Miguel Banares

Miguel Banares
Spanish National Research Council | CSIC · Institute of Catalysis and Petrochemistry

45.04
 · 
Ph.D. in Chemistry

About

252
Publications
20,181
Reads
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6,428
Citations
Introduction
Our group stands on spectroscopic understanding of catalysis. www.icp.csic.es/banares We focus on UNDERSTANDING STRUCTURE-PERFORMANCE relationships combining spectroscopy during catalytic reaction with simultaneous activity measurement (operando methodology, term which we coined in 2000) for real-time MONITORING OF CATALYTIC PROCESSES, CATALYST EVOLUTION and SYNTHESIS. We use essentially Raman spectroscopy and contrast with DFT calculations on structure and reactivity.
Research Experience
June 2014 - present
Spanish National Research Council
Position
  • Deputy Vice President for Scientific and Technical Areas
January 2002 - present
Spanish National Research Council
Position
  • Full Research Professor
January 1993 - April 1994
University of Notre Dame
Position
  • Research Associate

Publications

Publications (252)
Article
The aliovalent-substitution of cobalt into ceria lattice was demonstrated using a bimetallic CoCeBDC MOF to achieve a high degree of atomic level mixing in the CoCeOx catalyst. Spectroscopic analyses including X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and time-of-flight secondary ion mass spectrometry (ToF-SIMS) confirmed the succ...
Article
Raman and transmission FTIR spectroscopic techniques have been coupled in a new homemade reactor-cell designed in a joint CSIC-LCS collaboration. The set-up is easily adapted to any FTIR and fibre-coupled Raman spectrometers and gas analysis techniques. It allows simultaneous operando FTIR and Raman spectroscopic measurement, which provide compleme...
Article
In article number 1903525, Wei Han, King Lun Yeung, and co‐workers develop a synthesis approach to binary metal oxides by controlled thermal transformation of bimetallic metal–organic framework precursors. The approach is capable of manipulating the morphology and structure of binary metal oxides as high‐performance environmental catalysts for comp...
Article
Dry reforming and partial oxidation of biogas were studied using 0.5wt.% Rh/Al2O3 catalysts, both in-house prepared and commercial. The effects of O2 addition on syngas yield and biogas conversion were studied at 700 °C using different O2/CH4 ratios in the gas feeding stream: 0 (dry reforming), 0.12, 0.25, 0.45 and 0.50. The highest CH4 conversion,...
Article
Mixed transition metal oxides (MTMOs) have enormous potential applications in energy and environment. Their use as catalysts for the treatment of environmental pollution requires further enhancement in activity and stability. This work presents a new synthesis approach that is both convenient and effective in preparing binary metal oxide catalysts...
Article
A series of nanosized-bulk-supported Mo-V-Nb-Te catalysts has been prepared. With a new synthesis approach; nanocristalline aggregates of active phase are deposited on a support; this results in active and selective catalysts for propane oxidation into acrylic acid reaction, that require a low amount of active phase, and that exhibit better mechani...
Article
Based on unique oxygen storage capacity (OSC), ceria catalysts are widely investigated for remediation of volatile organic compounds (VOCs) over the recent decade. It is generally accepted that VOC oxidation on ceria is through Mars-van Krevelen mechanism, where lattice oxygen (OLat) reacts with adsorbed VOC molecule, followed by re-oxidation of re...
Article
Full-text available
The term operando was coined at the beginning of this century to gather the growing efforts devoted to establish structure-activity relationships by simultaneously characterizing a catalyst performance and the relevant surface chemistry during genuine catalytic operation. This approach is now widespread and consolidated; it has become an increasing...
Article
Faujasite zeolite-supported niobium-based catalysts (with Nb2O5 amounts of 5 and 15 wt%) were prepared by impregnation of NaY, HY, and HUSY zeolites using a niobum(V) ammonium oxalate complex. These obtained Nb-containing catalysts were calcined and thoroughly characterized by different physico-chemical techniques. The characterization results reve...
Article
This work investigates the effect of changing the vanadia/support interface on the redox properties of the material for the oxidative dehydrogenation reaction (ODH) of small alkanes. In particular, ternary V2O5/CeO2/SiO2 catalysts, are compared to vanadia on ceria and CeVO4 catalysts. Modifications in the CeO2 phase by effect of the silica support...
Article
A XANES study under reaction conditions has been performed with two different V-based catalytic systems, Mo-V-Nb-Te-O and V-Sb-O. For this study, an alumina-supported nanoscaled bulk catalyst has been used. In all cases XANES determined the average vanadium oxidation state during reaction. XANES also demonstrated that the nanosized phases are more...
Article
Full-text available
The assessment of an integral catalytic reactor facilitating operando spectroscopic measurements on a monolith has been carried out using NH3-SCR on a vanadia-based catalyst as a probe reaction. The NH3-SCR mechanism is revisited by studying the adsorbed ammonia and ionically bound ammonium ions and their relations to Lewis and Brønsted acid sites...
Article
A first European Conference on Computational Nanotoxicology, CompNanoTox, was held in November 2015 in Benahavís, Spain with the objectives to disseminate and integrate results from the European modeling and database projects (NanoPUZZLES, ModENPTox, PreNanoTox, MembraneNanoPart, MODERN, eNanoMapper and EU COST TD1204 MODENA) as well as to create s...
Article
Transition metal oxide overlayers are an important class of heterogeneous catalysts (sometimes referred to as monolayer catalysts), both for model studies and numerous industrial processes. To determine the molecular structures in such amorphous thin layers requires application of characterization methods that can perform in the absence of long-ran...
Article
A preliminary partial oxidation of NO to NO2 is helpful for low-temperature SCR. Oxidation of NO was evaluated over a Pt-based catalyst. Prior to the study, which was focused on the influence of the control of temperature over the catalytic results, PID process parameters of the catalytic reaction system were optimized showing that the unit control...
Article
Full-text available
The article describes the synthesis and properties of α-((4-cyanobenzoyl)oxy)-ω-methyl poly(ethylene glycol), the first poly(ethylene glycol) stabilizer for metal nanoparticles that is based on a cyano rather than a thiol or thiolate anchor group. The silver particles used to evaluate the effectiveness of the new stabilizer typically have a bimodal...
Book
In today’s nanotechnology and pharmaceutical research, alternative toxicology testing methods are crucial for ethically and commercially sound practice. This book provides practical guidelines on how to develop and validate quantitative nanostructure-toxicity relationship (QNTR) models, which are ideal for rapidly exploring the effects of a large n...
Article
Because of the ability to directly probe the catalyst under reaction conditions, operando studies have significantly improved the catalysis literature. The number of operando publications continues to increase. Historical and current operando spectroscopy studies concerning all catalyst types and applications are extensively reviewed.
Article
Immobilization of nanoparticles on inorganic supports has been recently developed, resulting in the creation of nanocomposites. Concerning titanium dioxide nanoparticles (TiO2 NPs(1)), these have already been developed in conjugation with clays, but so far there are no available toxicological studies on these nanocomposites. The present work intend...
Article
Full-text available
Retraction of ‘Efficient microwave-promoted acrylonitrile sustainable synthesis from glycerol’ by Vanesa Calvino-Casilda, M. Olga Guerrero-Pérez and Miguel Bañares, Green Chem., 2009, 11, 939–941.
Article
Brønsted acid ionic liquids (BAILs) have been prepared and applied for the first time - to the best of our knowledge - as efficient catalysts in the acetylation of glycerol with acetone to form solketal ((2,2-dimethyl-1,3-dioxolan-4-yl)methanol) at very mild reaction conditions (room temperature) and short reaction times. The BAILs showed a superio...
Article
The main objective of this work is to determine which kind of acidic sites, Brønsted (BAS) or Lewis (LAS), are more active and stable in the glycerol acetalization to solketal by means of Raman-monitoring. For this purpose, the mesoporous cellular foams (MCFs) were modified to obtain materials containing exclusively BAS occurring in different numbe...
Article
Catalysts from three different catalytic systems, Ni–Nb–O, Mo–V–Nb–Te–O and Sb–V–O, have been prepared, characterized, and tested during both ethane and propane ammoxidation reactions, in order to obtain acetonitrile and acrylonitrile, respectively. The catalytic results show that Mo–V–Nb–Te–O and Sb–V–O catalyze propane ammoxidation but are inacti...
Article
The surface structure and reactivity of vanadia supported on ceria catalysts were studied by Raman spectroscopy and methanol adsorption and temperature-programmed surface reaction (TPRS) of the adsorbed species monitored in situ by infrared spectroscopy. Monomeric and polymeric vanadia surface species and CeVO4 were identified on the catalysts. Met...
Article
Full-text available
A new monolithic reactor for operando Raman spectroscopy studies of honeycomb-shaped catalysts has been developed to obtain complete information on these systems, considering the effect of conformation on structure-activity relationships; this is illustrated by Raman-GC monitoring of alumina-supported vanadium phosphorous oxide phases during propan...
Article
The synthesis of mesostructured cellular foams (MCF) modified by niobium or tantalum source and functionalized with MPTMS (3-mercaptopropyl)trimethoxysilane was monitored in situ by Raman spectroscopy. The results from Raman monitoring prompted us to check for a possibility of shorter time synthesis of mesostructured cellular foams. A series of MCF...
Article
The catalytic activity of VOx species supported on TiO2 was investigated in the simultaneous destruction of NO and 1,2-dichlorobenzene (o-DCB), as typical pollutants molecules in the off-gases from municipal waste incinerator (MWI) plants. Catalysts with different vanadium loading were prepared in order to obtain different VOx species and character...
Article
Ionic Liquids (ILs) are valuable reaction media extremely useful in industrial sustainable organic synthesis. We describe here the study on the multicomponent reaction (MCR) between salicylaldehyde (2) and ethyl cyanoacetate (3), catalyzed by imidazolium sulfonates, to form chromenes 1, a class of heterocyclic scaffolds exhibiting relevant biologic...
Article
Full-text available
A series of V- and/or Ti-loading MCM-41 catalysts are successfully synthesized with a hydrothermal method. The photocatalytic and thermal epoxidations of cyclohexene in the presence of tert-butyl hydroperoxide (t-BuOOH) were investigated with real-time monitored by NIR-Raman spectroscopy. It suggests that both V- and Ti-loading can be responsible f...
Article
Mechanochemistry has played an important role in the synthesis of many novel compounds, in particular within the field of materials for solid state hydrogen storage applications. This work investigates reactive milling of ethane 1,2-di-amineborane (EDAB) and sodium hydride which yields the evolution of one equivalent of hydrogen and the formation o...
Article
We present, for the first time in literature, a systematic study of the molecular structure of the Wells-Dawson heteropolyacid H6P2W18O62.24H2O (HPA) dispersed on TiO2, SiO2, ZrO2 and Al2O3. The heteropolyacid-based materials were synthesized through a conventional impregnation method (in aqueous and ethanol media) at a loading that corresponds to...
Article
A modified successive ionic layer adsorption and reaction (SILAR) process was used for deposition of coupled CdS and CdSe quantum dots (QDs) on the surface of orientated ZnO nanorod arrays. This solution-based process provides a conformal and homogeneous QDs deposition along the ZnO nanorod arrays with no entry clogging. The prepared multi-heteroju...
Article
Full-text available
ZnO presents favorable thermodynamics, equilibrium constant and stability for H2S chemisorption and sepiolite has excellent sorptive and rheological properties to be employed as support. Four conformed ZnO/sepiolite composites are prepared, two by impregnation in zinc nitrate solution -one using activated carbon as dispersing and pore generating ag...
Conference Paper
Full-text available
The performance of two zeolites with different structures and acidity properties was evaluated on the biosorption of Cr(VI) and catalytic oxidation of ethyl acetate. The starting zeolites, HY and HZSM5, were modified by ion exchange treatments in order to obtain zeolites with different acidity and sodium content. Arthrobacter viscosus supported on...
Chapter
Over the past two decades, Raman spectroscopy has been extensively applied during catalytic oxidation reactions by mixed-metal oxides and metals under in situ and operando spectroscopy conditions, which has allowed the direct identification of the catalytic active sites involved in the oxidation reactions. Among the multiple spectroscopic technique...
Article
The combination of both infrared and Raman spectroscopy are powerful tools to obtain information of catalytic materials at a molecular level. The present investigation shows, a systematic study “in situ” about the effects of the temperature in the molecular structure of the supported phosphotungstic Wells-Dawson heteropolyacid (HPA). The infrared a...
Article
The acetalization of glycerol with acetone over modified mesoporous cellular foam materials has been widely investigated using in situ Raman spectroscopy during reaction. Mesoporous cellular foams (MCFs) modified by niobium or tantalum and (3-mercaptopropyl)trimethoxysilane (MP) followed by H2O2 treatment were used as catalysts in the acetalization...
Article
The effect of Nb when used as a promoter for vanadyl pyrophosphate, the catalyst for the oxidation of n-butane to maleic anhydride, was investigated. By means of both reactivity experiments and in situ Raman spectroscopy, it was found that the promoting effect shown by Nb occurred already for a very low amount of it, i.e., for a V/Nb atomic ratio a...
Article
Full-text available
There is a need to develop catalysts for the direct ammoxidation of ethane to acetonitrile. This work reports a series of bulk Ni-Nb-O catalysts with increasing niobium content, analysing the structure and the effect on acidity and redox properties and how these relate to Ni-Nb interaction. Niobium doping affects NiO lattice leading to progressivel...
Article
Periodic DFT calculations are used to simulate the early stages of hydration of dehydrated high-loading vanadia/titania catalysts. The hydration of molecularly dispersed vanadia is studied by successive additions of water molecules to initially dehydrated models. Special attention is paid to the formation and transformation between different surfac...
Article
The oxidation of phenol, cychohexanol and hydroquinone has been screened in the presence of copper(II) complexes with the Schiff-base salen ligand, 1,5-bis[(E)-5-chloro-2-hydroxybenzylideneamino]-1H-imidazole-4-carbonitrile, and encapsulated into NaY zeolite by using two different methods. The new heterogeneous catalysts were characterized by SEM,...
Chapter
One great advantage of Raman spectroscopy is that it can be applied to samples under almost any condition that is sensitive to molecular vibrations of the catalyst, the reactants, and the acting adsorbates. This chapter focuses on recent developments of operando Raman studies, which provide a deeper and broader understanding of the catalytic act an...
Article
ZnO supported Co3O4 nanoparticles are highly active in the transformation of renewable materials through carbonylation of glycerol with urea. The activity of the nanoparticles is modulated by their interaction with the ZnO support, which remarkably depends on the impregnation method. One catalyst series was impregnated by conventional impregnation...
Article
Catalysis is a complex multidisciplinary science that enables efficient performance in energy, automotive, chemical and pharmaceutical industries; most chemical reactions are catalyzed and it is a science that cannot be understood without spectroscopy. Spectroscopy is the enabling tool for knowledge-based design of highly efficient and stable catal...
Article
Operando means working, thus, this technique refers to the combination of a characterization study of the surface of a catalyst at the same time that the activity is being monitored. This approach, which permits the simultaneous characterization of both parameters in a single experiment, facili- tates uncovering the relationships between structure...
Article
Glycerol is a major by-product in biodiesel manufacturing, which surplus raises a critical need to transform it into high added-value products. In particular, glycerol carbonate is an important glycerol derivative being the most valuable intermediate for the production of glycidol, which is an added-value product of major industrial interest used,...
Article
Full-text available
Two series of supported nanoscaled NiO catalysts have been prepared using Nb2O5 supports with different surface areas. NiO nanoparticles interacting with Ni–O–Nb mixed phases are active and selective for ethane ammoxidation; both are required in order to have an active and selective catalyst. In this paper we report the dispersion of NiO nanopartic...
Article
This paper describes the design and setup of a high-throughput Raman system for an array of eight parallel catalytic reactors during reaction conditions. The "operando" methodology combines in situ spectroscopy during catalytic reaction with a simultaneous activity measurement. The high-throughput operando Raman system, multi-operando, is a device...
Article
Metal amidoboranes have been regarded as potential candidates for hydrogen storage applications, due to their high gravimetric capacities and their relatively low hydrogen desorption temperatures. Here, we report about the synthesis of calcium amidoborane (CaAB) by means of reactive milling of ammonia borane and calcium hydride. Structural properti...
Article
Full-text available
Operando means working, thus, this technique refers to the combination of a characterization study of the surface of a catalyst at the same time that the activity is being monitored. This approach, which permits the simultaneous characterization of both parameters in a single experiment, facilitates uncovering the relationships between structure an...
Article
Vanadium is a key component for selective and environmental catalysts. Supported vanadium oxide catalysts find many industrial applications for selective oxidation, ammoxidation, and reduction reactions for bulk and environ-mental processes. The properties of molecularly dispersed vanadium oxide species depend strongly on the nature of the support....
Conference Paper
The structural properties and oxidation state of vanadium in alumina-supported vanadium-phosphorous oxides at nearly monolayer coverage influence its catalytic performances. The population distribution V-V=O and V-IV=O species in the amorphous VPO phase strongly depends on the sample history. By using alumina-supported VPO instead of conventional b...
Article
We report a methodology to prepare nanoscaled supported-bulk MoVNbTeO catalysts in which the phases required to obtain an active and selective catalysts are nanoscaled on the surface of a support. Thus, a more economic catalytic material with improved mechanical properties can be obtained. The effect of vanadium content and atmosphere of calcinatio...
Article
Full-text available
Since niobium species have been described as being able to increase the catalytic properties of the Sb–V–O catalytic system, the main objective of the present paper is to design a non ordered-mesoporous Nb-containing material useful to be used as a support for this kind of catalysts. Such a material has been used as support for Sb–V–O active phases...
Article
In situ Raman spectroscopy was used to assess the progress of the Michael addition reaction between imidazole and ethyl acrylate in dry media over basic carbon catalysts. N-substituted imidazoles and their derivatives obtained under these reaction conditions are pharmaceutically important due to their pharmacodynamic properties. Real-time Raman mon...
Article
The main objective of the present contribution is to analyze the effect of composition, coverage and Te doping in the surface composition and catalytic behavior of supported-nanoscaled MoVNb(Te)O catalysts. Different spectroscopy techniques combine to afford such objective. The composition of the surface species has been studied by Raman and UV–Vis...
Article
The aim of this work was the evaluation of the performance of two zeolites with different structures (FAU and MFI) and acidity properties in the biosorption of Cr(VI) and catalytic oxidation of ethyl acetate. The starting zeolites, Y (FAU) and ZSM5 (MFI), were modified by ion exchange treatments with NaNO 3 in order to obtain zeolites with differen...
Article
Density Functional Theory (DFT) calculations have been performed for ethane, ethylene, propane, and propylene adsorption on the rutile VSbO4 structure to uncover the reaction mechanism during both ODH and ammoxidation reactions. This study is complementary to a previous paper in which the adsorption of ammonia on this structure was deeply analyzed,...
Article
The solvent-free liquid phase epoxidation of cyclohexene with tert-butyl hydroperoxide over alumina-supported VPO and VPO bulk catalysts has been widely investigated using in situ Raman spectroscopy. Real-time Raman monitoring provides non-invasive insight during epoxidation of cyclohexene in the presence of heterogeneous catalysts in the absence o...
Article
Alumina-supported VPO materials are efficient catalysts for acrylonitrile production by the propane ammoxidation reaction. In order to understand the structure-activity relationship and the nature of active sites, operando Raman-GC analyses follow the states of vanadium and phosphorous species on an alumina support during ammoxidation. These oxides...
Article
A monolithic vanadia-titania based catalyst has been subjected to studies with in situ FTIR spectroscopy coupled with mass spectrometry, during the SCR (Selective Catalytic Reduction) reaction. A device based on a transmission reactor cell for monolithic samples was constructed, dedicated to the study of surface species during reaction. After analy...
Article
Addition of H2S in the gasification gas stream has been found to improve naphthalene and ammonia conversion over ZrO2 and Y2O3-ZrO2 catalysts, whereas over SiO2-ZrO2 such effect has not been observed. The differences in the properties of the catalysts were studied by spectroscopic (MeOH-DRIFTS) and temperature-programmed methods (H2S-TPD and MeOH-T...
Article
The hydration process of dehydrated vanadia-titania catalysts at low loading is investigated using periodic DFT calculations. We focus on the early stages of the hydration process of the vanadia-titania in order to shed light onto the structural and dynamical changes occurring at the molecular level. Hydration is modeled by addition of successive w...
Article
In situ Attenuated Total Reflectance FTIR spectroscopy was used to study the carbonylation of glycerol with urea. Cobalt oxide nanoparticles, Co3O4, hierarchically dispersed on zinc oxide microparticles, ZnO, were used as catalysts. The present work demonstrates that in situ real-time attenuated total reflection ATR-FTIR spectroscopy is a valuable...
Article
Progress in nanomaterials and catalysis stands on three pillars: 1) synthesis of nanomaterials, including the preparation of hierarchically dispersed nanoparticles; 2) theoretical studies of materials that enable experimental results to be understood; and 3) advanced, in situ characterization during operation (operando methodology). This Research N...