Abstract
The reaction mechanisms of selective catalytic reduction (SCR) of nitric oxide (NO) by methane (CH4) over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models. Catalysts derived from different supports would lead to different reaction pathways, and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities. Higher ratios of Brønsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation. Strong Brønsted acid sites would not necessarily lead to better catalytic performance, however, since the active surface NOy species and the corresponding reaction routes were determined by the overall acidity strength of the support. The reaction routes where NO2 moiety was engaged as an important intermediate involved moderate oxidation of methane, the rate of which could determine the overall activity. The reaction involving NO moiety was likely to be determined by the step of reduction of NO. Therefore, to enhance the SCR activity of solid superacid catalysts, reactions between appropriate couples of active NOy species and activated hydrocarbon intermediates should be realized by modification of the support acidity.
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Li Y, Armor J N. Catalytic reduction of nitrogen oxides with methane in the presence of excess oxygen. Applied Catalysis B: Environmental, 1992, 1(4): 31–40
Kantcheva M, Cayirtepe I. FT-IR spectroscopic investigation of the surface reaction of CH4 with NOx species adsorbed on Pd/WO3-ZrO2 catalyst. Catalysis Letters, 2007, 115(3–4): 148–162
Fokema M D, Ying J Y. The selective catalytic reduction of nitric oxide with methane over nonzeolitic catalysts. Catalysis Reviews—Science and Engineering, 2001, 43(1–2): 1–29
Li Y, Armor J N. Selective catalytic reduction of NOx with methane over metal exchange zeolites. Applied Catalysis B: Environmental, 1993, 2(2–3): 239–256
Zhang X K, Walters A B, Vannice M A. Catalytic reduction of NO by CH4 over Li-promoted MgO. Journal of Catalysis, 1994, 146(2): 568–578
Feeley J S, Deeba M, Farrauto R J, Beri G, Haynes A. Lean NOx reduction with hydrocarbons over Ga/S-ZrOx and S-GaZr/zeolite catalysts. Applied Catalysis B: Environmental, 1995, 6(1): 79–96
Li N, Wang A Q, Tang J W, Wang X D, Liang D B, Zhang T. NO reduction by CH4 in the presence of excess O2 over Co/sulfated zirconia catalysts. Applied Catalysis B: Environmental, 2003, 43(2): 195–201
Li N, Wang A Q, Wang X D, Zheng M Y, Cheng R H, Zhang T. NO reduction by CH4 in the presence of excess O2 over Mn/sulfated zirconia catalysts. Applied Catalysis B: Environmental, 2004, 48(4): 259–265
Chin Y H, Pisanu A, Serventi L, Alvarez W E, Resasco D E. NO reduction by CH4 in the presence of excess O2 over Pd/sulfated zirconia catalysts. Catalysis Today, 1999, 54(4): 419–429
Cordoba L F, Sachtler W M H, de Correa C M. NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts. Applied Catalysis B: Environmental, 2005, 56(4): 269–277
Quincoces C E, Guerrero S, Araya P, Gonzalez MG. Effect of water vapor over Pd-Co/SZ catalyst for the NO selective reduction by methane. Catalysis Communications, 2005, 6(1): 75–80
Li N, Wang A Q, Lin L, Wang X D, Ren L L, Zhang T. NO reduction by CH4 in the presence of excess O2 over Pd/sulfated alumina catalysts. Applied Catalysis B: Environmental, 2004, 50(1): 1–7
Li N, Wang A Q, Ren W L, Zheng M Y, Wang X D, Zhang T. Pd/sulfated alumina: A new effective catalyst for the selective catalytic reduction of NO with CH4. Topics in Catalysis, 2004, 30–31(1–4): 103–105
Chin Y H, Alvarez W E, Resasco D E. Sulfated zirconia and tungstated zirconia as effective supports for Pd-based SCR catalysts. Catalysis Today, 2000, 62(2–3): 159–165
Chin Y H, Alvarez W E, Resasco D E. Comparison between methane and propylene as reducing agents in the SCR of NO over Pd supported on tungstated zirconia. Catalysis Today, 2000, 62(4): 291–302
Okumura K, Kusakabe T, Niwa M. Durable and selective activity of Pd loaded on WO3/ZrO2 for NO-CH4-O2 in the presence of water vapor. Applied Catalysis B: Environmental, 2003, 41(1–2): 137–142
Kantcheva M, Vakkasoglu A S. Cobalt supported on zirconia and sulfated zirconia II. Reactivity of adsorbed NOx compounds toward methane. Journal of Catalysis, 2004, 223(2): 364–371
Djega-Mariadassou G. From three-way to deNOx catalysis: A general model. Catalysis Today, 2004, 90(1–2): 27–34
Yang D, Li J H, Wen M F, Song C L. Selective catalytic reduction of NOx with methane over indium supported on tungstated zirconia. Catalysis Communications, 2007, 8(12): 2243–2247
Yang D, Li J H, Wen M F, Song C L. Selective catalytic reduction of NOx with CH4 over the In/sulfated TiO2 catalyst. Catalysis Letters, 2008, 122(1–2): 138–143
Miller J T, Glusker E, Peddi R, Zheng T, Regalbuto J R. The role of acid sites in cobalt zeolite catalysts for selective catalytic reduction of NOx. Catalysis Letters, 1998, 51(1–2): 15–22
Busca G. Spectroscopic characterization of the acid properties of metal oxide catalysts. Catalysis Today, 1998, 41(1–3): 191–206
Reshetenko T V, Avdeeva L B, Khassin A A, Kustova G N, Ushakov V A, Moroz E M, Shmakov A N, Kriventsov V V, Kochubey D I, Pavlyukhin Y T, Chuvilin A L, Ismagilov Z R. Coprecipitated iron-containing catalysts (Fe-Al2O3, Fe-Co-Al2O3, Fe-Ni-Al2O3) for methane decomposition at moderate temperatures: I. Genesis of calcined and reduced catalysts. Applied Catalysis A: General, 2004, 268(1–2): 127–138
Kantcheva M, Kucukkal M U, Suzer S. Spectroscopic investigation of species arising from CO chemisorption on titania-supported manganese. Journal of Catalysis, 2000, 190(1): 144–156
Adelman B J, Beutel T, Lei G D, Sachtler W M H. Mechanistic cause of hydrocarbon specificity over Cu/ZSM-5 and Co/ZSM-5 catalysts in the selective catalytic reduction of NOx. Journal of Catalysis, 1996, 158(1): 327–335
Hadjiivanov K I. Identification of neutral and charged NxOy surface species by IR spectroscopy. Catalysis Reviews, 2000, 42(1): 71–144
Wong M S N. Supremolecular templating of mesoporous zirconia-based nanocomposite catalysts. Dissertation for the Doctoral Degree. Boston: Massachusett Institute of Technology, 2000
Arata K. Preparation of superacids by metal oxides for reactions of butanes and pentanes. Applied Catalysis A: General, 1996, 146(1): 3–32
Mantilla A, Tzompantzi F, Ferrat G, López-Ortegac A, Alfaroa S, Gómezb R, Torres M. Oligomerization of isobutene on sulfated titania: Effect of reaction conditions on selectivity. Catalysis Today, 2005, 107–108: 707–712
Halász J, Kónya Z, Fudala Á, Béres A, Kiricsi I. Indium and gallium containing ZSM-5 zeolites: Acidity and catalytic activity in propane transformation. Catalysis Today, 1996, 31(3–4): 293–304
Ansell G P, Diwell A F, Golunski S E, Hayes J W, Rajaram R R, Truex T J, Walker A P. Mechanism of the lean NOx reaction over Cu/ZSM-5. Applied Catalysis B: Environmental, 1993, 2(1): 81–100
Kikuchi E, Ogura M, Terasaki I, Goto Y. Selective reduction of nitric oxide with methane on gallium and indium containing HZSM-5 catalysts: Formation of active sites by solid-state ion exchange. Journal of Catalysis, 1996, 161(1): 465–470
Li Y J, Armor J N. Selective catalytic reduction of NO with methane on gallium catalysts. Journal of Catalysis, 1994, 145(1): 1–9
Shelef M, Montreuil C N, Jen HW. NO2 formation over Cu-ZSM-5 and the selective catalytic reduction of NO. Catalysis Letters, 1994, 26(3–4): 277–284
Beutel T, Adelman B J, Sachtler W M H. FTIR study of the nitrogen isotopic exchange between adsorbed 15NO2 complexes and 14NO over Cu/ZSM-5 and Co/ZSM-5. Applied Catalysis B: Environmental, 1996, 9(1–4): 1–10
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Xu, S., Li, J., Yang, D. et al. Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH4 in excess oxygen. Front. Environ. Sci. Eng. China 3, 186–193 (2009). https://doi.org/10.1007/s11783-009-0016-5
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DOI: https://doi.org/10.1007/s11783-009-0016-5