供体增加的概念，提出一种开发用于分子氧活化的高活性和稳定催化剂的有效策略。制备具有氮空位的氮化碳用作载体以及电子阱，以与铂纳米颗粒构建协同催化剂。广泛的表征结合第一性原理计算表明，具有过量电子的氮空位可以通过强p-d耦合有效地稳定金属铂纳米颗粒。围绕空位的铂原子和悬空碳原子可以协同向吸附氧的反键轨道供电子。这种协同催化剂在甲苯氧化中表现出催化性能和耐久性的极大提高。引入富电子非氧化物载体是开发活性铂基氧化催化剂的创新策略，这可以想象地扩展到用于催化氧化的各种金属基催化剂。
