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Two series of zeolite Y were prepared with varying particle size (estimated 100 or 400 nm) by applying different synthesis gel composition ratios as well as different ageing and hydrothermal steps. Copper-containing zeolites Y were obtained through ion exchange, thoroughly characterized and tested for the selective catalytic reduction with NH3 (NH3-SCR-DeNOx). The catalytic activity of the prepared materials varied significantly due to the different nature of copper species. Results show that catalysts CuY 0h-A and CuY-24h-A (approx. particles size 2676 and 475 nm, respectively) facilitate a higher NO conversion both in the presence and absence of water vapor, exhibiting however stronger N2O formation above 250 °C. On the other hand, nearly X-ray amorphous Y-0h-B and Y-24h-B after ion- exchange led to decreased activity of CuY-0h-B and CuY-24h-B (approx. particles size 345 and 128 nm, respectively). Additional insight into the activity of both catalyst were obtained through in situ DR UV-Vis spectroscopy.

This contribution aims at analysing the current understanding about the influence of Al distribution, zeolite topology, ligands/reagents and oxidation state on ions mobility in Cu-zeolites, and its relevance toward reactivity of the metal sites. The concept of Cu mobilization has been originally observed in the presence of ammonia, favouring the activation of oxygen by formation of NH3 oxo-bridged complexes in zeolites and opening a new perspective about the chemistry in single-site zeolite-based catalysts, in particular in the context of the NH3-mediated Selective Catalytic Reduction of NOx (NH3-SCR) processes. A different mobility of bare Cu+/Cu2+ ions has been documented too, showing for Cu+ a better mobilization than for Cu2+ also in absence of ligands. These concepts can have important consequences for the formation of Cu-oxo species, active and selective in other relevant reactions, such as the direct conversion of methane to methanol. Here, assessing the structure, the formation pathways and reactivity of Cu-oxo mono- or multimeric moieties still represents a challenging playground for chemical scientists. Translating the knowledge about Cu ions mobility and redox properties acquired in the context of NH3-SCR reaction into the field of direct conversion of methane to methanol can have important implications for a better understanding of transition metal ions redox properties in zeolites and for an improved design of catalysts and catalytic processes.

Cu-exchanged chabazite is the catalyst of choice for NO

The design of sustainable procedures for the preparation of cobalt/carbon-based materials as an anode for hydrogen fuel production through electrocatalytic water splitting has attracted much interest in the last few years. Herein, a novel environmentally friendly approach for the development of stable and active catalysts for the oxygen evolution reaction (OER) is reported. In detail, the methodology aimed at developing a sequence of composites having a low cobalt loading ( MW/US > MW > conventional heating, with the best sample requiring an overpotential of 365 mV to deliver a current density of 10 mA cm_2 and a Tafel slope of 58 mV dec_1.

The speciation of framework-interacting CuII sites in Cu-chabazite zeolite catalysts active in the selective catalytic reduction of NOx with NH3 is studied, to investigate the influence of the Al content on the copper structure and their reactivity towards a NO/O2 mixture. To this aim, three samples with similar Cu densities and different Si/Al ratios (5, 15 and 29) were studied using in situ X-ray absorption spectroscopy (XAS), FTIR and diffuse reflectance UV-Vis during pretreatment in O2 followed by the reaction. XAS and UV-Vis data clearly show the main presence of Z2CuII sites (with Z representing a framework negative charge) at a low Si/Al ratio, as predicted. EXAFS wavelet transform analysis showed a non-negligible fraction of proximal Z2CuII monomers, possibly stabilized into two 6-membered rings within the same cage. These sites are not able to form Cu-nitrates by interaction with NO/O2. By contrast, framework-anchored Z[CuII(NO3)] complexes with a chelating bidentate structure are formed in samples with a higher Si/Al ratio, by reaction of NO/O2 with Z[CuII(OH)] sites or structurally similar mono- or multi-copper Zx[CuIIxOy] sites. Linear combination fit (LCF) analysis of the XAS data showed good agreement between the fraction of Z[CuII(OH)]/Zx[CuIIxOy] sites formed during activation in O2 and that of Z[CuII(NO3)] complexes formed by reaction with NO/O2, further confirming the chemical inertia of Z2CuII towards these reactants in the absence of solvating NH3 molecules., The speciation of the CuII sites in Cu-CHA catalysts for NH3-SCR is studied, to investigate the influence of the Al content on the structure and reactivity of these sites in a NO/O2 mixture.

The NH3-mediated selective catalytic reduction (NH3-SCR) of NOx over Cu-ion-exchanged chabazite (Cu-CHA) catalysts is the basis of the technology for abatement of NOx from diesel vehicles. A crucial step in this reaction is the activation of oxygen. Under conditions for low-temperature NH3-SCR, oxygen only reacts with CuI ions, which are present as mobile CuI diamine complexes [CuI(NH3)2]+. To determine the structure and reactivity of the species formed by oxidation of these CuI diamine complexes with oxygen at 200 °C, we have followed this reaction, using a Cu-CHA catalyst with a Si/Al ratio of 15 and 2.6 wt% Cu, by X-ray absorption spectroscopies (XANES and EXAFS) and diffuse reflectance UV-Vis spectroscopy, with the support of DFT calculations and advanced EXAFS wavelet transform analysis. The results provide unprecedented direct evidence for the formation of a [Cu2(NH3)4O2]2+ mobile complex with a side-on μ-η2,η2-peroxo diamino dicopper(II) structure, accounting for 80–90% of the total Cu content. These [Cu2(NH3)4O2]2+ are completely reduced to [CuI(NH3)2]+ at 200 °C in a mixture of NO and NH3. Some N2 is formed as well, which suggests the role of the dimeric complexes in the low-temperature NH3-SCR reaction. The reaction of [Cu2(NH3)4O2]2+ complexes with NH3 leads to a partial reduction of the Cu without any formation of N2. The reaction with NO results in an almost complete reduction to CuI, under the formation of N2. This indicates that the low-temperature NH3-SCR reaction proceeds via a reaction of these complexes with NO.

Cu-exchanged chabazite zeolites (Cu-CHA) are effective catalysts for the NH

The polymerization of amino acids (AAs) to peptides on oxide surfaces has attracted interest owing to its high importance in biotechnology, prebiotic chemistry, and origin of life theories. However, its mechanism is still poorly understood. We tried to elucidate the reactivity of glycine (Gly) from the vapor phase on the surface of amorphous silica under controlled atmosphere at 160 °C. Infrared (IR) spectroscopy reveals that Gly functionalizes the silica surface through the formation of ester species, which represent, together with the weakly interacting silanols, crucial elements for monomers activation and polymerization. Once activated, β-turns start to form as initiators for the growth of long linear polypeptides (poly-Gly) chains, which elongate into ordered structures containing both β-sheet and helical conformations. The work also points to the role of water vapor in the formation of further self-assembled β-sheet structures that are highly resistant to hydrolysis.

In the present work, various experimental and theoretical methods were combined to study in detail the modifying effect of differences in the order of deposition of components on the state of silver in bimetallic iron–silver samples based on mordenite. In each of the silver-containing samples, the formation of large (≥2 nm in diameter) varieties of silver was observed, which differed from the varieties in the other samples, and in varying degrees. The formation of large Ag NPs on the outer surface of mordenite is explained by the redox interaction of Ag+-Fe2+ and the selectivity of ion exchange. The local surrounding of Ag in the studied samples is different: for AgMOR—monatomic species dominate, FeAgMOR—silver dimers and AgFeMOR—metal particles. In all investigated samples, the partially charged intra-channel Agnδ+ clusters (~0.7 nm in size) were formed due to partial Ag+ reduction and subsequent Ag0 agglomeration into the mordenite channel. Most of the silver in the bulk of the zeolite is represented in the cationic state attached to the mordenite framework by differently coordinated electrostatic forces, which can be Ag-O, Ag-Si or Ag-Al, with variations in interatomic distances and do not depend on the order of metal deposition. In addition, the arrangement of the cations in the side pockets means that the transport channels of mordenite are free, which is favorable for the application of the materials under study in catalysis and adsorption.

The data management plan (DMP) gives an overview over the data generated in the project, how this data will be handled and stored and made publicly available. The DMP is a working document and will be updated during the lifetime of the project when necessary. As a minimum, the DPM will be updated in the context of the periodic evaluation/assessment of the project, and in time for the final review at the latest.

The direct methane to methanol (DMTM) conversion is often referred to as a ‘dream reaction’ with enormous potential to alter energy sector and chemical industry. After O2-activation, Cu-exchanged zeolites form CuxOy species that activate CH4 and release it in the form of CH3OH upon interaction with H2O. Despite extensive research efforts in the last years, several questions concerning the influence of materials composition and process parameters on the reaction mechanism remain open. Herein, we characterize Cu-MOR zeolites with different composition by operando X-ray absorption spectroscopy (XAS), monitoring their spectroscopic response under two characteristic DMTM reaction protocols varied in the duration of the key reaction steps. Linear Combination Fit (LCF) analysis of the time-resolved X-ray absorption near edge structure (XANES) spectra collected during CH4-loading and steam-assisted CH3OH extraction enabled to quantify the abundance of different Cu species during these two steps. Data analysis revealed a positive linear correlation between the methanol yield generated per incorporated copper and the Cu(I) component formed during the CH4-loading step. Cu(I) development during CH4-loading is accompanied by modifications in the extended X-ray absorption fine structure (EXAFS) spectra suggesting substantial rearrangement in the active site structure. The obtained results provide new mechanistic insights for the DMTM over Cu-MOR.

The local structural and electronic properties of Cu sites during the direct conversion of methane to methanol with molecular oxygen was followed by X-ray absorption spectroscopy (XAS) on a set of Cu-zeolites with different topology (large pore MOR and small pore CHA frameworks) and similar chemical composition (Si/Al ∼ 11 and 12, respectively). Two low loading (LL) and high loading (HL) samples were prepared by ion exchange, and their methanol productivity measured in laboratory fixed bed reactor tests, resulting in selectivity higher than 85%. Both Cu-MOR samples outperformed Cu-CHA ones, resulting in 0.28 and 0.26 molCH3OH/molCu for the LL (Cu/Al = 0.13) and HL (Cu/Al = 0.36) samples, vs 0.10 and 0.17 molCH3OH/molCu for LL and HL Cu-CHA, respectively (Cu/Al = 0.16 and 0.49). The evolution of Cu oxidation state and local coordination environment was followed in all the reaction steps (O2 activation, flush with He, CH4 dosage and subsequent CH3OH desorption by applying a wet stream) both during temperature changes (ramp in O2 up to 500 °C, cooling to 200 °C for subsequent steps, etc.) and in steady-state conditions. Strong similarities were observed in the local structure of Cu sites in all samples, which showed similar redox dynamics during O2 activation and subsequent cooling to 200 °C. Even though only qualitative considerations can be made on the overall spectral evolution, XANES indicates that not all the Cu(I) formed during CH4 loading belongs to active sites.

The Cu-exchanged CHA zeolite (Cu-CHA) is a promising catalyst for the NH3-assisted selective catalytic reduction (NH3-SCR) of harmful nitrogen oxides (NOx, x = 1, 2), combining high hydrothermal stability with good performance in the 200–550 °C range. Despite many recent breakthroughs in the molecular-scale understanding of this catalyst, several open questions remain to ultimately unravel the NH3-SCR mechanism across the operation-relevant temperature range. In this context, we apply in situ XAS and UV-vis–NIR spectroscopy to assess the nature and thermal stability of NH3-derived Cu-species in a commercial Cu-CHA deNOx catalyst. Both techniques evidence fast and complete ‘solvation’ by NH3 of the framework-coordinated CuII and CuI ions formed upon thermal activation of the catalyst. Our results confirm that NH3 desorption at T > 200 °C is accompanied by CuII → CuI reduction phenomena, while the compresence of pre-adsorbed NH3 with gas-phase NO greatly enhances the reduction rate and efficiency. By applying state-of-the-art multivariate curve resolution (MCR) analysis, we elaborate these insights in a quantitative picture of Cu-speciation during NH3 temperature-programmed desorption (TPD) and surface reaction (TPSR) experiments. MCR analysis confirms recent theoretical predictions for the thermal stability of [CuI(NH3)2]+ species and allows us to experimentally identify the framework-coordinated Ofw–CuI–NH3 intermediate formed upon desorption of a NH3 ligand from [CuI(NH3)2]+.

Temperature programmed reduction with NO (NO-TPR) is introduced as a characterization method, by monitoring the reduction of CuII to CuI in a mixture of NH3 and NO. Since the NO-TPR method is based on the oxidation and reduction half cycles of the NH3-SCR reaction, quantitative information about the amount of active Cu in Cu-CHA is obtained. Furthermore, information on the stability and reactivity of reaction intermediates in the NH3-SCR cycle is obtained as well. The reduction of the Cu is followed by monitoring the consumption of NO, after oxidation of the catalyst in O2 or a mixture of NO and O2 to form the CuII state. Two distinct states of the Cu are revealed. The first state, corresponding to the reduction of a Cu-oxide species, is reduced around 130 °C and is observed at low Cu content only. The second state corresponds to the reduction of a Cu-nitrate species around 200–230 °C. The low-temperature activity of Cu-chabazite catalysts with low Cu content show the same trend as the Cu-nitrate species observed in NO-TPR. The fraction of Cu-oxide in NO-TPR decreases with increasing Cu content, leading to a non-linear dependence of the NH3-SCR activity on the Cu-content. At high Cu content, all Cu forms a stable Cu-nitrate species, and the NH3-SCR activity becomes proportional to the Cu content. This agrees well with the known behavior of Cu-CHA catalysts, indicating that NO-TPR seems to be a viable method for the characterization of Cu-CHA materials as NH3-SCR catalysts.

ispartof: ADVANCED SYNTHESIS & CATALYSIS vol:363 issue:11 pages:2850-2860 status: published

Ammonia-mediated selective catalytic reduction (NH3-SCR) using Cu-exchanged chabazite zeolites as catalysts is one of the leading technologies for NOx removal from exhaust gases, with CuII/CuI redox cycles being the basis of the catalytic reaction. The amount of CuII ions reduced by NO/NH3 can be quantified by the consumption of NO during temperature-programmed reduction experiments (NO-TPR). In this article, we show the capabilities of in situ X-ray absorption near-edge spectroscopy (XANES), coupled with multivariate curve resolution (MCR) and principal component analysis (PCA) methods, in following CuII/CuI speciation during reduction in NO/NH3 after oxidation in NO/O2 at 50 °C on samples with different copper loading and pretreatment conditions. Our XANES results show that during the NO/NH3 ramp CuII ions are fully reduced to CuI in the 50–290 °C range. The number of species involved in the process, their XANES spectra and their concentration profiles as a function of the temperature were obtained by MCR and PCA. Mixed ligand ammonia solvated complexes [CuII(NH3)3(X)]+ (X = OH−/O− or NO3−) are present at the beginning of the experiment, and are transformed into mobile [CuI(NH3)2]+ complexes: these complexes lose an NH3 ligand and become framework-coordinated above 200 °C. In the process, multiple CuII/CuI reduction events are observed: the first one around 130 °C is identified with the reduction of [CuII(NH3)3(OH/O)]+ moieties, while the second one occurs around 220–240 °C and is associated with the reduction of the ammonia-solvated Cu-NO3− species. The nitrate concentration in the catalysts is found to be dependent on the zeolite Cu loading and on the applied pretreatment conditions. Ammonia solvation increases the number of CuII sites available for the formation of nitrates, as confirmed by infrared spectroscopy.

The development of new strategies for spatially controllable immobilization has encouraged the preparation of novel catalysts based on the organic-inorganic hybrid concept. In the present paper, a Cu-based multi-structured silica catalyst has been prepared and fully characterized. The inclusion of Cu(II) in &beta, cyclodextrins has been exploited with the double aim to stabilize the metal and to act as a source of Cu(I) catalytic sites. Multi-technique characterization by infrared, UV-visible, electron microscopy and X-ray absorption spectroscopies of the fresh and exhaust catalysts provided information on the local structure, redox properties and stability of the investigated hybrid systems. The catalytic system showed that copper nanospecies were dispersed on the support and hardly affected by the catalytic tests, confirming the stabilizing effect of &beta, CD, and likely of the N1-(3-Trimethoxysilylpropyl) diethylenetriamine spacer, as deduced by X-ray absorption spectroscopy analysis. Overall, we demonstrate a feasible approach to efficiently anchor Cu(II) species and to obtain a reusable single-site hybrid catalyst well suited for Cu(I)-catalyzed alkyne-azide cycloaddition.

Cu-exchanged zeolites have been shown to possess Cu-oxo species active towards the direct methane to methanol (DMTM) conversion, carried out through a chemical-looping approach. Different Cu-zeolites have been investigated for the DMTM process, with Cu-mordenite (Cu-MOR) being among the most active. In this context, an accurate determination of the local structure and nuclearity of selective Cu-oxo species responsible for an efficient DMTM conversion still represents an ongoing challenge for characterization methods, including synchrotron-based X-ray absorption spectroscopy (XAS). Herein, we explore the potential of an alternative analysis of Extended X-ray Absorption Fine Structure (EXAFS) data using wavelet transform (WT) to enhance the technique sensitivity to multimeric Cu species hosted in the MOR framework. Combining ex situ XAS measurements under model red-ox conditions with in situ data collected after the key steps of the DMTM process, we demonstrate how EXAFS-WT enables unambiguous detection of Cu–Cu scattering contributions from multimeric Cu-species. As also confirmed by complementary in situ IR spectroscopy results, these are observed to dynamically respond to the chemical environment over the different conditions probed. We finally report a proof-of-concept EXAFS fit using the WT representation, applied to the structural refinement of O2-activated Cu-MOR. The fitting results reveal a Cu local coordination environment consistent with mono-(μ-oxo) di-copper cores, with Cu–Cu separation of ∼3.1 A, paving the way to future applications and developments of the method in the field of Cu-zeolite research and beyond.

The direct conversion of methane to methanol (MTM) is a reaction that has the potential to disrupt a great part of the synthesis gas-derived chemical industry. However, despite many decades of research, active enough catalysts and suitable processes for industrial application are still not available. Recently, several copper-exchanged zeolites have shown considerable activity and selectivity in the direct MTM reaction. Understanding the nature of the active site in these materials is essential for any further development in the field. Herein, we apply multivariate curve resolution analysis of X-ray absorption spectroscopy data to accurately quantify the fraction of active Cu in Cu-MOR (MOR = mordenite), allowing an unambiguous determination of the active site nuclearity as a dicopper site. By rationalizing the compositional parameters and reaction conditions, we achieve the highest methanol yield per Cu yet reported for MTM over Cu-zeolites, of 0.47 mol/mol.

We have prepared and evaluated the physico-chemical and biological properties of four different hyaluronated mesoporous silica nanoparticles (MSNs) samples (MSN/HA). Hyaluronic acid (HA) with two different molecular weights (200 and 6.4 kDa) was used for the conjugation of aminopropyl-functionalized MSN (NH2-MSN), following two different procedures. Namely, samples HA200A and HA6.4A were prepared by reacting activated HA with NH2-MSN (method A), while samples HA200B and HA6.4B were obtained carrying out HA activation in the presence of the nanoparticles (method B). The four samples showed similar hydrophilicity, but clear differences in the HA loading, textural properties, surface charge and stability of the suspensions. More in detail, conjugation using low molecular weight HA with method A resulted in low HA loading, with consequent scarce effects on dispersity and stability in physiological media. The highest yield and corresponding best performances were obtained with method B using high molecular weight HA. HA loading and molecular weight also influenced in a concerted way the biological response towards the MSNs of CD44 target cancer cells (CD44+) and control cells (CD44−): MDA-MB-231 and A2780, respectively. The absence of cytotoxicity was assessed. Moreover, the targeting ability of the best performing MSN/HA was confirmed by cellular uptake studies.

Hybrid drug delivery systems (DDS) have been prepared by grafting poly(NIPAM-co-MPS) chains on multimodal porous silica nanoparticles having an inner mesoporous structure and an outer thin layer of micropores. The hybrid thermoresponsive DDS were fully characterized and loaded with a model drug. The in vitro drug release tests are carried out at below and above the lower critical solution temperature (LCST) of the copolymer. The results have revealed that due to the presence of small diameter (~1.3 nm) micropores at the periphery of the particles, the collapsed globules of the thermoresponsive copolymer above its LCST hinders the complete release of the drug which resulted in a reverse thermoresponsive drug release profile by the hybrid DDS.

The interaction of water molecules with the surface of hybrid silica-based mesoporous materials is studied by 29 Si, 1 H and 13 C solid-state NMR and IR spectroscopy, with the support of ab initio calculations. The surface of aminopropyl-grafted mesoporous silica nanoparticles is studied in the dehydrated state and upon interaction with controlled doses of water vapour. Former investigations described the interactions between aminopropyl and residual SiOH groups; the present study shows the presence of hydrogen-bonded species (SiOH to NH2 ) and weakly interacting "free" aminopropyl chains with restricted mobility, together with a small amount of protonated NH3+ groups. The concentration of the last-named species increased upon interaction with water, and this indicates reversible and fast proton exchange from water molecules to a fraction of the amino groups. Herein, this is discussed and explained for the first time, by a combination of experimental and theoretical approaches.

We present for the first time the application of metal-organic framework (MOF) mixed-matrix disks (MMD) for the automated flow-through solid-phase extraction (SPE) of environmental pollutants. Zirconium terephthalate UiO-66 and UiO-66-NH2 MOFs with different size (90, 200 and 300nm) have been incorporated into mechanically stable polyvinylidene difluoride (PVDF) disks. The performance of the MOF-MMDs for automated SPE of seven substituted phenols prior to HPLC analysis has been evaluated using the sequential injection analysis technique. MOF-MMDs enabled the simultaneous extraction of phenols with the concomitant size exclusion of molecules of larger size. The best extraction performance was obtained using a MOF-MMD containing 90nm UiO-66-NH2 crystals. Using the selected MOF-MMD, detection limits ranging from 0.1 to 0.2μgL-1 were obtained. Relative standard deviations ranged from 3.9 to 5.3% intra-day, and 4.7-5.7% inter-day. Membrane batch-to-batch reproducibility was from 5.2 to 6.4%. Three different groundwater samples were analyzed with the proposed method using MOF-MMDs, obtaining recoveries ranging from 90 to 98% for all tested analytes.

A series of poly(N-isopropylacrylamide-co-acrylamide) thermoresponsive random copolymers with different molecular weights and composition were synthesized and characterized by attenuated total reflectance Fourier-transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), size exclusion chromatography (SEC) and proton nuclear magnetic resonance (NMR) spectroscopy. The lower critical solution temperatures (LCST) of the copolymers were tuned by changing the mole ratios of monomers. Copolymer with highest molecular weight and LCST (41.2 °C) was grafted on SBA-15 type mesoporous silica particles by a two-step polymer grafting procedure. Bare SBA-15 and the thermoresponsive copolymergrafted (hybrid) SBA-15 particles were fully characterized by scanning electron microscope (SEM), ATR-FTIR, thermogravimetric analysis (TGA) and Brunauer-Emmett-Teller (BET) analyses. The hybrid particles were tested for their efficiency as temperature-sensitive systems for dermal delivery of the antioxidant rutin (quercetin-3-O-rutinoside). Improved control over rutin release by hybrid particles was obtained which makes them attractive hybrid materials for drug delivery.

The synthesis, characterization and catalytic performance of offretite with four distinct crystal morphologies (oval, hexagonal, broccoli-like, and spherical) are presented. As a member of the ABC-6 family of zeolite structures, offretite is likely to form intergrowths which can affect its shape-selective properties. Herein, a combination of experiments (SC-XRD, PXRD, benzene uptake and the methanol-to-hydrocarbon conversion) allows the determination of the mechanism and fraction of twinning. It is demonstrated that the catalysts with the same crystal aspect ratio (AR = 3) yield product spectra dominated by C2–C4 aliphatics. Such product selectivity is associated with zeolites with an 8-ring channel system. Interestingly, a significant production of bulky aromatics is seen for the catalyst with the spherical morphology (AS = 1.1) which is a manifestation of the 12-ring pore system of the OFF framework topology. This constitutes the first report of this behavior. The particular display of product shape selectivity can be ascribed to the catalyst particle morphology.

Natural purified mordenite from Palmarito de Cauto (ZP) deposit, Cuba, was subjected to a hydrothermal ion exchange process in acid medium with Fe2+ or Fe3+ salts (Fe2+ZP and Fe3+ZP). The set of samples was characterized regarding their textural properties, morphology, and crystallinity, and tested in the NO reduction with CO/C3H6. Infrared spectroscopy coupled with NO as a probe molecule was used to give a qualitative description of the Fe species&rsquo, nature and distribution. The exchange process caused an increase in the iron loading of the samples and a redistribution, resulting in more dispersed Fe2+ and Fe3+ species. When contacted with the NO probe, Fe2+ZP showed the highest intensity of nitrosyl bands, assigned to NO adducts on isolated/highly dispersed Fe2+/Fe3+ extra-framework sites and FexOy clusters. This sample is also characterized by the highest NO sorption capacity and activity in NO reduction. Fe3+ZP showed a higher intensity of nitrosonium (NO+) species, without a correlation to NO storage and conversion, pointing to the reactivity of small FexOy aggregates in providing oxygen atoms for the NO to NO+ reaction. The same sites are proposed to be responsible for the higher production of CO2 observed on this sample, and thus to be detrimental to the activity in NO SCR.

Copper exchanged CHA zeolites were investigated by in situ Diffuse Reflectance UV–vis-NIR spectroscopy in order to study the evolution of the copper environment in respect to the sample composition (2 samples differing in Si/Al and Cu content) and the activation procedure (in O2 or N2 from room temperature to 400 °C). In situ measurements allowed showing the different behavior of the two samples, both in the d-d and Ligand to Metal Charge Transfer regions, confirming a strong effect of the lattice composition to determine the copper environment and its reactivity. One of the two sample (Si/Al = 15 and Cu/Al = 0.5) was further investigated, in order to clarify the nature of the Cu-oxo species, formed along activation in oxygen. To shed light on this point, in situ measurements starting from a reduced form of the sample, obtained by activation in inert atmosphere at high temperature, were also considered. Additional suggestions on the nature of these species were obtained by resonant Raman measurements conducted in controlled atmosphere.

The direct stepwise transformation of CH4 to CH3OH over Cu-exchanged zeolites has been an intensively researched reaction as it can provide a solution for the utilization of this abundant feedstock. Up to date a commercial process is far from realization, which is why an understanding of the Cu speciation in zeolites as a function of reaction conditions as well as the development of a mechanistic view of the reaction are necessary to further advance the field. Herein we study Cu-exchanged ferrierite zeolite for the direct CH4 to CH3OH conversion by utilizing X-ray absorption spectroscopy (XAS), in order to assess the local structure and electronic properties of Cu through the reaction. A Cu-FER sample with a Cu/Al = 0.20 and Si/Al = 11 was subjected to three reaction cycles yielding ultimately 96 µmol $$_{{{\text{C}}{{\text{H}}_3}{\text{OH}}}}/{{\text{g}}_{{\text{zeolite}}}}$$ . Normalized to the Cu loading, this accounts for 0.33 mol $$_{{{\text{C}}{{\text{H}}_3}{\text{OH}}}}$$ /molCu, making the sample comparable to very active Cu-MOR materials reported in the literature. During O2 activation, a transient self-reduction regime of CuII to CuI ions was identified; eventually leading to mostly framework interacting CuII species. CH4 loading leads to a reduction of these CuII containing species; which are finally partially reoxidized during H2O-assisted CH3OH extraction. The speciation after CH4 activation as well as H2O-assisted CH3OH extraction was assessed via linear combination fitting analysis of the XAS data.

This contribution clarifies the overoxidation-preventing key step in the methane-to-methanol (MTM) conversion over copper mordenite zeolites. We followed the methane-to-methanol conversion over copper mordenite zeolites by NMR spectroscopy supported by DRIFTS to show that surface methoxy groups (SMGs) located at zeolite Brønsted sites are the key intermediates. The SMGs with chemical shift of 59 ppm are identical to those formed on a copper-free reference zeolite after reaction with methanol and react with water, methanol, or carbon monoxide to yield methanol, dimethyl ether, and acetate. This reactivity corroborates the location of SMGs at Brønsted sites. We find no evidence for stable SMGs directly at copper sites and explain mechanistically why H-form mordenites outperform their Na-form analogues. This finding is of interest for any future process that tries to trap the intermediate methane oxidation product towards methanol.

This is the peer reviewed version, which has been published in final form at https://doi.org/10.1002/cctc.201801542. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.

Aim: To elucidate whether different cytokinetic features (i.e., presence or absence of mitotic activity) may influence cell uptake and distribution of nanocarriers, in vitro tests on liposomes, mesoporous silica nanoparticles, poly(lactide-co-glycolide) nanoparticles and nanohydrogels were carried out on C2C12 murine muscle cells either able to proliferate as myoblasts (cycling cells) or terminally differentiate into myotubes (noncycling cells). Materials & methods: Cell uptake and intracellular fate of liposomes, mesoporous silica nanoparticles, poly(lactide-co-glycolide) nanoparticles and nanohydrogels were investigated by confocal fluorescence microscopy and transmission electron microscopy. Results: Nanocarrier internalization and distribution were similar in myoblasts and myotubes; however, myotubes demonstrated a lower uptake capability. Conclusion: All nanocarriers proved to be suitably biocompatible for both myoblasts and myotubes. The lower uptake capability of myotubes is probably due to different plasma membrane composition related to the differentiation process.

The use of nanoparticles as drug carriers in the field of skeletal muscle diseases has been poorly addressed and the interaction of nanoparticles with skeletal muscle cells has been investigated almost exclusively on C2C12 murine myoblasts. In this study we investigated the effects poly(lactide-co-glycolide) nanoparticles, mesoporous silica nanoparticles and liposomes, on the viability of primary human myoblasts and analyzed their cellular uptake and intracellular distribution in both primary human myoblasts and myotubes. Our data demonstrate that poly(lactide-co-glycolide) nanoparticles do not negatively affect myoblasts viability, contrarily to mesoporous silica nanoparticles and liposomes that induce a decrease in cell viability at the highest doses and longest incubation time. Poly(lactide-co-glycolide) nanoparticles and mesoporous silica nanoparticles are internalized by endocytosis, poly(lactide-co-glycolide) nanoparticles undergo endosomal escape whereas mesoporous silica nanoparticles always occur within vacuoles. Liposomes were rarely observed within the cells. The uptake of all tested nanoparticles was less prominent in primary human myotubes as compared to myoblasts. Our findings represent the first step toward the characterization of the interaction between nanoparticles and primary human muscle cells and suggest that poly(lactide-co-glycolide) nanoparticles might find an application for drug delivery to skeletal muscle.

The role of anatase TiO2 on the performance of VOx-TiO2 is studied by in situ spectroscopies on a series of catalysts with 1.9–9.7 V at/nm2. At low coverages, VOx is preferentially located at defect sites, spreading on the main TiO2 {101} and {100} facets at intermediate coverages. Bronsted sites concentration is maximum around 6 V atoms/nm2, and EPR shows a significant amount of V4+ at intermediate VOx densities, indicating the influence of TiO2 on their reducibility. The activity is proportional to the square of the VOx density up to 5.8 V atoms/nm2. All catalysts show the same activation energy for NH3-SCR of 56.9 ± 1.0 kJ/mol in the temperature range 160−280 °C, indicating that the reaction path does not change in the studied V coverage range. The activity does not follow the observed trends for Bronsted acid sites or reducibility, and it seems that the ability to form V-pairs is the only requirement for catalytic activity.

The small-pore Cu-CHA zeolite is today the object of intensive research efforts to rationalize its outstanding performance in the NH3-assisted selective catalytic reduction (SCR) of harmful nitrogen oxides and to unveil the SCR mechanism. Herein we exploit operando X-ray spectroscopies to monitor the Cu-CHA catalyst in action during NH3-SCR in the 150-400 °C range, targeting Cu oxidation state, mobility, and preferential N or O ligation as a function of reaction temperature. By combining operando XANES, EXAFS, and vtc-XES, we unambiguously identify two distinct regimes for the atomic-scale behavior of Cu active-sites. Low-temperature SCR, up to ∼200 °C, is characterized by balanced populations of Cu(I)/Cu(II) sites and dominated by mobile NH3-solvated Cu-species. From 250 °C upward, in correspondence to the steep increase in catalytic activity, the largely dominant Cu-species are framework-coordinated Cu(II) sites, likely representing the active sites for high-temperature SCR.

International audience; Mesoporous ionosilicas bearing ammonium groups appear as versatile adsorbent for anionic drugs. High amounts of the anionic drugs diclofenac and sulindac are irreversibly trapped within the materials whereas neutral species are hardly adsorbed. Our results open the route towards new ionic materials for wastewater treatment via ion exchange.

A series of mono and bimetallic catalysts based on a Fe-Ag mixture deposited on mordenite was prepared by ion-exchange and evaluated in the catalytic activity test of the de-NOx reaction in the presence of CO/C3H6. The activity results showed that the most active samples were the Fe-containing ones, and at high temperatures, a co-promoter effect of Ag on the activity of Fe catalysts was also observed. The influence of the order of cation deposition on catalysts formation and their physicochemical properties was studied by FTIR (Fourier Transform Infrared Spectroscopy) of adsorbed NO, XANES (X-ray Absorption Near-Edge Structure), and EXAFS (Extended X-ray Absorption Fine Structure) and discussed in terms of the state of iron. Results of Fe K-edge XANES oscillations showed that, in FeMOR catalysts, iron was present in a disordered state as Fe3+ and Fe2+. In FeAgMOR, the prevailing species was Fe3+, while in the AgFeMOR catalyst, the state of iron was intermediate or mixed between FeMOR and FeAgMOR. The Fe K-edge EXAFS results were characteristic of a disordered phase, the first coordination sphere being asymmetric with two different Fe-O distances. In FeAgMOR and AgFeMOR, coordination of Fe-O was similar to Fe2O3 with a few amount of Fe2+ species. We may conclude that, in the bimetallic FeAgMOR and AgFeMOR samples, a certain amount of tetrahedral Al3+ ions in the mordenite framework is replaced by Fe3+ ions, confirming the previous reports that these species are active sites for the de-NOx reaction. Based on the thermodynamic analysis and experimental data, also, it was confirmed that the order of deposition of the components influenced the mechanism of active sites&rsquo, formation during the two steps ion-exchange synthesis.

On our route towards a more sustainable future, the use of stranded and underutilized natural gas to produce chemicals would be a great aid in mitigating climate change, due to the reduced CO2 emissions in comparison to using petroleum. In this study, we investigate the performance of Cu-exchanged SSZ-13 and SAPO-34 microporous materials in the stepwise, direct conversion of methane to methanol. With the use of X-ray absorption spectroscopy, infrared (in combination with CO adsorption) and Raman spectroscopy, we compared the structure&ndash, activity relationships for the two materials. We found that SSZ-13 performed significantly better than SAPO-34 at the standard conditions. From CH4-TPR, it is evident that SAPO-34 requires a higher temperature for CH4 oxidation, and by changing the CH4 loading temperature from 200 to 300 &deg, C, the yield (&mu, mol/g) of SAPO-34 was increased tenfold. As observed from spectroscopy, both three- and four-fold coordinated Cu-species were formed after O2-activation, among them, the active species for methane activation. The Cu speciation in SAPO-34 is distinct from that in SSZ-13. These deviations can be attributed to several factors, including the different framework polarities, and the amount and distribution of ion exchange sites.

In this work, we show the potentiality of operando FTIR spectroscopy to follow the formation of Cu