Preparation of CuCe oxide catalyst for CWPO degradation of bisphenol A

doi:10.11949/0438-1157.20191050

Abstract

Abstract:

In order to overcome the limitation to loss of active components of Fenton as well as operation only under pH 2—3, a CuCe oxide catalyst was prepared by a citric acid complex method. A catalytic wet peroxide oxidation (CWPO) reaction system was also established, which aimed at degradation bisphenol A. The effects of calcination temperature, Cu/Ce molar ratio, H₂O₂ dosage, initial concentration of bisphenol A and pH on the structure of the catalyst and the performance of the CWPO were investigated. Possible degradation pathways were also analyzed.The results show that the catalyst has good high temperature stability and pH adaptability, and has high degradation performance for bisphenol A in the range of pH 1.6 to 7.9, and does not need to adjust the pH. The removal rates of BPA and TOC were 91.8% and 84.5%, respectively, with the concentration of Cu²⁺ at 19.3 mg·L^-1 after calcination of 450℃, Cu/Ce molar ratio at 1.0, catalyst dosage at 1 g·L^-1, hydrogen peroxide dosage at 196 mmol·L^-1, BPA concentration at 152 mg·L^-1, pH at 6.6, reaction temperature at 75℃ and reaction for 95 min. The possible degradation pathways of bisphenol A were proposed.

Key words: catalytic wet peroxide oxidation (CWPO), CuCe oxide catalyst, ·OH radical, bisphenol A, degradation

摘要：

为解决Fenton法存在活性组分流失及通常在pH 2～3条件下运行的局限性，采用柠檬酸络合法制备了CuCe氧化物催化剂，建立了双酚A非均相催化湿式过氧化氢氧化（CWPO）反应体系。考察了焙烧温度、Cu/Ce摩尔比、H₂O₂用量、双酚A初始浓度和pH对催化剂物化结构和CWPO性能的影响。并分析了可能的降解路径。结果表明：催化剂具有良好的高温稳定性和pH适应性，在pH 1.6～7.9范围内对双酚A都具有较高的降解性能，不需要调节pH。在焙烧温度450℃、Cu/Ce摩尔比1.0、催化剂用量1 g·L^-1、H₂O₂用量196 mmol·L^-1、BPA浓度152 mg·L^-1、pH 6.6、反应温度75℃、反应95 min后，BPA和TOC去除率分别为91.8%和84.5%,Cu²⁺析出浓度为19.3 mg·L^-1。推测了双酚A可能的降解路径。

关键词: 催化湿式过氧化氢氧化, CuCe氧化物催化剂, ·OH自由基, 双酚A, 降解

CLC Number:

X 703

Zhaojie JIAO, Ligong CHEN, Yunqi LIU, Xianming ZHANG, Haifeng GONG, Xu GAO. Preparation of CuCe oxide catalyst for CWPO degradation of bisphenol A[J]. CIESC Journal, 2020, 71(4): 1646-1656.

焦昭杰, 陈立功, 柳云骐, 张贤明, 龚海峰, 高旭. CuCe氧化物催化剂的制备及CWPO降解双酚A废水研究[J]. 化工学报, 2020, 71(4): 1646-1656.

Figures/Tables 13

Fig.1 XRD patterns of CuCe oxide catalysts

Table 1 Parameters of CuCe oxide catalysts

CuCe 催化剂	结晶度^①/%	平均晶粒尺寸/nm	晶胞参数
CuCe 催化剂	结晶度^①/%	平均晶粒尺寸/nm	a (α=90°)/?	b (β=90°)/?	c (γ=90°)/?
CC450	42.55	8.0	5.4045	5.4001	5.3241
CC550	45.43	9.6	5.4054	5.4219	5.4065
CC650	62.17	17.9	5.4032	5.4111	5.4071
CC750	63.14	32.5	5.4095	5.4096	5.4096
Cu₂Ce₁	63.81	20.7	5.3988	5.4100	5.4003
Cu₁Ce₂	56.57	15.8	5.4031	5.4167	5.4085
Cu₁Ce₃	52.58	12.5	5.4097	5.4133	5.4081

Fig.2 SEM images of CuCe oxide catalysts

Fig.3 H2-TPR profiles of CuCe oxide catalysts

Fig.4 Ce 3d, Cu 2p and O 1s XPS spectra of CuCe oxide catalysts

Table 2 XPS parameters of CuCe oxide catalysts

CuCe催化剂	晶格氧/%	吸附氧/%	羟基氧/%	Ce/%(质量分数)	Cu/%(质量分数)	O/%(质量分数)
Cu₁Ce₃	62.71	28.04	9.25	23.68	8.92	67.39
Cu₁Ce₂	69.16	18.07	12.77	25.22	8.49	66.30
Cu₂Ce₁	64.10	22.75	13.14	2.44	18.90	78.67
CC450	68.32	20.00	11.69	23.54	12.02	64.44
CC550	66.44	20.56	13.00	21.62	12.83	65.55
CC650	65.49	20.38	14.13	19.75	13.95	66.31
CC750	68.73	18.47	12.80	19.78	14.14	66.08

Fig.5 Effects of preparations on heterogeneous CWPO performance of bisphenol A (催化剂=1 g·L-1, BPA=152 mg·L-1, H2O2=196 mmol·L-1, pH=6.6, t=95 min, T=75℃)

Fig.6 Effect of H2O2 dosage on BPA degradation by CWPO (催化剂=1 g·L-1, BPA=152 mg·L-1, pH=6.6, T=75℃)

Fig.7 Effect of initial concentrations on BPA degradation by CWPO(催化剂=1 g·L-1, H2O2=196 mmol·L-1, pH=6.6, T=75℃)

Fig.8 Effect of pH on BPA degradation by CWPO(催化剂=1 g·L-1, H2O2 =196 mmol·L-1, BPA=152 mg·L-1)

Fig.9 Variations of ·OH concentration in CWPO system(催化剂=1 g·L-1, H2O2=196 mmol·L-1, BPA=152 mg·L-1, T=75℃)

Table 3 Possible major intermediates in BPA degradation process

Compound	Molecular weight	Tentative structure
benzaldehyde, 4-ethyl-	134
p-benzoquinone	108
phenol	94
styrene	104
p-isopropenylphenol	134
p-xylene	106
p-hydroxytoluene	108
o-cresol	108
phenol,-2,4-bis(1,1-dimethylethyl)-	206
phenol, 2,5-bis(1,1-dimethylethyl)-	206

Fig.10 Probable degradation pathway of BPA

References 33

34	王光毅, 李金钗. CuO纳米线的热氧化制备及其表面的ZnO纳米颗粒修饰[J]. 武汉大学学报（理学版）, 2011, 57(3): 220-224.
	Wang G Y, Li J C. Syntheses of CuO nanowires by thermal oxidation and surface modification by ZnO nanoparticles[J]. Journal of Wuhan University (Natural Science Edition), 2011, 57(3): 220-224.
35	Yao H C, Yao Y Y F. Ceria in automotive exhaust catalysts (Ⅰ): Oxygen storage[J]. Journal of Catalysis, 1984, 86: 254-265.
36	Zeng J, Zhou G L, Ai Y M, et al. Catalytic wet peroxide oxidation of chlorophenol over a Ce_0.86Cu_0.14-_xO₂ catalyst[J]. International Journal of Chemical Reactor Engineering, 2013, 11(1): 1-9.
37	He C, Yu Y C, Chen C W, et al. Facile preparation of 3D ordered mesoporous CuO_x-CeO₂ with notably enhanced efficiency for the low temperature oxidation of heteroatom-containing volatile organic compounds[J]. RSC Advances, 2013, 3: 19639-19656.
38	Zhu J K, Gao Q M, Chen Z. Preparation of mesoporous copper cerium bimetal oxides with high performance for catalytic oxidation of carbon monoxide[J]. Applied Catalysis B: Environmental, 2008, 81(2): 236-243.
39	Zeng S H, Wang Y, Liu K W, et al. CeO₂ nanoparticles supported on CuO with petal-like and sphere-flower morphologies for preferential CO oxidation[J]. International Journal of Hydrogen Energy, 2012, 37(16): 11640-11649.
40	Song Z X, Ning P, Zhang Q L, et al. The role of surface properties of silicotungstic acid doped CeO₂ for selective catalytic reduction of NO_x by NH₃: effect of precipitant[J]. Journal of Molecular Catalysis A: Chemical, 2016, 413: 15-23.
41	Dai Q G, Huang H, Zhu Y, et al. Catalysis oxidation of 1, 2-dichloroethane and ethyl acetate over ceria nanocrystals with well-defined crystal planes[J]. Applied Catalysis B: Environmental, 2012, 117/118: 360-368.
42	Sun M, Yu L, Yu J, et al. Catalytic combustion of dimethyl ether over Ce-doped cryptomelane type manganese oxide[J]. Journal of Fuel Chemistry and Technology, 2010, 38(1): 108-115.
43	Huang M, Xu C, Wu Z, et al. Photocatalytic discolorization of methyl orange solution by Pt modified TiO₂ loaded on natural zeolite[J]. Dyes and Pigments, 2008, 77(2): 327-334.
1	Bhatnagar A, Anastopoulos I. Adsorptive removal of bisphenol A (BPA) from aqueous solution: a review[J]. Chemosphere, 2017, 168: 885-902.
2	Im J, Ffler F L. Fate of bisphenol A in terrestrial and aquatic environments[J]. Environmental Science & Technology, 2016, 16(50): 8403-8416.
44	Chen W J, Zou C J, Liu Y, et al. The experimental investigation of bisphenol A degradation by Fenton process with different types of cyclodextrins[J]. Journal of Industrial and Engineering Chemistry, 2017, 56: 428-434.
3	Vom Saal F S, Nagel S C, Coe B L, et al. The estrogenic endocrine disrupting chemical bisphenol A (BPA) and obesity[J]. Molecular and Cellular Endocrinology, 2012, 354(1/2): 74-84.
4	Wang H, Ding Z, Shi Q M, et al. Anti-androgenic mechanisms of bisphenol A involve androgen receptor signaling pathway[J]. Toxicology, 2017, 387: 10-16.
5	Rodriguez-Mozaz S, López De Alda M J, Barceló D. Monitoring of estrogens, pesticides and bisphenol A in natural waters and drinking water treatment plants by solid-phase extraction–liquid chromatography-mass spectrometry[J]. Journal of Chromatography A, 2004, 1045(1/2): 85-92.
6	Yu L, Wang C P, Ren X H, et al. Catalytic oxidative degradation of bisphenol A using an ultrasonic-assisted tourmaline-based system: influence factors and mechanism study[J]. Chemical Engineering Journal, 2014, 252: 346-354.
7	Flint S, Markle T, Thompson S, et al. Bisphenol A exposure, effects, and policy: a wildlife perspective[J]. Journal of Environmental Management, 2012, 104: 19-34.
8	Fang L, Hong R, Gao J, et al. Degradation of bisphenol A by nano-sized manganese dioxide synthesized using montmorillonite as templates[J]. Applied Clay Science, 2016, 132/133: 155-160.
9	Mercogliano R, Santonicola S. Investigation on bisphenol A levels in human milk and dairy supply chain: a review[J]. Food and Chemical Toxicology, 2018, 114: 98-107.
10	Heidari H, Sedighi M, Zamir S M, et al. Bisphenol A degradation by Ralstonia eutropha in the absence and presence of phenol[J]. International Biodeterioration & Biodegradation, 2017, 119: 37-42.
11	Yang X J, Tian P F, Zhang C X, et al. Au/carbon as Fenton-like catalysts for the oxidative degradation of bisphenol A[J]. Applied Catalysis B: Environmental, 2013, 134(5): 145-152.
12	Noszczyńska M, Piotrowska-Seget Z. Bisphenols: application, occurrence, safety, and biodegradation mediated by bacterial communities in wastewater treatment plants and rivers[J]. Chemosphere, 2018, 201: 214-223.
13	Vijayalakshmi V, Senthilkumar P, Mophin-Kani K, et al. Bio-degradation of bisphenol A by Pseudomonas aeruginosa PAb1 isolated from effluent of thermal paper industry: kinetic modeling and process optimization[J]. Journal of Radiation Research and Applied Sciences, 2018, 11(1): 56-65.
14	Žerjav G, Kaplan R, Pintar A. Catalytic wet air oxidation of bisphenol A aqueous solution in trickle-bed reactor over single TiO₂ polymorphs and their mixtures[J]. Journal of Environmental Chemical Engineering, 2018, 6(2): 2148-2158.
15	Kaplan R, Erjavec B, Senila M, et al. Catalytic wet air oxidation of bisphenol A solution in a batch-recycle trickle-bed reactor over titanate nanotube-based catalysts[J]. Environmental Science and Pollution Research, 2014, 21(19): 11313-11319.
16	Mena I F, Diaz E, Rodriguez J J, et al. CWPO of bisphenol A with iron catalysts supported on microporous carbons from grape seeds activation[J]. Chemical Engineering Journal, 2017, 318: 153-160.
17	Yang S S, Wu P X, Yang Q L, et al. Regeneration of iron-montmorillonite adsorbent as an efficient heterogeneous Fenton catalytic for degradation of bisphenol A: structure, performance and mechanism[J]. Chemical Engineering Journal, 2017, 328: 737-747.
18	Cleveland V, Bingham J, Kan E. Heterogeneous Fenton degradation of bisphenol A by carbon nanotube-supported Fe₃O₄[J]. Separation and Purification Technology, 2014, 133: 388-395.
19	Zhang L L, Xu D, Hu C, et al. Framework Cu-doped AlPO₄ as an effective Fenton-like catalyst for bisphenol A degradation[J]. Applied Catalysis B: Environmental, 2017, 207: 9-16.
20	Chang Z, Zhao N, Liu J F, et al. Cu-Ce-O mixed oxides from Ce-containing layered double hydroxide precursors: controllable preparation and catalytic performance[J]. Journal of Solid State Chemistry, 2011, 184(12): 3232-3239.
21	Pachamuthu M P, Karthikeyan S, Maheswari R, et al. Fenton-like degradation of bisphenol A catalyzed by mesoporous Cu/TUD-1[J]. Applied Surface Science, 2017, 393: 67-73.
22	Zhang X Y, Ding Y B, Tang H Q, et al. Degradation of bisphenol A by hydrogen peroxide activated with CuFeO₂ microparticles as a heterogeneous Fenton-like catalyst: efficiency, stability and mechanism[J]. Chemical Engineering Journal, 2014, 236: 251-262.
23	Abdullah W N W, Bakar W A W A, Ali R, et al. Catalytic oxidative desulfurization technology of supported ceria based catalyst: physicochemical and mechanistic studies[J]. Journal of Cleaner Production, 2017, 162: 1455-1464.
24	Zhao B X, Shi B C, Zhang X L, et al. Catalytic wet hydrogen peroxide oxidation of H-acid in aqueous solution with TiO₂-CeO₂ and Fe/TiO₂-CeO₂ catalysts[J]. Desalination, 2011, 268(1/2/3): 55-59.
25	谢鹏, 聂天明, 邓黎丹, 等. 新型铜铈复合材料的制备及其脱硝性能的研究[J]. 华中师范大学学报(自然科学版), 2017, 51(3): 317-323.
	Xie P, Nie T M, Deng L D, et al. Preparation of novel Cu-Ce composited material and its performance of de NO_x[J]. Journal of Huazhong Normal University(Natural Sciences), 2017, 51(3): 317-323.
26	Hossain S T, Azeeva E, Zhang K, et al. A comparative study of CO oxidation over Cu-O-Ce solid solutions and CuO/CeO₂ nanorods catalysts[J]. Applied Surface Science, 2018, 455: 132-143.
27	Zedan A F, Polychronopoulou K, Asif A, et al. Cu-Ce-O catalyst revisited for exceptional activity at low temperature CO oxidation reaction[J]. Surface and Coatings Technology, 2018, 354: 313-323.
28	Liu Z, He C, Chen B, et al. CuO-CeO₂ mixed oxide catalyst for the catalytic decomposition of N₂O in the presence of oxygen[J]. Catalysis Today, 2017, 297: 78-83.
29	甘蓉丽, 罗光前, 许洋, 等. 低温等离子体协同铜铈催化剂脱除甲苯[J]. 化工进展, 2018, 37(9): 3416-3423.
	Gan R L, Luo G Q, Xu Y, et al. Removal of toluene by non-thermal plasma coupled with Cu-Ce catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(9): 3416-3423.
30	单文娟.铜-铈固溶体催化剂的制备、表征及甲醇氧化重整制氢的研究[D].大连: 中国科学院大连化学物理研究所, 2004.
	Shan W J. The preparation and characterization of Ce-Cu-O solid solution catalyst and the study on oxidative steam reforming of methanol[D]. Dalian: Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 2004.
31	Liu Z G, Zhou R X, Zheng X M. Comparative study of different methods of preparing CuO-CeO₂ catalysts for preferential oxidation of CO in excess hydrogen[J]. Journal of Molecular Catalysis A: Chemical, 2007, 267(1/2): 137-142.
32	王桂燕, 夏笠, 迂君. 有机硅功能化碳纳米球: 合成及可见光催化活性[J]. 无机化学学报, 2017, 33(2): 299-306.
	Wang G Y, Xia L, Yu J. Organosilane-functionalized carbon nanospheres: synthesis and visible light photocatalytic activity[J]. Chinese Journal of Inorganic Chemistry, 2017, 33(2): 299-306.
33	曹亚亚, 黄少斌, 尹佳芝. 不同煅烧温度制备的n-p型CeO₂/BiOBr光催化性能研究[J]. 分子催化, 2016, 30(2): 159-168.
	Cao Y Y, Huang S B, Yin J Z. Study on the photocatalytic activities of n-p type CeO₂/BiOBr composite prepared at different calcination temperatures[J]. Journal of Molecular Catalysis(China), 2016, 30(2): 159-168.

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