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Microporous activated carbons with remarkably high CO2 uptake have been synthesized using polyurethane (PU) commercial foams as precursors. The PU samples were pyrolyzed at different temperatures in N2 atmosphere and chemically activated with KOH. Adsorption isotherms at 0 °C and 25 °C and immersion calorimetry were applied to provide a deeper knowledge about the most relevant factors implied in CO2 capture process explaining, hence, the values of adsorption obtained. CO2 adsorption uptakes reached values of 7.4 mmol/g at 0 °C, 5.0 mmol/g at 25 °C and 2.7 mmol/g at 50 °C. The remarkably high values of CO2 uptake are closely related with the BET specific surface area of the carbon foams but also with the high volume of narrow micropores all the samples present a high volume of micropores (between 0.59 and 0.71 cm3/g) as also confirmed by immersion calorimetry. This work received financial support from MINECO (MAT2016-80285-p), GV (PROMETEOII/2014/004), H2020 Spain (MSCA-RISE-2016/NanoMed Project). Financial support of the National Council for Scientific and Technological Development (CNPq-Brazil) is also acknowledged.

Two micro-mesoporous carbons (MMCs): a disordered mesoporous carbon (DMC) and an ordered mesoporous carbon (OMC), synthesized by an easy, low-cost, and green method are proposed as efficient hydrocarbon sieves for the separation of C6 isomers: n-hexane (nHEX), 2-methylpenthane (2 MP) and 2,2-dimethylbutane (22DMB). Their textural characterization reveals a highly interconnected pore network within the DMC, while a reverse hierarchy of ordered mesopores only accessible through narrow micropores is found in the OMC. The pore texture strongly affects their adsorption performance by kinetic and molecular sieving effects; the narrow constrictions in the OMC allow adsorption of nHEX and partially 2 MP but not 22DMB, whereas the highly connected pore network of DMC allows adsorption of the three isomers. Multi-component adsorption isotherms calculated from the single-component experimental results by ideal adsorbed solution theory (IAST) demonstrates that the OMC material has a remarkably high selectivity for the adsorption of nHEX and nHEX + 2 MP from binary and ternary mixtures, respectively. To the best of the authors’ knowledge, such behavior has never been reported so far for carbon materials. Hence, this study shows that tannin-derived MMCs have great potential to be used as an eco-friendly and low-cost alternative for the selective separation of di-branched C6 isomers. Jimena Castro-Gutiérrez gratefully acknowledges CONACYT-SENER for the scholarship awarded (601021/438978) to support her PhD studies, resulting in the work presented herein. This study was partly funded by the French PIA project "Lorraine Université d’Excellence”, reference ANR-15-IDEX-04-LUE, and TALiSMAN project, funded by FEDER (2019-000214). Joaquín Silvestre-Albero would like to acknowledge the financial support from MINECO (PID2019-108453GB-C21) and H2020 (MSCA-RISE-2016/NanoMed Project).

The presence of porosity critically affects the performance of solid systems. The pore accessibility to adsorbate molecules and the corresponding adsorption/desorption behavior are crucial aspects to understand the properties of porous materials but are difficult to address, principally when dealing with narrow micropores. A prominent example is colloidal silica (Stöber) spheres whose microporosity, inaccessible for some adsorbates, can be readily filled by water molecules to a large extent but exhibiting a complex adsorption behavior with unexpected hystereses. Here, we perform water adsorption isotherms on Stöber spheres at different temperatures using an original analysis of the Dubinin-Radushkevich representation to examine both the accessibility to the microporosity and the formation of water multilayers on the outer sphere surface. The micropore filling (and emptying) is found to be limited by the kinetic energy of the water molecules, causing low-pressure hysteresis. We further discover that the (temperature-dependent) completion of the micropore filling delays the onset of multilayer adsorption, leading to hysteresis at a high relative pressure. The number of adsorbed water layers is determined, and the adsorption-induced swelling of the spheres is discussed., This work was funded by Spanish MINECO projects MAT2014-58731-JIN and MAT2016-80285-p, and Spanish MCIU project RTI2018-093921-B-C41.

The selectivity of 1-butene hydrogenation/isomerization on Pd catalysts is known to be particle size dependent. Here we show that combining well-defined model catalysts, atmospheric pressure reaction kinetics, DFT calculations and microkinetic modeling enables to rationalize the particle size effect based on the abundance and the specific properties of the contributing surface facets., The selectivity of Pd catalysts in 1-butene hydrogenation and isomerization depends on nanoparticle size. Herein, the authors show by combining experiment and modeling that the type and specific properties of the contributing surface facets are decisive for the selectivity.

The cleaning or removal of manganese stains on Cultural Heritage has not been much tested or successful so far. The aim of this article was to assess a new green cleaning gel for Mn-rich black-blue stains on different substrates. The black-blue stains were characterized at optical and chemical level through RGB data, colorimetry, optical microscope, FTIR, XRF and XPS. Mn-stained granite found on historical churches at Vila Real (North of Portugal) and glass jars of Leclanché cells, belonging to the ISEP’s Museum (Portugal) collection, were the ideal case studies to test the efficiency of Chitosan:Thiourea Dioxide (TD) cleaning gel. TD proved to be the best candidate to reduce insoluble manganese oxides, over Hydroxylamine Hydrochloride and Hydroxymethanesulfinic Acid. Cleaning assays performed on stained granite samples collected at a historical quarry and in situ application on stained granite churches showed the complete removal of the stains. Similar results were obtained on stained glass jars. This article presents an innovative, feasible and green Chitosan gel embedded with TD and phosphoric acid, applied to the cleaning of Mn-stained granite and glass substrates.

The catalytic reduction of nitrites over Pt-In catalysts supported on activated carbon has been studied in a semi-batch reactor, at room temperature and atmospheric pressure, and using hydrogen as the reducing agent. The influence of the indium content on the activity and selectivity was evaluated. Monometallic Pt catalysts are very active for nitrite reduction, but the addition of up to 1 wt% of indium significantly increases the nitrogen selectivity from 0 to 96%. The decrease in the accessible noble metal surface area reduces the amount of hydrogen available at the catalyst surface, this favoring the combination of nitrogen-containing intermediate molecules to promote the formation of N2 instead of being deeply hydrogenated into NH4+. Several activated carbon-supported Pt-In catalysts, activated under different calcination and reduction temperatures, have been also evaluated in nitrite reduction. The catalyst calcined and reduced at 400°C showed the best performance considering both the activity and the selectivity to nitrogen. This enhanced selectivity is ascribed to the formation of Pt-In alloy. The electronic properties of Pt change upon alloy formation, as it is demonstrated by XPS. This work was financially supported by Base-UIDB/50020/2020 and Programmatic-UIDP/50020/2020 Funding of LSRE-LCM, funded by natiunal funds through FCT/MCTES (PIDDAC). Financial support from Ministerio de Ciencia e Innovación (Spain, Project PID 2019-108453GB-C21 and PID 2020-116998RB-I00) is gratefully acknowledged.

This article discloses a rare and outstanding type of Mn-rich black-blue patina found on mural painting and granite ashlars located in the church of Sta. Marinha, north of Portugal, and conjectures the phenomenon associated to the appearance of such patinas in different surface materials. This Mn-patina reported on mural painting and their origin is probably assigned to manganese leaching from building materials (i.e., granite and phyllites). Stained mural painting and granite examined by XPS and SEM have showed patinas enriched with manganese (IV) oxide, potentially catalysed by a microbiota, like fungi, observed in SEM micrographs. The pigments used to depict mural painting and groundwater were also analysed by micro-Raman and ICP-MS, respectively, indicating that they are unlikely manganese sources. Unstained building materials, such as granite ashlars, historic joints, mortars and phyllite rocks, were also analysed by ICP-MS showing that historic joints and mortars present significant concentrations of manganese, possibly associated to their absorbing feature. The main materials with potential to impart manganese to Mn-rich patinas are granite ashlars and phyllites. The aim of this investigation is to reveal and ascertain the hypothetical sources and the phenomenon responsible for the Mn-rich black-blue patina appearance, both on mural painting and granite ashlars. We would like to thanks the financial support of the project BIO4MURAL—Biotechnology innovative solutions for the removal of pigmentation and preventive conservation of cultural and historically relevant mural painting was funded by FEDER through project reference POCI-01-0145-FEDER-029157—Operational Competitiveness and Internationalization Program and by National Funds from FCT—Foundation for Science and Technology (PTDC/HAR-ARQ/29157/2017); Alexandra Marco PhD research was supported by Foundation for Science and Technology (FCT) through POCH—Operational Human Capital Program, co-participated by the Social European Fund (FSE) and MCTES National Fund (SFRH/BD/125596/2016); Dr. David M. Freire-Lista is supported by FCT through Stimulus of Scientific Employment, Individual Support 2017. CEECIND/03568/2017. HERCULES Laboratory—Évora University and E-RHIS.pt infra-structure for the access to the platforms PT-MOLAB and PT-FIXLAB; and scientific collaboration through the Strategic Projects CITAR (UID/EAT/0622/2016), CBQF (UID/Multi/50016/2013) and GEOBIOTEC (UID/GEO/04035/2020).

Carbon dioxide (CO2) is both a primary contributor to global warming and a major industrial impurity. Traditional approaches to carbon capture involve corrosive and energy-intensive processes such as liquid amine absorption. Although adsorptive separation has long been a promising alternative to traditional processes, up to this point there has been a lack of appropriate adsorbents capable of capturing CO2 whilst maintaining low regeneration energies. In the context of CO2 capture, metal–organic frameworks (MOFs) have gained much attention in the past two decades as potential materials. Their tuneable nature allows for precise control over the pore size and chemistry, which allows for the tailoring of their properties for the selective adsorption of CO2. While many candidate materials exist, the amount of research into material shaping for use in industrial processes has been limited. Traditional shaping strategies such as pelletisation involve the use of binders and/or mechanical processes, which can have a detrimental impact on the adsorption properties of the resulting materials or can result in low-density structures with low volumetric adsorption capacities. Herein, we demonstrate the use of a series of monolithic MOFs (monoUiO-66, monoUiO-66-NH2 & monoHKUST-1) for use in gas separation processes., The use of metal–organic frameworks (MOFs) in industry has been limited due to a lack of shaping technologies. Monolithic MOFs (monoMOFs) offer a viable alternative to traditional shaping offering high density materials for adsorption processes.

The catalytic reduction of nitrites over Pt-In catalysts supported on activated carbon has been studied in a semi-batch reactor, at room temperature and atmospheric pressure, and using hydrogen as the reducing agent. The influence of the indium content on the activity and selectivity was evaluated. Monometallic Pt catalysts are very active for nitrite reduction, but the addition of up to 1 wt% of indium significantly increases the nitrogen selectivity from 0 to 96%. The decrease in the accessible noble metal surface area reduces the amount of hydrogen available at the catalyst surface, this favoring the combination of nitrogen-containing intermediate molecules to promote the formation of N2 instead of being deeply hydrogenated into NH4+. Several activated carbon-supported Pt-In catalysts, activated under different calcination and reduction temperatures, have been also evaluated in nitrite reduction. The catalyst calcined and reduced at 400°C showed the best performance considering both the activity and the selectivity to nitrogen. This enhanced selectivity is ascribed to the formation of Pt-In alloy. The electronic properties of Pt change upon alloy formation, as it is demonstrated by XPS.

Immersion calorimetry into liquids of different dimensions is a powerful tool to learn about the pore size and shape in nanoporous solids. In general, in the absence of specific interactions with the solid surface, the accessibility of the liquid probe molecule to the inner porosity and the associated enthalpy value decreases with an increase in its kinetic diameter (bulkier molecules have lower accessibility and packing density). Although this is true for the majority of solids (e.g., activated carbons and zeolites), this study anticipates that this is not straightforward in the specific case of metal–organic frameworks (MOFs). The evaluation of different hydrocarbons and their derivatives reveals the presence of reverse selectivity for C6 isomers (2,2-dimethylbutane > 2-methylpentane > n-hexane) in UiO-66 and HKUST-1, whereas size exclusion effects take place in ZIF-8. The immersion calorimetric findings have been compared with vapor adsorption isotherms and computational studies. Monte Carlo simulations suggest that the reverse selectivity in UiO-66 is attributed to the strong confinement of the dibranched hydrocarbons in the small tetragonal cages, whereas the presence of strong interactions with the open metal sites accounts for the preferential adsorption in HKUST-1. These results open the gate toward the application of immersion calorimetry for the prescreening of MOFs to identify in an easy, fast and reliable way interesting characteristics and/or properties such as separation ability, reversed hierarchy, pore-window size, presence of unsaturated metal sites, molecular accessibility, and so on. Authors would like to acknowledge financial support from MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004) and H2020 (MSCA-RISE-2016/NanoMed Project). P.Z.M. is grateful for start-up funds from the University of Sheffield.

Structural changes in ZIFs upon adsorption remain a paradigm due to the sensitivity of the adsorption mechanism to the nature of the organic ligands and gas probe molecules. Synchrotron X-ray diffraction under operando conditions clearly demonstrates for the first time that ZIF-4 exhibits a structural reorientation from a narrow-pore (np) to a new expanded-pore (ep) structure upon N2 adsorption, while it does not do so for CO2 adsorption. The existence of an expanded-pore structure of ZIF-4 has also been predicted by molecular simulations. In simulations the expanded structure was stabilized by entropy at high temperatures and by strong adsorption of N2 at low temperatures. These results are in perfect agreement with manometric adsorption measurements for N2 at 77 K that show the threshold pressure for breathing at ∼30 kPa. Inelastic neutron scattering (INS) measurements show that CO2 is also able to promote structural changes but, in this specific case, only at cryogenic temperatures (5 K). The authors would like to acknowledge financial support from the MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004), H2020 (MSCA-RISE-2016/NanoMed Project), Spanish ALBA synchrotron (Projects AV-2017021985 and IH-2018012591) and Oak Ridge beam time availability (Project IPTS-20843.1). JSA and JGL acknowledge financial support from UA (ACIE17-15) to cover all the expenses for INS measurements at Oak Ridge. JGL acknowledges GV (GRISOLIAP/2016/089) for the research contract.

Covalent organic frameworks (COFs) have emerged as a versatile materials platform for applications including chemical separations, water purification, chemical reaction engineering and energy storage. Their inherently low mechanical stability, however, frequently renders existing methods of pelletisation ineffective contributing to pore collapse, pore blockage or insufficient densification of crystallites. Here, we present a general process for the shaping and densifying of COFs into centimetre-scale porous monolithic pellets without the need for templates, additives or binders. This process minimises mechanical damage from shear-induced plastic deformation and further provides a network of interparticle mesopores that we exploit in accessing analyte capacities above those achievable from the intrinsic porosity of the COF framework. Using a lattice-gas model, we accurately capture the monolithic structure across the mesoporous range and tie pore architecture to performance characteristics in both gas storage and separation applications. Collectively, these findings represent a substantial step in the practical applicability of COFs and other mechanically weak porous materials.

Activated charcoal (AC) can be taken orally as enterosorbent for treatment of pathological states related to exogenous and endogenous intoxications. Synthesized granulated AC with a highly developed active surface (SBET ~2700 m2/g) was used as a medical countermeasure (MCM) to acute radiation sickness (ARS) in rats after total body X-ray irradiation. AC demonstrates positive results in ARS treatment, as expressed in, (i) a decrease in body weight loss, (ii) a protection of bone marrow (BM) cells colony formation capacity, (iii) a reduction of BM chromosomal aberrations and small intestine and spleen tissue damage, (iv) an amelioration of white blood cell count, and (v) a mitigation of superoxide ion generation rate in the liver. AC oral prescription seems to be perspective modality of ARS treatment. This research was funded by H2020-MSCA-RISE-2016 project, grant number 734641 acronym NanoMed.

The evaluation of the flexibility in zeolitic imidazolate frameworks (ZIFs) has been very useful to understand their performance in gas adsorption and separation applications. Here, we have evaluated the adsorption properties of a nanoporous mixed-linker ZIF-62 using a combination of gas adsorption measurements, grand canonical Monte Carlo simulations, and synchrotron X-ray powder diffraction under operando conditions. While adsorption studies in nanoporous ZIF-62 at 77 K and atmospheric pressure predict a large O2/N2 separation ability, computational studies anticipate that the observed differences must be attributed to kinetic restrictions of N2 to access the internal porosity at cryogenic temperatures. Interestingly, upon a small increase in the adsorption temperature (90 K vs 77 K), both N2 and O2 are able to access the inner porous structure through the promotion of a phase transition (ca. 3.8% volume expansion) upon gas adsorption. This narrow phase (np) to expanded phase (ep) structural transition in ZIF-62 is completely suppressed above 150 K. Based on the excellent molecular sieve properties of nanoporous ZIF-62 for O2/N2 at cryogenic temperatures, we extended our study to the adsorption of linear and branched hydrocarbons. This study predicts the preferential adsorption of alkanes over alkenes in ZIF-62 for small hydrocarbons (C2), while in the case of C3 hydrocarbons and above, the adsorption process is mainly defined by kinetic restrictions. J.S.-A. acknowledges financial support from the MINECO (Projects MAT2016-80285-p and PID2019-108453GB-C21). The authors acknowledge ALBA for providing beamtime (Project No. 2019023264). Computational work was supported by the Cambridge High-Performance Computing Service, the Cambridge Service for Data-Driven Discovery (CSD3).

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c08942., L.H.W. acknowledges the Fonds Wetenschappelijk Onderzoek (FWO) - Vlaanderen for a senior postdoctoral research fellowship and International Mobility fellowship under contract numbers of 12M1418N and V402319N, respectively. S.V.D.B., S.M.J.R., and J.W. acknowledge Fonds Wetenschappelijk Onderzoek (FWO) - Vlaanderen for Grants 11U1914N, 12T3519N, and 1103618N as well as the Research Board of Ghent University (BOF). J.A.R.N. acknowledges generous funding from the Spanish Ministry of Economy (CTQ2014- 53486-R) and FEDER from the European Union. Funding was also received from the European Union’s Horizon 2020 Research and Innovation Programme [ERC Consolidator Grant Agreement 647755 - DYNPOR (2015−2020)]. J.A.M. and C.E.A.K. gratefully acknowledge financial support from the Flemish Government (Long-term structural funding Methusalem and FWO support). Collaboration among universities was supported by the Belgian Government (IAP-PAI network)., Molecular separation of carbon dioxide (CO2) and methane (CH4) is of growing interest for biogas upgrading, carbon capture and utilization, methane synthesis and for purification of natural gas. Here, we report a new zeolitic-imidazolate framework (ZIF), coined COK-17, with exceptionally high affinity for the adsorption of CO2 by London dispersion forces, mediated by chlorine substituents of the imidazolate linkers. COK-17 is a new type of flexible zeolitic-imidazolate framework Zn(4,5-dichloroimidazolate)(2) with the SOD framework topology. Below 200 K it displays a metastable closed-pore phase next to its stable open-pore phase. At temperatures above 200 K, COK-17 always adopts its open-pore structure, providing unique adsorption sites for selective CO2 adsorption and packing through van der Waals interactions with the chlorine groups, lining the walls of the micropores. Localization of the adsorbed CO2 molecules by Rietveld refinement of X-ray diffraction data and periodic density functional theory calculations revealed the presence and nature of different adsorption sites. In agreement with experimental data, grand canonical Monte Carlo simulations of adsorption isotherms of CO2 and CH4 in COK-17 confirmed the role of the chlorine functions of the linkers and demonstrated the superiority of COK-17 compared to other adsorbents such as ZIF-8 and ZIF-71., FWO 12M1418N V402319N 11U1914N 12T3519N 1103618N, Spanish Ministry of Economy CTQ201453486-R, FEDER from the European Union, European Union's Horizon 2020 Research and Innovation Programme [ERC] 647755 - DYNPOR, Flemish Government (Long-term structural funding Methusalem), FWO, Belgian Government (IAP-PAI network)

Novel MOF-based polymer nanocomposite films were successfully prepared using Zr-based UiO-67 as a metal–organic framework (MOF) and polyurethane (PU) as a polymeric matrix. Synchrotron X-ray powder diffraction (SXRPD) analysis confirms the improved stability of the UiO-67 embedded nanocrystals, and scanning electron microscopy images confirm their homogeneous distribution (average crystal size ∼100–200 nm) within the 50 μm thick film. Accessibility to the inner porous structure of the embedded MOFs was completely suppressed for N2 at cryogenic temperatures. However, ethylene adsorption measurements at 25 °C confirm that at least 45% of the MOF crystals are fully accessible for gas-phase adsorption of nonpolar molecules. Although this partial blockage limits the adsorption performance of the embedded MOFs for ocular drugs (e.g., brimonidine tartrate) compared to the pure MOF, an almost 60-fold improvement in the adsorption capacity was observed for the PU matrix after incorporation of the UiO-67 nanocrystals. The UiO-67@PU nanocomposite exhibits a prolonged release of brimonidine (up to 14 days were quantified). Finally, the combined use of SXRPD, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) analyses confirmed the presence of the drug in the nanocomposite film, the stability of the MOF framework and the drug upon loading, and the presence of brimonidine in an amorphous phase once adsorbed. These results open the gate toward the application of these polymeric nanocomposite films for drug delivery in ocular therapeutics, either as a component of a contact lens, in the composition of lacrimal stoppers (e.g., punctal plugs), or in subtenon inserts. The authors would like to acknowledge financial support from MINECO (MAT2016-80285-p), Spanish ALBA Synchrotron (Project 2020014008), and H2020 (MSCA-RISE-2016/NanoMed Project). B.E.S. thanks the Minas Gerais Research Foundation (FAPEMIG CNPJ n21.949.888/0001-83) for a DPhil scholarship award. J.-C.T. thanks the EPSRC (Grant No. EP/N014960/1) and ERC Consolidator Grant (PROMOFS under the grant agreement 771575) for funding.

This review article is dedicated to the memory of Francisco (Paco) Rodriguez-Reinoso (Granada 1941 - Alicante 2020). Paco dedicated more than 56 years of his life to research on carbon materials, covering from their synthesis and characterization, to their evaluation using a range of processes such as gas adsorption/separation, heterogeneous catalysis, and drug delivery, among others. His extensive research was mainly performed in the Advanced Materials Laboratory (LMA) located at the University of Alicante, Spain. This research has been reflected in more than 400 research articles in high quality international journals. This review article summarizes some of Paco’s main achievements in carbon-related research emphasizing his main contributions and perspectives in the field.

Selective CO2 capture in industrial streams is of paramount importance to decrease actual emissions to the atmosphere, and to minimize the associated environmental concerns. Among the different possibilities to capture CO2, adsorption using nanoporous networks is one of the most promising approaches, provided that the adsorbent can be properly designed in terms of porous structure and surface chemistry. The material has to be designed to achieve a preferential interaction with CO2 versus other competing molecules (e.g., CH4, N2, O2, etc.) also present in the industrial effluents. Promising adsorbents for CO2 capture include activated carbons, zeolites, and metal–organic frameworks (MOFs), among others. This chapter will focus on activated carbon materials and the effect of the porous structure and surface chemistry in the selective adsorption of CO2. Although the chapter will concentrate mainly in physisorption processes, a final section will be introduced devoted to a novel approach for CO2 capture based on natural processes, the so-called solid state storage.

The structural deterioration of archetypical, well‐faceted metal–organic frameworks (MOFs) has been evaluated upon exposure to an acidic environment (H2S). Experimental results show that the structural damage highly depends on the nature of the hybrid network (e.g., softness of the metal ions, hydrophilic properties, among others) and the crystallographic orientation of the exposed facets. Microscopy images show that HKUST‐1 with well‐defined octahedral (111) facets is completely deteriorated, ZIF‐8 with preferentially exposed (110) facets exhibits a large external deterioration with the development of holes or cavities in the mesoporous range, whereas UiO‐66‐NH2 with (111) exposed facets, and PCN‐250 with (100) facets does not reflect any sign of surface damage. Despite the selectivity in the external deterioration, X‐ray diffraction and gas adsorption measurements confirm that indeed all MOFs suffer an important internal deterioration, these effects being more severe for MOFs based on softer cations (e.g., Cu‐based HKUST‐1 and Fe‐based PCN‐250). These structural changes have inevitable important effects in the final adsorption performance for CO2 and CH4 at low and high pressures., JSA would like to acknowledge financial support from the MINECO (Project MAT2016‐80285‐p). I.I. and D.M. would like to acknowledge financial support from the Spanish MINECO (Project RTI2018‐095622‐B‐100), and Catalan AGAUR (Project 2017 SGR 238), the ERC, under the EU‐FP7 (ERC‐Co 615954) and the CERCA Program/Generalitat de Catalunya. ICN2 is supported by the Severo Ochoa Program from the Spanish MINECO (Grant No. SEV‐2017‐0706).

Mitochondria play a key role in oncogenesis and constitute one of the most important targets for cancer treatments. Although the most effective way to deliver drugs to mitochondria is by covalently linking them to a lipophilic cation, the in vivo delivery of free drugs still constitutes a critical bottleneck. Herein, we report the design of a mitochondria-targeted metal–organic framework (MOF) that greatly increases the efficacy of a model cancer drug, reducing the required dose to less than 1% compared to the free drug and ca. 10% compared to the nontargeted MOF. The performance of the system is evaluated using a holistic approach ranging from microscopy to transcriptomics. Super-resolution microscopy of MCF-7 cells treated with the targeted MOF system reveals important mitochondrial morphology changes that are clearly associated with cell death as soon as 30 min after incubation. Whole transcriptome analysis of cells indicates widespread changes in gene expression when treated with the MOF system, specifically in biological processes that have a profound effect on cell physiology and that are related to cell death. We show how targeting MOFs toward mitochondria represents a valuable strategy for the development of new drug delivery systems. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (NanoMOFdeli), ERC-2016-COG 726380, and (SCoTMOF), ERC-2015-STG-677289. D.F.-J. and R.S.F. thank the Royal Society for funding through University Research Fellowships. C.F.K. acknowledges funding from the UK Engineering and Physical Sciences Research Council, EPSRC (grants EP/L015889/1 and EP/H018301/1), the Wellcome Trust (grants 3-3249/Z/16/Z and 089703/Z/09/Z) and the UK Medical Research Council, MRC (grants MR/K015850/1 and MR/K02292X/1), and Infinitus (China) Ltd. We thank EPSRC (grant EP/S009000/1).

A high-surface area activated carbon material (PPAC) prepared from a petroleum residue has been used as a host structure to promote the nucleation and growth of confined methane hydrates after the incorporation of additives. Sodium dodecyl sulfate (SDS), Leucine and Tetrahydrofuran (THF) have been evaluated either dissolved in the pre-impregnation media (ultrapure water) or incorporated in the carbon surface using a mechanochemical approach. High-pressure methane adsorption isotherms show that the mechanochemical approach does not improve the storage performance of the original carbon material due to the steric effects by the bulkier organic functionalities. Furthermore, the incorporation of the additives shifts the nucleation in narrow pores to higher pressures. On the contrary, when the additives are dissolved in water, high-pressure methane isotherms anticipate a modification in the kinetics and/or thermodynamics of the nucleation process. Whereas gas hydrates grown in large pores and/or the external surface exhibits a significant reduction in the induction time, the nucleation process in narrow micropores becomes more uniform and occurs in a narrower pressure window, slightly shifted to higher pressures. However, no changes in the total uptake at 10 MPa could be found. The situation is different when THF is dissolved in water. In this case, the nucleation takes place at pressures below the natural process (

Porous metal–organic frameworks (MOFs) capable of storing a relatively high amount of dry methane (CH4) in the adsorbed phase are largely explored; however, solid CH4 storage in confined pores of MOFs in the form of hydrates is yet to be discovered. Here we report a rational approach to form CH4 hydrates by taking advantage of the optimal pore confinement in relatively narrow cavities of hydrolytically stable MOFs. Unprecedentedly, we were able to isolate methane hydrate (MH) nanocrystals with an sI structure encapsulated inside MOF pores with an optimal cavity dimension. It was found that confined nanocrystals require cavities slightly larger than the unit cell crystal size of MHs (1.2 nm), as exemplified in the experimental case study performed on Cr-soc-MOF-1 vs smaller cavities of Y-shp-MOF-5. Under these conditions, the excess amount of methane stored in the pores of Cr-soc-MOF-1 in the form of MH was found to be ≈50% larger than the corresponding dry adsorbed amount at 10 MPa. More importantly, the pressure gradient driving the CH4 storage/delivery process could be drastically reduced compared to the conventional CH4-adsorbed phase storage on the dry Cr-soc-MOF-1 (≤3 MPa vs 10 MPa). G.M., M.E., and Y.B. thank the Aramco sponsored research fund (contract. 66600024505). We would like also to acknowledge the support by King Abdullah University of Science and Technology. J.S.A. would like to acknowledge financial support from the MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004), Oak Ridge beam time availability (Project IPTS-20859.1), and Spanish ALBA synchrotron (Project 2020014008). INS experiments were conducted at the VISION beamline (IPTS-20859) at the Spallation Neutron Source, Oak Ridge National Laboratory (ORNL), which is supported by the Scientific User Facilities Division, Office of Basic Energy Sciences (BES), U.S. Department of Energy (DOE), under contract no. DE-AC0500OR22725 with UT Battelle, LLC. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by the Laboratory Directed Research and Development programme and by Compute and Data Environment for Science (CADES) at ORNL.

Mesoporous MgO was synthesized by the nanoreplication method using CMK-3 carbon as a hard template and magnesium nitrate as a metal oxide precursor. The produced support was modified with different amounts of ammonium metavanadate solution. Various distributions of V-containing species on the MgO surface were found by XRD, low-temperature adsorption of N2, TEM, XPS and UV–vis-DR spectroscopy. At low V loadings isolated VO4 dominated. Increasing V content resulted in clustering of VO4 species and the formation of Mg3V2O8 crystallites. As found in temperature-programmed reduction (H2-TPR), the latter phase was clearly harder in reduction by H2 compared to highly dispersed VO4 forms. The developed materials appeared to be very active catalysts of oxidative dehydrogenation of ethylbenzene (ODH). The optimal catalytic performance was observed for the sample containing 10 wt% of vanadium. The initial ethylbenzene conversion of 63.6% at selectivity to styrene of 86.9% was achieved at temperature as low as 500 °C. A notable influence of carbonaceous deposit formed during the ODH reaction on the catalytic activity was discussed, including presentation of both coexisting superficial reaction mechanisms. A reasonable regeneration procedure to recover lost activity was developed. This work was supported by the Polish National Science Centre (grant no. 2013/09/B/ST5/03419). The research was carried out with the equipment purchased thanks to the financial support of the European Regional Development Fund in the framework of the Polish Innovation Economy Operational Program (contract no. POIG.02.01.00-12-023/08). S.J. received a doctoral scholarship from the Polish National Science Centre (grant no. 2016/20/T/ST5/00256). J.S.A. acknowledges financial support by MINECO (Project MAT2016-80285-p), H2020 (MSCA-RISE-2016/NanoMed Project), and GV (PROMETEOII/2014/004).

A series of xerogels with a properly designed porous structure and surface chemistry have been synthesized and evaluated as a host structure to promote the nucleation and growth of methane hydrates. Organic xerogels (OGs) have been synthesized from resorcinol-formaldehyde mixtures using a sol-gel approach and microwave heating. These xerogels are hydrophilic in nature and possess designed meso/macrocavities in the pore size range 5–55 nm. Carbon xerogels (CGs) have been synthesized from their organic counterparts after a carbonization treatment at high temperature. Interestingly, the carbonization process does not alter/modify substantially the porous network of the parent xerogels, while developing new micropores. Under water-supplying conditions, the two types of xerogels exhibit a large improvement in the methane adsorption capacity compared to the pure physisorption process taking place in dry conditions (up to 200% improvement), and associated with a significant hysteresis loop. These excellent values must be associated with the promoting effect of these xerogels in the water-to-hydrate conversion process. The comparison of OGs and CGs as a host structure anticipates that surface chemistry, total pore volume and pore size are critical parameters defining the extent and yield of the methane hydrate formation process., Authors would like to acknowledge financial support from the MINECO (projects MAT2016-80285-p and CTQ2017-87820-R). Principado de Asturias-FICYT-FEDER (Project PCTI-Asturias IDI/2018/000118) is also acknowledged. L.A. Ramírez-Montoya thanks CONACyT, México, for a post-doctoral grant (CVU No 330625, 2017).

Freezing/melting behavior of water confined in the nanopores of activated carbon materials has been evaluated using differential scanning calorimetry (DSC) at different water loadings, and after the application of an external stimulus. Under atmospheric pressure conditions, the DSC scans show a depression in the freezing/melting point of confined water compared to the bulk system. Interestingly, water confined in narrow micropores (pores below 0.7 nm) does not exhibit any phase transition, i.e. it is non-freezable water. Inelastic neutron scattering (INS) data confirm the presence of a distorted molecular assembly in narrow micropores, whereas synchrotron X-ray powder diffraction data (SXRPD) demonstrate the non-freezable nature of the water confined in these narrow-constrictions. Similar experiments under high-pressure CH4 give rise to a completely different scenario. Under high-pressure conditions methane hydrates are formed with a water-to-hydrate yield of 100% for the under-saturated and saturated samples, i.e. in the presence of an external stimulus even water in narrow micropores is prone to experience a liquid-to-solid phase transition. These results confirm the beneficial role of carbon as a host structure to promote nucleation and growth of methane hydrates with faster kinetics and a higher yield compared to the bulk system and to other porous materials. The authors would like to acknowledge financial support from the MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004), H2020 (MSCA-RISE-2016/NanoMed Project), Spanish ALBA synchrotron (Projects 2018022707 & 2019023322) and Oak Ridge beam time availability (Project IPTS-20843.1).

This paper reports the results of an international interlaboratory study led by the National Institute of Standards and Technology (NIST) on the measurement of high-pressure surface excess methane adsorption isotherms on NIST Reference Material RM 8850 (Zeolite Y), at 25 °C up to 7.5 MPa. Twenty laboratories participated in the study and contributed over one-hundred adsorption isotherms of methane on Zeolite Y. From these data, an empirical reference equation was determined, along with a 95% uncertainty interval (Uk=2). By requiring participants to replicate a high-pressure reference isotherm for carbon dioxide adsorption on NIST Reference Material RM 8852 (ZSM-5), this interlaboratory study also demonstrated the usefulness of reference isotherms in evaluating the performance of high-pressure adsorption experiments. The instruments of the Facility for Adsorbent Characterization and Testing were funded by the Advanced Research Projects Agency-Energy (ARPA-E) through Interagency Agreement № 1208-0000.

Direct hydrogenation of CO2 to methanol is an interesting method to recycle CO2 emitted e.g., during combustion of fossil fuels. However, it is a challenging process because both the selectivity to methanol and its production are low. The metal-organic frameworks are relatively new class of materials with a potential to be used as catalysts or catalysts supports, also in the reaction of MeOH production. Among many interesting structures, the UiO-66 draws significant attention owing to its chemical and thermal stability, developed surface area, and the possibility of tuning its properties e.g., by exchanging the zirconium in the nodes to other metal cations. In this work we discuss&mdash, for the first time&mdash, the performance of Cu supported on UiO-66(Ce/Zr) in CO2 hydrogenation to MeOH. We show the impact of the composition of UiO-66-based catalysts, and the character of Cu-Zr and Cu-Ce interactions on MeOH production and MeOH selectivity during test carried out for 25 h at T = 200 &deg, C and p = 1.8 MPa. Significant increase of selectivity to MeOH was noticed after exchanging half of Zr4+ cations with Ce4+, however, no change in MeOH production occurred. It was found that the Cu-Ce coexistence in the UiO-66-based catalytic system reduced the selectivity to MeOH when compared to Cu/UiO-66(Zr), which was ascribed to lower concentration of Cu0 active sites in Cu/UiO-66(Ce/Zr), and this was caused by oxygen spill-over between Cu0 and Ce4+, and thus, the oxidation of the former. The impact of reaction conditions on the structure stability of tested catalyst was also determined.

Oxygen-enriched boron carbonitrides – known as boron carbon oxinitrides, BCNOs – have exhibited remarkable properties with numerous works reporting on their performance as phosphors and some few ones as H2-adsorbents. However, the study of BCNOs capability for CO2 uptaking has yet to be achieved. Herein, we have designed a simple process for preparation of freestanding three-dimensional (3D) BCNO structures via pyrolysis of supramolecular gels formed by H-bonding of melamine, boric acid and glucose. The 3D porous materials obtained by pyrolysis of supramolecular gels containing glucose exhibited a seaweed-like 3D structure formed by BCNO nanocrystals embedded within a carbonaceous matrix with a certain content of amorphous hydrogenated carbon. The particularly narrow porosities exhibited by these samples proved effective for CO2 adsorption with uptakes of up to ca. 1.8 mmol/g at 25 °C. More interestingly, those samples prepared with high concentration of glucose behaved as molecular sieves and exhibited an excellent performance for CO2–CH4 separation, especially at low pressures with kH values of up to 1.04∙103. This work was supported by MINECO/FEDER (Project Numbers MAT2015-68639-R and MAT2016-80285-P). N. López-Salas also acknowledges MINECO/FEDER for a FPI research contract. C. Cuadrado-Collados and J. Gandara-Loe acknowledge UA and GV (GRISOLIAP/2016/089) for their respective research contracts.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 0997–1001, June, 2018. Active carbons were synthesized from a furfural copolymer using a polyester resin as an activator. The influence of the temperature of the thermal treatment of the carbon sorbents on the weights and ash contents of the obtained materials was established. The molecular structures of the carbons were studied by NMR spectroscopy.

Applying a density functional approach to slab models of planar, (111), and rough, (110), Pd surfaces, we determined the isomerization free energy barriers of 1-butene to be significantly lower than the hydrogenation barriers. Microkinetic modeling allows one to mirror the kinetic experiments on conversions of 1-butene at the corresponding single-crystal surfaces in a qualitative fashion. Despite the inherent limitations of such kinetic modeling, theoretical predictions are fully supported by experimental data using Pd model catalysts: i.e., Pd(111) and Pd(110) surfaces. The isomerization mechanism was calculated to proceed via an initial dehydrogenation of 1-butene to 1-buten-3-yl as an intermediate—in contrast to the commonly proposed 2-butyl intermediate, associated with the Horiuti–Polanyi mechanism. Our modeling results rule out the original assumption that isomerization has to start with a hydrogenation step to rationalize the dependence of isomerization on hydrogen. However, this hydrogen dependence may arise in the second step, after an initial dehydrogenation, as suggested by the experimental data under hydrogen-deficient conditions. J.S.-A. acknowledges financial support by Generalitat Valenciana (BEST/2007/045) and MEC/OEAD (Acciones Integradas HU2006-002) supporting a research stay in Vienna. This work was supported by grant no. 1527700033 of the A*STAR Science and Engineering Research Council as well as generous allotments of computational resources at the National Supercomputing Center Singapore and the A*STAR Computational Resource Center.

This article summarizes the methodology of synthesis, surface functionalization and structural properties of rice husk-derived nanostructured carbon enterosorbents (biochars) in connection with the preliminary in vitro study results of uraemic toxin adsorption in model experiments, as well as preclinical trials in vivo. The obtained nanostructured carbon sorbents were studied using a number of modern physicochemical methods of investigation: low-temperature nitrogen adsorption, isotherms recording and calculation of the specific surface area, pore volumes were carried out using the Autosorb-1 "Quantachrome" device. Scanning electron microscopy and EDS-analysis. Mercury intrusion porosimetry analysis of the ACs were accomplished using "Quantachrome Poremaster" data analysis software. In vitro adsorption results assessed by use of HPLC and UV-spectroscopy for the nanostructured carbon sorbents with respect to the investigated low-molecule toxins suggest that the rice husks-derived carbon enterosorbents modified with the functional groups are able to reduce clinically significant levels of uraemic toxins and are comparable to the commercial enterosorbents. Based on the results of the comparative analysis for biocompatibility of canine kidney epithelial cells it was determined that the samples of the modified sorbents CRH-P-450 and CRH-475-KOH-850-N do not exhibit cytotoxicity in comparison with the commercial carbon enterosorbent «Adsorbix Extra». According to the results of the in vivo studies, it was determined that there was a positive effect of the enterosorbent CRH-P-450 on uremia and intoxication. This study is supported by both the Programme of research activities under the project titled “Surface Functionalised Nanostructured Carbon Sorbents for Health and the Environment” sponsored by the Royal Academy of Engineering within the Industry Academia Partnership Programme (IAPP\1516\3) between the UK and Kazakhstan and also the project titled "Nanoporous and Nanostructured Materials for Medical Applications" (Reference #734641/Acronym: NanoMed) within the EU "Horizon 2020" programme under the umbrella of "Marie Skłodowska-Curie Research and Innovation Staff Exchange" (H2020-MSCA-RISE-2016), as well as by Kazakhstan government projects titled: "Nanostructured Carbon Sorbents for Enteral Detoxification" (2015-2017) funded by the Committee of Science of the Ministry of Education and Science of the Republic of Kazakhstan.

Free-standing high performance Li–S battery cathodes are currently attracting significant research efforts. Loose macroporous structures have been proposed by many to improve sulfur utilization and areal capacity. However, their low cathode sulfur densities and high electrolyte fractions lead to low cell volumetric and gravimetric capacities. We report here a compact free-standing Li–S cathode structure that delivers areal, volumetric and gravimetric capacities all exceeding those of typical Li-ion batteries. The cathodes, formed by pressure filtration of the constituents, are composed of highly micro/mesoporous nitrogen-doped carbon nanospheres (NCNSs) embedded in the macropores of a multi-walled carbon nanotube (MWCNT) network to form a dense structure. The MWCNT network facilitates low cathode impedance. The NCNSs maximize sulfur utilization and immobilization. These collectively result in high cathode volumetric capacity (1106 mA h cm−3) and low electrolyte requirement (6 μL mg−1 of sulfur), which together lead to high cell-level gravimetric capacity. Stable long-term cycling at 0.3C (2.5 mA cm−2 for 5 mg cm−2 areal sulfur-loading) has also been achieved, with the areal and volumetric capacities of the best remaining above typical Li-ion values over 270 cycles and the per-cycle capacity fading being only 0.1%. The facile preparation means significant potential for large scale use. CH acknowledges a Postdoctoral Fellowship provided by Loughborough University.

This work constitutes a guide towards the preparation of metal-organic framework materials (MOF) supported and/or confined in activated carbon monoliths (ACM). The resulting hybrid porous materials exhibit improved physico-chemical properties as compared with their parent constituents. The different hybrids were obtained exploring several experimental approaches, which were thoroughly discussed. All hybrids were characterized by N2 adsorption isotherms, SEM, TGA and XRD techniques. The characterization studies pointed out that the preparation conditions are of paramount importance in defining the nucleation and growth of HKUST-1, either outside of the carbon grains (surface coating), and/or in the internal pores (bulk confinement). While the surface coating was achieved by directly synthesizing the MOF in presence of the ACM (i.e. in-situ synthesis), bulk confinement is favored after applying an additional step that involves a pre-nucleation at low temperatures (5 °C). The hybrid material with the best performance, sample A5(1), shows enhanced mechanical properties compared to its parent counterparts, combined with high apparent surface area (up to 1300 m2/g), an improved crushing strength (about 8 times superior to ACM) and a geometrical density of around 0.45 cm3/g, which almost duplicates that of ACM. Last but not least, the adsorption behavior of the hybrid was tested for CO2 and CH4 adsorption. Application of IAST equation to the single component adsorption isotherms at room temperature gives rise to a CO2/CH4 selectivity factor of 5.5 in the hybrid material, larger than that on ACM (S = 3.5). This work was supported by MINECO projects: MAT2013-45008-p. MEC wants to thank the Spanish Government for the fellowship FPU AP2010-4920.

The development of intracrystalline mesoporosity within zeolites has been a long-standing goal in catalysis as it greatly contributes to alleviating the diffusion limitations of these widely used microporous materials. The combination of in situ synchrotron X-ray diffraction and liquid-cell transmission electron microscopy enabled the first in situ observation of the development of intracrystalline mesoporosity in zeolites and provided structural and kinetic information on the changes produced in zeolites to accommodate the mesoporosity. The interpretation of the time-resolved diffractograms together with computational simulations evidenced the formation of short-range hexagonally ordered mesoporosity within the zeolite framework, and the in situ electron microscopy studies allowed the direct observation of structural changes in the zeolite during the process. The evidence for the templating and protective role of the surfactant and the rearrangement of the zeolite crystal to accommodate intracrystalline mesoporosity opens new and exciting opportunities for the production of tailored hierarchical zeolites. We acknowledge the ALBA synchrotron for beamtime availability (Project ID: 2015021271) and the Center for Functional Nanomaterials at the Brookhaven National Laboratory for the Liq-TEM availability. The authors further acknowledge the CAPITA Project WAVES (EP7-NMP-266543) for financial support.

Widespread access to greener energy is required in order to mitigate the effects of climate change. A significant barrier to cleaner natural gas usage lies in the safety/efficiency limitations of storage technology. Despite highly porous metal-organic frameworks (MOFs) demonstrating record-breaking gas-storage capacities, their conventionally powdered morphology renders them non-viable. Traditional powder shaping utilising high pressure or chemical binders collapses porosity or creates low-density structures with reduced volumetric adsorption capacity. Here, we report the engineering of one of the most stable MOFs, Zr-UiO-66, without applying pressure or binders. The process yields centimetre-sized monoliths, displaying high microporosity and bulk density. We report the inclusion of variable, narrow mesopore volumes to the monoliths’ macrostructure and use this to optimise the pore-size distribution for gas uptake. The optimised mixed meso/microporous monoliths demonstrate Type II adsorption isotherms to achieve benchmark volumetric working capacities for methane and carbon dioxide. This represents a critical advance in the design of air-stable, conformed MOFs for commercial gas storage., While metal–organic frameworks exhibit record-breaking gas storage capacities, their typically powdered form hinders their industrial applicability. Here, the authors engineer UiO-66 into centimetre-sized monoliths with optimal pore-size distributions, achieving benchmark volumetric working capacities for both CH4 and CO2.

Ethylene (C2H4) management involves the usage of materials such as KMnO4 or processes such as ozone oxidation or combined photocatalysis/photochemistry. The ubiquity of C2H4, especially in an industrial context, necessitates a simpler and much more effective approach, and herein we propose the usage of tuneable polymer nanocomposites for the adsorption of C2H4 through the modification of the polymer matrices via the incorporation of nanocrystals of zeolitic imidazolate frameworks (nano-ZIFs). We demonstrate that the inclusion of ZIF-8 and ZIF-7 nanocrystals into polymeric matrices (Matrimid and polyurethane [PU]) yields robust nanocomposites that preserve the C2H4 adsorption/desorption capacity of nanocrystals while shielding it from degrading factors. We report new insights into the adsorption/desorption kinetics of the polymer and its corresponding nanocomposites, which can be tailored by exploiting the underlying polymeric molecular interactions. Importantly, we also elucidated the retention of the intrinsic structural framework dynamics of the nano-ZIFs even when embedded within the polymeric matrix, as evidenced from the breathing and gate-opening phenomena. Our findings pave the way for bespoke designs of novel polymer nanocomposites, which will subsequently impact the deployment of tailored nanomaterials for effective industrial applications. E. M. Mahdi would like to thank Yayasan Khazanah (YK) for the DPhil scholarship that made this work possible. The research in the MMC Lab (J.C.T.) was supported by the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement No 771575 - PROMOFS), and the EPSRC grant no. EP/N014960/1. The authors acknowledge the provision of the TGA and TEM by the Research Complex at Harwell (RCaH), in Rutherford Appleton Laboratory, Oxfordshire. J.S.A. acknowledges financial support by MINECO (Project MAT2016-80285-p), H2020 (MSCA-RISE-2016/NanoMed Project), and GV (PROMETEOII/2014/004).

[EN] Clathrates are well-known compounds whose low thermal stability makes them extremely rare and appreciated. Although their formation mechanism is still surrounded by many uncertainties, these ice-like structures have the potential to be an alternative for transport and storage of different gases, especially methane. For the formation of methane clathrates extreme pressure conditions and a narrow temperature window are needed. Microporous materials have been proposed to provide nucleation sites that, theoretically, promote clathrate formation at milder conditions. While activated carbons and Metal-Organic Frameworks (MOFs) have already been studied, very little is known about the role of zeolites in this field. In this work, we study the formation of methane clathrates in the presence of RHO zeolite. Experimental results based on adsorption and operando synchrotron X-Ray diffraction demonstrate the formation of clathrates at the surface of the zeolite crystals and reveal mechanistic aspects of this formation at mild conditions., ITQ belongs to University of Valencia (UPV) and to the Superior Council of Scientific Investigations (CSIC - Consejo Superior de Investigaciones Cientificas), also located in the UPV Campus. Financial support from Generalitat Valenciana (project PROMETEOII/2014/004) and MINECO (Project MAT2013-45008-P) is gratefully acknowledged. EVRF also thanks MINECO for his Ramon y Cajal fellow RYC-2012-11427 and the following projects: MAT2016-81732-ERC and MAT2017-86992-R. Alba synchrotron is also acknowledged for the experiment 2016021678.

A series of cerium-based UiO-66 was obtained via hydrothermal and sonochemical methods, using the same quantities of reagents (cerium ammonium nitrate (CAN), terephthalic acid (H2BDC)) and solvents) in each synthesis. The impact of synthesis method and metal to linker ratio on the structural and textural properties of obtained UiO-66(Ce), as well as their composition in terms of Ce4+/Ce3+ ratio, structure defects resulting from missing linker, and CO2 adsorption capacity was discussed. By using typical characterization techniques and methods, such as XRD, N2 and CO2 sorption, TGA, XPS, and SEM, it was shown that the agitation of reacting mixture during synthesis (caused by stirring or ultrasounds) allows to obtain structures that have more developed surfaces and fewer linker defects than when MOF was obtained in static conditions. The specific surface area was found to be of minor importance in the context of CO2 adsorption than the contribution of Ce3+ ions that were associated with the concentration of linker defects. This work was financed by a statutory activity subsidy from the Polish Ministry of Science and Higher Education for the Faculty of Chemistry of Wrocław University of Technology and Project No 0402/0100/17.

Gas clathrates are solid structures constituted by water molecules forming 3D networks through hydrogen bonding and isolated gas molecules trapped in their inner cavities. These structures have been well known for the last 30–40 years due to their abundance in nature (preferentially methane hydrates) and their relevance as a future fuel source. Similar hydrate structures have been reproduced at lab scale either in bulk conditions (pure water) or in the presence of additives, including the presence of nanoporous materials. It is highly accepted in the literature that the presence of confinement effects in the cavities of these nanoporous materials must exert an important influence in the gas hydrate nucleation and growth process. This chapter summarizes some of the last achievements in the gas hydrate formation process (mainly focusing in methane hydrates) in the presence of high-surface area nanoporous materials (e.g., activated carbons, metal-organic frameworks, zeolites, clays, and silicas) and the effect of the confined space in the formation/dissociation process.

This paper provides a detailed analysis of the recycling of Tetra Pak waste via pyrolysis to recover the most valuable solid products within its composition, char and aluminum, and the subsequent application of the char in the adsorption of mercury in aqueous solutions. The impact of the Tetra Pak pyrolysis conditions on the char and aluminum yields and their associated properties have been analyzed using a variety of physico-chemical techniques. Tetra Pak-derived chars showed outstanding mercury adsorption properties (up to 215.7 mg/g) that can be attributed to the heterogeneous surface chemistry composed mainly by oxygenated functional groups associated to C, Ca, Al and Si. Tetra Pak pyrolysis allowed an effective recovery of aluminum at pyrolysis temperatures of 600 and 800 °C. Higher temperatures, up to 1000 °C, promote its oxidation to aluminum oxide and hydroxide. These findings contribute to increase the versatility in the Tetra Pak reuse to develop new adsorbents with promising performance for water treatment and the associated recovery of aluminum for further industrial applications. This work was supported by Junta de Extremadura and Fondo Europeo para el Desarrollo Regional (GRU18035). JSA would like to acknowledge financial support from MINECO (projects MAT2016-80285-p & PID2019-108453GB-C21).

[EN] The presence of a highly tunable porous structure and surface chemistry makes metal-organic framework (MOF) materials excellent candidates for artificial methane hydrate formation under mild temperature and pressure conditions (2 degrees C and 3-5 MPa). Experimental results using MOFs with a different pore structure and chemical nature (MIL-100 (Fe) and ZIF-8) clearly show that the water-framework interactions play a crucial role in defining the extent and nature of the gas hydrates formed. Whereas the hydrophobic MOF promotes methane hydrate formation with a high yield, the hydrophilic one does not. The formation of these methane hydrates on MOFs has been identified for the first time using inelastic neutron scattering (INS) and synchrotron X-ray powder diffraction (SXRPD). The results described in this work pave the way towards the design of new MOF structures able to promote artificial methane hydrate formation upon request (confined or non-confined) and under milder conditions than in nature., We acknowledge the UK Science and Technology Facilities Council for the provision of beam time on the TOSCA spectrometer (Project RB1510448) and financial support from the European Commission under the 7th Framework Programme through the "Research Infrastructures" action of the "Capacities" Programme (NMI3-II Grant number 283883). J. S.-A. acknowledges financial support from MINECO Projects: MAT2013-45008-p and CONCERT Project-NASEMS (PCIN-2013-057) and from Generalitat Valenciana (PROMETEO2009/002). The authors acknowledge the Spanish synchrotron ALBA for beam time availability. E. V. R.-F. gratefully acknowledges a Ramon y Cajal grant (RyC-2012-11427). F. R. and J. L. J. acknowledge financial support from MINECO through projects MAT2012-38567-C02-01, Consolider Ingenio 2010-Multicat CSD-2009-00050 and Severo Ochoa SEV-2012-0267, and Generalitat Valenciana (Prometeo).

Corneal ectatic disorders are characterized by a progressive weakening of the tissue due to biomechanical alterations of the corneal collagen fibers. Carbon nanostructures, mainly carbon nanotubes (CNTs) and graphene, are nanomaterials that offer extraordinary mechanical properties and are used to increase the rigidity of different materials and biomolecules such as collagen fibers. We conducted an experimental investigation where New Zealand rabbits were treated with a composition of CNTs suspended in balanced saline solution which was applied in the corneal tissue. Biocompatibility of the composition was assessed by means of histopathology analysis and mechanical properties by stress-strain measurements. Histopathology samples stained with blue Alcian showed that there were no fibrous scaring and no alterations in the mucopolysaccharides of the stroma. It also showed that there were no signs of active inflammation. These were confirmed when Masson trichrome staining was performed. Biomechanical evaluation assessed by means of tensile test showed that there is a trend to obtain higher levels of rigidity in those corneas implanted with CNTs, although these changes are not statistically significant (p > 0.05). Implanting CNTs is biocompatible and safe procedure for the corneal stroma which can lead to an increase in the rigidity of the collagen fibers., The authors would like to acknowledge Professor K. Kaneko for the supply of the SWCNTs. They will also like to acknowledge the support of the Spanish Ministerio de Economia y Competitividad (MINECO) and FEDER funds under the project MAT2012-38359-C03-01. This publication has been sponsored in part with the funding of the framework of the Red Tematica de Investigacion Cooperativa en Salud (RETICS), Reference no. RD12/0034/0007, financed by the Instituto Carlos III-General Subdirection of Networks and Cooperative Investigation Centers (R&D&I National Plan 2008-2011) and the European Regional Development Fund (Fondo Europeo de Desarrollo Regional FEDER).

Nanostructured carbons with relatively high nitrogen content (3–8%) and different micro and mesoporosity ratio were prepared by activation of polyaniline (PANI) with a ZnCl2–NaCl mixture in the proportion of the eutectic (melting point 270 °C). It was found that the activated carbons consisted of agglomerated nanoparticles. ZnCl2 plays a key role in the development of microporosity and promotes the binding between PANI nanoparticles during heat treatment, whereas NaCl acts as a template for the development of mesoporosity of larger size. Carbons with high micropore and mesopore volumes, above 0.6 and 0.8 cm3/g, respectively, have been obtained. Furthermore, these materials have been tested for CO2 capture and storage at pressures up to 4 MPa. The results indicate that the nitrogen groups present in the surface do not seem to affect to the amount of CO2 adsorbed, not detecting strong interactions between CO2 molecules and nitrogen functional groups of the carbon, which are mainly pyridinic and pyrrolic groups. Authors acknowledge financial support from BroadBit Industry (BroadBit Slovakia s.r.o. Eötvösova ul. 12. 945 01, Komárno, Slovakia).

The synthesis method of metal&ndash, organic frameworks (MOFs) has an important impact on their properties, including their performance in catalytic reactions. In this work we report on how the performance of [Cu3(TMA)2(H2O)3]n (HKUST-1) and Ce@HKUST-1 in the reaction of CO oxidation depends on the synthesis method of HKUST-1 and the way the cerium active phase is introduced to it. The HKUST-1 is synthesised in two ways: via the conventional solvothermal method and in the presence of a cationic surfactant (hexadecyltrimethylammonium bromide (CTAB)). Obtained MOFs are used as supports for cerium oxide, which is deposited on their surfaces by applying wet and incipient wetness impregnation methods. To determine textural properties, structure, morphology, and thermal stability, the HKUST-1 supports and Ce@HKUST-1 catalysts are characterised using X-ray diffraction (XRD), N2 sorption, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). It is proven that the synthesis method of HKUST-1 has a significant impact on its morphology, surface area, and thermal stability. The synthesis method also influences the dispersion and the morphology of the deposited cerium oxide. Last but not least, the synthesis method affects the catalytic activity of the obtained material.

The microporous nature of monodisperse Stöber silica spheres is demonstrated in the literature, although usually via indirect evidence. Contradictorily, there also exist numerous reports of nonporosity based on conventional N2 adsorption isotherms, leading to a confusing scenario and questioning the evaluation methodology. Thus, there is the strong need of straight measure of microporosity in Stöber spheres, at best by available adsorption techniques, which must be further directly confronted with the standard nitrogen method. Here, for the first time, microporosity detection by N2 and CO2 adsorption is compared in Stöber spheres. We demonstrate that CO2 isotherms at 273 K allow direct detection and quantification of the microporosity (about 0.1 cm3/g in our samples), while N2 at 77 K cannot probe adequately the internal volume. We also show that a large amount of water fills the micropores under usual ambient conditions, also revealing the presence of small mesoporosity. Thus, the porous nature of Stöber spheres is investigated by a simple combination of adsorption isotherms, and the different accessibility of N2, CO2, and H2O molecules is discussed. We emphasize the inadequacy of standard N2 isotherms for micropore detection in Stöber silica, as the access of nitrogen molecules at cryogenic temperatures is kinetically restricted and may lead to erroneous conclusions. Instead, we propose CO2 isotherms as a simple and direct means for evaluation of microporosity. This work was funded by Spanish MINECO Projects MAT2014-58731-JIN, MAT2015-68075-R, MAT2016-80285-p, and SIFE2; Comunidad de Madrid Projects S2013/MIT-2740 and PHAMA_2.0; Generalitat Valenciana Project PROMETEOII/2014/004, and Project EU H2020 MSCARISE-2016/NanoMed.

This work reports the preparation and characterization of biomass-derived renewable microporous carbon nanoparticles obtained by microwave-assisted hydrothermal carbonization (MAHC), following by physical activation, of assai stone waste. Conventional routes (i.e. carbonization in furnace and chemical activation) was also investigated. The highest yield provided by MAHC combined with CO2 as activating agent resulted in nanocarbons with surface area of 1100 m2/g and a very narrow pore size distribution with a micropore volume of 0.45 cm3/g. Owing to the excellent combination of microporosity and high bulk density (0.89 g/cm3). The biomass-derived carbon shows great potential to be used as adsorbent for natural gas storage. Indeed, high pressure methane adsorption isotherm in volumetric basis revealed an uptake value of 140 V(STP)/V at 25 °C and 4 MPa. The authors would like to thank the Fundação de Amparo à Pesquisa do Estado do Amazonas, the National Council for Scientific and Technological Development (CNPq/Brazil) for financial support and Coordination for the Improvement of Higher Level Personnel (CAPES/Brazil) for the scholarships.