钙钛矿型复合氧化物的合成及光催化降解酸性红B的性能研究
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摘要
钙钛矿型氧化物(ABO_3)不但具有结构稳定，催化活性高等特点，而且可以通过改变A、B原子的类型制备出禁带宽度较窄，能大量吸收太阳光的催化剂。本文以A，B的硝酸盐为原料，以氨水或碳酸钠为沉淀剂，利用混合沉淀的方法合成了系列钙钛矿型氧化物。A选碱土金属元素Mg、Ca、Sr、Ba等及稀土金属元素La；B选过渡金属元素Cr、Mn、Fe、Co、Ni等。活性测试结果表明，A的影响相对较小，B的影响比较显著，总的变化趋势是，随着B原子序数的增大，光催化活性提高。
在所有的上述催化剂中，CaNiO_3的催化活性最高，XRD，TEM测试结果显示所合成CaNiO_3为纯度较高，粒径150～200nm的近球形颗粒。对比测试了CaNiO_3与TiO_2的光催化活性，结果表明，紫外光照射下二者的活性相当；在模拟太阳光照射下前者的活性高于后者，对酸性红B降解率分别为63％和47％。合成了CaFexNi_(1-X)O_3(x=0.1～0.9)型的复合氧化物催化剂，其中CaFe_(0.3)Ni_(0.7)O_3在模拟太阳光照射下对酸性红B的降解率可达到91％。进一步研究了Co，Ag负载对CaFe_(0.3)Ni_(0.7)O_3光催化活性的影响，结果显示负载Co使活性大幅度下降，而负载Ag使活性上升至96％以上。
研究了紫外光照射下，以CaNiO_3为催化剂，光催化降解酸性红B的动力学行为。确定反应级数为1.4，指前因子为：1.01×10~7 mol~(-0.4)L~(0.4)min~-(-1)，活化能Ea为：35.5 kJ·mol~(-1)。
对经不同时间降解的酸性红B进行红外以及紫外-可见光谱分析，根据分析结果推测了酸性红B的降解机理。首先是偶氮双键的消失，其次是萘环的断裂以及苯的开环。
考察了工艺条件对光催化降解酸性红B的影响：在废水溶液中加入H_2O_2后光催化活性提高，并且随着加入量的增大有增长的趋势；提高溶液的酸性有利于染料废水的降解；酸性红B废水溶液的初始浓度越高，光催化越难降解。
Perovskite oxides (ABO3) has stable structure and high photocatalytic activity ,further more
a catalyst which has more narrow band gap can be synthesized and can absorb more solar energy by altering the type of A and B. A series of perovskite oxides are synthesized by means of blend deposition using the nitrate of A and B as the raw materials, and ammonia or sodium carbonate
as sedimentation .A includes alkaline-earth metals such as Mg, Ca, Sr, Ba and rare-earth metals
La; while B includes transition metal Cr, Mn, Fe, Co and Ni. The result of activity evaluation indicates that the effect of A is low while the effect of B is remarkable comparatively. The normal tendency of change is that the photocatalytic activity improvements with the increases of
atomic number.
The activity of CaNiO3 is the highest among the above photocatalysts. The test result of
XRD and TEM shows that the purity of CaNiO3 is comparatively high and the particle shape is
approximately round ball whose diameter is in the range of 150-200nm. The photocatalytic activity of CaNiO3 and TiO2 is compared, and the result shows that the activity of the two photocatalysts are equal under the irradiation of UV while under imitation of sunlight the farmer's activity is higher than the latter's, and that the rate of degradation of acid red B is 63%
and 47% respectively. The compound oxides of CaFexNi1-xO3 (x=0.1-0.9) have been synthesized.
Among them, the activity of CaFe0.3Ni0.7O3 is the highest and under the imitation of sunlight, the rare of degradation of acid red B can reach 91%. The effect of load of Co and Ag on the CaFe0.3Ni0.7O3 is studied, and indicates that the activity of CaFe0.3Ni0.7O3 supporting Co is much
lower, while the activity of CaFeo.3Ni0.7O3 supporting Ag is increased and that the rate of degradation of acid red B is 96%.
The kinetics of degradation of acid red B under UV is studied over CaNiO3 catalyst. The
reaction order is defined to be 1.4. Pre-exponential factor in ko= 1.01 × 107 mol-0.4L0.4min-1, and the activation energy is Ea=35.5 kJ.mol-1.
Acid red B degraded in different time is analyzed by IR and UV-VIS spectra analysis. According to result, the mechanism of acid red B degradation is inferred, i.e., double bond of nitrogen is disappeared, firstly and then, naphthalene ring is broken and benzene ring is cracked.
The effects of experimental condition on photocatalytic degradation of acid red B are studied. The photocatalysis is improved by adding H2O2 into the solution and the activity is raised with the increase of the amount of H2O2. Increasing the acidity of the solution is benefited to decompose acid red B. The higher the initial concentration of acid red B, the more difficult the photocatalysis.
在所有的上述催化剂中，CaNiO_3的催化活性最高，XRD，TEM测试结果显示所合成CaNiO_3为纯度较高，粒径150～200nm的近球形颗粒。对比测试了CaNiO_3与TiO_2的光催化活性，结果表明，紫外光照射下二者的活性相当；在模拟太阳光照射下前者的活性高于后者，对酸性红B降解率分别为63％和47％。合成了CaFexNi_(1-X)O_3(x=0.1～0.9)型的复合氧化物催化剂，其中CaFe_(0.3)Ni_(0.7)O_3在模拟太阳光照射下对酸性红B的降解率可达到91％。进一步研究了Co，Ag负载对CaFe_(0.3)Ni_(0.7)O_3光催化活性的影响，结果显示负载Co使活性大幅度下降，而负载Ag使活性上升至96％以上。
研究了紫外光照射下，以CaNiO_3为催化剂，光催化降解酸性红B的动力学行为。确定反应级数为1.4，指前因子为：1.01×10~7 mol~(-0.4)L~(0.4)min~-(-1)，活化能Ea为：35.5 kJ·mol~(-1)。
对经不同时间降解的酸性红B进行红外以及紫外-可见光谱分析，根据分析结果推测了酸性红B的降解机理。首先是偶氮双键的消失，其次是萘环的断裂以及苯的开环。
考察了工艺条件对光催化降解酸性红B的影响：在废水溶液中加入H_2O_2后光催化活性提高，并且随着加入量的增大有增长的趋势；提高溶液的酸性有利于染料废水的降解；酸性红B废水溶液的初始浓度越高，光催化越难降解。
Perovskite oxides (ABO3) has stable structure and high photocatalytic activity ,further more
a catalyst which has more narrow band gap can be synthesized and can absorb more solar energy by altering the type of A and B. A series of perovskite oxides are synthesized by means of blend deposition using the nitrate of A and B as the raw materials, and ammonia or sodium carbonate
as sedimentation .A includes alkaline-earth metals such as Mg, Ca, Sr, Ba and rare-earth metals
La; while B includes transition metal Cr, Mn, Fe, Co and Ni. The result of activity evaluation indicates that the effect of A is low while the effect of B is remarkable comparatively. The normal tendency of change is that the photocatalytic activity improvements with the increases of
atomic number.
The activity of CaNiO3 is the highest among the above photocatalysts. The test result of
XRD and TEM shows that the purity of CaNiO3 is comparatively high and the particle shape is
approximately round ball whose diameter is in the range of 150-200nm. The photocatalytic activity of CaNiO3 and TiO2 is compared, and the result shows that the activity of the two photocatalysts are equal under the irradiation of UV while under imitation of sunlight the farmer's activity is higher than the latter's, and that the rate of degradation of acid red B is 63%
and 47% respectively. The compound oxides of CaFexNi1-xO3 (x=0.1-0.9) have been synthesized.
Among them, the activity of CaFe0.3Ni0.7O3 is the highest and under the imitation of sunlight, the rare of degradation of acid red B can reach 91%. The effect of load of Co and Ag on the CaFe0.3Ni0.7O3 is studied, and indicates that the activity of CaFe0.3Ni0.7O3 supporting Co is much
lower, while the activity of CaFeo.3Ni0.7O3 supporting Ag is increased and that the rate of degradation of acid red B is 96%.
The kinetics of degradation of acid red B under UV is studied over CaNiO3 catalyst. The
reaction order is defined to be 1.4. Pre-exponential factor in ko= 1.01 × 107 mol-0.4L0.4min-1, and the activation energy is Ea=35.5 kJ.mol-1.
Acid red B degraded in different time is analyzed by IR and UV-VIS spectra analysis. According to result, the mechanism of acid red B degradation is inferred, i.e., double bond of nitrogen is disappeared, firstly and then, naphthalene ring is broken and benzene ring is cracked.
The effects of experimental condition on photocatalytic degradation of acid red B are studied. The photocatalysis is improved by adding H2O2 into the solution and the activity is raised with the increase of the amount of H2O2. Increasing the acidity of the solution is benefited to decompose acid red B. The higher the initial concentration of acid red B, the more difficult the photocatalysis.
引文
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[4] 李太友．有机污染物的半导体光催化氧化研究进展综述．江汉大学学报，1999，16(3)：12
[5] 邱健斌，刘云珍，姚建年．TiO_2薄膜的制备及其光催化性能．化学试剂，2002，24(2)：80
[6] 武荣国，司民真．二氧化钛光催化及其在废水有机污染物处理中的应用展望．楚雄师专学报，2001，16(3)：51
[7] 郑敏，宋心远．印染废水光催化氧化作用机理解析．染整技术，2002，24(1)：42
[8] 刘飞跃，李秉环，徐银菘．半导体光催化降解废水有机污染物概述．广州化学，2001，26(3)：24
[9] E Bredow, K Jug. Study of photocatalytic formation and Reaction of OHRadicals at Anatase particles. J Phys Chem, 1995,99: 285
[10] 田中启一．光催化剂在水处理方面的应用．环境科学，1996，27(10)：68
[11] R W Matthews. War Res, 1986, 20: 569.
[12] 陈士夫．不同制备条件对TiO_2／beads光催化活性的影响．环境科学，1996，17(4)：33
[13] 许宜铭，陈文星，朱志杰．光化学法降解水中氯代苯酚的研究进展．环境科学，1990，9(6)：13
[14] 谭香萍，蒋伟川．水溶液中α-萘乙酸的光降解研究．环境科学，1995，16(2)：15
[15] 岳林海，樊帮堂．半导体的表面修饰与其光电化学应用．环境污染与防治，1994，16(4)：2
[16] 魏凤玉．H_2O_2／TiO_2氧化法处理氨基丁酸工业废水的研究．环境科学与技术，1998，(2)：14
[17] 程沧沧．附着态TiO_2光降解可溶性染料的研究．环境科学与技术，1998(2)：11
[18] 祝万鹏．光催化氧化法处理染料中间体H酸水溶液．环境科学，1996，17(4)：7
[19] 樊邦堂．环境化学．杭州：浙江大学出版社，1991．147
[20] 杨秋华，傅希贤，王俊珍，等．La_(1-x)Sr_xFeO_3光催化降解水溶性染料．应用化学，2000，17(6)：585
[21] 赵恒勤，陈建军，秦庆伟，等．纳米TiO_2的光催化作用及其应用研究进展．有色金属(冶炼部分)，2002，06：35
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