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Scientific Papers in SCI



2020


Química de Superficies y Catálisis

Elucidation of Water Promoter Effect of Proton Conductor in WGS Reaction over Pt-Based Catalyst: An Operando DRIFTS Study

Jurado, L; Garcia-Moncada, N; Bobadilla, LF; Romero-Sarria, F; Odriozola, JA
Catalysts, 10 (2020) 841

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A conventional Pt/CeO2/Al(2)O(3)catalyst physically mixed with an ionic conductor (Mo- or Eu-doped ZrO2) was tested at high space velocity (20,000 h(-1)and 80 L h(-1)g(cat)(-1)) under model conditions (only with CO and H2O) and industrial conditions, with a realistic feed. The promoted system with the ionic conductor physically mixed showed better catalytic activity associated with better water dissociation and mobility, considered as a rate-determining step. The water activation was assessed by operando diffuse reflectance infrared fourier transformed spectroscopy (DRIFTS) studies under reaction conditions and the Mo-containing ionic conductor exhibited the presence of both dissociated (3724 cm(-1)) and physisorbed (5239 cm(-1)) water on the Eu-doped ZrO(2)solid solution, which supports the appearance of proton conductivity by Grotthuss mechanism. Moreover, the band at 3633 cm(-1)ascribed to hydrated Mo oxide, which increases with the temperature, explains the increase of catalytic activity when the physical mixture was used in a water gas shift (WGS) reaction.


August, 2020 | DOI: 10.3390/catal10080841

Reactividad de Sólidos

ICTAC Kinetics Committee recommendations for analysis of multi-step kinetics

Vyazovkin, S; Burnham, AK; Favergeon, L; Koga, N; Moukhina, E; Perez-Maqueda, LA; Sbirrazzuoli, N
Thermochimica Acta, 689 (2020) 178597

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The present recommendations have been developed by the Kinetics Committee of the International Confederation for Thermal Analysis and Calorimetry (ICTAC). The recommendations provide guidance on kinetic analysis of multi-step processes as measured by thermal analysis methods such as thermogravimetry (TGA) and differential scanning calorimetry (DSC). Ways of detecting the multi-step kinetics are discussed first. Then, four different approaches to evaluation of kinetic parameters (the activation energy, the pre-exponential factor, and the reaction model) for individual steps are considered. The approaches considered include multi-step model-fitting as well as distributed reactivity, isoconversional, and deconvolution analyses. For each approach practical advice is offered on its effective usage. Due attention is also paid to the typical problems encountered and to the ways of resolving them. The objective of these recommendations is to help a non-expert with efficiently performing multi-step kinetic analysis and interpreting its results.


July, 2020 | DOI: 10.1016/j.tca.2020.178597

Fotocatálisis Heterogénea: Aplicaciones

Influence of Sr-doping on structural, optical and photocatalytic properties of synthesized Ca3(PO4)2

Y.Naciri; A.Hsini; Z.Ajmal; A.Bouddouch; B.Bakiz; J.A.Navío; A.Albourine; J-C.Valmalette; M.Ezahri; A.Benlhachemi
Journal of Colloid and Interface Science, 572 (2020) 269-280

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Well-crystallized Ca3(PO4)2 doped and un-doped nano-particles with the maximum strontium content (40 wt% Sr) followed by calcination at 800 °C for 3 h were synthesized via facile co-precipitation method. DTA/TGA, X-ray diffraction (XRD), energy dispersive scanning electron microscopy (SEM/EDX), UV–vis diffuse reflectance spectrum (UV–vis DRS), Raman spectroscopy and photoluminescence (PL) techniques were used for material characterization. The (XRD) patterns of as-synthesized Sr-doped Ca3(PO4)2 solid solution samples exhibited a systematic shift toward lower angles by possessing a single rhombohedral crystal structure without any secondary phases. The UV light driven photocatalytic activity was assessed for rhodamine B (RhB) degradation. As a result, ultrafast photodegradation activity was observed after Sr doping. Moreover, the 30 wt% Sr-Ca3(PO4)2 sample showed the highest photocatalytic degradation among the Sr-doped Ca3(PO4)2 samples toward RhB. It was further suggested that as-synthesized 30 wt% Sr-Ca3(PO4)2 superior photocatalytic performance is ascribed to the more proficient partition of photogenerated electron-hole pairs. Furthermore, the involved mechanism of superior photocatalytic performance of the 30 wt% Sr-Ca3(PO4)2 solid solution was also investigated. In addition, regeneration cycles indicated the higher stability of the photocatalyst to be effectively recycled up to four times without any considerable reduction in photocatalytic performance. Thus, these informations further provides us a scalable pathway to fabricate Sr doped Ca3(PO4)2 and its consequent use as an efficient photocatalyst for rhodamine B (RhB) contaminated wastewater treatment.


July, 2020 | DOI: 10.1016/j.jcis.2020.03.105

Materiales de Diseño para la Energía y Medioambiente

Sustainable, High-Barrier Polyaleuritate/Nanocellulose Biocomposites

Tedeschi, G; Guzman-Puyol, S; Ceseracciu, L; Benitez, JJ; Cataldi, P; Bissett, M; Heredia, A; Athanassiou, A; Heredia-Guerrero, JA
ACS Sistainable Chemistry & Engineering, 8 (2020) 10682-10690

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Free-standing and flexible biocomposite films formed by a polyaleuritate matrix and nanocellulose fillers (i.e., cellulose nanofibrils) have been fabricated by a sustainable process. For this, 9,10,16-trihydroxyhexadecanoic (aleuritic) acid from shellac and nanocellulose were blended at different ratios in water through a sonication process. Polymerization of the polyhydroxylated fatty acid into polyaleuritate was induced by a solvent-free, melting polycondensation reaction in the oven. These biocomposites were characterized to evaluate their chemical (by ATR-FTIR spectroscopy) and physical (e.g., density, thermal stability, rigidity, gas permeability, surface energy, etc.) properties. The compatibility between the polyester matrix and the polysaccharide fillers was excellent due to the interaction by H bonds of the polar groups of both components. The addition of nanocellulose increased all determined mechanical parameters as well as the wettability and the barrier properties, while the thermal stability and the water uptake were determined by the polyaleuritate matrix. The physical properties of these biocomposites were compared to those of petroleum-based plastics and bio-based polymers, indicating that the developed materials can represent a sustainable alternative for different applications such as packaging.


July, 2020 | DOI: 10.1021/acssuschemeng.0c00909

Química de Superficies y Catálisis

Evaluation of the Oxygen Mobility in CePO4-Supported Catalysts: Mechanistic Implications on the Water-Gas Shift Reaction

Navarro-Jaen, S; Bobadilla, LF; Romero-Sarria, F; Laguna, OH; Bion, N; Odriozola, JA
Journal of Physical Chemistry C, 124 (2020) 16391-16401

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The hexagonal and monoclinic phases of CePO4 have been demonstrated to be excellent catalytic supports for Pt-based water-gas shift (WGS) catalysts. Consequently, the elucidation of the WGS reaction mechanism in these materials constitutes a fundamental aspect in order to explain their catalytic behavior. Because the observed WGS reaction path is closely related to the absence or presence of oxygen vacancies in the support, the study of the oxygen mobility in these solids constitutes a key factor for the understanding of the structure of the materials and its influence on the reaction mechanism. In this study, the oxygen mobility in CePO4 supports and the corresponding Pt catalysts has been evaluated by means of isotopic exchange experiments using O-18(2) and (CO2)-O-18 as probe molecules. Results demonstrate that the evaluated solids present a low exchange activity when O-18(2) is used, indicating the absence of oxygen vacancies in these solids, thus suggesting a poor influence of the WGS redox mechanism. On the contrary, a high oxygen exchange activity is observed using (CO2)-O-18, demonstrating that the exchange in these materials takes place through the formation of carbonate-like intermediates, thus suggesting the associative mechanism of the WGS reaction as the preferred path in these solids. Operando diffuse reflectance infrared spectroscopy experiments under WGS reaction conditions confirm these results, proving that the WGS reaction in the studied materials takes place through a formate-mediated associative mechanism.


July, 2020 | DOI: 10.1021/acs.jpcc.0c03649

 

 

 

 

 

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