Ag-ZnO/生物质炭纳米复合材料的制备及协同可见光催化性能

黄慧玲; 张隐; 甘露; 潘明珠

doi:10.13801/j.cnki.fhclxb.20190801.001

Ag-ZnO/生物质炭纳米复合材料的制备及协同可见光催化性能

doi: 10.13801/j.cnki.fhclxb.20190801.001

南京林业大学　材料科学与工程学院，南京 210037

基金项目: 国家自然科学基金(31670556)；江苏省“青蓝工程”；南京林业大学杰出青年项目(NLJQ2015-02)

详细信息

作者简介:
黄慧玲（1992－），女，硕士研究生。主要研究方向为纳米氧化锌功能应用

张隐（1994－），女，硕士研究生。主要研究方向为生物质纳米复合材料

通讯作者:
潘明珠，博士，教授，研究方向为先进生物质复合材料　Email：mzpan@njfu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2019-05-05
- 录用日期: 2019-07-13
- 网络出版日期: 2019-08-01
- 刊出日期: 2020-05-15

Preparation and synergetic visible-light photocatalysis properties of Ag-ZnO/Biochar nanocomposites

College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China

摘要

摘要: 以醋酸锌(Zn(CH₃COO)₂·2H₂O)为锌源、硝酸银(AgNO₃)为掺杂源、纤维素纳米晶体(Cellulose nanocrystal, CNC)为生物模板，通过溶胶-凝胶法结合碳化处理，制备了Ag-ZnO/生物质炭(Biochar)复合材料。采用TEM、XRD、BET、UV-Vis DRS对所制得的Ag-ZnO/Biochar复合材料进行表征。以亚甲基蓝(MB)为模型污染物，评价Ag-ZnO/Biochar复合材料在可见光源照射下的光催化性能，进一步阐明其光催化机制。结果表明：碳化后纳米ZnO仍保持良好的分散性，球形Ag纳米粒子均匀分散在ZnO表面，形成Ag-ZnO/Biochar三元复合材料。与Ag-ZnO和ZnO/Biochar复合材料相比，Ag-ZnO/Biochar复合材料在可见光下的光催化降解率显著提高。这是由于生物质炭赋予复合体系良好的吸附性能，使MB的光催化降解反应持续发生；而Ag纳米粒子的表面等离子体共振(Surface plasmon resonance, SRP)效应则增强了复合体系在可见光区的吸收。其中，当AgNO₃、CNC、Zn(CH₃COO)₂·2H₂O的质量比为0.01:0.25:1时，制得的Ag-ZnO/Biochar复合材料在可见光下具有最佳的光吸收性能和MB降解效率：室温条件下，黑暗中吸附30 min，再用可见光照射120 min，即可达到99%的MB降解率，显著高于Ag-ZnO(约23%)和ZnO/Biochar复合材料(约64%)。
- 纳米ZnO /
- Ag掺杂 /
- 生物质炭 /
- 生物模板 /
- 可见光催化
Abstract: Biochar loaded Ag-doped ZnO composites (Ag-ZnO/Biochar) were prepared with a procedure of sol-gel method and carbonization using zinc acetate (Zn(CH₃COO)₂·2H₂O) as a zinc source, silver nitrate (AgNO₃) as doping source, and cellulose nanocrystal (CNC) as a morphological-inducing template, respectively. The obtained Ag-ZnO/Biochar composites were characterized by TEM, XRD, BET and UV-Vis DRS. The photocatalysis performance of Ag-ZnO/Biochar composites was investigated through the degradation of methylene blue (MB) under visible-light irradiation, and the photocatalysis mechanism of Ag-ZnO/Biochar composites was further studied. The results show that nano ZnO retains a good dispersion after carbonization, and Ag spherical nanoparticles are uniformly dispersed on the surface of ZnO to form Ag-ZnO/Biochar ternary composite. Compared with Ag-ZnO and ZnO/Biochar composites, the photocatalysis property of Ag-ZnO/Biochar composites in the visible-light region is significantly improved, which is attributed to the adsorption ability from biochar and the surface plasmon resonance (SPR) effect from Ag nanoparticles. In particular, the Ag-ZnO/Biochar composites has the best light absorption performance and an optimum degradation efficiency to MB at the mass ratio of 0.01:0.25:1 (AgNO₃:CNC:Zn(CH₃COO)₂·2H₂O), corresponding to 99% degradation rate of MB after the absorption for 30 min in dark condition and continuous irradiation for 120 min under 500 W visible-light at room temperature, which is significantly higher than Ag-ZnO (about 23%) and ZnO/Biochar composites (about 64%).
- nano ZnO /
- Ag-doped /
- biochar /
- bio-template /
- visible-light photocatalysis

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图 1 Ag-ZnO/Biochar复合材料的制备流程示意图

Figure 1. Schematic process of the preparation of Ag-ZnO/Biochar composites

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图 2 Ag-ZnO/Biochar复合材料的TEM图像

Figure 2. TEM images of Ag-ZnO/Biochar composites

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图 3 Ag-ZnO/Biochar复合材料的XRD图谱

Figure 3. XRD patterns of Ag-ZnO/Biochar composites

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图 4 Ag-ZnO/Biochar复合材料的N₂吸附-脱附等温曲线

Figure 4. N₂ adsorption/desorption isotherms curves of Ag-ZnO/Biochar composites

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图 5 Ag-ZnO/Biochar复合材料的UV-Vis 漫反射图谱

Figure 5. UV-Vis diffuse reflectance spectra of Ag-ZnO/Biochar composites

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图 6 Ag-ZnO/Biochar复合材料对亚甲基蓝(MB)的降解率及其催化机制：(a) MB的降解率曲线；(b) MB的降解率实物图；(c) 光催化机制

Figure 6. Degradation rate of methylene blue (MB) under visible-light by Ag-ZnO/Biochar composites: (a) Degradation curve of MB; (b) Degradation of MB; (c) Photocatalytic mechanism

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表 1 Ag-ZnO/Biochar复合材料配比

Table 1. Parameters for Ag-ZnO/Biochar composites preparation

Sample	Mass ratio Ag(NO)₃∶ CNC∶Zn(CH₃COO)₂·2H₂O
Ag-ZnO	0.03∶0∶1
ZnO/Biochar	0∶0.25∶1
Ag0.01-ZnO/Biochar	0.01∶0.25∶1
Ag0.03-ZnO/Biochar	0.03∶0.25∶1
Ag0.05-ZnO/Biochar	0.05∶0.25∶1

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表 2 Ag-ZnO/Biochar复合材料的比表面积及孔结构

Table 2. Specific surface area and pore texture of Ag-ZnO/Biochar composites

Sample	Surface Area/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Average pore diameter /nm
ZnO/Biochar	35.51	0.055	188.99
Ag0.01-ZnO/Biochar	53.78	0.059	115.66
Ag0.03-ZnO/Biochar	11.31	0.056	225.58
Ag0.05-ZnO/Biochar	28.30	0.070	174.41

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