AgI/NH<sub>2</sub>-UiO-66(Zr)异质结制备及其可见光催化性能

傅炀杰; 张可欣; 毛惠秀; 姬云; 王晓青; 王齐

doi:10.13801/j.cnki.fhclxb.20210927.001

AgI/NH₂-UiO-66(Zr)异质结制备及其可见光催化性能

doi: 10.13801/j.cnki.fhclxb.20210927.001

浙江工商大学　环境科学与工程学院，杭州 310018

基金项目: 国家自然科学基金(21876154，21477114)；浙江省自然科学基金(LR18B070001)

详细信息

通讯作者:
王齐，博士，教授，博士生导师，研究方向为环境光催化　E-mail：wangqi8327@zjgsu.edu.cn

中图分类号: O614
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出版历程
- 收稿日期: 2021-06-24
- 修回日期: 2021-08-20
- 录用日期: 2021-09-13
- 网络出版日期: 2021-09-29
- 刊出日期: 2022-07-30

Preparation and photocatalytic performance of AgI/NH₂-UiO-66(Zr) heterojunction

School of Environment Science and Engineering, Zhejiang Gongshang University, Hangzhou 310018, China

摘要

摘要: 开发可见光响应型金属有机框架材料(MOFs)异质结，有望高效利用太阳能进行催化降解/减毒环境污染物。以氯化锆(ZrCl₄)和2-氨基对苯二甲酸(2-ATA)为原料，用溶剂热法制备了NH₂-UiO-66(Zr)作为基底MOFs，采用对离子沉淀法在其表面负载AgI，制备一系列AgI/NH₂-UiO-66(Zr)异质结复合光催化剂。通过XRD、BET、TEM、UV-Vis DRS、FT-IR、TGA及光电化学测试等手段对材料进行结构和光电响应性质表征。以Cr(VI)为模型污染物，探究复合材料在可见光照射下的光催化性能，以及影响其性能的各种因素：pH、初始Cr(VI)浓度、催化剂投加量、捕获剂种类及浓度。实验结果显示：当AgI负载量为20%时，优选得到的AgI/NH₂-UiO-66(Zr)具有最佳的光催化性能，可见光照射120 min后，Cr(VI)还原率为97.8%，远高于纯AgI和NH₂-UiO-66(Zr)，拟合的一级动力学常数k分别是AgI和NH₂-UiO-66(Zr)体系的7.9倍和7.4倍。此外，异质结催化剂循环使用稳定性良好，循环5次后对Cr(VI)还原率仍保持在90%左右。
- 金属有机框架(MOFs) /
- AgI /
- 光催化 /
- NH₂-UiO-66 /
- Cr(VI)还原 /
- 异质结
Abstract: The development of visible-light-responsive metal organic framework materials (MOFs) heterojunctions is expected to make efficient use of solar energy for catalytic degradation/detoxification of environmental pollutants. Using zircomiun tetrachloride (ZrCl₄) and 2-aminoterephthalic acid (2-ATA) as raw materials, NH₂-UiO-66(Zr) was prepared as MOFs substrate by solvothermal method. A series of AgI/NH₂-UiO-66(Zr) heterojunction composites were prepared by counter ion deposition method. The materials were characterized by XRD, BET, TEM, UV-Vis DRS, FT-IR, TGA and photoelectrochemical tests. Taking Cr(VI) as a model pollutant, the photocatalytic performance of the composite was studied under visible light and various factors were also investigated, including pH, initial Cr(VI) concentration, catalyst loading amount, type and concentration of trapping agent. It is found that 20% AgI/NH₂-UiO-66(Zr) displays optimal photocatalytic performance. After 120 min of visible light irradiation, the Cr(VI) reduction efficiency is 97.8%, which is much higher than that of naked AgI and NH₂-UiO-66(Zr). The fitted first-order kinetic constant k is 7.9 and 7.4 times that in the AgI and NH₂-UiO-66(Zr) systems, respectively. In addition, the catalyst has good cyclic stability. After 5 cycles, the reduction rate of Cr(VI) still remain at about 90%.
- metal organic framework (MOFs) /
- AgI /
- photocatalysis /
- NH₂-UiO-66 /
- Cr(VI) reduction /
- heterojunction

HTML全文

图 1 AgI、NH₂-UiO-66(Zr)和AgI/NH₂-UiO-66(Zr)的XRD图谱

Figure 1. XRD patterns of AgI, NH₂-UiO-66(Zr) and AgI/NH₂-UiO-66(Zr)

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图 2 20%AgI/NH₂-UiO-66(Zr)的TEM和HRTEM图像

Figure 2. TEM image of 20%AgI/NH₂-UiO-66(Zr) at different scales and HRTEM of selected area

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图 3 AgI、NH₂-UiO-66(Zr)和AgI/NH₂-UiO-66(Zr)的N₂吸附-脱附曲线

Figure 3. N₂ adsorption-desorption curves of AgI, NH₂-UiO-66(Zr) and AgI/NH₂-UiO-66(Zr)

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图 4 NH₂-UiO-66(Zr)负载AgI前后的TGA曲线

Figure 4. TGA curves of NH₂-UiO-66(Zr) before and after AgI loading

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图 5 AgI、NH₂-UiO-66(Zr)和AgI/NH₂-UiO-66(Zr)的紫外-可见漫反射光谱图(插图：带隙图)

Figure 5. UV-Vis DRS of AgI, NH₂-UiO-66(Zr) and AgI/ NH₂-UiO-66(Zr) (Insert: Band gap)

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图 6 AgI、NH₂-UiO-66(Zr)和不同比例AgI/NH₂-UiO-66(Zr)在可见光下的光电流曲线

Figure 6. I-t curves of AgI, NH₂-UiO-66(Zr) and AgI/NH₂-UiO-66(Zr) at different ratios under visible light

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图 7 可见光照下AgI、NH₂-UiO-66(Zr)和AgI/NH₂-UiO-66(Zr)的交流阻抗谱

Figure 7. EIS nyquist plots of AgI, NH₂-UiO-66(Zr) and AgI/ NH₂-UiO-66(Zr) under visible light

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图 8 不同条件下不同比例AgI/NH₂-UiO-66(Zr)还原Cr(VI)的动力学曲线

Figure 8. Kinetic curves of Cr(VI) reduction of AgI/NH₂-UiO-66(Zr) at different ratios under different conditions

Mix—Mechanical mixing group of 20% AgI and NH₂-UiO-66(Zr)

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图 9 不同因素对AgI/NH₂-UiO-66(Zr)光催化还原Cr(VI)的影响

Figure 9. Effect of different factors on the photocatalytic reduction of Cr(VI) by AgI/NH₂-UiO-66(Zr)

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图 10 NH₂-UiO-66(Zr)和AgI/NH₂-UiO-66(Zr)光催化还原Cr(VI)的循环实验

Figure 10. Cyclic runs for NH₂-UiO-66(Zr) and AgI/NH₂-UiO-66(Zr) photocatalytic reduction of Cr(VI)

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图 11 AgI、NH₂-UiO-66(Zr)和AgI/NH₂-UiO-66(Zr)的Mott-Schottky曲线

Figure 11. Mott-Schottky plots of AgI, NH₂-UiO-66(Zr) and AgI/NH₂-UiO-66(Zr)

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图 12 AgI/ NH₂-UiO-66(Zr)光催化还原Cr(VI)机制图

Figure 12. Proposed mechanism for photocatalytic reduction of Cr(VI) by AgI/NH₂-UiO-66(Zr)

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