微波法制备羟基磷酸铜及光催化降解性能研究

doi:10.15541/jim20150413

无机材料学报 ›› 2016, Vol. 31 ›› Issue (4): 421-426.DOI: 10.15541/jim20150413

微波法制备羟基磷酸铜及光催化降解性能研究

胡晓霞¹, 赵林¹, 赵数煜², 李戎³, 邢彦军¹

(1. 东华大学化学化工与生物工程学院, 上海201620; 2. 上海交通大学化学化工学院, 上海 200240; 3. 东华大学国家染整工程技术中心, 上海201620)

收稿日期:2015-08-31 修回日期:2015-12-13 出版日期:2016-04-20 网络出版日期:2016-03-25
作者简介:胡晓霞(1987–), 女, 博士研究生. E-mail:18817333895@163.com
基金资助:
国家科技支撑计划项目(ID2012BAK30B03);央高校基本科研业务费专项资金(2232013A3-05, CUSF-DH-D- 2014036)

Microwave-assisted Preparation of Copper Hydroxyphosphate and Characterization of Photocatalysis under Visible Light

HU Xiao-Xia¹, ZHAO Lin¹, ZHAO Shu-Yu², LI Rong³, XING Yan-Jun¹

(1. College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai 201620, China; 2. School of Chemistry and Chemical Engineering, Shanghai Jiaotong University, Shanghai 200240, China; 3. National Engineering Research Center for Dyeing & Finishing of Textiles, Donghua University, Shanghai 201620, China)

Received:2015-08-31 Revised:2015-12-13 Published:2016-04-20 Online:2016-03-25
About author:HU Xiao-Xia. E-mail:18817333895@163.com
Supported by:
National Science and Technology Ministry (ID 2012BAK30B03);Fundamental Research Funds for the Central Uni-versities (2232013A3-05, CUSF-DH-D-2014036)

摘要/Abstract

摘要：

以氯化铜、磷酸二氢钠和尿素为原料, 加入模板剂十二烷基硫酸钠(SDS), 采用微波辅助加热法制备了具有不同规则结构的晶态羟基磷酸铜。实验研究了CuCl₂与NaH₂PO₄的摩尔比、模板剂种类和原料浓度等因素对合成羟基磷酸铜晶体的影响。产物采用XRD、SEM和Raman等进行表征, 并通过降解甲基蓝溶液(MB)测试了羟基磷酸铜的催化性能, 探讨了制备条件对产物光催化降解性能的影响。结果表明, 当n(Cu)/n(P)为2, [PO₄^3-]= 0.0025 mol/L, 微波加热温度80℃, 反应时间30 min, 尿素用量6.0 g, SDS用量为0.10 g时制备的羟基磷酸铜具有良好的光催化效果。实验还测试了催化剂的表面光电压谱, 并使用苯甲酸作为荧光探针, 叔丁醇为羟基自由基捕获剂初步验证了光催化反应中羟基磷酸铜的催化机理。

关键词: 羟基磷酸铜, 微波辅助法, 低温常压, 光催化性能

Abstract:

Copper hydroxyphosphate (Cu₂(OH)PO₄) was quickly synthesized by microwave-assisted method at low temperature (< 100℃) and normal atmosphere pressure, then characterized by XRD, SEM and Raman spectra. The synthesis parameters were investigated by a series of controled experiments. It is found that molar ratio, initial concentration of CuCl₂ and NaH₂PO₄, and surfactant species were crucial factors determining the formation and morphology of Cu₂(OH)PO₄. Cu₂(OH)PO₄ synthesized at different [PO₄^3-] (n(Cu)/n(P)=2) exhibited a various morphologies including grain-like, prism and long-prismatic. Addition of anionic surfactant and sodium dodecyl sulfate (SDS) greatly affects Cu₂(OH)PO₄ final morphology. The photocatalytic degradation of Cu₂(OH)PO₄ on methylene blue (MB) was evaluated with addition of H₂O₂ under visible light irradiation. The results showed that Cu₂(OH)PO₄ synthesized at conditions when n(Cu)/n(P)=2, [PO₄^3-]=0.0025 mol/L, 6.0 g urea and 0.10 g SDS, microwave heating at 80℃for 30 min exhibited best visible-light photo-degradation activity. The increase in HO· formation in the presence of Cu₂(OH)PO₄ and the inhibition of HO· generation by adding HO· scavengers (t-butanol) indicated that HO· generated in the reaction system was responsible for the enhanced MB decomposition. Cu₂(OH)PO₄ exhibited excellent stability and effectiveness after 5 consecutive runs in terms of photodegradation of MB.

Key words: copper hydrophosphate, microwave-assisted method, low temperature and normal pressure, photocatalysis

中图分类号:

TQ174

胡晓霞, 赵林, 赵数煜, 李戎, 邢彦军. 微波法制备羟基磷酸铜及光催化降解性能研究[J]. 无机材料学报, 2016, 31(4): 421-426.

HU Xiao-Xia, ZHAO Lin, ZHAO Shu-Yu, LI Rong, XING Yan-Jun. Microwave-assisted Preparation of Copper Hydroxyphosphate and Characterization of Photocatalysis under Visible Light[J]. Journal of Inorganic Materials, 2016, 31(4): 421-426.

图/表 11

图1 不同n(Cu)/n(P) 摩尔比制备Cu2(OH)PO4的XRD图谱

Fig. 1 XRD patterns of Cu2(OH)PO4 synthesized with different n(Cu)/n(P) (a) n(Cu)/n(P)=1; (b) n(Cu)/n(P)=2; (c) n(Cu)/n(P)=3; (d) n(Cu)/n(P)=4

图2 不同n(Cu)/n(P)摩尔比制备Cu2(OH)PO4的SEM照片

Fig. 2 SEM images of Cu2(OH)PO4 synthesized with n(Cu)/n(P) at 1 (a), 2 (b), 3 (c), and 4 (d)

图3 n(Cu)/n(P) =2制备Cu2(OH)PO4的拉曼光谱

Fig. 3 Raman spectrum of Cu2(OH)PO4 synthesized with n(Cu)/n(P) at 2

图4 n(Cu)/n(P) =2时, 不同初始[PO43-]下制备Cu2(OH)PO4的XRD图谱

Fig. 4 XRD patterns of Cu2(OH)PO4 synthesized with different [PO43-] concentrations (n(Cu)/n(P) =2) (a) 0.0025 mol/L; (b) 0.005 mol/L; (c) 0.010 mol/L; (d) 0.025 mol/L; (e) 0.100 mol/L

图5 n(Cu)/n(P) =2时, 不同初始[PO43-]下Cu2(OH)PO4的SEM照片

Fig. 5 SEM images of Cu2(OH)PO4 synthesized with different [PO43-] concentrations (n(Cu)/n(P) =2) (a) 0.0025 mol/L; (b) 0.005 mol/L; (c) 0.010 mol/L; (d) 0.025 mol/L; (e) 0.100 mol/L

图6 不同表面活性剂制备Cu2(OH)PO4的SEM照片

Fig. 6 SEM images of Cu2(OH)PO4 synthesized without and with different surfactants (a) Without surfactant; (b) CTAB (CMC, 0.04 g); (c) PVP (m(PVP)/ [Cu2+]= 20, 0.64 g); (d) SDS (0.10 g)

表1 制备条件对产物光催化降解性能的影响

Table 1 Influence of preparation conditions on the photocatalytic degradation of MB

Test	[PO₄^3-]/ (mol·L^-1)*	Temperature/℃	Time /min	Urea usage/g	SDS usage/g	Degradation efficiency /%
1	0.0025	80	30	6.0	0.10	52.91
2	0.0050	80	30	6.0	0.10	51.06
3	0.0100	80	30	6.0	0.10	47.30
4	0.0025	80	30	3.0	0.05	45.41
5	0.0025	80	30	6.0	0.05	50.79
6	0.0025	80	30	9.0	0.05	68.11
7	0.0025	70	30	6.0	0.10	44.19
8	0.0025	90	30	6.0	0.10	49.68
9	0.0025	95	30	6.0	0.10	60.08
10	0.0025	80	15	6.0	0.10	45.21
11	0.0025	80	60	6.0	0.10	51.61

图7 Cu2(OH)PO4的表面光电压谱

Fig. 7 Surface photovoltage spectrum of Cu2(OH)PO4

图8 Cu2(OH)PO4与H2O2的作用方式

Fig. 8 Possible mechanism in MB degradation by H2O2 over Cu2(OH)PO4 catalyst

图9 荧光强度与反应时间的关系

Fig. 9 Reaction time dependence of emission intensity (excited at 300 nm and detected at 409 nm) a: Cu2(OH)PO4/H2O2-BA; b: H2O2-BA

表2 Cu2(OH)PO4的循环光催化活性

Table 2 Degradation of MB in consecutive runs using the recycled Cu2(OH)PO4

Runs	Degradation efficiency/%
1	52.91
2	50.64
3	46.82
4	47.45
5	48.66

参考文献 12

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微波法制备羟基磷酸铜及光催化降解性能研究

Microwave-assisted Preparation of Copper Hydroxyphosphate and Characterization of Photocatalysis under Visible Light

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