CeO2-TiO2 Mixed Oxides Catalysts for Selective Catalytic Reduction of NOx with NH3: Structure-properties Relationships†

doi:10.7503/cjcu20160875

Abstract

Abstract:

A series of CeO₂-TiO₂ mixed oxides catalysts prepared by Co-precipitation method was investigated on selective catalytic reduction(SCR) of NO_x with NH₃. The properties of the catalysts were characterized using XRD, BET, XRF, XPS, H₂-TPR, NH₃-TPD and NO+O₂-TPD techniques. The results indicated that the crystal structure, crystallite size and catalytic NH₃-SCR activity over the catalysts presented a regular change with the increase of CeO₂ concentration. Particularly, the 50CeTi catalyst with amorphous structure of CeO₂-TiO₂ showed a higher BET surface area and a stronger surface acidity than other samples. Meanwhile, favorable Ce³⁺ and the surface adsorbed oxygen benefited the adsorption of NO_x and NH₃ molecules, which enhanced DeNO_x performance.

Key words: Selective catalytic reduction, CeO2-TiO2 mixed oxide, NOx, Crystal structure

CLC Number:

O643

TrendMD:

SUN Xiangli, HE Hong, SU Yaochao, YAN Jingfang, SONG Liyun, QIU Wenge. CeO₂-TiO₂ Mixed Oxides Catalysts for Selective Catalytic Reduction of NO_x with NH₃: Structure-properties Relationships^†[J]. Chem. J. Chinese Universities, 2017, 38(5): 814.

Figures/Tables 11

Fig.1 NH3-SCR activity of CeO2-TiO2 catalystsReaction condition: 1340 mg/m3 NO, 760 mg/m3 NH3, 6% O2, He balance, GHSV: 3×104 h-1. Temperature/℃: a. 140; b. 160; c. 180; d. 200; e. 220; f. 260.

Fig.2 NH3-SCR activity(A) and N2 selectivity(B) over the catalystsReaction conditions: 1340 mg/m3 NO, 760 mg/m3 NH3, 6% O2, He balance, GHSV: 3×104 h-1.■ TiO2; ● 10CeTi; ▲ 50CeTi; ▼ 90CeTi; ? CeO2.

Fig.3 NH3-SCR activity over the catalysts in the presence of H2O/SO2 at 270 ℃Reaction condition: 1340 mg/m3 NO, 760 mg/m3 NH3, 6% O2, 5% H2O, 860 mg/m3 SO2, N2 balance, GHSV: 3×104 h-1. ■ 10CeTi; ● 50CeTi; ▲ 90CeTi.

Fig.4 XRD patterns of the catalystsa. TiO2; b. 10CeTi; c. 20CeTi; d. 30CeTi;e. 40CeTi; f. 50CeTi; g. 60CeTi; h. 70CeTi;i. 80CeTi; j. 90CeTi; k. CeO2.

Table 1 Specific surface area, pore volume and average crystallite sizes of the catalysts

Sample	S_BET/(m²·g^-1)	Pore volume/(cm³·g^-1)	Crystallite size/nm
TiO₂	57.1	0.11	21
10CeTi	91.6	0.18	15
50CeTi	129.0	0.21
90CeTi	85.3	0.15	10
CeO₂	70.1	0.17	13

Fig.5 N2 adsorption-desorption isotherms of the catalystsa. TiO2; b. 10CeTi; c. 50CeTi; d. 90CeTi; e. CeO2.

Fig.6 H2-TPR profiles of the catalystsa. TiO2; b. 10CeTi; c. 50CeTi;d. 90CeTi; e. CeO2.

Table 2 XPS data and H2 consumption of the catalysts

Sample	Molar fraction(%)			Molar ratio(%)		H₂ consumption/(mmol· $g cat - 1$ )
Sample	Ce	Ti		O	Ce³⁺/(Ce³⁺+Ce⁴⁺)	O_α/(O_α+O_β)
TiO₂		36.1	63.9		12.2	0.13
10CeTi	1.7	34.7	63.6	32.1	13.3	0.35
50CeTi	7.3	24.2	68.5	18.5	25.5	2.30
90CeTi	18.1	4.1	77.8	18.7	35.7	4.04
CeO₂	25.6		74.4	14.8	15.1	0.73

Table 2 XPS data and H2 consumption of the catalysts

Sample	Molar fraction(%)			Molar ratio(%)		H₂ consumption/(mmol· $g cat - 1$ )
Sample	Ce	Ti		O	Ce³⁺/(Ce³⁺+Ce⁴⁺)	O_α/(O_α+O_β)
TiO₂		36.1	63.9		12.2	0.13
10CeTi	1.7	34.7	63.6	32.1	13.3	0.35
50CeTi	7.3	24.2	68.5	18.5	25.5	2.30
90CeTi	18.1	4.1	77.8	18.7	35.7	4.04
CeO₂	25.6		74.4	14.8	15.1	0.73

Fig.7 XPS spectra of Ti2p(A), Ce3d(B) and O1s(C) of the catalystsa.TiO2; b.10CeTi; c.50CeTi; d.90CeTi; e.CeO2.(C) Molar fraction of Oα: a. 12.2%; b. 13.3;c. 25.5%; d. 35.7%; e. 15.1%.

Fig.8 NH3-TPD(A) and NO+O2-TPD(B) profiles of the catalystsa. TiO2; b. 10CeTi; c. 50CeTi; d. 90CeTi; e. CeO2.

Table 3 Amounts of desorption species from the samples during NO+O2-TPD and NH3-TPD experiments

Sample	Desorption area in NO+O₂-TPD		Desorption area in NH₃-TPD, total N $H 3 *$
Sample	NO^*		N $O 2 *$
TiO₂	1.0	1.0	1.0
10CeTi	1.8	1.3	1.2
50CeTi	3.4	2.2	1.9
90CeTi	0.9	0.8	0.8
CeO₂	4.4	2.8	0.5

Table 3 Amounts of desorption species from the samples during NO+O2-TPD and NH3-TPD experiments

Sample	Desorption area in NO+O₂-TPD		Desorption area in NH₃-TPD, total N $H 3 *$
Sample	NO^*		N $O 2 *$
TiO₂	1.0	1.0	1.0
10CeTi	1.8	1.3	1.2
50CeTi	3.4	2.2	1.9
90CeTi	0.9	0.8	0.8
CeO₂	4.4	2.8	0.5

References 35

[1]	Liu N., Wang J. Q., Chen B. H., Li Y. X., Zhang R. D., Chem. J. Chinese Universities, 2016, 37(10), 1817—1825
	(刘宁, 王继琼, 陈标华, 李英霞, 张润铎.高等学校化学学报, 2016,37(10), 1817—1825)
[2]	Shan W. P., Liu F. D., Yu Y. B., He H., Chin. J. Catal., 2014, 35(8), 1251—1259
	(单文坡, 刘福东, 余运波, 贺泓.催化学报, 2014,35(8), 1251—1259)
[3]	Liu J. D., Huang Z. G., Li Z., Guo Q. Q., Li Q. Y., Chem. J. Chinese Universities, 2014, 35(3), 589—595
	(刘建东, 黄张根, 李哲, 郭倩倩, 李巧艳.高等学校化学学报, 2014,35(3), 589—595)
[4]	Tang C. J., Zhang H. L., Dong L., Catal. Sci. Technol., 2016, 6, 1248—1264
[5]	Li Q., Gu H. C., Li P., Zhou Y. H., Liu Y., Qi Z. N., Xin Y., Zhang Z. L., Chin. J. Catal., 2014, 35(8), 1289—1298
	(李倩, 谷华春, 李萍, 周钰浩, 刘莹, 齐中囡, 辛颖, 张昭良.催化学报, 2014,35(8), 1289—1298)
[6]	Li Z. G., Li J. H., Liu S. X., Ren X. N., Ma J., Su W. K., Peng Y., Catalysis Today, 2015, 258, 11—16
[7]	Yu M., Li C. T., Zeng G. M., Zhou Y., Zhang X. N., Xie Y., Applied Surface Science, 2015, 342, 174—182
[8]	Zhou A. Y., Yu D. Q., Yang L., Sheng Z. Y., Applied Surface Science, 2016, 378, 167—173
[9]	Chen L., Si Z. C., Wu X. D., Weng D., Appl. Mater. Interfaces, 2014, 6, 8134—8145
[10]	Liu J., Li X. Y., Zhao Q. D., Ke J., Xiao H. N., Lv X. J., Liu S. M., Tadé M., Wang S. B., Appl. Catal. B: Environ., 2017, 200, 297—308
[11]	Luo M. F., Chen J., Chen L. S., Lu J. Q., Feng Z. C., Li C., Chem. Mater., 2001, 13, 197—202
[12]	Gao X., Jiang Y., Zhong Yi., Luo Z. Y., Cen K. F. Journal of Hazardous Materials, 2010, 174, 734—739
[13]	Li P., Xin Y., Li Q., Wang Z. P., Zhang Z. L., Zheng L. R., Environ. Sci. Technol., 2012, 46, 9600—9605
[14]	Wang H. Q., Cao S., Fang Z., Yu F. X., Liu Y., Weng X. L., Wu Z. B., Applied Surface Science, 2015, 330, 245—252
[15]	Xiao X., Xiong S.C., Shi Y. J., Shan W. P., Yang S. J.,J. Phys. Chem. C, 2016, 120, 1066—1076
[16]	Song L. Y., Zhan Z. C., Liu X. J., He H., Qiu W. G., Zi X. H., Chin. J. Catal., 2014, 35(7), 1030—1035
	(宋丽云, 展宗城, 刘晓军, 何洪, 邱文革, 訾学红.催化学报, 2014,35(7), 1030—1035)
[17]	Chao J. D., He H., Song L. Y., Fang Y. J., Liang Q. M., Zhang G. G., Qiu W. G., Zhang R., Chem. J. Chinese Universities, 2015, 36(3), 523—530
	(晁晶迪, 何洪, 宋丽云, 房玉娇, 梁全明, 张桂臻, 邱文革, 张然.高等学校化学学报, 2015,36(3), 523—530)
[18]	Zhang T., Qu R. Y., Su W. K., Li J. H., Appl. Catal. B: Environ., 2015, 176/177, 338—346
[19]	Yan D. J., Yu Y., Huang X. M., Liu S. J., Liu Y. H., J. Fuel. Chem. Technol., 2016, 44(2), 232—238
[20]	Shi Z. N., Yang P., Tao F., Zhou R. X., Chem. Eng. J., 2016, 295, 99—108
[21]	Song Z. X., Zhang Q. L., Ning P., Liu X., Fan J., Huang Z. Z., J. Rare Earths, 2016, 34(7), 667—674
	(宋忠贤, 张秋林, 宁平, 刘昕, 樊洁, 黄真真.稀土学报, 2016,34(7), 667—674)
[22]	Chen L., Li J. H., Ge M. F., J. Phys. Chem. C, 2009, 113, 21177—21184
[23]	Su Y. F., Tang Z. C., Han W. L., Zhang P., Song Y., Lu G. X., Cryst. Eng. Comm., 2014, 16, 5189—5197
[24]	Ferrizz R. M., Gorte R. J., Vohs J. M., Catal. Lett., 2002, 82(1/2), 123—129
[25]	Bêche E., Charvin P., Perarnau D., Abanades S., Flamant G., Surface & Interface Analysis, 2008, 40(3/4), 264—267
[26]	Peng Y., Wang C. Z., Li J. H., Appl. Catal. B: Environ., 2014, 144, 538—546
[27]	Boningari T., Ettireddy P. R., Somogyvari A., Liu Y., Vorontsov A., McDonald C. A., Smirniotis P. G., J. Catal., 2015, 325, 145—155
[28]	Shan W. P., Liu F. D., He H., Shi X. Y., Zhang C. B., Catal. B: Environ., 2012, 115/116, 100—106
[29]	Chu X. L., Lu Z. S., Yang Z. X., Ma D. W., Zhang Y. X., Li S. S., Gao P. Y.,Phys. Lett. A, 2014, 378, 659—666
[30]	Xu W. Q., He H., Yu Y. B., J. Phys. Chem. C, 2009, 113, 4426—4432
[31]	Creaser D. A., Harrison P. G., Catal. Lett., 1994, 23, 13—24
[32]	Maqbool M. S., Pullur A. K., Ha H. P., Catal. B: Environ., 2014, 152/153, 28—37
[33]	Li X., Li J. H., Peng Y., Chang H. Z., Zhang T., Zhao S., Si W. Z., Hao J. M., Catal. B: Environ., 2016, 184, 246—257
[34]	Zhou A. Y., Yu D. Q., Yang L., Sheng Z. Y., Appl. Surf. Sci., 2016, 378, 167—173
[35]	Yang N. Z., Guo R. T., Pan W. G., Chen Q. L., Wang Q. S., Lu C. Z., Wang S. X., Appl. Surf. Sci., 2016, 378, 513—518

Related Articles 15

[1]	LIU Qingqing, WANG Pu, WANG Yongshuai, ZHAO Man, DONG Huanli. Synthesis and Topochemical Polymerization Study of Naphthalene/perylene Imides Substituted Diacetylene Derivatives [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220091.
[2]	SHI Naike, ZHANG Ya, SANSON Andrea, WANG Lei, CHEN Jun. Uniaxial Negative Thermal Expansion and Mechanism in Zn（NCN） [J]. Chem. J. Chinese Universities, 2022, 43(6): 20220124.
[3]	YUE Shengli, WU Guangbao, LI Xing, LI Kang, HUANG Gaosheng, TANG Yi, ZHOU Huiqiong. Research Progress of Quasi-two-dimensional Perovskite Solar Cells [J]. Chem. J. Chinese Universities, 2021, 42(6): 1648.
[4]	TIAN Xia,YANG Fuqun,YUAN Wei,ZHAO Lei,YAO Lei,ZHEN Xiaoli,HAN Jianrong,LIU Shouxin. Synthesis, Structure and Recognition Properties of Macrocyclic Crown Ethers with Oxadiazole ^† [J]. Chem. J. Chinese Universities, 2020, 41(3): 490.
[5]	LIU Dongmei,SU Yajing,LI Shanshan,XU Qiwei,LI Xia. Transition Metal Coordination Polymers Constructed by 4-(4-Carboxyphenoxy)isophthalic Acid: Synthesis, Crystal Structure, Fluorescence Sensing and Photocatalysis ^† [J]. Chem. J. Chinese Universities, 2020, 41(2): 253.
[6]	QIN Liulei,LIU Yang,GUAN Xiaoqin,ZHENG Xiaoyuan,ZHANG Ziyu,LIU Zunqi. Synthesis and Switchable Dielectric Properties of an Inorganic-organic Hybrid Complex [H₂(DABCO)CuCl₄]·H₂O ^† [J]. Chem. J. Chinese Universities, 2020, 41(1): 70.
[7]	ZHANG Ling,DUAN Hongchang,TAN Zhengguo,WU Qinming,MENG Xiangju,XIAO Fengshou. Recent Advances in the Preparation of 8MR Zeolites for the Selective Catalytic Reduction of NO_x(NH₃-SCR) in Diesel Engines ^† [J]. Chem. J. Chinese Universities, 2020, 41(1): 19.
[8]	LI Chunxiao, LI Jian, LIANG Wenjun, LIANG Quanming. Low Temperature NH₃-SCR Activity of Cr Doped V₂O₅-WO₃/TiO₂ Catalyst^† [J]. Chem. J. Chinese Universities, 2019, 40(7): 1447.
[9]	LI Bing,WANG Xuemin,BAI Fengying,LIU Shuqing. Synthesises, Structures and Antibacterial Activities of a Series of Rare Earth Nitrogen Heterocyclic Complexes^† [J]. Chem. J. Chinese Universities, 2019, 40(4): 632.
[10]	ZHU Hongtai,SONG Liyun,HE Hong,YIN Mengqi,CHENG Jie,SUN Yanming,LI Shining,QIU Wenge. Sulfur Tolerance of the CeTiO_x Catalysts for Selective Catalytic Reduction of NO with NH₃^† [J]. Chem. J. Chinese Universities, 2019, 40(2): 350.
[11]	WANG Dongmei,LIU Zihua,LI Guanghua,LIU Yunling,LI Chunxia. Synthesis, Structure and Fluorescent Property of Indium-based Bimetallic Metal-organic Frameworks^† [J]. Chem. J. Chinese Universities, 2018, 39(9): 1886.
[12]	TIAN Huan, ZHANG Menglong, WANG Lisha, TONG Bihai, ZHAO Zhuo. Synthesis of 4,13-Dithio Benzene and-18-Crown-6 and Its Selective Extractability on A $g + †$ [J]. Chem. J. Chinese Universities, 2018, 39(6): 1191.
[13]	ZHU Lei,HAN Junyan,CHANG Haizhen,QIU Yuyuan,ZHANG Yanan,PENG Danni,HU Wei,MIAO Shaobin. Different Pathways for the Cyclocondensation Reactions of 1,2-Diamine and 1,2-Diketone^† [J]. Chem. J. Chinese Universities, 2018, 39(12): 2686.
[14]	CHEN Qidan, TANG Junjie, FANG Qianrong. Highly Stable Fluorine Containing Hierarchical Porous Covalent Organic Framework^† [J]. Chem. J. Chinese Universities, 2018, 39(11): 2357.
[15]	LI Zheng, LI Rui, LI Xia. Synthesis, Crystal Structure and Fluorescent Properties of Transition Metal Complexes Constructed with 2-(3'-Carboxyphenoxy)benzoic Acid and N-Donor Ligands^† [J]. Chem. J. Chinese Universities, 2018, 39(11): 2363.

CeO₂-TiO₂ Mixed Oxides Catalysts for Selective Catalytic Reduction of NO_x with NH₃: Structure-properties Relationships^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 11

References 35

Related Articles 15

Recommended Articles

Metrics

Comments