NO Photo-oxidation and In-situ DRIFTS Studies on N-doped Bi2O2CO3/CdSe Quantum Dot Composite

doi:10.15541/jim20180299

Abstract

Abstract:

Photocatalyst of N-doped Bi₂O₂CO₃ (N-BOC)/CdSe quantun dots (QDs) composite was sucessfully prepared for degradation of nitric oxide (NO), an indoor air pollutant. The results of X-ray diffraction, transmisssion electron microscopy and X-ray photoelectron spectroscopy showed that after combination with CdSe QDs structure and morphology of N-BOC remained the same as before combination. Photocatalytic degradation of NO showed that introduction of CdSe QDs significantly enhanced the removal ratio of NO. Moreover, the generating ratio of toxic byproduct NO₂ decreased to 1%, which indicated efficient inhibition for the toxic byproduct generation. From UV-Vis absorption spectroscopy and photoluminescence spectroscopy, the CdSe QDs showed promotion on light absorption, and inhibition of charged recombination of photo-induced carriers. More importantly, only signals of NO₃ ^- were captured in in situ DRIFTS measurements, whilst the signals from NO₂ could be barely detected during photocatalytic process. Superoxide radicals (O₂ ^-) and holes (h ⁺) are considered to be possible active species in the reaction, which dominate the oxidation process from NO to NO₃ ^-.

Key words: bismuth subcarbonate, cadmium selenide quantum dots, photocatalysis, nitric oxide, in situ DRIFTS

CLC Number:

TQ174

Yang LIU, Shan YU, Kai-Wen ZHENG, Wei-Wei CHEN, Xing-An DONG, Fan DONG, Ying ZHOU. NO Photo-oxidation and In-situ DRIFTS Studies on N-doped Bi₂O₂CO₃/CdSe Quantum Dot Composite[J]. Journal of Inorganic Materials, 2019, 34(4): 425-432.

Figures/Tables 12

Fig. 1 Schematic diagram of photo-oxidation NO reaction equipment

Fig. 2 Photocatalytic removal ratio of NO (a) and generation of NO2 (b) in the presence of N-BOC and N-BOC/CdSe QDs under visible light irradiation (λ>420 nm), and photocatalytic recycling tests on N-BOC/CdSe QDs (1%) under visible light (c) and UV-Visible light (d) irradiation

Fig. 3 XRD patterns of N-BOC and N-BOC/CdSe QDs(1%) and their corresponding standard PDF card

Fig. 4 (a)TEM and (b)HRTEM images of N-BOC/CdSe QDs(1%)

Fig. 5 High-resolution XPS spectra of Bi 4f (a), O 1s (b), C 1s (c), and valance band (d) of N-BOC and N-BOC/CdSe QDs (1%) sample

Fig. 6 UV-Vis DRS of N-BOC and N-BOC/CdSe QDs Insets are the absorption spectrum of CdSe QDs dispersed in water (up) and enlarged spectra of N-BOC/CdSe QDs composite (down)

Fig. 7 Photoluminescence spectra of N-BOC and N-BOC/CdSe QDs (1%) Excitation wavelength: 280 nm

Table 1 Redox potentials of different active species

Species	Redox potential (NHE)
Species	Potential/eV	Ref.
O₂/?O₂^-	-0.28	[30]
NO/NO₂	0.94	[29]
NO/NO₃^-	1.03	[29]

Fig. 8 In situ DRIFTS of NO adsorption on N-BOC/CdSe QDs (1%) before (a), during (b) and after (c) visible light illumination

Table 2 Assignments of the IR bands observed during NO adsorption and photocatalysis over N-BOC/CdSe QDs

Wavenumber/cm^-1	Assignment	Ref.
935	Bidentate nitrite	[31]
949, 978	Monodentate nitrate	[32-35]
1002	Bridge nitrate	[32-35]
1024	Bidentate/monodentate nitrate	[8, 32-35]
1092, 1134	NO	[31]
1180	NO^-	[8,18]
1120	Bidentate nitrite	[18, 31]
1262	Monodentate nitrate	[18, 31]

Fig. 9 Proposed processes of NO adsorption and photocatalytic NO oxidation

Fig. 10 Schematic representation of the mechanism for photodegrading NO by N-BOC/CdSe QDs

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NO Photo-oxidation and In-situ DRIFTS Studies on N-doped Bi₂O₂CO₃/CdSe Quantum Dot Composite

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