bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dewetting-Alloying of Nicu Bilayers on TiO2 Surfaces for Noble Metal-Free Photocatalytic H2 Evolution
Authors: Altomare Marco , Spanu Davide , Recchia Sandro , Minguzzi Alessandro , Ghigna Paolo , Schmuki Patrik 
Published: May 2020

We present an approach to fabricate an efficient noble metal-free photocatalytic platform for H2 evolution and provide evidences that the photocatalyst active state forms via a photo-induced redox process in organic-water mixtures.
To fabricate the photocatalytic platform, NiCu bilayers (thickness in the range of a few nm) are deposited by Ar-plasma sputtering on anodic TiO2 nanocavity arrays.[1] A subsequent thermal treatment triggers solid-state dewetting[2,3] of the metal bilayer, i.e. owing to surface diffusion, the Ni and Cu films agglomerate and inter-mix forming NiCu bimetallic nanoparticles at the TiO2 surface.[4] This approach allows for a full control over key features of the NiCu nanoparticles, e.g. size, loading, composition and co-catalytic H2 generation ability. We found that dewetted-alloyed NiCu nanoparticles not only are significantly more reactive than their pure Ni or Cu counterparts, but also lead to H2 generation rates that approach those of noble metal (Pt) modified TiO2 nanocavities.
Characterization results (EDS-TEM, XPS and XRD) of the as-formed photocatalyst suggest the co-catalyst nanoparticles to feature a NiCu bimetallic core and an oxide (or hydroxide) shell – the latter presumably forms by surface oxidation under ambient conditions.
To identify the chemical state of the NiCu nanoparticles during photocatalysis, we carried out XAS operando experiments[5,6] (beam line P65 at DESY – Petra III, Hamburg, Germany) at the Cu K and Ni K edges, in fluorescence mode, under UV light illumination in degassed ethanol-water solutions.
Our results demonstrate that under operando conditions the co-catalyst is subjected to changes of the Ni and Cu chemical state:[7–9] we observe that surface Ni and Cu oxide species are reduced (by TiO2 conduction band electrons) in the early stage of illumination – this converts the co-catalyst nanoparticles into the active metallic NiCu phase.
[1] J. E. Yoo, K. Lee, M. Altomare, E. Selli, P. Schmuki, Angew. Chemie Int. Ed.
2013, 52, 7514–7517.
[2] C. V. Thompson, Annu. Rev. Mater. Res.
2012, 42, 399–434.
[3] M. Altomare, N. T. Nguyen, P. Schmuki, Chem. Sci.
2016, 7, 6865–6886.
[4] D. Spanu, S. Recchia, S. Mohajernia, O. Tomanec, Š. Kment, R. Zboril, P. Schmuki, M. Altomare, ACS Catal.
2018, 8, 5298–5305.
[5] M. Fracchia, P. Ghigna, A. Vertova, S. Rondinini, A. Minguzzi, Surfaces
2018, 1, 138–150.
[6] A. Minguzzi, O. Lugaresi, C. Locatelli, S. Rondinini, F. D’Acapito, E. Achilli, P. Ghigna, Anal. Chem.
2013, 85, 7009–7013.
[7] J. S. Schubert, J. Popovic, G. M. Haselmann, S. P. Nandan, J. Wang, A. Giesriegl, A. S. Cherevan, D. Eder, J. Mater. Chem. A
2019, 7, 18568–18579.
[8] B. Mei, K. Han, G. Mul, ACS Catal.
2018, 8, 9154–9164.
[9] M. J. Muñoz-Batista, D. Motta Meira, G. Colón, A. Kubacka, M. Fernández-García, Angew. Chemie Int. Ed.
2018, 57, 1199–1203.
(Invited) From Chromophores to Photoactive Materials: The SURMOF Approach
Authors: Wöll Christof 
Published: May 2020

Realizing molecular “Designer Solids” by programmed assembly of building units taken from libraries is a very appealing objective. Recently, metal-organic frameworks (MOFs) have attracted a huge interest in this context. Here, we will focus on the integration of chromophores into MOFs, as well as on several applications based on these highly versatile crystalline materials. For numerous MOF-based applications, in particular in the area of optics and photonics, the conventional solvothermal synthesis yielding MOF powders is not well suited. In the context of optical applications, a severe drawback is that the powder particles cause strong scattering, which makes a reliable determination of photophysical parameters difficult. To overcome these problems, we have developed a layer-by-layer (lbl) deposition method to produce well-defined, highly oriented and monolithic MOF thin films on a number of different substrates. The resulting films are referred to as SURMOFs [1,2]. The fabrication of hetero-multilayers (see Fig. 1) is rather straightforward with this lbl method. In this talk, we will describe the principles of SURMOF fabrication as well as the results of systematic investigations of electrical and photophysical properties exhibited by empty MOFs/SURMOFs [3] and after loading their pores with functional guests. Subsequently we will focus on employing SURMOFs for anisotropic exciton transport. Finally, we will point out that MOFs and SURMOFs are expected to play an important role in the digitalization of materials research.

References:

[1] J. Liu, Ch. Wöll, Chem. Soc. Rev. 46, 5730-5770 (2017)
[2] L. Heinke, Ch. Wöll, Advanced Materials 31 (26), 1970184 (2019)
[3] R. Haldar, L. Heinke, Ch. Wöll, Advanced Materials (2020), DOI: 10.1002/adma.201905227

Figure 1
(Invited) Exotic Electronic Excitation to Manipulate Electrochemical Potential of Electrons and Holes at Liquid/Solid Interfaces
Authors: Zhang Jinjiang , Zhou Ruifeng , Minamimoto Hiro , Murakoshi Kei 
Published: May 2020

Spectroelectrochemistry is powerful tool to investigate electronic sates and geometrical structures of electrified interfaces in-situ under the conditions where photonic and electronic energy conversion functionalities emerge. One can use plasmon-powered processes to expand the ability of the spectroscopy regarding sensitivities in space, time, and energy resolutions. As their characteristics on localization of surface plasmons into molecule scale, huge intensity gradient of electromagnetic field would break the limit of light-matter interactions via the modification of the selection rule of the electronic excitation process. I have discussed about the possibility for the surface-enhanced-Raman scattering (SERS) as the probe to monitor the exotic electronic excitation processes[1-7]. Based on the observation of a small number of molecules at the plasmonic metal nanostructures by SERS, possibilities leading to the future innovative photo-functionalities were demonstrated by showing improved properties at optical manipulation of electrons and molecules, and ions. In this presentation, we will show that the localized surface plasmons of the Au nanodimer structures prepared on defect-free graphene provide highly-confined electromagnetic field to generate holes and electrons of the electrochemical potentials beyond the limit of far field light illumination [8]. Novel non-zero wavevector excitation results in the generation of highly reductive and oxidative powers for electrochemical reactions. The present findings point to a novel approach to breaking the limit of opto-electronic interactions and photochemical reactions using various materials.

References

[1] K. Murakoshi and L. M. Liz-Marzán et al., ACS nano, DOI:10.1021/acsnano.9b04224 (2019)
[2] T. Konishi et al., J. Am. Chem. Soc., 135, 1009-1014 (2013)
[3] M. Takase et al., Nature Photonics, 7, 550-554 (2013)
[4] F. Nagasawa et al., J. Phys. Chem. Lett. 5, 14-19 (2014)
[5] H. Minamimoto et al., Faraday Discuss. 205, 261-269 (2017)
[6] F. Kato et al., ACS Photonics, 5, 788-796 (2018)
[7] X. Li et al., PhyChemChemPhys, 20, 14818-14827 (2018)
[8] J. Zhang et al., Nano Lett., 19, 7887-7894 (2019)
Record Capacitance Density from Three-Dimensional Silicon-Based Capacitor: Toward Effective on-Chip Energy Storage
Authors: Strambini Lucanos , Paghi Alessandro , Mariani Stefano , Sood Anjali , Kalliomaki Jess , Jarvinen Paivi , Toia Fabrizio Fausto Renzo , Scurati Mario , Morelli Marco , Lamperti Alessio , Barillaro Giuseppe 
Published: May 2020

The currently growing request for a continuous connectivity between people and things has increased exponentially the demand for portable and/or wearable electronics. Thus, high performance components with more compact size, lower power consumption, and increased energy storage capability are needed. Although electronic active components have downscaled and and their performance optimized over the years, passive elements (e.g., resistors, capacitors, and inductors) have made only little progress.
Supercapacitors (SCs) are electrochemical capacitors that can achieve very high capacitance density, in the order of 0.1–1 mF/mm2. Nonetheless, SC intrinsic low operation voltage (a few Volts) and reduced frequency range (up to a few hundreds of Hertz), together with their poor compatibility with integrated circuit (IC) processes have inhibited their electronic applications to date1. Dielectric capacitors (DCs) make use of solid-state dielectrics sandwiched between conductive electrodes. DCs can achieve high working frequencies, up to a several MHz, and large operating voltages, easily exceeding 5V 2. However, DC capacitance density is orders of magnitude smaller than that of SCs. Nowadays, it is still challenging to simultaneously achieve capacitors with high capacitance density, wide working frequency range, and small footprint for future electronic applications, with a fabrication process that is compatible with ICs technology.
Here, we demonstrate the possibility to integrate, on a silicon chip, 3D microcapacitors with capacitance density up to 1 μF/mm2 by leveraging the atomic layer deposition of conductive (TiN) and dielectric (Al2O3and HfAlOX) nanocoatings (20 and 40 nm) into trenches electrochemically etched in silicon with high aspect-ratio (up to 100). Power and energy densities of the 3D microcapacitors, namely, 566 W/cm2and 1.7 μWh/cm2, respectively, overcome those of most state-of-the-art dielectric capacitors and supercapacitors. Further, the 3D microcapacitors feature operating frequency up to 70kHz and show excellent stability with voltage (up to 16V) and temperature (up to 100°C), over 100 h of continuous operation (>108charge/discharge cycles) . These results pave a road for effective on-chip energy storage for consumer and wearable electronic applications.
(Invited) High Performance Carbon Composite Anodes for Sodium-Ion Batteries
Authors: Paranthaman Mariappan Parans 
Published: May 2020

Conductive networks of waste tire derived carbons were used to produce homogeneous composites via ball milling as a promising anode material for sodium-ion batteries. Sodium half-cells delivered reversible discharge capacities of 207 mAh g–1 at a current density of 37 mA g–1. Carbon composite materials showed impressive capacity retention with 88% after 100 cycles. Rate capability studies at 60 °C yielded enhanced capacity of 300 mAh g–1. From these remarkable results, the waste-tire derived carbon composites enabled stable alloying and dealloying processes as promising anodes for SIBs. We will also report our recent results on reducing the first cycle loss with carbon electrodes.
The research was sponsored by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division.
Porphyrins-based Materials as Efficient Donor in Organic Solar Cells
Authors: Harvey Pierre D. , Tanguy Loïc 
Published: May 2020

Twenty years after the discovery of bulk heterojunction solar cells (BHJSCs), porphyrins were underrepresented in the field of organic solar cells (OCSs)1 despite their high epsilon of 300 000 M-1cm-1 and their electron rich aromatic core, which make them a good electron donors. In 2012, a power conversion efficiency (PCE) of 8.08% for a BHJSC built with a small molecule containing a porphyrin core was reported.2 Then in 2017, a PCE of 6.44 % was reported for BHJSC constructed with a polymer containing a porphyrin inside the conjugated chain.3 These advances brought porphyrins at the center of attention in the field of OSCs. In 2019, using a planar non-fullerene acceptor and a porphyrin based-polymer, a 9.16% PCE was reported; a record for this type of dye.4 Both a high Voc of 1.01 V and a low Eloss of 0.45 eV, two BHJSC’s characteristics, make the porphyrin dyes competing with the most efficient donors of the field. Mechanistically speaking, like all donors porphyrin-based donors form interfacial charge transfer (CT) species with the acceptors where upon excitation, a charge separated (CS) state is produced efficiently. However, detailed investigations of the CT signature and photophysical traits of these species simply do exit due to the bulk nature of the materials. We designed a supramolecular porphyrin-graphene nanoribbon (GNR) model taking advantage of π-stacking effects between GNRs and anchoring pyrene groups. Upon selective excitation of the GNRs, the GNRs form excitons for which 95% are involved in an energy transfer with the π-stacked porphyrin-GNR CT species very efficiently (35%in 759 fs; 65% < 135 fs), then an electron transfer (charge separation) occurs from these excited CT species to the GNRs in the ps time scale.
1. Bucher, L.; Desbois, N.; Harvey, P.; Sharma, G.; Gros. C.; Porphyrins and BODIPY as Building Blocks for Efficient Donor Materials in Bulk Heterojunction Solar Cells. Solar RRL
2017, 1, 1700127.
2. Huang, Y.; Li, L.; Peng, X.; Peng, J.; Cao, Y.; Solution processed small molecule bulk heterojunction organic photovoltaics based on a conjugated donor–acceptor porphyrin. J. Mater. Chem.
2012, 22, 21841-21844.
3. Bucher, L.; Tanguy, L.; Fortin, D.; Desbois, N.; Harvey, P.; Sharma, G.; Gros, C.; A Very Low Band Gap Diketopyrrolopyrrole–Porphyrin Conjugated Polymer. Chempluschem
2017, 82, 625-630.
4. Tanguy, L.; Malhotra, P.; Singh, S.; Brisard, G.; Sharma, G.; Harvey, P.; A 9.16% Power Conversion Efficiency Organic Solar Cell with a Porphyrin Conjugated Polymer Using a Nonfullerene Acceptor. ACS Appl. Mater. Interfaces
2019, 11, 31, 28078-28087.

Figure 1
Porphyrin-Hexabenzocoronene-Conjugates and Fullerenes
Authors: Jux Norbert , Lungerich Dominik , Hölzel Helen , Ruppel Michael , Martin Max 
Published: May 2020

We will present architectures based on porphyrins and hexaarylbenzenes/ hexabenzocoronenes and fullerene C60. Special emphasis lies on crystal packing phenomena.
We report on the synthesis, characterization, and properties of some of these novel systems.[1-4]

References

[1] D. Lungerich, J. F. Hitzenberger, M. Marcia, F. Hampel, T. Drewello, N. Jux, Angew. Chem. Int. Ed..
2014,
53, 12231-12235.
[2] D. Lungerich, J. F. Hitzenberger, W. Donaubauer, T. Drewello, N. Jux, Chem. Eur. J.
2016, 22, 16755-16759.
[3] M. M. Martin, D. Lungerich, P. Haines, F. Hampel, N. Jux, Angew. Chem. Int. Ed.
2019, 59; 8932-8937.
[4] M. M. Martin, D. Lungerich, F. Hampel, J. Langer, T. K. Ronson, N. Jux, Chem. Eur. J.
2019; doi.org/10.1002/chem.201904005

Figure 1
Oxidative C-N Fusion of Pyridinyl-Based Porphyrins
Authors: Berthelot Mathieu , Hoffmann Guillaume , Bousfiha Asmae , Mankou Makaya Amelle , Echaubard Julie , Roger Julien , Cattey Hélène , Romieu Anthony , Lucas Dominique , Fleurat-Lessard Paul , Devillers Charles H. 
Published: May 2020

Porphyrins provide an extremely flexible synthetic scaffold for numerous applications such as artificial photosynthesis, photodynamic therapy, molecular recognition, oxidation/reduction catalysts and molecular materials.[1] The fusion of one or several hydrocarbon(s) or aromatic heterocycle(s) onto the porphyrin periphery forces the porphyrin core and the substituent to be coplanar, that enhances the electronic communication between both fragments. This implies important changes in the optical and electrochemical properties of the fused porphyrin compared to the parent porphyrin core such as decrease of the HOMO/LUMO gap, bathochromic shift in it absorption/emission spectra and large absorption and fluorescence in the NIR range. [[2],[3]] For this reason, π-extension of porphyrins has attracted much attention over the last two decades owing to their potential applications in near infrared electroluminescence displays, non-linear optical materials, photodynamic therapy, photovoltaic solar cells and molecular materials. [2,[4]] Nowadays, π-extended C-C linked porphyrins are commonly obtained using toxic and/or expensive chemicals, often under harsh conditions. [3,[5]] Due to the extension of the conjugation path, the oxidation potential decreases which may lead to over-oxidation during the fusion process.
In this work, we present the mild and selective chemical and electrochemical synthesis of new π-extended porphyrins generated via intramolecular oxidative C-N coupling of peripheral pyridinyl fragment(s) with the porphyrin core. [[6]] As compared to their precursors, these fused pyridinium-porphyrins exhibit higher oxidation potential that prevents their over-oxidation.

[1]. Kadish, K. M.; Smith, K. M.; Guillard, R. In The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: 2000; Vol. 1-20.

[2]. Zimmerman, J.D.; Diev, V.V.; Hanson, K.; Lunt, R.R.; Yu, E.K.; Thompson, M.E.; Forrest, S.R. Adv. Mater. 2010, 22, 2780-2783.

[3]. Davis, N.K.S.; Thompson, A.L.; Anderson, H.L. J. Am. Chem. Soc.
2011, 133, 30-31.

[4]. Matsuo, Y.; Stao, Y.; Niinomi, T.. Soga, I.; Nakamura, E. J. Am. Chem. Soc.
2009, 131, 16048-16050.

[5]. (a) Brennan, B. J.; Kenney, M. J.; Liddell, P. A.; Cherry, B. R.; Li, J.; Moore, A. L.; Moore, T. A.; Gust, D. Chem. Commun.
2011, 47, 10034-10036. (b) Scigaj, M.; Gryko, D. T. Org. Biomol. Chem.
2011, 9, 8178-8181. (c) Davis, N. K. S.; Thompson, A. L.; Anderson, H. L. J. Am. Chem. Soc.
2011, 133, 30-31. (d) Lewtak, J. P.; Gryko, D. T. Chem.
Commun.
2012, 48, 10069-10086. (e) Mori, H.; Tanaka, T.; Osuka, A. J. Mater.
Chem. C
2013, 1, 2500-2519.

[6]. Berthelot, M.; Hoffmann, G.; Bousfiha, A.; Echaubard, J.; Roger, J.; Cattey, H.; Romieu, A.; Lucas, D.; Fleurat-Lessard, P.; Devillers, C. H. Chem. Commun.
2018, 54, 5414

Figure 1
Cobalt Corroles: From Monomolecular Binding to Porous Organic Polymers (POPs) for the Selective Detection of Carbon Monoxide (CO)
Authors: Gros Claude P. , Brandes Stéphane , Quesneau Valentin , Yang Jian , Desbois Nicolas , Vanotti Meddy , Blondeau-Patissier Virginie , Kadish Karl M. 
Published: May 2020

Detection of carbon monoxide (CO) at few ppm levels is a critical point for quality control of domestic and industrial environment. CO is responsible for thousands of intoxications and hundreds of deaths per year in the world. Moreover, CO is a residual gas found in the industrial dihydrogen used for Proton Exchange Membrane fuel cell, and deactivates the fuel cell prematurely. Corroles have beenlargely used in sensing applications.[1] Cobalt corroles display high binding affinity for carbon monoxide even in the presence of nitrogen and dioxygen.[2] The affinity of the Co(III) metallocorroles for CO is directly correlated with the Lewis acid character of the metal center. Therefore, structural modifications on the aromatic ring have a direct influence on the reactivity of the metal complex. We have recently obtained very low CO detection level (ppm) using SAW devices functionalized by cobalt corrole deposited as a film on a guiding layer of silica or a gold surface.[3] Tetra-coordinated cobalt corroles were found to be not so stable over time. A new approach was developed, using labile axial ligands as a protective group of the tetra-coordinated metal complexes. We will present the e-chem and spectro e-chem properties of the cobalt complexes with different axial ligands. As our previous work on the synthesis of porous sol-gel materials functionalized by cobalt corroles gave us also encouraging results for CO sorption and detection[4], we have prepared new porous structured materials functionalized by corrole complexes for gas detection applications. Among all the methods of synthesis of porous architectures, organic materials belonging to the POP (Porous Organic Polymer) family are an appealing and original approach in this research field.[5] We will thus describe the synthesis of new POPs functionalized by cobalt corroles (Fig. 1). Their selective sorption properties for CO over N2, O2and CO2will be also presented.
Authors would like to acknowledge the ANR program (CO3SENS project), the FEDER and the “Région Bourgogne” for financial support, and for the allocation of a PhD grant (JCE Program).

REFERENCES:[1] Paolesse, R.; Nardis,S.; Monti, D.; Stefanelli, M.; Di Natale, C., Chem. Rev.
2017, 117, 2517–2583;[2] J.-M. Barbe, G. Canard, S. Brandès, F. Jerôme, G. Dubois, R. Guilard, Dalton Trans.
2004, 1208-1214; [3] M. Vanotti, C. Theron, S. Poisson, V. Quesneau, M. Naitana, V. Soumann, S. Brandès, N. Desbois, C. Gros, T.-H. Tran-Thi, V. Blondeau-Patissier, Proceedings
2017, 1, 444-447; [4] J. M. Barbe, G. Canard, S. Brandès, R. Guilard, Chem. Eur. J.
2007, 13, 2118-2129; [5] S. Brandès, V. Quesneau, O. Fonquernie, N. Desbois, V. Blondeau-Patissier, C. P. Gros, Dalton Trans.
2019, 48, 11651-11662 (Cover).

Figure 1
Multicomponent Layer-By-Layer Films of Chitosan/Phthalocyanine/AuNPs As Biosensing Platforms
Authors: Rodriguez-Mendez Maria Luz , Salvo-Comino Coral , Garcia-Hernandez Celia , Rodriguez-Valentin Javier , Garcia-Cabezon Cristina , Martin-Pedrosa Fernando 
Published: May 2020

The search of new biosensing platforms is crucial to improve the performance of electrochemical biosensors. In this work, Layer by Layer films containing combinations of materials with different functionalities were used to design electrochemical biosensor platforms for phenols detection [1-3]. Catechol and hydroquinone biosensors were obtained by depositing tyrosinase (Tyr) or laccase (Lac) on the surface of LbL films formed by alternating layers of chitosan (CHI), a cationic species which acted as enzyme linker, and layers of two anionic electrocatalytic materials (sulfonated copper phthalocyanine, CuPcS and citrate capped gold nanoparticles, AuNPs). Films with different sequences [(CHI)-(AuNPs)]2, [(CHI)-(CuPc)]2, [(CHI)-(CuPc)-(CHI)-(AuNPs)]2 [(CHI)-(AuNPs)-(CHI)-(CuPc)]2, and [(CHI)-(AuNPs/CuPc)]2 (with CuPcS and AuNP mixed in the same layer) were characterized by UV–visible, FTIR spectroscopy and AFM.
It was demonstrated that the resulting films provided an efficient immobilization surface for phenol oxidases. At the same time, the LbL platform improved the electron transfer between the enzymes and the electrode surface. Although all the biosensors obtained exhibited excellent performances, the sequence of the anionic and cationic layers strongly influenced the electron transfer process. The best results were obtained when CuPcS was present in the last layer which caused a 2-fold increase in the intensity over the response of the biosensor without the LbL platform. The [CHI-AuNP-CHI-CuPcS]2-Tyr bioelectrode showed an LOD of 8.7∙10-4 mM (S/N=3) for catechol and of 7.77∙10-4 mM (S/N=3) for hydroquinone. The LbL platform was not so efficient for laccase and the [CHI-AuNP-CHI-CuPcS]-Lac biosensor showed a LOD of 1.84∙10-2 mM (S/N=3) for catechol and of 1.27∙10-3 mM (S/N=3) for hydroquinone.

References

[1] C. Medina-Plaza, L.N. Furini, C.J.L. Constantino, J.A. De Saja, M.L. Rodriguez-Mendez, Synergistic electrocatalytic effect of nanostructured mixed films formed by functionalised gold nanoparticles and bisphthalocyanines, Anal. Chim. Acta. 851 (2014) 95–102. doi:10.1016/j.aca.2014.08.049.
[2] C. García-Hernández, C. García-Cabezón, F. Martín-Pedrosa, J. A. De Saja, and M. L. Rodríguez-Méndez, Layered composites of PEDOT:PSS/nanoparticles and PEDOT:PSS/phthalocyanines as electron mediators in sensors and biosensors, Belstein J. Nanotech. 7 (2016) 1948-1959
[3] E. G. R. Fernandes, L.C. Brazaca, M.L Rodríguez-Méndez, J.A. de Saja and V. Zucolotto, Immobilization of Lutetium Bisphthalocyanine in Nanostructured Biomimetic Sensors Using the LbL Technique for Phenol Detection, Biosens. Bioelectr. 26 (2011) 4715- 4719.

Acknowledgements

Financial support by MINECO-FEDER (RTI2018-097990-B-I00) and the Junta de Castilla y Leon FEDER (VA275P18) and AFM UVA01is gratefully acknowledged.