硼碘共掺杂氮化碳的制备及光解水制氢性能

doi:10.7503/cjcu20200084

摘要/Abstract

摘要：

以三聚氰胺为原料, 氧化硼为硼源, 碘化铵为碘源, 采用一步煅烧法合成了硼、碘共掺杂氮化碳催化剂(CNBI). 利用X射线衍射仪、透射电子显微镜、傅里叶变换红外光谱仪、 X射线光电子能谱仪、紫外-可见光分光光度计及电化学工作站等对样品进行表征和分析, 利用可见光照射下光解水制氢反应来评价其催化性能. 研究结果表明, B, I元素均匀分散掺杂入氮化碳共轭骨架形成B, I共掺杂CN半导体材料. 相比于未掺杂材料CN, B, I共掺杂CN样品禁带宽度略微降低, 光吸收能力增强, 光生电子-空穴对的分离效率提高, 这主要归因于B, I元素的电负性差异有助于氮化碳光生电子和空穴的重新分散. 共掺杂样品CNBI(0.1, 0.3)具有最佳光解水制氢性能, 在可见光照射下产氢速率达104.3 μmol/h, 分别是纯CN(22.74 μmol/h)的4.6倍, B掺杂氮化碳CNB(0.1)(51.92 μmol/h) 的2.0倍及碘掺杂氮化碳CNI(0.3)(33.37 μmol/h) 的3.1倍.

关键词: 氮化碳, 光催化, 硼, 碘共掺杂, 制氢

Abstract:

Boron and iodine co-doped carbon nitride(CNBI) catalysts were synthesized using boron oxide as the boron source, ammonium iodide as the iodine source and melamine as the raw-material by one-step calcination method. The samples were characterized and analyzed using X-ray powder diffractometer(XRD), transmission electron microscope(TEM), Fourier transform infrared spectrometer(FTIR), X-ray photoelectron spectrometer(XPS), ultraviolet-visible(UV-Vis) spectrophotometer and electrochemical workstation. The performance of the catalysts was tested by hydrogen production from water under visible light irradiation. The results indicated that the B and I elements were uniformly dispersed and doped into the CN conjugate skeleton to form B, I co-doped CNBI semiconductor materials. Compared with undoped CN, the band gap of co-doped catalysts was slightly reduced, the light absorption range was expanded. The separation efficiency of photo-generated electron-hole pairs was improved, mainly due to the difference in electronegativity of the B and I elements, which helps redispersed the photo-generated carriers of CN. The CNBI(0.1,0.3) sample had the best photocatalytic hydrogen production performance, and hydrogen production rate was 104.30 μmol/h under visible light irradiation, which is 4.6 times that of pure CN(22.74 μmol/h), 2.0 times of CNB(0.1)(51.92 μmol/h) and 3.1 times of CNI(0.3)(33.37 μmol/h), respectively.

Key words: g-C₃N₄, Photocatalysis, Boron, iodine co-doping, Hydrogen evolution

中图分类号:

O643

TrendMD:

祝玉鑫, 欧阳杰, 宋艳华, 唐盛, 崔言娟. 硼碘共掺杂氮化碳的制备及光解水制氢性能. 高等学校化学学报, 2020, 41(7): 1645.

ZHU Yuxin, OUYANG Jie, SONG Yanhua, TANG Sheng, CUI Yanjuan. Preparation of Boron and Iodine co-Doped Carbon Nitride and Its Performance in Photocatalytic Hydrogen Evolution from Water^†. Chem. J. Chinese Universities, 2020, 41(7): 1645.

图/表 8

Fig.1 XRD patterns(A) and FTIR(B) spectra of CN(a), CNB(b), CNI(c) and CNBI(d) samples

Fig.2 TEM images of CN(A, C) and CNBI(B, D)

Fig.3 Full survey XPS spectra of CN and CNBI(A) and high resolution XPS spectra of C1s(B), N1s(C) and B1s(D) of CNBI

Fig.4 N2 adsorption-desorption isotherms(A) and the corresponding BJH pore-size distributions(B) of CN, CNB, CNI and CNBI samples

Fig.5 H2 evolution of B-doped CN samples(A), I-doped CN samples(B), B, I co-doped samples(C) and four samples(D) (A) a. CN; b. CNB(0.05); c. CNB(0.1); d. CNB(0.15); e. CNB(0.2). (B) a. CN; b. CNI(0.1); c. CNI(0.2); d. CNI(0.3); e. CNI(0.35). (C) a. CN; b. CNB; c. CNI; d. CNB(0.1, 0.1); e. CNB(0.1, 0.2); f. CNB(0.1, 0.3); g. CNB(0.1, 0.35).

Fig.6 UV-Vis diffuse reflectance absorbance spectra(A), band gap values of samples(B), Mott-Schottky plots of CN(C) and CNBI(D)

Fig.7 Steady-state PL spectra(A), transient photocurrent response(B) and impedance spectroscopy of CN and CNBI samples(C)

Fig.8 Stability of H2 evolution(A) and XRD patterns before and after reaction(B) of CNBI sample

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