Studies of the hydrogen held by solids: XXII. The surface chemistry of reduced molybdenaalumina catalysts

The surface hydroxyl concentrations of a fresh molybdenaalumina catalyst (8% Mo) and of the alumina from which it was made have been determined as a function of the temperature of pretreatment. Similar data were obtained for catalysts reduced with H₂ or with CO. In all cases, the hydroxyl concentrations decreased with increasing pretreatment temperatures. The difference between the curves for the parent alumina and the molybdenaalumina preparation made from it provided a measure of the number of hydroxyl groups eliminated as the epitaxial monolayer of molybdena was grown onto the surface. The values obtained (1.7 ± 0.6 OH/Mo) showed that the surface hydroxyl groups of alumina are replaced by molybdate anions. When the catalyst was reduced with CO to about $\text{e}\text{Mo}\text{= 1.5}$ (average valence, Mo^+4.5), the curve obtained was almost identical with that for the unreduced catalyst, but when the catalyst was reduced with H₂, values for the retained hydrogen were higher than for the oxidized catalyst and approached those of the parent alumina as its evacuation temperature was increased to 550 °C. This increase in hydroxyl concentration was in agreement with earlier deductions.The hydroxyl region of the infrared spectra of similar preparations was recorded. Four distinct bands could be characterized for the parent alumina at 3780, 3740, 3705, and 3650 cm^?1 and a shoulder at 3795 cm^?1. The same bands were present on the oxidized catalyst, but with lower intensities and with altered intensity ratios; i.e., some bands were affected more than others as hydroxyl groups were replaced by molybdena species. Spectra from catalysts reduced with CO were indistinguishable in the OH region from those for the unreduced catalyst. No new bands appeared when the catalysts were reduced with H₂, but the intensities of bands attributable to alumina OH increased with the 3795 cm^?1 band strengthening noticeably more than the others. Thus, the new hydroxyl groups introduced on reduction are probably alumina OH rather than MoOH as previously supposed. A form of hydrogen which is chemisorbed but which can be removed from the catalyst as H₂ on evacuation at the reduction temperature also appeared in the OH region, mainly as a continuous contribution to the low frequency edge. From absorption coefficients derived from the present data, it was deduced that about twice as many hydrogen atoms were present in the H₂ formed than were supplied by these OH groups; i.e., the chemisorption appears heterolytic with half the atoms unseen by ir. A search was made for a band attributable to MoH, but without success. A brief study was made of this adsorption process, which was found to be slow but reversible, and to have a positive pressure dependence. When the catalyst was reduced with CO, rather than with H₂, a portion of the CO remained irreversibly chemisorbed in electronically comparable amounts. Infrared spectra of such samples contained a band at about 1585 cm^?1 attributable to a carbonate species. Data for the two reducing gases differed in that no reversibly chemisorbed CO was observed. At room temperature, CO was also chemisorbed as a linear species with the stretching frequency (2190 cm^?1) higher than that of the gaseous molecule (2143 cm^?1).     

NO adsorption on Cu-ZSM-5: assignment of IR band at 2133 cm−1

The adsorption of nitrogen oxides on Cu-ZSM-5 was studied by infrared spectroscopy to elucidate the species associated with the band at 2133 cm^–1. The band was found for both NO and NO₂ adsorption. Labeling experiments with¹⁵NO revealed that the associated surface species contained nitrogen and, most likely, an N-O bond. Co-adsorption experiments of NO and oxygen produced adsorbed nitronium, NO ₂ ⁺ , as the principal, associated species. Adsorption of nitrogen oxides on dispersed CuO and the HZSM-5 support demonstrated that the 2133 cm^–1 band was not necessarily associated with copper ions. A relatively strong correlation between the bands at 2133 and 3615 cm^–1 indicates that the primary adsorption sites of NO ₂ ⁺ are the strongly protic, bridging Si(OH)Al framework hydroxyls. Once these were filled, other, weaker acid sites began to adsorb NO ₂ ^O .     

Infrared Spectra and Surface Reactions of HCl,DCl and Cl2 Adsorbed on Germanium

Adsorption of HCl, DCl and Cl₂ on high surface area germanium films was studied by means of IR absorption spectra. The films were prepared by high temperature evaporation of germanium in a helium atmosphere. On adsorption of HCl and DCl two main absorptions appeared at 460 cm^?1 and 408 cm^?1 and additional weaker bands at 2050 cm^?1 and 2920 cm^?1 (with HCl) and at 1313 cm^?1 (with DCl). The spectra indicate that both gases undergo dissociation on adsorption. In the case of Cl₂ the bands at 460 cm^?1 and 408 cm^?1 appeared in the spectrum; here again strong evidence exists that dissociative adsorption takes place. Mass spectrometer analysis showed that the desorption product consists mainly of GeCl₄.     

DRIFT Studies of Adsorbed CO Over Sulfided K–Rh–Mo/Al2O3 Catalysts: Detection of Rh–Mo–S Phase

Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was used to study the nature of active species in K–Rh–Co–MoS₂/Al₂O₃ catalyst by means of probing with CO molecule. The effects of K addition to Rh and interaction between Mo and Rh were studied with varying K and Mo loadings over 1 wt% Rh/Al₂O₃ catalyst. In sulfided Rh–Mo/Al₂O₃, the formation of Rh–Mo–S phase was evidenced first time by a band at 2,095 cm^?1. The introduction of Co to K–Rh–MoS₂/Al₂O₃ catalyst showed the existence of both Rh and Co promoted MoS₂ sites, but the CO absorption frequencies in DRIFT spectra are significantly at lower side compared to Co free Rh–Mo catalyst. The stabilities of CO band from Rh and Co promoted and unpromoted MoS₂ sites are studied at different temperatures. When activated carbon used as support, bands for both promoted and unpromoted MoS₂ sites were appeared, but the intensity of these bands were decreased largely compared to alumina based catalyst, resulted from the coverage of added K not only on the support surface but also on the active metal components due to the neutral nature of activated carbon.     

CO adsorption on supported and promoted Ag epoxidation catalysts

CO was used to probe the nature of adsorption sites on Ag/α-Al₂O₃ epoxidation catalysts and to investigate the effect of Cs and Cl promoters by employing diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and chemisorption measurements. In contrast to previous studies, IR absorption bands for CO chemisorbed on reduced, supported Ag crystallites were observed; however, CO adsorption occurred on only 3–7% of the total Ag surface at 300 K and coverage depended on both the pretreatment and CO pressure utilized. No irreversible CO adsorption occurred on the alumina, whereas linearly bonded CO was the dominant species on the metallic Ag sites. After a 30-min purge, the bands due to these chemisorbed forms of CO decreased in intensity while a band due to bridge-bonded CO increased in intensity, which implies that CO reoriented as the surface concentration of CO decreased. In the presence of Cs, similar behavior was observed and the band intensity of the bridge-bonded CO increased. After reduction at 673 K, cesium suboxides appeared to be formed based on the formation of carbonyl complexes at 2028, 1950, and 1869 cm⁻¹. On reduced Ag catalysts, electronic effects of Cs and Cl were observed and adsorbed CO gave a lower frequency, i.e., 2018 and 2009 cm⁻¹ for Cs-promoted samples reduced at 473 and 673 K, respectively, due to an increase in the electron density on surface Ag atoms, while this band occurred at a higher frequency of 2129 cm⁻¹ with a CsCl-promoted Ag catalyst due to a net decrease in the electron density on surface Ag atoms. After CO adsorption on O-covered Cs-promoted and CsCl-promoted catalysts, a band between 1520 and 1491 cm⁻¹ existed which was assigned to a COO⁻ stretching mode in a carbonate species formed on composite AgCs_xO_y sites. These studies with CO provide evidence that reduction at 673 K following a calcination step can lead to redistribution of Cs atoms.     

Surface characterization of plasma-treated poly-p-xylylene films

Plasma-treated poly-p-xylylene films have been characterized by neutron activation oxygen analysis, internal reflection (IRS) and transmission infrared spectroscopy, transmission electron microscopy (TEM), and surface contact angle measurements. The results indicate that an oxygen plasma roughens the surface and that oxygen is incorporated into the surface. Oxygen is not detected in the bulk of the sample. The infrared transmission spectra exhibited no carbonyl band, but the relative band intensities changed, indicating a change in ring substitution by a loss of chlorine in the chlorinated poly-p-xylylenes. The IRS spectra of the surface of films treated with oxygen plasma did contain carbonyl bands at 1730 and 1640 cm^?1. Argon and helium plasmas generally decreased the water contact angle measured on plasma-treated poly-p-xylylene surfaces more than oxygen or nitrogen plasma treatments. Regardless of the plasma utilized, the water contact angles increased with time after the treatment but did not recover to the original level. IRS spectra of the surface of films treated with argon plasma contained carbonyl bands at 1730 and 1695 cm^?1. The adhesion of a polyurethane thermosetting material to a poly-p-xylylene surface is greatly improved if a plasma treatment is used prior to the application of the polyurethane. The degree of improvement in adhesion was dependent on the type of plasma and the treatment time.     

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.     

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.     

Skeletal Isomerization of Linear Butenes on Boron Promoted Ferrierite: Effect of the Catalyst Preparation Technique

Potassium and acid ferrierites were impregnated with boron species by wet and incipient wetness techniques. All samples display a medium-intensity band at 3,450–3,470 cm⁻¹ associated to Si−OH···O groups corresponding to boron-containing units. The 1,398–1,404 cm⁻¹ band assigned to the B–O stretching in BO₃ units does not appear on boron–potassium–ferrierite prepared by wet impregnation. Catalytic performance during the linear butene skeletal isomerization was measured. At 300 °C, boron impregnated by incipient wetness technique on acid ferrierite reduces both linear butene conversion at a short time and isobutene yield in all time range. Boron–potassium–ferrierite prepared by wet impregnation has a suitable acidity to promote isobutene production. At 450 °C, this sample shows the best performance, being the isobutene yield 1.7 times higher than the acid-ferrierite one and reaching the highest isobutene selectivity (92%). This performance is maintained with time. Both isobutene yield and by-product distribution are strongly affected by temperature; dimer intermediates are formed. Finally, both kinds of hydroxyl groups corresponding to 3,466 and 3,635 cm⁻¹ bands influence the isobutene production whereas BO₃ sites are inactive for this reaction.     

FTIR indication of CO interaction with O2− ions: A new adsorption form in the gap between chemi- and physisorbed CO

The IR bands around 2140 cm⁻¹ appearing after low temperature (T > 77 K) CO adsorption on oxide and zeolite powders have been, as a rule, assigned to physisorbed CO. However, the bands vary with different samples, which suggests specific adsorption. It is concluded that in these cases CO is polarized by surface oxygen anions because at the conditions at which “physisorbed” CO is formed all cationic sites are already occupied. Studying a titanium oxynitride sample where no physically adsorbed CO was observed proved the hypothesis. Upon oxidation of the sample and creation of surface O²⁻ anions, bands at 2141 and 2136 cm⁻¹ appeared after low-temperature CO adsorption. It was suggested that analysis of the bands around 2140 cm⁻¹ could provide information on the characteristics on the solids, in particular on surface basicity.     

Formation and catalytic activity of partially oxidized Pd nanoparticles

Combining multi molecular beam (MB) experiments and in-situ time-resolved infrared reflection absorption spectroscopy (TR-IRAS), we have studied the formation and catalytic activity of Pd oxide species on a well-defined Fe₃O₄ supported Pd model catalyst. It was found that for oxidation temperatures up to 450 K oxygen predominantly chemisorbs on metallic Pd whereas at 500 K and above (~10⁻⁶ mbar effective oxygen pressure) large amounts of Pd oxide are formed. These Pd oxide species preferentially form a thin layer at the particle/support interface. Their formation and reduction is fully reversible. As a consequence, the Pd interface oxide layer acts as an oxygen reservoir providing oxygen for catalytic surface reactions. In addition to the Pd interface oxide, the formation of surface oxides was also observed for temperatures above 500 K. The extent of surface oxide formation critically depends on the oxidation temperature resulting in partially oxidized Pd particles between 500 and 600 K. It is shown that the catalytic activity of the model catalyst for CO oxidation decreases significantly with increasing surface oxide coverage independent of the composition of the reactants. We address this deactivation of the catalyst to the weak CO adsorption on Pd surface oxides, leading to a very low reaction probability.     

IN SITU visualization of water adsorption in cellulose nanofiber film with micrometer spatial resolution using micro-FTIR imaging

Hygroscopic behavior is an inherent characteristic of nanocellulose film which strongly affects its applications. In order to gain a better understanding of water adsorption, micro-Fourier transform infrared (FTIR) imaging was used to investigate the water adsorption in cellulose nanofiber film with a spatial resolution of 20 um. Four spectral peaks at 2905?cm^?1, 1428?cm^?1, 1371?cm^?1, and 1317?cm^?1 attributed to CH and CH₂ groups were used to generate 2D micro-FTIR images of cellulose distribution, and the most intense peak at 3348?cm^?1 was employed to generate 2D micro-FTIR image of OH group distribution. On this basis, difference 2D micro-FTIR images of OH group distribution at different relative humidity (RH) levels demonstrated the development of adsorbed water distribution in cellulose nanofiber film during the water adsorption process. The study results confirmed that the micro-FTIR imaging was one promising tool for in situ visualization of water adsorption with micron-scale resolution.     

Band-gap tuning of monolayer graphene by oxygen adsorption

We have performed high-resolution angle-resolved photoemission spectroscopy of oxygen-adsorbed monolayer graphene grown on 6H–SiC(0 0 0 1). We found that the energy gap between the π and π¹ bands gradually increases with oxygen adsorption to as high as 0.45 eV at the 2000 L oxygen exposure. A systematic shrinkage of the π¹ electron Fermi surface was also observed. The present result strongly suggests that the oxidization is a useful technique to create and control the band gap in monolayer graphene.     

The effect of temperature on the infrared absorption frequencies of polyethylene and ethylene–propylene copolymer films

The frequency shifts of the six prominent infrared absorption bands were measured for films of polyethylene and ethylene–propylene copolymer as a function of temperature. Three bands (at 720, 731, and 1473 cm^?1) shifted to higher frequency, and three bands (at 1463, 2849, and 2918 cm^?1) shifted unexpectedly to lower frequency as the sample temperature was decreased. The greatest shift occurred with the CH₂ rocking band, which increased from 730.2 to 734.2 cm^?1 as the temperature was decreased from 313 to 22°K. The shift usually ceased in the temperature range from 40 to 110°K, probably because some kind of molecular motion ceased. Four mechanisms are discussed in an attempt to account for the different frequency shifts: bulk contraction with decreasing temperature, an increase in dispersion forces between chains, variation in the length and coupling of the vibrating chain molecule, and a change in the planar zigzag conformation of the chain molecule. Thermal contraction is sufficient to explain most of the observed frequency shifts. The CH₂ stretching modes (2849 and 2918 cm^?1) may be shifted to lower frequency by an increase in the dispersion forces between chains, caused by contraction. The displacement of the 1463 cm^?1 band-shift curve is an indication of the sample density. The displacements of the 1473 and 731 cm^?1 band-shift curves are indications of the proportion of propylene in the ethylene copolymer.     

Infrared spectra of dinitrogen adsorbed on bimetallic lanthanide (Eu or Yb)–Ni/SiO2 catalysts

Bimetallic lanthanide (Ln: Eu or Yb)–Ni/SiO₂ catalysts prepared by the use of dissolution of lanthanide metals in liquid ammonia have been studied by infrared spectroscopy for dinitrogen adsorption. The infrared spectra were measured at 133–300 K using Ln–Ni/SiO₂ obtained when the Eu or Yb metal dissolved in liquid ammonia reacted with 20 mass% Ni/SiO₂ in different ratios. Infrared spectra for Eu–Ni/SiO₂ showed absorption bands at 2336, 2265, 2254 and 2227 cm⁻¹ at 133 K, which disappeared upon evacuation. The adsorbed state was found to be all molecular from the isotope shift using ²⁸N₂ and z³⁰N₂₈. The bands at 2254 and 2227 cm⁻¹ of them were assigned to new adsorbed dinitrogen species resulting from synergetic interactions between the europium and nickel metal. The concentration of adsorbed dinitrogen on Eu–Ni/² varied markedly with the Eu/Ni ratios, and particularly, it increased in the region of high Eu content. Upon introduction of ytterbium onto nickel, new bands at 2254 and 2226 cm^−- similarly appeared. However, the dependence of dinitrogen adsorption as a function of Yb content in Yb–Ni/SiO²> was somewhat different from that for Eu–Ni/SiO₂. The effects of lanthanide on the surface of Ln–Ni/SiO₂ were discussed in connection with the variation in catalytic properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

CO hydrogenation over supported cobalt catalysts: FTIR and gravimetric studies

The hydrogenation of CO over supported cobalt catalysts has been studied using in situ FTIR spectroscopy and gravimetry at P = 6 bar, T = 473–723 K and H₂/CO = 2–3. On both silica- and alumina-supported catalysts IR absorption bands corresponding to linearly adsorbed CO on metallic cobalt were observed. On alumina an additional pair of bands at lower frequencies was attributed to bridge-bonded CO. Absorption bands corresponding to adsorbed hydrocarbons (3050–2700 cm^?1) and to oxygen containing species (1800–1200 cm^?1) were found to correspond to adsorbed products or unreactive species. The gravimetric studies showed a significant difference between the supports. On the silica-supported catalyst the weight uptake decreased with increasing temperature (473–573 K). The weight increase during reaction was attributed to adsorbed hydrocarbon reaction products. On the alumina-supported catalyst the weight uptake increased with increasing temperature, and there was also a significant weight increase with the support alone. Most of the weight uptake can be attributed to the formation of stable formate and carbonate species on the alumina support. At 723 K the deposits formed were stable in H₂, and the shape of the curves indicated different mechanisms for deposition of material. In particular the Co/Al₂O₃ sample showed a very high and linear rate of weight gain, which was an order of magnitude higher than for the other samples.     

Acid centers in sulfated, phosphated and/or aluminated zirconias

On sulfated ZrO₂, the comparison of the effects of adsorbing water or ammonia on the infrared bands between 1400 and 1000 cm^?1 suggests that besides structural Lewis sites on the surface of ZrO₂, strong Lewis sites are made from chemisorbed SO₃. Upon adsorption of water, SO₃ is converted, partially, into a surface sulfated species which may act as strong Brønsted sites. At moderate surface hydration, both types of sites may coexist. The catalytic activity in the isomerization of isobutane is a function of the overall nominal surface density in SO₄. The acid sites on the surface of phosphated mesoporous zirconia are attributable to surface P–OH groups working as weak Brønsted sites. On both sulfated and phosphated zirconia, surface coating of alumina stabilizes the porosity, but it does not modify the nature of their acid centers.     

Microcalorimetric, FTIR, and DFT studies of the adsorption of isobutene on silica

Microcalorimetric measurements, infrared spectroscopic studies(FTIR), and quantum-chemical calculations based on density-functional theory(DFT) were made of the interactions of isobutene with silica at 300 K. On the basis of DFT calculations and FTIR spectra, most of isobutene adsorbs reversibly on silica at 300 K, involving the interaction of the π-bond with hydroxyl groups on the surface. The average energy of these interactions is ~45kJ/mol at a surface coverage of ~400 μmol of isobutene per gram of silica. The formation of butoxy and 2-methyl-1-propoxy species upon reaction of isobutene with silanol groups appears to be limited kinetically at 300 K. While the enthalpies of formation of these species from gaseous isobutene and silanol groups are calculated to be -55 and -40 kJ/mol, respectively, the activation energies for the formation of these species from adsorbed isobutene are estimated from DFT to be 172 and 226 kJ/mol, respectively. These high activation barriers are caused by the required localization of positive charge in the corresponding transition states, which is made difficult by the weak acidity of silica. Minor amounts of surface butoxy might form on silica at 300K, perhaps on defect or impurity sites, and these species may be responsible for the higher heats of adsorption (56±2 kJ/mol) measured at low surface coverages on silica. This revised version was published online in July 2006 with corrections to the Cover Date.     

Dynamic infrared measurements of poly(vinyl chloride) in the vicinity of the glass transition

The temperature dependences of some selected infrared bands of poly(vinylchloride) in the vicinity of the glass transition were examined. The intensities of 1333 and 1427 cm^?1 bands changed discontinuouly at T_g; on the other hand, 2920 cm^?1 did not show any significant changes at this temperature. From these results, the nature of the temperature dependence of infrared intensity of the polymer was discussed. The procedure introduced in this work offers a rapid method for the determination of the T_g as compared with the conventional infrared methods.     

A Fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO₂ and CO₂/H₂ on a silica-supported caesium-doped copper catalyst. Adsorption of CO₂ on a “caesium”/silica surface resulted in the formation of CO₂ ⁻ and complexed CO species. Exposure of CO₂ to a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm⁻¹. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and H₂, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.