Abstract：Graphite carbonaceous materials are widely used in electronic equipment, composite materials, batteries, and sensors because of their good electrical, mechanical and thermal properties. However, the current high energy consumption, high pollution, high cost, and uncontrollable production is the core problem that needs to be solved urgently. Therefore, the method of obtaining graphitic carbon structures in nanoscale devices by using simpler and low-cost manufacturing techniques is an attractive area for exploration. Surface plasmon technology has attracted wide attention because of its environmental friendliness and low energy consumption. Using plasmon technology to induce graphitization of macromolecular chain polymers is a promising preparation technology. As a base metal, Cu has the advantages of high yield and low price. Based on the surface plasmon technology, this paper uses laser radiation to graphitize polyacrylonitrile on the metal surface by irradiating polyacrylonitrile (PAN)+carbon nanotubes (CNT) on the rough Cu surface. PAN/Cu and PAN+CNT/Cu were systematically studied to obtain the best graphitization conditions by changing the substrate etching time, annealing temperature, annealing time, and laser intensity. The experimental results show that with PAN as the probe molecule, the surface-enhanced Raman scattering (SERS) effect was observed on the copper substrate etched by 2.5 mol·L-1 nitric acid for 15 minutes. The enhancement factor is 1.39×104. By using the Raman laser as the light source, when the annealing temperature is 140 ℃, it can be observed that there are fewer defects in the graphitized PAN molecular structure and the disappearance of carbon-nitrogen triple bonds, and the ID/IG can reach 1.160 8. The CNT is further used to change the photocatalytic performance of rough copper substrates. We use nitric acid-modified multi-walled carbon nanotubes (MWCNT) combined with PAN to improve the catalytic system. When 2% CNTs are incorporated, PAN can achieve graphitization at 40 ℃ by surface plasmons. The ID/IG can reach 0.942 1，and the introduction of laser greatly improves the controllability of graphitization sites. We attribute it to the catalysis of PAN by hot electrons generated on the copper surface under laser irradiation. It is proposed that there may be two mechanisms of catalysis and graphitization. One is that hot electrons graphitize PAN through CNT, the other is that hot electrons act on O2 near PAN through CNT, and PAN is graphitized through ·O-2.
孙 楠，谭红琳，张正东，任 翔，周 燕，刘建琪，蔡晓明，蔡金明. 碳纳米管掺杂聚丙烯腈/铜室温环化为石墨的拉曼光谱分析及形成机制研究[J]. 光谱学与光谱分析, 2022, 42(09): 2983-2988.
SUN Nan, TAN Hong-lin, ZHANG Zheng-dong, REN Xiang, ZHOU Yan, LIU Jian-qi, CAI Xiao-ming, CAI Jin-ming. Raman Spectroscopy Analysis and Formation Mechanism of Carbon
Nanotubes Doped Polyacrylonitrile/Copper Cyclized to Graphite
at Room Temperature. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2022, 42(09): 2983-2988.
[1] Shilpa, Das S K, Afzal M, et al. Carbon, 2016, 108, 135.
[2] Gao S, Zhang Z, Liu K, et al. Applied Catalysis B Environmental, 2016, 188：245.
[3] Zhang P, Song T, Wang T, et al. RSC Advances, 2017, 7(29): 17873.
[4] Zhang P, Song T, Wang T, et al. International Journal of Hydrogen Energy, 2017, 42(21): 14511.
[5] Zhang P, Song T, Wang T, et al. Journal of Materials Chemistry A, 2017, 5(43): 22772.
[6] Zhang P, Wang T, Zeng H. Applied Surface Science, 2017, 391: 404.
[7] Yao G Y, Zhao Z Y, Liu Q L, et al. Solar Energy Materials and Solar Cells, 2020, 208：110385.
[8] Maitra T, Sharma S, Srivastava A, et al. Carbon, 2012, 50(5): 1753.
[9] Wang X X，Pang Z Y，Yang H，et al. Results Phys.，2019, 14：102446.
[10] Xian T，Di L J，Sun X F，et al. Nanoscale Res. Lett.，2019, 14：397.
[11] Wang Y, Jiang F, Chen J, et al. Nanomaterials, 2020, 10(1): 178.
[12] Zhang C, Jiang S Z, Yang C, et al. Sci. Rep., 2016, 6: 25243.
