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CESEP’19 is the eighth international conference on Carbon for Energy Storage and Environment Protection. The conference is organized by the Spanish Group of Carbon (GEC) and will be held in Alicante, Spain. Carbon materials play a major role in a large number of highly specialized applications -as structural and functional materials- related with current industrial challenges. The underlying reasons for this are their flexible coordination chemistry that allows almost infinite possibilities of structures, and their ability to react with other heteroatoms to incorporate functional groups that determine the self-organization, chemical stability and reactivity. Topical areas include structural and nanotextural characterization, gas separation and gas storage, solar energy conversion, carbon as catalyst and catalyst support, adsorption of gas-phase pollutants, carbon in green chemistry and recycling processes, carbon for water production and remediation, supercapacitors, lithium batteries and other advanced batteries, fuel cells, biological and health applications of carbons, carbon materials in sensor and biosensor, in-situ and operando studies, simulation and computational methods, demonstration systems.

5 figures.-- Supporting information available., The sluggish kinetics of the oxygen evolution reaction (OER) is one of the most limiting factors for the development of many “green” electrochemical devices. Expensive ruthenium and iridium oxide electrodes are often used as advanced electrocatalysts to overcome this limitation. However, these materials are rare in nature, which further limit the implementation of this kind of electrochemical device on a global scale. Compounds based on transition metals and boron have proven to be promising alternatives to commercial electrocatalysts due to their high catalytic properties and robust stability under working conditions. However, such compounds are often obtained through expensive synthetic routes that often involve the use of supports, which increases the cost of electrocatalysts. Here, we present an easy and support-free synthesis of bimetallic borates based on the introduction of transition metals into cobalt borates. Depending on the metal, different morphologies, structural order, surface chemistry, and, most importantly, electrocatalytic properties toward the OER have been obtained. Among all the transition metals, nickel is the one that most improves the catalytic activity of cobalt borate for the OER in an alkaline electrolyte. An overpotential of 230 mV, similar to that of commercial and state-of-the-art electrocatalysts, was obtained by using a support-free synthesis route for the preparation of this catalyst., This study was partly supported by the French PIA project “Lorraine Université d’Excellence”, reference ANR-15-IDEX-04-LUE, and the TALiSMAN project funded by ERDF (2019-000214). SGD thanks the Ministerio de Universidades, the European Union, and the University of Oviedo for the financial support (MU-21-UP2021-030 30267158). JQB thanks the Ministerio de Universidades, the European Union, and the University of Alicante for the financial support (MARSALAS21-21).

To date, thermal nanoimprint lithography (NIL) for patterning hybrid perovskites has always involved an intricate etching step of a hard stamp material or its master. Here, we demonstrate for the first time the successful nanopatterning of a perovskite film by NIL with a low-cost polymeric stamp. The stamp consists of a dichromated gelatin grating structured by holographic lithography. The one-dimensional grating is imprinted into a perovskite film at 95 °C and 90 MPa for 10 min, resulting in a high quality second-order distributed feedback (DFB) laser. The laser exhibits an excellent performance with a threshold of 81 μJ/cm2, a line width of 0.32 nm, and a pronounced linear polarization. This novel approach enables cost-effective fabrication of high-quality DFB lasers compatible with different perovskite compositions and photonic nanostructures for a wide range of applications. We acknowledge the support of the Karlsruhe School of Optics & Photonics (KSOP) financed by the Ministry of Science, Research and the Arts of Baden-Wrttemberg as part of the sustainability financing of the projects of the Excellence Initiative II. We also acknowledge financial support through Germany’s Excellence Strategy via the Excellence Cluster 3D Matter Made to Order (3DMM2O, EXC-2082/1-390761711) and the Karlsruhe Nano Micro Facility (KNMFi). The group at the University of Alicante acknowledges financial support from the “Ministerio de Ciencia e Innovación/Agencia Estatal de Investigación” (MCIN/AEI) of Spain, the European Regional Development Fund, European Social Funds (project PID2020-106114GBI00), and the Conselleria de Innovación, Universidades y Sociedad Digital de la Comunidad Valenciana (Grant No. AICO/2021/093). V.B. acknowledges financial support from the University of Alicante to perform a research stay at KIT in the frame of his PhD.

Engineering the surface chemistry of carbon-based materials is of crucial importance in tuning their intrinsic properties, including electrical conductivity, wettability, electroactivity, adsorption potential, reactivity, physical and chemical stability. Intense research has recently focused on understanding the role of surface oxygen functional groups when carbon materials are in contact with an electrolyte or solvent in order to tailor and improve them for technological applications. For this purpose, their synthesis method and/or further oxidation treatments should be carefully selected, since they can substantially influence not only the oxygen content, but also the nature of the oxygen moieties, which could be decisive in determining the surface properties of the resulting material. The combined use of different chemical, spectroscopic and electrochemical techniques, provides unique and reliable information about the contribution of a specific oxygen-containing group in the surface (electro)chemistry of carbon-based materials. This paper provides a discussion of the role of oxygen heteroatoms in the surface electrochemistry of a carbon material as they relate to their influence on both its electroactivity and reactivity. G.A.M. and B.M.S thanks Ministerio de Universidades (grant number: FPU18/05127 and FPU20/03969). The authors would like to thank PID2019-105923RB-I00 and PID2021-123079OB-I00 projects funded by MCIN/AEI/10.13039/501100011033 and “ERDF A way of making Europe”.

Covalent functionalization of multi-walled carbon nanotubes (MWCNTs) and oxidized MWCNTs (o-MWCNTs) with chlorodiphenylphosphine (Ph2PCl) has been studied by cyclic voltammetry in organic medium. Depending the upper potential limit used in the electrochemical functionalization, different amount of phosphorus incorporation n is obtained, as result of the formation of radical species during the electrochemical oxidation of the Ph2PCl. The electrochemical oxidation of Ph2PCl promotes the covalent attachment of diphenylphosphine-like structure on the carbon nanotube surface. At the same time, the incorporation of Cl on the carbon nanotubes is observed during the functionalization. Furthermore, the presence of oxygen surface groups on the MWCNTs provides a favorable attachment of the Ph2P ∙ + species, which has promoted preferentially the formation of C-P bonds, whereas the amount of Cl is reduced. The authors would like to thank MINCIN (PID2019-105923RB-I00) for the financial support.

Pt nanoparticles were incorporated on carbon black (Vulcan XC-72R) and an activated carbon (F400) using a fast and efficient microwave method. For the preparation, a Pt solution was contacted with the corresponding carbon sample and heated up to 110°C in a microwave oven using an optimised heating rate. TEM images revealed that the carbon-supported Pt nanoparticles had a small average particle size and high dispersion. These Pt-based electrocatalysts showed both high electrocatalytic activity and selectivity towards the 4-electron pathway for the oxygen reduction reaction (ORR) in acid and alkaline media. In addition, they presented excellent stability and resistance to CO poisoning. Moreover, the as-prepared electrocatalysts exhibited outstanding electrocatalytic behaviour for the hydrogen evolution reaction (HER). It should be highlighted that, even though our Pt-based electrocatalysts have much lower loadings than that of the commercial Pt/C sample (used as reference), the electroactive surface areas of as-prepared electrocatalysts were higher compared to the reference electrocatalyst. Such small and well-dispersed Pt NPs with an enhanced electroactive surface area and strong interaction with the carbon support, led to an improvement of the current density normalised by Pt loading (A gPt−1). The authors would like to thank PID2019-105923RB-I00 and PID2021-123079OB-I00 projects project funded by MCIN/AEI/10.13039/501100011033 and “ERDF A way of making Europe”, the Generalitat Valenciana (GRISOLIA/2020/114) and CONACYT project SEP-CB-2014-01-237118 and FORDECYT-2018-8-297525 for their financial support.

HKUST-1-based composites have been synthesized through the incorporation of synthetic graphite flakes in the MOF synthesis media. The presence of flakes gives rise to high quality HKUST-1 crystals, combining different morphologies (octahedral-shape crystals, cauliflower-shape crystals and truncated pyramids). The incorporation of graphite in the composites improves the structural stability of the embedded nanocrystals upon a conforming step at 377 kg/cm2 (0.5 tons), with limited structural damage (below 10% BET surface area reduction as compared to the 40% observed for pure HKUST-1). Furthermore, composites exhibit a significant improvement in thermal management, associated with the excellent thermal and electrical properties of the graphite microdomains incorporated. The improved stability of the composites is also reflected in the adsorption performance for hydrogen at atmospheric pressure and cryogenic temperatures, with a significant preservation of the adsorption properties (gravimetric capacity

This work evaluates the effect on the adsorption and desorption kinetics of propene and toluene (used as probe molecules for vehicle cold-start emissions) of the isomorph framework substitution of Zr, W, and V on commercial ZSM-5 and beta zeolites. TG-DTA and XRD characterization data indicated that: (i) Zr does not modify the crystalline structure of the parent zeolites, (ii) W develops a new crystalline phase, and (iii) V causes the breakdown of the zeolite structure during the aging step. The CO2 and N2 adsorption data revealed that the substituted zeolites present a narrower microporosity than pristine zeolites. As a consequence of all these modifications, the modified zeolites feature different adsorption capacity and kinetics of HCs, so, different hydrocarbon trapping ability than pristine zeolites. However, a clear correlation is not observed between the changes in the porosity/acidity of zeolites and the adsorption capacity and kinetics, which depends on: (i) the zeolite (ZSM-5 or BEA), (ii) the hydrocarbon (toluene or propene), and (iii) the cation to be inserted (Zr, W, or V). This research was funded by Ministerio de Ciencia e Innovacion (MINCINN: PID2019-105542RB-I00/AEI/10.13039/501100011033 project), the European Union (FEDER Funds), and the Generalitat Valenciana (CIPROM/2021-070).

This study presents an integrated approach combining aqueous phase reforming (APR) and hydrodeoxygenation (HDO) for the hydrotreatment of guaiacol, a model compound representing lignin-derived phenols in pyrolysis bio-oils. The APR process enables in-situ H2 generation, eliminating the need for an external hydrogen source. We examine the interplay between metal species, the Pt-promoting effect on Ni–Pt catalyst supported on activated carbon (AC), and the choice of hydrogen source (methanol or glycerol). Amongst the monometallic catalysts, a 1% Pt/AC catalyst notably achieved over 96% guaiacol conversion at 300 °C with either hydrogen source. Interestingly, when 0.5–1% of the Ni loading is replaced with Pt, the resulting bimetallic Ni–Pt/AC catalysts demonstrate a significant improvement in guaiacol conversion, reaching 70% when methanol is employed as the hydrogen source. Surprisingly, no comparable enhancement in guaiacol conversion is observed when employing glycerol as the hydrogen source. This observation underlines one of the pivotal effects of the hydrogen source on catalyst performance. X-ray photoemission spectroscopy (XPS) pinpointed strong Ni–Pt interactions in the catalyst. It also revealed distinctive electronic features of Ni–Pt/AC, which are favourable for steering selectivity towards cyclohexanol rather than phenol when Pt loading is increased from 0.5 to 1%. Moreover, Pt enhanced catalyst stability by inhibiting the oxidation of Ni sites and mitigating Ni–Pt phase sintering. Overall, our findings offer important insights into integrating APR and HDO processes, the promotion effect of Pt, and the importance of hydrogen source selection in terms of guaiacol conversion and catalyst stability. Financial support for this work was provided by the Department of Chemical and Process Engineering at the University of Surrey and the EPSRC grant EP/R512904/1 as well as the Royal Society Research Grant RSGR1180353. Authors would also like to acknowledge Spanish Ministry of Science and Innovation through the projects MAT2016-80285-P, RYC2018-024387-I, JC2019-040560-I. RR acknowledges the financial support provided by the ERC Consolidator Grant (LIGNINFIRST, project number 725762). This work was also partially funded by the University of Seville via the VI PPIT grant scheme for talented researchers and the Junta de Andalucia PAIDI2020 programme through the CLEVER-BIO project P20_00667.

Guefoams (guest-containing foams) are a new-class of open-cell cellular materials that extend the properties of conventional foams by incorporating guest phases that convert them into multifunctional materials. This manuscript describes the development of pitch-derived composite guefoams that contain two types of inclusions: iron nanoparticles embedded in the cellular skeleton and activated carbon particles as guest phases. The activated carbon particles significantly increase the specific surface area and gas adsorption capacity. When these materials are exposed to low-intensity magnetic fields, the iron nanoparticles confer a high magneto-inductive capacity that enables ultrafast heating and rapid desorption of adsorbed species. The ability of these materials to act as preconcentrators for volatile organic compounds (VOCs) is demonstrated in this work using toluene as a proof of concept. The Guefoams developed here have greater preconcentration capabilities than current state-of-the-art systems while also being significantly more energy efficient due to the magnetic induction controlled desorption process. This unparalleled blend of properties makes these guefoams a valuable tool for energy-efficient VOCs management. This work was supported by the Spanish Agencia Estatal de Investigación (AEI), the Spanish Ministry of Science and Innovation, and the European Union (FEDER and NextGenerationEU funds) [grants MAT2016-77742-C2-2-P and PDC2021-121617-C21]. The author would also like to acknowledge the financial support received from the Conselleria d'Innovació, Universitats, Ciència, i Societat Digital of the Generalitat Valenciana through grant GVA-COVID19/2021/097.

Phenylboronic acids (BAs) are important synthetic receptors that bind reversibly to cis-diols enabling their use in molecular sensing. When conjugated to magnetic iron oxide nanoparticles, BAs have potential for application in separations and enrichment. Realizing this will require a new understanding of their inherent binding modes and measurement of their binding capacity and their stability in/extractability from complex environments. In this work, 3-aminophenylboronic acid was functionalized to superparamagnetic iron oxide nanoparticles (MNPs, core diameter 8.9 nm) to provide stable aqueous suspensions of functionalized particles (BA-MNPs). The progress of sugar binding and its impact on BA-MNP colloidal stability were monitored through the pH-dependence of hydrodynamic size and zeta potential during incubation with a range of saccharides. This provided the first direct observation of boronate ionization pKa in grafted BA, which in the absence of sugar shifted to a slightly more basic pH than free BA. On exposure to sugar solutions under MNP-limiting conditions, pKa moved progressively to lower pH as maximum capacity was gradually attained. The pKa shift is shown to be greater for sugars with greater BA binding affinity, and on-particle sugar exchange effects were inferred. Colloidal dispersion of BA-MNPs after binding was shown for all sugars at all pHs studied, which enabled facile magnetic extraction of glucose from agarose and cultured extracellular matrix expanded in serum-free media. Bound glucose, quantified following magnetophoretic capture, was found to be proportional to the solution glucose content under glucose-limiting conditions expected for the application. The implications for the development of MNP-immobilized ligands for selective magnetic biomarker capture and quantitation from the extracellular environment are discussed. The authors would like to acknowledge the financial support from Science Foundation Ireland under Grant Agreements 13/CDA/2155 and 16/IA/4584, the work was also co-funded under the European Regional Development Fund (13/RC/2073_2). P.B.P. acknowledges the Government of Spain - Ministry of Education, Culture and Sports for the FPU grant (FPU14/04589).

7 figures, 1 table.-- Supplementary information available. © 2023. This manuscript version is made available under the CC-BY-NC-ND 4.0 license https://creativecommons.org/licenses/by-nc-nd/4.0/, In this study, efficient electrodes for the hydrogen evolution reaction (HER) based on low-cost and metal-free carbon catalysts are presented. Phytic acid, a biosourced molecule containing carbon (C) and phosphorus (P), was found to be an excellent precursor for producing carbon materials with high P content, depending on the carbonization temperature, from 27.9 wt% at 700 °C to 7.3 wt% at 1000 °C. A green and easy route to produce P-doped carbon materials by heat treatment of this biosourced precursor without the need for additional reagents is thus proposed. We show that the conversion of P-O-type groups into P-C-type species is of paramount importance for improving the catalytic activity in HER of P-doped carbon materials. P-C-type groups appear to be the key factor in the electrocatalytic activity, reaching an onset potential of - 0.27 V. This study sheds light on the origin of the catalytic activity of P-doped carbons, in which P is expected to modify the homogenous distribution of the electron density of undoped carbons and increase their catalytic performance., This study was partially supported by the French PIA project “Lorraine Université d’Excellence”, reference ANR-15-IDEX-04-LUE, and the TALiSMAN and TALisMAN2 projects funded by ERDF. SGD thanks the Ministerio de Universidades, the European Union, and the University of Oviedo for the financial support (MU-21-UP2021-030 30267158). JQB thanks the Ministerio de Universidades, the European Union, and the University of Alicante for the financial support (MARSALAS21-21).

Large graphene-like molecules with four zigzag edges are ideal gain medium materials for organic near-infrared (NIR) lasers. However, synthesizing them becomes increasingly challenging as the molecular size increases. In this study, we introduce a new intramolecular radical-radical coupling approach and successfully synthesize two fused triangulene dimers (1a/1b) efficiently. X-ray crystallographic analysis of 1a indicates that there is no intermolecular π-π stacking in the solid state. When the more soluble derivative 1b is dispersed in polystyrene thin films, amplified spontaneous emission in the NIR region is observed. Using 1b as the active gain material, we fabricate solution-processed distributed feedback lasers that exhibit a narrow emission linewidth at around 790 nm. The laser devices also exhibit low thresholds with high photostability. Our study provides a new synthetic strategy for extended nanographenes, which have diverse applications in electronics and photonics. J.W. acknowledges financial support from the NRF Investigatorship Award (NRF-NRFI05-2019-0005), the A*STAR AME grant (A20E5c0089) and start-up grant from the Joint School of National University of Singapore and Tianjin University@Fuzhou. The group at the University of Alicante thanks financial support from the “Ministerio de Ciencia e Innovación” (MCIN) of Spain and the European Regional Development Fund (grant No. PID2020-119124RB-I00) and from the Generalitat Valenciana though grant No. AICO/2021/093. Besides, this study part of the Advanced Materials program supported by the Spanish MCIN with funding from European Union NextGenerationEU and by Generalitat Valenciana (grant no. MFA/2022/045). Z.S. is grateful to the financial support from National Natural Science Foundation of China (Grant No. 21971187, 22222110), Natural Science Foundation of Tianjin (19JCJQJC62700) and the Haihe Laboratory of Sustainable Chemical Transformations.

In this work, the determination of different metals (i.e., Al, Cr, Cu, Mn, Ni and V) in engine lubricating oils by microwave plasma atomic emission spectrometry (MP AES) has been revisited. For this purpose, a new multinebulizer in combination with the standard dilution analysis (SDA) calibration methodology has been used. The microwave plasma is very unstable and may even extinguish when organic solvents are directly introduced. This problem can be avoided by the synergetic combination of the SDA calibration and the new multinebulizer since it allows the determination of analytes in complex matrices due to the simultaneous introduction of organic and aqueous solutions, favoring the plasma stabilization. Furthermore, the SDA calibration also corrects the matrix effects associated with complex matrices. For the purpose of comparison, the same study has been performed using conventional calibration methodologies (i.e., external calibration (EC), internal standard calibration (IS) and standard addition calibration (SA)). To compare the analytical performances, the analytical figures of merit (i.e., limit of detection and limit of quantification) and the accuracy (i.e., trueness and precision) of the results have been evaluated. The results obtained show very similar values for the SDA calibration compared to the other calibrations with a much lower consumption of reagents, resources and with a higher easiness of operation. In addition, the total analysis time has also been evaluated, which has emphasized the great advantage of the synergetic association of SDA calibration with the multinebulizer in chemical analysis. The authors would like to thank the Spanish Ministry of Science and Innovation (PID2021-126155OB-I00) and the Regional Government of Valencia (Spain) (CIPROM/2021/062, INVEST/2022/70) for the financial support.

The present work aims to assess the impact of morphology and reducibility on lanthanum-doped ceria nanocatalysts with controlled morphology on the NO oxidation reaction. Specifically, samples were prepared using a hydrothermal method incorporating lanthanum at varying molar concentrations (0, 5, 10, and 15 mol.%) into ceria with a controlled morphology (nanocubes and nanorods). The structural, compositional, and redox characterization of these catalysts has been performed via scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), X-ray energy dispersive spectroscopy (X-EDS), inductively coupled plasma (ICP), hydrogen temperature-programmed reduction (H2-TPR), and oxygen storage capacity (OSC). NO oxidation catalytic tests were conducted, and the results were compared with estimated curves (obtained by considering the proportions of the corresponding components), which revealed the presence of a synergistic effect between lanthanum and ceria. The degree of enhancement was found to depend on both the morphology and the amount of lanthanum incorporated into CeO2. These findings may facilitate the optimization of features concerning ceria-based nanocatalysts for the removal of NOx emissions from exhaust gases. This research was funded by Generalitat Valenciana (CIPROM/2021/070 project), the Spanish Ministry of Science and Innovation/Research Spanish Agency (PID2019-105542RB-I00/AEI/10.13039/501100011033, PID2020-113006RB-I00/AEI/10.13039/501100011033 and PID2020-113809RB-C33 projects), and UE-FEDER funding.

Carbon materials constitute a broad family of solids that encompass a high variety of physical and chemical properties, including morphology. These materials have shown to be very useful as catalysts supports and, in this context, also for the heterogenization of metal complexes owing catalytic properties. This work is mainly, the summary of the results obtained in several research projects focused on developing heterogenized molecular catalysts by exploiting the properties of a plethora of carbon materials to address several immobilization procedures. Spanish government (PB98-0983, PPQ2002-1025, MAT2009-07150, Prometeo 2009/047, MAT2012-32832, CTQ2015-66080-R, PROMETEOII/2014/010, RTI2018-095291-B-I00, PROMETEO/2018/076).

This work describes the development and characterization of fluorescent nanocomposite hydrogels, with high swelling and absorption capacity, and prepared using a green protocol. These fluorescent materials are obtained by incorporating, for the first time, polyfluorenes-based nanoparticles with different emission bands—poly[9,9-dioctylfluorenyl-2,7-diyl] (PFO) and poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(1,4-benzo-{2,1,3}-thiadiazole)] (F8BT)—into a three-dimensional polymeric network based on polyacrylamide. To this end, two strategies were explored: incorporation of the nanoparticles during the polymerization process (in situ) and embedment after the hydrogel formation (ex situ). The results show that the combination of PFO nanoparticles introduced by the ex situ method provided materials with good storage stability, homogeneity and reproducibility properties, allowing their preservation in the form of xerogel. The fluorescent nanocomposite hydrogels have been tested as a transportable and user-friendly sensing platform. In particular, the ability of these materials to specifically detect the enzyme alkaline phosphatase (ALP) has been evaluated as a proof-of-concept. The sensor was able to quantify the presence of the enzyme in an aqueous sample with a response time of 10 min and LOD of 21 nM. Given these results, we consider that this device shows great potential for quantifying physiological ALP levels as well as enzyme activity in environmental samples. This work was funded by the Spanish Ministry of Science and Innovation (TED2021-129894B-I00). The study forms part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and Generalitat Valenciana (MFA/2022/058). DLS, FESEM and Fluorescence lifetime spectrometer equipment acquisition funded by Generalitat Valenciana–Conselleria d’Educació Investigació Cultura i Esport and EUFEDER “Una forma de hacer Europa” (GVA-IDIFEDER/2018/020 and GVA-IDIFEDER/2021/036).

The transformation of non-edible lignocellulosic biomass into high added-value chemicals and biofuels associated with lower energy process requirements is a promising strategy for meeting the actual demands of clean energy. Here, we report the study of the non-catalytic conversion of biomass wastes issued from two Amazonian abundant fruits (cupuaçu shell and assai stone) into liquid valuable chemicals. The parent biomass samples were first comprehensively characterized using TG, XRD, and FTIR; then, they were pretreated by ball milling and by chemical processing in ionic liquid, and finally, they were hydrothermally treated to be converted into chemical products benefiting from their hemicellulose and cellulose contents. The results revealed the importance of the pretreatments in the conversion rate, while the selectivity into main chemical products (such glucose, HFM, furfural, xylose) is not affected by the pretreatments neither physical nor chemical ones. The conversion of both biomasses and their products’ distribution were comprehensively discussed, with the highest conversion obtained using assai stone biomass (90%). This study could pave the way for investigating the non-catalytic route of biomass conversion, as a lesser energy process, resulting in a cost-effective conversion process. This work was supported by the national and regional Spanish governments (RTI2018–095291-B-100, PID2021–123079OB-I00 project funded by MCIN/AEI/10.13039/501100011033 and by ERDF A way of making Europe (European Union) and CIPROM/2021/070) (Generalitat Valenciana) and the University of Alicante (VIGROB-136).

A new natural deep eutectic solvent (NADES)-based analytical method for mercury speciation in water samples is presented. A NADES (i.e., decanoic acid:DL-menthol in a molar ratio of 1:2) is used as an environmentally friendly extractant for separation and preconcentration using dispersive liquid–liquid microextraction before LC-UV–Vis. Under optimal extraction conditions (i.e., NADES volume, 50 µL; sample pH, 12; volume of the complexing agent, 100 µL; extraction time, 3 min; centrifugation speed, 3000 rpm; and centrifugation time, 3 min), the limit of detection values were 0.9 µg L−1 for the organomercurial species and 3 µg L−1 for Hg2+, which had a slightly higher value. The relative standard deviation (RSD, n = 6) has been evaluated at two concentration levels (25 and 50 µg L−1) obtaining values for all the mercury complexes within the range of 6–12% and 8–12%, respectively. The trueness of the methodology has been evaluated using five real water samples from four different sources (i.e., tap, river, lake, and wastewater). The recovery tests have been performed in triplicate obtaining relative recoveries between 75 and 118%, with RSD (n = 3) between 1 and 19%, for all the mercury complexes in surface water samples. However, wastewater sample showed a significant matrix effect (recoveries ranged between 45 and 110%), probably due to the high amount of organic matter. Finally, the greenness of the method has also been evaluated by the analytical greenness metric for sample preparation (i.e., AGREEprep). Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. The Spanish Ministry of Science and Innovation (PID2021-126155OB-I00) and the Regional Government of Valencia (Spain) (CIPROM/2021/062) provided financial support for this study.

SiC is one of the most important ceramics at present due to its excellent properties and wide range of applications. The industrial production method, known as the Acheson method, has not changed in 125 years. Because the synthesis method in the laboratory is completely different, laboratory optimisation may not be extrapolated to the industrial level. In the present study, the results at the industrial level and at the laboratory level of the synthesis of SiC are compared. These results show that it is necessary to make a more detailed analysis of the coke than the traditional one; therefore, the Optical Texture Index (OTI) should be included, as well as the analysis of the metals that form the ashes. It has been found that the main influencing factors are OTI and the presence of Fe and Ni in the ashes. It has been determined that the higher the OTI, as well as the Fe and Ni content, the better the results obtained. Therefore, the use of regular coke is recommended in the industrial synthesis of SiC. The authors acknowledge the financial support given by the “Ministerio de Ciencia e innovación” through the project PID2020-116998RB-I00 and the “Generalitat Valenciana” for the projects CIPROM/2021/022 and PRTR-C17.I1.

Interzeolite transformation has been used to produce a novel family of hierarchical catalysts featuring excellent textural properties, strong acidity, and superior catalytic performance for the Friedel–Crafts alkylation of indole with benzhydrol, the Claisen–Schmidt condensation of benzaldehyde and hydroxyacetophenone, and the cracking of polystyrene. Intermediate solids of the FAU interzeolite transformation into BEA display both increased accessibility─due to the development of mesoporosity─and strong acidity─caused by the presence of ultrasmall crystals or zeolitic fragments in their structure. The use of surfactants allows for the development of the hierarchical catalysts with very narrow pore size distribution. The properties of interzeolite transformation intermediates (ITIs) can be fine-tuned simply by stopping the interconversion at different times. The authors thank the European Commission for funding through the H2020-MSCA-RISE-2019 program (Ref. ZEOBIOCHEM-872102) and the Spanish MINECO and AEI/FEDER, UE, through Project Ref. RTI2018-099504-B-C21. N.L. also acknowledges the University of Alicante support (UATALENTO17-05). M.J.M. thanks the Generalitat Valenciana for a PhD fellowship (GRISOLIAP/2020/165). Carlos A. Trujillo and Nelcari T. Ramírez M. express their gratitude to the Universidad Nacional de Colombia for providing physical and technical resources for this research also to Minciencias and Ecopetrol in the frame of Contract 0402-2013.

Graphene-based materials were synthesized by electrochemical exfoliation method (cathodic method) starting from a graphite sheet. In the established methodology, an initial immersion in H2SO4 was applied, followed by cathodic expansion in potassium sulphate, where the effect of the applied voltage was studied. Finally, by ultrasound treatment, the exfoliation was achieved to produce a dispersion of few layer graphene material. Once the optimum procedure was established, Pt nanoparticles were incorporated using H2PtCl6.6H2O. This incorporation was studied at each stage of the graphene-based material synthesis to determine which was the most adequate to obtain the highest Pt dispersion and the best distribution of the Pt nanoparticles. In this sense, the incorporation of Pt in the graphene-based material colloidal dispersion by stirring for 3 h and sonication for 1 h, results in Pt nanoparticles with an average size of around 1 nm with an excellent distribution in the carbon material. The performance of this catalyst was compared with the commercial Pt/C electrocatalyst, showing a great oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) activity, exceeding it by far when comparing the mass-specific activity (A gPt−1) In addition, it presents excellent stability and selectivity toward the 4-electron pathway in ORR, which is the most energy-efficient, and using half of the platinum loading compared to the commercial material. The authors would like to thank PID2019-105923RB-I00 and PID2021-123079OB-I00 projects funded by MCIN/AEI/10.13039/501100011033 and “ERDF A way of making Europe”, and the Generalitat Valenciana (GRISOLIA/2020/114) for the financial support.

Se analiza un conjunto de tres discos de cerámica procedentes de los niveles del Hierro Antiguo de Peña Negra. Presentan diferentes acabados y estarían provistos de asas, por lo que deben interpretarse como tapaderas de grandes recipientes de almacenaje. Se ha realizado el estudio petrográfico y mineralógico mediante microdifracción de rayos X (µDRX). Los resultados indican que se trata de piezas de composición relativamente homogénea y de probable producción local, cocidas a baja temperatura. Se revisa el hallazgo de objetos similares en otros contextos del Hierro Antiguo, destacando los recuperados en el Noreste peninsular y el Valle del Ebro, donde además se localizan discos-tapadera realizados en yeso similares a dos ejemplares recuperados en Peña Negra, donde es un material frecuente empleado en la construcción y en la fabricación de objetos. A set of three ceramic discs from the Early Iron Age levels of Peña Negra are analysed. They exhibit differences in surface treatment and would have been fitted with handles, so they should be interpreted as lids of large storage vessels. Samples of each disc were studied by means of petrographic and mineralogical analysis (X-ray micro-diffraction, µDRX). Resulting data indicate that those are pieces of relatively homogeneous composition and that were probably locally produced, fired at low temperatures. The discovery of similar objects in other Early Iron Age contexts is reviewed, highlighting those recovered in the Northeast of the Iberian Peninsula and the Ebro Valley, where gypsum discs have also been found, similar to two examples found in Peña Negra. In this site, gypsum was commonly used as raw material in building activities and other crafts. Este trabajo se ha realizado en el marco del proyecto del Ministerio de Ciencia, Innovación y Universidades HAR2017-87495-P, “Fenicios e indígenas en el Sureste de la península ibérica: Bronce Final y Hierro Antiguo entre el Vinalopó y el Segura” y del proyecto de la Generalitat Valenciana AICO/2021/189, “Construyendo territorios entre el Bronce Final y el Ibérico Antiguo en los extremos de la Comunitat Valenciana (ConstrucTERR)”. El trabajo instrumental se ha financiado con una ayuda de la Fundación Palarq (Analíticas 2019), desarrollada en el marco de un convenio de colaboración con la Universidad de Alicante para la coordinación y desarrollo del proyecto “Estudio de investigación para llevar a cabo analítica de cerámica prehistórica” (FUNDACIONPALARQ1-19X). También con la Ayuda para la utilización de los Servicios Técnicos de Investigación del Vicerrectorado de Investigación y Transferencia de Conocimiento de la Universidad de Alicante (UAUSTI19-15). María Pastor Quiles es investigadora Juan de la Cierva-formación (FJC2019-039469-I) financiada por el Ministerio de Ciencia e Innovación y el Institut Català d’Arqueologia Clàssica. Miguel del Pino Curbelo disfruta de un contrato del programa Viera y Clavijo, financiado por la Universidad de Las Palmas de Gran Canaria.

High surface area mixed oxide 8.7% NiO-CeO2 nanoparticles (122 m2/g; 6–7 nm) were prepared using a reversed microemulsion method, and were tested for dry methane reforming (DRM). The catalytic activity of these nanoparticles remains stable under the severe conditions of DRM (700 °C), and they show better carbon resistance than conventional NiO-CeO2 catalysts prepared without control of the size. The activity and selectivity of nanoparticles and reference catalyst are similar, but nanoparticles reduce by 63% the accumulation of carbon during the DRM tests, which is a key feature for this reaction. XPS and H2-TPR suggest that the improved carbon resistance of the nanoparticles is the better interaction and cooperation between NiO and CeO2 mixed phases. In nanoparticles, the participation of cerium cations in the redox processes taking place during DRM stabilize cationic species of nickel. On the contrary, the catalyst prepared without control of the size suffered segregation of Ni during DRM reaction, and segregated Ni explains the higher catalytic formation of carbon. Project supported by the Generalitat Valenciana (Project PROMETEO/2018/076; ACA GRISOLIAP/2017/185; EBG APOSTD/2019/030), MINECO (CTQ2015-67597-C2-2-R), MICINN (PID2019-105960RB-C22) and European Union FEDER funds.

Donor–Acceptor (D–A) naphthalimides (NI) are highly fluorescent multitask compounds that have demonstrated success in a variety of optoelectronic applications, among which, thin film organic lasers (TFOLs) are not included. Here we assess the potential of various NI derivatives for lasing applications by investigating their amplified spontaneous emission (ASE) properties when dispersed in polystyrene thin films. To overcome the relatively low ASE photostability measured in the NIs, a series of peryleneimides (PI) derivatives, with similar chemical structure but with more extended π-conjugation, is synthesized and reported here, together with a complete characterization of their optical and ASE properties, both in solution and thin film. Most investigated compounds show ASE, with emissions at different wavelengths spanning from the blue to the red, depending on the derivative. Furthermore, surface emitting TFOLs with top-layer polymeric distributed feedback resonators are fabricated and characterized. This work represents an advance in the field of low-cost TFOLs, by including two families of successful laser dyes, NIs and PIs, the latter with significantly better photostability. The group at the University of Alicante acknowledges financial support from the “Ministerio de Ciencia e Innovación/Agencia Estatal de investigación” (MCIN/AEI) of Spain, European Regional Development Fund and European Social Funds (project PID2020-106114GB-I00) and from the Conselleria de Innovación, Universidades y Sociedad Digital de la Comunidad Valenciana (Grant No. AICO/2021/093). The team of the University of Castilla la Mancha acknowledges financial support from the MCIN/AEI of Spain (project PID2020-119636GB-I00 and RED2018-102331-T) and by FEDER Una manera de hacer Europa and Junta de Comunidades de Castilla-La Mancha (JCCM-FEDER) (SBPLY/17/180501/000189 and SBPLY/17/180501/000114). B. Donoso is grateful for a FPU predoctoral contract (FPU16/05099). I. Torres-Moya thanks to the Junta de Comunidades de Castilla-La Mancha for a post-doctoral contract (SBPLY/19/180501/000346). Finally, we acknowledge the computer resources, technical assistance, and expertise provided by the High Performance Computing Service of UCLM.

Metal–organic frameworks (MOFs) are porous hybrid materials with countless potential applications. Most of these rely on their porous structure, tunable composition, and the possibility of incorporating and expanding their functions. Although functionalization of the inner surface of MOF crystals has received considerable attention in recent years, methods to functionalize selectively the outer crystal surface of MOFs are developed to a lesser extent, despite their importance. This article summarizes different types of post-synthetic modifications and possible applications of modified materials such as: catalysis, adsorption, drug delivery, mixed matrix membranes, and stabilization of porous liquids. The authors acknowledge financial support by Ministerio de Ciencia e Innovación (PID2020-116998RB-I00), Ministerio de Educación y Formación Profesional (PRX21/00407), Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital (CIPROM/2021/022), and the King Abdullah University of Science and Technology (KAUST). This study forms part of the Advanced Materials programme and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana.

Carbon-ceramic composites (C/Cer) have been prepared by chemical vapor deposition of coal tar pitch onto clay substrates and characterized by thermogravimetric analyses, powder X-ray diffraction, Raman spectroscopy, and scanning and transmission electron microscopies (SEM and TEM). The study of the dc electrical conductivity, together with the determination of the Hall voltage sign, proves that such C/Cer composites are n-type semiconductors. Our results demonstrate that: 1) the mechanism of electrical conduction of C/Cer semiconductors proceeds through the pathways expected for amorphous solids (ie. variable-range hopping and heat-activated pathways at low and high temperatures, respectively); and 2) their transport properties are strongly dependent on the clay components, as evidenced by microscopy experiments. The authors would like to thank the financial support from Ministerio de Ciencia e Innovación (grant No. PID2019-105542RB-I00/AEI/10.13039/501100011033 ), the European Union (FEDER Funds), and Generalitat Valenciana (grant No. PROMETEO CIPROM/2021/70 ).

Zeolitic imidazolate frameworks (ZIFs) have been profusely used as catalysts for inserting CO2 into organic epoxides (i.e., epichlorohydrin) through cycloaddition. Here, we demonstrate that these materials suffer from irreversible degradation by leaching. To prove this, we performed the reactions and analyzed the final reaction mixtures by elemental analysis and the resulting materials by different microscopies. We found that the difference in catalytic activity between three ZIF-67 and one ZIF-L catalysts was related to the rate at which the materials degraded. Particularly, the {100} facet leaches faster than the others, regardless of the material used. The catalytic activity strongly depended on the amount of leached elements in the liquid phase since these species are extremely active. Our work points to the instability of these materials under relevant reaction conditions and the necessity of additional treatments to improve their stability. The authors acknowledge financial support by Ministerio de Ciencia e Innovación (PID2020-116998RB-I00), Ministerio de Educación y Formación Profesional (PRX21/00407), Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital (CIPROM/2021/022 and MFA/2022/057), and the King Abdullah University of Science and Technology (KAUST). This study forms part of the Advanced Materials Program and was supported by MCIN with funding from European Union NextGenerationEU (PRTR-C17.I1) and by Generalitat Valenciana.

Los microplásticos son pequeñas partículas de material plástico de tamaño inferior a 5 mm que ya se encuentran en la totalidad del medio ambiente, incrementándose cada vez más las cantidades que se vierten a los océanos, lo que ha generado gran preocupación científica y social en los últimos años, despertando el interés por conocer el impacto que estas partículas pueden tener en la salud y el medio ambiente. En la actualidad no existe un método estandarizado para el análisis de microplásticos, con lo que cada laboratorio utiliza una técnica diferente, que van desde las técnicas espectroscópicas como Espectroscopía infrarroja con transformada de Fourier (FTIR) o espectroscopia Raman hasta las técnicas cromatográficas como la pirólisis acoplada a cromatografía de gases-masas (Pyr-CG-MS) o la termoextracción-desorción acoplada a cromatografía de gases-masas (TED-CG-MS). Todas estas técnicas han probado ser útiles para la detección e identificación de microplásticos, cada una de ellas con sus ventajas y desventajas, pero es necesario optimizarlas y encontrar un método más eficiente, robusto y a la vez que sea rápido y económico para que pueda estar al alcance desde el laboratorio más avanzado hasta el más modesto y que se puedan comparar los estudios realizados por los diferentes grupos. Se han estudiado y optimizado algunas de estas técnicas, como es la Calorimetría Diferencial de Barrido (DSC), donde se ha conseguido cuantificar, no solo los microplásticos formados por polímeros semicristalinos, sino también los constituidos por polímeros amorfos utilizando su temperatura de transición vítrea. Por otro lado, las técnicas cromatográficas son muy útiles en el análisis, tanto cualitativo como cuantitativo, de microplásticos, ya que se trata de técnicas muy robustas que proporcionan cromatogramas que pueden considerarse huellas dactilares de los compuestos que se analizan, no presentando interferencias entre los diferentes polímeros y siendo técnicas mucho más selectivas que el DSC. En esta Tesis Doctoral se ha escogido la TED-CG-MS como técnica cromatográfica, ya que, al presentar la fase de termoextracción, por un lado podemos escoger el tipo y características de los compuestos que se quiere retener seleccionando el sorbente adecuado, y por otro lado, los compuestos más pesados, bien por formar parte de la composición de los microplásticos o por estar presentes en la matriz de la muestra, no se introducen en la columna cromatográfica, evitando muchos de los interferentes y abaratando el coste de mantenimiento de los equipos. Tradicionalmente, en esta técnica se utilizan equipos de Análisis Termogravimétrico (TGA) en la fase de termoextracción. Estos equipos presentan el inconveniente de utilizar pocillos muy pequeños donde alojar la muestra, con lo que solo se puede analizar una porción del filtro. Esto puede acarrear diferentes problemas, entre los que destaca la pérdida de masa o la contaminación debida a la manipulación del filtro. También se debe tener en cuenta que los microplásticos son partículas sólidas que se encuentran suspendidas en el medio, con lo que al filtrar la muestras éstas quedan distribuidas de manera heterogénea en la superficie del filtro, por lo que los resultados van a depender mucho de la porción de filtro que se analice. Como parte de la optimización de la técnica se ha utilizado un horno tubular para pirolizar el filtro completo, evitando la manipulación y los problemas derivados de la heterogeneidad de la muestra, además de que al pirolizar una mayor masa de muestra esta será mucho más representativa, consiguiendo señales cromatográficas más intensas, con lo que se pueden disminuir los límites de cuantificación. Otro aspecto a optimizar de esta técnica es el sorbente con el que atrapar los compuestos de termodescomposición, pues de las características que posea este sorbente va a depender los compuestos que posteriormente se podrán analizar mediante cromatografía. En la presente Tesis Doctoral se estudiaron materiales de carbón como alternativa al polidimetilsiloxano (PDMS) tradicional, constatando que estos carbones presentan una mayor capacidad de adsorción y la posibilidad de retención de los compuestos clorados provenientes de la descomposición del policloruro de vinilo (PVC). Otro aspecto muy importante en el análisis de microplásticos es la presencia de otros contaminantes que pueden interferir en los resultados cuando las muestras presentan una matriz compleja, por lo que deben eliminarse en la medida de lo posible. Tras comparar varias metodologías y concentraciones, utilizar una oxidación con H2O2 al 30 % en proporción 1:20 ha resultado ser la estrategia óptima para eliminar la materia orgánica presente, así como se aconseja realizar una hidrólisis enzimática con celulasa en las muestras de entrada a las plantas depuradoras para eliminar la gran cantidad de celulosa presente que dificulta la filtración de las muestras acuosas. Para probar la eficacia de todos estos métodos y técnicas en muestras reales se realizaron muestreos en diferentes plantas de tratamiento de aguas dentro del Grupo Veolia, abarcando diferentes matrices, desde agua potable, marina, desalada e incluso residual. Como resultado de esta Tesis se ha conseguido optimizar y validar una metodología para el análisis de microplásticos en muestras de agua, obteniéndose en Labaqua la acreditación por parte de la Entidad Nacional de Acreditación en España (ENAC) bajo el sistema de calidad ISO 17025, con número de acreditación de Labaqua 109/LE285, para el análisis cualitativo de microplásticos en muestras de agua potable, marina y continental. Esta metodología se ha introducido en la cartera de productos de Labaqua, S.A.

La preocupación creciente por el aumento y posibles efectos adversos, en la salud y el medioambiente, ocasionados por los contaminantes emergentes (CEs) demanda el estudio de sus procesos de degradación y el desarrollo de tecnologías eficientes para su eliminación. La oxidación anódica directa es uno de los métodos más simples y eficientes para la eliminación de contaminantes orgánicos de elevada toxicidad y/o refractarios. No obstante, la viabilidad de esta tecnología dependerá del desarrollo de electrodos estables, de bajo coste y con elevada actividad catalítica. Entre las diversas composiciones propuestas en la literatura, los óxidos de estaño dopados con antimonio y pequeñas cantidades de Pt (SnO2-Sb-Pt) constituyen una de las más prometedoras. Sin embargo, hasta ahora no existen estudios de la oxidación de CEs sobre estos electrodos, y todavía se desconoce la naturaleza de su comportamiento electrocatalítico. En este trabajo se presenta un estudio fundamental y comparativo de la respuesta electrocatalítica de 3 electrodos de composición Ti/SnO2-Sb(13%met.)-Pt(0, 3, 13%met.) frente a la oxidación y eliminación de 3 CEs, concretamente, glifosato, paraquat y diclofenaco. La respuesta de estos electrodos se compara, además, con la de electrodos comerciales de Ti/Pt y Si/BDD. En particular, se analiza la naturaleza del ánodo en la capacidad para la generación de radicales hidroxilo y la facilidad y eficiencia en la oxidación y eliminación de CEs, analizando la formación y eliminación de los intermedios de reacción. Para ello, se utiliza la voltametría cíclica, técnicas espectroelectroquímicas (IR o UV) in-situ y/o experimentos de electrolisis en celda filtro-prensa en diversas condiciones que, sin tratar de emular ningún caso real de tratamiento de aguas, son adecuadas para dicho estudio electrocatalítico. Los resultados obtenidos muestran que los electrodos de Ti/SnO2-Sb dopados con Pt (3-13%met.) son capaces de oxidar y mineralizar los CEs estudiados, mostrando una respuesta electrocatalítica considerablemente mejor que la del ánodo comercial Ti/Pt, además de un coste mucho menor. Por otro lado, a pesar de mostrar una respuesta de oxidación/eliminación inferior, los electrodos de SnO2-Sb-Pt se presentan como una alternativa más económica y práctica, y de menor consumo energético, a la del ánodo comercial Si/BDD. De forma muy interesante, el estudio demuestra que, a pesar de disminuir la capacidad de generación de radicales hidroxilo, la presencia de Pt en SnO2-Sb cataliza la oxidación de los CEs. Los experimentos espectroelectroquímicos sugieren que dichos efectos electrocatalíticos podrían deberse a interacciones específicas del Pt con los CEs. Considerando que desde hace años se asume que la eficiencia de oxidación anódica se basa fundamentalmente en la generación de OHs, los resultados de esta tesis evidencian otros efectos/mecanismos eficientes de oxidación que son capaces de complementar y/o ser determinantes en esta tecnología de tratamiento de contaminantes.

Platinum is considered the reference catalyst in many electrochemical devices such as electrolyzers or fuel cells. Nevertheless, the large-scale commercialization of these Pt-based devices is limited by the prohibitive cost of platinum as well as its quantity and availability. Regardless of its price and scarcity, it is well known that the oxygen reduction reaction (ORR) with Pt in acidic media is slow compared to that in alkaline media. Due to the lower overpotentials in the latter case, the possibility of using Pt-free catalysts opens the door to new catalyst research. Among them, the development of carbon-based catalysts, either metal-free or with non-precious metals, from the conversion of biomass precursors by various synthetic processes has recently become a challenging goal, as biomass represents an eco-friendly source of carbon. The surface chemistry, textural properties and structure of carbonaceous materials make it complex to identify the origin of ORR catalytic activities. This review provides a critical discussion of the influence of the physicochemical and electrochemical properties of biomass-derived, carbon-based electrocatalysts for the ORR reported over the past decade. This study was partly supported by the French PIA project “Lorraine Université d’Excellence”, reference ANR-15-IDEX-04-LUE and the TALiSMAN project funded by ERDF (2019–000214). JQB thanks the Ministerio de Universidades, the European Union and the University of Alicante for the financial support of his Margarita Salas fellowship (MARSALAS21-21).

Polypyrrole (PPy) has been prepared by oxidative polymerization of pyrrole and used as a raw material for the preparation of N-doped activated carbons. Thus, PPy has been pyrolyzed at 900 °C and then activated with steam under different activation conditions (time and temperature). This has allowed for the preparation of activated carbons with different porosity development and nitrogen content, as well as distinctive distribution of nitrogen species. It has been observed that the presence of nitrogen functionalities favors water adsorption at low relative pressures but, at relative pressures higher than 0.5 it is determined by the porosity development. Financial support from Ministerio de Ciencia e Innovación (Spain, Project PID2019-108453GB-C21) is gratefully acknowledged. Open access funding enabled and organized by Projekt DEAL.

Preparation of TiO2 using the hydrothermal treatment in NH4OH solution and subsequent thermal heating at 500–700 °C in Ar was performed in order to introduce some titania surface defects. The highest amount of oxygen vacancies and Ti3+ surface defects were observed for a sample heat-treated at 500 °C. The presence of these surface defects enhanced photocatalytic properties of titania towards the deactivation of two bacteria species, E. coli and S. epidermidis, under artificial solar lamp irradiation. Further modification of TiO2 was targeted towards the doping of Cu species. Cu doping was realized through the impregnation of the titania surface by Cu species supplied from various copper salts in an aqueous solution and the subsequent heating at 500 °C in Ar. The following precursors were used as a source of Cu: CuSO4, CuNO3 or Cu(CH3COO)2. Cu doping was performed for raw TiO2 after a hydrothermal process with and without NH4OH addition. The obtained results indicate that Cu species were deposited on the titania surface defects in the case of reduced TiO2, but on the TiO2 without NH4OH modification, Cu species were attached through the titania adsorbed hydroxyl groups. Cu doping on TiO2 increased the absorption of light in the visible range. Rapid inactivation of E. coli within 30 min was obtained for the ammonia-reduced TiO2 heated at 500 °C and TiO2 doped with Cu from CuSO4 solution. Photocatalytic deactivation of S. epidermidis was greatly enhanced through Cu doping on TiO2. Impregnation of TiO2 with CuSO4 was the most effective for inactivation of both E. coli and S. epidermidis. This research was funded by the West Pomeranian University of Technology in Szczecin Rector Grant for PhD students of Doctoral School; grant number ZUT/29/2022.

The Stipa tenacissima S. is an endemic species of the Western Mediterranean countries, which grows on the semi-arid grounds of North Africa and South Spain. This biomass offers an abundant, renewable, and low-cost precursor for the production of activated carbon (AC). In that context, ACs were prepared by chemical activation of Stipa tenacissima leaves (STL) using phosphoric acid (H3PO4). The effects of activation temperature and impregnation ratio on the textural and chemical surface properties of the prepared activated carbons were investigated. Activation temperatures of 450 and 500 °C turned out to be the most suitable to produce activated carbons with well-developed porous textures. The best results in terms of developed surface area (1503 m2/g) and micropore volume (0.59 cm3/g) were observed for an STLs to phosphoric acid ratio of 1:2 and a carbonization temperature of 450 °C. The adsorption capacity of the optimal activated carbon was found to be 110 mg/g for the atenolol drug. The adsorption equilibrium was well explained by the pseudo-second-order model and Langmuir isotherm. This study showed that the chemical activation method using H3PO4 as an activating agent was suitable for developing STL-based activated carbon prepared for the removal of atenolol drug in an aqueous solution and compared with commercial activated carbon supplied by Darco.

A series of UiO-66 materials with different functional groups (−H, −NH2, and −NO2) have been evaluated for the adsorption and release of a common ocular drug such as brimonidine tartrate. UiO-66 samples were synthesized under solvothermal conditions and activated by solvent exchange with ethanol. Experimental results suggest that the incorporation of surface functionalities gives rise to the development of structural defects (missing linker defects) but without altering the basic topology of the UiO-66 framework. These defects improve the adsorption performance of the parent metal–organic framework (MOF), while the bulkier functionalities infer slower release kinetics, with the associated benefits for prolonged delivery of brimonidine. Among the evaluated MOFs, defective UiO-66-NO2 can be proposed as the most promising candidate due to the combination of a larger brimonidine volumetric uptake (680 mg/cm3), a prolonged delivery (period of up to 25 days), a small particle size, and a larger instability. Contrariwise, at high concentrations UiO-66-NO2 has higher toxicity toward human retinal pigment epithelium cells (ARPE-19) compared to the pure and NH2-functionalized UiO-66. Authors would like to acknowledge financial support from the Ministerio de Ciencia e Innovación (Project PID2019-108453GB-C21), H2020 (Project MSCA-RISE-2016/NanoMed) and Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital (Project CIPROM/2021/022).

One way to exploit CO2 is to use it as a feedstock for the production of cyclic carbonates via its reaction with organic epoxides. As far as we know, there is still no heterogeneous catalyst that accelerates the reaction in a selective, efficient and industrially usable way. Cobalt and zinc-based zeolitic imidazole frameworks (ZIFs) have been explored as heterogeneous catalysts for this reaction. In particular, we have prepared ZIF-8 and ZIF-67 catalysts, which have been modified by partial replacement of 2-methylimidazole by 1,2,4-triazole, in order to introduce uncoordinated nitrogen groups with the metal. The catalysts have shown very good catalytic performance, within the best of the heterogeneous catalysts tested in the cycloaddition of CO2 with epichlorohydrin. The catalytic activity is due ultimately to defects on the outer surface of the crystal, and varies in the order of ZIF-67-m > ZIF-67 > ZiF-8-m = ZIF-8. Notably, reactions take place under mild reaction conditions and without the use of co-catalysts. The authors acknowledge financial support by MINECO (Spain) through the projects MAT2017-86992-R and CTQ2017-88171-P, “Ministerio de Ciencia e innovación” (PID2020-116998RB-I00), Ministerio de Educación y Formación Profesional (PRX21/00407), and Conselleria de Innovacion, Universidades, Ciencia y Sociedad Digital (CIPROM/2021/022, MFA/2022/048).

Life Cycle Assessment (LCA) is applied to eco-design the H3PO4-assisted hydrothermal carbonization (HTC) process converting biomass residue into high-value products. The main innovation of the process relies on the combination of the H3PO4-assisted HTC with the activation treatment of the obtained hydrochar, resulting in activated carbon that is then functionalized. In addition, the liquid phase obtained from HTC is eventually purified to extract levulinic acid. Under average conditions at the laboratory scale (reference), the LCA showed that electricity consumption is the main contributor (45–70%) to impacts on climate change, photochemical ozone formation, acidification, freshwater eutrophication, freshwater ecotoxicity and fossil resources use. Pyridine, the main chemical used in the functionalization stage, contributes to impacts on human toxicity and on marine eutrophication respectively by 77.3% and 47.3%. Building on these results, two further scenarios were studied, one considering the maximum capacity of each equipment and another one assuming the potential improvements once the process will be upscaled. The scenarios were validated in a series of laboratory scale tests. Depending on the environmental impact category chosen, the results showed a reduction potential of 30–65% as compared to the reference scenario. These findings confirm the added value of LCA in the ecodesign of technologies and pave the way to further improvements of the technology itself but also of the LCA methodology used for the assessment. This research was partially supported by the MICINN, FEDER (RTI2018-095291-B-I00). JCG thanks for her predoctoral scholarships (GRISOLIA/2018/105) and (BEFPI/2020/067) funded by the Generalitat Valenciana and DST thanks MICINN for the “Juan de la Cierva” contract (IJCI-2016-27636).

Porous organic molecular materials represent an emergent field of research in Chemistry and Materials Science due to their unique combination of properties. To enhance their performance and expand the number of applications, the incorporation of hierarchical porosity is required, as exclusive microporosity entails several limitations. However, the integration of macropores in porous organic molecular materials is still an outstanding challenge. Herein, we report the first example of a hydrogen-bonded organic framework (MM-TPY) with hierarchical skeletal morphology, containing stable micro- and macroporosity. The crystal size, from micro to centimetre scale, can be controlled in a single step without using additives or templates. The mechanism of assembly during the crystal formation is compatible with a skeletal crystal growth. As proof of concept, we employed the hierarchical porosity as a platform for the dual, sequential and selective co-recognition of molecular species and microparticles. J.F.-S. thanks “Ramón y Cajal“ program (RYC2019-02794-I), MINECO (Spain) (Projects PID2019−104778GB−I00 and Excellence Unit “Maria de Maeztu” CEX2019−000919−M) and Generalitat Valenciana (SEJI/2020/034). E.V.R.F. thanks Ministerio de Ciencia e innovación (PID2020-116998RB-I00) and Ministerio de Educación y Formación Profesional (PRX21/00407).

Several porous materials, especially natural fibres and polyurethane foams, are frequently used as sound absorbers in multiple noise reduction applications. Notwithstanding their excellent absorption performance, these materials usually lack the structural strength and fire resistance required for use in aggressive environments or situations requiring structural stability. This paper proposes the design of open-pore polymer and aluminum cellular materials with non-stochastic structures for sound absorption. These materials were fabricated using additive manufacturing (polymeric materials) and the replication method (aluminum materials), which involves infiltrating porous preforms formed by compacting spheres of a martyr material, such as NaCl, with liquid aluminum. The proposed materials can be employed as a resonator system when backed by an air cavity, with the change in cavity depth used to tune its sound absorption peak. Following the standard ASTM E1050, the sound absorption of these materials was investigated. In addition, the sound absorption performance of the materials was predicted using an Equivalent Circuit Method model. The experimental results are consistent with those predicted by the model, highlighting the potential of the microstructural and configurational design of these materials as sound absorbers. Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature. This research was undertaken at the Department of Mechanical Engineering at the Massachusetts Institute of Technology with support from the University of Alicante (Grants. ACIE19-04 and ACIE20-04). J.M. Molina gratefully acknowledges partial financial support from the Spanish “Agencia Estatal de Investigación” (AEI) and European Union (FEDER funds) through grant PDC2021-121617-C21 and the financial support from the Conselleria d'Innovació, Universitats, Ciència, i Societat Digital of the Generalitat Valenciana through grant GVA-COVID19/2021/097. L.P. Maiorano also acknowledges the financial support from the University of Alicante through grant UAFPU2019-33 "Programa Propio para el fomento de la I+D+i del Vicerrectorado de Investigación y Transferencia de Conocimiento".

Purpose: The purpose of this study was to improve the biomechanical properties of the cornea through the incorporation of carbon nanostructures. Methods: Healthy Japanese rabbits were used to evaluate the effect of carbon nanostructures’ incorporation in the cornea. Rabbits were divided in two groups A and B. In each of these groups, the corneas were divided in (i) corneas not submitted to any treatment (the control group), (ii) corneas modified either with carbon nanostructures (group A), or with the traditional cross-linking technology (group B). After modification, rabbits were euthanized at different time intervals. The biomechanical properties of the treated corneas were evaluated using the inflation method. Results: Biomechanical tests based on the inflation method show that the incorporation of carbon nanostructures to the cornea and their proper distribution within it gives rise to a large improvement in the mechanical properties and tangential elastic modulus (up to 155%). These results anticipate that this novel and easy approach based on nanotechnology is able to compete with the actual cross-linking technology applied in clinical ophthalmology using a photosensitive molecule, such as riboflavin and unpleasant UV-A radiation. Conclusions: The incorporation of carbon nanostructures (single-walled carbon nanotubes and graphene) in corneal stroma is proposed as a promising alternative to improve the mechanical properties in the treated eyes. The proper dispersion of the carbon nanostructures a few days after implementation (down to 60 micrometers depth) explains the successful results achieved. Translational Relevance: Nanotechnology applied to the eye constitutes a promising approach for ocular tissue reinforcement. The authors thank the support from the Spanish Ministry of Economy and Competitiveness through the Cooperation Health Research Thematic Network “Prevention, Early detection, Treatment and Rehabilitation of Ocular Pathologies”, sub-program “Optical Diopter” (RD16/0008). Financial supports from the National Natural Science Foundation of China (U20A20338) and Key R&D Program of Zhejiang Province (2021C04019) are acknowledged.

An on-line synthesis of CDots is proposed for the first time, using the flow injection analysis (FIA) technique, which was coupled, in a single system, to the analytical determination of aluminium in water samples. The nanoparticles were obtained from the carbonization of glucose and iron(III) in an acidic medium, and their photoluminescence increased in the presence of aluminium ions. Under optimal experimental conditions, the proposed method has shown an acceptable linearity range –between 0.04 and 3.0 mg L−1 (R2 = 0.9999) – and a detection limit of 0.007 mg L−1. The analysis of drinking water and groundwater samples showed good accuracy (recoveries ranged between 91 – 113%) and RSD% < 13. The on-line system exhibited a high sample throughput (36 h−1), since no incubation time was required. Financial support from Universidad Nacional del Sur (PGI 24/Q099 and 24/Q123, CONICET 11220200102603CO, CONICET 11220200103198CO and the ANPCyT PICT-2019-04458 (2021-2023) is gratefully acknowledged. This research was part of the Ph.D. thesis of Damian Uriarte, which was supported by a doctoral grant funded by Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET). M. Garrido and C.E. Domini wish to thank CONICET.

This research work focuses on a preliminary study of the behaviour of several ceria-praseodymia mixed oxides along with three model catalysts under isotopic oxygen pulses at different temperatures in an attempt to investigate their ability to interact with 18O2 (uptaking/releasing/exchanging) with their own lattice oxygen, under conditions which could simulate those existing in GDI exhaust gases. Furthermore, these ceria-praseodymia mixed oxides were studied to explore their responses towards soot combustion under two consecutive 18O2 pulses at 500 oC. It was observed that the capacity of oxygen activation and uptake is very dependent on the nature of the catalyst. Ce1-xPrxO2-δ catalysts present different responses in the O2 activation and uptake processes, as a function of temperature, praseodymium content and method of preparation. Moreover, some of these ceria-praseodymia formulations exhibited high soot combustion activity with a marked intervention of unlabelled active oxygen species during the inert period after the 18O2 pulse. The authors gratefully acknowledge the financial support of Generalitat Valenciana (CIPROM/2021/070 project) and the Spanish Ministry of Science and Innovation/Research Spanish Agency (PID2019-105542RB-I00 /AEI/10.13039/501100011033 project) and the UE-FEDER funding. JCMM acknowledges Spanish Ministry of Science and Innovation for the financial support through a FPU grant (FPU17/00603). MCR also wants to thank the University of Alicante for the financial support for the internship (INV19-07).

LaNi1-xCoxO3 perovskite materials were synthesized by a sol-gel method for use in electrochemical reactions which involve molecular oxygen. The metal oxides were characterized by different physicochemical techniques and it was observed that the incorporation of Co induces some changes in the surface of the materials that affect the electrocatalytic activity. The different perovskite metal oxides were mixed with carbon black (Vulcan) to improve their electrocatalytic performance. The results from TPR and TPD techniques supported the XPS interpretation suggesting that a stronger interaction between carbon material and metal oxides can be obtained by physically mixing the two materials. This interaction improves the electron transfer and enhances the catalytic activity. Among the as-prepared materials, it was observed that the electrocatalytic performance of LaNi1-xCoxO3 perovskite/Vulcan materials is higher than that of LaNiO3/Vulcan for ORR, but similar towards OER. It is claimed that Co3+ is more catalytic for ORR, while Ni3+ favors the OER. Moreover, the presence of Co stimulates the formation of chemisorbed oxygen species, which also favor the electron transfer. Metal oxides containing both cations show higher stability, being this effect more notorious for OER. LaNi0.5Co0.5O3/Vulcan seems a suitable bifunctional catalyst for both electrochemical reactions. The authors thank to the Ministerio de Ciencia e Innovación (PID2019-105923RB-I00) for financial support. J.X.F.-L. gratefully acknowledges MINECO for financial support through an FPI contract (BES-2017-081598).

Papain is a cysteine endopeptidase of vegetal origin (papaya (Carica papaya L.) with diverse applications in food technology. In this review we have focused our attention on its application in the production of bio-peptides by hydrolysis of proteins from fish residues. This way, a residual material, that can become a contaminant if dumped without control, is converted into highly interesting products. The main bioactivity of the produced peptides is their antioxidant activity, followed by their nutritional and functional activities, but peptides with many other bioactivities have been produced. Thera are also examples of production of hydrolysates with several bioactivities. The enzyme may be used alone, or in combination with other enzymes to increase the degree of hydrolysis. We gratefully recognize the support from the Ministerio de Ciencia e Innovación from Spanish Government (project number CTQ2017-86170-R) and CSIC for the project AEP045. The FPU fellowship (Ministerio de Educacion) for Mr. Morellon–Sterling is gratefully recognized. Dr. Tacias-Pascacio thanks the financial support from “Programa para el Desarrollo Profesional Docente” (PRODEP) from Mexican Government. ABM would like to thank Ministerio de Ciencia Innovación y Universidades and FEDER (Project RTI2018-095291-B-I00) and the Generalitat Valenciana (PROMETEOII/2018/076) for financial support.

The development of porous materials with hierarchical porous structures is currently of great interest. These materials exhibit properties representative of different pore scales and thus open up the possibility of being used in new applications. In this paper, a method for the preparation of silver foams with hierarchical porous structures is discussed. Here, the replication method, which is typically used to produce coarse-pore foams, is merged with dealloying, which is commonly used to manufacture small-pore foams. For this purpose, packed NaCl particles (hard template) were infiltrated with 75%Al–25%Ag alloy (whose so-called soft template is the Al-rich phase). Both the hard and soft templates were removed by water dissolution and dealloying with HCl or NaOH solutions, respectively. Extensive characterization of the resulting materials revealed pores ranging from a few nanometers to hundreds of micrometers. The materials were characterized by their antibacterial performance against Gram-positive and Gram-negative bacteria and showed significantly higher activity than both silver foams prepared by sintering pure Ag particles and silver nanofoams produced by chemical dealloying. The combinations of pores of different sizes and the resulting high internal specific surface area have a decisive influence on the antibacterial capacity of these new materials. The authors acknowledge partial financial support from the Spanish Agencia Estatal de Investigación (AEI) and the European Union (FEDER funds) through grant MAT2016-77742-C2-2-P. F.C.D. also acknowledges financial support from the Generalitat Valenciana through the “Santiago Grisolía” grant (code GRISOLIA/2017/187).

Funder: University of Cambridge, Funder: Office of Energy Efficiency and Renewable Energy, We are currently witnessing the dawn of hydrogen (H2) economy, where H2 will soon become a primary fuel for heating, transportation, and long-distance and long-term energy storage. Among diverse possibilities, H2 can be stored as a pressurized gas, a cryogenic liquid, or a solid fuel via adsorption onto porous materials. Metal-organic frameworks (MOFs) have emerged as adsorbent materials with the highest theoretical H2 storage densities on both a volumetric and gravimetric basis. However, a critical bottleneck for the use of H2 as a transportation fuel has been the lack of densification methods capable of shaping MOFs into practical formulations while maintaining their adsorptive performance. Here, we report a high-throughput screening and deep analysis of a database of MOFs to find optimal materials, followed by the synthesis, characterization, and performance evaluation of an optimal monolithic MOF (monoMOF) for H2 storage. After densification, this monoMOF stores 46 g L-1 H2 at 50 bar and 77 K and delivers 41 and 42 g L-1 H2 at operating pressures of 25 and 50 bar, respectively, when deployed in a combined temperature-pressure (25-50 bar/77 K → 5 bar/160 K) swing gas delivery system. This performance represents up to an 80% reduction in the operating pressure requirements for delivering H2 gas when compared with benchmark materials and an 83% reduction compared to compressed H2 gas. Our findings represent a substantial step forward in the application of high-density materials for volumetric H2 storage applications.

2 schemes, 8 figures.-- Supplementary information available., A series of nanostructured boron-TiO2 photocatalysts (B-X-TiO2-T) were prepared by sol–gel synthesis using titanium tetraisopropoxide and boric acid. The effects of the synthesis variables, boric acid amount (X) and crystallization temperature (T), on structural and electronic properties and on the photocatalytic performance for propene oxidation, are studied. This reaction accounts for the remediation of pollution caused by volatile organic compounds, and it is carried out at low concentrations, a case in which efficient removal techniques are difficult and costly to implement. The presence of boric acid during the TiO2 synthesis hinders the development of rutile without affecting the textural properties. X-ray photoelectron spectroscopy analysis reveals the interstitial incorporation of boron into the surface lattice of the TiO2 nanostructure, while segregation of B2O3 occurs in samples with high boron loading, also confirmed by X-ray diffraction. The best-performing photocatalysts are those with the lowest boron loading. Their high activity, outperforming the equivalent sample without boron, can be attributed to a high anatase and surface hydroxyl group content and efficient photo-charge separation (photoelectrochemical characterization, PEC), which can explain the suppression of visible photoluminescence (PL). Crystallization at 450 °C renders the most active sample, likely due to the development of a pure anatase structure with a large surface boron enrichment. A shift in the wavelength-dependent activity profile (PEC data) and the lowest electron–hole recombination rate (PL data) are also observed for this sample., The authors thank funding to the Spanish Ministry of Science, Innovation and Universities and FEDER, project of reference RTI2018-095291-B-I00, GV/FEDER (PROMETEO/2018/076), and University of Alicante (VIGROB-136) for financial support. Financial support from Spanish MICINN/AEI under projects PID2019-104272RB-C51/AEI/10.13039/501100011033 and PID2019-104272RB-C53/AEI/10.13039/501100011033 and the Diputación General de Aragón under project T03_20R (Grupo Reconocido) is acknowledged.

According to our knowledge, single-atom Pd catalysts supported on covalent triazine frameworks (CTF) have not been studied in the production of hydrogen from formic acid. Therefore, we synthesized 1 wt % Pd single-atom catalysts based on CTF-1, pyCTF, and bipyCTF supports and tested them in the gas-phase decomposition of formic acid. The results were compared with those obtained for a Pd catalyst supported on mesoporous graphitic-type carbon (Pd/C) with nanoparticles (∼2.3 nm). The catalysts were characterized by high-angle annular dark-field/scanning transmission electron microscopy (HAADF/STEM), extended X-ray absorption fine structure/X-ray absorption near-edge structure (EXAFS/XANES), and X-ray photoelectron spectroscopy (XPS) methods. The following order of catalytic activity was obtained: Pd/CTF-1 > Pd/C > Pd/pyCTF ≥ Pd/bipyCTF. The best performance of the Pd/CTF-1 catalyst was associated with Pd2+–C2N2 sites. Pd2+–N4 sites formed on pyCTF and bipyCTF supports showed lower catalytic activity. The selectivity trend at temperatures above 500 K was as follows: Pd/bipyCTF > Pd/pyCTF > Pd/CTF-1 > Pd/C. For the Pd/bipyCTF catalyst, the selectivity reached 99.8%, which is very high for this temperature range. These results may be important for the development of CTF-based catalysts for hydrogen production reactions. This work was supported by the Russian Science Foundation (Grant 22-23-00608). H.S.J. is grateful for the Ghent University and UGent Concerted Research Action funding via GOA010-17 for the synthesis and characterization of the CTF-based supports.

The aim of this study was to determine the adsorption performance of a petroleum pitch-based activated carbon (PPAC1:3) before and after a post-treatment with H2S. In the first step, a microporous activated carbon (PPAC1:3) with a highly developed porous structure was produced through a chemical activation route with KOH. Afterward, the synthesized activated carbon was thermally treated yielding two different series of functionalized activated carbons: (i) a series of carbons were treated directly with H2S at elevated temperatures (600 °C and 800 °C), and (ii) a series of carbons were generated by combining an oxidation treatment with plasma followed by H2S treatment at elevated temperatures (600 °C and 800 °C). The chemical and structural characteristics of the S-doped and S-/O-co-doped porous carbons were investigated by means of different experimental techniques, such as XRD, RAMAN, FESEM, XPS, TPD, N2, and CO2 adsorption, and finally tested in CO2 and CH4 adsorption at atmospheric and high pressure. The functionalized porous carbons possessed specific surface areas of 2420–2690 m2/g, total pore volume of 1.05–1.18 cm3/g, and sulfur content up to 2.55 atom % (the sulfur content of the original carbon was 0.19%). After a careful analysis of the carbon dioxide and methane uptake at atmospheric (0.1 MPa) and high pressure (4 MPa), adsorption results confirm that the microporous structure is the main structural parameter defining the adsorption performance and, to a lower extent, the surface chemistry. Overall, a significant improvement in the total uptake can be appreciated after the H2S treatment. This research was funded by MCIN, and NATO. The authors would like to acknowledge financial support from the Ministerio de Ciencia e Innovación—MCIN (projects PID2019-108453GB-C21, MCIN/AEI/10.13039/501100011033 and EU “NextGeneration/PRTR” (project PCI2020-111968/3D-Photocat)), and NATO SPS program (project G5683).

MXenes are a new family of 2D carbides or nitrides that have attracted attention due to their layered structure, tunable surface groups and high electrical conductivity. Here, we report for the first time that Ti 2 CT x MXene catalyses the selective oxidative dehydrogenation of n -butane to butenes and 1,3-butadiene. This catalyst showed higher intrinsic activity compared to commercial TiC and TiO 2 samples in terms of C 4 olefin formation rate. We propose that the stabilisation of structural vacancies and the change in composition (from a carbide to a mixed phase oxide) in the MXene causes its higher catalytic activity. These vacancies can lead to a higher concentration of unpaired electrons in the MXene-derived material, enhancing its nucleophilic properties and favouring the production of olefins. We thank the Netherlands Organization for Scientific Research (NWO) for the grant “Developing novel catalytic materials for converting CO2, methane and ethane to high-value chemicals in a hybrid plasma-catalytic reactor” (China.15.119). EVRF thanks the “Ministerio de Ciencia e innovación” grant (PID2020-116998RB-I00).