Surface carbonyl species of copper supported on dealuminated Y zeolite

Mießner, H.; Landmesser, H.; Jaeger, N. I.; Richter, Klaus

doi:10.1039/a702959d

Cited by 37 publications

(32 citation statements)

References 21 publications

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“…10,19,23,24 This is demonstrated on Figure S4 from the Supporting Information. Introduction of water at ambient temperature to the CO-precovered sample leads to shift of the carbonyl band from 2158 to 2132 cm -1 ( Figure S4, spectrum a indicates that the π-component of the Cu + -CO bond remains practically the same.…”

Section: Adsorption Of Comentioning

confidence: 82%

“…It has also been reported that each cationic position is characterized by a critical cationic radius of hosted cations in order geminal species to be formed. 12,13 In these cases 4 found with Cu + ions in other zeolites 24,[27][28][29][30]33,34 and porous materials. 46 Note that when CO is adsorbed on oxide supported copper, the Cu + -CO species formed are characterized by an IR band around 2130 cm -1 which is associated with the higher coordination number of Cu + in these cases.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Surprising Coordination Chemistry of Cu⁺Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N₂, and H₂O on Cu–ZSM-5

et al. 2015

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Cations exchanged in zeolites are generally characterized by a low coordination number and can thus attach simultaneously more than one small guest molecule. For instance, Cu + ions in ZSM-5 can accept, at low temperature, up to three CO and up to two NO molecules. However, only one N 2 molecule can be coordinated to such sites. Although mixed aqua-carbonyl and aqua-dinitrogen complexes are formed, no mixed carbonyl-nitrosyl, carbonyl-dinitrogen or nitrosyl-dinitrogen species can be produced. Thus, adsorption of NO on CO precovered sample results in segregation of the CO adsorption layer according to the reaction: 2 Cu + -CO + 2 NO → Cu + (CO) 2 + Cu + (NO) 2 . Adsorption of N 2 on NO precovered sample leads to a similar process: 2 dinitrogen complexes are produced during CO -N 2 coadsorption. The role of the ligand and the nature of the bond on the formation of geminal and mixed-ligand complexes are discussed. the change of the ligand does not affect the process and consequently mixed ligand species, e.g. Na + (CO)(N 2 ) in NaY, have been isolated. 2 For catalysis, the formation of geminal ad-species with transition metal cations in zeolites is more important. However, in these cases the situation could be complicated. 11 First of all, the socalled "complex-specified" geminal species can be produced with particular cation-adsorbate systems. For instance, with Rh + cations CO forms Rh + (CO) 2 dicarbonyls irrespective of the support. These species do not produce monocarbonyls upon decomposition. 14,15,39 In this case the driving force of the formation of the complexes is the achievement of a stable electron configuration. However, even in these cases the cation coordination is important. Thus, while only dicarbonyls are formed with oxide-supported rhodium, Rh + (CO) 3 and Rh + (CO) 4 species are produced with Rh + sites in zeolites. 14,15 Copper-exchanged zeolites are subjected to a continued interest. They are effective catalysts in many reactions, e.g. selective catalytic reduction of NO x with hydrocarbons, 40,41 decomposition of NO 42 and N 2 O, 43 oxidation of methane to methanol, 44 oxidative carbonylation of methanol to dimethyl carbonate, 45 etc. That is why the coordination state of copper in zeolites has attracted the interest of many researchers. In what follows we shall concentrate on Cu + sites because they demonstrate fascinating coordination chemistry.In 1994 Zechina et al. 18 reported that CO adsorption at room temperature on Cu I -ZSM-5 resulted in formation of Cu + (CO) 2 dicarbonyl species characterized by two IR bands: ν s at 2178 and ν as at 2151 cm -1 . Decrease of the CO equilibrium pressure led to loss of one of the CO ligands and conversion of these species into monocarbonyls (2157 cm -1 ). In contrast, at low temperature a large part of dicarbonyls were converted into tricarbonyls (2190, 2164 and 2140 cm -1 ). Later on, the results were confirmed by other authors 21,22,26 and similar situation was also . EXPERIMENTAL The starting zeolite material was prepared by calcination of NH 4 ZSM-5...

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Section: Adsorption Of Comentioning

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Surprising Coordination Chemistry of Cu⁺Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N₂, and H₂O on Cu–ZSM-5

et al. 2015

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“…There are many works reporting formation of copper di-(and even tri-) carbonyls after CO adsorption on zeolites [58][59][60][61][62][63]. However, typically the ν as and ν s modes are observed around 2178 and 2151 cm −1 .…”

Section: Co Adsorption On Oxidized Cm2mentioning

confidence: 94%

“…They are usually observed in two spectral regions: (1) around 2160 cm −1 (with most zeolite samples [58][59][60][61][62][63]) and around 2130 cm −1 (when copper is supported on oxides [60,[64][65][66][67][68][69][70][71]). At high CO equilibrium pressures Cu + ions in zeolites form dicarbonyls, and even tricarbonyls at low temperatures [58][59][60][61][62][63]. Formation of dicarbonyls was also proposed recently for oxide-supported copper [64][65][66].…”

Section: Introductionmentioning

confidence: 99%

Copper-modified mesoporous MCM-41 silica: FTIR and catalytic study

Tsoncheva

Venkov

Dimitrov

et al. 2004

Journal of Molecular Catalysis A: Chemical

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“…In contrast, the high-frequency band representing the rhenium carbonyl in zeolite DAY 773 matches the 2036cm À1 band of Re(CO) 3 {OMg} x {HOMg} 3Àx 16 on MgO calcined at 973 K. The high-frequency n CO band characterizing rhenium carbonyls on highly dehydroxylated MgO shifts to higher wavenumbers with increasing calcination temperature and increasing surface dehydroxylation. 15,67,68 Thus, we infer that the bonding sites in zeolite DAY 773 withdraw electron density from rhenium of the rhenium carbonyls to a degree nearly matching that of the sites on highly dehydroxylated MgO. 69 Rhenium carbonyls bonded to thin oxide films are also characterized by a high-frequency n CO band at relatively high wavenumbers (2050 cm À1 for Re(CO) 3 {OSi} 3 on a SiO 2 film grown on Mo(110); 39 the red shift is similar to those of MgO-supported Re(CO) 3 .…”

Section: Identification Of Supported Rhenium Carbonylsmentioning

confidence: 99%

A rhenium carbonyl bonded to highly dealuminated zeolite Y: structure determination by infrared and X-ray absorption spectroscopies

Enderle

Gates

2004

Phys. Chem. Chem. Phys.

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Surface carbonyl species of copper supported on dealuminated Y zeolite

Cited by 37 publications

References 21 publications

Surprising Coordination Chemistry of Cu⁺Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N₂, and H₂O on Cu–ZSM-5

Surprising Coordination Chemistry of Cu⁺Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N₂, and H₂O on Cu–ZSM-5

Copper-modified mesoporous MCM-41 silica: FTIR and catalytic study

A rhenium carbonyl bonded to highly dealuminated zeolite Y: structure determination by infrared and X-ray absorption spectroscopies

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Surface carbonyl species of copper supported on dealuminated Y zeolite

Cited by 37 publications

References 21 publications

Surprising Coordination Chemistry of Cu+Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N2, and H2O on Cu–ZSM-5

Surprising Coordination Chemistry of Cu+Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N2, and H2O on Cu–ZSM-5

Copper-modified mesoporous MCM-41 silica: FTIR and catalytic study

A rhenium carbonyl bonded to highly dealuminated zeolite Y: structure determination by infrared and X-ray absorption spectroscopies

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Surprising Coordination Chemistry of Cu⁺Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N₂, and H₂O on Cu–ZSM-5

Surprising Coordination Chemistry of Cu⁺Cations in Zeolites: FTIR Study of Adsorption and Coadsorption of CO, NO, N₂, and H₂O on Cu–ZSM-5