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2022


Highly Anisotropic Organometal Halide Perovskite Nanowalls Grown by Glancing-Angle Deposition


Castillo-Seoane, J; Contreras-Bernal, L; Obrero-Perez, JM; Garcia-Casas, X; Lorenzo-Lazaro, F; Aparicio, FJ; Lopez-Santos, C; Rojas, TC; Anta, JA; Borras, A; Barranco, A; Sanchez-Valencia, JR
Advanced Materials (2022) 2107739
Nanotecnología en Superficies y Plasma - Materiales Nanoestructurados y Microestructura

ABSTRACT ▼

Polarizers are ubiquitous components in current optoelectronic devices as displays or photographic cameras. Yet, control over light polarization is an unsolved challenge, since the main drawback of the existing display technologies is the significant optical losses. In such a context, organometal halide perovskites (OMHP) can play a decisive role given their flexible synthesis with tunable optical properties such as bandgap and photoluminescence, and excellent light emission with a low non-radiative recombination rate. Therefore, along with their outstanding electrical properties have elevated hybrid perovskites as the material of choice in photovoltaics and optoelectronics. Among the different OMHP nanostructures, nanowires and nanorods have lately arisen as key players in the control of light polarization for lighting or detector applications. Herein, the fabrication of highly aligned and anisotropic methylammonium lead iodide perovskite nanowalls by glancing-angle deposition, which is compatible with most substrates, is presented. Their high alignment degree provides the samples with anisotropic optical properties such as light absorption and photoluminescence. Furthermore, their implementation in photovoltaic devices provides them with a polarization-sensitive response. This facile vacuum-based approach embodies a milestone in the development of last-generation polarization-sensitive perovskite-based optoelectronic devices such as lighting appliances or self-powered photodetectors.


Marzo, 2022 | DOI: 10.1002/adma.202107739

Analysis of Dry Reforming as direct route for gas phase CO2 conversion. The past, the present and future of catalytic DRM technologies


le Sache, E; Reina, TR
Progress in Energy and Combustion Science, 89 (2022) 100970
Química de Superficies y Catálisis

ABSTRACT ▼

Transition to low carbon societies requires advanced catalysis and reaction engineering to pursue green routes for fuels and chemicals production as well as CO2 conversion. This comprehensive review provides a fresh perspective on the dry reforming of methane reaction (DRM) which constitutes a straightforward approach for effective CO2 conversion to added value syngas. The bottleneck for the implementation of this process at industrial scale is the development of highly active and robust heterogeneous catalysts able to overcome the CO2 activation barrier and deliver sufficient amount of the upgrading products at the desired operation conditions. Also, its high energy demand due to the endothermic nature of the reaction imposes extra difficulties. This review critically discusses the recent progresses on catalysts design ranging from traditional metal-supported catalysts to advanced structured and nanostructured systems with promising performance. The main advantages and culprits of the different catalytic systems are introduced aiming to inspire the catalysis community to further refine these formulations towards the development of "supercatalysts" for DRM. Besides the design of increasingly complex catalyst morphologies as well as other promising alternatives aiming at reducing the energy consumption of the process or tackle deactivation through reactor design are introduced.


Marzo, 2022 | DOI: 10.1016/j.pecs.2021.100970

Evidence of new Ni-O-K catalytic sites with superior stability for methane dry reforming


Azancot, L; Blay, V; Blay-Roger, R; Bobadilla, LF; Penkova, A; Centeno, MA; Odriozola, JA
Applied Catalysis B-Environmental, 307 (2022) 121148
Química de Superficies y Catálisis

ABSTRACT ▼

Liquid fuels produced via Fischer-Tropsch synthesis from biomass-derived syngas constitute an attractive and sustainable energy vector for the transportation sector. This study focuses on the role of potassium as a promoter in Ni-based catalysts for reducing coke deposition during catalytic dry reforming. The study provides a new structural link between catalytic performance and physicochemical properties. We identify new Ni-O-K chemical states associated with high stability in the reforming process, evidenced by different characterization techniques. The nickel particles form a core surrounded by a Ni-O-K phase layer (Ni@Ni-O-K) during the reduction of the catalyst. This phase likely presents an alkali-nickelate-type structure, in which nickel is stabilized in oxidation state + 3. The Ni-O-K formation induces essential changes in the electronic, physical, structural, and morphological properties of the catalysts, notably enhancing their long-term stability in dry reforming. This work thus provides new directions for designing more efficient catalysts for sustainable gas-to-liquids processes.


Junio, 2022 | DOI: 10.1016/j.apcatb.2022.121148

Characterization of Re-Mo/ZSM-5 catalysts: How Re improves the performance of Mo in the methane dehydroaromatization reaction


Lopez-Martin, A; Sini, MF; Cutrufello, MG; Caballero, A; Colon, G
Applied Catalysis B-Environmental, 304 (2022) 120960
Materiales y Procesos Catalíticos de Interés Ambiental y Energético

ABSTRACT ▼

In this study, the promoting effect of rhenium addition as a co-dopant on Mo/ZSM-5 catalysts system has been analysed. Hence, bimetallic (Re-Mo/ZSM-5) catalysts have been synthesized using a sequential impregnation methodology. The catalytic performance for direct aromatization of methane reaction has been determined and correlated with their physical and chemical state combining multiple characterization techniques. An important synergy between Mo and Re, affected by the sequential impregnation, has been observed. Thus, Re1-Mo4/ZSM-5 in which Re has been incorporated first shows notably higher aromatic yields and stability against deactivation. Characterization results suggest that catalytic enhancement is due to the important effect of Re presence in close interaction with Mo. Improved evolution of ethane through C-C coupling would be correlated to this catalytic performance. As we discuss, Mo nature and location in the bimetallic systems are strongly conditioned by Re and the impregnation sequence and favours such intermediate step.


Mayo, 2022 | DOI: 10.1016/j.apcatb.2021.120960

Plasma engineering of microstructured piezo-Triboelectric hybrid nanogenerators for wide bandwidth vibration energy harvesting


Garcia-Casas, X; Ghaffarinehad, A; Aparicio, FJ; Castillo-Seoane, J; Lopez-Santos, C; Espinos, JP; Cotrino, J; Sanchez-Valencia, JR; Barranco, A; Borras, A
Nano Energy, 91 (2022) 106673
Nanotecnología en Superficies y Plasma

ABSTRACT ▼

We introduce herein the advanced application of low-pressure plasma procedures for the development of piezo and triboelectric mode I hybrid nanogenerators. Thus, plasma assisted deposition and functionalization methods are presented as key enabling technologies for the nanoscale design of ZnO polycrystalline shells, the formation of conducting metallic cores in core@shell nanowires, and for the solventless surface modification of polymeric coatings and matrixes. We show how the perfluorinated chains grafting of polydimethylsiloxane (PDMS) provides a reliable approach to increase the hydrophobicity and surface charges at the same time that keeping the PDMS mechanical properties. In this way, we produce efficient Ag/ZnO convoluted piezoelectric nanogenerators supported on flexible substrates and embedded in PDMS compatible with a contact-separation triboelectric architecture. Factors like crystalline texture, ZnO thickness, nanowires aspect ratio, and surface chemical modification of the PDMS are explored to optimize the power output of the nanogenerators aimed for harvesting from low-frequency vibrations. Just by manual triggering, the hybrid device can charge a capacitor to switch on an array of color LEDs. Outstandingly, this simple three-layer architecture allows for harvesting vibration energy in a wide bandwidth, thus, we show the performance characteristics for frequencies between 1 Hz and 50 Hz and demonstrate the successful activation of the system up to ca. 800 Hz.


Enero, 2022 | DOI: 10.1016/j.nanoen.2021.106673

Au and Pt Remain Unoxidized on a CeO2-Based Catalyst during the Water-Gas Shift Reaction


Reina, TR; Gonzalez-Castano, M; Lopez-Flores, V; Martinez, LMT; Zitolo, A; Ivanova, S; Xu, WQ; Centeno, MA; Rodriguez, JA; Odriozola, JA
Journal of the American Chemical Society, 144 (2022) 446-453
Química de Superficies y Catálisis

ABSTRACT ▼

The active forms of Au and Pt in CeO2-based catalysts for the water-gas shift (WGS) reaction are an issue that remains unclear, although it has been widely studied. On one hand, ionic species might be responsible for weakening the Ce-O bonds, thus increasing the oxygen mobility and WGS activity. On the other hand, the close contact of Au or Pt atoms with CeO2 oxygen vacancies at the metal-CeO2 interface might provide the active sites for an efficient reaction. In this work, using in situ X-ray absorption spectroscopy, we demonstrate that both Au and Pt remain unoxidized during the reaction. Remarkable differences involving the dynamics established by both species under WGS atmospheres were recognized. For the prereduced Pt catalyst, the increase of the conversion coincided with a restructuration of the Pt atoms into cuboctahedrical metallic particles without significant variations on the overall particle size. Contrary to the relatively static behavior of Pt-0, Au-0 nanoparticles exhibited a sequence of particle splitting and agglomeration while maintaining a zero oxidation state despite not being located in a metallic environment during the process. High WGS activity was obtained when Au atoms were surrounded by oxygen. The fact that Au preserves its unoxidized state indicates that the chemical interaction between Au and oxygen must be necessarily electrostatic and that such an electrostatic interaction is fundamental for a top performance in the WGS process.


Enero, 2022 | DOI: 10.1021/jacs.1c10481

Electrocatalytic CO2 conversion to C-2 products: Catalysts design, market perspectives and techno-economic aspects


Ruiz-López, E; Gandara-Loe, J; Baena-Moreno, F; Reina, TR; Odriozola, JA
Renewable & Sustainable Energy Reviews, 161 (2022) 112329
Química de Superficies y Catálisis

ABSTRACT ▼

The energy crisis caused by the incessant growth in global energy demand joint to its associated greenhouse emissions motivates the urgent need to control and mitigate atmospheric CO2 levels. Leveraging CO2 as carbon pool to produce value-added products represents a cornerstone of the circular economy. Among the CO2 utilization strategies, electrochemical reduction of CO2 conversion to produce fuels and chemicals is booming due to its versatility and end-product flexibility. Herein most of the studies focused on C-1 products although C-2 and C2+ compounds are chemically and economically more appealing targets requiring advanced catalytic materials. Still, despite the complex pathways for C2+ products formation, their multiple and assorted applications have motivated the search of suitable electrocatalysts. In this review, we gather and analyse in a comprehensive manner the progress made regarding C2+ products considering not only the catalyst design and the electrochemistry features but also techno-economic aspects in order to envisage the most profitable scenarios. This state-of-the-art analysis showcases that electrochemical reduction of CO2 to C-2 products will play a key role in the decarbonisation of the chemical industry paving the way towards a low-carbon future.


Junio, 2022 | DOI: 10.1016/j.rser.2022.112329

Plasma assisted CO2 dissociation in pure and gas mixture streams with a ferroelectric packed-bed reactor in ambient conditions


Navascues, P; Cotrino, J; Gonzalez-Elipe, AR; Gomez-Ramirez, A
Chemical Engineering Journal, 430 (2022) 133066
Nanotecnología en Superficies y Plasma

ABSTRACT ▼

Carbon dioxide decomposition is a challenging target to combat climate change. Nonthermal plasmas are advantageous for this purpose because they operate at ambient conditions and can be easily scaled-up. In this study, we attempt the CO2 splitting into CO and O-2 in a parallel plate packed-bed plasma reactor moderated with Lead Zirconate Titanate (PZT) as fermelectric component, achieving conversion rates and energy efficiencies higher than those obtained with BaTiO3 in our experimental device. The analysis of the reaction mechanisms with optical emission spectroscopy under various operating conditions has shown a direct correlation between energy efficiency and intensity of CO* emission bands. These results and those obtained with a LiNbO3 plate placed onto the active electrode suggest that high temperature electrons contribute to the splitting of CO2 through an enhancement in the formation of CO2+ intermediate species. Results obtained for CO2 + O-2 mixtures confirm this view and suggest that back recombination processes involving CO and O-2 may reduce the overall splitting efficiency. The study of mixtures of CO2 and dry air has proved the capacity of fermelectric packed-bed reactors to efficiently decompose CO2 with no formation of harmful NxOy subproducts in conditions close to those in real facilities. The found enhancement in energy efficiency with respect to that found for the pure gas decomposition supports that new reaction pathways involving nitrogen molecules are contributing to the dissociation reaction. We conclude that PZT moderated packed-bed plasma reactors is an optimum alternative for the decompositon of CO2 in real gas flows and ambient conditions.


Febrero, 2022 | DOI: 10.1016/j.cej.2021.133066

Albero: An alternative natural material for solar energy storage by the calcium-looping process


Moreno, V; Arcenegui-Troya, J; Sanchez-Jimenez, P; Perejon, A; Chacartegui, R; Valverde, JM; Perez-Maqueda, LA
Chemical Engineering Journal, 440 (2022) 135707
Reactividad de Sólidos

ABSTRACT ▼

Large-scale thermochemical energy storage (TCES) is gaining relevance as an alternative to current thermal energy storage systems in Concentrated Solar Power plants. Among the different systems, the reversible reaction between CaO and CO2 stands out due to the wide availability and low cost of the raw material: limestone. Direct solar absorption of the storage media would improve the efficiency of solar-to-thermal energy storage due to reduced thermal transfer barriers, but the solar optical absorption of CaCO3 is poor. In this work, we propose the use of a Ca-rich calcarenite sedimentary rock so-called albem as an alternative to limestone. We demonstrate that this reddish material exhibits an average solar absorptance that is approximately ten times larger than limestone. Moreover, the multicycle carbonation/calcination performance under different experimental conditions has been studied by thermogravimetry, and similar values to those exhibited for limestone have been obtained. Besides, the material is cheap (6 Elton), and simulations showed that the use of this material would significantly improve the overall CaL-CSP efficiency at the industrial level.


Julio, 2022 | DOI: 10.1016/j.cej.2022.135707

Ionomer-Free Nickel-Iron bimetallic electrodes for efficient anion exchange membrane water electrolysis


Lopez-Fernandez, E; Gomez-Sacedon, C; Gil-Rostra, J; Espinos, JP; Gonzalez-Elipe, AR; Yubero, F; De Lucas-Consuegra, A
Chemical Engineering Journal, 433 (2022) 133774
Nanotecnología en Superficies y Plasma

ABSTRACT ▼

A bottleneck for the deployment of the Anion Exchange Membrane Water Electrolysis (AEMWE) is the manufacturing of efficient and long lasting anodes and cathodes for the cells. Highly performant bimetallic Ni/Fe catalyst films with various atomic ratios have been prepared by magnetron sputtering in an oblique angle configuration (MS-OAD) and used as anodes for AEMWE. Electrocatalytic experiments in a small three-electrode cell and a thorough analysis of the electrode properties with various physico-chemical characterization tech-niques have been used to select the nanostructured anode catalyst which, depicting an optimized Ni/Fe ratio, presents the maximum activity for the oxygen evolution reaction. These anode layers are then scale-up for their integration in an AEMWE cell where the influence of assembly conditions and the effect of adding an ionomer to the anodes have been studied. The obtained results have demonstrated the outstanding properties of the fabri-cated bimetallic films in terms of activity, stability, and operation under ionomer-free conditions. Current density values around 400 and 600 mA cm(-2) at 40??& nbsp;and 60 C (2.0 V), respectively, much higher than those obtained with pure Ni, were obtained with an optimized membrane electrode assembly. The high yield obtained with these electrodes gains further relevance when considering that the current yield per unit mass of the anodic active phase catalyst (i.e., 1086 mA mg(-1) at 2.0 V and 40??) is the highest among equivalent values reported in literature. The possibilities and prospects of the use of bimetallic catalyst films prepared by MS-OAD for AEMWE are discussed.


Abril, 2022 | DOI: 10.1016/j.cej.2021.133774

Iron-catalyzed graphitization for the synthesis of nanostructured graphitic carbons


Hunter, RD; Ramirez-Rico, J; Schnepp, Z
Journal of Materials Chemistry A, 10 (2022) 4489-4516
Materiales de Diseño para la Energía y Medioambiente

ABSTRACT ▼

Carbons are versatile and diverse materials that have numerous applications across energy and environmental sciences. Carbons with a graphitic structure are particularly appealing due to their high chemical stability, large surface areas and high thermal and electronic conductivity. Numerous methods exist to produce nanostructured graphitic carbons but some of these can be energy-intensive and/or have problems with scalability. One option that is being increasingly explored is the process of iron-catalyzed graphitization. This simply involves the pyrolysis of carbon-rich precursors in the presence of an iron catalyst and has been used to produce carbons with a wide range of structures and properties. This review will examine the current field of iron-catalyzed graphitization, with a focus on molecular organic or biomass precursors. Bio-derived precursors are particularly attractive as a potential option for sustainable production of graphitic carbons. We start with a brief introduction to some key carbon structures, the current applications in which they are employed and some of the key methods that have been developed to produce nanostructured graphitic carbons. We will then review the history of catalytic graphitization before evaluating the wide range of conditions and precursors that have been employed in catalytic graphitization. Finally, this review will investigate the current challenges facing iron-catalyzed graphitization, looking particularly at the limitations of the current understanding of the mechanistic aspects of graphitization, with a view to outlining where research in this field might progress.


Febrero, 2022 | DOI: 10.1039/d1ta09654k

Optoelectronic Devices Based on Scaffold Stabilized Black-Phase CsPbI3 Nanocrystals


Romero-Perez, C; Rubino, A; Calio, L; Calvo, ME; Miguez, H
Advanced Optical Materials (2022) 2102112
Materiales Ópticos Multifuncionales

ABSTRACT ▼

The optoelectronic properties of lead halide perovskites are intimately related to their crystalline phase. For the case of cesium lead iodide (CsPbI3) several polymorphs meet the Goldschmidt tolerance factor, which determines their stability, and form broad band absorber and luminescent phases. However, at room temperature none of them are stable, which prevents their use in optoelectronics. In this work, bare CsPbI3 nanocrystals are synthesized in the sub-10 nm range in the "black", light emitting, crystalline phase, using a pore controlled SiO2 matrix that limits crystal size and confers a certain degree of strain that favors their stability. Quantum confinement effects allow the tuning of the optical properties of the CsPbI3 nanocrystals by means of the crystal size. Their suitability as optoelectronic materials is demonstrated by building scaffold supported CsPbI3 quantum dot based photovoltaic and light emitting devices.


Enero, 2022 | DOI: 10.1002/adom.202102112

Greaseproof, hydrophobic, and biodegradable food packaging bioplastics from C6-fluorinated cellulose esters


Guzman-Puyol, S; Tedeschi, G; Goldoni, L; Benitez, JJ; Ceseracciu, L; Koschella, A; Heinze, T; Athanassiou, A; Heredia-Guerrera, JA
Food Hydrocolloids, 128 (2022) 107562
Materiales de Diseño para la Energía y Medioambiente

ABSTRACT ▼

Tridecafluorononanoic acid (TFNA), a C6-fluorinated carboxylic acid, was esterified with cellulose at different molar ratios (0:1, 1:1, 2:1, and 3:1) in a trifluoroacetic acid (TFA):trifluoroacetic anhydride (TFAA):CHCl3 (2:1:1, v:v:v) solvent mixture. Free-standing films were obtained for all formulations and are presented as alternatives to composites and blends of paper with fluorinated molecules. Mechanical properties were investigated by tensile tests, and a plasticizer effect of fluorinated chains was observed. Interestingly, the wettability of these new cellulose derivatives was similar or even better than other common cellulose derivatives and fluorinated poly-mers employed in food packaging. Hydrodynamic properties were also improved by addition of TFNA, resulting in materials with water vapor permeability values comparable to other cellulose-based food packaging materials. In addition, films with the higher amounts of TFNA showed the required oil resistance for papers used in food packaging applications, as determined by the Kit Test. Finally, the biodegradation of these C6-fluorinated cel-lulose esters, assessed by biological oxygen demand (BOD) in seawater, was higher than typical bio-based polymers used in food packaging. The bioplastic synthesized at a molar ratio 1:1 (TFNA:cellulose) showed excellent performances in terms of greaseproof, hydrophobicity, ductility, and biodegradability, representing a sustainable alternative to typical plastics used in food packaging.


Julio, 2022 | DOI: 10.1016/j.foodhyd.2022.107562

Molecular Interface Engineering via Triazatruxene-Based Moieties/NiOx as Hole-Selective Bilayers in Perovskite Solar Cells for Reliability


Hemasiri, NH; Calio, L; Pegu, M; Kazim, S; Ahmad, S
Solar RRL (2022) 2100793
Materiales Ópticos Multifuncionales

ABSTRACT ▼

Interface engineering is an effective approach to decrease nonradiative recombination and the energy barrier at the perovskite/hole transporting layer (HTL) interfaces. To overcome such limitations, an organic semiconductor (DTT-EHDI2) is proposed, which is, composed of dithienothiophene (DTT) as the core and a planar triazatruxene incorporating an alkyl chain as the side group. This is noted to be an effective interfacial layer for inverted planar perovskite solar cells (PSCs). The altered interface effectively minimizes the detrimental charge recombination and tailors the photoinduced charge transfer dynamics at the interface of the inorganic HTL/perovskite. The pi-conjugation in DTT-EHDI2 induces high hole mobility and electrical conductivity via electron-donating properties and strong pi-pi intermolecular interaction. The synergetic approach leads to a substantial performance enhancement in dopant-free DTT-EHDI2-based inverted planar PSCs, achieving 18.15% power conversion efficiency with negligible hysteresis effect. The present approach provides an effective direction of the cost-effective thiophene derivative as an interfacial agent to escalate the optoelectronic performances in photovoltaics.


Enero, 2022 | DOI: 10.1002/solr.202100793

Effect of Steam Injection during Carbonation on the Multicyclic Performance of Limestone (CaCO3) under Different Calcium Looping Conditions: A Comparative Study


Troya, JJA; Moreno, V; Sanchez-Jimenez, PE; Perejon, A; Valverde, JM; Perez-Maqueda, LA
ACS Sustainable Chemistry & Engineering, 10 (2022) 850-859
Reactividad de Sólidos

ABSTRACT ▼

This study explores the effect of steam addition during carbonation on the multicyclic performance of limestone under calcium looping conditions compatible with (i) CO2 capture from postcombustion gases (CCS) and with (ii) thermochemical energy storage (TCES). Steam injection has been proposed to improve the CO2 uptake capacity of CaO-based sorbents when the calcination and carbonation loops are carried out in CCS conditions: at moderate carbonation temperatures (∼650 °C) under low CO2 concentration (typically ∼15% at atmospheric pressure). However, the recent proposal of calcium-looping as a TCES system for integration into concentrated solar power (CSP) plants has aroused interest in higher carbonation temperatures (∼800–850 °C) in pure CO2. Here, we show that steam benefits the multicyclic behavior in the milder conditions required for CCS. However, at the more aggressive conditions required in TCES, steam essentially has a neutral net effect as the CO2 uptake promoted by the reduced CO2 partial pressure but also is offset by the substantial steam-promoted mineralization in the high temperature range. Finally, we also demonstrate that the carbonation rate depends exclusively on the partial pressure of CO2, regardless of the diluting gas employed.


Enero, 2022 | DOI: 10.1021/acssuschemeng.1c06314

Effect of Steam Injection during Carbonation on the Multicyclic Performance of Limestone (CaCO3) under Different Calcium Looping Conditions: A Comparative Study


Troya, JJA; Moreno, V; Sánchez-Jiménez, PE; Perejon, A; Valverde, JM; Perez-Maqueda, LA
ACS Sustanaible Chemistry & Engineering, 10 (2022) 850-859
Reactividad de Sólidos

ABSTRACT ▼

This study explores the effect of steam addition during carbonation on the multicyclic performance of limestone under calcium looping conditions compatible with (i) CO2 capture from postcombustion gases (CCS) and with (ii) thermochemical energy storage (TCES). Steam injection has been proposed to improve the CO2 uptake capacity of CaO-based sorbents when the calcination and carbonation loops are carried out in CCS conditions: at moderate carbonation temperatures (similar to 650 degrees C) under low CO2 concentration (typically similar to 15% at atmospheric pressure). However, the recent proposal of calcium-looping as a TCES system for integration into concentrated solar power (CSP) plants has aroused interest in higher carbonation temperatures (similar to 800-850 degrees C) in pure CO2. Here, we show that steam benefits the multicyclic behavior in the milder conditions required for CCS. However, at the more aggressive conditions required in TCES, steam essentially has a neutral net effect as the CO2 uptake promoted by the reduced CO2 partial pressure but also is offset by the substantial steam-promoted mineralization in the high temperature range. Finally, we also demonstrate that the carbonation rate depends exclusively on the partial pressure of CO2, regardless of the diluting gas employed.


Enero, 2022 | DOI: 10.1021/acssuschemeng.1c06314

Rhodamine 6G and 800 intermolecular heteroaggregates embedded in PMMA for near-infrared wavelength shifting


Castillo-Seoane, J; Gonzalez-García, L; Obrero-Pérez, JM; Aparicio, FJ; Borras, A; Gonzalez-Elipe, AR; Barranco, A; Sanchez-Valencia, JR
Journal of Materials Chemistry C
Nanotecnología en Superficies y Plasma

ABSTRACT ▼

The opto-electronic properties of small-molecules and functional dyes usually differ when incorporated into solid matrices with respect to their isolated form due to an aggregation phenomenon that alters their optical and fluorescent properties. These spectroscopic modifications are studied in the framework of the exciton theory of aggregates, which has been extensively applied in the literature for the study of molecular aggregates of the same type of molecules (homoaggregation). Despite the demonstrated potential of the control of the heteroaggregation process (aggregation of different types of molecules), most of the reported works are devoted to intramolecular aggregates, complex molecules formed by several chromophores attached by organic linkers. The intramolecular aggregates are specifically designed to hold a certain molecular structure that, on the basis of the exciton theory, modifies their optical and fluorescent properties with respect to the isolated chromophores that form the molecule. The present article describes in detail the incorporation of Rhodamine 6G (Rh6G) and 800 (Rh800) into polymeric matrices of poly-(methyl methacrylate), PMMA. The simultaneous incorporation of both dyes results in an enhanced fluorescent emission in the near-infrared (NIR), originating from the formation of ground-state Rh6G-Rh800 intermolecular heteroaggregates. The systematic control of the concentration of both rhodamines provides a model system for the elucidation of the heteroaggregate formation. The efficient energy transfer between Rh6G and Rh800 molecules can be used as wavelength shifters to convert effectively the light from visible to NIR, a very convenient wavelength range for many practical applications which make use of inexpensive commercial detectors and systems.


Marzo, 2022 | DOI: 10.1039/d1tc06167d

The SrCO3/SrO system for thermochemical energy storage at ultra-high temperature


Amghar, N; Ortiz, C; Perejon, A; Valverde, JM; Maqueda, LP; Jimenez, PES
Solar Energy Materials and Solar Cells, 238 (2022) 111632
Reactividad de Sólidos

ABSTRACT ▼

Thermochemical energy storage (TCES) has attracted interest in the last years due to the possibility of attaining high energy densities, seasonal storage capacity and greater efficiencies than currently commercial thermal energy storage systems using molten salts. This work analyses the potential of an ultra-high temperature TCES system based on the SrCO3/SrO system. The process relies upon the reversible decomposition of SrCO3 into SrO and CO2. As proposed in previous works for the integration of the Ca-Looping process to store energy in CSP plants, both the calcination (endothermic) and carbonation (exothermic) reactions are carried out in a closed CO2 loop. At these conditions, the required temperature to attain full calcination in short residence times is around 1400 degrees C whereas carbonation takes place at about 1200 degrees C. Using this process, the energy density potentially achievable by the storage material is very high (around 2000 MJ/m(3)) while the ultra-high carbonation temperature would improve thermoelectric efficiency. The enhancement of the multicycle performance of the SrCO3/SrO system using refractory additives is also explored. Even though current commercial CSP plants with tower technology cannot yet operate at these ultra-high temperatures, recent advances in the development of high-temperature solar receivers could allow operation at 1400 degrees C in the medium term. Finally, a conceptual model of the integration of the SrCO3/SrO system in a CSP plant supports higher overall efficiency and energy density, but lower solar-to-electric efficiency due to thermal losses.


Mayo, 2022 | DOI: 10.1016/j.solmat.2022.111632

Z-scheme WO3/PANI heterojunctions with enhanced photocatalytic activity under visible light: A depth experimental and DFT studies


Y. Naciri; A.Hsini; A.Bouziani; K.Tanji; B.El Ibrahimi; M.N.Ghazza; B. Bakiz; A.Albourine; A.Benlhachemi; J.A. Navío
Chemosphere, 292 (2022) 133468
Fotocatálisis Heterogénea: Aplicaciones

ABSTRACT ▼

A WO3@PANI heterojunction photocatalyst with a various mass ratio of polyaniline to WO3 was obtained via the in situ oxidative deposition polymerization of aniline monomer in the presence of WO3 powder. The characterization of WO3@PANI composites was carried via X-ray diffraction (XRD), scanning electron microscopy (SEM-EDS), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet–visible diffuse reflection spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) and photoluminescence spectroscopy (PL). The photocatalytic efficiency of WO3@PANI photocatalysts was assessed by following the decomposition of the Rhodamine B (RhB) dye under visible light irradiation (λ >420 nm). The results evidenced the high efficiency of the WO3@PANI (0.5 wt %) nanocomposite in the photocatalytic degradation of RhB (90% within 120 min) under visible light irradiation 3.6 times compared to pure WO3. The synergistic effect between PANI and WO3 is the reason for the increased photogenerated carrier separation. The superior photocatalytic performance of the WO3@PANI catalyst was ascribed to the increased visible light in the visible range and the efficient charge carrier separation. Furthermore, the Density Functional Theory study (DFT) of WO3@PANI was performed at the molecular level, to find its internal nature for the tuning of photocatalytic efficiency. The DFT results indicated that the chemical bonds connected the solid-solid contact interfaces between WO3 and PANI. Finally, a plausible photocatalytic mechanism of WO3@PANI (0.5 wt %) performance under visible light illumination is suggested to guide additional photocatalytic activity development.


Abril, 2022 | DOI: 10.1016/j.chemosphere.2021.133468

Insight into the role of temperature, time and pH in the effective zirconium retention using clay minerals


Pavon, E; Alba, MD
Journal of Environmental Chemical Engineering, 308 (2022) 114635
Química de Superficies y Catálisis

ABSTRACT ▼

The use of zirconium in chemical industries generates a potential risk of Zr contamination in the environment, with particular concern for the decommissioning of uranium-graphite reactors. Among the natural adsorbents employed for the treatment of nuclear waste, clay minerals showed a very high affinity adsorption for radionuclides, but the influence of the chemical composition, pressure, temperature and time reaction have not yet been analysed on deep. Thus, the objective of this research is to explore several experimental conditions for an actual prediction of the behaviour of zirconium immobilization by clay minerals. The results have shown that factors such as zirconium cation nature (Zr4+ or ZrO2+), temperature, time and pH influence the extent of zirconium immobilization by clay minerals and the zirconium phases generated. At moderate conditions, zirconium tectosilicates are formed and evolve to zircon at high temperature and a longer time reaction.


Abril, 2022 | DOI: 10.1016/j.jenvman.2022.114635

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