分子筛包嵌Ag团簇新型双功能材料用于水体杀菌

张志杨; 高卫民

doi:10.13801/j.cnki.fhclxb.20200311.001

分子筛包嵌Ag团簇新型双功能材料用于水体杀菌

doi: 10.13801/j.cnki.fhclxb.20200311.001

张志杨^,,
高卫民

中冶华天工程技术有限公司　水环境技术研究院，南京 210019

基金项目: 南京市科技计划(201805015)；中华全国总工会职工创新补助资金(2017-1203)

详细信息

通讯作者:
张志杨，博士，工程师，研究方向为分子筛基复合材料设计和性能　E-mail：15751863907@163.com

中图分类号: TB331
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- 被引次数: 0
出版历程
- 收稿日期: 2019-11-08
- 录用日期: 2020-02-25
- 网络出版日期: 2020-03-12
- 刊出日期: 2020-10-15

Ag clusters enclosed into zeolite as a new bi-functional material for water sterilization

ZHANG Zhiyang^,,
GAO Weimin

Institute of Water Environment of Technology, MCC Huatian Engineering & Technology Corporation, Nanjing 210019, China

摘要

摘要: 为了有效杀死水体中大肠杆菌并同时吸附其死亡过程中释放的内毒素，采用原位合成法首次合成了X型分子筛包嵌Ag纳米团簇的新型双功能材料(Ag@NaX)，高倍透射电镜和扫描透射电镜分析结果表明该材料中Ag纳米团簇分布均一、平均尺寸在1.03 nm，且大部分Ag纳米团簇位于分子筛的孔道中。将材料用于水体中大肠杆菌的去除，该材料表现出非常优异的杀菌性能，当杀菌时间保持在20 min，2.5 mg/100 mL的材料使用量(Ag的负载量质量分数约为1.07wt%)就可以完全杀死水体中的大肠杆菌，并且分子筛可以快速高效地吸附大肠杆菌死亡过程中释放的内毒素，使水体中内毒素的含量能够保持在8×10⁻⁹g/100 mL，低于相关饮用水规定中内毒素含量的安全标准。在Ag纳米粒子与分子筛的密切协同下该复合材料同时具备优异的杀菌和吸附的双重功能。分子筛骨架可以有效地阻碍Ag纳米团簇的流失，使材料具有非常优异的稳定性，在多次使用后，材料的杀菌性能仍然能够得到较好的保持。
- 分子筛 /
- 包嵌 /
- Ag团簇 /
- 双功能 /
- 杀菌 /
- 吸附
Abstract: For effectively killing the bacillus coli in the water and adsorbing endotoxin released on the death at the same time, the new bi-functional material of Ag nanoclusters enclosed into X-zeolite (Ag@NaX) was prepared by in-situ synthesis method for the first time. The results of HR-TEM and STEM show that most of the Ag clusters are uniformly located at the zeolite cages, whose average size is 1.03 nm. This bi-functional material was used for killing the bacillus coli in water and showed an excellent performance. The amount of 2.5 mg/100 mL material (1.07wt% mass fraction of Ag loading) could totally remove the bacillus coli at 20 min. The endotoxin released on the death is also adsorbed by the zeolite efficiently, leading to the amount of endotoxin keeping at 8×10⁻⁹g/100 mL, whose amount is lower than the safety standards of endotoxin for drinking water in relevant regulations. The composite material has excellent bi-function of sterilization and adsorption at the same time under the join effects of Ag clusters and zeolite endow. The material has a excellent stability due to the Ag clusters is effectively prevented from losing by the zeolite skeleton, which leads to the performance of this material keeping well after several numbers of using.
- zeolite /
- enclosing /
- Ag clusters /
- bi-functional /
- sterilization /
- adsorption

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图 1 X型分子筛包嵌Ag纳米团簇(Ag@NaX)双功能材料制备流程示意图

Figure 1. Schematic diagram of the preparation process of bi-functional material of Ag naoclusters (Ag@NaX) enclosed into X-zeolite

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图 2 NaX、Ag₂O@NaX和Ag@NaX复合材料的XRD图谱(a)、N₂吸附-脱附曲线(b)和FTIR图谱(c)

Figure 2. XRD spectra(a), N₂ adsorption/desorption isotherms(b) and FTIR spectra(c) of NaX, Ag₂O@NaX and Ag@NaX composites

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图 3 Ag@NaX复合材料的HR-TEM图像和Ag纳米团簇尺寸分布(a)以及SEM图像和EDX分析结果(b)

Figure 3. HR-TEM image and size distribution of Ag nanoclusters(a) and SEM image and EDX analysis results(b) of Ag@NaX composites

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图 4 Ag@NaX复合材料使用前后的XRD图谱

Figure 4. XRD spectra of Ag@NaX composite before and after being used

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图 5 Ag@NaX复合材料使用后的HR-TEM图像和Ag纳米团簇尺寸分布

Figure 5. HR-TEM image and size distribution of Ag nanoclusters for Ag@NaX-used

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图 6 Ag@NaX复合材料用于水体杀菌机制示意图

Figure 6. Schematic diagram of of the mechanism of water sterilization by Ag@NaX composite

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表 1 Ag@NaX复合材料和NaX样品的X射线荧光光谱分析结果

Table 1. Analysis results of X-ray fluorescence spectrum for Ag@NaX composite and NaX

Sample	SiO₂/wt%	Al₂O₃/wt%	Na₂O/wt%	Ag₂O/wt%	Others/wt%	Chemical formula	Ag content/wt%
NaX	50.63	32.97	16.19	-	0.21	Na₈₃Al₈₃Si₁₀₉O₃₈₄	-
Ag@NaX	50.95	33.10	14.25	1.15	0.55	Ag@Na_78.5Al₈₃Si₁₀₉O₃₈₄	1.07

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表 2 NaX和Ag@NaX复合材料的杀菌性能

Table 2. Sterilization performance of NaX and Ag@NaX composite

Concentration/(mg·(100 mL)⁻¹)	Number of bacterial colony/(CFU·(100 mL)⁻¹)						Disinfection rate/%
Concentration/(mg·(100 mL)⁻¹)	1 min	5 min	10 min	20 min	30 min	60 min	1 min	10 min	60 min
^a1.0	1 400	56	25	8	5	2	89.23	99.81	99.99
^a2.5	250	14	0	0	0	0	98.08	100	100
^a5.0	0	0	0	0	0	0	100	100	100
^b5.0	11 500	10 430	10 200	10 250	10 230	10 120	13.04	21.54	22.15
Notes: ^a—Ag@NaX; ^b—NaX.

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表 3 Ag@NaX复合材料对杀菌过程中释放出的内毒素的吸附性能

Table 3. Adsorption performance of released endotoxin during the sterilization for Ag@NaX composite

Concentration/(mg·(100 mL)⁻¹)	Endotoxin concentration/(4×10⁻¹⁰(g·100 mL)⁻¹)						Adsorption rate/%
Concentration/(mg·(100 mL)⁻¹)	1 min	5 min	10 min	20 min	30 min	60 min	1 min	10 min	60 min
1.0	109	106	118	76	69	54	78.2	76.4	89.2
2.5	35	24	21	20	20	20	93.0	95.8	96.0
5.0	25	24	19	20	17	15	95.0	96.2	97.0

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表 4 Ag@NaX复合材料的杀菌稳定性

Table 4. Stability of sterilization for Ag@NaX composite

Entry	Number of usage
Entry	1	2	3	4	5	6	7	8	9	10*
Number of bacterial colony/(CFU·(100 mL)⁻¹)	0	0	0	0	0	0	0	25	1 360	0
Endotoxin concentration/(4×10⁻¹⁰(g·100 mL)⁻¹)	20	21	19	17	21	18	19	22	115	19
Note: *—Calcination at 500℃ for 4 h.

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表 5 Ag@NaX复合材料循环过程中水体中Ag⁺的浓度

Table 5. Ag⁺ concentration in water during recycling of Ag@NaX composite

	Number of usage
	1	2	3	4	5	6	7	8
Ag⁺ concentration/(ug·L⁻¹)	4.5	0.8	0.4	0.4	0.2	0	0	0

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