Skip to main content
Disciplines
Automotive Business IT + Informatics Construction + Real Estate Electrical Engineering + Electronics Energy + Sustainability Insurance + Risk Finance + Banking Management + Leadership Marketing + Sales Mechanical Engineering + Materials
Events
DE
EN
Books
Journals
Topic Page
Marketing
Start single access now
Access for companies
EXTENDED SEARCH
Log in
Top
Topics in Catalysis
Published in: Topics in Catalysis 1-2/2017

29-09-2016 | Original Paper

Identification and Quantification of Copper Sites in Zeolites by Electron Paramagnetic Resonance Spectroscopy

Authors: Anita Godiksen, Peter N. R. Vennestrøm, Søren B. Rasmussen, Susanne Mossin

Published in: Topics in Catalysis | Issue 1-2/2017

Log in

Activate our intelligent search to find suitable subject content or patents.

search-config
loading …

Abstract

Recent quantitative electron paramagnetic resonance spectroscopy (EPR) data on different copper species present in copper exchanged CHA zeolites are presented and put into context with the literature on other copper zeolites. Results presented herein were obtained using ex situ and in situ EPR on copper ion exchanged into a CHA zeolite with Si/Al = 14 ± 1 to obtain Cu/Al = 0.46 ± 0.02. The results shed light on the identity of different copper species present after activation in air. Since the EPR signal is quantifiable, the content of the different EPR active species has been elucidated and Cu2+ in 2Al positions in the 6-membered rings (6mr) of the CHA structure has been characterized. Some copper species are found not to give an EPR signal at ambient or high temperatures. Fortunately, treatments with different gasses under in situ conditions are able to trigger an EPR signal and thus reveal information about the reactivity and the quantity of some of the otherwise EPR silent species. In this way the [Cu–OH]+ species in copper substituted low-Al zeolites has been indirectly observed and quantified. EPR active Cu2+ species have been followed under reduction and oxidation with gas mixtures relevant for the selective catalytic reduction of NO with NH3 (NH3-SCR) revealing that all Cu2+ in 6mr are easily reduced and oxidized at 200 °C. Furthermore, a stable [Cu–NO3]+ species is identified in Cu-CHA after exposure to NO and O2, but is not stable in 2Al 6mr sites of the CHA structure under the applied conditions.
previous article Catalyzed Particulate Filter Regeneration by Platinum Versus Noble Metal-Free Catalysts: From Principles to Real Application
next article Optimal Operating Conditions of Coupled Sequential NOx Storage/Reduction and Cu/CHA Selective Catalytic Reduction Monoliths

Dont have a licence yet? Then find out more about our products and how to get one now:

Springer Professional "Wirtschaft+Technik"

Online-Abonnement

Mit Springer Professional "Wirtschaft+Technik" erhalten Sie Zugriff auf:

  • über 102.000 Bücher
  • über 537 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Finance + Banking
  • Management + Führung
  • Marketing + Vertrieb
  • Maschinenbau + Werkstoffe
  • Versicherung + Risiko

Jetzt Wissensvorsprung sichern!

inform now

Springer Professional "Technik"

Online-Abonnement

Mit Springer Professional "Technik" erhalten Sie Zugriff auf:

  • über 67.000 Bücher
  • über 390 Zeitschriften

aus folgenden Fachgebieten:

  • Automobil + Motoren
  • Bauwesen + Immobilien
  • Business IT + Informatik
  • Elektrotechnik + Elektronik
  • Energie + Nachhaltigkeit
  • Maschinenbau + Werkstoffe




 

Jetzt Wissensvorsprung sichern!

inform now
Literature
1.
Gao F, Kwak JH, Szanyi J, Peden CHF (2013) Current understanding of Cu-exchanged chabazite molecular sieves for use as commercial diesel engine DeNOx catalysts. Top Catal 56:1441–1459CrossRef
2.
Beale AM, Gao F, Lezcano-Gonzalez I et al (2015) Recent advances in automotive catalysis for NOx emission control by small-pore microporous materials. Chem Soc Rev 44:7371–7405CrossRef
3.
Deka U, Lezcano-Gonzalez I, Weckhuysen BM, Beale AM (2013) Local environment and nature of Cu active sites in zeolite-based catalysts for the selective catalytic reduction of NOx. ACS Catal 3:413–427CrossRef
4.
EU Commission (2011) Commission Regulation (EU) No 582/2011 of 25 May 2011. Off J Eur Union L 167: 1
5.
Meier WM, Olson DH, Baerlocher C (1996) Atlas of zeolite structure types. Zeolites 17:1–230CrossRef
6.
Iwamoto M, Hamada H (1991) Removal of nitrogen monoxide from exhaust gases through novel catalytic processes. Catal Today 10:57–71CrossRef
7.
Kwak JH, Tonkyn RG, Kim DH et al (2010) Excellent activity and selectivity of Cu-SSZ-13 in the selective catalytic reduction of NOx with NH3. J Catal 275:187–190CrossRef
8.
Janssens TVW, Falsig H, Lundegaard LF et al (2015) A consistent reaction scheme for the selective catalytic reduction of nitrogen oxides with ammonia. ACS Catal 5:2832–2845CrossRef
9.
Paolucci C, Verma A, Bates S et al (2014) isolation of the copper redox steps in the standard selective catalytic reduction on Cu-SSZ-13. Angew Chem Int Ed 53:11828–11833CrossRef
10.
Gao F, Walter ED, Kollar M et al (2014) Understanding ammonia selective catalytic reduction kinetics over Cu/SSZ-13 from motion of the Cu ions. J Catal 319:1–14CrossRef
11.
Giordanino F, Vennestrøm PNR, Lundegaard LF et al (2013) Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios. Dalton Trans 42:12741–12761CrossRef
12.
Godiksen A, Stappen FN, Vennestrøm PNR et al (2014) Coordination environment of copper sites in Cu-CHA zeolite investigated by electron paramagnetic resonance. J Phys Chem C 118:23126–23138CrossRef
13.
Andersen CW, Bremholm M, Vennestrøm PNR et al (2014) Location of Cu 2+ in CHA zeolite investigated by X-ray diffraction using the Rietveld/maximum entropy method. IUCrJ 1:382–386CrossRef
14.
Stoll S, Schweiger A (2006) EasySpin, a comprehensive software package for spectral simulation and analysis in EPR. J Magn Reson 178:42–55CrossRef
15.
Addison AW, Yokoi H (1977) Spectroscopic and redox properties of pseudotetrahedral copper (II) complexes. Their relationship to copper proteins. Inorg Chem 16:1341–1349CrossRef
16.
Peisach J, Blumberg WE (1974) Structural implications derived from the analysis of electron paramagnetic resonance spectra of natural and artificial copper proteins. Arch Biochem Biophys 165:691–708CrossRef
17.
Sakaguchi U, Addison AW (1979) Spectroscopic and redox studies of some copper(II) Complexes with bio- mimetic donor atoms : implications for protein copper centres. J Chem Soc Dalton Trans 4:600–608CrossRef
18.
Carl PJ, Larsen SC (2000) EPR study of copper-exchanged zeolites: effects of correlated g- and A-strain, Si/Al ratio, and parent zeolite. J Phys Chem B 104:6568–6575CrossRef
19.
Carl PJ, Larsen SC (1999) Variable-temperature electron paramagnetic resonance studies of copper-exchanged zeolites. J Catal 182:208–218CrossRef
20.
Öpik U, Pryce MHL (1957) Jahn–Teller effect. I. A survey of the static problem. Proc R Soc Lond A 238:425–447CrossRef
21.
Jahn HA, Teller E (1937) Stability of polyatomic molecules in degenerate electronic states. I. Orbital degeneracy. Proc R Soc Lond A 161:220–235CrossRef
22.
Bendix J (2004) Ligfield. Compr Coord Chem 2:673–676
23.
Piligkos S, Bendix J, Weihe H et al (2008) A ligand-field study of the ground spin-state magnetic anisotropy in a family of hexanuclear Mn(III) single-molecule magnets. Dalton Trans 17:2277–2284CrossRef
24.
Broser I, Schulz M (1969) Elektronenspinresonanz an Kupferdozierten ZnO-Einkristallen. Solid State Commun 7:651–655CrossRef
25.
Narayana M, Kevan L (1983) Detection of a new trigonal bipyramidal copper species in Cu–CaX zeolite by electron spin resonance and electron spin echo modulation analysis. J Chem Phys 78:3573–3578CrossRef
26.
Vanelderen P, Vancauwenbergh J, Sels BF, Schoonheydt RA (2013) Coordination chemistry and reactivity of copper in zeolites. Coord Chem Rev 257:483–494CrossRef
27.
Dědeček J, Kaucký D, Wichterlová B (2000) Co2+ ion siting in pentasil-containing zeolites, part 3. Co2+ ion sites and their occupation in ZSM-5: a VIS diffuse reflectance spectroscopy study. Micropor Mesopor Mater 35–36:483–494
28.
Conesa JC, Soria J (1979) Electron spin resonance of copper-exchanged Y zeolites. J Chem Soc Faraday Trans 1(75):291–293
29.
Nicula A, Stamires D, Turkevich J (1965) Paramagnetic resonance absorption of copper ions in porous crystals. J Chem Phys 42:3684–3692CrossRef
30.
Kucherov A, Gerlock J (1994) In situ determination by esr of the oxidation state of copper in Cu-ZSM-5 in flowing He and O2 up to 500 °C. J Phys Chem 98:4892–4894CrossRef
31.
Kucherov AV, Slinkin AA (1989) Change of Cu(II) cation coordination in H-ZSM-5 channels upon the sorption of n-hexane and xenon: ESR spectroscopic evidence. J Phys Chem 93:864–867CrossRef
32.
Gao F, Walter ED, Karp EM et al (2013) Structure–activity relationships in NH3-SCR over Cu-SSZ-13 as probed by reaction kinetics and EPR studies. J Catal 300:20–29CrossRef
33.
Larsen SC, Aylor A, Bell AT, Reimer JA (1994) Electron paramagnetic resonance studies of copper ion-exchanged ZSM-5. J Phys Chem 98:11533–11540CrossRef
34.
Anderson MW, Kevan L (1987) Study of Cu2+-doped zeolite NaH-ZSM-5 by electron spin resonance and electron spin echo modutation spectroscopies. J Phys Chem 91:4174–4179CrossRef
35.
Kucherov A, Gerlock J, Jen H, Shelef M (1995) In situ esr monitoring of the coordination and oxidation states of copper in Cu-ZSM-5 up to 500 °C in flowing gas mixtures: 1. Interaction with He, O2, NO, NO2 and H2O. Zeolites 15:9–14CrossRef
36.
Pierloot K, Delabie A, Groothaert MH, Schoonheydt RA (2001) A reinterpretation of the EPR spectra of Cu(II) in zeolites A, Y and ZK4, based on ab initio cluster model calculations. Phys Chem Chem Phys 3:2174–2183CrossRef
37.
Vanelderen P, Vancauwenbergh J, Tsai M-L et al (2014) Spectroscopy and redox chemistry of copper in mordenite. ChemPhysChem 15:91–99CrossRef
38.
Oliva C, Selli E, Ponti A et al (1997) FTIR and EPR characterisation of copper-exchanged mordenites and beta zeolites. J Chem Soc Faraday Trans 93:2603–2608CrossRef
39.
Borfecchia E, Lomachenko KA, Giordanino F et al (2015) Revisiting the nature of Cu sites in the activated Cu-SSZ-13 catalyst for SCR reaction. Chem Sci 6:548–563CrossRef
40.
Shwan S, Skoglundh M, Lundegaard LF et al (2014) Solid-state ion-exchange of copper into zeolites facilitated by ammonia at low temperature. ACS Catal 5:16–19CrossRef
41.
Yu J-S, Kevan L (1990) Temperature dependence of copper(II) migration and formation of new copper(II) species during catalytic propylene oxidation on copper(II)-exchanged Y zeolite and comparison with X zeolite. J Phys Chem 94:7612–7620CrossRef
42.
Seo SM, Lim WT, Seff K (2012) Crystallographic verification that copper(II) coordinates to four of the oxygen atoms of zeolite 6-rings. Two single-crystal structures of fully dehydrated, largely Cu2+ exchanged zeolite Y (FAU, Si/Al = 1.56). J Phys Chem C 116:963–974CrossRef
43.
Deka U, Eilertsen EA, Emerich H et al (2012) Confirmation of isolated Cu2+ ions in SSZ-13 zeolite as active sites in NH3-selective catalytic reduction. J Phys Chem C 116:4809–4818CrossRef
44.
Groothaert MH, Pierloot K, Delabie A, Schoonheydt RA (2003) Identification of Cu(II) coordination structures in Cu-ZSM-5, based on a DFT/ab initio assignment of the EPR spectra. Phys Chem Chem Phys 5:2135–2144CrossRef
45.
De Tavernier S, Schoonheydt RA (1991) Coordination of Cu2+ in synthetic mordenites. Zeolites 11:155–163CrossRef
46.
Kucherov AV, Slinkin AA, Kondrat’ev DA et al (1985) Cu2+-cation location and reactivity in mordenite and ZSM-5: esr-study. Zeolites 5:320–324CrossRef
47.
Bates SA, Verma AA, Paolucci C et al (2014) Identification of the active Cu site in standard selective catalytic reduction with ammonia on Cu-SSZ-13. J Catal 312:87–97CrossRef
48.
Göltl F, Bulo RE, Sautet P (2013) What makes copper-exchanged SSZ-13 zeolite efficient at cleaning car exhaust gases? J Phys Chem Lett 4:2244–2249CrossRef
49.
Göltl F, Sautet P, Hermans I (2016) The impact of finite temperature on the coordination of Cu cations in the zeolite SSZ-13. Catal Today 267:41–46CrossRef
50.
Delabie A, Pierloot K, Groothaert MH et al (2001) The siting of Cu(II) in mordenite: a theoretical spectroscopic study. Phys Chem Chem Phys 4:134–145CrossRef
51.
Moreno-González M, Hueso B, Boronat M et al (2015) Ammonia-containing species formed in Cu-chabazite as per in situ EPR, solid-state NMR, and DFT calculations. J Phys Chem Lett 6:1011–1017CrossRef
52.
Packet D, Dehertogh W, Schoonheydt RA (1985) Spectroscopy of Cu(II) coordinated to lattice oxygens in zeolites. In: Drzaj B, Hocevar S, Pevojnik S (eds) Zeolites: synthesis, structure, technology, and application. Elsevier, Amsterdam, pp 351–358
53.
Schoonheydt RA (1993) Transition metal ions in zeolites: siting and energetics of Cu2+. Catal Rev 35:129–168CrossRef
54.
LoJacono M, Fierro G, Dragone R et al (1997) Zeolite chemistry of CuZSM-5 revisited. J Phys Chem B 5647:1979–1984CrossRef
55.
Conesa JC, Soria J (1978) Electron spin resonance of undetected copper(II) ions in Y zeolite. J Phys Chem 82:1847–1850CrossRef
56.
Valyon J, Hall WK (1993) On the preparation and properties of CuZSM-5 catalysts for NO decomposition. Catal Lett 19:109–119CrossRef
57.
Verma AA, Bates SA, Anggara T et al (2014) NO oxidation: a probe reaction on Cu-SSZ-13. J Catal 312:179–190CrossRef
58.
Gao F, Wang Y, Washton NM et al (2015) Effects of alkali and alkaline earth cocations on the activity and hydrothermal stability of Cu/SSZ-13 NH 3 -SCR catalysts. ACS Catal 5:6780–6791CrossRef
59.
Günter T, Carvalho H, Doronkin DE et al (2015) Structural snapshots of the SCR reaction mechanism on Cu-SSZ-13. Chem Commun 51:9227–9230CrossRef
60.
Kieger S, Delahay G, Coq B, Neveu B (1999) Selective catalytic reduction of nitric oxide by ammonia over Cu-FAU catalysts in oxygen-rich atmosphere. J Catal 183:267–280CrossRef
61.
Kwak JH, Lee JH, Burton SD et al (2013) A common intermediate for N2 formation in enzymes and zeolites: side-on Cu-nitrosyl complexes. Angew Chem Int Ed Engl 52:9985–9989CrossRef
Metadata
Title
Identification and Quantification of Copper Sites in Zeolites by Electron Paramagnetic Resonance Spectroscopy
Authors
Anita Godiksen
Peter N. R. Vennestrøm
Søren B. Rasmussen
Susanne Mossin
Publication date
29-09-2016
Publisher
Springer US
Published in
Topics in Catalysis / Issue 1-2/2017
Print ISSN: 1022-5528
Electronic ISSN: 1572-9028
DOI
https://doi.org/10.1007/s11244-016-0731-7

Other articles of this Issue 1-2/2017

Topics in Catalysis 1-2/2017 Go to the issue

Original Paper

Catalytic Abatement of VOC Over Novel Pt Fiberglass Catalysts

Original Paper

Catalyzed Particulate Filter Regeneration by Platinum Versus Noble Metal-Free Catalysts: From Principles to Real Application

Original Paper

Strong Enhancement of deSoot Activity of Transition Metal Oxides by Alkali Doping: Additive Effects of Potassium and Nitric Oxide

Original Paper

Promoting Effect of Co, Cu, Cr and Fe on Activity of Ni-Based Alloys in Catalytic Processing of Chlorinated Hydrocarbons

ORIGINAL PAPER

The Nature of Synergetic Effect of Manganese Oxide and Platinum in Pt–MnOX–Alumina Oxidation Catalysts

Original Paper

Effect of Alumina Phase Transformation on Stability of Low-Loaded Pd-Rh Catalysts for CO Oxidation

Premium Partners

    Image Credits