Co-Ce共掺杂对TiO_2催化剂室温可见光催化脱硝性能的影响
|
摘要
将钛酸丁酯作为Ti源,硝酸铈作为Ce源,硝酸钴作为Co源,采用溶胶-凝胶水热法制备出Ce-TiO_2和Ce-Co-TiO_2催化剂。对所制备的改性TiO_2催化剂进行BET、XRD、SEM、UV-vis、XPS、NH_3-TPD等表征分析测试,并以NO为研究对象对不同改性TiO_2催化剂进行了可见光催化实验,探究改性TiO_2催化剂脱除NO的效率。结果表明,以硝酸铈为Ce源(掺杂物质的量比1%),硝酸钴为Co源(掺杂物质的量比5%),在水热反应温度为160℃的条件下反应24 h后在200℃下煅烧得到的Ce(1%)-Co(5%)-TiO_2催化剂性能最好。其对浓度为762μg/m~3的NO可见光催化效率高达92.69%,在浓度提高至1148μg/m~3时在室温下的可见光催化效率仍可达85.94%,与纯TiO_2相比效率提高了近50%。而且Ce (1%)-Co (5%)-TiO_2催化剂的抗硫性能与连续使用次数都比商用催化剂(掺杂有V_2O_5的商用TiO_2)好。
Ce-TiO_2 and Ce-Co-TiO_2 powders were prepared by the sol-gel hydrothermal method with butyl titanate as the source of Ti, cerium nitrate as the source of Ce, cobalt nitrate for Co source. The modified TiO_2 catalysts were characterized with BET, XRD, SEM, UV-vis, XPS and NH_3-TPD. The NO reduction efficiency by visible light over the modified TiO_2 catalysts was carried out. The experimental results show that the catalyst Ce(1% molar)-Co(5% molar)-TiO_2 prepared under the conditions of 24 h hydrothermal synthesis at 160 and 200 ℃of calcination showed the best performance. At room temperature, the visible light catalytic efficiency of the catalyst reached 92.69% when the NO initial concentration was 762 μg/m~3. When the NO initial concentration was 1148 μg/m~3, the visible light catalytic efficiency could still reach 85.94%, which was improved by nearly 50% compared with pure TiO_2. Moreover, it was found that in the resistance of SO_2 and continuous usage, the efficiency of the Ce(1%)-Co(5%)-TiO_2 catalyst was better than the commercial catalysts(TiO_2 with V_2O_5 doping).
Ce-TiO_2 and Ce-Co-TiO_2 powders were prepared by the sol-gel hydrothermal method with butyl titanate as the source of Ti, cerium nitrate as the source of Ce, cobalt nitrate for Co source. The modified TiO_2 catalysts were characterized with BET, XRD, SEM, UV-vis, XPS and NH_3-TPD. The NO reduction efficiency by visible light over the modified TiO_2 catalysts was carried out. The experimental results show that the catalyst Ce(1% molar)-Co(5% molar)-TiO_2 prepared under the conditions of 24 h hydrothermal synthesis at 160 and 200 ℃of calcination showed the best performance. At room temperature, the visible light catalytic efficiency of the catalyst reached 92.69% when the NO initial concentration was 762 μg/m~3. When the NO initial concentration was 1148 μg/m~3, the visible light catalytic efficiency could still reach 85.94%, which was improved by nearly 50% compared with pure TiO_2. Moreover, it was found that in the resistance of SO_2 and continuous usage, the efficiency of the Ce(1%)-Co(5%)-TiO_2 catalyst was better than the commercial catalysts(TiO_2 with V_2O_5 doping).
引文
[1] 中国电力企业联合会. 中国电力行业年度发展报告[M]. 北京: 中国市场出版社, 2018.(China Electricity Council. China Power Industry Annual Development Report[M]. Beijing: China Market Press, 2018.)
[2] 国家环境保护总局. 火电厂大气污染物排放标准[S].(State Environmental Protection Administration. Thermal power plant emission standards for atmospheric pollutants[S].)
[3] ZHANG D R, LIU H L, HAN S Y, PIAO W X. Synthesis of Sc and V-doped TiO2 nanoparticles and photodegradation of rhodamine-B[J]. J Ind Eng Chem, 2013, 19(6): 1838-1844.
[4] REDDY B M, KHAN A. Structural characterization of CeO2-TiO2 and V2O5/CeO2-TiO2 catalysts by Raman and XPS techniques[J]. J Phys Chem B, 2003, 107(22): 5162-5167.
[5] 袁春华, 谢英娜. 钴掺杂二氧化钛光催化剂制备及光催化活性[J]. 无机盐工业, 2011, 43(11): 31-33.(YUAN Chun-hua, XIE Ying-na. Preparation of cobalt-doped titania photocatalysts and photocatalytic activity thereof[J].Inorg Chem Ind, 2011, 43(11): 31-33.)
[6] LI X H, ZHANG S L, JIA Y, LIU X X, ZHONG Q. Selective catalyticoxidation of NO with O2 over Ce-doped MnOx/TiO2 catalysts[J]. Nat Gas Chem, 2012, 1(1): 17-24.
[7] 宋林云, 吴玉程, 李云, 叶敏, 谢挺, 黄新民. 介孔Co-TiO2的制备及其光催化性能研究[J]. 武汉理工大学学报, 2007, 39(10): 66-69.(SONG Lin-yun, WU Yu-cheng, LI Yun, YE Min, XIE Ting, HUANG Xin-min. Preparation and photocatalytic performance of mesoporous Co-TiO2[J]. J Wuhan Univ Technol, 2007, 39(10): 66-69.)
[8] 李伟, 张成, 李鑫, 谭鹏, 方庆艳, 陈刚. Ho掺杂对Mn-Ce /TiO2低温SCR催化剂的脱硝性能影响[J]. 燃料化学学报, 2017, 45(12): 1508-1513.(LI Wei, ZHANG Cheng, LI Xin, TANG Peng, FANG Qing-yan, CHEN Gang. Influence of Ho doping on the deNOx performance of Mn-Ce/TiO2 low temperature SCR catalyst[J]. J Fuel Chem Technol, 2017, 45(12): 1508-1513.)
[9] 徐文青, 赵俊, 王海蕊, 朱廷钰, 李鹏, 荆鹏飞. TIO2负载Mn-Co复合氧化物催化剂上NO催化氧化性能[J]. 物理化学学报, 2013, 29(2): 385-390.(XU Wen-qing, ZHAO Jun, WANG Hai-xin, ZHU Ting-yu, ZHAO Peng, JING Peng-fei. Catalytic oxidation activity of NO on TIO2-supported Mn-Co composite oxide catalysts[J]. Acta Phys-Chim Sin, 2013, 29(2): 385-390.)
[10] 陈爽, 姚淑华, 石中亮. 花瓣状铈掺杂纳米TiO2光催化剂的制备及其光催化活性[J].中南大学学报(自然科学版), 2016, 47(5): 1487-1493.(CHEN Shuang, YAO Shu-hua, SHI Zhong-liang. Preparation and photocatalytic activity of petal-like doped nano TiO2 photocatalyst using hydrothermal method[J]. J Cent S Univ (Sci Technol), 2016, 47(5): 1487-1493.)
[11] MURPHY A. Band-gap determination from diffuse reflectance measurements of semiconductor films, and application to photoelectrochemical water-splitting[J]. Sol Energy Mater Sol Cells, 2007, 91(14): 1326.
[12] SENTHIL R A, THEERTHAGIRI J, SELVI A, MADHAVAN J. Synthesis and characterization of low-cost g-C3N4/TiO2 composite with enhanced photocatalytic performance undervisible-light irradiation[J]. Opt Mate, 2017, 64: 533-539.
[13] 陈其凤, 姜东, 徐耀, 吴东, 孙予罕. 溶胶-凝胶-水热法制备Ce-Si/TiO2及其可见光催化性能[J].物理化学学报, 2009, 25(4): 617-623.(CHEN Qi-feng, JIANG Dong, XU Yao, WU Dong, SUN Yu-han. Preparation of Ce-Si/TiO2 by sol-gel hydrothermal method and its photocatalytic performance[J]. Acta Phys-Chim Sin, 2009, 25(4): 617-623.)
[14] 张璐, 谢健, 李国强, 张洪良. 掺杂Ce4+对溶胶-凝胶法制备二氧化钛薄膜的结构和光催化特性的影响[J].半导体光电, 2013, 34(1): 98-102.(ZHANG Lu, XIE Jian, LI Guo-qaing, ZHANG Hong-liang. Effect of Ce4+-doping on structural and photocatalytic properties of sol-gel prepared titanium dioxide thin-films[J]. Semicond Optoelectron, 2013, 34(1): 98-102.)
[15] 祝豪杰, 武军. Co掺杂锐钛矿型TiO2可见光催化特性机理研究[J]. 杭州电子科技大学学报, 2012, 32(5): 21-24.(ZHU Hao-jie, WU Jun. The visible light catalytic properties and mechanism of Co co-doped anatase TiO2[J]. J Hangzhou Elect Sci Technol Univ, 2012, 32(5): 21-24.)
[16] 冯云桑, 刘少光, 陈成武, 吴进明, 徐玉松. Co-Ce氧化物对MnOx/TiO2低温SCR脱硝催化剂的影响[J]. 材料热处理学报, 2014, 35(6): 26-33.(FENG Yun-Sang, LIU Shang-guang, CHEN Cheng-wu, WU Jin-ming, XU Yu-song. Effect of doping Co-Ce oxide on MnOx/TiO2 low-temperature SCR DeNOx catalys[J]. Trans Mater Heat Treat, 2014, 35(6): 26-33.)
[17] 于国峰, 韦彦斐, 金瑞奔, 朱虹, 顾震宇, 潘理黎. Mn-Ce-Co/TiO2催化剂低温脱硝活性研究[J]. 环境科学学报, 2012, 32(7): 1743-1749.(YU Guo-feng, WEI Yan-pei, JIN Rui-ben, ZHU Hong, GU Zhen-yu, PAN Li-li. The research of Mn-Ce-Co/TiO2 catalyst denitration on low temperature[J]. J Environ Sci-China, 2012, 32(7): 1743-1749.)
[18] 张前程, 张凤宝, 张国亮, 张晓萍.超细钴掺杂二氧化钛的制备、表征及气相光催化性能[J]. 燃料化学学报, 2004, 32(2): 240-243.(ZHANG Qian-cheng, ZHANG Feng-bao, ZHANG Guo-liang, ZHANG Xiao-ping. Preparation and characterization of ultrafine TiO2 doped with Co and its performance in gas-phase photocatalytic oxidation[J]. J Fuel Chem Technol, 2004, 32(2): 240-243.)
[19] LI J Y, SONG Z X, NING P, ZHANG Q L, LIU X, LI H, HUANG Z Z. Influence of calcination temperature on selective catalytic reduction of NOx with NH3 over CeO2-ZrO2-WO3 catalyst[J]. J Rare Earths, 2015, 33(7): 726-735.
[20] 廖永进, 张亚平, 余岳溪, 李娟, 郭婉秋, 汪小蕾. MnOx/WO3/TiO2低温选择性催化还原NOx机理的原位红外研究[J]. 化工学报, 2016, 67(12): 5031-5039.(LIAO Yong-jin, ZHANG Ya-ping, YU Yue-xi, LI Juan, GUO Wang-qiu, WANG Xiao-lei. In situ FT-IR studies on low temperature NH3-SCR mechanism of NOx over MnOx /WO3 /TiO2 catalyst[J]. CIESC J, 2016, 67(12): 5031-5039.)
[21] 刘晓飒, 陈淑俊, 赵铁英, 李德艳, 白小鸽, 李留琴. 吡啶-热脱附-红外法确定催化剂酸性[J]. 工业催化, 2015, 23(10): 817-820.(LIU Xiao-da, CHEN Shu-jun, ZHAO Tie-ying, LI De-yan, BAI Xiao-ge, LI Liu-qin. Pyridine-thermal desorption-infrared method for characterization catalyst acidity[J]. Ind Catal, 2015, 23(10): 817-820.)
[22] 束韫, 张凡, 王洪昌, 朱金伟. SO2和H2O对CeO2/TiO2/堇青石催化剂选择催化还原NOx 性能的影响[J]. 燃料化学学报, 2014, 42(9): 1111-1118.(SU Wen, ZHANG Fan, WANG Hong-chang, ZHU Jin-wei. The influence of SO2 and H2O for selective catalytic reduction of NOx of CeO2/TiO2/cordierite[J]. J Fuel Chem Technol, 2014, 42(9): 1111-1118.)
[23] 彭莉莉. CoOx/ZrO2催化氧化NO性能研究[D]. 湘潭: 湘潭大学, 2012.(PENG Li-li. The research of CoOx/ZrO2 catalytic oxidation NO[D]. Xiangtan: Xiangtan University, 2012. )
[24] YU H, WEI W, QIAN Z, CAO J J, HUANG R J, HO W K, SHUN C L. In situ fabrication of α-Bi2O3/(BiO)2CO3 nanoplate heterojunctions with tunable optical property and photocatalytic activity[J]. Sci Reports, 2016, 6(2): 34-35.
[25] LI H, SHI J G, ZHAO K, ZHANG L Z. Sustainable molecular oxygen activation with oxygen vacancies on the {001} facets of BiOCl nanosheets under solar light[J]. Nanoscale, 2014, 6(23): 14168-14173.
[26] 魏凤玉, 倪良锁. 硼硫共掺杂TiO2的光催化性能及掺杂机理[J]. 催化学报, 2007, 28(10): 905-909.(WEI Feng-yu, Ni Liang-suo. Photocatalytic performance and doping mechanism of B-S Co-doped TiO2[J]. Chin J Catal, 2007, 28(10): 905-909.)Influence of Co-Ce co-doping on photocatalytic DeNOx of TiO2 catalyst at room temperatureWANG Shu-qin WU Jin-jin DU Zhi-hui使用铈与钴对TiO2进行掺杂: 降低了催化剂的禁带宽度,提高了对可见光的利用率,提升了光催化性能。J Fuel Chem Technol, 2019, 47(3): 370-377改性菱铁矿催化剂的催化脱硝活性及抗硫性研究陈鑫归柯庭顾少宸
[2] 国家环境保护总局. 火电厂大气污染物排放标准[S].(State Environmental Protection Administration. Thermal power plant emission standards for atmospheric pollutants[S].)
[3] ZHANG D R, LIU H L, HAN S Y, PIAO W X. Synthesis of Sc and V-doped TiO2 nanoparticles and photodegradation of rhodamine-B[J]. J Ind Eng Chem, 2013, 19(6): 1838-1844.
[4] REDDY B M, KHAN A. Structural characterization of CeO2-TiO2 and V2O5/CeO2-TiO2 catalysts by Raman and XPS techniques[J]. J Phys Chem B, 2003, 107(22): 5162-5167.
[5] 袁春华, 谢英娜. 钴掺杂二氧化钛光催化剂制备及光催化活性[J]. 无机盐工业, 2011, 43(11): 31-33.(YUAN Chun-hua, XIE Ying-na. Preparation of cobalt-doped titania photocatalysts and photocatalytic activity thereof[J].Inorg Chem Ind, 2011, 43(11): 31-33.)
[6] LI X H, ZHANG S L, JIA Y, LIU X X, ZHONG Q. Selective catalyticoxidation of NO with O2 over Ce-doped MnOx/TiO2 catalysts[J]. Nat Gas Chem, 2012, 1(1): 17-24.
[7] 宋林云, 吴玉程, 李云, 叶敏, 谢挺, 黄新民. 介孔Co-TiO2的制备及其光催化性能研究[J]. 武汉理工大学学报, 2007, 39(10): 66-69.(SONG Lin-yun, WU Yu-cheng, LI Yun, YE Min, XIE Ting, HUANG Xin-min. Preparation and photocatalytic performance of mesoporous Co-TiO2[J]. J Wuhan Univ Technol, 2007, 39(10): 66-69.)
[8] 李伟, 张成, 李鑫, 谭鹏, 方庆艳, 陈刚. Ho掺杂对Mn-Ce /TiO2低温SCR催化剂的脱硝性能影响[J]. 燃料化学学报, 2017, 45(12): 1508-1513.(LI Wei, ZHANG Cheng, LI Xin, TANG Peng, FANG Qing-yan, CHEN Gang. Influence of Ho doping on the deNOx performance of Mn-Ce/TiO2 low temperature SCR catalyst[J]. J Fuel Chem Technol, 2017, 45(12): 1508-1513.)
[9] 徐文青, 赵俊, 王海蕊, 朱廷钰, 李鹏, 荆鹏飞. TIO2负载Mn-Co复合氧化物催化剂上NO催化氧化性能[J]. 物理化学学报, 2013, 29(2): 385-390.(XU Wen-qing, ZHAO Jun, WANG Hai-xin, ZHU Ting-yu, ZHAO Peng, JING Peng-fei. Catalytic oxidation activity of NO on TIO2-supported Mn-Co composite oxide catalysts[J]. Acta Phys-Chim Sin, 2013, 29(2): 385-390.)
[10] 陈爽, 姚淑华, 石中亮. 花瓣状铈掺杂纳米TiO2光催化剂的制备及其光催化活性[J].中南大学学报(自然科学版), 2016, 47(5): 1487-1493.(CHEN Shuang, YAO Shu-hua, SHI Zhong-liang. Preparation and photocatalytic activity of petal-like doped nano TiO2 photocatalyst using hydrothermal method[J]. J Cent S Univ (Sci Technol), 2016, 47(5): 1487-1493.)
[11] MURPHY A. Band-gap determination from diffuse reflectance measurements of semiconductor films, and application to photoelectrochemical water-splitting[J]. Sol Energy Mater Sol Cells, 2007, 91(14): 1326.
[12] SENTHIL R A, THEERTHAGIRI J, SELVI A, MADHAVAN J. Synthesis and characterization of low-cost g-C3N4/TiO2 composite with enhanced photocatalytic performance undervisible-light irradiation[J]. Opt Mate, 2017, 64: 533-539.
[13] 陈其凤, 姜东, 徐耀, 吴东, 孙予罕. 溶胶-凝胶-水热法制备Ce-Si/TiO2及其可见光催化性能[J].物理化学学报, 2009, 25(4): 617-623.(CHEN Qi-feng, JIANG Dong, XU Yao, WU Dong, SUN Yu-han. Preparation of Ce-Si/TiO2 by sol-gel hydrothermal method and its photocatalytic performance[J]. Acta Phys-Chim Sin, 2009, 25(4): 617-623.)
[14] 张璐, 谢健, 李国强, 张洪良. 掺杂Ce4+对溶胶-凝胶法制备二氧化钛薄膜的结构和光催化特性的影响[J].半导体光电, 2013, 34(1): 98-102.(ZHANG Lu, XIE Jian, LI Guo-qaing, ZHANG Hong-liang. Effect of Ce4+-doping on structural and photocatalytic properties of sol-gel prepared titanium dioxide thin-films[J]. Semicond Optoelectron, 2013, 34(1): 98-102.)
[15] 祝豪杰, 武军. Co掺杂锐钛矿型TiO2可见光催化特性机理研究[J]. 杭州电子科技大学学报, 2012, 32(5): 21-24.(ZHU Hao-jie, WU Jun. The visible light catalytic properties and mechanism of Co co-doped anatase TiO2[J]. J Hangzhou Elect Sci Technol Univ, 2012, 32(5): 21-24.)
[16] 冯云桑, 刘少光, 陈成武, 吴进明, 徐玉松. Co-Ce氧化物对MnOx/TiO2低温SCR脱硝催化剂的影响[J]. 材料热处理学报, 2014, 35(6): 26-33.(FENG Yun-Sang, LIU Shang-guang, CHEN Cheng-wu, WU Jin-ming, XU Yu-song. Effect of doping Co-Ce oxide on MnOx/TiO2 low-temperature SCR DeNOx catalys[J]. Trans Mater Heat Treat, 2014, 35(6): 26-33.)
[17] 于国峰, 韦彦斐, 金瑞奔, 朱虹, 顾震宇, 潘理黎. Mn-Ce-Co/TiO2催化剂低温脱硝活性研究[J]. 环境科学学报, 2012, 32(7): 1743-1749.(YU Guo-feng, WEI Yan-pei, JIN Rui-ben, ZHU Hong, GU Zhen-yu, PAN Li-li. The research of Mn-Ce-Co/TiO2 catalyst denitration on low temperature[J]. J Environ Sci-China, 2012, 32(7): 1743-1749.)
[18] 张前程, 张凤宝, 张国亮, 张晓萍.超细钴掺杂二氧化钛的制备、表征及气相光催化性能[J]. 燃料化学学报, 2004, 32(2): 240-243.(ZHANG Qian-cheng, ZHANG Feng-bao, ZHANG Guo-liang, ZHANG Xiao-ping. Preparation and characterization of ultrafine TiO2 doped with Co and its performance in gas-phase photocatalytic oxidation[J]. J Fuel Chem Technol, 2004, 32(2): 240-243.)
[19] LI J Y, SONG Z X, NING P, ZHANG Q L, LIU X, LI H, HUANG Z Z. Influence of calcination temperature on selective catalytic reduction of NOx with NH3 over CeO2-ZrO2-WO3 catalyst[J]. J Rare Earths, 2015, 33(7): 726-735.
[20] 廖永进, 张亚平, 余岳溪, 李娟, 郭婉秋, 汪小蕾. MnOx/WO3/TiO2低温选择性催化还原NOx机理的原位红外研究[J]. 化工学报, 2016, 67(12): 5031-5039.(LIAO Yong-jin, ZHANG Ya-ping, YU Yue-xi, LI Juan, GUO Wang-qiu, WANG Xiao-lei. In situ FT-IR studies on low temperature NH3-SCR mechanism of NOx over MnOx /WO3 /TiO2 catalyst[J]. CIESC J, 2016, 67(12): 5031-5039.)
[21] 刘晓飒, 陈淑俊, 赵铁英, 李德艳, 白小鸽, 李留琴. 吡啶-热脱附-红外法确定催化剂酸性[J]. 工业催化, 2015, 23(10): 817-820.(LIU Xiao-da, CHEN Shu-jun, ZHAO Tie-ying, LI De-yan, BAI Xiao-ge, LI Liu-qin. Pyridine-thermal desorption-infrared method for characterization catalyst acidity[J]. Ind Catal, 2015, 23(10): 817-820.)
[22] 束韫, 张凡, 王洪昌, 朱金伟. SO2和H2O对CeO2/TiO2/堇青石催化剂选择催化还原NOx 性能的影响[J]. 燃料化学学报, 2014, 42(9): 1111-1118.(SU Wen, ZHANG Fan, WANG Hong-chang, ZHU Jin-wei. The influence of SO2 and H2O for selective catalytic reduction of NOx of CeO2/TiO2/cordierite[J]. J Fuel Chem Technol, 2014, 42(9): 1111-1118.)
[23] 彭莉莉. CoOx/ZrO2催化氧化NO性能研究[D]. 湘潭: 湘潭大学, 2012.(PENG Li-li. The research of CoOx/ZrO2 catalytic oxidation NO[D]. Xiangtan: Xiangtan University, 2012. )
[24] YU H, WEI W, QIAN Z, CAO J J, HUANG R J, HO W K, SHUN C L. In situ fabrication of α-Bi2O3/(BiO)2CO3 nanoplate heterojunctions with tunable optical property and photocatalytic activity[J]. Sci Reports, 2016, 6(2): 34-35.
[25] LI H, SHI J G, ZHAO K, ZHANG L Z. Sustainable molecular oxygen activation with oxygen vacancies on the {001} facets of BiOCl nanosheets under solar light[J]. Nanoscale, 2014, 6(23): 14168-14173.
[26] 魏凤玉, 倪良锁. 硼硫共掺杂TiO2的光催化性能及掺杂机理[J]. 催化学报, 2007, 28(10): 905-909.(WEI Feng-yu, Ni Liang-suo. Photocatalytic performance and doping mechanism of B-S Co-doped TiO2[J]. Chin J Catal, 2007, 28(10): 905-909.)Influence of Co-Ce co-doping on photocatalytic DeNOx of TiO2 catalyst at room temperatureWANG Shu-qin WU Jin-jin DU Zhi-hui使用铈与钴对TiO2进行掺杂: 降低了催化剂的禁带宽度,提高了对可见光的利用率,提升了光催化性能。J Fuel Chem Technol, 2019, 47(3): 370-377改性菱铁矿催化剂的催化脱硝活性及抗硫性研究陈鑫归柯庭顾少宸