磷酸修饰ZnO/ZnAl_2O_4纳米复合球状光催化剂及其活性
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摘要
采用一步水热法制备ZnO/ZnAl_2O_4复合光催化剂前驱体。用不同量的磷酸溶液通过浸渍蒸干法对样品进行修饰,并于不同温度下焙烧获得高活性ZnO/ZnAl_2O_4纳米复合光催化剂。采用XRD、SEM、TEM、BET和TG-DTA等技术对所得样品进行表征。在模拟太阳光下,以光催化降解甲基橙和还原CO_2评价样品的光催化活性,并考察磷酸修饰量、样品焙烧温度对光催化活性的影响。结果表明:磷酸修饰可提高样品的高温稳定性、晶化程度及比表面积。当磷酸修饰量为n(Zn):n(P)为100:2.0时,经500℃焙烧后所得样品的光催化活性最佳。当光催化剂用量为0.5 g/L时,在60 min内对25 mg/L甲基橙溶液的脱色率达到98%,较未修饰样品的提高15.3%。对最佳条件下所得样品进行CO_2光催化还原,当催化剂用量为1.0 g/L、反应6 h后,所得还原产物中甲醇的生成量为1.60mmol/g。
ZnO/ZnAl_2O_4 precursor was synthesized by one-pot hydrothermal method. Phosphoric acid(H_3PO_4) was loaded on the precursor by an impregnation and steam seasoning process to obtain ZnO/ZnAl_2O_4 composite photocatalyst with high photocatalytic activity after calcination. The as-prepared samples were characterized by XRD, SEM, TEM, BET and TG-DTA techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange(MO) and reduction of CO_2 under the simulated sunlight irradiation. The effects of the amount of H_3PO_4 modification and calcinations temperature on the photocatalytic activities of the samples were investigated. The results indicate that H_3PO_4 modification improves the high temperature stability, degree of crystallization and specific surface area of the samples. The maximum of 98% photocatalytic decoloration rate of MO is achieved within 60 min at 0.5 g/L concentration of sample obtained at the mole ratio of Zn to P 100:2 and the calcination temperature of 500 ℃, which increases by 15.3% compared to that of bare ZnO/ZnAl_2O_4. Meanwhile, the main reduction products, methanol, the maximum yield of 1.60 mmol/g within 6 h is obtained at 1.0 g/L concentration of the same sample.
ZnO/ZnAl_2O_4 precursor was synthesized by one-pot hydrothermal method. Phosphoric acid(H_3PO_4) was loaded on the precursor by an impregnation and steam seasoning process to obtain ZnO/ZnAl_2O_4 composite photocatalyst with high photocatalytic activity after calcination. The as-prepared samples were characterized by XRD, SEM, TEM, BET and TG-DTA techniques. The photocatalytic activities of the samples were evaluated by degradation of methyl orange(MO) and reduction of CO_2 under the simulated sunlight irradiation. The effects of the amount of H_3PO_4 modification and calcinations temperature on the photocatalytic activities of the samples were investigated. The results indicate that H_3PO_4 modification improves the high temperature stability, degree of crystallization and specific surface area of the samples. The maximum of 98% photocatalytic decoloration rate of MO is achieved within 60 min at 0.5 g/L concentration of sample obtained at the mole ratio of Zn to P 100:2 and the calcination temperature of 500 ℃, which increases by 15.3% compared to that of bare ZnO/ZnAl_2O_4. Meanwhile, the main reduction products, methanol, the maximum yield of 1.60 mmol/g within 6 h is obtained at 1.0 g/L concentration of the same sample.
引文
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[17]董伟霞,严常青,包启富,章丝丝,罗婷,李斌.Nb掺杂下Ca Ti2O4(OH)2片状结构的溶剂热制备及光催化性能研究[J].人工晶体学报,2016,45(3):762-766.DONG Wei-xia,YAN Chang-chun,BAO Qi-fu,ZHANG Si-si,LUO Ting,LI Bin.Solvothermal preparation and photocatalytic properties of Nb-doped Ca Ti2O4(OH)2[J].Journal of Synthetic Crystals,2016,45(3):762-766.
[18]ZHANG Li,YAN Jian-hui,ZHOU Min-jie,YANG Ya-hui,LIU You-nian.Fabrication and photocatalytic properties of sphere-in-spheres Zn O/Zn Al2O4 composite hollow microspheres[J].Appl Surf Sci,2013,268:237-245.
[19]孟庆强,孙婉婷,栾云博,井立强.磷酸修饰对纳米Fe2O3热稳定性及光催化性能的影响[J].高等学校化学学报,2014,35(8):1782-1787.MENG Qing-qiang,SUN Wan-ting,LUAN Yun-bo,JING Li-qiang.Effects of phosphate modification on the thermal stability and photocatalytic activity of nanosized Fe2O3[J].Chemical Journal of Chinese Universities,2014,35(8):1782-1787.
[20]CAI Jia-bai,WU Xue-qing,LI Shun-xing,ZHENG Feng-ying.Controllable location of Au nanoparticles as cocatalyst onto Ti O2@Ce O2 nanocomposite hollow spheres for enhancing photocatalytic activity[J].Applied Catalysis B,2017,201:12-21.
[21]SING K S W.Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity(Recommendations 1984)[J].Pure Appl Chem,1985,57(4):603-619.
[22]姜聚慧,光景,刘玉民,吕华,李爽,张鹏.三维分级花球结构Bi2WO6的制备及其光催化性能研究[J].人工晶体学报,2015,44(12):3571-3576.JIANG Ju-hui,GUANG Jing,LIU Yu-min,LüHua,LI Shuang,ZHANG Peng.Preparation and photocatalytic properties of three-dimensional hierarchical Bi2WO6 with flower-like structures[J].Journal of Synthetic Crystals,2015,44(12):3571-3576.
[23]PENG Yin,CHEN Qing-guo,WANG Dan,ZHOU Hai-yan,XU An-wu.Synthesis of one-dimensional WO3-Bi2WO6heterojunctions with enhanced photocatalytic activity[J].Crystengcomm,2014,17(3):569-576.
[24]SHEN Shao-hua,CHEN Xiao-bo,REN Feng,KRONAWITTER C X,MAO S S,GUO Lie-jin.Solar light-driven photocatalytic hydrogen evolution over Zn In2S4 loaded with transition-metal sulfides[J].Nanoscale Research Letters,2011,6:290-296.
[2]DOM R,CHARY A,SUBASRI R,HEBALLAR N,BORSE P H.Int.Solar hydrogen generation ion from spinel Zn Fe2O4photocatalyst:Effect of synthesis methods[J].J Energy Res,2015,39(10):1378-1390.
[3]LEE K,RUDDY D A,DUKOVIC G,NEALEET N R.Synthesis,optical,and photocatalytic properties of cobalt mixed-metal spinel oxides Co(Al1-x Gax)2O4[J].Mater Chem A,2015,15(3):8115-8122.
[4]TONG Jin-hui,ZHANG Qian-ping,BO Li-li,SU Ling-di,WANG Qi-zhao.Effectively photocatalytic aerobic oxidation of benzyl alcohol catalyzed by spinel Co-Ni ferrite under visible light irradiation[J].J Sol-Gel Sci Technol,2015,76(1):19-26.
[5]ZAHARIEVA K,RIVES V,TSVETKOV M,CHERKEZOVAZHELEVA Z,KUNEV B,TRUJILLANO R.Preparation,characterization and application of nanosized copper ferrite photocatalysts for dye degradation under UV irradiation[J].Materials Chemistry and Physics,2015,160:27-278.
[6]LI Yun-fei,SHEN Jian-hua,HU Yan-jie,QIU Sheng-jie,MIN Guo-quan,SONG Zhi-tong,SUN Zhuo,LI Chun-zhong.General flame approach to chainlike MFe2O4 spinel(M=Cu,Ni,Co,Zn)nanoaggregates for reduction of nitroaromatic compounds[J].Ind Eng Chem Res,2015,54(40):9750-9757.
[7]SONG Gui-xian,XIN Feng,YIN Xiao-hong.Photocatalytic reduction of carbon dioxide over Zn Fe2O4/Ti O2 nanobelts heterostructure in cyclohexanol[J].Journal of Colloid and Interface Science,2015,442:60-66.
[8]DOM R,CHARY A S,SUBASRI R,HEBALKAR N K,BORSE P H.Solar hydrogen generation from spinel Zn Fe2O4 photocatalyst:Effect of synthesis methods[J].Int J Energy Res,2015,39(10):1378-1390.
[9]梁建,张彩霞,何霞,董海亮,申燕强,许并设.Zn O/Ni O纳米异质结的合成及其光催化性能的研究[J].人工晶体学报,2014,43(12):3129-3134.LIANG Jian,ZHANG Cai-xia,HE Xia,DONG Hai-liang,SHEN Yan-qiang,XU bing-she.Synthesis and photocatalytic properties of Zn O/In2O3 heteronanostructures[J].Journal of Synthetic Crystals,2014,43(12):3129-3134.
[10]ZULFIQAR AHMED M N,CHANDRASEKHAR B K,JAHGIRDAR A A,NAGABHUSHANA H,NAGABHUSHANA B M.Photocatalytic activity of nanocrystalline Zn O,α-Fe2O3 and Zn Fe2O4/Zn O[J].Appl Nanosci,2015,5(8):961-968.
[11]BU Yu-yu,CHEN Zhuo-yuan.Role of polyaniline on the photocatalytic degradation and stability performance of the polyaniline/silver/silver phosphate composite under visible light[J].ACS Appl Mater Interfaces,2014,6(20):17589-17598.
[12]HUANG Hong-wei,CHEN Gong,ZHANG Yi-he.Two Bi-based phosphate photocatalysts:Crystal structure,optical property and photocatalytic activity[J].Inorganic Chemistry Communications,2014,44:46-49.
[13]WANG Gang,HUANG Bai-biao,MA Xiang-chao,WANG Ze-yan,QIN Xiao-yan,ZHANG Xiao-yang,DAI Ying,WHANGHO M H.Cu2(OH)PO4,a near-infrared-activated photocatalyst[J].Angew Chem Int Ed,2013,52(18):4810-4813.
[14]秦旭,井立强,薛连鹏,栾云博,付宏刚.磷酸对Ti O2纳米粒子光催化剂的改性[J].无机化学学报,2008,24(7):1108-1112.QIN Xu,JING Li-qiang,XUE Lian-peng,LUAN Yun-bo,FU Hong-ganget.Phosphorous acid modified Ti O2 nanoparticle photocatalysts[J].Journal of Inorganic Chemistry,2008,24(7):1108-1112.
[15]杨丽丽,都玲,于杨,张文杰.磷酸处理HZSM-5负载Ti O2光催化降解活性艳红X-3B[J].材料工程,2014,42(9):94-99.YANG Li-li,DU Ling,YU Yang,ZHANG Wen-jie.Photocatalytic degradation of reactive brilliant red X-3B on Ti O2supported on HZSM-5[J].Journal of Materials Engineering,2014,42(9):94-99.
[16]SUN Yan-qing,ZHOU Yu-ming,WANG Zhi-qiang,YE Xiao-yun.Structural and morphological transformations of Zn-Al layered double hydroxides through hydrothermal treatment[J].Applied Surface Science,2009,255:6372-6377.
[17]董伟霞,严常青,包启富,章丝丝,罗婷,李斌.Nb掺杂下Ca Ti2O4(OH)2片状结构的溶剂热制备及光催化性能研究[J].人工晶体学报,2016,45(3):762-766.DONG Wei-xia,YAN Chang-chun,BAO Qi-fu,ZHANG Si-si,LUO Ting,LI Bin.Solvothermal preparation and photocatalytic properties of Nb-doped Ca Ti2O4(OH)2[J].Journal of Synthetic Crystals,2016,45(3):762-766.
[18]ZHANG Li,YAN Jian-hui,ZHOU Min-jie,YANG Ya-hui,LIU You-nian.Fabrication and photocatalytic properties of sphere-in-spheres Zn O/Zn Al2O4 composite hollow microspheres[J].Appl Surf Sci,2013,268:237-245.
[19]孟庆强,孙婉婷,栾云博,井立强.磷酸修饰对纳米Fe2O3热稳定性及光催化性能的影响[J].高等学校化学学报,2014,35(8):1782-1787.MENG Qing-qiang,SUN Wan-ting,LUAN Yun-bo,JING Li-qiang.Effects of phosphate modification on the thermal stability and photocatalytic activity of nanosized Fe2O3[J].Chemical Journal of Chinese Universities,2014,35(8):1782-1787.
[20]CAI Jia-bai,WU Xue-qing,LI Shun-xing,ZHENG Feng-ying.Controllable location of Au nanoparticles as cocatalyst onto Ti O2@Ce O2 nanocomposite hollow spheres for enhancing photocatalytic activity[J].Applied Catalysis B,2017,201:12-21.
[21]SING K S W.Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity(Recommendations 1984)[J].Pure Appl Chem,1985,57(4):603-619.
[22]姜聚慧,光景,刘玉民,吕华,李爽,张鹏.三维分级花球结构Bi2WO6的制备及其光催化性能研究[J].人工晶体学报,2015,44(12):3571-3576.JIANG Ju-hui,GUANG Jing,LIU Yu-min,LüHua,LI Shuang,ZHANG Peng.Preparation and photocatalytic properties of three-dimensional hierarchical Bi2WO6 with flower-like structures[J].Journal of Synthetic Crystals,2015,44(12):3571-3576.
[23]PENG Yin,CHEN Qing-guo,WANG Dan,ZHOU Hai-yan,XU An-wu.Synthesis of one-dimensional WO3-Bi2WO6heterojunctions with enhanced photocatalytic activity[J].Crystengcomm,2014,17(3):569-576.
[24]SHEN Shao-hua,CHEN Xiao-bo,REN Feng,KRONAWITTER C X,MAO S S,GUO Lie-jin.Solar light-driven photocatalytic hydrogen evolution over Zn In2S4 loaded with transition-metal sulfides[J].Nanoscale Research Letters,2011,6:290-296.