微波诱导水解法制备纳米TiO_2及光催化降解盐酸四环素
|
摘要
采用微波诱导水解法快速制备了纳米TiO_2光催化剂,通过XRD、TEM、SEM、BET和EDS技术对其进行了表征。该方法可在10 min内制备出平均粒径约7.5 nm的锐钛矿相纳米TiO_2。采用该催化剂(加入量0.5 g/L)对盐酸四环素(TC,100 mg/L)进行紫外光催化降解,40 min时降解率高达92.9%,60 min时TOC去除率为81.7%,明显优于市售P25纳米TiO_2。这主要归功于所制备纳米TiO_2表面残留的有机物提高了光生电子-空穴对的分离能力,以及纳米粒子的小尺寸效应和较大的比表面积。溶液p H为9时TC的降解率更高。该催化剂具有较好的光催化稳定性。活性基团捕获实验表明,纳米TiO_2光催化降解TC过程中空穴起主要作用。
The nano TiO_2 photocatalyst was rapidly prepared by microwave-induced hydrolysis,and characterized by XRD,TEM,SEM,BET and EDS. The anatase phase TiO_2 with an average grain size of about 7.5 nm was prepared by the method in 10 min. The tetracycline hydrochloride(TC)was degraded by the photocatalyst under UV light. Under the conditions of TC mass concentration 100 mg/L,and catalyst amount 0.5 g/L,the degradation rate of TC reached 92.9% after 40 min irradiation and the removal rate of TOC reached 81.7% after 60 min irradiation,which was much better than those by commercial P25 nano TiO_2. It was due to the increased separation ability of photogenerated electronhole pairs because of organic residue on the surface of as-prepared nano TiO_2,and the small-size effect and large specific surface area of the nano particles. The degradation rate of TC was higher at the initial solution p H of 9. The catalyst had good photocatalytic stability. The results of active-group-capture experiments showed that the holes in nano TiO_2 played a leading role in the process of photocatalytic degradation of TC.
The nano TiO_2 photocatalyst was rapidly prepared by microwave-induced hydrolysis,and characterized by XRD,TEM,SEM,BET and EDS. The anatase phase TiO_2 with an average grain size of about 7.5 nm was prepared by the method in 10 min. The tetracycline hydrochloride(TC)was degraded by the photocatalyst under UV light. Under the conditions of TC mass concentration 100 mg/L,and catalyst amount 0.5 g/L,the degradation rate of TC reached 92.9% after 40 min irradiation and the removal rate of TOC reached 81.7% after 60 min irradiation,which was much better than those by commercial P25 nano TiO_2. It was due to the increased separation ability of photogenerated electronhole pairs because of organic residue on the surface of as-prepared nano TiO_2,and the small-size effect and large specific surface area of the nano particles. The degradation rate of TC was higher at the initial solution p H of 9. The catalyst had good photocatalytic stability. The results of active-group-capture experiments showed that the holes in nano TiO_2 played a leading role in the process of photocatalytic degradation of TC.
引文
[1]汪琼,张政,陈宗华,等.Bi2Ti2O7/Ti O2异质结对盐酸四环素的光催化降解效果评价[J].南京师大学报(自然科学版),2017,40(2):149-155,160.
[2]俞幼萍,高品,刘保江,等.新型光-类芬顿催化剂纳米Fe VO4的制备及其对盐酸四环素的降解性能[J].环境工程学报,2017,11(1):401-407.
[3]胡秀虹,汤承浩,吴林冬,等.Zr掺杂Ti O2介孔材料光催化降解头孢氨苄[J].化工环保,2017,37(4):460-465.
[4]PALOMINOS R A,MONDACA M A,GIRALDO A,et al.Photocatalytic oxidation of the antibiotic tetracycline on Ti O2 and Zn O suspensions[J].Catal Today,2009,144(1/2):100-105.
[5]王红涛,吴玄,赵慧敏,等.分子印迹膜修饰Ti O2纳米管及其光催化降解盐酸四环素[J].科学通报,2011,56(35):2965-2969.
[6]WANG Y,ZHANG H,CHEN L.Ultrasound enhanced catalytic ozonation of tetracycline in a rectangular air-lift reactor[J].Catal Today,2011,175(1):283-292.
[7]康勤书,汪圣尧,沈敏,等.(010)晶面暴露的Bi2Mo O6纳米片对土霉素和四环素的可见光催化降解[J].华中农业大学学报,2014,33(5):67-72.
[8]胡洪营,王超,郭美婷.药品和个人护理用品(PPCPs)对环境的污染现状与研究进展[J].生态环境.2005,14(6):947-952.
[9]孙蕾,马国华.Ti O2/Ni3[Si2O5][OH]2复合光催化材料对盐酸四环素的光降解研究[J].功能材料,2017,48(3):3133-3138.
[10]JEONG J,SONG W H,COOPER W J,et al.Degradation of tetracycline antibiotics:mechanisms and kinetic studies for advanced oxidation/reduction processes[J].Chemosphere,2010,78(5):533-540.
[11]WANG D S,XIAO L B,LUO Q Z,et al.Highly efficient visible light Ti O2 photocatalyst prepared by solgel method at temperatures lower than 300℃[J].J Hazard Mater,2011,192(1):150-159.
[12]ZHU X D,WANG Y J,SUN R J,et al.Photocatalytic degradation of tetracycline in aqueous solution by nanosized Ti O2[J].Chemosphere,2013,92(8):925-932.
[13]WANG Y,ZHANG H,ZHANG J H,et al.Degradation of tetracycline in aqueous media by ozonation in an internal loop-lift reactor[J].J Hazard Mater,2011,192(1):35-43.
[2]俞幼萍,高品,刘保江,等.新型光-类芬顿催化剂纳米Fe VO4的制备及其对盐酸四环素的降解性能[J].环境工程学报,2017,11(1):401-407.
[3]胡秀虹,汤承浩,吴林冬,等.Zr掺杂Ti O2介孔材料光催化降解头孢氨苄[J].化工环保,2017,37(4):460-465.
[4]PALOMINOS R A,MONDACA M A,GIRALDO A,et al.Photocatalytic oxidation of the antibiotic tetracycline on Ti O2 and Zn O suspensions[J].Catal Today,2009,144(1/2):100-105.
[5]王红涛,吴玄,赵慧敏,等.分子印迹膜修饰Ti O2纳米管及其光催化降解盐酸四环素[J].科学通报,2011,56(35):2965-2969.
[6]WANG Y,ZHANG H,CHEN L.Ultrasound enhanced catalytic ozonation of tetracycline in a rectangular air-lift reactor[J].Catal Today,2011,175(1):283-292.
[7]康勤书,汪圣尧,沈敏,等.(010)晶面暴露的Bi2Mo O6纳米片对土霉素和四环素的可见光催化降解[J].华中农业大学学报,2014,33(5):67-72.
[8]胡洪营,王超,郭美婷.药品和个人护理用品(PPCPs)对环境的污染现状与研究进展[J].生态环境.2005,14(6):947-952.
[9]孙蕾,马国华.Ti O2/Ni3[Si2O5][OH]2复合光催化材料对盐酸四环素的光降解研究[J].功能材料,2017,48(3):3133-3138.
[10]JEONG J,SONG W H,COOPER W J,et al.Degradation of tetracycline antibiotics:mechanisms and kinetic studies for advanced oxidation/reduction processes[J].Chemosphere,2010,78(5):533-540.
[11]WANG D S,XIAO L B,LUO Q Z,et al.Highly efficient visible light Ti O2 photocatalyst prepared by solgel method at temperatures lower than 300℃[J].J Hazard Mater,2011,192(1):150-159.
[12]ZHU X D,WANG Y J,SUN R J,et al.Photocatalytic degradation of tetracycline in aqueous solution by nanosized Ti O2[J].Chemosphere,2013,92(8):925-932.
[13]WANG Y,ZHANG H,ZHANG J H,et al.Degradation of tetracycline in aqueous media by ozonation in an internal loop-lift reactor[J].J Hazard Mater,2011,192(1):35-43.