Selective catalytic reduction of NO_x with ethanol and other C_1-4 oxygenates over Ag/Al₂O₃ catalysts: A review

Abstract

Research results regarding selective catalytic reduction (SCR) of NO_x with ethanol and other C_1-4 oxygenates as reductants over silver-alumina catalysts are summarized. The aspects of the process mechanism, nature of active sites, role of alumina and silver (especially in the formation of bifunctional active sites), effects of reductants and reaction conditions are discussed. It has been determined that key stages of the process include formation of reactive enolic species, their interaction with NO_x and formation of nitroorganic compounds which transform to NCO_ads species and further to N₂. The results obtained over various silver-alumina catalysts demonstrate the perspectives of their application for reducing the level of nitrogen oxides in engine emissions, including in the presence of water vapor and sulfur oxides. Ways to improve the catalysts for the SCR of NO_x with C_1-4 oxygenates are outlined.

Graphical abstract

Keywords

SCR / nitrogen oxides / silver-alumina catalyst / silver species / ethanol / oxygenates

References

[1] Lammel G, Graßl H. Greenhouse effect of NO_x. Environmental Science and Pollution Research International, 1995, 2(1): 40–45

[2] Chossière G P, Malina R, Ashok A, Dedoussi I C, Eastham S D, Speth R L, Barrett S R H. Public health impacts of excess NO_x emissions from Volkswagen diesel passenger vehicles in Germany. Environmental Research Letters, 2017, 12(3): 034014

[3] Boningari T, Smirniotis P G. Impact of nitrogen oxides on the environment and human health: Mn-based materials for the NO_x abatement. Current Opinion in Chemical Engineering, 2016, 13: 133–141

[4] Skalska K, Miller J S, Ledakowicz S. Trends in NO_x abatement: A review. Science of the Total Environment, 2010, 408(19): 3976–3989

[5] Granger P, Parvulescu V I. Catalytic NO_x abatement systems for mobile sources: From three-way to lean burn after-treatment technologies. Chemical Reviews, 2011, 111(5): 3155–3207

[6] Pârvulescu V I, Grange P, Delmon B. Catalytic removal of NO. Catalysis Today, 1998, 46(4): 233–316

[7] Roy S, Hegde M S, Madras G. Catalysis for NO_x abatement. Applied Energy, 2009, 86(11): 2283–2297

[8] Piumetti M, Bensaid S, Fino D, Russo N. Catalysis in diesel engine NO_x after treatment: A review. Catalysis. Structure & Reactivity, 2015, 1(4): 155–173

[9] Orlik S N, Mironyuk T V, Boichuk T M. Structural functional design of catalysts for conversion of nitrogen (I, II) oxides. Theoretical and Experimental Chemistry, 2012, 48(2): 73–97

[10] Chen H Y, Chang H L R. Development of low temperature three-way catalysts for future fuel efficient vehicles. Johnson Matthey Technology Review, 2015, 59(1): 64–67

[11] Wang J, Chen H, Hu Z, Yao M, Li Y. A review on the Pd-based three-way catalyst. Catalysis Reviews. Science and Engineering, 2015, 57(1): 79–144

[12] Burch R, Breen J P, Meunier F C. A review of the selective reduction of NO_x, with hydrocarbonds under lean-burn conditions with non-zeolitic oxide and platinum group metal analysis. Applied Catalysis B: Environmental, 2002, 39(4): 283–303

[13] Li J, Chang H, Ma L, Hao J, Yang R T. Low-temperature selective catalytic reduction of NO_x with NH₃ over metal oxide and zeolite catalysts—a review. Catalysis Today, 2011, 175(1): 147–156

[14] Guan B, Zhan R, Lin H, Huang Z. Review of state of the art technologies of selective catalytic reduction of NO_x from diesel engine exhaust. Applied Thermal Engineering, 2014, 66(1-2): 395–414

[15] Li J, Chang H, Ma L, Hao J, Yang R T. Low-temperature selective catalytic reduction of NO_x with NH₃ over metal oxide and zeolite catalysts—a review. Catalysis Today, 2011, 175(1): 147–156

[16] Brandenberger S, Kröcher O, Tissler A, Althoff R. The state of the art in selective catalytic reduction of NO_x by ammonia using metal-exchanged zeolite catalysts. Catalysis Reviews. Science and Engineering, 2008, 50(4): 492–531

[17] Lehtoranta K, Vesala H, Koponen P, Korhonen S. Selective catalytic reduction operation with heavy fuel oil: NO_x, NH₃, and particle emissions. Environmental Science & Technology, 2015, 49(7): 4735–4741

[18] Yim S D, Kim S J, Baik J H, Nam I, Mok Y S, Lee J H, Cho B K, Oh S H. Decomposition of urea into NH₃ for the SCR process. Industrial & Engineering Chemistry Research, 2004, 43(16): 4856–4863

[19] Gao F, Tang X, Yi H, Zhao S, Li C, Li J, Shi Y, Meng X. A review on selective catalytic reduction of NO_x by NH₃ over Mn-based catalysts at low temperatures: Catalysts, mechanisms, kinetics and DFT calculations. Catalysts, 2017, 7(7): 199

[20] Roy S, Baiker A. NO_x storage-reduction catalysis from mechanism and materials properties to storage-reduction performance. Chemical Reviews, 2009, 109(9): 4054–4091

[21] Liu G, Gao P X. A review of NO_x storage/reduction catalysts: Mechanism, materials and degradation studies. Catalysis Science & Technology, 2011, 1(4): 552–568

[22] Mrad R, Aissat A, Cousin R, Courcot D, Siffert S. Catalysts for NO_x selective catalytic reduction by hydrocarbons (HC-SCR). Applied Catalysis A, General, 2015, 504: 542–548

[23] Kannisto H, Ingelsten H H, Skoglundh M. Ag-Al₂O₃ catalysts for lean NO_x reduction-influence of preparation method and reductant. Journal of Molecular Catalysis A Chemical, 2009, 302(1-2): 86–96

[24] Popovych N O, Soloviev S O, Orlyk S M. Selective reduction of nitrogen oxides (NO_x) with oxygenates and hydrocarbons over bifunctional silver–alumina catalysts: A review. Theoretical and Experimental Chemistry, 2016, 52(3): 133–151

[25] Ström L, Carlsson P A, Skoglundh M, Härelind H. Hydrogen-assisted SCR of NO_x over alumina-supported silver and indium catalysts using C₂-hydrocarbons and oxygenates. Applied Catalysis B: Environmental, 2016, 181: 403–412

[26] Härelind H, Gunnarsson F, Vaghefi S M S, Skoglundh M, Carlsson P A. Influence of the carbon-carbon bond order and silver loading on the formation of surface species and gas phase oxidation products in absence and presence of NO_x over silver-alumina catalysts. ACS Catalysis, 2012, 2(8): 1615–1623

[27] Shimizu K, Satsuma A, Hattori T. Catalytic performance of Ag–Al₂O₃ catalyst for the selective catalytic reduction of NO by higher hydrocarbons. Applied Catalysis B: Environmental, 2016, 2000, 25(4): 239–247

[28] D’Agostino C, Chansai S, Bush I, Gao C, Mantle M D, Hardacre C, James S L, Gladden L F. Assessing the effect of reducing agents on the selective catalytic reduction of NO_x over Ag/Al₂O₃ catalysts. Catalysis Science & Technology, 2016, 6(6): 1661–1666

[29] da Silva R, Cataluña R, Martínez-Arias A. Selective catalytic reduction of NO_x using propene and ethanol over catalysts of Ag/Al₂O₃ prepared by microemulsion and promotional effect of hydrogen. Catalysis Today, 2009, 143(3-4): 242–246

[30] Kameoka S, Ukisu Y, Miyadera T. Selective catalytic reduction of NO_x with CH₃OH, C₂H₅OH and C₃H₆ in the presence of over O₂ Ag/Al₂O₃ catalyst: Role of surface nitrate species. Physical Chemistry Chemical Physics, 2000, 2(3): 367–372

[31] Miyadera T. Alumina-supported silver catalysts for the selective reduction of nitric-oxide with propene and oxygen-containing organic-compounds. Applied Catalysis B: Environmental, 1993, 2(2-3): 199–205

[32] Kim J Y, Kim Y H, Han S, Choi S H, Lee J S. Photocatalytic synthesis of oxygenated hydrocarbons from diesel fuel for mobile deNO_x application. Journal of Catalysis, 2013, 302: 58–66

[33] Sultana A, Sasaki M, Suzuki K, Hamada H. Physical mixture of Ag/Al₂O₃ and Zn/ZSM-5 as an active catalyst component for selective catalytic reduction of NO_x with n-C₁₀H₂₂. Applied Catalysis A, General, 2013, 466: 179–184

[34] Tham Y F, Chen J Y, Dibble R W. Development of a detailed surface mechanism for the selective catalytic reduction of NO_x with ethanol on silver alumina catalyst. Proceedings of the Combustion Institute, 2009, 32(2): 2827–2833

[35] Worch D, Suprun W, Gläser R. Fe- and Cu-oxides supported on g-Al₂O₃ as catalysts for the selective catalytic reduction of NO with ethanol. Part I : Catalyst preparation, characterization, and activity. Chemical Papers, 2014, 68(9): 1228–1239

[36] Shimokawabe M, Kuwana A, Oku S, Yoshida K, Arai M. SCR of NO by DME over Al₂O₃ based catalysts: Influence of noble metals and Ba additive on low-temperature activity. Catalysis Today, 2011, 164(1): 480–483

[37] Kameoka S, Chafik T, Ukisu Y, Miyadera T. Role of organic nitro compounds in selective reduction of NO_x with ethanol over different supported silver catalysts. Catalysis Letters, 1998, 51(1-2): 11–14

[38] Bartolomeu R, Azambre B, Westermann A, Fernandes A, Bértolo R, Hamoud H I, Henriques C, Da Costa P, Ribeiro F. Investigation of the nature of silver species on different Ag-containing NO_x reduction catalysts: On the effect of the support. Applied Catalysis B: Environmental, 2014, 150-151: 204–217

[39] Miyadera T, Yoshida K. Alumina-supported catalysts for the selective reduction of nitric oxide by propene. Chemistry Letters, 1993, 22(9): 1483–1486

[40] Takagi K, Kobayashi T, Ohkita H, Mizushima T, Kakuta N, Abe A, Yoshida K. Selective reduction of NO on Ag/Al₂O₃ catalysts prepared from boehmite needles. Catalysis Today, 1998, 45(1-4): 123–127

[41] Shimizu K, Satsuma A, Hattori T. Metal oxide catalysts for selective reduction of NO_x by hydrocarbons: Toward molecular basis for catalyst design. Catalysis Surveys from Asia, 2001, 4(2): 115–123

[42] Miyadera T. Selective reduction of nitric oxide with ethanol over an alumina-supported silver catalyst. Applied Catalysis B: Environmental, 1997, 13(2): 157–165

[43] Fogel S, Doronkin D E, Gabrielsson P, Dahl S. Optimisation of Ag loading and alumina characteristics to give Sulphur-tolerant Ag/Al₂O₃ catalyst for H₂-assisted NH₃-SCR of NO_x. Applied Catalysis B: Environmental, 2012, 125: 457–464

[44] Richter M, Fricke R, Eckelt R. Unusual activity enhancement of NO conversion over Ag/Al₂O₃ by using a mixed NH₃/H₂ reductant under lean conditions. Catalysis Letters, 2004, 94(1-2): 115–118

[45] Tamm S, Andonova S, Olsson L. Silver as storage compound for NO_x at low temperatures. Catalysis Letters, 2014, 144(4): 674–684

[46] Lee J, Schmieg S J, Oh S H. Catalytic reforming of ethanol to acetaldehyde for lean-NO_x emission control. Industrial & Engineering Chemistry Research, 2004, 43(20): 6343–6348

[47] Schmal M, Cesar D V, Souza M M V M, Guarido C E. Drifts and TPD analyses of ethanol on Pt catalysts over Al₂O₃ and ZrO₂—partial oxidation of ethanol. Canadian Journal of Chemical Engineering, 2011, 89(5): 1166–1175

[48] Barresi A A, Baldi G. Reaction mechanisms of ethanol deep oxidation over platinum catalyst. Chemical Engineering Communications, 1993, 123(1): 17–29

[49] Ozbek M O, Onal I, Van Santen R A. Why silver is the unique catalyst for ethylene epoxidation. Journal of Catalysis, 2011, 284(2): 230–235

[50] Torbina V V, Vodyankin A A, Ten S, Mamontov G V, Salaev M A, Sobolev V I, Vodyankina O V. Ag-based catalysts in heterogeneous selective oxidation of alcohols: A review. Catalysts, 2018, 8(10): 447

[51] Millar G J, Collins M. Industrial production of formaldehyde using polycrystalline silver catalyst. Industrial & Engineering Chemistry Research, 2017, 56(33): 9247–9265

[52] Liotta L F. Catalytic oxidation of volatile organic compounds on supported noble metals. Applied Catalysis B: Environmental, 2010, 100(3-4): 403–412

[53] She X, Flytzani-Stephanopoulos M. The role of Ag-O-Al species in silver-alumina catalysts for the selective catalytic reduction of NO_x with methane. Journal of Catalysis, 2006, 237(1): 79–93

[54] Musi A, Massiani P, Brouri D, Trichard J M, Da Costa P. On the characterisation of silver species for SCR of NO_x with ethanol. Catalysis Letters, 2009, 128(1-2): 25–30

[55] Bogdanchikova N, Meunier F C, Avalos-Borja M, Breen J P, Pestryakov A. On the nature of the silver phases of Ag/Al₂O₃ catalysts for reactions involving nitric oxide. Applied Catalysis B: Environmental, 2002, 36(4): 287–297

[56] Kim Y C, Park N C, Shin J S, Lee S R, Lee Y J, Moon D J. Partial oxidation of ethylene to ethylene oxide over nanosized Ag/α-Al₂O₃ catalysts. Catalysis Today, 2003, 87(1-4): 153–162

[57] Pârvulescu V I, Cojocaru B, Pârvulescu V, Richards R, Li Z, Cadigan C, Granger P, Miquel P, Hardacre C. Sol-gel-entrapped nano silver catalysts-correlation between active silver species and catalytic behavior. Journal of Catalysis, 2010, 272(1): 92–100

[58] Seyedmonir S R, Strohmayer D E, Geoffroy G L, Vannice M A. Characterization of supported silver catalysts I. Adsorption of O₂, H₂, N₂O, and the H₂-titration of adsorbed oxygen on well-dispersed Ag on TiO₂. Journal of Catalysis, 1984, 87(2): 424–436

[59] Chongterdtoonskul A, Suttikul T, Santikunaporn M, Schwank J W, Chavadej S. Effect of diluent gas on ethylene epoxidation activity over various Ag-based catalysts on selective oxide supports. Journal of Molecular Catalysis A Chemical, 2014, 386: 5–13

[60] Sayah E, Brouri D, Wu Y, Musi A, Da Costa P, Massiani P A. TEM and UV-visible study of silver reduction by ethanol in Ag-alumina catalysts. Applied Catalysis A, General, 2011, 406(1-2): 94–101

[61] Shimizu K I, Sugino K, Sawabe K, Satsuma A. Oxidant-free dehydrogenation of alcohols heterogeneously catalyzed by cooperation of silver clusters and acid-base sites on alumina. Chemistry (Weinheim an der Bergstrasse, Germany), 2009, 15(10): 2341–2351

[62] Wu Q, He H, Yu Y. In situ DRIFTS study of the selective reduction of NO_x with alcohols over Ag/Al₂O₃ catalyst: Role of surface enolic species. Applied Catalysis B: Environmental, 2005, 61(1-2): 107–113

[63] Kim M K, Kim P S, Kwon H J, Nam I S, Cho B K, Oh S H. Simulation of OHC/SCR process over Ag/Al₂O₃ catalyst for removing NO_x from diesel engine. Chemical Engineering Journal, 2012, 209: 280–292

[64] Flura A, Courtois X, Can F, Royer S, Duprez D. A study of the NO_x selective catalytic reduction with ethanol and its by-products. Topics in Catalysis, 2013, 56(1-8): 94–103

[65] Deng H, Yu Y, He H. Adsorption states of typical intermediates on Ag/Al₂O₃ catalyst employed in the selective catalytic reduction of NO_x by ethanol. Chinese Journal of Catalysis, 2015, 36(8): 1312–1320

[66] Yan Y, Yu Y, He H, Zhao J. Intimate contact of enolic species with silver sites benefits the SCR of NO_x by ethanol over Ag/Al₂O₃. Journal of Catalysis, 2012, 293: 13–26

[67] Zuzaniuk V, Meunier F C, Ross J R H. Differences in the reactivity of organo-nitro and nitrito compounds over Al₂O₃-based catalysts active for the selective reduction of NO_x. Journal of Catalysis, 2001, 202(2): 340–353

[68] Yu Y B, Gao H W, He H. FTIR, TPD and DFT studies of intermediates on Ag/Al₂O₃ during the selective catalytic reduction of NO by C₂H₅OH. Catalysis Today, 2004, 93-95: 805–809

[69] Wu Q, Yu Y, He H. Mechanistic study of selective catalytic reduction of NO_x with C₂H₅OH and CH₃OCH₃ over Ag/Al₂O₃ by in situ DRIFTS. Chinese Journal of Catalysis, 2006, 27(11): 993–997

[70] Yu Y, He H, Feng Q, Gao H, Yang X. Mechanism of the selective catalytic reduction of NO_x by C₂H₅OH over Ag/Al₂O₃. Applied Catalysis B: Environmental, 2004, 49(1): 159–171

[71] Yeom Y H, Li M, Sachtler W M H, Weitz E. A study of the mechanism for NO_x reduction with ethanol on g-alumina supported silver. Journal of Catalysis, 2006, 238(1): 100–110

[72] Bion N, Saussey J, Haneda M, Daturi M. Study by in situ FTIR spectroscopy of the SCR of NO_x by ethanol on Ag/Al₂O₃-Evidence of the role of isocyanate species. Journal of Catalysis, 2003, 217(1): 47–58

[73] Shimizu K, Shibata J, Satsuma A, Hattori T. Mechanistic causes of the hydrocarbon effect on the activity of Ag–Al₂O₃ catalyst for the selective reduction of NO. Physical Chemistry Chemical Physics, 2001, 3(5): 880–884

[74] Lee J H, Schmieg S J, Oh S H. Improved NO_x reduction over the staged Ag/Al₂O₃ catalyst system. Applied Catalysis A, General, 2008, 342(1-2): 78–86

[75] Kopasz J P, Wilkenhoener R, Ahmed S, Carter J D, Krtunpelt M. Fuel-flexible partial oxidation reforming of hydrocarbons for automotive applications, U.S. DOE Report ANL/CMT/CP-98970, 1999

[76] Zaera F. The surface chemistry of hydrocarbon partial oxidation catalysis. Catalysis Today, 2003, 81(2): 149–157

[77] Oakley A, Zhao H, Ladommatos N, Ma T. Dilution effects on the controlled auto-ignition (CAI) combustion of hydrocarbon and alcohol fuels. SAE Technical Papers, 2001, 2001-01-3606

[78] Williams R M, Pang S H, Medlin J W. O–H versus C–H bond scission sequence in ethanol decomposition on Pd(111). Surface Science, 2014, 619: 114–118

[79] Gunnarsson F, Pihl J A, Toops T J, Skoglundh M, Härelind H. Lean NO_x reduction over Ag/alumina catalysts via ethanol-SCR using ethanol/gasoline blends. Applied Catalysis B: Environmental, 2017, 202: 42–50

[80] Pihl J A, Toops T J, Fisher G B, West B H. Selective catalytic reduction of nitric oxide with ethanol/gasoline blends over a silver/alumina catalyst. Catalysis Today, 2014, 231: 46–55

[81] Herreros J M, George P, Umar M, Tsolakis A. Enhancing selective catalytic reduction of NO_x with alternative reactants/promoters. Chemical Engineering Journal, 2014, 252: 47–54

[82] Dong H, Shuai S, Li R, Wang J, Shi X, He H. Study of NO_x selective catalytic reduction by ethanol over Ag/Al₂O₃ catalyst on a HD diesel engine. Chemical Engineering Journal, 2008, 135(3): 195–201

[83] He H, Zhang X, Wu Q, Zhang C, Yu Y. Review of Ag/Al₂O₃-reductant system in the selective catalytic reduction of NO_x. Catalysis Surveys from Asia, 2008, 12(1): 38–55

[84] Kattel S, Ramírez P J, Chen J G, Rodriguez J A, Liu P. Active sites for CO₂ hydrogenation to methanol on Cu/ZnO catalysts. Science, 2017, 355(6331): 1296–1299

[85] Meunier F C, Breen J P, Zuzaniuk V, Olsson M, Ross J R H. Mechanistic aspects of the selective reduction of NO by propene over alumina and silver-alumina catalysts. Journal of Catalysis, 1999, 187(2): 493–505

[86] Zhang X, He H, Gao H, Yu Y. Experimental and theoretical studies of surface nitrate species on Ag/Al₂O₃ using DRIFTS and DFT. Spectrochimica Acta. Part A: Molecular and Biomolecular Spectroscopy, 2008, 71(4): 1446–1451

[87] Kameoka S, Chafik T, Ukisu Y, Miyadera T. Reactivity of surface isocyanate species with NO, O₂ and NO+O₂ in selective reduction of NO_x over Ag/Al₂O₃ and Al₂O₃ catalysts. Catalysis Letters, 1998, 55(3-4): 211–215

[88] Yeom Y H, Wen B, Sachtler W M H, Weitz E. NO_x reduction from diesel emissions over a nontransition metal zeolite catalyst: A mechanistic study using FTIR spectroscopy. Journal of Physical Chemistry B, 2004, 108(17): 5386–5404

[89] Johnson W L II, Fisher G B, Toops T J. Mechanistic investigation of ethanol SCR of NO_x over Ag/Al₂O₃. Catalysis Today, 2012, 184(1): 166–177

[90] Yu Y B, He H, Feng Q C. Novel enolic surface species formed during partial oxidation of CH₃CHO, C₂H₅OH, and C₃H₆ on Ag/Al₂O₃: An in situ DRIFTS study. Journal of Physical Chemistry B, 2003, 107(47): 13090–13092

[91] Okazaki N, Shiina Y, Itoh H, Tada A, Iwamoto M. Marked difference in activity of alumina catalysts for selective catalytic reduction of nitrogen monoxide by ethene in excess oxygen. Catalysis Letters, 1997, 49(3): 1–6

[92] Mhadeshwar A B, Winkler B H, Eiteneer B, Hancu D. Microkinetic modeling for hydrocarbon (HC)-based selective catalytic reduction (SCR) of NO_x on a silver-based catalyst. Applied Catalysis B: Environmental, 2009, 89(1-2): 229–238

[93] Sultana A, Haneda M, Fujitani T, Hamada H. Influence of Al₂O₃ support on the activity of Ag/Al₂O₃ catalysts for SCR of NO with decane. Catalysis Letters, 2007, 114(1-2): 96–102

[94] Zhang R, Kaliaguine S. Lean reduction of NO by C₃H₆ over Ag/alumina derived from Al₂O₃, AlOOH and Al(OH)₃. Applied Catalysis B: Environmental, 2008, 78(3-4): 275–287

[95] Deng H, Yu Y, He H. Discerning the role of Ag–O–Al entities on Ag/g-Al₂O₃ surface in NO_x selective reduction by ethanol. Journal of Physical Chemistry C, 2015, 119(6): 3132–3142

[96] Thibault-Starzyk F, Seguin E, Thomas S, Daturi M, Arnolds H, King D A. Real-time infrared detection of cyanide flip on silver-alumina NO_x removal catalyst. Science, 2009, 324(5930): 1048–1051

[97] Can F, Flura A, Courtois X, Royer S, Blanchard G, Marécot P, Duprez D. Role of the alumina surface properties on the ammonia production during the NO_x SCR with ethanol over Ag/Al₂O₃ catalysts. Catalysis Today, 2011, 164(1): 474–479

[98] Popovich N A, Kiriienko P I, Soloviev S, Orlik S N, Dzwigaj S. Role of active components of an Ag/Al₂O₃/cordierite catalyst in selective reduction of NO by ethanol. Theoretical and Experimental Chemistry, 2012, 48(4): 258–264

[99] Popovych N, Kirienko P, Soloviev S, Orlyk S. Selective catalytic reduction of NO_x by C₂H₅OH over Ag/Al₂O₃/cordierite: Effect of the surface concentration of silver. Catalysis Today, 2012, 191(1): 38–41

[100] Dzwigaj S, Popovych N, Kyriienko P, Krafft J M, Soloviev S. The similarities and differences in structural characteristics and physico-chemical properties of AgAlBEA and AgSiBEA zeolites. Microporous and Mesoporous Materials, 2013, 182: 16–24

[101] Popovych N, Kyriienko P, Soloviev S, Orlyk S, Dzwigaj S. Catalytic properties of AgAlBEA and AgSiBEA zeolites in H₂-promoted selective reduction of NO with ethanol. Microporous and Mesoporous Materials, 2015, 203: 163–169

[102] Valanidou L, Theologides C, Zorpas A A, Savva P G, Costa C N. A novel highly selective and stable Ag/MgO-CeO₂-Al₂O₃ catalyst for the low-temperature ethanol–SCR of NO. Applied Catalysis B: Environmental, 2011, 107(1-2): 164–176

[103] Shi Y, Pan H, Zhang Y, Li W. Promotion of MgO addition on SO₂ tolerance of Ag/Al₂O₃ for selective catalytic reduction of NO_x with methane at low temperature. Catalysis Communications, 2008, 9(5): 796–800

[104] Flura A, Can F, Courtois X, Royer S, Duprez D. High-surface-area zinc aluminate supported silver catalysts for low-temperature SCR of NO with ethanol. Applied Catalysis B: Environmental, 2012, 126: 275–289

[105] Shimizu K, Sawabe K, Satsuma A. Unique catalytic features of Ag nanoclusters for selective NO_x reduction and green chemical reactions. Catalysis Science & Technology, 2011, 1(3): 331–334

[106] Bion N, Saussey J, Hedouin C, Seguelong T, Daturi M. Evidence by in situ FTIR spectroscopy and isotopic effect of new assignments for isocyanate species vibrations on Ag/Al₂O₃. Physical Chemistry Chemical Physics, 2001, 3(21): 4811–4816

[107] Deng H, Yu Y, Liu F, Ma J, Zhang Y, He H. Nature of Ag species on Ag/g-Al₂O₃: A combined experimental and theoretical study. ACS Catalysis, 2014, 4(8): 2776–2784

[108] Kyriienko P, Popovych N, Soloviev S, Orlyk S, Dzwigaj S. Remarkable activity of Ag/Al₂O₃/cordierite catalysts in SCR of NO with ethanol and butanol. Applied Catalysis B: Environmental, 2013, 140-141: 691–699

[109] Popovych N O, Kyriienko P I, Soloviev S O, Orlyk S M. Selective reduction of NO by C₃ and C₈ alkanes over silver catalysts on structured Al₂O₃ cordierite supports. Theoretical and Experimental Chemistry, 2015, 51(2): 122–126

[110] Chaieb T, Delannoy L, Louis C, Thomas C. On the origin of the optimum loading of Ag on Al₂O₃ in the C₃H₆-SCR of NO_x. Applied Catalysis B: Environmental, 2013, 142–143: 780–784

[111] Xu G, Ma J, Wang L, Xie W, Liu J, Yu Y, He H. Insight into the origin of sulfur tolerance of Ag/Al₂O₃ in the H₂-C₃H₆-SCR of NO_x. Applied Catalysis B: Environmental, 2019, 244: 909–918

[112] Wachs I E, Madix R J. The jxidation of ethanol on Cu(110) and Ag(110) catalysts. Applied Surface Science, 1978, 1(3): 303–328

[113] Deng H, Yu Y, He H. Water effect on preparation of Ag/Al₂O₃ catalyst for reduction of NO_x by ethanol. Journal of Physical Chemistry C, 2016, 120(42): 24294–24301

[114] Xu G, Yu Y, He H. Silver valence state determines the water tolerance of Ag/Al₂O₃ for the H₂-C₃H₆-SCR of NO_x. Journal of Physical Chemistry C, 2018, 122(1): 670–680

[115] He H, Li Y, Zhang X, Yu Y, Zhang C. Precipitable silver compound catalysts for the selective catalytic reduction of NO_x by ethanol. Applied Catalysis A, General, 2010, 375(2): 258–264

[116] Iglesias-Juez A, Fernandez-Garcıa M, Martınez-Arias A, Schay Z, Koppany Z, Hungrıa A B, Fuerte A, Anderson J A, Conesa J C, Soria J. Catalytic properties of Ag/Al₂O₃ catalysts for lean NO_x reduction processes and characterisation of active silver species. Topics in Catalysis, 2004, 30/31(1-4): 65–70

[117] Korhonen S T, Beale A M, Newton M A, Weckhuysen B M. New insights into the active surface species of silver alumina catalysts in the selective catalytic reduction of NO. Journal of Physical Chemistry C, 2011, 115(4): 885–896

[118] Iliopoulou E F, Evdou A P, Lemonidou A A, Vasalos I A. Ag/alumina catalysts for the selective catalytic reduction of NO_x using various reductants. Applied Catalysis A, General, 2004, 274(1): 179–189

[119] Männikkö M, Wang X, Skoglundh M, Härelind H. Characterization of the active species in the silver/alumina system for lean NO_x reduction with methanol. Catalysis Today, 2016, 267: 76–81

[120] Männikkö M, Wang X, Skoglundh M, Härelind H. Silver/alumina for methanol-assisted lean NO_x reduction—on the influence of silver species and hydrogen formation. Applied Catalysis B: Environmental, 2016, 180: 291–300

[121] Kim M K, Kim P S, Baik J H, Nam I S, Cho B K, Oh S H. DeNO_x performance of Ag/Al₂O₃ catalyst using simulated diesel fuel-ethanol mixture as reductant. Applied Catalysis B: Environmental, 2011, 105(1-2): 1–14

[122] Golay S, Doepper R, Renken A. In-situ characterisation of the surface intermediates for the ethanol dehydration reaction over g-alumina under dynamic conditions. Applied Catalysis A, General, 1998, 172(1): 97–106

[123] Liu X, Klust A, Madix R J, Friend C M. Structure Sensitivity in the Partial Oxidation of Styrene, Styrene Oxide, and Phenylacetaldehyde on Silver Single Crystals. Journal of Physical Chemistry C, 2007, 111(9): 3675–3679

[124] Özbek M O, Önal I, Vansanten R A. Ethylene epoxidation catalyzed by silver oxide. ChemCatChem, 2011, 3(1): 150–153

[125] Sato K, Yoshinari T, Kintaichi Y, Haneda M, Hamada H. Remarkable promoting effect of rhodium on the catalytic performance of Ag/Al₂O₃ for the selective reduction of NO with decane. Applied Catalysis B: Environmental, 2003, 44(1): 67–78

[126] Bethke K A, Kung H H. Supported Ag catalysts for the lean reduction of NO with C₃H₆. Journal of Catalysis, 1997, 172(1): 93–102

[127] More P M. Effect of active component addition and support modification on catalytic activity of Ag/Al₂O₃ for the selective catalytic reduction of NO_x by hydrocarbon—A review. Journal of Environmental Management, 2017, 188: 43–48

[128] Xie S, Yu Y, Wang J, He H. Effect of SO₂ on the performance of Ag-Pd/Al₂O₃ for the selective catalytic reduction of NO_x with C₂H₅OH. Journal of Environmental Sciences (China), 2006, 18(5): 973–978

[129] Zhang C, He H, Shuai S, Wang J. Catalytic performance of Ag/Al₂O₃-C₂H₅OH-Cu/Al₂O₃ system for the removal of NO_x from diesel engine exhaust. Environmental Pollution, 2007, 147(2): 415–421

[130] Brookshear D W, Pihl J A, Toops T J, West B, Prikhodko V. The selective catalytic reduction of NO_x over Ag/Al₂O₃ with isobutanol as the reductant. Catalysis Today, 2016, 267: 65–75

[131] Montemore M M, Medlin J W. Predicting and comparing C–M and O–M bond strengths for adsorption on transition metal surfaces. Journal of Physical Chemistry C, 2014, 118(5): 2666–2672

[132] Montemore M M, Medlin J W. A unified picture of adsorption on transition metals through different atoms. Journal of the American Chemical Society, 2014, 136(26): 9272–9275

[133] Zhang R, Gellman A J. Straight-chain alcohol adsorption of the silver(110) surface. Journal of Physical Chemistry, 1991, 95(19): 7433–7437

[134] Sexton B A, Rendulic K D, Huges A E. Decomposition pathways of C₁-C₄ alcohols adsorbed on on platinum (111). Surface Science Letters, 1982, 121(1): 181–198

[135] Rossi P F, Rossi P. Heats of adsorption of aliphatic alcohols on α-Al₂O₃ at 25°C−200°C. I. Variations with experimental temperature. Adsorption Science and Technology, 1996, 13(4): 215–229

[136] Rossi P F, Rossi P. Heats of adsorption of aliphatic alcohols on α-Al₂O₃ at 25°C–200°C. II. Variations with chain length. Adsorption Science and Technology, 1997, 15(1): 69–77

[137] Ukisu Y, Miyadera T, Abe A, Yoshida K. Infrared study of catalytic reduction of lean NO_x with alcohols over alumina-supported silver catalyst. Catalysis Letters, 1996, 39(3): 265–267

[138] Tamm S, Ingelsten H H, Skoglundh M, Palmqvist A E C. Mechanistic aspects of the selective catalytic reduction of NO_x by dimethyl ether and methanol over g-Al₂O₃. Journal of Catalysis, 2010, 276(2): 402–411

[139] Tamm S, Ingelsten H H, Skoglundh M, Palmqvist A E C. Differences between Al₂O₃ and Ag/Al₂O₃ for lean reduction of NO_x with dimethyl ether. Topics in Catalysis, 2009, 52(13): 1813–1816

[140] Tamm S, Ingelsten H H, Palmqvist A E C. DME as reductant for continuous lean reduction of NO_x over ZSM-5 catalysts. Catalysis Letters, 2008, 123(3-4): 233–238

[141] Yu Y, Song X, He H. Remarkable influence of reductant structure on the activity of alumina-supported silver catalyst for the selective catalytic reduction of NO_x. Journal of Catalysis, 2010, 271(2): 343–350

[142] Kim M K, Kim P S, Cho B K, Nam I S, Oh S H. Enhanced NO_x reduction and byproduct removal by (HC+ OHC)/SCR over multifunctional dual-bed monolith catalyst. Catalysis Today, 2012, 184(1): 95–106

[143] Chansai S, Burch R, Hardacre C, Norton D, Bao X, Lewis L. Investigating the promotional effect of methanol on the low temperature SCR reaction on Ag/Al₂O₃. Applied Catalysis B: Environmental, 2014, 160–161: 356–364

[144] Satokawa S. Enhancing the NO/C₃H₈/O₂ reaction by using H₂ over Ag/Al₂O₃ catalysts under lean-exhaust conditions. Chemistry Letters, 2000, 29(3): 294–295

[145] Breen J P, Burch R. A review of the effect of the addition of hydrogen in the selective catalytic reduction of NO_x with hydrocarbons on silver catalysts. Topics in Catalysis, 2006, 39(1-2): 53–58

[146] Zhang X, He H, Ma Z. Hydrogen promotes the selective catalytic reduction of NO_x by ethanol over Ag/Al₂O₃. Catalysis Communications, 2007, 8(2): 187–192

[147] Shimizu K I, Tsuzuki M, Satsuma A. Effects of hydrogen and oxygenated hydrocarbons on the activity and SO₂-tolerance of Ag/Al₂O₃ for selective reduction of NO. Applied Catalysis B: Environmental, 2007, 71(1-2): 80–84

[148] Goula M A, Charisiou N D, Papageridis K N, Delimitis A, Papista E, Pachatouridou E, Iliopoulou E F, Marnellos G, Konsolakis M, Yentekakis I V. A comparative study of the H₂-assisted selective catalytic reduction of nitric oxide by propene over noble metal (Pt, Pd, Ir)/g-Al₂O₃ catalysts. Journal of Environmental Chemical Engineering, 2016, 4(2): 1629–1641

[149] Gu H, Chun K M, Song S. The effects of hydrogen on the efficiency of NO_x reduction via hydrocarbon-selective catalytic reduction (HC-SCR) at low temperature using various reductants. International Journal of Hydrogen Energy, 2015, 40(30): 9602–9610

[150] Yu Y, Li Y, Zhang X, Deng H, He H, Li Y. Promotion effect of H₂ on ethanol oxidation and NO_x reduction with ethanol over Ag/Al₂O₃ catalyst. Environmental Science & Technology, 2015, 49(1): 481–488

[151] Popovych N O, Kyriienko P I, Soloviev S O, Orlyk S M, Dzwigaj S. Influence of partial dealumination of BEA zeolites on physicochemical and catalytic properties of AgAlSiBEA in H₂-promoted SCR of NO with ethanol. Microporous and Mesoporous Materials, 2016, 226: 10–18

[152] Xu G, Yu Y, He H. A low-temperature route triggered by water vapor during the ethanol-SCR of NO_x over Ag/Al₂O₃. ACS Catalysis, 2018, 8(4): 2699–2708

[153] Xu G, Ma J, He G, Yu Y, He H. An alumina-supported silver catalyst with high water tolerance for H₂ assisted C₃H₆-SCR of NO_x. Applied Catalysis B: Environmental, 2017, 207: 60–71

[154] Sumiya S, Saito M, He H, Feng Q C, Takezawa N, Yoshida K. Reduction of lean NO_x by ethanol over Ag/Al₂O₃ catalysts in the presence of H₂O and SO₂. Catalysis Letters, 1998, 50(1-2): 87–91

[155] Abe A, Aoyama N, Sumiya S, Kakuta N, Yoshida K. Effect of SO₂ on NO_x reduction by ethanol over Ag/Al₂O₃ catalyst. Catalysis Letters, 1998, 51(1-2): 5–9

[156] Houel V, Millington P, Pollington S, Poulston S, Rajaram R R, Tsolakis A. Chemical deactivation of Ag/Al₂O₃ by sulphur for the selective reduction of NO_x using hydrocarbons. Catalysis Today, 2006, 114(4): 334–339

[157] Hu Y, Griffiths K. Selective catalytic reduction of NO in the presence of SO₂ and O₂: The poisoning effect of SO_x under oxygen rich and lean conditions. Surface Science, 2018, 676: 23–29

[158] Wu Q, Feng Q, He H. Disparate effects of SO₂ on the selective catalytic reduction of NO by C₂H₅OH and IPA over Ag/Al₂O₃. Catalysis Communications, 2006, 7(9): 657–661

[159] Hickey N, Fornasiero P, Kaspar J, Graziani M, Martra G, Coluccia S, Biella S, Prati L, Rossi M. Improvement of SO_x-resistance of silver lean-DeNO_x catalysts by supporting on CeO₂-containing zirconia. Journal of Catalysis, 2002, 209(1): 271–274

[160] Hickey N, Boscarato I, Kašpar J, Bertinetti L, Botavina M, Martra G. Effect of the support on activity of silver catalysts for the selective reduction of NO by propene. Applied Catalysis B: Environmental, 2010, 100(1-2): 102–115

[161] Liotta L F, Di Carlo G, Pantaleo G, Venezia A M, Deganello G, Merlone Borla E, Pidria M. Combined CO/CH₄ oxidation tests over Pd/Co₃O₄ monolithic catalyst: Effects of high reaction temperature and SO₂ exposure on the deactivation process. Applied Catalysis B: Environmental, 2007, 75(3-4): 182–188

[162] Soloviev S O, Kyriienko P I, Popovych N O. Effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in the three-way catalysis reactions (CO/NO/C_nH_m). Journal of Environmental Sciences (China), 2012, 24(7): 1327–1333

[163] Masuda K, Tsujimura K, Shinoda K, Kato T. Silver-promoted catalyst for removal of nitrogen oxides from emission of diesel engines. Applied Catalysis B: Environmental, 1996, 8(1): 33–40

Acknowledgments

The author expresses his gratitude to Prof. Svitlana M. Orlyk and Dr. Nataliia O. Popovych for useful discussions.

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