Ag<sub>3</sub>PO<sub>4</sub>/羟基磷灰石复合光催化剂的制备及对亚甲基蓝的高效降解

宋萃; 戚明颖; 刘金芳; 祝茜

doi:10.13801/j.cnki.fhclxb.20200220.001

Ag₃PO₄/羟基磷灰石复合光催化剂的制备及对亚甲基蓝的高效降解

doi: 10.13801/j.cnki.fhclxb.20200220.001

山东大学海洋学院，威海 264209

基金项目: 山东大学（威海）—迪尚集团校企协同竞帆计划

详细信息

通讯作者:
祝茜，博士，教授，研究方向为海洋生物学　E-mail：qianzhu@sdu.edu.cn

中图分类号: O643.32+2
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- 被引次数: 0
出版历程
- 收稿日期: 2019-11-27
- 录用日期: 2020-01-20
- 网络出版日期: 2020-02-20
- 刊出日期: 2020-06-15

Preparation of Ag₃PO₄/HAP composite photocatalyst and its efficient degradation of methylene blue

Marine College, Shandong University, Weihai 264209, China

摘要

摘要: 以天然废弃物牡蛎壳为原料，利用沉淀法和水热法制备出高纯度的羟基磷灰石(HAP)，负载Ag₃PO₄后制备出具有可见光响应的复合光催化剂Ag₃PO₄/HAP，并以亚甲基蓝（MB）为反应模型考察了不同催化剂的降解性能。利用SEM、TEM、XRD、BET、XPS、UV-Vis、电子自旋共振（ESR）等仪器对样品进行表征。结果表明，两种方法均可合成HAP材料，但水热法合成的材料纯度更高，且合成出了纳米等级的HAP；Ag₃PO₄的添加未改变HAP的组成和结构，却改善了材料对可见光的吸收性能。与沉淀法相比，水热法制备的HAP具有更好的吸附性能，其比表面积为46.63 m²·g^-1；且随着Ag₃PO₄质量的增加，复合材料的比表面积逐渐增大。水热法制备的Ag₃PO₄/HAP表现出了较高的活性，其中1:2-Ag₃PO₄/HAP催化剂的表现更突出，在10 min时即可达到50%的降解率，并在40 min内达到完全降解；经自由基捕获实验证实，参与降解反应的主要活性物种为•O₂⁻和h⁺。
- 牡蛎壳 /
- 羟基磷灰石 /
- Ag₃PO₄ /
- 光催化 /
- 亚甲基蓝
Abstract: High purity hydroxyapatite (HAP) was synthesized via the precipitation method and hydrothermal method, with oyster shells as raw material. After Ag₃PO₄ particles were loaded on the HAP support, the Ag₃PO₄/HAP photocatalysts show a pronounced photocatalytic activity upon decomposition of methylene blue (MB) dye in aqueous solution under visible light. The as-synthesized samples were characterized by SEM, TEM, XRD, BET, XPS, UV-Vis and electron spin resonance(ESR). The results show that HAP could be synthesized by both methods, but higher purity and nano-sized HAP are synthesized by the hydrothermal method. The addition of Ag₃PO₄ does not change the composition and structure of HAP, but improves its absorption property of visible light. Compared with the precipitation method, hydrothermal prepared HAP has the better adsorption performance, and its specific surface area is 46.63 m²·g^-1. And the specific surface areas of Ag₃PO₄/HAP composites (hydrothermal method) increase gradually with the increase of Ag₃PO₄ content. Therefore, the hydrothermal preparation of Ag₃PO₄/HAP shows higher activity, and the 1:2-Ag₃PO₄/HAP produces the highest photocatalytic activity; its degradation rate of MB is up to 50% within 10 min of irradiation and its complete degradation is almost done at 40 min. The free radical capture experiment confirms that the main active species involved in the degradation reaction are •O₂⁻and h⁺.
- oyster shells /
- hydroxyapatite /
- Ag₃PO₄ /
- photocatalysis /
- methylene blue

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图 1 光催化反应装置示意图

Figure 1. Schematic diagram of photocatalytic reactor

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图 2 HAP和Ag₃PO₄/HAP(H)复合材料的XRD图谱

Figure 2. XRD patterns of HAP and Ag₃PO₄/HAP(H) composites

HAP(H)—HAP(Hydrothermal method)

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图 3 HAP和Ag₃PO₄/HAP(H)复合材料的SEM图像和TEM图像

Figure 3. SEM images and TEM images of HAP and Ag₃PO₄/HAP(H) composites

（(a) HAP(P); ((b),(e),(g)) HAP(H); (c) 1:4-Ag₃PO₄/HAP(H); ((d),(f),(h)) 1:2-Ag₃PO₄/HAP(H)）

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图 4 HAP和Ag₃PO₄/HAP复合材料的N₂吸附-脱附等温曲线

Figure 4. N₂ adsorption-desorption isotherm curves of HAPand Ag₃PO₄/HAP composites

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图 5 HAP(H)和1:2-Ag₃PO₄/HAP(H)复合材料催化剂的XPS图谱

Figure 5. XPS spectra of HAP(H) and 1:2-Ag₃PO₄/HAP(H) composite photocatalyst（(a) HAP(H) and 1:2-Ag₃PO₄/HAP(H) composite;(b) 1:2-Ag₃PO₄/HAP(H) composite）

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图 6 HAP(H)和1:2-Ag₃PO₄/HAP(H)复合材料的紫外-可见吸收光谱Fig. 6 UV-Vis absorption spectroscopy of HAP(H) and 1:2-Ag₃PO₄/HAP(H) composites

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图 7 不同催化剂降解亚甲基蓝（MB）溶液的可见光催化性能比较

Figure 7. Comparison of photoactivity for degradation of methylene blue(MB) by different catalysts under visible light irradiation

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图 8 1:2-Ag₃PO₄/HAP(H)复合材料催化剂的稳定性

Figure 8. Catalytic stability of 1:2-Ag₃PO₄/HAP(H) composite

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图 9 1:2-Ag₃PO₄/HAP(H)复合材料的自由基捕获实验(a)和ESR实验(b)结果

Figure 9. Material captured test of free radicals(a) and the ESR experimental results(b) of 1:2-Ag₃PO₄/HAP(H)

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表 1 Ag₃PO₄/羟基磷灰石(HAP)复合材料的质量配比

Table 1. Mass ratios of Ag₃PO₄/hydroxyapatite(HAP) composites

Sample	Mass of AgNO₃/g	Mass of HAP/g
1∶4-Ag₃PO₄/HAP	0.25	1
1∶3-Ag₃PO₄/HAP	0.33	1
1∶2-Ag₃PO₄/HAP	0.50	1
Note: HAP—Hydroxyapatite.

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表 2 HAP和Ag₃PO₄/HAP 复合材料的孔结构Table 2 Pore texture of HAP and Ag₃PO₄/HAP composites

Sample	Surface area/ (m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Average pore diameter/nm
HAP(P)	39.68	0.303	25.86
1∶4-Ag₃PO₄/HAP(P)	37.80	0.240	24.93
HAP(H)	46.63	0.384	24.18
1∶4-Ag₃PO₄/HAP(H)	26.17	0.222	24.76
1∶3-Ag₃PO₄/HAP(H)	45.83	0.362	21.63
1∶2-Ag₃PO₄/HAP(H)	59.95	0.423	19.83

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