液相合成彩色氮化碳及其光电化学特性研究

doi:10.6023/A20120575

摘要/Abstract

减小带隙值和获得有序二维微结构是提高氮化碳光电化学性能的关键. 通过调控尿素和柠檬酸的比例, 采用室温熟化工艺, 合成出不同颜色的氮化碳材料, 成功地将其带隙减小至1.74 eV, 并获得了由有序二维网络构建的多孔微结构. 所得氮化碳获得了一定光电转换性能, 并随着带隙值的减小和二维网络结构的构建, 表现出少见的光诱导电荷存储行为.

关键词: 氮化碳, 光电转换, 电荷存储, 赝电容, 太阳能

Reducing the band gap value and obtaining an ordered two-dimensional microstructure are crucial to improving the photoelectrochemical performance of carbon nitrides. By adjusting the ratio of urea and citric acid and ripening the precursor at the room temperature, we synthesize the carbon nitride materials with different colors of orange, green and blue. The resultant blue sample has a narrowed band gap of 1.74 eV and the strong absorption to the light in 550~700 nm wavelength range. The photoelectrochemical solar cell is fabricated using the synthesized carbon nitrides as light absorber, TiO₂ as electron transporter and I₃^–/I^– as the redox shuttle in electrolyte. The orange carbon nitride has typical photoelectric conversion performance with J_sc=0.65 mA•cm^–2, V_oc=530 mV and ff=0.64. The blue carbon nitride has obvious enhanced J_sc of 1.03 mA•cm^–2 owing to the obvious enhanced visible light absorption, while the deeply decreased ff of 0.33. The cyclic voltammetry tests demonstrate the electrode reaction properties of the fabricated carbon nitride-based cell under illumination. It turns out that the cell based on the blue carbon nitride has obvious photo-induce pseudocapacitive behavior with an area specific capacitance of 4.9 mF•cm^–2. TEM (Transmission electron microscope), XRD (X-ray diffraction), FTIR (Fourier transform infrared spectroscopy) and XPS (X-ray photoelectron spectroscopy) reveal the microstructure characteristics of the colored carbon nitrides. The orange one is carbon nitride quantum dots with the particle size less than 10 nm. The blue one is a carbon nitride polymer containing graphite domains with oxidized boundaries, forming three-dimensional porous structure constructed by an ordered two-dimensional network. The green one has a mixture microstructure as well as the medium photoelectrochemical properties between the former two, which are both photoelectric conversion and photo-induced charge storage performance.

Key words: carbon nitrides, photoelectric conversion, charge storage, pseudo-capacitance, solar energy

引用此文

何利蓉, 唐笑, 张灵, 李艳虹, 相国涛, 周贤菊, 凌发令, 姚璐, 蒋浩. 液相合成彩色氮化碳及其光电化学特性研究[J]. 化学学报, 2021, 79(4): 506-512.

Lirong He, Xiao Tang, Ling Zhang, Yanhong Li, Guotao Xiang, Xianju Zhou, Faling Ling, Lu Yao, Hao Jiang. Study on Photoelectrochemical Properties of Colorful Carbon Nitrides Synthesized in Liquid-Phase[J]. Acta Chimica Sinica, 2021, 79(4): 506-512.

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图/表 8

图1. 三种不同颜色样品的(a)照片, (b)吸收光谱和(c)透射光谱及相应的Tauc图和光学带隙值: (d)橙色, (e)绿色, (f)蓝色

Figure 1. (a) Pictures, (b) absorption spectra and (c) transmission spectra of different color samples. Tauc plots and optical band gap values of (d) orange, (e) green and (f) blue samples

图2. 柠檬酸与尿素以不同质量比反应所得样品的TEM图片: (a) 1:10(橙色), (b) 1:1(绿色), (c) 1:0.5(蓝色)

Figure 2. TEM images of samples obtained when the mass ratio of citric acid to urea are (a) 1:10 (orange), (b) 1:1 (green) and (c) 1:0.5 (blue)

图3. 柠檬酸与尿素质量比分别为1:10(橙色)、1:1(绿色)、1:0.5(蓝色)时所得产物的(a) XRD图谱和(b) FITR光谱

Figure 3. (a) XRD patterns and (b) FITR spectra of samples obtained when the mass ratio of citric acid to urea are 1:10 (orange), 1:1 (green), and 1:0.5 (blue)

图4. 柠檬酸与尿素质量比分别为1:10(橙色样品)、1:1(绿色样品)、1:0.5(蓝色样品)时所得产物的XPS图谱: (a) 总谱; (b) C1s谱; (c) N1s谱; (d) O1s谱

Figure 4. XPS spectra of samples obtained when the mass ratios of citric acid to urea are 1:10 (orange sample), 1:1 (green sample), and 1:0.5 (blue sample): (a) survey spectra; (b) C1s; (c) N1s; (d) O1s

		Orange	Green	Blue
Atomic ratio (%)	C	54.18	55.97	57.35
	N	13.87	12.22	7.11
	O	30.36	29.34	32.7
N/C		0.26	0.22	0.12

表1. 所合成不同颜色氮化碳的元素成分表

Table 1. Atomic percentage of C, N and O of the sample

图5. (a)不同颜色氮化碳的PL光谱(激发波长为468 nm); (b)橙色氮化碳的J-V曲线(插图为相应光电极); (c)绿色氮化碳的J-V曲线(插图为相应光电极); (c)蓝色氮化碳的J-V曲线(插图为相应光电极)

Figure 5. (a) PL spectra of carbon nitrides with different color (excitation wavelength is 468 nm); (b) J-V curve of the orange carbon nitride (the inset is corresponding photoelectrode); (c) J-V curve of the green carbon nitride (the inset is corresponding photoelectrode); (d) J-V curve of the blue carbon nitride (the inset is corresponding photoelectrode)

图6. 不同颜色氮化碳所组装的电池在光照(100 mW•cm–2)和暗态下进行电化学特性测试(固定电压扫描速度为50 mV•s–1, 恒电流密度为0.4 mA•cm–2): (a)橙色氮化碳电池在光照下的CV曲线; (b)绿色氮化碳电池在光照和暗态下的CV曲线; (c)蓝色氮化碳电池在光照和暗态下的CV曲线; (d)橙色氮化碳电池在光照下的GCD曲线; (e)绿色氮化碳电池在光照和暗态下的GCD曲线; (f)蓝色氮化碳电池在光照和暗态下的GCD曲线

Figure 6. Electrochemical properties of the cells assembled with the colorful carbon nitrides are tested under light (100 mW•cm–2) and dark (voltage scanning speed is 50 mV•s–1, constant current density is 0.4 mA•cm–2): (a) CV curve of the cell assemble with the orange carbon nitride under light; (b) CV curve of the cell assemble with the green carbon nitride under light and dark; (c) CV curve of the cell assemble with the blue carbon nitride under light and dark; (d) GCD curve of the cell assemble with the orange carbon nitride under light; (e) GCD curve of the cell assemble with the green carbon nitride under light and dark; (f) GCD curve of the cell assemble with the blue carbon nitride under light and dark

图7. (a)蓝色氮化碳电池在不同太阳光辐照度下的恒电流充放电曲线; (b)相应面积比电容与辐照度的关系

Figure 7. (a) GCD of the cells assemble with the blue carbon nitride tested under illumination with different irradiance; (b) relationship between the corresponding area specific capacitance and irradiance

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