微晶纤维素基复合材料的制备及其对亚甲基蓝的催化降解性能

陈嘉川; 戢德贤; 林兆云; 杨桂花; 侯慧敏

doi:10.13801/j.cnki.fhclxb.20200416.001

微晶纤维素基复合材料的制备及其对亚甲基蓝的催化降解性能

doi: 10.13801/j.cnki.fhclxb.20200416.001

齐鲁工业大学(山东省科学院)　生物基材料与绿色造纸国家重点实验室制浆造纸科学与技术教育部重点实验室，济南 250353

基金项目: 国家重点研发计划(2017YFB0307900)；国家自然科学基金(31670595；31770628)；泰山学者工程；山东省高等学校科技计划(J18KA091)；生物基材料与绿色造纸国家重点实验室开放基金(ZZ20190205)

详细信息

通讯作者:
杨桂花，博士，教授，研究方向为制浆造纸绿色化学技术与生物基功能材料制备　E-mail: ygh@qlu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2020-01-21
- 录用日期: 2020-03-18
- 网络出版日期: 2020-04-16
- 刊出日期: 2020-12-15

Preparation of modified microcrystalline cellulose based composite and its catalytic degradation performance on methylene blue

State Key Laboratory of Biobased Material and Green Papermaking/Key Lab of Pulp & Paper Science and Technology of Education Ministry of China, Qilu University of Technology, Shandong Academy of Sciences, Ji'nan 250353, China

摘要

摘要: 以微晶纤维素(MCC)为原料，通过在其表面负载纳米氧化铜颗粒(CuO NPs)，添加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CuO NPs@MCC–Si–N(OH)₂复合材料。探讨了DEA添加量对CuO NPs@MCC–Si–N(OH)₂性能的影响，表征并分析了改性微晶纤维素红外光谱、晶体结构、表面形貌和热稳定性。结果表明，CuO NPs可成功负载在MCC表面，硅烷偶联剂可提高复合材料的分散性与接枝胺基的能力，进而增强其催化活性，使硼氢化钠(NaBH₄)与亚甲基蓝(MB)氧化还原反应效率增加，快速降解MB染色剂。通过优化发现DEA用量为20wt%时制得的CuO NPs@MCC–Si–N(OH)₂催化效果最佳，CuO NPs@MCC–Si–N(OH)₂和NaBH₄的用量分别为30 mg和10 mg，处理30 mL 3 mmol/L MB溶液5 min后，MB去除率可达99.71%，五次循环性测试后，去除率为93.24%。
- 微晶纤维素 /
- 3-氯丙基三甲氧基硅烷 /
- 二乙醇胺 /
- 亚甲基蓝 /
- 催化 /
- 降解
Abstract: Microcrystalline cellulose (MCC) was used as raw materials and loaded with CuO nanoparticles (CuO NPs). Then, 3-chloropropyltrimethoxysilane (CPTES) and diethanolamine (DEA) were added for grafting reaction to prepare CuO NPs@MCC–Si–N(OH)₂. CuO NPs@MCC–Si–N(OH)₂ was characterized with FTIR, XRD, thermal gravimetric analysis and morphology analysis. The results show that CuO NPs can be successfully loaded on the surface of MCC, and silane coupling agent can improve the dispersion of the composite and the ability to graft amine groups, thus enhancing its catalytic activity, and increasing the redox reaction efficiency of sodium borohydride (NaBH₄) and methylene blue (MB). Hence, MB stain is degraded rapidly. It’s also found that CuO NPs@MCC–Si–N(OH)₂ with 20wt% DEA shows the best catalytic effect, and the highest removal efficiency is 99.71% after treating 30 mL MB solution (3 mmol/L) with 30 mg CuO NPs@MCC–Si–N(OH)₂ and 10 mg NaBH₄ within 5 min, and the removal rate is 93.24% after five cycles.
- microcrystalline cellulose /
- 3-chloropropyltriethoxysilane /
- diethanolamine /
- methylene blue /
- catalytic /
- degradation

HTML全文

图 1 改性微晶纤维素 (MCC)(a)和不同二乙醇胺 (DEA)添加量的纳米CuO颗粒(CuO NPs)@MCC–Si–N(OH)₂(b)的FTIR图谱

Figure 1. FTIR spectra of modified microcrystalline cellulose (MCC) (a) and CuO nanoparticles (CuO NPs)@MCC–Si–N(OH)₂with different contents of diethanolamine (DEA) (b）

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图 2 MCC及改性MCC的SEM图像

Figure 2. SEM images of MCC and modified MCC

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图 3 改性MCC（a）和不同DEA添加量的CuO NPs@MCC–Si–N(OH)₂（b）的XRD图谱

Figure 3. XRD spectra of modified MCC(a) and CuO NPs@MCC–Si–N(OH)₂with different additions of DEA(b)

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图 4 改性MCC和不同DEA添加量的CuO NPs@MCC–Si–N(OH)₂的TG (a)及DTG (b)曲线

Figure 4. TG (a) and DTG (b) curves of modified MCC and CuO NPs@MCC–Si–N(OH)₂with different additions of DEA

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图 5 DEA添加量（a）、CuO NPs@MCC–Si–N(OH)₂用量（b）、反应时间（c）和MB浓度(d)对MB催化降解性能的影响

Figure 5. Effect of DEA addition amount (a), dosage of CuO NPs@MCC–Si–N(OH)₂(b), reaction time (c) and MB concentration (d) on degradation properties of MB

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表 1 亚甲基蓝 (MB) 标样的浓度与吸光度

Table 1. Concentration and absorbance of methylene blue (MB) standards

No.	Concentration/(mg·L⁻¹)	Absorbance
1	6.40	0.36672
2	5.12	0.32067
3	3.84	0.22950
4	2.56	0.14548
5	1.28	0.06453

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表 2 改性MCC的FTIR图谱带分析

Table 2. Band characteristics of FTIR spectra related to MCC and grafted MCC

Wavenumber/cm⁻¹	Peak attribution
3 200-3 600	—OH stretching vibration absorption peak in hydroxyl group and carboxyl group
2 935	Methylene—C—H stretching vibration absorption peak
1 740	—C=O stretching vibration absorption peak
1 260	Si—C stretching vibration absorption peak
800	Si—O—C stretching vibration absorption peak
560	Cu—O stretching vibration absorption peak

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表 3 不同DEA添加量、CuO NPs@MCC–Si–N(OH)₂用量、反应时间和MB浓度时催化MB的去除率和去除量

Table 3. Removal rate and amount of MB catalyted by CuO NPs@MCC–Si–N(OH)₂with different DEA addition amounts, dosage of CuO NPs@MCC–Si–N(OH)₂, reaction time and concentration of MB

Fixed factor	Research factor (variable)	Range of variable	Removal rate of MB/%	Removal amount of MB/mg
Dosage of CuO NPs@MCC–Si–N(OH)₂10 mg Dosage of NaBH₄10 mg Reaction time 5 min MB 30 mL 2 mmol/L	DEA addition amount	5wt%	92.50±0.21	17.76±0.04
		10wt%	95.16±0.15	18.27±0.03
		15wt%	95.70±0.15	18.37±0.03
		20wt%	97.15±0.10	18.65±0.02
DEA addition amount 20wt% Dosage of NaBH₄ 10 mg Reaction time 5 min MB 30 mL 2 mmol/L	Dosage of CuO NPs@MCC–Si–N(OH)₂	10 mg	97.15±0.10	18.65±0.02
		20 mg	98.23±0.12	18.86±0.02
		30 mg	99.71±0.10	19.14±0.02
		40 mg	99.84±0.09	19.17±0.02
		50 mg	99.87±0.08	19.18±0.02
DEA addition amount 20wt% Dosage of CuO NPs@MCC–Si–N(OH)₂30 mg Dosage of NaBH₄ 10 mg MB 30 mL 2 mmol/L	Reaction time	1 min	92.50±0.41	17.76±0.08
		3 min	95.76±0.29	18.39±0.06
		5 min	99.71±0.10	19.14±0.02
		7 min	99.80±0.07	19.16±0.01
		9 min	99.80±0.09	19.16±0.02
Dosage of CuO NPs@MCC–Si–N(OH)₂30 mg DEA addition amount 20wt% Dosage of NaBH₄10 mg Reaction time 5 min	Concentration of MB	1 mmol/L	99.78±0.07	9.58±0.01
		2 mmol/L	99.71±0.10	19.14±0.02
		3 mmol/L	99.18±0.16	28.56±0.03
		4 mmol/L	40.53±5.76	15.56±1.11
		5 mmol/L	31.37±6.81	15.02±1.31

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