Effect of Oxygen on Photocatalytic Nitrogen Fixation Performance of N Vacancy-embedded Graphitic Carbon Nitride †

doi:10.7503/cjcu20190463

Abstract

Abstract:

N vacancy and oxygen co-doped g-C₃N₄ with outstanding N₂ photofixation ability was synthesized by dielectric barrier discharge plasma treatment. XRD, UV-Vis, N₂ adsorption, SEM, XPS, PL and TPD were used to characterize the as-prepared catalysts. The result shows that plasma treatment does not change the morphology of as-prepared catalyst but introduce nitrogen vacancies and oxygen into g-C₃N₄ lattice simultaneously. The as-prepared co-doped g-C₃N₄ displays the ammonium ion production rate as high as 5.9 mg·L ^-1·h ^-1· $g cat - 1$ , which is 2.2 and 20 times that of individual N vacancy-doped g-C₃N₄ and neat g-C₃N₄, as well as good catalytic stability. Experimental and density functional theory(DFT) calculation results indicate that, compared with individual N vacancies doping, the introduction of oxygen can promote the activation ability of N vacancies to N₂ molecule, leading to the promoted N₂ photofixation performance.

Key words: Graphitic carbon nitride, Nitrogen photofixation, Co-doping, Photocatalysis, Plasma treatment

CLC Number:

O644

TrendMD:

ZHAO Yanfeng,SUN Xiaolong,HU Shaozheng,WANG Hui,WANG Fei,LI Ping. Effect of Oxygen on Photocatalytic Nitrogen Fixation Performance of N Vacancy-embedded Graphitic Carbon Nitride ^†[J]. Chem. J. Chinese Universities, 2020, 41(1): 132.

Figures/Tables 9

Fig.1 N2 photofixation ability over as-prepared catalysts(A), NH4+ production ability of OCN(VN) in aprotic solvent DMF or using AgNO3 as the electron scavenger(B), N2 photofixation ability of reused OCN(VN)(C) and comparison of NH4+ production rate over OCN(VN) and other catalysts(D)

Fig.2 Mass spectra of the indophenol prepared from different atmosphere

Fig.3 XRD patterns(A), UV-Vis spectra(B), plots of transformed Kubelka-Munk function vs. the energy of light(C) and N2 adsorption-desorption isotherms(D) of as-prepared catalysts

Fig.4 SEM and HRTEM(inset) images of NCN(A) and SEM images of CN(VN)(B), OCN(C) and OCN(VN)(D)

Fig.5 XPS spectra in the region of C1s(A), N1s(B), O1s(C) and VB XPS(D) of as prepared catalysts

Fig.6 Diagram of possible structure of OCN(VN)

Fig.7 N2-TPD curves of as-prepared NCN, CN(VN), OCN and OCN(VN)

Fig.8 EIS(A) and PL(B) spectra of NCN, CN(VN), OCN and OCN(VN) and comparison of their PL intensity under Ar and N2 atmospheres(C) and the possible electrons transfer route(inset)(C)

Fig.9 Optimal N2 adsorption model and the charge density difference of the N2 molecule adsorbed on CN(VN)(A) and OCN(VN)(B)

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