Preparation and photocatalytic hydrogen production performance of N-g-C3N4/CoS2 composites
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摘要: 氮化碳(CN)是目前最具发展前景的非金属催化剂之一，但由于其特殊的电子结构导致分子内载流子分离效率较差，其光催化活性不理想。为了改善其光催化性能，首先以尿素和柠檬酸为原料，利用高温缩合方法得到N掺杂的g-C3N4(NCN)。然后通过光沉积的方法成功制备了CoS2修饰的NCN光催化复合材料(NCN/CoS2)。CoS2的引入有效增强的氮化碳的光生载流子分离效率。同时N的掺杂有效调控氮化碳的带隙，拓宽了氮化碳的可见光响应范围。光催化产氢结果显示，在可见光照射(λ > 420 nm)下，NCN/10CoS2复合材料具有最佳的光催化产氢性能(73.8 μmol·g−1·h−1)，分别为NCN(15.0 μmol·g−1· h−1和CN/10CoS2(7.1 μmol·g−1· h−1)的4.9和10.4倍。Abstract: Carbon nitride (CN) is one of the most promising non-metal catalysts currently, but its photocatalytic activity is not ideal due to its poor carrier separation efficiency within molecules caused by its unique electronic structure. In order to improve its photocatalytic performance, N-doped g-C3N4(NCN) was firstly prepared by high temperature condensation method using urea and citric acid as raw materials. Then, the CoS2-modified NCN composites (NCN/CoS2) were successfully prepared by photodeposition. The introduction of CoS2 effectively enhances the photogenerated carrier separation efficiency of carbon nitride. At the same time, N doping effectively regulates the band gap of carbon nitride and broadens the visible light response range of carbon nitride. The photocatalytic hydrogen production results show that under visible light irradiation (λ > 420 nm), the NCN/10CoS2 presents the best photocatalytic hydrogen production performance (73.8 μmol·g−1·h−1), which is 4.9 and 10.4 times higher than that of NCN (15.0 μmol·g−1·h−1) and g-C3N4/10CoS2 (7.1 μmol·g−1·h−1), respectively.
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Key words:
- g-C3N4 /
- N-doping /
- CoS2 /
- photocatalysis /
- hydrogen production
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图 1 氮化碳(CN)、N掺杂的g-C3N4(NCN)和NCN/CoS2的XRD谱图
Figure 1. XRD patterns of carbon nitride (CN)、N-doped g-C3N4(NCN) and NCN/CoS2
图 4 NCN/10 CoS2的TEM图(a~b)和C、N、Co和S的元素分布图(c~g)
Figure 4. TEM images of NCN/10 CoS2 (a~b) and the corresponding element mapping for C, N, Co, and S (c~g)
图 5 NCN和NCN/10 CoS2的(a)吸附-脱附等温线和(b)孔径分布图
Figure 5. N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of NCN and NCN/10 CoS2
图 6 NCN和NCN/10 CoS2(a)UV-vis漫反射光谱和(b)带隙图
Figure 6. UV-Vis diffuse reflection spectrum(a)and band-gap diagram(b)of NCN和NCN/10 CoS2
图 8 CN、NCN和NCN/10 CoS2的光电流图
Figure 8. Transient photocurrent responses of CN, NCN and NCN/10 CoS2
图 9 样品的光解水制氢性能(a)和NCN/10 CoS2的产氢稳定性测试(b)
Figure 9. Hydrogen evolution rate of the samples(a)and stability test of H2 evolution over NCN/10 CoS2(b)
图 11 NCN/10 CoS2的光催化机理图
Figure 11. The photocatalytic mechanism diagram of NCN/10 CoS2
表 1 CN和NCN/10CoS2中的C/N原子比
Table 1. C/N atomic ratio of CN and NCN/10CoS2
Samples C/at% N/at% C/N CN 42.77 57.23 0.75 NCN/10 CoS2 39.07 60.83 0.64 
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表 2 NCN和NCN/10 CoS2的比表面积和孔体积
Table 2. Specific surface areas and pore volumes of the NCN and NCN/10 CoS2
Samples Surface area/(m2·g−1) Pore volume/(cm3·g−1) NCN 61.51 0.23 NCN/10 CoS2 65.90 0.25
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表 3 非贵金属助催化剂修饰氮化碳的产氢性能
Table 3. Hydrogen production performance of g-C3N4 modified with non-noble metal catalyst
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