Tunable Synthesis of Hierarchical BiOCl Microspheres for Efficient Photocatalytic Degradation of Pharmaceutical Wastewater†

doi:10.7503/cjcu20141073

Abstract

Abstract:

A series of hierarchical BiOCl microspheres with different sizes was prepared with a diethylene glycol(DEG) mediated solventhermal method using BiCl₃ as precursor and urea as a precipitant. The obtained samples were characterized by powder X-ray diffraction(XRD) and scanning electron microscopy(SEM). The results suggest that the crystallinity and size could be influenced by precipitants dosage(molar ratio of urea to BiCl₃) and solventhermal time. BiOCl microspheres with sizes of 1—5 μm were synthesized by tuning reaction conditions. The as-prepared BiOCl exhibited high photocatalytic efficiency towards the degradation of carbamazepine(CBZ) and sulfamethoxazole(SMZ) under UV light irradiation. Especially, BiOCl samples obtained at precipitants dosages of 10∶1 and 15∶1 with hydrothermal time of 30 min exhibited superior photocatalytic activity to TiO₂(P25). The results indicate that the hierarchical BiOCl microspheres are promising candidate for the removal of the recalcitrant pharmaceutical contaminants.

Key words: Tunable synthesis, BiOCl, Photocatalysis, Carbamazepine(CBZ), Sulfamethoxazole(SMZ)

CLC Number:

O643

TrendMD:

ZHAO Xiaoxia, GAO Xiaoya, ZHANG Xiaochao, LI Rui, WANG Yawen, WANG Yunfang, FAN Caimei. Tunable Synthesis of Hierarchical BiOCl Microspheres for Efficient Photocatalytic Degradation of Pharmaceutical Wastewater^†[J]. Chem. J. Chinese Universities, 2015, 36(5): 955.

Figures/Tables 9

Fig.1 XRD patterns of as-prepared BiOCl photocatalysts with different Co(NH2)2/BiCl3 molar ratios(a—d) and hydrothermal time(e—h)n[CO(NH2)2]/n(BiCl3): a. 8∶1; b. 10∶1; c. 15∶1; d. 20∶1. Hydrothermal time/h: e. 4; f. 24; g. 48; h. 72.

Fig.2 SEM images of as-prepared BiOCl photocatalysts with different Co(NH2)2/BiCl3 molar ratio(A—D) and hydrothermal time(E—I)n[CO(NH2)2]/n(BiCl3): (A) 8∶1; (B) 10∶1; (C) 15∶1; (D) 20∶1. Hydrothermal time/h: (E) 4; (F) 24; (G) 48; (H) 72. (I) is the HRSEM image of the sample of (G).

Fig.3 SEM images of BiOCl photocatalysts in mixed solvent(A) and with different hydrothermal time(B, C)n[CO(NH2)2]/n(BiCl3)=10∶1. (A) V(DEG)∶V(H2O)=1∶1; (B) hydrothermal time: 10 min; (C) hydrothermal time: 20 min.

Fig.4 UV-Vis absorption of DEG before(a) and after(b) the addition of BiCl3

Scheme 1 Formation mechanism of hierarchical BiOCl microspheres

Fig.5 XRD pattern(A) and SEM image(B) of TiO2(P25) and photodegradation of CBZ(C) and SMZ(D)

Fig.6 Photodegradation of CBZ(A) and SMZ(B) solution upon UV light irradiation in the presence of BiOCl prepared at n[CO(NH2)2]/n(BiCl3)=15∶1 (A) [CBZ]0=2.5 mg/L; (B) [SMZ]0=5 mg/L.

Fig.7 Photodegradation of CBZ and SMZ upon UV light irradiation in the presence of different BiOCl photocatalysts[CBZ]0=2.5 mg/L, [SMZ]0=5 mg/L, [BiOCl]=0.5 g/L. n[CO(NH2)2]/n(BiCl3): a. 8∶1; b. 10∶1; c. 15∶1; d. 20∶1. Hydrothermal time/h: e. 4; f. 24; g. 48; h. 72.

Fig.8 Effect of initial concentrations of CBZ and SMZ on their degradation rate under simulated solar light irradiation in the presence of BiOCl[CBZ]0/(mg·L-1): a. 2.5, b. 5, c. 10; [SMZ]0/(mg·L-1): d. 5, e. 10, f. 20; [BiOCl]=0.5 g/L.

References 29

[1]	Aguinaco, A. , Beltrá, n F. J. , Sagasti J. J., P. , Gimeno, O. , Chem. Eng. J., 2014, 235, 46- 51
[2]	Hoque M., E. , Cloutier, F. , Arcieri, C. , McInnes, M. , Sultana, T. , Murray, C. , Vanrolleghem P., A. , Metcalfe C., D. , Sci. Total Environ., 2014, 487, 801- 812
[3]	Lv, M. , Sun, Q. , Hu A., Y. , Hou L., Y. , Li J., W. , Cai, X. , Yu C., P. , J. Hazard. Mater., 2014, 280, 696- 705
[4]	Mohapatra D., P. , Brar S., K. , Tyagi R., D. , Picard, P. , Surampalli R., Y. , Sci. Total Environ., 2014, 470, 58- 75
[5]	Zhang Y., J. , Geiß, en S. U. , Gal C., M. , Chemosphere, 2008, 73, 1151- 1161
[6]	Lekkerkerker-Teunissen, K. , Benotti M., J. , Snyder S., A. , Dijk H. C., V. , Sep. Purif. Technol., 2012, 96, 33- 43
[7]	Donner, E. , Kosjek, T. , Qualmann, S. , Kusk K., O. , Heath, E. , Revitt D., M. , Ledin, A. , Andersen H., R. , Sci. Total Environ., 2013, 443, 870- 876
[8]	Liu J., L. , Wong M., H. , Environ. Int., 2013, 59, 208- 224
[9]	刘建新, 王韵芳, 王雅文, 樊彩梅. 物理化学学报, 2014, 30, 729- 737
	Liu J., X. , Wang Y., F. , Wang Y., W. , Fan C., M. , Acta Phys. Chim. Sin., 2014, 30, 729- 737
[10]	龙明策, 万磊, 曾曾, 刘伊依, 陈渊源. 物理化学学报, 2012, 28, 2917- 2923
	Long M., C. , Wan, L. , Zeng, C. , Liu Y., Y. , Chen Y., Y. , Acta Phys. Chim. Sin., 2012, 28, 2917- 2923
[11]	戚克振, 王艳, 付嘉琦, Rengaraj Selvaraj, 王贵昌. 高等学校化学学报, 2014, 35( 12), 2523- 2528
	Qi K., Z. , Wang, Y. , Fu J., Q. , Rengaraj, S. , Wang G., C. , Chem. J. Chinese Universities, 2014, 35( 12), 2523- 2528
[12]	Zhang X., C. , Liu X., X. , Fan C., M. , Wang Y., W. , Wang Y., F. , Liang Z., H. , Appl. Catal. B, 2013, 132, 332- 341
[13]	姬磊, 于瑞敏, 王浩人, 陈丽铎, 汪怀远. 高等学校化学学报, 2015, 36( 3), 551- 558
	Ji, L. , Yu R., M. , Wang H., R. , Chen L., D. , Wang H., Y. , Chem. J. Chinese Universities, 2015, 36( 3), 551- 558
[14]	王艳, 张小超, 赵丽军, 赵晓霞, 史宝萍, 樊彩梅. 高等学校化学学报, 2014, 35( 12), 2624- 2631
	Wang, Y. , Zhang X., C. , Zhao L., J. , Zhao X., X. , Shi B., P. , Fan C., M. , Chem. J. Chinese Universities, 2014, 35( 12), 2624- 2631
[15]	Chen, F. , Liu H., Q. , Bagwasi, S. , Shen X., X. , Zhang J., L. , J. Photoch. Photobio. A, 2010, 215, 76- 80
[16]	Peng S., J. , Li L., L. , Zhu P., N. , Wu Y., Z. , Srinivasan, M. , Mhaisalkar S., G. , Ramakrishna, S. , Yan Q., Y. , Chem. Asian J., 2013, 8, 258- 268
[17]	Tong, H. , Ouyang S., X. , Bi Y., P. , Umezawa, N. , Oshikiri, M. , Ye J., H. , Adv. Mater., 2012, 24, 229- 251
[18]	董占能, 赵兵, 郭玉忠. 昆明理工大学学报, 2000, 25, 58- 61
	Dong Z., N. , Zhao, B. , Guo Y., Z. , J. Kunming University Sci. Technol., 2000, 25, 58- 61
[19]	Xiong J., Y. , Cheng, G. , Qin, F. , Wang, R. , Sun H., Z. , Chen, R. , Chem. Eng. J., 2013, 220, 228- 236
[20]	Hirano, M. , Morikawa, H. , Chem. Mater., 2003, 15, 2561- 2566
[21]	蒋琪英, 沈娟, 钟国清. 化学进展, 2006, 18, 1634- 1645
	Jiang Q., Y. , Shen, J. , Zhong G., Q. , Prog. Chem., 2006, 18, 1634- 1645
[22]	Duan, F. , Zheng, Y. , Liu, L. , Chen M., Q. , Xie, Y. , Mater. Lett., 2010, 64, 1566- 1569
[23]	Ren K., X. , Zhang, K. , Liu, J. , Luo H., D. , Huang Y., B. , Yu X., B. , Cryst. Eng. Commmu., 2012, 14, 4384- 4390
[24]	Zhang, X. , Ai Z., H. , Jia F., L. , Zhang L., Z. , J. Phys. Chem. C, 2008, 112, 747- 753
[25]	Toyoda, M. , Nanbu, Y. , Nakazawa, Y. , Hirano, M. , Inagaki, M. , Appl. Catal. B, 2004, 49, 227- 232
[26]	王龙. 几种纳米材料的制备及其安全性评价, 成都: 四川大学, 2007)
	Wang, L. , Preparation and Bio-safe Assessing of Several Nanomaterials Including Nano-ZnO, Nano-Mn3O4 and Ce-doped Nano-TiO2, Sichuan Uversity, Chengdu, 2007(
[27]	刘晓霞, 樊彩梅, 王韵芳, 王雅文, 张小超, 梁镇海. 中国科学: 化学, 2012, 42, 1145- 1151
	Liu X., X. , Fan C., M. , Wang Y., F. , Wang Y., W. , Zhang X., C. , Liang Z., H. , Scientia Sinica Chimica, 2012, 42, 1145- 1151
[28]	Deng, J. , Shao Y., S. , Gao N., Y. , Deng, Y. , Zhou S., Q. , Hu X., H. , Chem. Eng. J., 2013, 228, 765- 771
[29]	Wang A., M. , Li Y., Y. , Estrada A., L. , Appl. Catal. B, 2011, 102, 378- 386