氧掺杂对VN-g-C3N4催化剂光催化固氮性能的影响

doi:10.7503/cjcu20190463

摘要/Abstract

摘要：

采用介质阻挡放电等离子体法合成了氧原子掺杂的具有氮空穴的石墨相氮化碳催化剂(g-C₃N₄), 并对催化剂的结构和形貌进行了表征分析. 结果表明, 等离子体处理没有改变催化剂的形貌, 并同时将氮空穴和氧原子引入了g-C₃N₄的晶格. 在可见光条件下, 制备的共掺杂g-C₃N₄催化剂的铵离子产率高达5.9 mg·L ^-1·h ^-1· $g cat - 1$ , 分别是具有氮空穴的g-C₃N₄和纯g-C₃N₄的2.2倍和20倍, 同时还表现出优异的催化稳定性. 密度泛函理论计算结果显示, 与具有氮空穴的g-C₃N₄相比, 氧原子的引入能提高氮空穴对反应物氮气分子的活化能力, 提高光催化固氮性能.

关键词: 石墨相氮化碳, 固氮, 共掺杂, 光催化, 等离子体处理

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

中图分类号:

O644

TrendMD:

赵艳锋,孙效龙,胡绍争,王辉,王菲,李萍. 氧掺杂对V_N-g-C₃N₄催化剂光催化固氮性能的影响. 高等学校化学学报, 2020, 41(1): 132.

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 ^†. Chem. J. Chinese Universities, 2020, 41(1): 132.

图/表 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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氧掺杂对V_N-g-C₃N₄催化剂光催化固氮性能的影响

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

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