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

doi:10.15541/jim20150413

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 11

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

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

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

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

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

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)

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

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

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

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

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

References 12

[1]	XIAO F S, SUN J M, MENG X J, et al.A novel catalyst of copper hydroxyphosphate with high activity in wet oxidation of aromatics.Applied Catalysis A: General, 2001, 207(1/2): 267-271.
[2]	MENG X J, LIN K F, YANG X Y, et al.Catalytic oxidation of olefins and alcohols by molecular oxygen under air pressure over Cu2(OH)PO4 and Cu4O(PO4)2 catalysts.Journal of Catalysis, 2003, 218(2): 460-464.
[3]	XIAO F S, SUN J M, MENG X J, et al.Synthesis and structure of copper hydroxyphosphate and its high catalytic activity in hydroxylation of phenol by H2O2.Journal of Catalysis, 2001, 199(2): 273-281.
[4]	MENG X J, LIN K F, SUN J M, et al.Catalytic epoxidation of styrene over copper hydroxyphosphate Cu2(OH)PO4.Catalysis Letters, 2001, 71(3): 241-244.
[5]	SREENIVASULU P, VISWANADHAM A, NANDAN D, et al.Synthesis and catalytic applications of amine interacted Cu2(OH) PO4 nanoplates (copper NPs) and tubes (copper NTs).RSC Advances, 2013, 3(3): 729-732.
[6]	ZHAN Y Z, LI H L, CHEN Y L.Copper hydroxyphosphate as catalyst for the wet hydrogen peroxide oxidation of azo dyes,Journal of Hazardous Materials, 2010, 180(1/2/3): 481-485.
[7]	CHO I S, KIM D W, LEE S, et al.Synthesis of Cu2PO4OH hierarchical superstructures with photocatalytic activity in visible light,Advanced Functional Materials, 2008, 18(15): 2154-2162.
[8]	MENG X J, XIAO F S.Novel copper phosphates with high catalytic activities under mild conditions. Acta Physico-Chimica Sinica, 2004, 20(S): 939-945.
[9]	CUI L, HUI K N, HUI K S, et al.Facile microwave-assisted hydrothermal synthesis of TiO2 nanotubes.Material Letter, 2012, 75(5): 175-178.
[10]	付伟伟. Ti-V-Cu过渡金属化合物能源材料-催化材料的合成与制备. 长春, 吉林大学博士学位论文, 2013.
[11]	沈启慧. 无机功能材料的合成方法研究. 长春, 吉林大学博士学位论文, 2008.
[12]	ZHANG X Y, DING Y B, TANG X Y, et al.Degradation of bisphenol A by hydrogen peroxide activated with CuFeO2 microparticles as a heterogeneous Fenton-like catalyst: efficiency, stability and mechanism.Chemical Engineering Journal, 2014, 236: 251-262.

[1]	MA Binbin, ZHONG Wanling, HAN Jian, CHEN Liangyu, SUN Jingjing, LEI Caixia. ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity [J]. Journal of Inorganic Materials, 2024, 39(8): 937-944.
[2]	CAO Qingqing, CHEN Xiangyu, WU Jianhao, WANG Xiaozhuo, WANG Yixuan, WANG Yuhan, LI Chunyan, RU Fei, LI Lan, CHEN Zhi. Visible-light Photodegradation of Tetracycline Hydrochloride on Self-sensitive Carbon-nitride Microspheres Enhanced by SiO₂ [J]. Journal of Inorganic Materials, 2024, 39(7): 787-792.
[3]	WANG Zhaoyang, QIN Peng, JIANG Yin, FENG Xiaobo, YANG Peizhi, HUANG Fuqiang. Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation [J]. Journal of Inorganic Materials, 2024, 39(4): 383-389.
[4]	WU Lin, HU Minglei, WANG Liping, HUANG Shaomeng, ZHOU Xiangyuan. Preparation of TiHAP@g-C₃N₄ Heterojunction and Photocatalytic Degradation of Methyl Orange [J]. Journal of Inorganic Materials, 2023, 38(5): 503-510.
[5]	LING Jie, ZHOU Anning, WANG Wenzhen, JIA Xinyu, MA Mengdan. Effect of Cu/Mg Ratio on CO₂ Adsorption Performance of Cu/Mg-MOF-74 [J]. Journal of Inorganic Materials, 2023, 38(12): 1379-1386.
[6]	SUN Chen, ZHAO Kunfeng, YI Zhiguo. Research Progress in Catalytic Total Oxidation of Methane [J]. Journal of Inorganic Materials, 2023, 38(11): 1245-1256.
[7]	MA Xinquan, LI Xibao, CHEN Zhi, FENG Zhijun, HUANG Juntong. BiOBr/ZnMoO₄ Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties [J]. Journal of Inorganic Materials, 2023, 38(1): 62-70.
[8]	CHEN Hanxiang, ZHOU Min, MO Zhao, YI Jianjian, LI Huaming, XU Hui. 0D/2D CoN/g-C₃N₄ Composites: Structure and Photocatalytic Performance for Hydrogen Production [J]. Journal of Inorganic Materials, 2022, 37(9): 1001-1008.
[9]	XUE Hongyun, WANG Congyu, MAHMOOD Asad, YU Jiajun, WANG Yan, XIE Xiaofeng, SUN Jing. Two-dimensional g-C₃N₄ Compositing with Ag-TiO₂ as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde [J]. Journal of Inorganic Materials, 2022, 37(8): 865-872.
[10]	CHI Congcong, QU Panpan, REN Chaonan, XU Xin, BAI Feifei, ZHANG Danjie. Preparation of SiO₂@Ag@SiO₂@TiO₂ Core-shell Structure and Its Photocatalytic Degradation Property [J]. Journal of Inorganic Materials, 2022, 37(7): 750-756.
[11]	WANG Xiaojun, XU Wen, LIU Runlu, PAN Hui, ZHU Shenmin. Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel [J]. Journal of Inorganic Materials, 2022, 37(7): 731-740.
[12]	LIU Xuechen, ZENG Di, ZHOU Yuanyi, WANG Haipeng, ZHANG Ling, WANG Wenzhong. Selective Oxidation of Biomass over Modified Carbon Nitride Photocatalysts [J]. Journal of Inorganic Materials, 2022, 37(1): 38-44.
[13]	ZHANG Xian, ZHANG Ce, JIANG Wenjun, FENG Deqiang, YAO Wei. Synthesis, Electronic Structure and Visible Light Photocatalytic Performance of Quaternary BiMnVO₅ [J]. Journal of Inorganic Materials, 2022, 37(1): 58-64.
[14]	LIU Peng, WU Shimiao, WU Yunfeng, ZHANG Ning. Synthesis of Zn_0.4(CuGa)_0.3Ga₂S₄/CdS Photocatalyst for CO₂ Reduction [J]. Journal of Inorganic Materials, 2022, 37(1): 15-21.
[15]	WANG Luping, LU Zhanhui, WEI Xin, FANG Ming, WANG Xiangke. Application of Improved Grey Model in Photocatalytic Data Prediction [J]. Journal of Inorganic Materials, 2021, 36(8): 871-876.