Strong modification of Pt-CO interaction caused by alloying with chromium in Pt-Cr/HZSM-5 catalysts

The catalysts Pt/HZSM-5 and Pt-Cr/HZSM-5 are characterized by FTIR spectroscopy using CO as a probe molecule, and by transmission electron microscopy. The major fraction of the metal phase detected in the micrographs exhibits particles in the range of 1–3 nm uniformly distributed in the zeolite crystals. Nanodiffraction analysis of single particles confirmed the formation of fcc Pt-Cr alloy with lattice constanta = 0.386 nm. The infrared spectra at 300 K exhibit bands assigned to CO linearly bonded to zeolite-hosted metal particles at 2089 cm^–1 for Pt/HZSM-5, and at 2120 and 2092 cm^–1 for Pt-Cr/HZSM-5. The temperature increase to 610 K resulted in a strong shift of the 2089 cm^–1 band for Pt/HZSM-5 by 25 cm^–1 and a slight shift of the corresponding bands for Pt-Cr/HZSM-5 by 6 cm^–1. The differences are referred to different electron backdonation capacities of the CO binding Pt surface atoms of the metal particles. The lower capacity for the Pt-Cr/HZSM-5 sample is due to alloying in the metal particles.     

Interaction of methane with surface of alumina studied by FT-IR spectroscopy

Methane adsorption on alumina was investigated by FT-IR spectroscopy at 173 K. Adsorbed methane gives four distinct IR bands at 3008, 3000, 2900 and 1305 cm^–1 which are attributed to v₁ (2900 cm^–1), v₃ (3008, 3000 cm^–1), and v₄ (1305 cm^–1) modes of methane respectively. The appearance of the v₁ mode indicates that the T_d symmetry of methane is distorted by the adsorption. The intensities of these bands increase significantly with outgassing temperatures of alumina, reach their maxima at an outgassing temperature near 773 K, and then decrease with further higher outgassing temperatures. Two hydroxyls with IR bands at 3750 and 3665 cm^–1 are perturbed evidently by the adsorbed CH₄ thereby resulting in two redshifted bands at 3707 and 3640 cm^–1. Coadsorbed CO slightly affects the adsorbed CH₄ indicating the very weak interaction between CH₄ and surface cations of alumina. It is proposed that the adsorbed CH₄ on alumina is formed mainly via the interaction of CH₄ with both surface hydroxyl and c.u.s. oxygen anion.     

Infrared and adsorption study of strong metal-support interaction in diluted platinum-alumina catalysts

Diffuse reflectance IR spectroscopy along with H₂ and CO adsorption measurements were applied to the study of 0.3% Pt/--Al₂O₃ catalyst precalcined in an air flow at 1023 K and then reduced at 773 and 973 K in hydrogen. Reduction of the catalyst at 973 K results in formation of supported metallic Pt particles in SMSI (strong metal-support interaction) state, as evidenced by the sharp decrease of Pt ability to chemisorb H, at room temperature as well as the significant lowering of thermal stability of linear Pt-CO complexes. Spectroscopically the effect of SMSI is manifested by the slight increase of the singleton frequency of linearly adsorbed CO from 2050 to 2060 cm^–1 together with the decrease of the dipole-dipole shift from 40 to 15 cm^–1 and by a large decrease of absorption band extinction.     

Interactions between interfacial water and CO adsorbed on Pt and Pt-Ru alloy surfaces under electrochemical conditions: Density-functional theory study

The structural and electronic properties of interfacial water and adsorbed CO on platinum and platinum/ruthenium alloy have been studied via density-functional theory calculations to gain insight into the water-adsorbate interaction under electrochemical conditions. The computational simulations reveal a new interpretation for the interaction of adsorbed CO and water at the electrochemical interfaces. The new interaction model rationalizes the observed quantitative relationship between infrared intensities for adsorbed bridging CO and water molecules that impart a high-frequency O-H stretch, ca. 3630-3660 cm⁻¹ on pure Pt and 3600-3620 cm⁻¹ on PtRu alloy. The theoretical modeling indicates that the observed feature common to both pure Pt and PtRu alloy surfaces is due to interfacial water molecules firmly hydrogen-bonded to bridging CO.     

Characterization of the Pt-C bond of CO adsorbed by small Pt particles in a NaX zeolite by IR diffuse reflectance spectroscopy

The unusual properties of small (1–2 nm) Pt particles within a zeolite support are documented by diffuse reflectance infrared spectroscopy of the metal-carbon bond of linearly adsorbed CO. The wave number of the metal-carbon stretching frequency is found to be about 60 cm^–1 higher compared to larger particles (2–3 nm) or to the bulk metal. The stronger bond is attributed to a negative charge on the small metal particles.     

Adsorption/oxidation of CO on highly dispersed Pt catalyst studied by combined electrochemical and ATR-FTIRAS methods: Part 1. ATR-FTIRAS spectra of CO adsorbed on highly dispersed Pt catalyst on carbon black and carbon un-supported Pt black

Elecrochemical ATR-FTIRAS measurements were conducted for the first time to investigate nature of CO adsorbed under potential control on a highly dispersed Pt catalyst with average particle size of 2.6 nm supported on carbon black (Pt/C) and carbon un-supported Pt black catalyst (Pt-B). Each catalyst was uniformly dispersed by 10 μg Pt/cm² and fixed by Nafion^® film of 0.05 μm thick on a gold film chemically deposited on a Si ATR prism window. Adsorption of CO was conducted at 0.05 V on the catalysts in 1 and 100% CO atmospheres, for which CO coverage, θ_CO, was 0.69 and 1, respectively. Two well-defined ν(CO) bands free from band anomalies assigned to atop CO (CO(L)) and symmetrically bridge bonded CO (CO(B)_sym.) were observed. It was newly found that the CO(L) band was spitted into two well-defined peaks, particularly in 1% CO, from very early stage of adsorption, which was interpreted in terms of simultaneous occupation of terrace and step-edge sites, denoted as CO(L)_terrace and CO(L)_edge, respectively. This simultaneous occupation was commonly observed in our work both on Pt/C and Pt-B. A new band was also observed around 1950 cm⁻¹ in addition to the bands of CO(L) and CO(B)_sym., which was assigned to asymmetric bridge CO, CO(B)_asym., adsorbed on (1 0 0) terraces, based on our previous ECSTM observation of CO adsorption structures on (1 0 0) facet. The CO(B)_asym. on the Pt/C, particularly in 100% CO atmosphere, results in growth of a sharp band at 3650 cm⁻¹ accompanied by a concomitant development of a band around 3500 cm⁻¹. The former and the latter are assigned to ν(OH) vibrations of non-hydrogen bonded and hydrogen bonded water molecules adsorbed on Pt, respectively, interpreted in term of results from a bond scission of the existing hydrogen bonded networks by CO(L)s and from a promotion of new hydrogen bonding among water molecules presumably by CO(B)_asym..It was found that the frequency ν(CO) of CO(L) both on Pt/C and Pt-B is lower than that on bulky polycrystalline electrode Pt(poly) or different crystal planes of Pt single-crystal electrodes by 30-40 cm⁻¹ at corresponding potentials, which implies a stronger electronic interaction between CO and Pt nano-particles and/or an increased contribution of step-edge sites on the particles. Determination of the band intensities of CO(L), CO(B)_asym. and CO(B)_sym. has led us to conclude a much higher bridged occupation of sites at Pt nano-particles than Pt(poly) electrodes.     

Electronic state and location of Pt metal clusters in KL zeolite: FTIR study of CO chemisorption

Electronic state and location of Pt metal clusters supported on KL zeolite are studied by FTIR spectroscopy of adsorbed CO. Investigation of the CO adsorption was performed within the wide CO pressure range (from 4×10^?3 to 10² Pa) and supplemented by the study of the CO desorption at elevated temperature. Comparison of the data on CO adsorption and desorption at increased temperature reveals the existence of two groups of Pt particles in the sample. The first group of the particles is localized on the outer surface of the zeolite microcrystals and in the near surface region; they exhibit CO bands at 2060-2050 cm^?1 close to those of Pt supported on conventional supports. The particles of the second group are encaged inside zeolite channels and their electronic structure is presumably strongly perturbed by the zeolite framework. CO adsorbed on the Pt particles of this group exhibits coverage dependent bands at frequencies in the range 1960-1920 cm^?1. The marked downward shift of thevCO band is attributed to the increase of electron density on these particles.     

Infrared spectroscopy and microcalorimetry studies of CO adsorption on sulfated zirconia supported platinum catalysts

Carbon monoxide adsorption has been investigated on Pt particles supported on a high surface area zirconia and sulfated zirconias. The accessibility of the Pt surface determined from the comparison of H₂ chemisorption and transmission electron microscopy depends on two parameters: the temperature of treatment in air used to dehydroxylate sulfated zirconia, and the temperature of reduction. An oxidative pretreatment at 823 K yields a poor accessibility of Pt (0.03 < H/Pt < 0.05) whatever the temperature of reduction, whereas a Pt dispersion of 0.6 can be obtained by oxidation at 673 K followed by a mild reduction at 473 K. FTIR spectroscopy of adsorbed CO on Pt/ZrO₂ shows besides the normal linear species at 2065 cm^–1, a band at 1650 cm^–1 which is attributed to CO bridged between Pt and Zr atoms. On Pt/ZrO₂-SO ₄ ^2– , all bridged species tend to disappear, as well as the dipole-dipole coupling andv _CO is shifted by 57 cm^–1 to higher frequencies. These results are attributed to sulfur adsorption on Pt which decreases the electron back-donation from Pt to the 2 ^* antibonding orbital of CO. The lower initial heat of CO adsorption observed on Pt/ZrO₂-SO^4/2– supports this proposal.     

Infrared Study of Benzene Hydrogenation on Pt/SiO2 Catalyst by Co-adsorption of CO and Benzene

FT-IR spectra of the co-adsorption of benzene and CO have been performed to identify the preferred adsorption sites of hydrogen and benzene on a Pt/SiO₂ catalyst for hydrogenation of benzene. Results of CO adsorbed on atop sites on Pt/SiO₂ includes: an α peak at 2091 cm⁻¹, a β peak at 2080 cm⁻¹ and a γ peak at 2067 cm⁻¹ indicating three kinds of adsorption sites for dissociative hydrogen on Pt/SiO₂. The site of lowest CO stretching frequency offers stronger adsorbates–metal interaction for benzene and hydrogen. Hydrogen binding on the site of lowest CO stretching frequency before benzene adsorption significantly enhances the reaction rate of benzene hydrogenation.     

IR study of the interaction of hydroxyl groups of silica gel with Cr species of Phillips' type catalysts

Spectroscopic evidence for the interaction of hydroxyl groups and chromium ions was obtained using a catalyst prepared from chromyl chloride. A new OH peak, observed at 3705 cm^–1 after pumping away CO gas, is attributed to the direct interaction of OH with the low-valent chromium. This peak shifts to 3590 cm^–1 on contact with O₂ at room temperature and it is assigned to a hydroxyl interacting with the oxidized chromium. New assignments are also proposed for IR bands of CO presorbed on the catalyst. The peak due to CO at 2188 cm^–1 decreases as the OH intensity at 3705 cm^–1 increases, suggesting that the former peak arises from adsorption on Cr(II) species to which two oxygen atoms are attached.     

Infrared spectroscopy of carbon monoxide adsorbed on Pt/L zeolite

A series of 0.6 wt% Pt/MBaL zeolites, where M is Li, Na, K, Rb or Cs, were prepared and characterized by transmission electron microscopy, chemisorption, and infrared spectroscopy of adsorbed carbon monoxide. Greater than 90% of the exposed platinum in the samples is associated with small clusters, less than 7 Å across, inside the zeolite channels. The remaining fraction of exposed platinum is on 100–500 Å crystallites outside the channels. Adsorption of carbon monoxide on the platinum at 25 °C produces a broad infrared band whose maximum shifts from 2065 to 2025 cm^–1 as the alkali cations in the zeolite are changed from Li to Cs. This shift is indicative of electron transfer between the cations and the platinum clusters. Heating the Pt/L catalysts to 225 °C produces new infrared bands at 2020–2015, 1975, and 1935–1920 cm^–1. The appearance of these low-frequency bands strongly suggests that the CO-covered platinum clusters change their structure during heating. We propose that the new structure is one in which the carbon monoxide molecules insert into spaces between the framework atoms of the L zeolite.     

Formation of Ni(CO)4 during the Interaction between CO and Silica-Supported Nickel Catalyst: an FTIR Spectroscopic Study

The formation of Ni(CO)₄ during interaction of CO with silica-supported highly dispersed nickel metal (d _av4 nm) was investigated by FTIR spectroscopy. At temperatures below 145 K, in addition to linear and bridged nickel carbonyls, CO adsorption on Ni⁰/SiO₂ leads to the formation of Ni(CO) _x (x=2, 3) subcarbonyls (band at ca. 2090 cm^–1) and negligible amounts of Ni(CO)₄ adsorbed on SiO₂ (band at 2048 cm^–1). Up to this temperature CO causes no detectable erosion of the metal surface. Above 145 K the rate of interaction between CO and the nickel particles significantly increases. Until 235 K Ni(CO)₄ mainly remains in the adsorbed state, while at still higher temperatures the equilibrium between adsorbed and gaseous Ni(CO)₄ (band at 2058 cm^–1) is shifted towards the latter. It is assumed that subcarbonyls formed on defect sites of the metal surface are precursors of the nickel tetracarbonyl. Successive adsorption–evacuation cycles of CO at room temperature result in a decrease in the amount of the Ni(CO)₄ formed, probably due to a reduction of the number of defect metal sites. On the basis of ¹²CO and ¹³CO coadsorption, an alternative interpretation of the band at 2048 cm^–1 to species containing isolated Ni(CO)₃ groups is proposed.     

Some Insights into the Preparation of Pt/γ-Al2O3 Catalysts for the Enantioselective Hydrogenation of α-Ketoesters

Pt/γ-Al₂O₃ catalysts were prepared by two different impregnation methods and characterized by XRD, TEM, and CO chemisorption. The Pt particle sizes ranged in 2.4–23.3 nm for these 5.0 wt% Pt/γ-Al₂O₃ catalysts. The catalysts were also characterized by FT-IR spectroscopy using CO as a probe molecule before and after the chiral modification with cinchonidine. Two IR bands (2078 and 2060 cm^-1) due to CO linearly adsorbed on the Pt/γ-Al₂O₃ catalyst, calcined at 500 °C before reduction in sodium formate solution were observed, whereas only one IR band at ～2070 cm^-1 was observed for other catalysts. A red shift of the IR band was observed after chiral modification of all the catalysts, except the one with the largest Pt particle size and lowest Pt dispersion. The catalytic performance of the cinchonidine-modified Pt/γ-Al₂O₃ catalysts was tested for the enantioselective hydrogenations of ethyl pyruvate and ethyl 2-oxo-4-phenylbutyrate (EOPB). A 95% ee value was obtained for the ethyl pyruvate hydrogenation and about 83% ee was achieved for the enantioselective hydrogenation of EOPB under the optimized preparation and reaction conditions. It is deduced that the interaction of Pt with γ-Al₂O₃ is a crucial factor for obtaining high activity and that the adsorption abilities (adsorption of reactant, solvent and chiral modifier molecules) of the catalyst surface affect the catalytic performance significantly.     

The adsorption of Sn on Pt(1 1 1) and its influence on CO adsorption as studied by XPS and FTIR

The coverage of Sn on Pt(1 1 1) which is obtained by electrochemical deposition from 5×10⁻⁵ M Sn²⁺ in 0.5 M H₂SO₄ has been determined by XPS for different deposition times. Complete suppression of hydrogen adsorption corresponds to a coverage of ?_max=0.35 (Sn to surface Pt atoms).Co-adsorption of CO with Sn on Pt(1 1 1) has been studied by FTIR spectroscopy. The IR spectra of the stretching vibration of CO can be interpreted in terms of the vibrational signature of the Pt(1 1 1)/CO system and no vibrational bands associated with CO on Sn are detected. At high Sn coverages, the 1840 cm⁻¹ band associated with bridge-bonded CO and the 2070 cm⁻¹ band assigned to on-top CO are present, however, no hollow site adsorption which is characterized by the 1780 cm⁻¹ band is revealed within the resolution of the experiment. This vibrational signature corresponds to a less compressed adlayer compared to the (2×2)-3CO saturation structure on Pt(1 1 1). At lower Sn coverages, signatures from both the compressed and the less compressed CO adlayer structures are seen in the spectra. From earlier structural and electrochemical studies it is known that Sn is adsorbed in 2D islands and influences CO molecules in its neighbourhood electronically. This leads to a disappearance of the IR band from CO adsorbed in the hollow site at high Sn coverages and to higher population of the weakly adsorbed state of CO for all Sn-modified surfaces, i.e. a relative increase of the amount of CO oxidised at low potentials. In addition to this electronic effect, Sn also exerts a co-catalytic effect at low Sn coverages on that part of CO which is adsorbed at a larger distance from Sn due to a bi-functional mechanism. The IR spectra shows for the Sn-modified Pt(1 1 1) surface that the transition from the compressed CO adlayer which is characterized by the hollow site adsorption of CO to the less compressed one which exhibits a characteristic band associated with bridge-bonded CO occurs already at 250 mV instead of 400 mV.     

Diffuse reflectance IR study of noble metals supported on basic carriers. Part I: Pt supported on Al-Mg hydrotalcite

The state of metallic Pt supported on alumina-magnesia hydrotalcite was investigated using diffuse reflectance FT-IR spectra of adsorbed CO and terminal Pt hydrides formed upon hydrogen dissociative chemisorption on metal at room temperature. On hydrotalcite surface metallic Pt exists in three different forms, such as neutral and negatively charged metallic particles as well as slightly negatively charged clusters encapsulated between layers of support. Negative charging on Pt particles results in decrease of singleton frequency of linearly adsorbed CO by 70 cm^-1 and frequency of Pt-H bond vibration by 50-100 cm^-1. It was also established that negatively charged Pt is less sulfur resistant than neutral Pt particles. This revised version was published online in July 2006 with corrections to the Cover Date.     

Surface-Enhanced Vibrational Spectroscopy: SERS and SEIRA

With respect to the origin of single-molecule sensitivity in surface-enhanced Raman scattering, elastic scattering and emission spectra were investigated for Ag particles adsorbed with dye. The scattering peak observed at 600–650 nm was extinguished during the inactivation process of an enormous SERS signal, whereas localized surface plasmon (LSP) peaks located at 520 nm and 730 nm did not change significantly. The scattering peak at 600–650 nm arises from increased electromagnetic coupling between the LSP of adjacent Ag particles through dye molecules. In addition, distinct emission peaks were observed at 550–600 nm and 600–750 nm for hot Ag particles with adsorbates. These bands were attributed to emissive relaxation of metal electrons and fluorescence of molecules, respectively. Furthermore, the shorter wavelength peak showed invariant Stokes shift irrespective of excitation wavelengths, most probably arising from inelastic scattering of excited electrons by adsorbed molecules. The adsorbed state of CO and related species on the Pt film electrode was investigated using attenuated total reflection—surface-enhanced infrared absorption spectroscopy. Intermediate species were found on the bare Pt surface in 1 mM CH₃OH + HClO₄ solutions at +0.2 V ≤ E ≤ +0.6 V that give absorption peaks at 1405 cm⁻¹ and 1300 cm⁻¹. These bands can be attributed to carbonate species or -COH. Water molecules located at the hydrophobic interfaces between CO and electrolyte solutions were evidenced by a quite high OH stretch absorption at 3664–3646 cm⁻¹, as well as a lower broad peak at ca. 3480 cm⁻¹.     

Unusual Forms of Molecular Hydrogen Adsorption by Cu+1 Ions in the Copper-Modified ZSM-5 Zeolite

DRIFT and IR transmittance spectra of H₂ adsorbed at 77 K or at room temperature by the copper-modified ZSM-5 zeolite pre-evacuated or pre-reduced in CO at 873 K indicated several unusual forms of adsorbed hydrogen. H–H stretching frequencies of adsorbed species at 3075–3300 cm^–1 are by about 1000 cm<>^–1<> lower than in the free hydrogen molecules. This indicates unusually strong perturbation of adsorbed hydrogen by reduced Cu<>⁺¹<> ions that has been never before reported neither for hydrogen nor for adsorption of other molecules by any cationic form of zeolites or oxides.     

The effect of water on the infrared spectra of CO adsorbed on Pt/K L-zeolite

The effect of water on the infrared spectrum of adsorbed CO has been studied for a Pt/K L-zeolite sample. The red shift of the CO spectra and the intensity transfers to lower frequency bands observed with increasing uptake of water are attributed to an increased electron density of the metal particles. Adsorption of CO under ``wet' conditions results in an increase in the ratio of integrated intensities of bridged to linear CO species, consistent with an increase in the electron density on the metal particles. It is proposed that the water molecules associated with the zeolite cations modify the metal-support interaction via the zeolite lattice. This revised version was published online in July 2006 with corrections to the Cover Date.     

In-situ FT-IRAS study of the CO oxidation reaction over Ru(001): III. Observation of a 2140 cm−1 C-O stretching vibration

Utilizing Fourier Transform Reflection Absorption-Infrared Spectroscopy (FT-IRAS), we have investigated the CO oxidation reaction in-situ on a Ru(001) surface at high ( 10 Torr) pressures. Under certain temperature and reactant (CO and O₂) partial pressure conditions, we observe for the first time on unsupported Ru a weakly adsorbed CO species which is characterized by an unusually high C-O stretching frequency of 2140 cm^–1. A similar feature has been identified previously on small Ru particles in supported catalysts and attributed by some to a multicarbonyl species (–Ru(CO) _n ,n > 1). By following the intensity of this feature on Ru(001) relative to other peaks in the spectra, we believe that the 2140 cm^–1 peak observed here is most likely due to a highly perturbed linearly adsorbed monocarbonyl on partially oxidized Ru sites generated by locally high concentrations of coadsorbed oxygen.Sandia National Laboratories is supported by the United States Department of Energy under contract number DE-AC04-76DP00789.     

Dendrimer templates for heterogeneous catalysts: Bimetallic Pt–Au nanoparticles on oxide supports

Polyamidoamine (PAMAM) dendrimers were used to template Pt, Au, and bimetallic Pt–Au dendrimer encapsulated nanoparticles (DENs) in solution. Adjusting the solution pH allowed for slow, spontaneous adsorption of the nanoparticles onto silica, alumina, and titania. After dendrimer removal, the catalysts were characterized with infrared spectroscopy of adsorbed CO and tested with CO oxidation catalysis. Infrared spectroscopy of the monometallic Pt catalysts showed a slight shift in the CO stretching frequency for the different supports. For the bimetallic catalysts, infrared spectra showed CO adsorbed on both Pt and on Au sites. Spectra collected during CO desorption showed substantial interactions between the two bands, confirming the presence of bimetallic particles on all the supports. The bimetallic catalysts were found to be more active than the monometallic catalysts and had lower apparent activation energies. The titania supported Pt–Au catalyst was resistant to deactivation during an extended treatment at 300 °C. Correlations between IR spectra and catalytic activity showed differences between the mono- and bimetallic materials and implicated a bimetallic Pt–Au ensemble at the catalytic active site. This is the first study to show that DENs are appropriate precursors for studying support effects on catalysis by metal nanoparticles, although the magnitude of the effects were small.