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Suspending ionic single-atom catalysts in porphyrinic frameworks for highly efficient aerobic oxidation at room temperature
Journal of Catalysis ( IF 7.3 ) Pub Date : 2017-12-11 , DOI: 10.1016/j.jcat.2017.11.022
Wei-Long He , Xiu-Li Yang , Min Zhao , Chuan-De Wu

Room temperature and atmosphere pressure are highly desired catalytic conditions for aerobic oxidation of inert sp3 CH bonds. To meet this challenge, we developed a simple strategy by suspending ionic single atoms (ISAs) inside the anionic pores of metal–organic frameworks (MOFs). CZJ-22-Cu, consisting of suspended ISA copper(II) inside the anionic pores, exhibits exceptionally high catalytic efficiency in aerobic oxidation of ethers to esters at room temperature and atmosphere pressure, in which turnover number (TON) 77,100 and turnover frequency (TOF) 7710 h−1 have been realized for aerobic oxidation of isobenzofuran. The unmatched catalytic properties of CZJ-22-Cu are attributed to the unique features of suspended ISAs inside the anionic pores, which result in high surface free energy of redox-active centers, and the substrate-selective accumulation nature of the inside pores, which would significantly improve the reactivity and reaction rate.



中文翻译:

卟啉骨架中悬浮的离子型单原子催化剂,可在室温下高效地进行好氧氧化

室温和大气压是惰性sp 3 C H键的好氧氧化的理想催化条件。为了应对这一挑战,我们通过将离子单原子(ISA)悬浮在金属-有机骨架(MOF)的阴离子孔内而开发了一种简单的策略。CZJ-22-Cu由阴离子孔内的悬浮ISA铜(II)组成,在室温和大气压下将醚好氧氧化成酯时表现出极高的催化效率,其中周转数(TON)为77,100,周转频率为( TOF)7710小时-1已经实现了异苯并呋喃的好氧氧化。CZJ-22-Cu的无与伦比的催化性能归因于阴离子孔内悬浮ISA的独特特征,这导致氧化还原活性中心的表面自由能高,以及内部孔对基质的选择性积聚性质,将大大提高反应性和反应速度。

更新日期:2017-12-11
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