Quantitative Analysis of Adsorbate Concentrations by Diffuse Reflectance FT-IR

Fully quantitative analyses of DRIFTS data are required when the surface concentrations and the specific rate constants of reaction (or desorption) of adsorbates are needed to validate microkinetic models. The relationship between the surface coverage of adsorbates and various functions derived from the signal collected by DRIFTS is discussed here. The Kubelka-Munk and pseudoabsorbance (noted here as absorbance, for the sake of brevity) transformations were considered, since those are the most commonly used functions when data collected by DRIFTS are reported. Theoretical calculations and experimental evidence based on the study of CO adsorption on Pt/SiO2 and formate species adsorbed on Pt/CeO2 showed that the absorbance (i.e., ) log 1/R������¢, with R������¢ ) relative reflectance) is the most appropriate, yet imperfect, function to give a linear representation of the adsorbate surface concentration in the examples treated here, for which the relative reflectance R������¢ is typically > 60%. When the adsorbates lead to a strong signal absorption (e.g., R������¢ < 60%), the Kubelka-Munk function is actually more appropriate. The absorbance allows a simple correction of baseline drifts, which often occur during time-resolved data collection over catalytic materials. Baseline corrections are markedly more complex in the case of the other mathematical transforms, including the function proposed by Matyshak and Krylov (Catal. Today 1995, 25, 1-87), which has been proposed as an appropriate representation of surface concentrations in DRIFTS spectroscopy.

Development of a Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) Cell for the In Situ Analysis of Co-Electrolysis in a Solid Oxide Cell

Co-electrolysis of carbon dioxide and steam has been shown to be an efficient way to produce syngas, however further optimisation requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the solid oxide cell (SOC) during operation. Whilst electrochemical measurements are currently conducted in situ, many analytical techniques can only be used ex situ and may even be destructive to the cell (e.g. SEM imaging of microstructure). In order to fully understand and characterise co-electrolysis, in situ monitoring of the reactants, products and SOC is necessary. Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) is ideal for in situ monitoring of co-electrolysis as both gaseous and adsorbed CO and CO2 species can be detected, however it has previously not been used for this purpose. The challenges of designing an experimental rig which allows optical access alongside electrochemical measurements at high temperature and operates in a dual atmosphere are discussed. The rig developed has thus far been used for symmetric cell testing at temperatures from 450[degree]C to 600[degree]C. Under a CO atmosphere, significant changes in spectra were observed even over a simple Au|10Sc1CeSZ|Au SOC. The changes relate to a combination of CO oxidation, the water gas shift reaction and carbonate formation and decomposition processes, with the dominant process being both potential and temperature dependent.

Quantitative analysis of the reactivity of formate species seen by DRIFTS over a Au/Ce(La)O2 water–gas shift catalyst: First unambiguous evidence of the minority role of formates as reaction intermediates

The reactivity of the species formed at the surface of a Au/Ce(La)O2 catalyst during the water������¢���¯���¿���½���¯���¿���½gas shift (WGS) reaction were investigated by operando diffuse reflectance Fourier transform spectroscopy (DRIFTS) at the chemical steady state during isotopic transient kinetic analyses (SSITKA). The exchanges of the reaction product CO2 and of formate and carbonate surface species were followed during an isotopic exchange of the reactant CO using a DRIFTS cell as a single reactor. The DRIFTS cell was a modified commercial cell that yielded identical reaction rates to that measured over a quartz plug-flow reactor. The DRIFTS signal was used to quantify the relative oncentrations of the surface species and CO2. The analysis of the formate exchange curves between 428 and 493 K showed that at least two levels of reactivity were present. ������¢���¯���¿���½���¯���¿���½Slow formates������¢���¯���¿���½���¯���¿���½ displayed an exchange rate constant 10- to 20-fold slower than that of the reaction product CO2. ������¢���¯���¿���½���¯���¿���½Fast formates������¢���¯���¿���½���¯���¿���½ were exchanged on a time scale similar to that of CO2. Multiple nonreactive readsorption of CO2 took place, accounting for the kinetics of the exchange of CO2(g) and making it impossible to determine the number of active sites through the SSITKA technique. The concentration (in mol g������¢���¯���¿���½���¯���¿���½1) of formates on the catalyst was determined through a calibration curve and allowed calculation of the specific rate of formate decomposition. The rate of CO2 formation was more than an order of magnitude higher than the rate of decomposition of formates (slow + fast species), indicating that all of the formates detected by DRIFTS could not be the main reaction intermediates in the production of CO2. This work stresses the importance of full quantitative analyses (measuring both rate constants and adsorbate concentrations) when investigating the role of adsorbates as potential reaction intermediates, and illustrates how even reactive species seen by DRIFTS may be unimportant in the overall reaction scheme.

On the complexity of the water-gas shift reaction mechanism over a Pt/CeO2 catalyst: Effect of the temperature on the reactivity of formate surface species studied by operando DRIFT during isotopic transient at chemical steady-state

The present report investigates the role of formate species as potential reaction intermediates for the WGS reaction (CO + H2O -> CO2 + H-2) over a Pt-CeO2 catalyst. A combination of operando techniques, i.e., in situ diffuse reflectance FT-IR (DRIFT) spectroscopy and mass spectrometry (MS) during steady-state isotopic transient kinetic analysis (SSITKA), was used to relate the exchange of the reaction product CO2 to that of surface formate species. The data presented here suggest that a switchover from a non-formate to a formate-based mechanism could take place over a very narrow temperature range (as low as 60 K) over our Pt-CeO2 catalyst. This observation clearly stresses the need to avoid extrapolating conclusions to the case of results obtained under even slightly different experimental conditions. The occurrence of a low-temperature mechanism, possibly redox or Mars van Krevelen-like, that deactivates above 473 K because of ceria over-reduction is suggested as a possible explanation for the switchover, similarly to the case of the CO-NO reaction over Cu, I'd and Rh-CeZrOx (see Kaspar and co-workers [1-3]). (c) 2006 Elsevier B.V. All rights reserved.

Formation of Ammonia during the NO-H-2 Reaction over Pt/ZrO2

The mechanism for the formation of NH3 during the NO-H-2 reaction over Pt/ZrO2 was studied. Steady-state isotopic transient kinetic analysis was carried out with isotopic switching from (NO)-N-15-D-2 to (NO)-N-14-D-2, and the results revealed that formation of N-2 and N2O was associated with linearly adsorbed NO on the Pt surface, whereas ammonia formation was associated with NDx species adsorbed on ZrO2. The adsorbed NHx species were not observed on the surface of ZrO2 during NH3 adsorption. From transient kinetic experiments, the formation rates of NHx species and of gaseous NH3 agreed with each other, suggesting that the NHx species on ZrO2 was an ammonia intermediate. The NDx species did not react with D-2 directly, but H-D exchange occurred easily. The addition of H2O to the NO-H-2 feed gas enhanced the formation of NH3. In situ diffuse reflectance spectra and transient kinetic analysis revealed that H2O enhanced the conversion of NHx species to NH3.

Synthesis, Structure, and Spectroscopic Properties of the New Lanthanum(III) Fluoride Oxomolybdate(VI) La3FMo4O16

La3FMo4O16 crystallizes in the triclinic crystal system with space group P (1) over bar [a = 724.86(2) pm, b = 742.26(2) pm, c = 1469.59(3) pm, a = 101.683(2)degrees, beta 102.118(2)degrees, gamma = 100.279(2)degrees] with two formula units per unit cell. The three crystallographically independent La3+ cations show a coordination number of nine each, with one F- and eight O2- anions forming distorted monocapped square antiprisms. The fluoride anion is coordinated by all three lanthanum cations to form a nearly planar triangle. Besides three crystallographically independent tetrahedral [MoO4](2-) units, a fourth one with a higher coordination number (CN = 4 +1) can be found in the crystal structure, forming a dimeric entity with a formula of [Mo2O8](4-) consisting of two edge-connected square pyramids. Several spectroscopic measurements were performed on the title compound, such as infrared, Raman, and diffuse reflectance spectroscopy. Furthermore, La3FMo4O16 was investigated for its capacity to work as host material for doping with luminescent active cations, such as Ce3+ or Pr3+. Therefore, luminescence spectroscopic as well as EPR measurements were performed with doped samples of the title compound. Both the pure and the doped compounds can be synthesized by fusing La2O3, LaF3 and MoO3 (ratio 4:1:12; ca. 1 % CeF3 and PrF3 as dopant, respectively) in evacuated silica ampoules at 850 degrees C for 7 d.

Nano-structural investigation of Ag/Al2O3 catalyst for selective removal of O-2 with excess H-2 in the presence of C2H4

Ag/gamma-Al2O3 catalysts have been characterized in-depth during different thermo-chemical treatments by in situ diffuse reflectance UV-visible spectroscopy and quasi in situ Transmission Electron Microscopy. The combination of these techniques indicates that sintering and redispersion of silver is clearly observed from the increases and decreases in the absorption band intensity over the range of 250-600 nm due to the presence of silver clusters and silver nanoparticles. These results allow us to study the effect of the reaction feed on the metal dispersion at different operation conditions and discuss the formation of active sites during the selective catalytic reduction of O-2 with excess H-2 in the presence of unsaturated hydrocarbons. In this case high catalytic activity and selectivity toward the oxygen removal was achieved for this catalyst. (C) 2010 Elsevier B.V. All rights reserved.

Fabrication of cerium oxide nanoparticles: Characterization and optical properties

Ceria (CeO2) is a technologically important rare earth material because of its unique properties and various engineering and biological applications. A facile and rapid method has been developed to prepare ceria nanoparticles using microwave with the average size 7 nm in the presence of a set of ionic liquids based on the bis (trifluoromethylsulfonyl) imide anion and different cations of 1-alkyl-3-methyl-imidazolium. The structural features and optical properties of the nanoparticles were determined in depth with X-ray powder diffraction, transmission electron microscope, N-2 adsorption-desorption technique, dynamic light scattering (DLS) analysis, FTIR spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, and Diffuse reflectance spectroscopy. The energy band gap measurements of nanoparticles of ceria have been carried out by UV-visible absorption spectroscopy and diffuse reflectance spectroscopy. The surface charge properties of colloidal ceria dispersions in ethylene glycol have been also studied. To the best of our knowledge, this is the first report on using this type of ionic liquids in ceria nanoparticle synthesis. (C) 2011 Elsevier Inc. All rights reserved.

Electrochemistry of Hg(II) Salts in Room-Temperature Ionic Liquids

The electrochemistry of HgCl(2) and [Hg(NTf(2))(2)] ([NTf(2)](-) = bis-{(trifluoromethyl)sulfonyl}imide) has been studied in room temperature ionic liquids. It has been found that the cyclic voltammetry of Hg(II) is strongly dependent on a number of factors (e.g., concentration, anions present in the mixture, and nature of the working electrode) and differs from that found in other media. Depending on conditions, the cyclic voltammetry of Hg(II) can give rise to one, two, or four reduction peaks, whereas the reverse oxidative scans show two to four peaks. Diffuse reflectance UV-vis spectroscopy and X-ray powder diffraction have been used to aid the assignment of the voltammetric waves.

Promotion of Ceria Catalysts by Precious Metals: Changes in Nature of the Interaction under Reducing and Oxidizing Conditions

By depositing ceria over supported precious metal (PM) catalysts and characterizing them with in situ diffuse reflectance UV (DR UV) and in situ Raman spectroscopy, we have been able to prove a direct correlation between a decrease in ceria band gap and the work function of the metal under reducing conditions. The PM ceria interaction results in changes on the ceria side of the metal ceria interface, such that the degree of oxygen vacancy formation on the ceria surface also correlates with the precious metal work function. Nevertheless, conclusive evidence for a purely electronic interaction could not be provided by X-ray photoelectron spectroscopy (XPS) analysis. On the contrary, the results highlight the complexity of the PM ceria interaction by supporting a spillover mechanism resulting from the electronic interaction under reducing conditions. Under oxidizing conditions, another effect has been observed; namely, a structural modification of ceria induced by the presence of PM cations. In particular, we have been able to demonstrate by in situ Raman spectroscopy that, depending on the PM ionic radius, it is possible to create PM ceria solid solutions. We observed that this structural modification prevails under an oxidizing atmosphere, whereas electronic and chemical interactions take place under reducing conditions.

DRIFTS/MS/Isotopic Labeling Study on the NO-Moderated Decomposition of a Silica-Supported Nickel Nitrate Catalyst Precursor

In the preparation of silica-supported nickel oxide from nickel nitrate impregnation and drying, the replacement of the traditional air calcination step by a thermal treatment in 1% NO/Ar prevents agglomeration, resulting in highly dispersed NiO. The mechanism by which NO prevents agglomeration was investigated by using combined in situ diffuse reflectance infrared fourier transform (DRIFT) spectroscopy and mass spectrometry (MS). After impregnation and drying, a supported nickel hydroxynitrate phase with composition Ni(3)(NO(3))(2)(OH)(4) had been formed. Comparison of the evolution of the decomposition gases during the thermal decomposition of Ni(3)(NO(3))(2)(OH)(4) in labeled and unlabeled NO and O(2) revealed that NO scavenges oxygen radicals, forming NO(2). The DRIFT spectra revealed that the surface speciation evolved differently in the presence of NO as compared with in O(2) or Ar. It is proposed that oxygen scavenging by NO depletes the Ni(3)(NO(3))(2)(OH)(4) phase of nitrate groups, creating nucleation sites for the formation of NiO, which leads to very small (similar to 4 nm) NiO particles and prevents agglomeration.

The water-gas shift reaction over CeO/CuO:Operando SSITKA-DRIFTS-mass spectrometry study of low temperature mechanism

An inverse CeO2/CuO catalyst has been investigated by operando steady-state isotopic transient kinetic analysis (SSITKA) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under 3% CO +3% H2O reactant mixture at 473 K with the aim of determining intermediates involved in the water gas shift reaction at relatively low temperatures. Among the various species detected in the infrared spectra which may be involved in the reaction, i.e. formates, copper carbonyls and carbonates, a particular type of carbonate species is identified as a reaction intermediate on the basis of detailed analysis of the spectra during isotopic exchange in comparison with the change in the corresponding isotopically labelled CO2 product. 

In-situ Monitoring of Solid Oxide Electrolysis Cells

High temperature co-electrolysis of steam and carbon dioxide using a solid oxide cell (SOC) has been shown to be an efficient route to produce syngas (CO + H-2), which can then be converted to synthetic fuel. Optimization of co-electrolysis requires detailed understanding of the complex reactions, transport processes and degradation mechanisms occurring in the SOC during operation. Thermal imaging, Raman spectroscopy and Diffuse Reflectance Infrared Fourier Transform Spectroscopy are being developed to probe in-situ both the reactions occurring during operation and any associated changes within the structure of the electrodes and electrolyte. Here we discuss the challenges in designing experimental apparatus suitable for high temperature operation with optical spectroscopic access to the areas of the SOC that are of interest. In particular, issues with sealing, temperature gradients, signal strength and cell configuration are discussed and final designs are presented. Preliminary results obtained during co-electrolysis operation are also presented.

The interaction between adsorbed OH and O-2 on TiO2 surfaces

Reduced TiO2 (110) surfaces usually have OH groups as a result of H2O dissociation at oxygen vacancy defects. Because of excess electrons due to OH adsorption, OH/TiO2. exhibit interesting properties favorable to further O-2 or H2O adsorption. Both O-2 and H2O can adsorb and easily diffuse on the OH/TiO2 surface; such behavior plays a significant role in photocatalysis, heterogeneous catalysis, electronic devices and sensors. Indeed, the processes of H2O dissociation, O-2 and H2O diffusion on Such TiO2 surfaces, in the presence of OH groups, are important issues in their own right. Herein, the most recent experimental and theoretical progresses in understanding the interactions between adsorbed OH groups and O-2, or H2O, over TiO2 (110) surfaces and their implications will be reviewed. (c) 2009 Elsevier Ltd. All rights reserved.

Assessment of the Activity of Photocatalytic Paint Using a Simple Smart Ink Designed for High Activity Surfaces

The use of an acid violet 7 (AV7) smart ink to assess the activity of photocatalytic paint is demonstrated. A linear correlation is established between the change in oxidized dye concentration, as measured by diffuse reflectance, and the change in the green component of the RGB color values, obtained using a portable hand-held scanner, suggesting that such tests can be monitored easily using an inexpensive piece of hand-held office equipment, as opposed to an expensive lab-based instrument, such as a diffuse reflectance UV/vis spectrophotometer. The bleaching of the AV7 follows first order kinetics, at a rate that is linearly dependent upon the UVA irradiance (0.30–3.26 mW cm–2). A comparison of relative rate of bleaching of the AV7 ink with the relative rate of removal of NOx, as determined using the ISO test (ISO 22197-1:2007), established a linear relationship between the two sets of results and the relevance of this correlation is discussed briefly.