A novel series membranes based on non-linear all-aromatic polyimides (PIs) was investigated with the aim to understand how the PI backbone geometry and local electrostatics govern gas transport and the ability to separate CO₂/CH₄ mixtures. Non-linear 3-ring aromatic diamines, with exocyclic bond angles varying between 120 and 134°, enable the design of high Tg (>276 °C) PIs. A polar 1,3,4-oxadiazole diamine (ODD) (μ = 3D) monomer and a non-polar m-terphenyl diamine (TPD) reference monomer were synthesized and coupled with 3 dianhydrides, i.e. ODPA, ODDA, and 6FDA. In 6FDA-based membranes CO₂ permeabilities (P_CO2) are the highest of the series. The 6FDA-ODD membrane shows excellent membrane performance with high P_CO2 values at all feed pressures. Up to 12 bar (6 bar CO₂) none of the membranes reached their plasticization pressure. The non-linear backbone geometry promotes CO₂ permeability, whereas the presence of an electrostatic dipole moment associated with the 1,3,4-oxadiazole heterocycle governs CO₂/CH₄ separation selectivity.

A novel electrochemical glucose sensor was developed, based on a multiwall carbon nanotubes (MWCNTs)-copper-1,3,5-benzenetricarboxylic acid (CuBTC)-epoxy composite electrode, named MWCNT-CuBTC. The electrode nanocomposite was prepared by a two-roll mill procedure and characterized morphostructurally by scanning electron microscopy (SEM). The CuBTC formed defined crystals with a wide size distribution, which were well dispersed and embedded in the MWCNTs. Its electrical conductivity was determined by four-point probe contact (DC) conductivity measurements. The electroactive surface area, determined using cyclic voltammetry (CV), was found to be 6.9 times higher than the geometrical one. The results of the electrochemical measurements using CV, linear sweep voltammetry (LSV), differential pulse voltammetry (DPV), chronoamperometry (CA) and multiple pulse amperometry (MPA) showed that the MWCNT-CuBTC composite electrode displayed high electrocatalytic activity toward the oxidation of glucose and, as a consequence, very high sensitivity. The best sensitivity of 14,949 µAmM⁻¹cm⁻¹ was reached using MPA at the potential value of 0.6 V/SCE, which was much higher in comparison with other copper-based electrodes reported in the literature. The good analytical performance, low cost and simple preparation method make this novel electrode material promising for the development of an effective glucose sensor.

Cu-based metal-organic framework (MOF) microdevices are applied in sampling and preconcentration of nerve agents (NAs) diluted in gaseous streams. An in situ electrochemical-assisted synthesis of a Cu-benzene-1,3,5-tricarboxylate (BTC) thick film is carried out to functionalize a Cu-modified glass substrate. This simple, rapid, reproducible, and easy-to-integrate MOF synthesis approach enables the microfabrication of functional micro-preconcentrators with a large Brunauer-Emmett-Teller (BET) surface area (above 2000 cm2) and an active pore volume (above 90 nL) for the efficient adsorption of nerve agent molecules along the microfluidic channel 2.5 cm in length. The equilibrium adsorption capacity of the bulk material has been characterized through thermogravimetric analysis after exposure to controlled atmospheres of a sarin gas surrogate, dimethyl methylphosphonate (DMMP), in both dry and humid conditions (30% RH at 293 K). Breakthrough tests at the ppm level (162 mg/m3) reveal equilibrium adsorption capacities up to 691 mg/g. The preconcentration performance of such μ-devices when dealing with highly diluted surrogate atmosphere, i.e., 520 ppbV (2.6 mg/m3) at 298 K, leads to preconcentration coefficients up to 171 for sample volume up to 600 STP cm3. We demonstrate the potentialities of Cu-BTC micro-preconcentrators as smart first responder tools for "on-field" detection of nerve agents in the gas phase at relevant conditions.

High performance and commercially attractive mixed-matrix membranes were developed for H₂/CO₂ separation via a scalable hollow fiber spinning process. Thin (~300 nm) and defect-free selective layers were successfully created with a uniform distribution of the nanosized (~60 nm) zeolitic-imidazole framework (ZIF-8) filler within the polymer (polybenzimidazole, PBI) matrix. These membranes were able to operate at high temperature (150 °C) and pressure (up to 30 bar) process conditions required in treatment of pre-combustion and syngas process gas streams. Compared with neat PBI hollow fibers, filler incorporation into the polymer matrix leads to a strong increase in H₂ permeance from 65 GPU to 107 GPU at 150 °C and 7 bar, while the ideal H₂/CO₂ selectivity remained constant at 18. For mixed gas permeation, there is competition between H₂ and CO₂ transport inside ZIF-8 structure. Adsorption of CO₂ in the nanocavities of the filler suppresses the transport of the faster permeating H₂ and consequently decreases the H₂ permeance with total feed pressure down to values equal to the pure PBI hollow fibers for the end pressure of 30 bar. Therefore, the improvement of fiber performance for gas separation with filler addition is compromised at high operating feed pressures, which emphasizes the importance of membrane evaluation under relevant process conditions.

Producing aromatics directly from the smallest hydrocarbon building block, methane, is attractive because it could help satisfy increasing demand for aromatics while filling the gap created by decreased production from naphtha crackers. The system that catalyzes the direct methane dehydroaromatization (MDA) best so far is Mo supported on zeolite. Mo has shown to outperform other transition metals (TMs). Here we attempt to explain the superiority of Mo by directly comparing Fe and Mo supported on HZSM-5 zeolite. To determine the most important parameters responsible for the superior performance of Mo, detailed characterization using X-ray absorption spectroscopy (XAS) techniques combined with catalytic testing and theoretical calculations are performed. The higher abundance of mono- A nd dimeric sites for the Mo system, their ease of carburization in methane, as well as intrinsically lower activation energy barriers of breaking the methane C-H bond over Mo explain the better catalytic performance. In addition, a pretreatment in CO is presented to more easily carburize Fe and thereby improve its catalytic performance.

Linear energy scaling laws connect the kinetic and thermodynamic parameters of key elementary steps for heterogeneously catalyzed reactions over defined active sites on open surfaces. Such scaling laws provide a framework for a rapid computational activity screening of families of catalysts, but they also effectively impose a fundamental limit on the theoretically attainable activity. Understanding the limits of applicability of the linear scaling laws is therefore crucial for the development of predictive models in catalysis. In this work, we computationally investigate the role of secondary effects of the active site environment on the reactivity of defined Fe complexes in ZSM-5 zeolite toward methane oxofunctionalization. The computed C-H activation barriers over Fe-sites at different locations inside the zeolite pores generally follow the associated reaction enthalpies and the hydrogen affinities of the active site, reflecting the O-H bond strength. Nevertheless, despite the close similarity of the geometries and intrinsic reactivities of the considered active complexes, substantial deviations from these linear scaling relations are apparent from the DFT calculations. We identify three major factors behind these deviations, namely, (1) confinement effects due to the zeolite micropores, (2) coordinative flexibility, and (3) multifunctionality of the active site. The latter two phenomena impact the mechanism of the catalytic reaction by providing a cooperative reaction channel for the substrate activation or by enabling the stabilization of the intrazeolite complex along the reaction path. These computational findings point to the need for the formulation of multidimensional property-Activity relationships accounting for both the intrinsic chemistry of the reactive ensembles and secondary effects due to their environmental and dynamic characteristics.

Mesoporous nitrogen-doped carbon nanoparticles with atomically dispersed iron sites (named mesoNC-Fe) are synthesized via high-temperature pyrolysis of an Fe containing ZIF-8 MOF. Hydrolysis of tetramethyl orthosilicate (TMOS) in the MOF framework prior to pyrolysis plays an essential role in maintaining a high surface area during the formation of the carbon structure, impeding the formation of iron (oxide) nanoparticles. To gain inside on the nature of the resulting atomically dispersed Fe moieties, HERFD-XANES, EXAFS and valence-to-core X-ray emission spectroscopies have been used. The experimental spectra (both XAS and XES) combined with theoretical calculations suggest that iron has a coordination sphere including a porphyrinic environment and OH/H₂O moieties responsible for the high activity in CO₂ electroreduction. DFT calculations demonstrate that CO formation is favored in these structures because the free energy barriers of *COOH formation are decreased and the adsorption of *H is impeded. The combination of such a unique coordination environment with a high surface area in the carbon structure of mesoNC-Fe makes more active sites accessible during catalysis and promotes CO₂ electroreduction.

Methane dehydroaromatization (MDA) over Mo/HZSM-5 has been hypothesized in literature to proceed via a two-step mechanism: methane is first converted to ethylene on the molybdenum (Mo) functionality and then ethylene is oligomerized, cyclized and dehydrogenated on the Brønsted acid sites (BAS) of the HZSM-5 support. This hypothesis is tested by studying the conversion of ethylene at the same conditions as used for MDA, namely 700 °C, atmospheric pressure, and by co-feeding experiments with H₂ and CH₄. Our results suggest that ethylene is not the main intermediate for MDA, because the aromatic selectivities obtained from methane conversion are higher than selectivities measured during ethylene conversion. Furthermore, carbonaceous deposits formed during MDA have a lower density, are more hydrogenated and more active than the ones formed during ethylene aromatization (EDA). Similarly as for MDA, an activation period in which Mo carburizes to its active phase and an induction period, in which aromatics formation rates increase to their maximum are observed for ethylene conversion. The induction period, which was explained by the buildup of a hydrocarbon pool (HCP) is much faster with methane than with ethylene. This period, is attributed to a slow buildup of hydrocarbons, strongly adsorbed on Mo sites, because it is only observed with catalysts containing Mo. Hydrogen co-feeding with ethylene leads to the formation of more reactive coke species and a significantly prolonged lifetime of the catalyst, but not to a faster buildup of the HCP.

A mathematical model is used to predict adsorption isotherms from experimentally measured breakthrough curves. Using this approach, by performing only breakthrough experiments for a mixture of two (or more) components, one can obtain pure component adsorption isotherms up to the pressure of the experiment. As a case study, the adsorption of an equimolar mixture of CO₂ and CH₄ in zeolite ITQ-29 is investigated. Pure component linear adsorption isotherms for CO₂ and CH₄ are predicted by fitting the theoretical breakthrough curves to the experimental ones. Henry coefficients obtained from our approach are in excellent agreement with those measured experimentally. A similar procedure is applied to predict the complete Langmuir adsorption isotherm from breakthrough curves at high pressures. The resulting adsorption isotherms are in very good agreement with those measured experimentally. In our model for transient adsorption, mass transfer from the gas phase to the adsorbed phase is considered using the Linear Driving Force model and dispersion of the gas phase in the packed bed is taken into account. IAST is used to compute the equilibrium loadings for a mixture of gases. The influence of the dispersion coefficient and the effective mass transfer coefficient on the shape of breakthrough curves is investigated and discussed. Rough estimations of these values are sufficient to predict adsorption isotherms from breakthrough curves.

The catalytic performance of the bifunctional catalyst Mo/HZSM-5 for methane dehydroaromatization (MDA) depends on the Mo dispersion and on zeolite acidity. Here we separately quantify the effect of dispersion and the effect of acidity on aromatic yields and coke selectivity. Also, the effect of porosity on the same is quantitatively assessed. For that, a suite of 17 samples with varying Mo dispersion were synthesized by means of several methods, including chemical vapor deposition with MoCl ₅ , MoO ₂ Cl ₂ and Mo(CO) ₆ as precursors and the conventional methods, incipient wetness impregnation and solid ion exchange. These catalysts were characterized with pyridine IR-spectroscopy, XPS, UV–vis spectroscopy, N ₂ adsorption, XRD, TGA and ²⁷ Al MAS NMR. The combined results yielded a measure of how much Mo is anchored to the zeolite as well-defined cationic species and how much is present as bigger clusters on the outer surface of the zeolite. Through relating these characterization results to the catalytic behavior of the catalysts, it was found that the maximum instantaneous benzene and naphthalene yields as well as the integral selectivities during methane dehydroaromatization linearly increase with the amount of Mo present as mono- or dimeric species. At the same time, the selectivity to coke increases with the amount of Mo present as bigger clusters or nanoparticles on the outer surface of the zeolite. The number of Mo cationic sites is the most important factor determining the activity of Mo/HZSM-5 for low loadings of Mo. But at higher loadings, the high rate of aromatics formation requires an easily accessible pore structure as well.

We report the preparation and electrocatalytic performance of silver-containing gas diffusion electrodes (GDEs) derived from a silver coordination polymer (Ag-CP). Layer-by-layer growth of the Ag-CP onto porous supports was applied to control Ag loading. Subsequent electro-decomposition of the Ag-CP resulted in highly selective and efficient CO₂-to-CO GDEs in aqueous CO₂ electroreduction. Afterward, the metal-organic framework (MOF)-mediated approach was transferred to a gas-fed flow electrolyzer for high current density tests. The in situ formed GDE, with a low silver loading of 0.2 mg cm^-2, showed a peak performance of j_CO ≈ 385 mA cm^-2 at around -1.0 V vs RHE and stable operation with high FE_CO (>96%) at j_Total = 300 mA cm^-2 over a 4 h run. These results demonstrate that the MOF-mediated approach offers a facile route for manufacturing uniformly dispersed Ag catalysts for CO₂ electrochemical reduction by eliminating ill-defined deposition steps (drop-casting, etc.) while allowing control of the catalyst structure through self-assembly.

The elimination of the additional defect healing post‐treatment step in asymmetric hollow fiber manufacturing would result in a significant reduction in membrane production cost. However, obtaining integrally skinned polymeric asymmetric hollow fiber membranes with an ultrathin and defect‐free selective layer is quite challenging. In this study, P84® asymmetric hollow fiber membranes with a highly thin (~56 nm) defect‐free skin were successfully fabricated by fine tuning the dope composition and spinning parameters using volatile additive (tetrahydrofuran, THF) as key parameters. An extensive experimental and theoretical study of the influence of volatile THF addition on the solubility parameter of the N‐methylpyrrolidone/THF solvent mixture was performed. Although THF itself is not a solvent for P84®, in a mixture with a good solvent for the polymer, like N‐Methyl‐2‐pyrrolidone (NMP), it can be dissolved at high THF concentrations (NMP/THF ratio > 0.52). The as‐spun fibers had a reproducible ideal CO2/N2 selectivity of 40, and a CO2 permeance of 23 GPU at 35 °C. The fiber production can be scaled‐up with retention of the selectivity.

Membranes with high selectivity and permeance are needed to reduce energy consumption in hydrogen purification and pre-combustion CO ₂ capture. Polybenzimidazole (PBI) is one of the leading membrane materials for this separation. In this study, we present superior novel supported PBI (poly(p-phenylene benzobisimidazole), PBDI) membranes prepared by a facile interfacial polymerization (IP) method. The effect of IP reaction duration, operating temperature and pressure on membrane separation performance was systematically investigated. The best performance was achieved for membranes prepared in a 2 h reaction time. The resulting membranes display an ultrahigh mixed-gas H ₂ /CO ₂ selectivity of 23 at 423 K together with an excellent H ₂ permeance of 241 GPU, surpassing the membrane performance of conventional polymers (the 2008 Robeson upper bound). These separation results, together with the facile manufacture, pressure resistance, long-term thermostability (>200 h) and economic analysis, recommend the PBDI membranes for industrial use in H ₂ purification and pre-combustion CO ₂ capture. Besides, PBDI membranes possess high selectivities towards H ₂ /N ₂ (up to 60) and H ₂ /CH ₄ (up to 48) mixtures, indicating their potential applications in ammonia synthesis and syngas production.

The mechanism of methane activation on Mo/HZSM-5 is poorly described, despite the great interest in methane dehyd roa romatization (MDA) to replace oil refineries for producing aromatics. It is difficult to assess the exact nature of the active site due to fast coking. By pre-carburizing Mo/HZSM-5 with carbon monoxide, the active site for MDA can be isolated and studied without the formation of coke. This strategy helped us examine how methane is activated on the catalytic site by carrying out MDA using isotopically labelled methane (^{1 3} C H ₄ ) . We show that carbon originating from the preformed carbide is incorporated into the main products of the reaction, ethylene and benzene, demonstrating the dynamic nature of these active sites.

Separation of propylene/propane is one of the most challenging and energy consuming processes in the chemical industry. Propylene demand is increasing and a 99.5% purity is required for industrial purposes. Adsorption based solutions are the most promising alternatives to improve the economical/energetic efficiency of the process. Zeolitic Imidazolate Frameworks (ZIFs) combine the desired characteristics from both MOFs and zeolites: tunability and flexibility from metal organic frameworks, and exceptional thermal and chemical stability from zeolites. In order to enlighten the role of the cation in the sodalite ZIF-8 framework for propane/propylene separation, dynamic breakthrough measurements have been performed over ZIF-8(Zn), ZIF-67 (i.e. ZIF-8(Co)) and MUV-3 (i.e. ZIF-8(Fe)), all isostructural materials based on the same linker (2-methylimidazole). Cation substitution has a remarkable influence in the framework flexibility, and, consequently, in SOD-ZIF selectivity for light hydrocarbons. The differences between the crystallographic pore sizes of the material and the molecular dimensions of propane and propylene are so small, that the slightest change in the framework causes notable advantages/disadvantages in the final application. While cobalt is known to promote a more rigid framework resulting in an adsorption selectivity towards propane, iron presents the inverse effect yielding selectivity to propylene. Zinc has an intermediate effect. A threshold pressure in the isotherm is observed for propylene uptake by ZIF-67 at 273 and 298 K, and only at the lower temperature for ZIF-8. Inlet mixture composition does not highly influence the adsorptive selectivity, although it clearly affects the pure hydrocarbon recovery. Over ZIF-67 breakthrough experiments at 298 K yield a temporary pure propylene flow representing 10–15% of the amount fed. ZIF-67 is a promising candidate for propylene/propane adsorptive separation.

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.

The active sites on the methane dehydroaromatization (MDA) catalyst Mo/HZSM-5 are very hard to characterize, because they are present in various geometries and sizes and only form under reaction conditions with methane at 700 °C. To address these issues an experimental strategy is presented that enables distinguishing different active sites for MDA present on Mo/HZSM-5 and helps determining the Mo charge, nuclearity and chemical composition. This approach combines a CO pretreatment to separate the active Mo site formation from coke formation, quasi-in situ spectroscopic observations using DNP, ¹³C NMR, CO IR and theory. This allows the discrimination between three different types of active sites. Distinct spectroscopic features were observed corresponding to two types of mono- or dimeric Mo (oxy-)carbide sites as well as a third site assigned to Mo₂C nanoparticles on the outer surface of the zeolite. Their formal Mo oxidation state was found to be between 4+ and 6+. Dynamic nuclear polarization (DNP) measurements of samples carburized in CO as well as in CH₄ confirm the assignment and also show that accumulated aromatic carbon covers the bigger Mo nanoparticles on the outer surface of the zeolite, causing deactivation. It was previously observed that after an initial period where no desired products are formed yet, benzene starts slowly forming until reaching its maximum productivity. Direct observation of the active site with ¹³C NMR confirmed that Mo-sites do not transform further once benzene starts forming, meaning that they are fully activated during the period where no desired products are observed yet. Therefore the slow increase of the benzene formation rate cannot be attributed to a further transformation of Mo sites.

The cobalt-based ZIF-67 has been evaluated for the adsorptive propylene/propane separation in a fixed bed. Characterization techniques and dynamic measurements have been performed over ZIF-67 to evaluate its potential in this defiant process. Cobalt promotes a more rigid framework than zinc in the isostructural ZIF-8. Although the adsorption affinity of ZIF-67 for both hydrocarbons is similar, the lower flexibility of the framework makes ZIF-67 behave with a clear preference towards propane. This inverse selectivity promotes the enrichment in propylene content upon breakthrough, and may simplify the separation scheme. Therefore, ZIF-67 adsorptive separation is presented as an alternative to energy-demanding distillation.