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2023


Reactividad de Sólidos

Nanocrystalline Skinnerite (Cu3SbS3) Prepared by High-Energy Milling in a Laboratory and an Industrial Mill and Its Optical and Optoelectrical Properties

Dutkova, E; Sayagues, MJ; Fabian, M; Balaz, M; Kovac, J; Kovac, J; Stahorsky, M; Achimovicova, M; Bujnakova, ZL
Molecules, 28 (2023) 1

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Copper, antimony and sulfur in elemental form were applied for one-pot solid-state mechanochemical synthesis of skinnerite (Cu3SbS3) in a laboratory mill and an industrial mill. This synthesis was completed after 30 min of milling in the laboratory mill and 120 min in the industrial mill, as corroborated by X-ray diffraction. XRD analysis confirmed the presence of pure monoclinic skinnerite prepared in the laboratory mill and around 76% monoclinic skinnerite, with the secondary phases famatinite (Cu3SbS4; 15%), and tetrahedrite (Cu11.4Sb4S13; 8%), synthesized in the industrial mill. The nanocrystals were agglomerated into micrometer-sized grains in both cases. Both samples were nanocrystalline, as was confirmed with HRTEM. The optical band gap of the Cu3SbS3 prepared in the laboratory mill was determined to be 1.7 eV with UV-Vis spectroscopy. Photocurrent responses verified with I-V measurements under dark and light illumination and Cu3SbS3 nanocrystals showed similar to 45% enhancement of the photoresponsive current at a forward voltage of 0.6 V. The optical and optoelectrical properties of the skinnerite (Cu3SbS3) prepared via laboratory milling are interesting for photovoltaic applications.


Enero, 2023 | DOI: 10.3390/molecules28010326

Química de Superficies y Catálisis

Formic Acid Dehydrogenation over Ru- and Pd-Based Catalysts: Gas- vs. Liquid-Phase Reactions

Ruiz-Lopez, E; Pelaez, MR; Ruz, MB; Leal, MID; Tejada, MM; Ivanova, S; Centeno, MA
Materials, 16 (2023) 472

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Formic acid has recently been revealed to be an excellent hydrogen carrier, and interest in the development of efficient and selective catalysts towards its dehydrogenation has grown. This reaction has been widely explored using homogeneous catalysts; however, from a practical and scalable point of view, heterogeneous catalysts are usually preferred in industry. In this work, formic acid dehydrogenation reactions in both liquid- and vapor-phase conditions have been investigated using heterogeneous catalysts based on mono- or bimetallic Pd/Ru. In all of the explored conditions, the catalysts showed good catalytic activity and selectivity towards the dehydrogenation reaction, avoiding the formation of undesired CO.


Enero, 2023 | DOI: 10.3390/ma16020472

Química de Superficies y Catálisis

Engineering morphologies of yttrium oxide supported nickel catalysts for hydrogen production

Zhang, RB; Tu, ZA; Meng, S; Feng, G; Lu, ZH; Yu, YZ; Reina, TR; Hu, FY; Chen, XH; Ye, RP
Rare Metals, 42 (2023) 176-188

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The catalytic performance is highly related to the catalyst structure. Herein, a series of Ni nanoparticles supported on Y2O3 with different morphologies were successfully synthesized via hydrothermal process screening different pH environments. These Ni/Y2O3 catalysts were applied to efficiently produce COx-free H-2 through ammonia decomposition. We identify a significant impact of Y2O3 supports on nickel nanoclusters sizes and dispersion. The experimental results show that Ni/Y11 catalyst achieves 100% ammonia decomposition conversion under a gas hour space velocity (GHSV) of 12,000 ml.h(-1).g(cat)(-1) and temperature of 650 degrees C. Such a high level of activity over Ni/Y11 catalyst was attributed to a large specific surface area, appropriate alkalinity, and small Ni nanoparticles diameter with high dispersion.


Enero, 2023 | DOI: 10.1007/s12598-022-02136-5

Materiales y Procesos Catalíticos de Interés Ambiental y Energético

Methanation of CO2 over High Surface Nickel/Aluminates Compounds Prepared by a Self-Generated Carbon Template

Roudane, S; Bettahar, N; Caballero, A; Holgado, JP
Catalysts, 13 (2023) 142

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Catalytic gas-phase hydrogenation of CO2 into CH4 was tested under three different nickel/aluminate catalysts obtained from precursors of hexaaluminate composition (MAl16O19, M = Mg, Ca, Ba). These catalysts were prepared using a carbon template method, where carbon is self-generated from a sol-gel that contains an excess of citric acid and the Al and M salts (Ba2+, Ca2+, Mg2+) by two-step calcination in an inert/oxidizing atmosphere. This procedure yielded Ni particles decorating the surface of a porous high surface area matrix, which presents a typical XRD pattern of aluminate structure. Ni particles are obtained with a homogeneous distribution over the surface and an average diameter of ca 25-30 nm. Obtained materials exhibit a high conversion of CO2 below 500 degrees C, yielding CH4 as a final product with selectivity >95%. The observed trend with the alkaline earth cation follows the order NiBaAlO-PRx > NiCaAlO-PRx > NiMgAlO-PRx. We propose that the high performance of the NiBaAlO sample is derived from both an appropriate distribution of Ni particle size and the presence of BaCO3, acting as a CO2 buffer in the process.


Enero, 2023 | DOI: 10.3390/catal13010142

Materiales Nanoestructurados y Microestructura

Microstructure and activity of Pd catalysts prepared on commercial carbon support for the liquid phase decomposition of formic acid

Arzac, GM; Montes, O; Fernández, A
International Journal of Hydrogen Energy, 48 (2023) 2628-2639

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In this work, a series of Pd catalysts supported on commercially available activated carbon (Norit (R)) were prepared by employing different metal precursors (Pd(NO3)2 and Na2PdCl4) by the impregnation-reduction method at different pH. Catalysts were tested for the liquid phase decomposition of formic acid to generate hydrogen. The best results, in terms of small particle size and high catalytic activity were achieved for the Pd/C sample prepared by using Pd(NO3)2 salt impregnated at pH = 2.5, and reduced with sodium borohydride. The particle size of the best Pd/C catalyst is (4.1 +/- 1.4) nm with initial TOFs of 2929 and 683 h-1 at 60 and 30 degrees C respectively and an apparent activation energy of 40 kJ mol-1. Samples prepared by using Na2PdCl4 precursor, consisted of particles with higher size and thus lower activity than the ones prepared with Pd(NO3)2. Regardless the Pd precursor employed, the best results in terms of particle size and activity were achieved at the point of zero charge of the support when the Pd species and the carbon surface were both neutral. The impregnation pH not only determines the particle size, but also the nature of the reducing agent does. The catalytic activity was shown to be size-dependent and it was shown that a mixture of surface Pd0 and PdII oxidation states is beneficial for the activity. When comparing with literature catalysts with similar composition, we found that our best catalyst is competitive enough and that Norit (R) support could be promising for future studies on this reaction.


Enero, 2023 | DOI: 10.1016/j.ijhydene.2022.10.149

 

 

 

 

 

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