Preparation of carbon supported cerium doped zinc oxide composite material and its photocatalytic properties study in degradation of methylene blue dye
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摘要: 以竹粉为碳源、ZnCl2为锌源、六水合硝酸铈(Ⅲ)(Ce(NO3)3·6H2O)为铈源,采用一锅法制备得到新型竹炭负载Ce掺杂ZnO复合材料(Ce-ZnO/BC)。利用XRD、FTIR、SEM、EDS、BET、XPS、紫外-可见光漫反射光谱(DRS)及光致荧光光谱(PL)对所制备复合材料进行全面表征,并对其光催化降解有机染料性能进行了研究。获得了催化材料的最佳制备条件:ZnCl2与竹粉浸渍比为3∶10,煅烧温度为500℃,Ce(NO3)3·6H2O加入量为ZnCl2的2.5%。所得材料分别以日光和紫外光为光源,在暗处吸附20 min,光照120 min、亚甲基蓝(MB)溶液50 mL(10 mg·L−1),催化剂用量为40 mg 条件下,对MB降解率分别为92.2%和93.7%。并且研究结果表明,其催化MB降解符合一级反应动力学原理,催化剂具有一定的重复使用性能。Abstract: Carbon supported cerium doped zinc oxide composite material was prepared using bamboo as carbon source, ZnCl2 as zinc source, Ce(NO3)3·6H2O as cerium source, in one-pot method. These materials were fully characterized by XRD, FTIR, SEM, EDS, BET, XPS, UV-Vis diffuse reflection spectrum (DRS) and photoluminescence spectroscopy (PL). Their properties in photocatalytic degradation of organic dyes were studied at the same time. The optimized preparing condition of the material was obtained as follows: impregnation ratio of ZnCl2 to bamboo is 3∶10 by mass, calcination temperature is 500℃ and the addition amount of ZnCl2 is 2.5% of bamboo. The degradation rates of methylene blue (MB) under sunlight and ultraviolet are 92.2% and 93.7%, respectively, under the following condition: dark adsorption time 20 min, illumination time 120 min, 50 mL MB (10 mg·L−1) and catalyst amount 40 mg. Moreover, kinetic studies of the reaction proved that the photocatalytic degradation of MB catalyzed by this material follows the first order reaction kinetics principle. And the catalyst can be reused several times.
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Key words:
- bamboo charcoal /
- ZnO /
- composite /
- degradation /
- catalyst support
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表 1 ZnO/BC和Ce-ZnO/BC材料制备及命名
Table 1. Preparation and nomenclature of ZnO/BC and Ce-ZnO/BC
Photocatalyst Temperature/℃ (mZnCl2/mBamboo)/% (mCe(NO3)3•6H2O/mZnCl2)/% 300 ℃-ZnO/BC-0.3 300 0.3 — 400 ℃-ZnO/BC-0.3 400 0.3 — 500 ℃-ZnO/BC-0.3 500 0.3 — 600 ℃-ZnO/BC-0.3 600 0.3 — 700 ℃-ZnO/BC-0.3 700 0.3 — 500 ℃-ZnO/BC-0.2 500 0.2 — 500 ℃-ZnO/BC-0.4 500 0.4 — 1.25%Ce-ZnO/BC 500 — 1.25 2.5%Ce-ZnO/BC 500 — 2.5 5%Ce-ZnO/BC 500 — 5 7.5%Ce-ZnO/BC 500 — 7.5 10%Ce-ZnO/BC 500 — 10 表 2 系列材料的EDS分析结果
Table 2. EDS characterization results of different materials
Entry Photocatalyst Atom fraction/at% C Zn Ce 1 300℃-ZnO/BC-0.3 75.84 0.38 — 2 400℃-ZnO/BC-0.3 84.78 2.97 — 3 500℃-ZnO/BC-0.3 87.31 5.73 — 4 600℃-ZnO/BC-0.3 87.64 1.51 — 5 700℃-ZnO/BC-0.3 90.16 1.41 — 6 500℃-ZnO/BC-0.2 92.10 2.06 — 7 500℃-ZnO/BC-0.4 79.21 15.09 — 8 1.25%Ce-ZnO/BC 89.69 4.37 0.03 9 2.5%Ce-ZnO/BC 84.42 5.46 0.16 10 5%Ce-ZnO/BC 83.11 5.24 0.29 11 7.5%Ce-ZnO/BC 83.17 6.29 0.49 12 10%Ce-ZnO/BC 82.79 6.11 0.61 表 3 Ce-ZnO/BC和ZnO/BC光催化剂在日光下的一级反应动力常数ka和R2
Table 3. First order reaction rate constant (ka) and R2 of photocatalysts under sunlight irradiation of Ce-ZnO/BC and ZnO/BC
Entry Photocatalyst Linear regression equation ka/min−1 R2 1 500℃-ZnO/BC-0.3 Y=0.0128X+0.0241 0.0128 0.981 2 1.25%Ce-ZnO/BC Y=0.0186X−0.075 0.0186 0.974 3 2.5%Ce-ZnO/BC Y=0.0205X+0.0929 0.0205 0.999 4 5%Ce-ZnO/BC Y=0.0164X+0.0593 0.0164 0.998 5 7.5%Ce-ZnO/BC Y=0.0141X+0.072 0.0141 0.987 6 10%Ce-ZnO/BC Y=0.0123X+0.0652 0.0123 0.996 表 4 Ce-ZnO/BC和ZnO/BC光催化剂在紫外光下的ka和R2
Table 4. ka and R2 of photocatalysts under UV irradiation of Ce-ZnO/BC and ZnO/BC
Entry Photocatalyst Linear regression equation ka/min−1 R2 1 500℃-ZnO/BC-0.3 Y=0.0079X+0.1978 0.0079 0.934 2 1.25%Ce-ZnO/BC Y=0.0106X+0.1235 0.0106 0.974 3 2.5%Ce-ZnO/BC Y=0.0231X−0.2397 0.0231 0.923 4 5%Ce-ZnO/BC Y=0.0119X+0.0652 0.0119 0.933 5 7.5%Ce-ZnO/BC Y=0.0083X+0.1693 0.0083 0.967 6 10%Ce-ZnO/BC Y=0.0084X+0.1683 0.0084 0.966 -
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