Please wait a minute...
Shopping Cart Email List Chinese
Advanced Search Fig/Tab
Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

Postal Subscription Code 80-974

2018 Impact Factor: 1.701

Featured Articles  |  Most Downloaded  |  Most Reading
Online Submission Subscribe to Our RSS Content Feed
Front. Mater. Sci.    2016, Vol. 10 Issue (2) : 211-223    https://doi.org/10.1007/s11706-016-0331-2
RESEARCH ARTICLE
Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1--<?Pub Caret?>x/TiO2
Xujuan CHEN1,Xiaoliang SUN1,Cairong GONG1,*(),Gang LV2,Chonglin SONG2
1. School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
2. State Key Laboratory of Engines, Tianjin University, Tianjin 300072, China
 Download: PDF(1755 KB)   HTML
 Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

Copper--cerium--zirconium catalysts loaded on TiO2 prepared by a wet impregnation method were investigated for NH3-selective catalytic reduction (SCR) of NOx. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Br?nsted acid sites are more important than Lewis acid sites at low temperature. For the NH3+NO+O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH4+ (at low temperature) and NH3 coordinated (at high temperature), playing a crucial role in the NH3-SCR process. Two different reaction routes, the L-H mechanism at low temperature (<200°C) and the E-R mechanism at high temperature (>200°C), are presented for the SCR reaction over CuCe0.25Zr0.75/TiO2 catalyst.
Keywords CuCe0.25Zr0.75/TiO2      catalyst      selective catalytic reduction (SCR)      diffuse reflectance infrared transform spectroscopy (DRIFT)      reaction mechanism     
Corresponding Author(s): Cairong GONG   
Issue Date: 11 May 2016
 Cite this article:   
Xujuan CHEN,Xiaoliang SUN,Cairong GONG, et al. Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1--<?Pub Caret?>x/TiO2[J]. Front. Mater. Sci., 2016, 10(2): 211-223.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-016-0331-2
https://academic.hep.com.cn/foms/EN/Y2016/V10/I2/211
Fig.1  NH3-TPD curves of CuCexZr1-x/TiO2 catalysts.
Fig.2  NO-TPD curves of CuCexZr1-x/TiO2 catalysts.
Fig.3  DRIFT spectra of the CuCe0.25Zr0.75/TiO2 catalyst arising from NH3 adsorption at 50°C (a), 150°C (b), 200°C (c), 250°C (d), 300°C (e), 350°C (f), and 400°C (g).
Fig.4  DRIFT spectra of the CuCe0.25Zr0.75/TiO2 catalyst arising from the NO+O2 co-adsorption at 50°C (a), 150°C (b), 200°C (c), 250°C (d), 300°C (e), 350°C (f), and 400°C (g).
Fig.5  DRIFT spectra of the CuCe0.25Zr0.75/TiO2 catalyst pre-treated by exposure to NH3 followed by exposure to NO+O2 at (a) 170°C and (b) 375°C for various time.
Fig.6  DRIFT spectra of the CuCe0.25Zr0.75/TiO2 catalyst pre-treated by exposure to NO+O2 followed by exposure to NH3 at (a) 170°C and (b) 375°C for various time.
Fig.7  DRIFT spectra of the CuCe0.25Zr0.75/Ti catalyst arising from the NH3+NO+O2 co-adsorption at 50°C (a), 100°C (b), 150°C (c), 200°C (d), 250°C (e), 300°C (f), 350°C (g), and 400°C (h).
Fig.1  Catalytic activities for the NOx reduction by NH3 on CuCexZr1-x/TiO2 catalysts.
Fig.2  The yield of N2O as a function of reaction temperature for CuCexZr1-x/TiO2 catalysts.
Fig.1  

(a) The stability and effects of (b) SO2 and (c) H2O on the SCR of NOx with NH3 over CuCe0.25Zr0.75/TiO2 catalyst.

<?Pub Caret?>
Fig.1  TEM images and EDX analyses for the Cu/TiO2 catalyst and the CuCe0.25Zr0.75/TiO2 catalyst.
1 Johnson T V. Review of diesel emissions and control. International Journal of Engine Research, 2009, 10(5): 275–285
2 Nakajima F, Hamada I. The state-of-the-art technology of NOx control. Catalysis Today, 1996, 29(1–4): 109–115
3 Lietti L, Forzatti P, Bregani F. Steady-state and transient reactivity study of TiO2-supported V2O5–WO3 De–NOx catalysts: Relevance of the vanadium–tungsten interaction on the catalytic activity. Industrial & Engineering Chemistry Research, 1996, 35(11): 3884–3892
4 Casagrande L, Lietti L, Nova I, . SCR of NO by NH3 over TiO2-supported V2O5–MoO3 catalysts: reactivity and redox behavior. Applied Catalysis B: Environmental, 1999, 22(1): 63–77
5 Zhang R, Teoh W Y, Amal R, . Catalytic reduction of NO by CO over Cu/CexZr1-xO2 prepared by flame synthesis. Journal of Catalysis, 2010, 272(2): 210–219
6 Fedeyko J M, Chen B, Chen H Y. Mechanistic study of the low temperature activity of transition metal exchanged zeolite SCR catalysts. Catalysis Today, 2010, 151(3–4): 231–236
7 Centi G, Nigro C, Perathoner S, . Role of the support and of adsorbed species on the behavior of Cu-based catalysts for NO conversion. Catalysis Today, 1993, 17(1–2): 159–166
8 Centi G, Perathoner S. Adsorption and reactivity of NO on copper-on-alumina catalysts: II. Adsorbed species and competitive pathways in the reaction of NO with NH3 and O2. Journal of Catalysis, 1995, 152(1): 93–102
9 Komatsu T, Ogawa T, Yashima T. Nitrate species on Cu-ZSM-5 catalyst as an intermediate for the reduction of nitric oxide with ammonia. Journal of Physical Chemistry, 1995, 99(35): 13053–13055
10 Kwon D W, Nam K B, Hong S C. The role of ceria on the activity and SO2 resistance of catalysts for the selective catalytic reduction of NOx by NH3. Applied Catalysis B: Environmental, 2015, 166–167: 37–44
11 Xu W, Yu Y, Zhang C, . Selective catalytic reduction of NO by NH3 over a Ce/TiO2 catalyst. Catalysis Communications, 2008, 9(6): 1453–1457
12 Shen Y, Zhu S, Qiu T, . A novel catalyst of CeO2/Al2O3 for selective catalytic reduction of NO by NH3. Catalysis Communications, 2009, 11(1): 20–23
13 Chen L, Li J, Ge M, . Enhanced activity of tungsten modified CeO2/TiO2 for selective catalytic reduction of NOx with ammonia. Catalysis Today, 2010, 153(3–4): 77–83
14 Gao X, Du X, Cui L, . A Ce–Cu–Ti oxide catalyst for the selective catalytic reduction of NO with NH3. Catalysis Communications, 2010, 12(4): 255–258
15 Cheng K, Liu J, Zhang T, . Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5–WO3/CeO2–TiO2 catalyst. Journal of Environmental Sciences, 2014, 26(10): 2106–2113
16 Liu K, Liu F, Xie L, . DRIFTS study of a Ce-W mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. Catalysis Science & Technology, 2015, 5(4): 2290–2299
17 Pang L, Fan C, Shao L, . The Ce doping Cu/ZSM-5 as a new superior catalyst to remove NO from diesel engine exhaust. Chemical Engineering Journal, 2014, 253: 394–401
18 Dou B, Lv G, Wang C, . Cerium doped copper/ZSM-5 catalysts used for the selective catalytic reduction of nitrogen oxide with ammonia. Chemical Engineering Journal, 2015, 270: 549–556
19 Thevenin P O, Alcalde A, Pettersson L J, . Catalytic combustion of methane over cerium-doped palladium catalysts. Journal of Catalysis, 2003, 215(1): 78–86
20 Bin F, Song C, Lv G, . Selective catalytic reduction of nitric oxide with ammonia over zirconium-doped copper/ZSM-5 catalysts. Applied Catalysis B: Environmental, 2014, 150–151: 532–543
21 Topsøe N Y. Characterization of the nature of surface sites on vanadia–titania catalysts by FTIR. Journal of Catalysis, 1991, 128(2): 499–511
22 Topsøe N Y. Mechanism of the selective catalytic reduction of nitric oxide by ammonia elucidated by in situ on-line Fourier transform infrared spectroscopy. Science, 1994, 265(5176): 1217–1219
23 Topsøe N Y, Topsoe H, Dumesic J A. Vanadia/titania catalysts for selective catalytic reduction (SCR) of nitric-oxide by ammonia: I. Combined temperature-programmed in-situ FTIR and on-line mass-spectroscopy studies. Journal of Catalysis, 1995, 151(1): 226–240
24 Topsøe N Y, Dumesic J A, Topsoe H. Vanadia–titania catalysts for selective catalytic reduction of nitric-oxide by ammonia: II. Studies of active sites and formulation of catalytic cycles. Journal of Catalysis, 1995, 151(1): 241–252
25 Chen T, Guan B, Lin H, . In situ DRIFTS study of the mechanism of low temperature selective catalytic reduction over manganese–iron oxides. Chinese Journal of Catalysis, 2014, 35(3): 294–301
26 Ramis G, Busca G, Bregani F, . Fourier transform-infrared study of the adsorption and coadsorption of nitric oxide, nitrogen dioxide and ammonia on vanadia–titania and mechanism of selective catalytic reduction. Applied Catalysis, 1990, 64: 259–278
27 Lietti L, Svachula J, Forzatti P, . Surface and catalytic properties of vanadia–titania and tungsta–titania systems in the selective catalytic reduction of nitrogen oxides. Catalysis Today, 1993, 17(1–2): 131–139
28 Kijlstra W S, Brands D S, Smit H I, . Mechanism of the selective catalytic reduction of NO with NH3 over MnOx/Al2O3. Journal of Catalysis, 1997, 171(1): 219–230
29 Qi G, Yang R T. Characterization and FTIR studies of MnOx–CeO2 catalyst for low-temperature selective catalytic reduction of NO with NH3. Journal of Physical Chemistry B, 2004, 108(40): 15738–15747
30 Pena D A, Uphade B S, Reddy E P, . Identification of surface species on titania-supported manganese, chromium, and copper oxide low-temperature SCR catalysts. Journal of Physical Chemistry B, 2004, 108(28): 9927–9936
31 Li Q, Gu H, Li P, . In situ IR studies of selective catalytic reduction of NO with NH3 on Ce–Ti amorphous oxides. Chinese Journal of Catalysis, 2014, 35(8): 1289–1298
32 Sun X, Gong C, Lv G, . Effect of Ce/Zr molar ratio on the performance of Cu–Cex–Zr1-x/TiO2 catalyst for selective catalytic reduction of NOx with NH3 in diesel exhaust. Materials Research Bulletin, 2014, 60: 341–347
33 Busca G, Lietti L, Ramis G, . Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts: A review. Applied Catalysis B: Environmental, 1998, 18(1–2): 1–36
34 Chmielarz L, Kuśtrowski P, Zbroja M, . SCR of NO by NH3 on alumina or titania pillared montmorillonite modified with Cu or Co: Part II. Temperature programmed studies. Applied Catalysis B: Environmental, 2004, 53(1): 47–61
35 Pena D A, Uphade B S, Smirniotis P G. TiO2 supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH3: I. Evaluation and characterization of first row transition metals. Journal of Catalysis, 2004, 221(2): 421–431
36 Si Z, Weng D, Wu X, . Modifications of CeO2–ZrO2 solid solutions by nickel and sulfate as catalysts for NO reduction with ammonia in excess O2. Catalysis Communications, 2010, 11(13): 1045–1048
37 Li J, Hao J, Fu L, . The activity and characterization of sol–gel Sn/Al2O3 catalyst for selective catalytic reduction of NOx in the presence of oxygen. Catalysis Today, 2004, 90(3–4): 215–221
38 Li J, Zhu Y, Ke R, . Improvement of catalytic activity and sulfur-resistance of Ag/TiO2–Al2O3 for NO reduction with propene under lean burn conditions. Applied Catalysis B: Environmental, 2008, 80(3–4): 202–213
39 Shimizu K I, Satsuma A, Hattori T. Selective catalytic reduction of NO by hydrocarbons on Ga2O3/Al2O3 catalysts. Applied Catalysis B: Environmental, 1998, 16(4): 319–326
40 Larrubia M A, Ramis G, Busca G. An FT-IR study of the adsorption of urea and ammonia over V2O5–MoO3–TiO2 SCR catalysts. Applied Catalysis B: Environmental, 2000, 27(3): L145–L151
41 Ramis G, Yi L, Busca G. Ammonia activation over catalysts for the selective catalytic reduction of NOx and the selective catalytic oxidation of NH3. An FT-IR study. Catalysis Today, 1996, 28(4): 373–380
42 Yang X, Zhao B, Zhuo Y, . DRIFTS study of ammonia activation over CaO and sulfated CaO for NO reduction by NH3. Environmental Science & Technology, 2011, 45(3): 1147–1151
43 Lin C H, Bai H. Surface acidity over vanadia/titania catalyst in the selective catalytic reduction for NO removal - in situ DRIFTS study. Applied Catalysis B: Environmental, 2003, 42(3): 279–287
44 Centeno M, Carrizosa I, Odriozola J. In situ DRIFTS study of the SCR reaction of NO with NH3 in the presence of O2 over lanthanide doped V2O5/Al2O3 catalysts. Applied Catalysis B: Environmental, 1998, 19(1): 67–73
45 Xu W, He H, Yu Y. Deactivation of a Ce/TiO2 catalyst by SO2 in the selective catalytic reduction of NO by NH3. Journal of Physical Chemistry C, 2009, 113(11): 4426–4432
46 Ramis G, Busca G, Lorenzelli V, . Fourier transform infrared study of the adsorption and coadsorption of nitric oxide, nitrogen dioxide and ammonia on TiO2 anatase. Applied Catalysis, 1990, 64(0): 243–257
47 Ramis G, Angeles Larrubia M. An FT-IR study of the adsorption and oxidation of N-containing compounds over Fe2O3/Al2O3 SCR catalysts. Journal of Molecular Catalysis A Chemical, 2004, 215(1–2): 161–167
48 Chen L, Li J, Ge M. DRIFT study on cerium-tungsten/titania catalyst for selective catalytic reduction of NOx with NH3. Environmental Science & Technology, 2010, 44(24): 9590–9596
49 Lin S D, Gluhoi A C, Nieuwenhuys B E. Ammonia oxidation over Au/MOx/γ-Al2O3-activity, selectivity and FTIR measurements. Catalysis Today, 2004, 90(1–2): 3–14
50 Wang J, Yan Z, Liu L, . In situ DRIFTS investigation on the SCR of NO with NH3 over V2O5 catalyst supported by activated semi-coke. Applied Surface Science, 2014, 313: 660–669
51 Hadjiivanov K, Knözinger H. Species formed after NO adsorption and NO+ O2 co-adsorption on TiO2: an FTIR spectroscopic study. Physical Chemistry Chemical Physics, 2000, 2(12): 2803–2806
52 Martínez-Arias A, Soria J, Conesa J C, . NO reaction at surface oxygen vacancies generated in cerium oxide. Journal of the Chemical Society, Faraday Transactions, 1995, 91(11): 1679–1687
53 Shan W, Liu F, He H, . A superior Ce–W–Ti mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. Applied Catalysis B: Environmental, 2012, 115–116: 100–106
54 Cao F, Su S, Xiang J, . The activity and mechanism study of Fe–Mn–Ce/γ-Al2O3 catalyst for low temperature selective catalytic reduction of NO with NH3. Fuel, 2015, 139: 232–239
55 Liu F, He H. Selective catalytic reduction of NO with NH3 over manganese substituted iron titanate catalyst: Reaction mechanism and H2O/SO2 inhibition mechanism study. Catalysis Today, 2010, 153(3–4): 70–76
56 Richter M, Trunschke A, Bentrup U, . Selective catalytic reduction of nitric oxide by ammonia over egg-shell MnOx/NaY composite catalysts. Journal of Catalysis, 2002, 206(1): 98–113
57 Salker A V, Weisweiler W. Catalytic behaviour of metal based ZSM-5 catalysts for NOx reduction with NH3 in dry and humid conditions. Applied Catalysis A: General, 2000, 203(2): 221–229
58 Gilardoni F, Weber J, Baiker A. Mechanism of the vanadium oxide-catalyzed selective reduction of NO by NH3. A quantum chemical modeling. Journal of Physical Chemistry A, 1997, 101(34): 6069–6076
59 Koebel M, Elsener M, Madia G. Reaction pathways in the selective catalytic reduction process with NO and NO2 at low temperatures. Industrial & Engineering Chemistry Research, 2001, 40(1): 52–59
60 Gao X, Liu S, Zhang Y, . Low temperature selective catalytic reduction of NO and NO2 with NH3 over activated carbon-supported vanadium oxide catalyst. Catalysis Today, 2011, 175(1): 164–170
61 Devadas M, Kröcher O, Elsener M, . Influence of NO2 on the selective catalytic reduction of NO with ammonia over Fe-ZSM5. Applied Catalysis B: Environmental, 2006, 67(3–4): 187–196
62 Liu F, He H, Zhang C, . Mechanism of the selective catalytic reduction of NOx with NH3 over environmental-friendly iron titanate catalyst. Catalysis Today, 2011, 175(1): 18–25
63 Eigenmann F, Maciejewski M, Baiker A. Selective reduction of NO by NH3 over manganese–cerium mixed oxides: Relation between adsorption, redox and catalytic behavior. Applied Catalysis B: Environmental, 2006, 62(3–4): 311–318
[1] Jingze ZHANG, Sheng ZHU, Yulin MIN, Qunjie XU. Mn-doped perovskite-type oxide LaFeO3 as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions[J]. Front. Mater. Sci., 2020, 14(4): 459-468.
[2] Elias ASSAYEHEGN, Ananthakumar SOLAIAPPAN, Yonas CHEBUDIE, Esayas ALEMAYEHU. Influence of temperature on preparing mesoporous mixed phase N/TiO2 nanocomposite with enhanced solar light photocatalytic activity[J]. Front. Mater. Sci., 2019, 13(4): 352-366.
[3] Vijaya KUMARI, Anuj MITTAL, Jitender JINDAL, Suprabha YADAV, Naveen KUMAR. S-, N- and C-doped ZnO as semiconductor photocatalysts: A review[J]. Front. Mater. Sci., 2019, 13(1): 1-22.
[4] Palepu Teja RAVINDAR, Vidya Sagar CHOPPELLA, Anil Kumar MOKSHAGUNDAM, M. KIRUBA, Sunil G. BABU, Korupolu Raghu BABU, L. John BERCHMANS, Gosipathala SREEDHAR. Enhanced visible-light-driven photocatalysis of Bi2YO4Cl heterostructures functionallized by bimetallic RhNi nanoparticles[J]. Front. Mater. Sci., 2018, 12(4): 405-414.
[5] M. Mohamed Jaffer SADIQ, U. Sandhya SHENOY, D. Krishna BHAT. Synthesis of BaWO4/NRGO‒g-C3N4 nanocomposites with excellent multifunctional catalytic performance via microwave approach[J]. Front. Mater. Sci., 2018, 12(3): 247-263.
[6] Huan-Yan XU, Yuan WANG, Tian-Nuo SHI, Hang ZHAO, Qu TAN, Bo-Chao ZHAO, Xiu-Lan HE, Shu-Yan QI. Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: combination mechanism and affecting parameters[J]. Front. Mater. Sci., 2018, 12(1): 21-33.
[7] Jin ZHANG, Li-Li PENG, Ying TANG, Huijie WU. Convenient synthesis of twin-Christmas tree-like PbWO4 microcrystals and their photocatalytic properties[J]. Front. Mater. Sci., 2017, 11(2): 139-146.
[8] V. CHELLASAMY, P. THANGADURAI. Structural and electrochemical investigations of nanostructured NiTiO3 in acidic environment[J]. Front. Mater. Sci., 2017, 11(2): 162-170.
[9] Qinglin SHENG, Dan ZHANG, Yu SHEN, Jianbin ZHENG. Synthesis of hollow Prussian blue cubes as an electrocatalyst for the reduction of hydrogen peroxide[J]. Front. Mater. Sci., 2017, 11(2): 147-154.
[10] Hang ZHAO,Ling WENG,Wei-Wei CUI,Xiao-Rui ZHANG,Huan-Yan XU,Li-Zhu LIU. In situ anchor of magnetic Fe3O4 nanoparticles onto natural maifanite as efficient heterogeneous Fenton-like catalyst[J]. Front. Mater. Sci., 2016, 10(3): 300-309.
[11] Huan-Yan XU,Tian-Nuo SHI,Hang ZHAO,Li-Guo JIN,Feng-Chun WANG,Chun-Yan WANG,Shu-Yan QI. Heterogeneous Fenton-like discoloration of methyl orange using Fe3O4/MWCNTs as catalyst: process optimization by response surface methodology[J]. Front. Mater. Sci., 2016, 10(1): 45-55.
[12] Jin WANG,Tomoya HIGASHIHARA. Effects of catalyst loading amount on the synthesis of poly(3-hexylthiophene) via externally initiated Kumada catalyst-transfer polycondensation[J]. Front. Mater. Sci., 2014, 8(4): 383-390.
[13] He FENG, Ping-Zhan SI, Xiao-Fei XIAO, Chen-Hao JIN, Sen-Jiang YU, Zheng-Fa LI, Hong-Liang GE. Large scale synthesis of FeS coated Fe nanoparticles as reusable magnetic photocatalysts[J]. Front Mater Sci, 2013, 7(3): 308-311.
[14] Hong LIN, Ye ZHANG, Gang WANG, Jian-Bao LI. Cobalt-based layered double hydroxides as oxygen evolving electrocatalysts in neutral eletrolyte[J]. Front Mater Sci, 2012, 6(2): 142-148.
[15] LI Zai-feng, LI Jin-yan, YUAN Wei, SUN Bao-qun, ZHANG Fu-tao, WANG Zeng-lin. Investigation of effects of dibutyltin dilaurate on reaction injection molding polyurethane-urea kinetics, morphology and mechanical properties by FTIR[J]. Front. Mater. Sci., 2008, 2(1): 99-104.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed