铜基石墨烯复合催化剂的合成与表征

doi:10.11949/0438-1157.20200075

摘要/Abstract

摘要：

采用原位水热法制备了Cu/rGO催化剂并引入对苯二甲酸(TPA)对Cu基石墨烯复合材料进行改性研究，探究了不同溶剂、水热时间、沉淀pH对引入TPA的Cu/rGO催化剂材料微观结构特性的影响。通过XRD、FT-IR、XPS和SEM表征技术分析了催化剂的形貌结构及物化性质。考察了催化剂用于二乙醇胺脱氢的催化性能。在V_(乙醇)∶V_(水)=1∶1为溶剂，沉淀pH为13.0，160℃水热10 h，制备的催化剂性能最好，亚氨基二乙酸收率为86.55%，与没有添加TPA的Cu/rGO催化剂相比收率提高20%。TPA的加入，增强了GO片层间的相互作用，增加了GO片层间的有机官能团，稳定Cu₂O并使其结晶度较好，增加催化剂活性位点，以提高反应速率。且粒径约为10 nm左右的Cu纳米粒子均匀分布在褶皱状片层结构的rGO表面，提高催化剂抗烧结性能。

关键词: 催化剂, 氧化, 制备, 烧结, 还原氧化石墨烯, 对苯二甲酸

Abstract:

A Cu/rGO catalyst was prepared by in-situ hydrothermal method and terephthalic acid (TPA) was introduced to modify the copper-based graphene composite material. The effects of different solvents, hydrothermal time and precipitation pH on microstructure characteristics of Cu/rGO catalyst material introduced by TPA were investigated. The effect of different molar ratios of copper and melamine on the catalyst was studied. Scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N₂ physical adsorption and desorption test (BET) were used to investigate the morphology and structure of the catalyst. The catalytic performance of the catalyst for the dehydrogenation of diethanolamine was investigated. The results showed that with ethanol and water volume ratio of 1∶1 for the bases for solvent, the pH of the solution was 13.0, and reaction under 160℃ for 10 h, the preparation of the catalyst performance was the best, IDA yield was 86.55%. Compared with Cu/rGO catalyst without TPA, the yield of iminodiacetic acid increased by 20%. The addition of TPA and GO showed the best reduction effect, the interaction between TPA and GO were the strongest and stable Cu₂O, make its crystallinity better, and increase the catalyst active site, to improve the reaction rate. GO has a folded lamellar structure. After reduction, the Cu nanoparticles with a particle size of about 10 nm are evenly distributed on the rGO surface of the corrugated sheet structure to improve the anti-sintering performance of the catalyst.

Key words: catalyst, oxidation, preparation, sintering, reduced graphene oxide, terephthalic acid

中图分类号:

O 643.36

王永胜, 兰小林, 邱天, 张新平, 吴莹莹, 陈莉, 徐伟祥, 郭栋杰, 段正康. 铜基石墨烯复合催化剂的合成与表征[J]. 化工学报, 2020, 71(6): 2889-2899.

Yongsheng WANG, Xiaolin LAN, Tian QIU, Xinping ZHANG, Yingying WU, Li CHEN, Weixiang XU, Dongjie GUO, Zhengkang DUAN. Synthesis and characterization of copper-based graphene composite catalyst[J]. CIESC Journal, 2020, 71(6): 2889-2899.

图/表 12

图1 有机配体与Cu2+的相互作用关系图

Fig.1 Diagram of interaction between organic ligand and Cu2+

图2 Cu/rGO催化剂制备流程图，其中红色小球为Cu0，蓝色小球为Cu2O

Fig.2 Preparation flow chart of Cu/rGO catalyst, wherein red pellet is Cu0 and blue pellet is Cu2O

图3 不同水热时间后水热产物(a)与水热后催化剂前体及还原后 Cu/rGO催化剂(b)XRD谱图

Fig.3 XRD patterns of hydrothermal products after different hydrothermal times (a), precursor of hydrothermal catalyst and reduced Cu/rGO catalyst (b)

图4 不同pH下水热产物(a)及其还原产物(b)的XRD谱图

Fig.4 XRD patterns of hydrothermal products (a) and their reduction products (b) at different pH

图5 有无添加TPA的两种催化剂在还原前、后的XRD谱图

Fig.5 XRD patterns of the two catalysts with or without addition of TPA before and after reduction

图6 有无添加TPA的两种催化剂在水热后与N2焙烧后的FT-IR谱图

Fig.6 FT-IR spectra of two catalysts with and without TPA after hydrothermal and N2 calcination

图7 不同溶剂条件下催化剂在水热后(a)与N2焙烧后(b)的FT-IR谱图

Fig.7 FT-IR spectra of the catalysts after hydrothermal (a) and N2 calcined (b) under different solvent conditions

图8 不同沉淀pH条件下催化剂在水热后(a)与N2焙烧后(b)的FT-IR谱图

Fig.8 FT-IR spectra of the catalysts after hydrothermal (a) and N2 calcined (b) with different precipitation pH

图9 不同水热时间条件下催化剂经水热(a)与N2焙烧(b)的FT-IR谱图

Fig.9 FT-IR spectra of catalysts hydrothermal (a) and N2 calcined (b) under different hydrothermal conditions

图10 GO（插图为GO的XRD图）(a)、水热后CuO/rGO(b)和还原后的Cu/rGO的SEM图(c)；Cu/rGO的TEM图(d)

Fig.10 SEM images of GO（inset: XRD pattern of GO）(a), hydrothermal products CuO/rGO (b) and Cu/rGO after reduction (c); TEM image of Cu/rGO (d)

图11 样品的XPS谱图

Fig.11 XPS spectra of samples

表1 催化剂用于催化二乙醇胺脱氢制亚氨基二乙酸的性能测试结果

Table 1 Catalytic performance of samples in dehydrogenation of diethanolamine

序号	催化剂制备条件	反应时间/h	初次排气温度/℃	IDA 收率/%
1	Cu/rGO(无TPA)	5.4	163.4	68.82
2	水	4.2	158.0	76.89
3	V_(乙二醇)∶V_(水)=1∶1	3.7	145.5	82.24
4	V_(乙醇)∶V_(水)=1∶1	3.1	129.6	86.55
5	pH= 12.0	3.9	156.1	78.21
6	pH= 11.0	4.5	162.3	70.96
7	pH= 7.0	6.5	167.2	29.37
8	水热2 h	5.9	162.1	35.26
9	水热6 h	4.4	159.9	68.19
10	GO	3.0	—	—

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