CaF_2(Tm~(3+))/TiO_2光催化剂的制备及其对海水养殖废水中氨氮的降解研究
|
摘要
采用溶胶凝胶法制备了CaF_2(Tm~(3+))/TiO_2光催化剂,并用扫描电子显微镜(SEM),X射线衍射(XRD)等手段对其晶型、粒径以及形貌进行了表征。对比分析了可见光下纯TiO_2和CaF_2(Tm~(3+))/TiO_2光催化剂对模拟海水养殖废水中氨氮的降解情况。结果表明,CaF_2(Tm~(3+))/TiO_2光催化剂粒径基本在15～25nm,晶型为锐钛矿型;CaF_2(Tm~(3+))的掺杂提升了TiO_2对可见光的利用率,使光催化效率大幅提升;CaF_2(Tm~(3+))/TiO_2光催化剂对海水养殖废水中氨氮的适宜光催化降解条件为CaF_2(Tm~(3+))掺杂比10%(摩尔分数)、CaF_2(Tm~(3+))/TiO_2光催化剂投加量0.6g/L、氨氮初始质量浓度100mg/L、H2O2质量浓度0.3g/L、pH=10.0、反应时间2.0h,在此条件下,氨氮去除率可达近90%;光催化降解氨氮的最终降解产物为N_2,处理比较彻底。
The CaF_2(Tm~(3+))/TiO_2 photocatalyst was prepared by sol-gel method.The crystal form,morphology and particle size of CaF_2(Tm~(3+))/TiO_2 photocatalyst were characterized by scanning electron microscope(SEM)and X-ray diffraction(XRD).The photocatalytic degradation of ammonia nitrogen by pure TiO_2 and CaF_2(Tm~(3+))/TiO_2 photocatalyst was compared in visible light.The results showed that the particle size of CaF_2(Tm~(3+))/TiO_2 photocatalyst was ranged 15-25 nm,and its crystal form was anatase type.The doping of CaF_2(Tm~(3+))could enhance the utilization of visible light by TiO_2,which greatly improved the photocatalytic efficiency.The suitable reaction conditions for photocatalytic degradation were as follows:the CaF_2(Tm~(3+))doping ratio was 10%(molar ratio),the dosage of CaF_2(Tm~(3+))/TiO_2 photocatalyst was 0.6 g/L,the initial mass concentration of ammonia nitrogen was 100 mg/L,the mass concentration of H_2O_2 was 0.3 g/L,pH was 10.0,reaction time was 2.0 h.Under this condition,the ammonia nitrogen removal rate could reach nearly 90%.The final photocatalytic degradation product of ammonia nitrogen was N_2,which indicated that the degtadation of ammonia nitrogen was complete.
The CaF_2(Tm~(3+))/TiO_2 photocatalyst was prepared by sol-gel method.The crystal form,morphology and particle size of CaF_2(Tm~(3+))/TiO_2 photocatalyst were characterized by scanning electron microscope(SEM)and X-ray diffraction(XRD).The photocatalytic degradation of ammonia nitrogen by pure TiO_2 and CaF_2(Tm~(3+))/TiO_2 photocatalyst was compared in visible light.The results showed that the particle size of CaF_2(Tm~(3+))/TiO_2 photocatalyst was ranged 15-25 nm,and its crystal form was anatase type.The doping of CaF_2(Tm~(3+))could enhance the utilization of visible light by TiO_2,which greatly improved the photocatalytic efficiency.The suitable reaction conditions for photocatalytic degradation were as follows:the CaF_2(Tm~(3+))doping ratio was 10%(molar ratio),the dosage of CaF_2(Tm~(3+))/TiO_2 photocatalyst was 0.6 g/L,the initial mass concentration of ammonia nitrogen was 100 mg/L,the mass concentration of H_2O_2 was 0.3 g/L,pH was 10.0,reaction time was 2.0 h.Under this condition,the ammonia nitrogen removal rate could reach nearly 90%.The final photocatalytic degradation product of ammonia nitrogen was N_2,which indicated that the degtadation of ammonia nitrogen was complete.
引文
[1]黄晓婷,张再利,刘伟,等.生物活性炭处理循环海水养殖废水及其影响因子研究[J].环境科学学报,2011,31(11):2380-2386.
[2]崔毅,陈碧鹃,陈聚法.黄渤海海水养殖自身污染的评估[J].应用生态学报,2005,16(1):180-185.
[3]胡海燕.海水养殖废水氨氮处理研究[D].青岛:中国海洋大学,2007.
[4] ABEYSINGHE D H,SHANABLEH A,RIGE N.Biofilters for water reuse in aquaculture water[J].Science and Technology,1996,34(11):253-260.
[5]杨冰洋.二氧化钛及其复合物的光催化性能研究[D].北京:北京交通大学,2016.
[6]李博超,王海波,卓宁泽.稀土上转换发光材料的概述[J].中国照明电器,2015(6):10-14.
[7]王佳忆,王学江,黄嘉瑜,等.Br-N共掺杂TiO2/磁性炭复合材料的制备及其可见光催化性能[J].复合材料学报,2017,34(4):662-670.
[8] XU D X,LIAN Z W,FU M L,et al.Advanced near-infrareddriven photocatalyst:fabrication,characterization,and photocatalytic performance ofβ-NaYF4∶Yb3+,Tm3+@TiO2core@shell microcrystals[J].Applied Catalysis B:Environmental,2013,142/143:377-386.
[9] HAO J B,LU Z D,YIN Y D,et al.Upconversion luminescence with tunable lifetime in NaYF4∶Yb,Er nanocrystals:role of nanocrystal size[J].Nanoscale,2013,5(3):944-952.
[10] WANG F,LIU X.Upconverrsion multicolor fine-tuning:visible to near-infrared emission from lanthanide-doped NaYF4nanoparticles[J].Journal of America Chemistry Society,2008,130(17):5642-5643.
[11]田婧,罗华锋.稀土上转换纳米发光材料研究进展[J].化学教育,2014,35(20):1-4.
[12] REN L,QI X,LIU Y D,et al.Upconversion-P25-graphene composite as an advanced sunlight drivenphotocatalytic hybrid material[J].Journal of Materials Chemistry,2012,22(23):11765-11771.
[13]郑保战.TiO2光电催化性能及其应用研究[D].成都:四川大学,2007.
[14]蒋岳文.靛酚蓝分光光度法测定海水中的氨氮[J].海洋环境科学,1990,9(1):75-80.
[15]季秋忆,于晓彩,张健,等.可见光下利用ZrO2(Er3+)/TiO2光催化降解海水中柴油污染[J].材料导报,2017,31(增刊1):368-373.
[16] NAGAVENI K,SIVALINGAM G,HEGDE M S,et al.Solar potocatalytic degradation of dyes:high activity of combustion synthesiszed nano TiO2[J].Applide Catalysis B:Environmental,2004,48:83-93.
[17] WEI T Y,WAN C C.Heterogeneous photocatalytic oxidation of phenol withtitanium dioxide powders[J].Industrial and Engineering Chemistry Research,1991,30(6):1293-1300.
[18]刘云庆,于晓彩,吴云英,等.紫外可见上转换剂/TiO2复合光催化剂在海洋石油污染处理中的应用[J].大连海洋大学学报,2014,29(4):420-424.
[19]刘佳,龙天渝,陈前林,等.Cu/La共掺杂TiO2光催化氧化水中的氨氮[J].环境工程学报,2013,7(2):457-462.
[20]于晓彩,尚晓琳,季秋忆,等.纳米Ce/SnO2在海水养殖废水处理中光催化性能研究[J].海洋环境科学,2016,35(4):501-506.
[21]张翠粉,戴建军.氨氮废水物化法处理技术探讨[J].污染防治技术,2006,19(3):19-21.
[2]崔毅,陈碧鹃,陈聚法.黄渤海海水养殖自身污染的评估[J].应用生态学报,2005,16(1):180-185.
[3]胡海燕.海水养殖废水氨氮处理研究[D].青岛:中国海洋大学,2007.
[4] ABEYSINGHE D H,SHANABLEH A,RIGE N.Biofilters for water reuse in aquaculture water[J].Science and Technology,1996,34(11):253-260.
[5]杨冰洋.二氧化钛及其复合物的光催化性能研究[D].北京:北京交通大学,2016.
[6]李博超,王海波,卓宁泽.稀土上转换发光材料的概述[J].中国照明电器,2015(6):10-14.
[7]王佳忆,王学江,黄嘉瑜,等.Br-N共掺杂TiO2/磁性炭复合材料的制备及其可见光催化性能[J].复合材料学报,2017,34(4):662-670.
[8] XU D X,LIAN Z W,FU M L,et al.Advanced near-infrareddriven photocatalyst:fabrication,characterization,and photocatalytic performance ofβ-NaYF4∶Yb3+,Tm3+@TiO2core@shell microcrystals[J].Applied Catalysis B:Environmental,2013,142/143:377-386.
[9] HAO J B,LU Z D,YIN Y D,et al.Upconversion luminescence with tunable lifetime in NaYF4∶Yb,Er nanocrystals:role of nanocrystal size[J].Nanoscale,2013,5(3):944-952.
[10] WANG F,LIU X.Upconverrsion multicolor fine-tuning:visible to near-infrared emission from lanthanide-doped NaYF4nanoparticles[J].Journal of America Chemistry Society,2008,130(17):5642-5643.
[11]田婧,罗华锋.稀土上转换纳米发光材料研究进展[J].化学教育,2014,35(20):1-4.
[12] REN L,QI X,LIU Y D,et al.Upconversion-P25-graphene composite as an advanced sunlight drivenphotocatalytic hybrid material[J].Journal of Materials Chemistry,2012,22(23):11765-11771.
[13]郑保战.TiO2光电催化性能及其应用研究[D].成都:四川大学,2007.
[14]蒋岳文.靛酚蓝分光光度法测定海水中的氨氮[J].海洋环境科学,1990,9(1):75-80.
[15]季秋忆,于晓彩,张健,等.可见光下利用ZrO2(Er3+)/TiO2光催化降解海水中柴油污染[J].材料导报,2017,31(增刊1):368-373.
[16] NAGAVENI K,SIVALINGAM G,HEGDE M S,et al.Solar potocatalytic degradation of dyes:high activity of combustion synthesiszed nano TiO2[J].Applide Catalysis B:Environmental,2004,48:83-93.
[17] WEI T Y,WAN C C.Heterogeneous photocatalytic oxidation of phenol withtitanium dioxide powders[J].Industrial and Engineering Chemistry Research,1991,30(6):1293-1300.
[18]刘云庆,于晓彩,吴云英,等.紫外可见上转换剂/TiO2复合光催化剂在海洋石油污染处理中的应用[J].大连海洋大学学报,2014,29(4):420-424.
[19]刘佳,龙天渝,陈前林,等.Cu/La共掺杂TiO2光催化氧化水中的氨氮[J].环境工程学报,2013,7(2):457-462.
[20]于晓彩,尚晓琳,季秋忆,等.纳米Ce/SnO2在海水养殖废水处理中光催化性能研究[J].海洋环境科学,2016,35(4):501-506.
[21]张翠粉,戴建军.氨氮废水物化法处理技术探讨[J].污染防治技术,2006,19(3):19-21.