Effect of TiO2 crystal phase on oxidation efficiency of H2O2/O3

doi:10.11949/j.issn.0438-1157.20141858

Abstract

Abstract:

The oxidation efficiency of H₂O₂/O₃ catalyzed by titanium dioxide (TiO₂) for acetic acid (HAc) degradation, a probe compound for hydroxyl radical in ozonation, was investigated, with a focus on the effect of TiO₂ crystal phase. The results indicated that the addition of TiO₂ showed negative effect on the oxidation efficiency when the initial pH was at 7.0 and 10.0, and among all crystal phases of TiO₂ anatase had the biggest negative effect. However, when the initial pH was at 3.0, rutile could significantly improve the oxidation efficiency of the H₂O₂/O₃ system, and anatase had negligible effect. The mechanism study showed that there existed a good correlation between degradation rate of HAc and concentration of H₂O₂ (or its decomposition rate). Both anatase and rutile could accelerate decomposition of H₂O₂ at initial pH of 7.0 and 10.0, and faster was for the former than the latter. Too high decomposition rate of H₂O₂ could reduce removal rate of HAc at the two pH, because the conjugate base HO₂^- of H₂O₂ generated could react with ozone to effectively produce hydroxyl radicals (·OH). At initial pH 3.0, the oxidation efficiency of H₂O₂/O₃ system was very low due to the difficulty of H₂O₂ deprotonation, so the concentration of H₂O₂ had almost no change. Addition of TiO₂ could markedly accelerate the decomposition rate of H₂O₂, including deprotonation step, and anatase made H₂O₂ decomposition finish in 5 min and too fast, leading to have no effect on the oxidation efficiency. However, rutile had no such high decomposition rate for H₂O₂ and could generate HO₂^--similar species which could react with ozone to produce hydroxyl radicals (·OH) to degrade acetic acid. The batch test carried out also gave a similar result. Therefore, it can be concluded that suitable initiator and its concentration may play an important role in ozone-based advanced oxidation process, and that too high concentration of initiator might lead to rapid consumption of oxidants. The amounts of superoxide ion radical (·O₂^-) in H₂O₂/O₃, anatase TiO₂/H₂O₂/O₃ and rutile TiO₂/H₂O₂/O₃ systems were determined by capturing method of Nitro Blue Tetrazolium Chloride (NBT), the order was as follows: H₂O₂/O₃< rutile TiO₂/H₂O₂/O₃< anatase TiO₂/H₂O₂/O₃, which was in accord with the results of the results of HAc degradation.

Key words: ozone, hydrogen peroxide, oxidation, catalyst, titanium dioxide, crystal phase, radical

摘要：

研究了不同物相TiO₂对H₂O₂/O₃氧化效能的影响,目标有机物为羟基自由基探针化合物乙酸。结果表明,在初始pH为7.0和10.0时,加入TiO₂反而降低了H₂O₂/O₃的氧化效率,其中锐钛矿TiO₂比金红石TiO₂的减弱作用更为明显。当初始pH为3.0时,金红石TiO₂能显著提高H₂O₂/O₃的氧化效率,但锐钛矿TiO₂影响不明显。机理分析表明,H₂O₂浓度及其衰减速率与乙酸的去除效率有很大的相关性。在pH为7.0和10.0时,两种物相TiO₂均能加快H₂O₂的分解,其中锐钛矿TiO₂作用更为显著。此条件下HO₂^-能有效引发臭氧分解产生羟基自由基,故H₂O₂过快分解反而降低了乙酸的去除效果。在pH为3.0时,H₂O₂去质子化反应困难,故O₃/H₂O₂氧化效率极低,H₂O₂浓度也几乎不变。加入TiO₂能明显提高H₂O₂的分解速率,相比金红石TiO₂,锐钛矿TiO₂使H₂O₂在5 min内基本分解完毕,但其对H₂O₂/O₃氧化效率几乎没有影响。饱和臭氧水分解速度的批处理实验也有相似的结果。由此可见,合适引发剂浓度可能是保证臭氧类高级氧化技术较高效率的关键,否则只会导致氧化剂的无效过快分解。利用氯化硝基四氮唑蓝法对比分析了酸性条件下H₂O₂/O₃、锐钛矿TiO₂/H₂O₂/O₃和金红石TiO₂/H₂O₂/O₃体系产生超氧自由基(·O₂^-)的量,其大小顺序为:H₂O₂/O₃< 金红石TiO₂/H₂O₂/O₃< 锐钛矿TiO₂/H₂O₂/O₃,这与前面结果吻合很好。

关键词: 臭氧, 双氧水, 氧化, 催化剂, 二氧化钛, 物相, 自由基

CLC Number:

X703

NI Jinlei, PENG Ruofan, TONG Shaoping, MA Chun'an. Effect of TiO₂ crystal phase on oxidation efficiency of H₂O₂/O₃[J]. CIESC Journal, 2015, 66(10): 3950-3956.

倪金雷, 彭若帆, 童少平, 马淳安. 不同物相TiO₂对H₂O₂/O₃氧化效能的影响[J]. 化工学报, 2015, 66(10): 3950-3956.

References 30

[1]	Legube B, Leitner N K V. Catalytic ozonation: a promising advanced oxidation technology for water treatment [J]. Catalysis Today, 1999, 53(1): 61-72.
[2]	Kasprzyk-Hordern B, Ziólek M, Nawrocki J. Catalytic ozonation and methods of enhancing molecular ozone reactions in water treatment [J]. Applied Catalysis B: Environmental, 2003, 46(4): 639-669.
[3]	Zeng Z Q, Wang J F, Li Z H, Sun B C, Shao L, Li W J, Chen J F, Zou H K. The advanced oxidation process of phenol solution by O3/H2O2 in a rotating packed bed [J]. Ozone: Science & Engineering, 2013, 35(2): 101-108.
[4]	Nawrocki J. Catalytic ozonation in water: controversies and questions. discussion paper [J]. Applied Catalysis B: Environmental, 2013, 142-143: 465-471.
[5]	Pines D S, Reckhow D A. Effect of dissolved cobalt(Ⅱ) on the ozonation of oxalic acid [J]. Environmental Science and Technology, 2002, 36(19): 4046-4051.
[6]	Beltrán F J, Rivas F J, Montero-de-Espinosa R. Iron type catalysts for the ozonation of oxalic acid in water [J]. Water Research, 2005, 39(15): 3553-3564.
[7]	Li Wenwen(李文文), Liu Pengpeng(刘朋朋), Zhang Hua(张华), Shi Rui(石锐), Tong Shaoping(童少平), Ma Chun'an(马淳安). Degradation of acetic acid by Ti(Ⅳ)-catalyzed H2O2/O3 [J]. CIESC Journal (化工学报), 2010, 61(7): 1790-1795.
[8]	Tong S P, Zhao S Q, Lan X F, Ma C A. A kinetic model of Ti(Ⅳ)-catalyzed H2O2/O3 process in aqueous solution [J]. Journal of Environmental Sciences, 2011, 23(12): 2087-2092.
[9]	Xiao H, Liu R P, Zhao X, Qu J H. Enhanced degradation of 2,4-dinitrotoluene by ozonation in the presence of manganese(Ⅱ) and oxalic acid [J]. Journal of Molecular Catalysis A: Chemical, 2008, 286(1/2): 149-155.
[10]	Dorota B M, Jacek S, Stanislaw L. Kinetic studies of n-butylparaben degradation in H2O2/UV system [J]. Ozone: Science & Engineering, 2012, 34(5): 354-358.
[11]	Qi F, Xu B B, Chen Z L, Ma J, Sun D Z, Zhang L Q. Influence of aluminum oxides surface properties on catalyzed ozonation of 2,4,6-trichloroanisole [J]. Separation and Purification Technology, 2009, 66: 405-410.
[12]	Zhang T, Li C J, Ma J, Tian H, Qiang Z M. Surface hydroxyl groups of synthetic a-FeOOH in promoting ·OH generation from aqueous ozone: property and activity relationship [J]. Applied Catalysis B: Environmental, 2008, 82: 131-137.
[13]	Ikhlaq A, Brown D R, Kasprzyk-Hordern B. Mechanisms of catalytic ozonation: an investigation into superoxide ion radical and hydrogen peroxide formation during catalytic ozonation on alumina and zeolites in water [J]. Applied Catalysis B: Environmental, 2013, 129: 437-449.
[14]	Bauman M, Lobnik A, Hribernik A. Decolorization and modeling of synthetic wastewater using O3 and H2O2/O3 processes [J]. Ozone: Science & Engineering, 2011, 33(1): 23-30.
[15]	Kurniawan T A, Lo W H, Chan G Y S. Radicals-catalyzed oxidation reactions for degradation of recalcitrant compounds from landfill leachate [J]. Chemical Engineering Journal, 2006, 125(1): 35-57.
[16]	Inagaki M, Nonaka R, Tryba B, Morawski A W. Dependence of photocatalytic activity of anatase powders on their crystallinity [J]. Chemosphere, 2006, 64: 437-445.
[17]	Hirakawa T, Yawata K, Nosaka Y. Photocatalytic reactivity for O2-·and·OH radical formation in anatase and rutile TiO2 suspension as the effect of H2O2 addition [J]. Applied Catalysis A: General, 2007, 325: 105-111.
[18]	Daimon T, Hirakawa T, Kitazawa M, Suetake J, Nosaka Y. Formation of singlet molecular oxygen associated with the formation of superoxide radicals in aqueous suspensions of TiO2 photocatalysts [J]. Applied Catalysis A: General, 2008, 340: 169-175.
[19]	Song S, Liu Z W, He Z Q, Zhang A L, Chen J M, Yang Y P, Xu X H. Impacts of morphology and crystallite phases of titanium oxide on the catalytic ozonation of phenol [J]. Environmental Science and Technology, 2010, 44: 3913-3918.
[20]	Rosal R, Rodríguez A, Gonzalo M S, García-Calvo E. Catalytic ozonation of naproxen and carbamazepine on titanium dioxide [J]. Applied Catalysis B: Environmental, 2008, 84: 48-57.
[21]	Yang Y, Ma J, Qin Q, Zhai X. Degradation of nitrobenzene by nano-TiO2 catalyzed ozonation [J]. Journal of Molecular Catalysis A: Chemical, 2007, 267: 41-48.
[22]	Jerry C, Meryer P A, Marrone J W T. Acetic acid oxidation and hydrolysis supercritical water [J]. AIChE Journal, 1995, 41(9): 2108-2121.
[23]	Sellers R M. Spectrophotometric determination of hydrogen peroxide using potassium titanium (Ⅳ) oxalate [J]. The Analyst, 1980, 150(1255): 950-954.
[24]	Bader H, Hoigne J. Determination of ozone in water by the indigo method [J]. Water Research, 1981, 15(4): 449-456.
[25]	Merchant M, Hardy R, Williams S. Quantitative detection of superoxide ions in whole blood of the American alligator (alligator mississippiensis) [J]. Spectroscopy Letters, 2008, 41: 199-203.
[26]	Hulea V, Dumitriu E, Patcas F, Ropot R, Graffin Patrick, Moreau Patrice. Cyclopentene oxidation with H2O2 over Ti-containing zeolites [J]. Applied Catalysis A: General, 1998, 170: 169-175.
[27]	Casuscelli S G, Eimer G A, Canepa A, Heredia A C, Poncio C E, Crivello M E, Perez C F, Aguilar A, Herrero E R. Ti-MCM-41 as catalyst for a-pinene oxidation study of the effect of Ti content and H2O2 addition on activity and selectivity [J]. Catalysis Today, 2008, 133/134/135: 678-683.
[28]	Lanao M, Ormad M P, Ibarz C, Miguel N, Ovelleiro J L. Bactericidal effectiveness of O3, O3/H2O2 and O3/TiO2 on clostridium perfringens [J]. Ozone: Science & Engineering, 2008, 30(6): 431-438.
[29]	Moussavi G, Yazdanbakhsh A, Heidarizad M. The removal of formaldehyde from concentrated synthetic wastewater using O3/MgO/H2O2 process integrated with the biological treatment [J]. Journal of Hazardous Materials, 2009, 171(1/2/3): 907-913.
[30]	Staehelin J, Hoigne J. Decomposition of ozone in water in the presence of organic solutes acting as promoters and inhibitors of radical chain reactions [J]. Environmental Science and Technology, 1985, 19(12): 1206-1213.

Effect of TiO₂ crystal phase on oxidation efficiency of H₂O₂/O₃

不同物相TiO₂对H₂O₂/O₃氧化效能的影响

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References 30

Related Articles 15

Recommended Articles 0

Metrics

Comments

[1]	Yitong LI, Hang GUO, Hao CHEN, Fang YE. Study on operating conditions of proton exchange membrane fuel cells with non-uniform catalyst distributions [J]. CIESC Journal, 2023, 74(9): 3831-3840.
[2]	Baiyu YANG, Yue KOU, Juntao JIANG, Yali ZHAN, Qinghong WANG, Chunmao CHEN. Chemical conversion of dissolved organic matter in petrochemical spent caustic along a wet air oxidation pretreatment process [J]. CIESC Journal, 2023, 74(9): 3912-3920.
[3]	Jie CHEN, Yongsheng LIN, Kai XIAO, Chen YANG, Ting QIU. Study on catalytic synthesis of sec-butanol by tunable choline-based basic ionic liquids [J]. CIESC Journal, 2023, 74(9): 3716-3730.
[4]	Xuejin YANG, Jintao YANG, Ping NING, Fang WANG, Xiaoshuang SONG, Lijuan JIA, Jiayu FENG. Research progress in dry purification technology of highly toxic gas PH₃ [J]. CIESC Journal, 2023, 74(9): 3742-3755.
[5]	Xin YANG, Xiao PENG, Kairu XUE, Mengwei SU, Yan WU. Preparation of molecularly imprinted-TiO₂ and its properties of photoelectrocatalytic degradation of solubilized PHE [J]. CIESC Journal, 2023, 74(8): 3564-3571.
[6]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[7]	Jintong LI, Shun QIU, Wenshou SUN. Oxalic acid and UV enhanced arsenic leaching from coal in flue gas desulfurization by coal slurry [J]. CIESC Journal, 2023, 74(8): 3522-3532.
[8]	Feifei YANG, Shixi ZHAO, Wei ZHOU, Zhonghai NI. Sn doped In₂O₃ catalyst for selective hydrogenation of CO₂ to methanol [J]. CIESC Journal, 2023, 74(8): 3366-3374.
[9]	Kaixuan LI, Wei TAN, Manyu ZHANG, Zhihao XU, Xuyu WANG, Hongbing JI. Design of cobalt-nitrogen-carbon/activated carbon rich in zero valent cobalt active site and application of catalytic oxidation of formaldehyde [J]. CIESC Journal, 2023, 74(8): 3342-3352.
[10]	Xiaokun HE, Rui LIU, Yuan XUE, Ran ZUO. Review of gas phase and surface reactions in AlN MOCVD [J]. CIESC Journal, 2023, 74(7): 2800-2813.
[11]	Pan LI, Junyang MA, Zhihao CHEN, Li WANG, Yun GUO. Effect of the morphology of Ru/α-MnO₂ on NH₃-SCO performance [J]. CIESC Journal, 2023, 74(7): 2908-2918.
[12]	Yajie YU, Jingru LI, Shufeng ZHOU, Qingbiao LI, Guowu ZHAN. Construction of nanomaterial and integrated catalyst based on biological template: a review [J]. CIESC Journal, 2023, 74(7): 2735-2752.
[13]	Bin LI, Zhenghu XU, Shuang JIANG, Tianyong ZHANG. Clean and efficient synthesis of accelerator CBS by hydrogen peroxide catalytic oxidation method [J]. CIESC Journal, 2023, 74(7): 2919-2925.
[14]	Yuming TU, Gaoyan SHAO, Jianjie CHEN, Feng LIU, Shichao TIAN, Zhiyong ZHOU, Zhongqi REN. Advances in the design, synthesis and application of calcium-based catalysts [J]. CIESC Journal, 2023, 74(7): 2717-2734.
[15]	Qiyu ZHANG, Lijun GAO, Yuhang SU, Xiaobo MA, Yicheng WANG, Yating ZHANG, Chao HU. Recent advances in carbon-based catalysts for electrochemical reduction of carbon dioxide [J]. CIESC Journal, 2023, 74(7): 2753-2772.