复合催化材料纳米氧化铜颗粒(CuO NPs)@纤维素纳米纤丝(CNF)-Si-N(OH)2的制备及其对4-硝基苯酚的催化还原性能
doi: 10.13801/j.cnki.fhclxb.20220406.002
Preparation of catalytic composite copper oxide nanoparticles (CuO NPs)@cellulose nanofiber (CNF)-Si-N(OH)2 and its catalytic reduction of 4-nitrophenol
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摘要: 针对目前降解工业废水中4-硝基苯酚(4-NP)的催化剂效率低，催化活性差等问题，以桉木漂白化学浆为原料，通过超微粒研磨机和高压均质机处理制备得到直径50~100 nm和长度1500~2000 nm的纤维素纳米纤丝(CNF)，在其表面原位负载纳米氧化铜颗粒(CuO NPs)，并通过3-氯丙基三甲氧基硅烷(CPTES)与二乙醇胺(DEA)进行接枝反应制备得到复合催化材料-CuO NPs@CNF-Si-N(OH)2。探讨了DEA添加量对CuO NPs@CNF–Si–N(OH)2的性能影响，采用Zeta电位、FTIR、XRD、XPS、热重分析和形貌分析等方法对复合材料进行了表征。结果表明，CuO NPs被原位还原并成功负载在CNF表面，其直径约为3.84 nm，负载量为3.83wt%，通过硅烷化改性及接枝胺基可提高CuO NPs在复合材料表面的分散性及稳定性，进而增强了其催化活性。CNF基复合催化材料对4-NP的催化还原结果显示，DEA添加量为20wt%下的CuO NPs@CNF-Si-N(OH)2对4-NP催化还原性能最佳，在180 s内可催化还原98.39%的4-NP，且反应符合伪一级动力学模型，表观速率常数为5.50×10−3 s−1，转化效率为1723.41 h−1，研究结果可为高性能催化复合材料的制备提供新思路和新途径。Abstract: In view of the low efficiency and poor catalytic activity of 4-nitrophenol (4-NP) catalysts for degradation of industrial wastewater, eucalyptus wood bleaching chemical pulp was used as the raw material and treated with ultrafine grinder and high pressure homogenizer to produce cellulose nanofiber (CNF) with the diameter of 50-100 nm and the length of 1500-2000 nm. Then, copper oxide nanoparticles (CuO NPs) were in-situ loaded onto CNF, 3-chloropropyltrimethoxysilane (CPTES) and diethanolamine (DEA) were added for grafting reaction to obtain the catalytic composite of CuO NPs@CNF-Si-N(OH)2. The catalytic composite was characterized with Zeta potential, FTIR, XRD, XPS, thermal gravimetric analysis and morphology analysis. The results show that CuO NPs are in-situ loaded on CNF, and the grafting of amine groups can make the loading of CuO NPs more uniform and stable. In addition, it is also found that CuO NPs@CNF-Si-N(OH)2 show the optimal catalytic performance with 20wt% DEA. Furthermore, 98.39% of 4-NP is catalytically reduced after 180 s, and the reaction fit the pseudo-first order kinetics equation, in which the reacting constant reaches 5.50×10−3 s−1 and the turnover frequency achieves 1723.24 h−1. The composite catalysts of CuO NPs@CNF-Si-N(OH)2 exhibite excellent recycling performance, and 94.42% of 4-NP can be catalytically reduced after a recycling time of 8. The results can provide a new idea and approach for the preparation of high-performance catalytic composite.
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Key words:
- cellulose nanofibers /
- 3-chloropropyltriethoxysilane /
- diethanolamine /
- 4-nitrophenol /
- catalytic /
- reduction
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图 1 纤维素纳米纤丝(CNF)基复合材料的制备及对4-硝基苯酚(4-NP)催化还原示意图
Figure 1. Schematic diagram of preparation of cellulose nanofiber (CNF) based catalytic composite and its catalytic reduction of 4-nitrophenol (4-NP)
4-AP—4-aminophenol; NPs—Nanoparticles; CPTES—3-chloropropyltrimethoxysilane
图 2 CNF及CNF基复合催化材料的Zeta电位图
Figure 2. Zeta potential diagram of CNF and CNF based catalytic composite
图 3 CNF与CNF基复合催化材料的XPS图谱 (a)及CuO纳米颗粒(NPs)@CNF中Cu2p分析图 (b)
Figure 3. XPS spectra of CNF and CNF based catalytic composite (a) and Cu2p spectra (b) of CuO nanoparticles (NPs)@CNF composite
图 4 CNF及CNF基复合催化材料的FTIR图谱
Figure 4. FTIR spectra of CNF and CNF based catalytic composite
图 5 CNF及CNF基复合催化材料的XRD图谱
Figure 5. XRD patterns of CNF and CNF based catalytic composite
图 6 CNF及CNF基复合催化材料的TG (a) 与DTG (b) 曲线
Figure 6. TG (a) and DTG (b) curves of CNF and CNF based catalytic composite
图 7 CNF (a) 及CNF基复合催化材料 ((b)~(d)) 的TEM图像及CuO NPs@CNF的HRTEM图像 (e)
Figure 7. TEM images of CNF (a), CNF based catalytic composite ((b)-(d)) and HRTEM image of CuO NPs@CNF (e)
图 8 (a) 4-NP还原过程中各阶段的光学图片；(b) CNF及CNF基复合催化材料在180 s内还原4-NP的紫外-可见分光光谱图；(c) 不同DEA含量(5wt%~20wt%)的CuO NPs@CNF-Si-N(OH)2 180 s内还原4-NP的紫外-可见分光光谱图；(d) CNF、CuO NPs及CNF基复合催化材料的动力学曲线
Figure 8. (a) Color changes of 4-NP solution after adding CuO NPs@CNF-Si-N(OH)2; (b) UV-vis absorption spectra after adding CNF and CNF based catalytic composite for 180 s; (c) UV-vis absorption spectra after adding CuO NPs@CNF-Si-N(OH)2 grafted with different DEA contents (5wt%-20wt%) for 180 s; (d) Kinetic curves of CNF, CuO NPs and CNF based catalytic composite
A0−Absorbance of the mixture at the initial moment of reaction; At−Absorbance at 400 nm (4-NP) after reaction time t
图 9 不同回用次数下CuO NPs@CNF-Si-N(OH)2对4-NP的转化率
Figure 9. Conversion yield of 4-NP using the CuO NPs@CNF-Si-N(OH)2 with 20 wt% DEA dosage
表 1 CNF及CNF基复合催化材料的热重特征温度表
Table 1. The characteristic temperature of TG thermograms of CNF and CNF based catalytic composite
Sample T1/°C T2/°C Residual mass/% Mass loss/% CNF 324.76 356.00 11.43 84.56 CuO NP@CNF 321.67 352.67 14.31 81.59 CuO NP@CNF-Si 322.19 354.84 12.06 83.74 CuO NP@CNF-Si-N(OH)2 318.68 354.59 13.41 83.54 Notes: T1—Initial temperature of extrapolation; T2—Temperature at maximum rate of mass change. 
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表 2 不同催化剂对4-NP的催化还原性能分析
Table 2. Catalytic performance of the CuO NPs and CNF based catalytic composite
Sample Temperature/K Molar ratio of
4-NP/catalystTime Apparent rate
constant K/s−1Conversion
yield/%CuO NPs 298 87∶1 180 s 0.60×10−3 46.14 CuO NPs@CNF 298 87∶1 180 s 1.30×10−3 71.82 CuO NPs@CNF-Si 298 87∶1 180 s 1.50×10−3 84.46 CuO NPs@CNF-Si-N(OH)2 (5 wt% DEA) 298 87∶1 180 s 2.20×10−3 86.71 CuO NPs@CNF-Si-N(OH)2 (10 wt% DEA) 298 87∶1 180 s 3.00×10−3 87.92 CuO NPs@CNF-Si-N(OH)2 (15 wt% DEA) 298 87∶1 180 s 4.70×10−3 90.90 CuO NPs@CNF-Si-N(OH)2 (20 wt% DEA) 298 87∶1 180 s 5.50×10−3 98.39
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表 3 CNF基复合催化材料与其他纳米纤维素基复合催化材料的转化效率分析
Table 3. Comparison of catalytic performance of the CNF based catalytic composite with other reported metal nanoparticles based catalysts
Sample Temp/K Molar ratio of4-NP/ catalyst TOF/h−1 Reference CuO NPs@CNF 298 87∶1 407.31 This work CuO NPs@CNF-Si-N(OH)2 (20 wt% DEA) 298 87∶1 1723.24 This work CuO NPs@GO 298 150∶1 816.2 [5] Au NPs@CNF 298 150∶1 563 [32] Au NPs@PDDA/NCC 298 37∶1 212 [7] Au NPs@CNCs 298 30∶1 109 [33] Ag NPs@CNCs/CTAB 298 97.2∶1 1077.3 [34] Notes: TOF—Turnover Frequency; CCF—Carboxymethylated cellulose fibers; GO—Graphene oxide; PDDA—Poly(diallyldimethylammonium chloride); NCC—Nanocellulose crystal; CNC—Cellulose nanocrystal; CTAB—Hexadecyl-trimethylammonium bromide.
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表 4 CuO NPs@CNF-Si-N(OH)2与其他纤维素基复合催化材料的回用效果分析
Table 4. Comparison of the conversion of the CNF based nanohybrids with other reported cellulose based composite
Sample Catalyst Carrier Repeated times Conversion yield Reference CuO NPs@CNF-Si-N(OH)2 (20 wt% DEA) CuO NPs Cellulose nanofibers 8 94.42% This work Ag NPs@ MOF‐199 s/CCFs Ag NPs Cellulose fibers 5 91.0% [35] Ag NPs@CFP Ag NPs Cellulose filter paper 4 90.0% [36] Ag NPs@CMFs Ag NPs Cellulose microfibers 6 87.0% [37] Fe3O4/Ag@NFC Ag NPs Nanofibrillated cellulose 7 81.8% [38] Notes: CFP—cellulose filter paper; CMF—cellulose microfiber; NFC—Nanofibrillated cellulose.
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