Effect of the metal deposition order on structural, electronic and catalytic properties of tio2-supported bimetallic au-ag catalysts in 1-octanol selective oxidation

42-01-09/169/2021-4 CTQ2017-86170-RAu and Ag were deposited on TiO2 modified with Ce, La, Fe or Mg in order to obtain bimetallic catalysts to be used for liquid-phase oxidation of 1-octanol. The effects of the deposition order of gold and silver, and the nature of the support modifying additives and redox pretreatments on the catalytic properties of the bimetallic Au-Ag catalysts were studied. Catalysts were characterized by low-temperature nitrogen adsorption–desorption, energy dispersive spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and ultraviolet-visible diffuse reflectance spectroscopy. It was found that pretreatments with hydrogen and oxygen at 300◦C significantly decreased the activity of AuAg catalysts (silver was deposited first) and had little effect on the catalytic properties of AgAu samples (gold was deposited first). The density functional theory method demonstrated that the adsorption energy of 1-octanol increased for all positively charged AuxAgyq (x + y = 10, with a charge of q = 0 or +1) clusters compared with the neutral counterparts. Lanthanum oxide was a very effective promoter for both monometallic and bimetallic gold and silver catalysts in the studied process.publishersversionpublishe

Properties of iron-modified-by-silver supported on mordenite as catalysts for nox reduction

A series of mono and bimetallic catalysts based on a Fe-Ag mixture deposited on mordenite was prepared by ion-exchange and evaluated in the catalytic activity test of the de-NOx reaction in the presence of CO/C3H6. The activity results showed that the most active samples were the Fe-containing ones, and at high temperatures, a co-promoter effect of Ag on the activity of Fe catalysts was also observed. The influence of the order of cation deposition on catalysts formation and their physicochemical properties was studied by FTIR (Fourier Transform Infrared Spectroscopy) of adsorbed NO, XANES (X-ray Absorption Near-Edge Structure), and EXAFS (Extended X-ray Absorption Fine Structure) and discussed in terms of the state of iron. Results of Fe K-edge XANES oscillations showed that, in FeMOR catalysts, iron was present in a disordered state as Fe3+ and Fe2+. In FeAgMOR, the prevailing species was Fe3+, while in the AgFeMOR catalyst, the state of iron was intermediate or mixed between FeMOR and FeAgMOR. The Fe K-edge EXAFS results were characteristic of a disordered phase, the first coordination sphere being asymmetric with two different Fe-O distances. In FeAgMOR and AgFeMOR, coordination of Fe-O was similar to Fe2O3 with a few amount of Fe2+ species. We may conclude that, in the bimetallic FeAgMOR and AgFeMOR samples, a certain amount of tetrahedral Al3+ ions in the mordenite framework is replaced by Fe3+ ions, confirming the previous reports that these species are active sites for the de-NOx reaction. Based on the thermodynamic analysis and experimental data, also, it was confirmed that the order of deposition of the components influenced the mechanism of active sites’ formation during the two steps ion-exchange synthesis

Effect of gold electronic state on the catalytic performance of nano gold catalysts in n-octanol oxidation

UIDB/50006/2020 project VIU-RSCBMT-65/2019 project 18-29-24037 (Russia) MINECO project CTQ2017-86170-R (Spain)This study aims to identify the role of the various electronic states of gold in the catalytic behavior of Au/MxOy/TiO2 (where MxOy are Fe2O3 or MgO) for the liquid phase oxidation of n-octanol, under mild conditions. For this purpose, Au/MxOy/TiO2 catalysts were prepared by deposition-precipitation with urea, varying the gold content (0.5 or 4 wt.%) and pretreatment conditions (H2 or O2), and characterized by low temperature nitrogen adsorption-desorption, X-ray powder diffraction (XRD), energy dispersive spectroscopy (EDX), scanning transmission electron microscopy-high angle annular dark field (STEM HAADF), diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy of CO adsorption, temperature-programmable desorption (TPD) of ammonia and carbon dioxide, and X-ray photoelectron spectroscopy (XPS). Three states of gold were identified on the surface of the catalysts, Au0, Au1+ and Au3+, and their ratio determined the catalysts performance. Based on a comparison of catalytic and spectroscopic results, it may be concluded that Au+ was the active site state, while Au0 had negative effect, due to a partial blocking of Au0 by solvent. Au3+ also inhibited the oxidation process, due to the strong adsorption of the solvent and/or water formed during the reaction. Density functional theory (DFT) simulations confirmed these suggestions. The dependence of selectivity on the ratio of Brønsted acid centers to Brønsted basic centers was revealed.publishersversionpublishe

Effect of the Metal Deposition Order on Structural, Electronic and Catalytic Properties of TiO2-Supported Bimetallic Au-Ag Catalysts in 1-Octanol Selective Oxidation

Au and Ag were deposited on TiO2 modified with Ce, La, Fe or Mg in order to obtain bimetallic catalysts to be used for liquid-phase oxidation of 1-octanol. The effects of the deposition order of gold and silver, and the nature of the support modifying additives and redox pretreatments on the catalytic properties of the bimetallic Au-Ag catalysts were studied. Catalysts were characterized by low-temperature nitrogen adsorption–desorption, energy dispersive spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and ultraviolet-visible diffuse reflectance spectroscopy. It was found that pretreatments with hydrogen and oxygen at 300 °C significantly decreased the activity of AuAg catalysts (silver was deposited first) and had little effect on the catalytic properties of AgAu samples (gold was deposited first). The density functional theory method demonstrated that the adsorption energy of 1-octanol increased for all positively charged AuxAgyq (x + y = 10, with a charge of q = 0 or +1) clusters compared with the neutral counterparts. Lanthanum oxide was a very effective promoter for both monometallic and bimetallic gold and silver catalysts in the studied process

Identification of Subnanometric Ag Species, Their Interaction with Supports and Role in Catalytic CO Oxidation

The nature and size of the real active species of nanoparticulated metal supported catalysts is still an unresolved question. The technique of choice to measure particle sizes at the nanoscale, HRTEM, has a practical limit of 1 nm. This work is aimed to identify the catalytic role of subnanometer species and methods to detect and characterize them. In this frame, we investigated the sensitivity to redox pretreatments of Ag/Fe/TiO2, Ag/Mg/TiO2 and Ag/Ce/TiO2 catalysts in CO oxidation. The joint application of HRTEM, SR-XRD, DRS, XPS, EXAFS and XANES methods indicated that most of the silver in all samples is in the form of Ag species with size <1 nm. The differences in catalytic properties and sensitivity to pretreatments, observed for the studied Ag catalysts, could not be explained taking into account only the Ag particles whose size distribution is measured by HRTEM, but may be explained by the presence of the subnanometer Ag species, undetectable by HRTEM, and their interaction with supports. This result highlights their role as active species and the need to take them into account to understand integrally the catalysis by supported nanometals

Influence of the Valence of Iron on the NO Reduction by CO over Cu-Fe-Mordenite

A comprehensive study of the catalytic properties of the copper-iron binary system supported on mordenite, depending on the iron valence—CuFe2MOR and CuFe3MOR—was carried out, and redox ability has been considered as a decisive factor in determining catalytic efficiency. Acidity was studied by TPD-NH3, DRIFT-OH, and DRT methods. The total acidity of both samples was high. The Brönsted acidity is similar for both bimetallic samples and is explained by the acidity of zeolite; Lewis acidity varies greatly and depends on the exchange cations. A screening DRIFT study of CO and NO has shown redox capacity and demonstrated a potential for using these materials as catalysts for ambient protection. CuFe2MOR demonstrated stable Cu and Fe species, while CuFe3MOR showed redox dynamic species. As expected, CuFe3MOR displayed higher catalytic performance in NO reduction via CO oxidation, because of the easily reduced intermediate NO-complex adsorbed on the metallic Cu and Fe sites, which were observed through in situ DRIFT study

Causes of Activation and Deactivation of Modified Nanogold Catalysts during Prolonged Storage and Redox Treatments

The catalytic properties of modified Au/TiO2 catalysts for low-temperature CO oxidation are affected by deactivation and reactivation after long-term storage and by redox treatments. The effect of these phenomena on the catalysts was studied by HRTEM, BET, SEM, FTIR CO, XPS and H2 TPR methods. The main cause for the deactivation and reactivation of catalytic properties is the variation in the electronic state of the supported gold, mainly, the proportion of singly charged ions Au+. The most active samples are those with the highest proportion of singly charged gold ions, while catalysts with a high content of trivalent gold ions are inactive at low-temperatures. Active states of gold, resistant to changes caused by the reaction process and storage conditions, can be stabilized by modification of the titanium oxide support with transition metals oxides. The catalyst modified with lanthanum oxide shows the highest stability and activity.We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).This work was funded by CONACYT project 260409 and PAPIIT-UNAM project IT200114 (Mexico); CSIC project 201180E104 and MINECO project CTQ2013-41507-R (Spain); and Government Program “Science” of Tomsk Polytechnic University, grant No. 4.1187.2014/K (Russia)

Identification of Subnanometric Ag Species, Their Interaction with Supports and Role in Catalytic CO Oxidation

The nature and size of the real active species of nanoparticulated metal supported catalysts is still an unresolved question. The technique of choice to measure particle sizes at the nanoscale, HRTEM, has a practical limit of 1 nm. This work is aimed to identify the catalytic role of subnanometer species and methods to detect and characterize them. In this frame, we investigated the sensitivity to redox pretreatments of Ag/Fe/TiO2, Ag/Mg/TiO2 and Ag/Ce/TiO2 catalysts in CO oxidation. The joint application of HRTEM, SR-XRD, DRS, XPS, EXAFS and XANES methods indicated that most of the silver in all samples is in the form of Ag species with size <1 nm. The differences in catalytic properties and sensitivity to pretreatments, observed for the studied Ag catalysts, could not be explained taking into account only the Ag particles whose size distribution is measured by HRTEM, but may be explained by the presence of the subnanometer Ag species, undetectable by HRTEM, and their interaction with supports. This result highlights their role as active species and the need to take them into account to understand integrally the catalysis by supported nanometals.We acknowledge support by the CSIC Open Access Publication Initiative through its Unit of Information Resources for Research (URICI).This research was supported by Government Program “Science” of Tomsk Polytechnic University, Grant No. 4.1187.2014/K, CONACYT Project 260409 and PAPIIT-UNAM Project IT200114 (Mexico), CSIC project 201480E077 and MINECO Project CTQ2013-41507-R (Spain). We gratefully thank O. Martynyuk, G. Torres Otañez, Z. I. Bedolla Valdez, E. Flores, F. Ruiz Medina, A. Olivas Sarabia, I. Gradilla, J. Mendoza, E. M. Aparicio Ceja, J. Peralta, David A. Domínguez, M. Sainz, R. Valdez Castro, M. Martínez, B. Acosta Ruelas, F. Ramírez Hernández and M. López Cisneros for valuable technical assistance

Bimetallic AgFe Systems on Mordenite: Effect of Cation Deposition Order in the NO Reduction with C3H6/CO

Mono- and bimetallic systems of Ag, Fe, and Ag&ndash;Fe exchanged in sodium mordenite zeolite were studied in the reaction of NO reduction. The transition metal cations Ag and Fe were introduced by ion exchange method both at room temperature and 60 &deg;C; modifying the order of component deposition in bimetallic systems. These materials were characterized by Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), ultraviolet-visible spectroscopy (UV-Vis), X-Ray photoelectron Spectroscopy (XPS) and High-resolution transmission electron microscopy (HR-TEM). The XPS and UV&ndash;Vis spectra of bimetallic samples revealed that under certain preparation conditions Ag+ is reduced with the participation of the Fe2+/Fe3+ ions transition and is present in the form of a Ag reduced state in different proportions of Agm clusters and Ag0 NPs, influenced by the cation deposition order. The catalytic results in the NO reduction reaction using C3H6/CO under an oxidizing atmosphere show also that the order of exchange of Ag and Fe cations in mordenite has a strong effect on catalytic active sites for the reduction of NO