Please wait a minute...

Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2017, Vol. 11 Issue (2) : 6
Promotion of transition metal oxides on the NH3-SCR performance of ZrO2-CeO2 catalyst
Weiman Li1,2,3,Haidi Liu1,3,Yunfa Chen1,3()
1. State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
2. University of Chinese Academy of Sciences, Beijing 100049, China
3. Center for Excellence in Urban Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China
Download: PDF(371 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Manganese and chromium oxides promote the NH3-SCR activity of Zr-Ce mixed oxide.

Cr-Zr-Ce mixed oxide exhibited>80% NOx conversion at a wide temperature window.

More acid sites and higher reducibility may responsible for the high SCR ability.

Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H2 temperature-programmed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited>80% NOx conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr6+. The present mixed oxide can be a candidate for the low temperature abatement of NOx.

Keywords NH3-selective catalytic reduction      NOx      Low temperature      Cr-Zr-Ce     
Corresponding Author(s): Yunfa Chen   
Issue Date: 23 March 2017
 Cite this article:   
Weiman Li,Haidi Liu,Yunfa Chen. Promotion of transition metal oxides on the NH3-SCR performance of ZrO2-CeO2 catalyst[J]. Front. Environ. Sci. Eng., 2017, 11(2): 6.
E-mail this article
E-mail Alert
Articles by authors
Weiman Li
Haidi Liu
Yunfa Chen
Fig.1  SCR activity of different samples
Fig.2  XRD patterns of Zr-Ce, Mn-Zr-Ce, and Cr-Zr-Ce samples, respectively
Fig.3  TEM images of as-prepared (a) Zr-Ce, (b) Mn-Zr-Ce, and (c) Cr-Zr-Ce catalysts
Fig.4  N2 adsorption–desorption isotherms curves and (inset) pore size distributions calculated from the desorption branch of as-synthesized catalysts
sample specific surface/(m2·g−1) average pore size/nm BJH pore volume /(mL·g−1) Ce3+/(Ce3+ + Ce4+)/% Oβ/(Oα + Oβ)/%
Zr-Ce 76.53 5.87 0.091 13.7 33.9
Mn-Zr-Ce 109.64 9.81 0.25 15.3 48.9
Cr-Zr-Ce 168.95 7.14 0.31 15.8 53.6
Tab.1  BET results and XPS surface atomic ratios of different samples
Fig.5  H2-TPR analysis of three samples
Fig.6  (a) Cr 2p and Mn 2p XPS spectra of Cr-Zr-Ce and Mn-Zr-Ce sample, respectively; (b) Zr 3d XPS spectra of different samples; (c) O 1s XPS spectra of different samples; (d) Ce 3d XPS spectra of different samples
Fig.7  In situ DRIFT spectras of three catalysts in (a) NH3 + air, (b) NO+ air, and (c) NH3 + NO+ air flow, respectively
30 Chen L, Si Z, Wu X, Weng D. DRIFT study of CuO-CeO2-TiO2 mixed oxides for NOx reduction with NH3 at low temperatures. ACS Applied Materials & Interfaces, 2014, 6(11): 8134–8145 pmid: 24848157
31 Liu Z, Zhu J, Li J, Ma L, Woo S I. Novel Mn-Ce-Ti mixed-oxide catalyst for the selective catalytic reduction of NOx with NH3. ACS Applied Materials & Interfaces, 2014, 6(16): 14500–14508 pmid: 25046245
32 Xu W Q, He H, Yu Y. Deactivation of a Ce/TiO2 catalyst by SO2 in the selective catalytic reducti on of NO by NH3. Journal of Physical Chemistry C, 2009, 113(11): 4426–4432
33 Li J, Peng Y, Chang H, Li X, Crittenden J C, Hao J. Chemical poison and regeneration of SCR catalysts for NOx removal from stationary sources. Frontiers of Environmental Science & Engineering, 2016, 10(3): 413–427
1 Busca G, Lietti L, Ramis G, Berti F. 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
2 Qi G, Yang R T. A superior catalyst for low-temperature NO reduction with NH3. Chemical Communications (Cambridge, England), 2003, 34(7): 848–849 pmid: 12739642
3 Li P, Xin Y, Li Q, Wang Z, Zhang Z, Zheng L. Ce-Ti amorphous oxides for selective catalytic reduction of NO with NH3: confirmation of Ce-O-Ti active sites. Environmental Science & Technology, 2012, 46(17): 9600–9605 pmid: 22888951
4 Liu H D, Wei L Q, Yue R L, Chen Y F. CrOx–CeO2 binary oxide as a superior catalyst for NO reduction with NH3 at low temperature in presence of CO. Catalysis Communications, 2010, 11(9): 829–833
5 Liu H D, Li W M. Huang Y P, Chen Y F. Reaction mechanism of NH3-selective catalytic reduction for NO on CrOx-CeO2 binary oxide. Wuji Huaxue Xuebao, 2013, 29(11): 2399–2404 (in Chinese)
6 Jiang B, Deng B, Zhang Z, Wu Z, Tang X, Yao S, Lu H. Effect of Zr addition on the low-temperature SCR activity and SO2 tolerance of Fe–Mn/Ti catalysts. Journal of Physical Chemistry C, 2014, 118(27): 14866–14875
7 Li Y, Cheng H, Li D, Qin Y, Xie Y, Wang S. WO3/CeO2-ZrO2, a promising catalyst for selective catalytic reduction (SCR) of NOx with NH3 in diesel exhaust. Chemical communications (Cambridge, England), 2008, (12): 1470–1472 pmid: 18338059
8 Liu Z, Su H, Li J, Li Y. Novel MoO3/CeO2-ZrO2 catalyst for the selective catalytic reduction of NOx by NH3. Catalysis Communications, 2015, 65: 51–54
9 Hori C E, Permana H, Ng Y K, Brenner A, More K, Rahmoeller K M, Belton D. Thermal stability of oxygen storage properties in a mixed CeO2-ZrO2 system. Applied Catalysis B: Environmental, 1998, 16(2): 105–117
10 Yashima M, Sekikawa T, Sato D, Nakano H, Omoto K. Crystal structure and oxide-ion diffusion of nanocrystalline, compositionally homogeneous ceria–zirconia Ce0.5Zr0.5O2 up to 1176 K. Crystal Growth & Design, 2013, 13(2): 829–837
11 Yu X, Li J, Wei Y, Zhao Z, Liu J, Jin B, Duan A, Jiang G. Three-dimensionally ordered macroporous MnxCe1–xOd and Pt/Mn0.5Ce0.5Od catalysts: synthesis and catalytic performance for soot oxidation. Industrial & Engineering Chemistry Research, 2014, 53(23): 9653–9664
12 Liu Z, Yi Y, Li J, Woo S I, Wang B, Cao X, Li Z. A superior catalyst with dual redox cycles for the selective reduction of NO(x) by ammonia. Chemical communications (Cambridge, England), 2013, 49(70): 7726–7728 pmid: 23877875
13 Christou S Y, Alvearez-Galvan M C, Fierro J L G, Efstathiou A M. Suppression of the oxygen storage and release kinetics in Ce0.5Zr0.5O2 induced by P, Ca and Zn chemical poisoning. Applied Catalysis B: Environmental, 2011, 106(1–2): 103–113
14 Chen Z H, Yang Q, Li H, Li X, Wang L, Chi Tsang S. Cr-MnOx mixed-oxide catalysts for selective catalytic reduction of NOx with NH3 at low temperature. Journal of Catalysis, 2010, 276(1): 56–65
15 Zhang L, Shi L, Huang L, Zhang J, Gao R, Zhang D. Rational design of high-performance De NOx catalysts based on MnxCo3–xO4 nanocages derived from metal–organic frameworks. ACS Catalysis, 2014, 4(6): 1753–1763
16 Liu B, Liu Y, Li C, Hu W, Jing P, Wang Q, Zhang J. Three-dimensionally ordered macroporous Au/CeO2-Co3O4 catalysts with nanoporous walls for enhanced catalytic oxidation of formaldehyde. Applied Catalysis B: Environmental, 2012, 127: 47–58
17 Rahman A, Mohamed M H, Ahmed M, Aitani A M. Characterization of chromia/alumina catalysts by X-ray photoelectron spectroscopy, proton induced X-ray emission and thermogravimetric analysis. Applied Catalysis A, General, 1995, 121(2): 203–216
18 Cai W, Zhong Q, Ding J, Bu Y. Solvent effects during the synthesis of Cr/Ce0.2Zr0.8O2 catalysts and their activities in NO oxidation. Chemical Engineering Journal, 2015, 270: 1–8
19 Tang W X, Wu X, Li D, Wang Z, Liu G, Liu H, Chen Y. Oxalate route for promoting activity of manganese oxide catalysts in total VOCs’ oxidation: effect of calcination temperature and preparation method. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2014, 2(8): 2544–2554
20 Kapteijn F, Singoredjo L, Andreini A, Moulijn J A. Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia. Applied Catalysis B: Environmental, 1994, 3(2–3): 173–189
21 Cai S, Zhang D, Zhang L, Huang L, Li H, Gao R, Shi L, Zhang J. Comparative study of 3D ordered macroporous Ce0.75Zr0.2M0.05O2-delta (M= Fe, Cu, Mn, Co) for selective catalytic reduction of NO with NH3. Catalysis Science & Technology, 2014, 4(1): 93–101
22 Putla S, Amin M H, Reddy B M, Nafady A, Al Farhan K A, Bhargava S K. MnO(x) nanoparticle-dispersed CeO2 nanocubes: a remarkable heteronanostructured system with unusual structural characteristics and superior catalytic performance. ACS Applied Materials & Interfaces, 2015, 7(30): 16525–16535 pmid: 26214855
23 Dall’Acqua L, Nova I, Lietti L, Ramis G, Busca G, Giamello E. Spectroscopic characterisation of MoO3/TiO2 deNOx-SCR catalysts: redox and coordination properties. Physical Chemistry Chemical Physics, 2000, 2(21): 4991–4998
24 Kijlstra W S, Daamen J C M L, van de Graaf J M, van der Linden B, Poels E K, Bliek A. Inhibiting and deactivating effects of water on the selective catalytic reduction of nitric oxide with ammonia over MnOx/Al2O3. Applied Catalysis B: Environmental, 1996, 7(3–4): 337–357
25 Casapu M, Kröcher O, Mehring M, Nachtegaal M, Borca C, Harfouche M, Grolimund D. Characterization of Nb-containing MnOx–CeO2 catalyst for low-temperature selective catalytic reduction of NO with NH3. Journal of Physical Chemistry C, 2010, 114(21): 9791–9801
26 Peng Y, Li K, Li J. Identification of the active sites on CeO2–WO3 catalysts for SCR of NOx with NH3: an in situ IR and Raman spectroscopy study. Applied Catalysis B: Environmental, 2013, 140– 141: 483–492
27 Underwood G M, Miller T M, Grassian V H. Transmission FT-IR and Knudsen cell study of the heterogeneous reactivity of gaseous nitrogen dioxide on mineral oxide particles. Journal of Physical Chemistry A, 1999, 103(31): 6184–6190
28 Liu Z, Zhu J, Li J, Ma L, Woo S I. Novel Mn-Ce-Ti mixed-oxide catalyst for the selective catalytic reduction of NOx with NH3. ACS Applied Materials & Interfaces, 2014, 6(16): 14500–14508 pmid: 25046245
29 Machida M, Uto M, Kurogi D, Kijima T. Solid-gas interaction of nitrogen oxide adsorbed on MnOx-CeO2: a DRIFTS study. Journal of Materials Chemistry, 2001, 11(3): 900–904
[1] FSE-17011-OF-LWM_suppl_1 Download
Related articles from Frontiers Journals
[1] Rencheng Zhu, Jingnan Hu, Liqiang He, Lei Zu, Xiaofeng Bao, Yitu Lai, Sheng Su. Effects of ambient temperature on regulated gaseous and particulate emissions from gasoline-, E10- and M15-fueled vehicles[J]. Front. Environ. Sci. Eng., 2021, 15(1): 14-.
[2] Quanming Liang, Jian Li, Hong He, Wenjun Liang, Tiejun Zhang, Xing Fan. Effects of SO2 on the low temperature selective catalytic reduction of NO by NH3 over CeO2-V2O5-WO3/TiO2 catalysts[J]. Front. Environ. Sci. Eng., 2017, 11(4): 4-.
[3] Tiejun Zhang, Jian Li, Hong He, Qianqian Song, Quanming Liang. NO oxidation over Co-La catalysts and NOx reduction in compact SCR[J]. Front. Environ. Sci. Eng., 2017, 11(2): 4-.
[4] Christian GEORGE, Anne BEELDENS, Fotios BARMPAS, Jean-François DOUSSIN, Giuseppe MANGANELLI, Hartmut HERRMANN, Jörg KLEFFMANN, Abdelwahid MELLOUKI. Impact of photocatalytic remediation of pollutants on urban air quality[J]. Front. Environ. Sci. Eng., 2016, 10(5): 2-.
[5] Di CUI,Ang LI,Tian QIU,Rui CAI,Changlong PANG,Jihua WANG,Jixian YANG,Fang MA,Nanqi REN. Improvement of nitrification efficiency by bioaugmentation in sequencing batch reactors at low temperature[J]. Front. Environ. Sci. Eng., 2014, 8(6): 937-944.
[6] Caiting LI, Qun LI, Pei LU, Huafei CUI, Guangming ZENG. Characterization and performance of V2O5/CeO2 for NH3-SCR of NO at low temperatures[J]. Front Envir Sci Eng, 2012, 6(2): 156-161.
Full text