Acta Phys. -Chim. Sin. ›› 2018, Vol. 34 ›› Issue (3): 270-277.doi: 10.3866/PKU.WHXB201707071

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DFT Study of POM-Supported Single Atom Catalyst (M1/POM, M = Ni, Pd, Pt, Cu, Ag, Au, POM = [PW12O40]3-) for Activation of Nitrogen Molecules

Yueqi YIN,Mengxu JIANG,Chunguang LIU*()   

  • Received:2017-05-22 Published:2017-12-18
  • Contact: Chunguang LIU
  • Supported by:
    the Natural Science Foundation of China(21373043)


Molecular geometries, electronic structure, and infrared spectroscopy of a series of polyoxometalate (POM)-supported single atom catalyst (SACs) (M1/POM (M = Ni, Pd, Pt, Cu, Ag, Au, POM = [PW12O40]3-) have been studied based on density factional theory (DFT) combined with natural bond orbital (NBO) analysis method. The results show that Pt1/POM has a higher reactivity for activation of N2 relevant to the others. The interaction between the isolated Pt atom and N2 arises from an orbital mixture, which is formed by the dxz and dyz orbital of Pt atom and the π* anti-bond orbit of N2 molecule. The electron transfer from Pt atom to the nitrogen molecule leads to a weakened N≡N bond. The N≡N bond distance increases when compared with the free N2 molecule. All results indicate an effective activation of the nitrogen molecules. For DFT-derived IR spectra, the four characteristic peaks of Keggin-type POM split into five because of introduction of the isolated metal atom.

Key words: Single atom catalyst, Artificial nitrogen fixation, Density functional theory, Electronic structure, Infrared spectroscopy