Metal-organic framework loaded manganese oxides as efficient catalysts for low-temperature selective catalytic reduction of NO with NH<sub>3</sub>

doi:10.1007/s11705-017-1668-5

Front. Chem. Sci. Eng.

2017, Vol. 11

Issue (4) : 594-602 https://doi.org/10.1007/s11705-017-1668-5

RESEARCH ARTICLE

Metal-organic framework loaded manganese oxides as efficient catalysts for low-temperature selective catalytic reduction of NO with NH₃

Minhua Zhang^1,², Baojuan Huang^1,², Haoxi Jiang^1,², Yifei Chen^1,²(

)

¹. Key Laboratory for Green Chemical Technology of Ministry of Education, R&D Center for Petrochemical Technology, Tianjin University, Tianjin 300072, China
². Collaborative Innovation Center of Chemical Science and Engineering, Tianjin 300072, China

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Abstract

A mild in-situdeposition method was used to fabricate Mn-based catalysts on a UiO-66 carrier for the selective catalytic reduction of NO by NH₃ (NH₃-SCR). The catalyst with 8.5 wt-% MnO_x loading had the highest catalytic activity for NH₃-SCR with a wide temperature window (100–290 °C) for 90% NO conversion. Characterization of the prepared MnO_x/UiO-66 catalysts showed that the catalysts had the crystal structure and porosity of the UiO-66 carrier and that the manganese particles were well-distributed on the surface of the catalyst. X-ray photoelectron spectroscopy analysis showed that there are strong interactions between the MnO_x and the Zr oxide secondary building units of the UiO-66 which has a positive effect on the catalytic activity. The 8.5 wt-% MnO_x catalyst maintained excellent activity during a 24-h stability test and exhibited good resistance to SO₂ poisoning.

Keywords metal-organic framework selective catalytic reduction manganese oxides deNO_x SO₂ resistance

Corresponding Author(s): Yifei Chen

Just Accepted Date: 19 June 2017 Online First Date: 26 September 2017 Issue Date: 06 November 2017

Cite this article:

Minhua Zhang,Baojuan Huang,Haoxi Jiang, et al. Metal-organic framework loaded manganese oxides as efficient catalysts for low-temperature selective catalytic reduction of NO with NH₃[J]. Front. Chem. Sci. Eng., 2017, 11(4): 594-602.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-017-1668-5
https://academic.hep.com.cn/fcse/EN/Y2017/V11/I4/594

Fig.1 SCR activity of MnO_x/UiO-66 catalysts. Reaction conditions: 500 ppm NO, 500 ppm NH₃, 5.0 vol-% O₂, Ar to balance, gas flow rate=100 mL?min^?¹, GHSV= 50000 h^?¹, 50?310 °C

Fig.2 XRD patterns of UiO-66, MnO_x/UiO-66-DP and MnO_x/UiO-66-MM

Tab.1 Mn content and physical parameters of the MnO_x/UiO-66 catalysts

Fig.3 SEM images of catalysts: (a) UiO-66; (b,c) 8.5 wt-%-MnO_x/UiO-66-DP; and (d) MnO_x/UiO-66-MM

Fig.4 (a) TEM image; (b) high-angle annular dark field (HAADF) image and (c?f) element distributions of 8.5 wt-%-MnO_x/UiO-66-DP catalyst

Fig.5 XPS spectra of (a) Zr, (b) Mn and (c) O for the different catalysts

Tab.2 Surface atomic concentrations for the different catalysts

Fig.6 The stability tests at 200 °C over the 8.5 wt-%-MnO_x/UiO-66-DP catalyst. Reaction conditions: 500 ppm NO, 500 ppm NH₃, 5.0 vol-% O₂, 100 ppm SO₂ (when used), 5 vol-% H₂O (when used), and Ar balance

Fig.7 XRD patterns of the 8.5 wt-%-MnO_x/UiO-66-DP catalyst after use with SO₂, H₂O and SO₂+H₂O and durability test for 24 h

Tab.3 Physical properties of 8.5 wt-%-MnO_x/UiO-66-DP catalyst after activity tests at 200 °C

1	Zhang Y, Zheng Y, Zou H, Zhang X. One-step synthesis of ternary MnO2-Fe2O3-CeO2-Ce2O3/CNT catalysts for use in low-temperature NO reduction with NH3. Catalysis Communications, 2015, 71: 46–50 https://doi.org/10.1016/j.catcom.2015.08.011
2	Liu C, Shi J W, Gao C, Niu C. Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NOx with NH3: A review. Applied Catalysis A, General, 2016, 522: 54–69 https://doi.org/10.1016/j.apcata.2016.04.023
3	Boningari T, Smirniotis P G. Impact of nitrogen oxides on the environment and human health: Mn-based materials for the NOx abatement. Current Opinion in Chemical Engineering, 2016, 13: 133–141 https://doi.org/10.1016/j.coche.2016.09.004
4	Li J, Chang H, Ma L, Hao J, Yang R T. Low-temperature selective catalytic reduction of NOx with NH3 over metal oxide and zeolite catalysts—A review. Catalysis Today, 2011, 175(1): 147–156 https://doi.org/10.1016/j.cattod.2011.03.034
5	Wang T, Zhu C, Liu H, Xu Y, Zou X, Xu B, Chen T. Performance of selective catalytic reduction of NO with NH3over natural manganese ore catalysts at low temperature. Environmental Technology, doi: 10.1080/09593330.2017.1300190
6	Millo F, Rafigh M, Fino D, Miceli P. Application of a global kinetic model on an SCR coated on filter (SCR-F) catalyst for automotive applications. Fuel, 2017, 198: 183–192 https://doi.org/10.1016/j.fuel.2016.11.082
7	Ma T, Takeuchi K. Technology choice for reducing NOx emissions: An empirical study of Chinese power plants. Energy Policy, 2017, 102: 362–376 https://doi.org/10.1016/j.enpol.2016.12.043
8	Liu C, Gao G, Shi J W, He C, Li G, Bai N, Niu C. MnOx-CeO2 shell-in-shell microspheres for NH3-SCR de-NOx at low temperature. Catalysis Communications, 2016, 86: 36–40 https://doi.org/10.1016/j.catcom.2016.08.003
9	Yu C, Dong L, Chen F, Liu X, Huang B. Low-temperature SCR of NOx by NH3 over MnOx/SAPO-34 prepared by two different methods: A comparative study. Environmental Technology, 2016, 38(8): 1030–1042 https://doi.org/10.1080/09593330.2016.1216170
10	Deorsola F A, Andreoli S, Armandi M, Bonelli B, Pirone R. Unsupported nanostructured Mn oxides obtained by solution combustion synthesis: Textural and surface properties, and catalytic performance in NOx SCR at low temperature. Applied Catalysis A, General, 2016, 522: 120–129 https://doi.org/10.1016/j.apcata.2016.05.002
11	Kang M, Park E D, Kim J M, Yie J E. Manganese oxide catalysts for NOx reduction with NH3 at low temperatures. Applied Catalysis A, General, 2007, 327(2): 261–269 https://doi.org/10.1016/j.apcata.2007.05.024
12	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 https://doi.org/10.1016/0926-3373(93)E0034-9
13	Yang S, Qi F, Xiong S, Dang H, Liao Y, Wong P K, Li J. MnOx supported on Fe-Ti spinel: A novel Mn based low temperature SCR catalyst with a high N2 selectivity. Applied Catalysis B: Environmental, 2016, 181: 570–580 https://doi.org/10.1016/j.apcatb.2015.08.023
14	Shen B, Zhang X, Ma H, Yao Y, Liu T. A comparative study of Mn/CeO2, Mn/ZrO2 and Mn/Ce-ZrO2 for low temperature selective catalytic reduction of NO with NH3 in the presence of SO2 and H2O. Journal of Environmental Sciences (China), 2013, 25(4): 791–800 https://doi.org/10.1016/S1001-0742(12)60109-0
15	Qiu L, Meng J, Pang D, Zhang C, Ouyang F. Reaction and characterization of Co and Ce doped Mn/TiO2 catalysts for low-temperature SCR of NO with NH3. Catalysis Letters, 2015, 145(7): 1500–1509 https://doi.org/10.1007/s10562-015-1556-x
16	Ettireddy P R, Ettireddy N, Boningari T, Pardemann R, Smirniotis P G. Investigation of the selective catalytic reduction of nitric oxide with ammonia over Mn/TiO2 catalysts through transient isotopic labeling and in situ FT-IR studies. Journal of Catalysis, 2012, 292: 53–63 https://doi.org/10.1016/j.jcat.2012.04.019
17	Smirniotis P G, Sreekanth P M, Pena D A, Jenkins R G. Manganese oxide catalysts supported on TiO2, Al2O3, and SiO2-A comparison for low-temperature SCR of NO with NH3. Industrial & Engineering Chemistry Research, 2006, 45(19): 6436–6443 https://doi.org/10.1021/ie060484t
18	Singoredjo L, Korver R, Kapteijn F, Mouhjn J. Alumina supported manganese oxides for the low-temperature selective catalytic reduction of nitic oxide with ammonia. Applied Catalysis B: Environmental, 1992, 1(4): 297–316 https://doi.org/10.1016/0926-3373(92)80055-5
19	Silva P, Vilela S M, Tome J P, Almeida Paz F A. Multifunctional metal-organic frameworks: From academia to industrial applications. Chemical Society Reviews, 2015, 44(19): 6774–6803 https://doi.org/10.1039/C5CS00307E
20	Peterson G W, Mahle J J, De Coste J B, Gordon W O, Rossin J A. Extraordinary NO2 removal by the metal-organic framework UiO-66-NH2. Angewandte Chemie International Edition in English, 2016, 55(21): 6235–6238 https://doi.org/10.1002/anie.201601782
21	Xue W, Li Z, Huang H, Yang Q, Liu D, Xu Q, Zhong C. Effects of ionic liquid dispersion in metal-organic frameworks and covalent organic frameworks on CO2 capture: A computational study. Chemical Engineering Science, 2016, 140: 1–9 https://doi.org/10.1016/j.ces.2015.10.003
22	Wang K, Li C, Liang Y, Han T, Huang H, Yang Q, Liu D, Zhong C. Rational construction of defects in a metal-organic framework for highly efficient adsorption and separation of dyes. Chemical Engineering Journal, 2016, 289: 486–493 https://doi.org/10.1016/j.cej.2016.01.019
23	Zhang H, Chen D, Ma H, Cheng P. Real-time detection of traces of benzaldehyde in benzyl alcohol as a solvent by a flexible lanthanide microporous metal-organic framework. Chemistry, 2015, 21(44): 15854–15859 https://doi.org/10.1002/chem.201502033
24	Xu H, Liu X F, Cao C S, Zhao B, Cheng P, He L N. A porous metal-organic framework assembled by [Cu30] nanocages: Serving as recyclable catalysts for CO2 fixation with aziridines. Advancement of Science, 2016, 3(11): 1600048
25	Cavka J H, Jakobsen S, Olsbye U, Guillou N, Lamberti C, Bordiga S, Lillerud K P. A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. Journal of the American Chemical Society, 2008, 130(42): 13850–13851 https://doi.org/10.1021/ja8057953
26	Liu X, Demir N K, Wu Z, Li K. Highly water-stable zirconium metal-organic framework UiO-66 membranes supported on alumina hollow fibers for desalination. Journal of the American Chemical Society, 2015, 137(22): 6999–7002 https://doi.org/10.1021/jacs.5b02276
27	Chavan S, Vitillo J G, Gianolio D, Zavorotynska O, Civalleri B, Jakobsen S, Nilsen M H, Valenzano L, Lamberti C, Lillerud K P, Bordiga S H. H2 storage in isostructural UiO-67 and UiO-66 MOFs. Physical Chemistry Chemical Physics, 2012, 14(5): 1614–1626 https://doi.org/10.1039/C1CP23434J
28	Arrozi U S F, Wijaya H W, Patah A, Permana Y. Efficient acetalization of benzaldehydes using UiO-66 and UiO-67: Substrates accessibility or Lewis acidity of zirconium. Applied Catalysis A, General, 2015, 506: 77–84 https://doi.org/10.1016/j.apcata.2015.08.028
29	Ebrahim A M, Levasseur B, Bandosz T J. Interactions of NO2 with Zr-based MOF: Effects of the size of organic linkers on NO2 adsorption at ambient conditions. Langmuir, 2013, 29(1): 168–174 https://doi.org/10.1021/la302869m
30	Ebrahim A M, Bandosz T J. Ce(III) doped Zr-based MOFs as excellent NO2 adsorbents at ambient conditions. ACS Applied Materials & Interfaces, 2013, 5(21): 10565–10573 https://doi.org/10.1021/am402305u
31	Wu H, Chua Y S, Krungleviciute V, Tyagi M, Chen P, Yildirim T, Zhou W. Unusual and highly tunable missing-linker defects in zirconium metal-organic framework UiO-66 and their important effects on gas adsorption. Journal of the American Chemical Society, 2013, 135(28): 10525–10532 https://doi.org/10.1021/ja404514r
32	Vandichel M, Hajek J, Vermoortele F, Waroquier M, De Vos D E, Van Speybroeck V. Active site engineering in UiO-66 type metal-organic frameworks by intentional creation of defects: A theoretical rationalization. CrystEngComm, 2015, 17(2): 395–406 https://doi.org/10.1039/C4CE01672F
33	Mounfield W P III, Taborga Claure M, Agrawal P K, Jones C W, Walton K S. Synergistic effect of mixed oxide on the adsorption of ammonia with metal-organic frameworks. Industrial & Engineering Chemistry Research, 2016, 55(22): 6492–6500 https://doi.org/10.1021/acs.iecr.6b01045
34	Yang Q, Zhong C, Chen J F. Computational study of CO2 storage in metal-organic frameworks. Journal of Physical Chemistry C, 2008, 112(5): 1562–1569 https://doi.org/10.1021/jp077387d
35	Zhang X, Wang P, Wu X, Lv S, Dai J. Application of MnOx/HNTs catalysts in low-temperature NO reduction with NH3. Catalysis Communications, 2016, 83: 18–21 https://doi.org/10.1016/j.catcom.2016.05.003
36	Schaate A, Roy P, Godt A, Lippke J, Waltz F, Wiebcke M, Behrens P. Modulated synthesis of Zr-based metal-organic frameworks: From nano to single crystals. Chemistry, 2011, 17(24): 6643–6651 https://doi.org/10.1002/chem.201003211
37	Valenzano L, Civalleri B, Chavan S, Bordiga S, Nilsen M H, Jakobsen S, Lillerud K P, Lamberti C. Disclosing the complex structure of UiO-66 metal organic framework: A synergic combination of experiment and theory. Chemistry of Materials, 2011, 23(7): 1700–1718 https://doi.org/10.1021/cm1022882
38	Liu R, Ji L, Xu Y, Ye F, Jia F. Catalytic performance and SO2 tolerance of tetragonal-zirconia-based catalysts for low-temperature selective catalytic reduction. Journal of Materials Research, 2016, 31(17): 2590–2597 https://doi.org/10.1557/jmr.2016.283
39	Long J, Wang S, Ding Z, Wang S, Zhou Y, Huang L, Wang X. Amine-functionalized zirconium metal-organic framework as efficient visible-light photocatalyst for aerobic organic transformations. Chemical Communications, 2012, 48(95): 11656–11658 https://doi.org/10.1039/c2cc34620f
40	Rungtaweevoranit B, Baek J, Araujo J R, Archanjo B S, Choi K M, Yaghi O M, Somorjai G A. Copper nanocrystals encapsulated in Zr-based metal-organic frameworks for highly selective CO2 hydrogenation to methanol. Nano Letters, 2016, 16(12): 7645–7649 https://doi.org/10.1021/acs.nanolett.6b03637
41	Andreoli S, Deorsola F A, Pirone R. MnOx-CeO2 catalysts synthesized by solution combustion synthesis for the low-temperature NH3-SCR. Catalysis Today, 2015, 253: 199–206 https://doi.org/10.1016/j.cattod.2015.03.036
42	Fang D, Xie J, Hu H, Yang H, He F, Fu Z. Identification of MnOx species and Mn valence states in MnOx/TiO2 catalysts for low temperature SCR. Chemical Engineering Journal, 2015, 271: 23–30 https://doi.org/10.1016/j.cej.2015.02.072
43	Alayoglu S, Beaumont S K, Zheng F, Pushkarev V V, Zheng H, Iablokov V, Liu Z, Guo J, Kruse N, Somorjai G A. CO2 hydrogenation studies on Co and CoPt bimetallic nanoparticles under reaction conditions using TEM, XPS and NEXAFS. Topics in Catalysis, 2011, 54(13-15): 778–785 https://doi.org/10.1007/s11244-011-9695-9
44	Thirupathi B, Smirniotis P G. Nickel-doped Mn/TiO2 as an efficient catalyst for the low-temperature SCR of NO with NH3: Catalytic evaluation and characterizations. Journal of Catalysis, 2012, 288: 74–83 https://doi.org/10.1016/j.jcat.2012.01.003
45	Pappas D K, Boningari T, Boolchand P, Smirniotis P G. Novel manganese oxide confined interweaved titania nanotubes for the low-temperature selective catalytic reduction (SCR) of NOx by NH3. Journal of Catalysis, 2016, 334: 1–13 https://doi.org/10.1016/j.jcat.2015.11.013
46	Wang P, Sun H, Quan X, Chen S. Enhanced catalytic activity over MIL-100(Fe) loaded ceria catalysts for the selective catalytic reduction of NO with NH3 at low temperature. Journal of Hazardous Materials, 2015, 301: 512–521 https://doi.org/10.1016/j.jhazmat.2015.09.024
47	Shan W, Liu F, He H, Shi X, Zhang C. 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 https://doi.org/10.1016/j.apcatb.2011.12.019
48	Jiang H, Wang Q, Wang H, Chen Y, Zhang M. MOF-74 as an efficient catalyst for the low-temperature selective catalytic reduction of NOx with NH3. ACS Applied Materials & Interfaces, 2016, 8(40): 26817–26826 https://doi.org/10.1021/acsami.6b08851

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