Formation of copper nanoparticles in LTL nanosized zeolite: spectroscopic characterization.

The state of copper species stabilized in nanosized LTL zeolite subjected to various post-synthesis treatments was unveiled by a range of spectroscopic techniques. FTIR and UV-Vis studies demonstrated that the reduction process of copper in the LTL nanosized zeolite leads to the formation of different species including Cu2+, Cu+ and Cu nanoparticles (Cu NPs). The adsorption of probe molecules (NO and CO) was used to selectively monitor the copper species in the LTL nanosized zeolite upon oxidation and reduction post-synthesis treatments. Both the Cu2+ and Cu+ species were probed by NO and CO, respectively. The amount of Cu+ in the LTL zeolite nanocrystals was about 43% as determined by FTIR, while the amount of Cu NPs was about 55% determined by the UV-Vis spectroscopic characterization. These results were complemented by EPR, 29Si and 63Cu MAS NMR spectroscopic data. The EPR spectroscopy was further applied to monitor the effective reduction of the Cu2+ species and their re-oxidation, while the 63Cu MAS NMR verified the presence of Cu NPs in the LTL nanosized zeolite crystals.

[1]  S. Mintova,et al.  Formation of Copper Nanoparticles in LTL Nanosized Zeolite: Kinetics Study , 2016 .

[2]  Y. Sasson,et al.  A new mechanism for allylic alcohol isomerization involving ruthenium nanoparticles as a ‘true catalyst’ generated through the self-assembly of supramolecular triruthenium clusters , 2016 .

[3]  David Farrusseng,et al.  Perspectives on zeolite-encapsulated metal nanoparticles and their applications in catalysis , 2016 .

[4]  Weimin Yang,et al.  Recent advances of pore system construction in zeolite-catalyzed chemical industry processes. , 2015, Chemical Society reviews.

[5]  Arnaud Travert,et al.  Probing zeolites by vibrational spectroscopies. , 2015, Chemical Society reviews.

[6]  V. Valtchev,et al.  Nanosized microporous crystals: emerging applications. , 2015, Chemical Society reviews.

[7]  M. Mihaylov,et al.  Surprising Coordination Chemistry of Cu+ Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N2, and H2O on Cu–ZSM-5 , 2015 .

[8]  Elisa Borfecchia,et al.  A Consistent Reaction Scheme for the Selective Catalytic Reduction of Nitrogen Oxides with Ammonia , 2015 .

[9]  F. Deng,et al.  Paramagnetic relaxation enhancement solid-state NMR studies of heterogeneous catalytic reaction over HY zeolite using natural abundance reactant. , 2015, Solid state nuclear magnetic resonance.

[10]  K. Chakarova,et al.  Disproportionation of associated Cu2+ sites in Cu-ZSM-5 to Cu+ and Cu3+ and FTIR detection of Cu3+(NO)x (x = 1, 2) species , 2014 .

[11]  D. Esquivel,et al.  Transition metal exchanged β zeolites: Characterization of the metal state and catalytic application in the methanol conversion to hydrocarbons , 2013 .

[12]  Y. Sasaki,et al.  Drastic sensitivity enhancement in 29Si MAS NMR of zeolites and mesoporous silica materials by paramagnetic doping of Cu2+. , 2013, Physical chemistry chemical physics : PCCP.

[13]  Yugang Sun,et al.  Controlled synthesis of colloidal silver nanoparticles in organic solutions: empirical rules for nucleation engineering. , 2013, Chemical Society reviews.

[14]  Bert M. Weckhuysen,et al.  Local Environment and Nature of Cu Active Sites in Zeolite-Based Catalysts for the Selective Catalytic Reduction of NOx , 2013 .

[15]  M. Daturi,et al.  Zeolite MCM-22 Modified with Au and Cu for Catalytic Total Oxidation of Methanol and Carbon Monoxide , 2013 .

[16]  M. Marelli,et al.  Size controlled copper nanoparticles hosted in mesoporous silica matrix: Preparation and characterization , 2012 .

[17]  J. Zou,et al.  Synthesis, growth mechanism and thermal stability of copper nanoparticles encapsulated by multi-layer graphene , 2012 .

[18]  Yugang Sun.  Watching nanoparticle kinetics in liquid , 2012 .

[19]  Wei Chen,et al.  Copper nanoclusters: Synthesis, characterization and properties , 2012 .

[20]  L. Mafra,et al.  Structural Characterization of Zeolites by Advanced Solid State NMR Spectroscopic Methods , 2012 .

[21]  Qing Yang,et al.  Application of Noble Metal Nanoparticles in Organic Reactions , 2011 .

[22]  Frédéric Thibault-Starzyk,et al.  Analysing and understanding the active site by IR spectroscopy. , 2010, Chemical Society reviews.

[23]  Adriano Zecchina,et al.  Probing the surfaces of heterogeneous catalysts by in situ IR spectroscopy. , 2010, Chemical Society reviews.

[24]  C. Grey,et al.  Investigation of the Conversion Reaction Mechanisms for Binary Copper(II) Compounds by Solid-State NMR Spectroscopy and X-ray Diffraction , 2009 .

[25]  S. Mintova,et al.  Colloidal zeolites as host matrix for copper nanoclusters , 2006 .

[26]  C. Griesinger,et al.  Structural characterization of copper(II) binding to alpha-synuclein: Insights into the bioinorganic chemistry of Parkinson's disease. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[27]  M. Daturi,et al.  Cu state and behaviour in MCM-41 mesoporous molecular sieves modified with copper during the synthesis––comparison with copper exchanged materials , 2004 .

[28]  M. Daturi,et al.  FTIR spectroscopic study of low temperature NO adsorption and NO + O2 coadsorption on H-ZSM-5. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[29]  A. Knop‐Gericke,et al.  Study of copper nanoparticles formation on supports of different nature by UV-visible diffuse reflectance spectroscopy , 2004 .

[30]  K. Hadjiivanov,et al.  FTIR study of CO and NO adsorption and coadsorption on a Cu/SiO2 catalyst: Probing the oxidation state of copper , 2001 .

[31]  K. Hadjiivanov.  Identification of Neutral and Charged N x O y Surface Species by IR Spectroscopy , 2000 .

[32]  K. Hadjiivanov,et al.  FTIR Study of Low-Temperature CO Adsorption on Cu-ZSM-5: Evidence of the Formation of Cu2+(CO)2 Species , 2000 .

[33]  C. Lamberti,et al.  Oxidation States of Copper Ions in ZSM-5 Zeolites. A Multitechnique Investigation. , 2000, The journal of physical chemistry. B.

[34]  F. Geobaldo,et al.  FTIR study of CO adsorbed at low temperature on zeolite L - Evidence for an ordered distribution of aluminium atoms , 1997 .

[35]  Siglinda Perathoner,et al.  Nature of active species in copper-based catalysts and their chemistry of transformation of nitrogen oxides , 1995 .

[36]  R. Schoonheydt.  Transition metal ions in zeolites: siting and energetics of Cu2+ , 1993 .

[37]  K. Hadjiivanov,et al.  Low-temperature CO adsorption on Cu2+/TiO2 catalysts , 1992 .

[38]  J. M. Nicol,et al.  FTi.r. studies of copper-containing Y zeolites: Part 1. Location of copper (I)-carbonyl complexes , 1988 .

[39]  G. T. Kerr.  Chemistry of crystalline aluminosilicates. VI. Preparation and properties of ultrastable hydrogen zeolite Y , 1969 .