Chinese Journal of Catalysis ›› 2018, Vol. 39 ›› Issue (6): 1017-1026.DOI: 10.1016/S1872-2067(18)63075-X

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In situ doping brushite on zinc manganese oxide toward enhanced water oxidation performance: Mimicry of an oxygen-evolving complex

Miao Jiang, Junying Chen, Yingwei Li   

  1. State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
  • Received:2018-02-04 Revised:2018-03-22 Online:2018-06-18 Published:2018-05-16
  • Contact: 10.1016/S1872-2067(18)63075-X
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (21436005, 21576095, 21706078), Fundamental Research Funds for the Central Universities (2017PY004, 2017MS088), the State Key Laboratory of Pulp and Paper Engineering (201710, 2017ZD04), China Postdoctoral Science Foundation (2016M590771, 2017T100625), Guangdong Natural Science Foundation (2016A050502004, 2016A030310413, 2017A030310029, 2017A030312005), and Science and Technology Program of Guangzhou (201804020009).

Abstract:

We report in situ doping of brushite on zinc manganese oxide (ZMO), fabricated by calcining a Mn(Ⅱ) oxalate-impregnated metal-organic framework. The doping process was conducted in combination with the photocatalytic water oxidation reaction which was catalyzed by ZMO in neutral phosphate-buffered aqueous solution containing[Ru(bpy)3]2+-Na2S2O8 and calcium(Ⅱ) triflate salt, exhibiting greatly enhanced water oxidation performance with optimized turnover frequency of 0.18 mmolO2 molMn-1 s-1. Different analytical techniques indicated that photodeposited calcium-phosphate (CaP) acted as a co-catalyst to promote the O2evolution activity of ZMO. This system involved the use of manganese oxide and calcium ion, and the operation was conducted under ambient temperature and neutral conditions, thus, it efficiently mimicked the oxygen-evolving complex in photosystem Ⅱ.

Key words: Zinc manganese oxide, Brushite, Metal-organic frameworks, Water oxidation, Oxygen-evolving complex