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The potential dependence of the rate of dehydration of formic acid to adsorbed CO (COad) on Pt at pH 1 has been studied on a polycrystalline Pt surface by time-resolved surface-enhanced infrared absorption spectroscopy in the attenuated total reflection mode (ATR-SEIRAS) with simultaneous recording of current transients after a potential step. A range of formic acid concentrations has been used to obtain a deeper insight into the mechanism of the reaction. Our experiments have allowed us to confirm that the potential dependence of the rate of dehydration has a bell shape, going through a maximum around the potential of zero total charge (pztc) of the most active site. The analysis of the integrated intensity and frequency of the bands corresponding to COL and COB/M shows a progressive population of the active sites on the surface. The observed potential dependence of the rate of formation of COad is consistent with a mechanism in which the reversible electroadsorption of HCOOad is followed by its rate-determining reduction to COad. L.P.-M. acknowledges a doctoral scholarship within the Leverhulme Centre for Doctoral Training in Sustainable Production of Chemicals and Materials (Grant DS-2017-073).

In this paper NiW/γ-Al2O3catalysts were prepared by consecutive impregnation of a W/γ-Al2O3 catalyst with an aqueous solution of nickel salt. The structural control of the nickel ion precursor in the impregnation solution was achieved by the addition of 1, 2-cyclohexanediamine-N, N, N’, N’-tetraacetic acid (CyDTA) as a chelating agent at different pH. The influence of the sulfidation pressure (1 bar vs 40 bar) on the activity and structure of the NiW catalysts was investigated. The catalysts performances were tested in hydrodesulfurization (HDS) of thiophene after sulfidation at atmospheric or high pressure. The catalysts were characterized by X-Ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) and infrared spectroscopy of adsorbed CO (IR/CO) to explain the modification in surface species composition due to the chelating agent CyDTA and sulfiding conditions. NiW catalysts prepared in presence of CydTA and sulfided under high pressure displayed the highest HDS activity. These two factors enhanced the sulfidation degree of W-based species as characterized by XPS. A linear correlation was found between the HDS activity and the sulfidation degree. In addition, chelating agent addition induced a decrease on metal-support interaction, as pointed out by TPR, and strongly favored the creation of CUS sites on the NiWS phase as seen by IR/CO. All these features favored a high catalytic activity. In addition, high pressure sulfidation not only leads to more active NiW catalysts but improved the butene-over-butane ratio., J.A. de los Reyes and V.A. Suarez Toriello acknowledge CONACYT-SENER funding for financial support. The authors thank financial support from Instituto Politécnico Nacional (Proyecto SIP 20201116 and 20201629) and the Mexican National Council for Science and Technology (CONACyT; project CB-2017-2018 # A1-S-32418).

The CO2 electroreduction reaction (CO2RR) is a promising avenue to convert greenhouse gases into high-value fuels and chemicals, in addition to being an attractive method for storing intermittent renewable energy. Although polycrystalline Cu surfaces have long been known to be unique in their capabilities of catalyzing the conversion of CO2 to higher-order C1 and C2 fuels, such as hydrocarbons (CH4, C2H4, etc.) and alcohols (CH3OH, C2H5OH), product selectivity remains a challenge. Rational design of more selective catalysts would greatly benefit from a mechanistic understanding of the complex, multiproton, and multielectron conversion of CO2. In this study, we select three metal catalysts (Pt, Au, Cu) and apply in situ surface enhanced infrared absorption spectroscopy (SEIRAS) and ambient-pressure X-ray photoelectron spectroscopy (APXPS), coupled to density-functional theory (DFT) calculations, to get insight into the reaction pathway for the CO2RR. We present a comprehensive reaction mechanism for the CO2RR and show that the preferential reaction pathway can be rationalized in terms of metal-carbon (M-C) and metal-oxygen (M-O) affinity. We show that the final products are determined by the configuration of the initial intermediates, C-bound and O-bound, which can be obtained from CO2 and (H)CO3, respectively. C1 hydrocarbons are produced via OCH3,ad intermediates obtained from O-bound CO3,ad and require a catalyst with relatively high affinity for O-bound intermediates. Additionally, C2 hydrocarbon formation is suggested to result from the C-C coupling between C-bound COad and (H)COad, which requires an optimal affinity for the C-bound species, so that (H)COad can be further reduced without poisoning the catalyst surface. It is suggested that the formation of C1 alcohols (CH3OH) is the most challenging process to optimize, as stabilization of the O-bound species would both accelerate the formation of key intermediates (OCH3,ad) but also simultaneously inhibit their desorption from the catalyst surface. Our findings pave the way toward a design strategy for CO2RR catalysts with improved selectivity, based on the experimental/theoretical reaction mechanisms that have been identified. These results also suggest that designing the electronic structure of the catalyst is not the sole determining factor to achieve highly selective CO2RR catalysis; rather, tuning additional experimental reaction conditions such as electrolyte-intermediate interactions also become critical.

7 pags, 6 figs, 2 tabs. -- Supplementary data associated with this article can be found, inthe online version, atdoi:10.1016/j.jelechem.2011.05.015., Inhibition by CO of the corrosion of Fe, Ni, and three alloys, containing either Fe and large amounts of Ni (Incoloy 825) or large amounts of Fe (Uniloy-420 and N80 steels) in solutions containing between 7.5% and 28% HCl was studied using potentiodynamic polarization curves, gravimetric tests, and FTIRS. In all cases, but Uniloy-420 in 28% HCl, a clear inhibition of corrosion in the presence of CO in the solution was shown by the gravimetric tests and from cyclic voltammetry, the inhibition being higher in the case of Ni and Ni-containing alloys. CO chemisorbed on Fe and/or Ni atoms present on the alloy surface was identified as the species responsible for corrosion inhibition. The inhibition of corrosion is higher in the cases of Ni and Incoloy 825. © 2011 Elsevier B.V. All rights reserved.

The liquid phase hydrogenation of naphthalene was performed in the presence of CO over a commercial Ni/SiO2-Al2O3 catalyst. Naphthalene was hydrogenated even in the presence of CO at elevated temperatures, accompanying the hydrogenation of CO. Two activation energy values were obtained for the naphthalene hydrogenation depending on the reaction temperature. FT-IR measurement of the adsorbed CO was also carried out. Hydrogenation of the adsorbed CO created sites active for naphthalene hydrogenation.

Integrated studies of CO adsorption on TiO2 materials of different morphology and surface complexity identify, for the first time, frustrated translational CO modes by detecting their combination with the CO stretching mode (νCO). All the considered materials exhibit IR spectra with low-intensity bands in the 2235-2205 cm(-1) range, a region where components due to strong Lewis acid Ti(4+) sites may be present as well. These observations lead to a powerful method for associating high-wavenumber bands to TiO2 surface features and interpreting IR spectra of drastically complex/defective TiO2 materials. The proposed band assignment is based on vibrational analyses of CO-TiO2 theoretical models, indicating that the frustrated translational mode with frequency in the 30-50 cm(-1) range involved in the observed combination bands is perpendicular to the Ti(4+) rows. Our results reveal that this low-energy CO mode is much more sensitive than νCO in probing the TiO2 surface topography, and that its higher-energy components can be specifically associated with the presence of steps on the (101) faces. In a broader perspective, the frustrated translational CO mode surface sensitivity could become a key tool for detecting specific defective sites on TiO2 surfaces.

The steam reforming of phenol in the low-temperature range of 350-550°C was studied over 0.5wt% Rh supported on Ce 0.15Zr 0.85O 2, Zr 0.93La 0.07O 2, and Ce 0.13Zr 0.83La 0.04O 2 mixed metal oxides. The reforming specific activity (per gram of catalyst basis) was found to depend on (a) Rh dispersion, (b) the concentration (μmolg -1) of labile oxygen species of support, as determined by " oxygen storage capacity" measurements, and (c) the promotion of the water-gas shift (WGS) reaction rate, all of which largely influenced by the support chemical composition. The addition of 4atom% La 3+ into the Ce 0.15Zr 0.85O 2 crystal structure was found to largely promote the dispersion of Rh, to increase significantly (by a factor of 1.75) the concentration of surface basic sites (μmolm -2) of Ce 0.13Zr 0.83La 0.04O 2 compared to Ce 0.15Zr 0.85O 2 support, to prevent to a large extent the inhibiting role of hydrogen in the rate of WGS reaction, and to influence significantly the concentration and structure of surface reaction intermediates of the WGS, namely: formate (HCOO-) and -OH groups formed on the support, and adsorbed CO formed on the Rh metal. The 0.5wt% Rh/Ce 0.13Zr 0.83La 0.04O 2 catalyst led to a significantly better performance towards steam reforming of phenol in terms of phenol conversion, H 2-yield, and CO/CO 2 product ratio in the 350-450°C range compared to a commercial Ni-based catalyst (44wt% Ni) used for steam reforming reactions. At 400°C, the 0.5wt% Rh/Ce 0.13Zr 0.83La 0.04O 2 catalyst exhibited approximately 54% and 50%, respectively, higher phenol conversion and hydrogen yield, compared to the Ni-based industrial catalyst. The significantly lower CO/CO 2 product ratio obtained in the case of Rh/Ce 0.13Zr 0.83La 0.04O 2 compared to that obtained in the other supported-Rh catalysts is in agreement with the higher kinetic rate for the WGS reaction observed in the former catalyst. © 2012 Elsevier B.V. 117-118 81 95 Cited By :21

The influence of calcination and reduction conditions on the surface properties of high loading Ni/MgO catalysts (18 wt% Ni) was studied. IR spectra of adsorbed CO show that the increase of the calcination temperature decreases the reducibilty of the Ni phase as diffusion of Ni 2+ into the bulk of MgO particles is enhanced. CO adsorption (10 Torr) produces various carbonyls (mono- and poly-carbonyls, linear and bridged), the distribution of the different types depending on pretreatment conditions. Disruption of metal Ni particles by CO attack on edge and corner sites produces tetra-carbonyl species subsequently stabilized on Mg 2+ O 2− sites. Disproportionation of CO is also observed, monitored by the appearance of bands due to carbonate-like species as a consequence of the adsorption of CO 2 on the basic matrix. The activity for the Boudouard reaction decreases upon pretreatments at the highest temperature as the smoothing of metal particles reduces the concentration of Ni sites in the lowest coordination, which promote CO dissociation.

The interfaces: K/Cu(115) and CO/Cu(115) have been characterized using surface sensitive techniques, including low energy electron diffraction and photoelectron spectroscopy. K adatoms show tendency to occupy the sites close to the step edges. At low temperature (near 125 K), after completion of two layers, potassium grows in 3D islands (the Stranski-Krastanov mode). At higher temperature, e.g. at room temperature, potassium introduces reconstruction of the substrate even at low coverages. Calibration of the alkali coverage, up to completion of the first layer, using the work function changes curve has been confirmed as a very convenient and precise procedure. The adsorbed state of CO at 130 K has been identified by registration of core levels obtained by the use synchrotron radiation photoelectron spectroscopy. The characteristics of the main is and satellite peaks have been analyzed in context of substrate geometry and compared with the ones of other copper planes. There are no indications of dissociative adsorption of CO, only residual carbon and oxygen were found after adsorbate desorption around 220 K. CO molecules show a strong tendency to "on top" adsorption in sites far from the step edges of the Cu(115) surface.

Herein, it was investigated for the first time the electro-oxidation of ethanol on Pt and PtRu electrodeposits in acidic media by using in situ surface enhanced infrared absorption spectroscopy with attenuated total reflection (ATR-SEIRAS). The experimental setup circumvents the weak absorbance signals related to adsorbed species, usually observed for rough, electrodeposited surfaces, and allows a full description of the CO coverage with the potential for both catalysts. The dynamics of adsorption-oxidation of CO was accessed by ATR-SEIRAS experiments (involving four ethanol concentrations) and correlated with expressions derived from a simple kinetic model. Kinetic analysis suggests that the growing of the CO adsorbed layer is nor influenced by the presence of Ru neither by the concentration of ethanol. The results suggest that the C-C scission is not related to the presence of Ru and probably happens at Pt sites. Neste trabalho, investigou-se pela primeira vez a eletrooxidação de etanol em eletrodepósitos de Pt e PtRu em meio ácido através da técnica de absorção e reflexão de infravermelho em superfície com reflexão total atenuada (ATR-SEIRAS) in situ. O desenho experimental elimina as fracas absorbâncias associadas a espécies adsorvidas, usualmente observadas para superfícies eletrodepositadas (rugosas), e permite que se acompanhe o recobrimento superficial por CO em função do potencial, para ambos os catalisadores. A dinâmica da adsorção-oxidação de CO foi acompanhada por ATR-SEIRAS (para quatro concentrações de etanol) e correlacionada com expressões derivadas de um modelo cinético simples. A análise cinética sugere que o desenvolvimento da camada de CO não é influenciado pela presença de Ru ou pela concentração de etanol. Os resultados apontam que a quebra da ligação C-C independe do recobrimento com Ru e provavelmente acontece em sítios de Pt.