Monolithic Supports Research Articles

Quantitative assessment of the 3D pore space and microglobule clustering network to understand chromatographic transport phenomena in polymeric monolithic columns

The 3D pore space and microglobule clustering network of polymer monolithic columns, which exhibited similar external porosity but significantly different chromatographic dispersion and permeability characteristics, were subjected to tomographic imaging followed by stereological analyses. The morphologies of the monolithic support structures were examined using serial-block-face scanning electron microscopy. The statistically computed characteristic chord-length, hydraulic radius and tortuosity of the pore are strongly associated to chromatographic transport processes, in particular, eddy dispersion and mass-transfer resistance contributing to chromatographic dispersion, and permeability of monolithic columns. Moreover, Giddings’ trans-column velocity bias has been quantified in monoliths for the first time. With demonstrated method robustness, the proposed morphological descriptors and the streamlined analysis workflow provide novel insights bridging the structure-performance relationship for future chromatography column design.

Ultrastable monolithic electrodes with single-atom platinum-oxygen sites for efficient hydrogen evolution in acidic conditions

PtNC single-atom catalysts (SACs) single-atom catalysts (SACs) are promising for acidic hydrogen evolution reaction (HER) but suffer from instability at high current densities, limiting their large-scale application. Herein, PtO bonds are constructed to securely anchor atomically dispersed Pt for single-atom (SA) catalysis, utilizing etched vertical graphene (EVG) nanosheets as monolithic supports (Pt-SAs/EVG). Compared to PtNC, the resultant PtO4 coordination demonstrates improved stability while maintaining significant catalytic activity. When applying this catalyst in the acidic HER, a high turnover frequency (34.6 s−1) is achieved at 70 mV, accompanied by exceptional durability exceeding 100 h at −100 mA cm−2. Theoretical analyses indicate that the PtO bonds confer stability to the Pt atoms, facilitating the efficient adsorption of protons and the subsequent desorption of hydrogen. The prepared Pt-SAs/EVG can also be directly employed as the cathode to afford stable operation at 0.5 A cm−2 in a proton exchange membrane electrolyzer cell. This study offers novel insights into enhancing the performance of SACs for industrial applications in electrocatalysis.

Fabrication of Highly Efficient ZIF-8@PEI Monoliths for CO2 Capture Using Phosphorylated Cellulose Nanofiber as a Binder.

This study involves the synthesis and comparison of zeolitic imidazolate frameworks (ZIFs), specifically ZIF-8 and ZIF-67 pristine with a commercial zeolite, emphasizing their CO2 affinity and sorption capability. To overcome challenges persisting in the handling and integration of these materials into industrial adsorption processes, particularly when limited to microcrystalline fine powders, we present herein an innovative manufacturing method to produce standalone monolithic supports. This process involves pseudoplastic paste formulations utilizing polyethylenimine (PEI) as a coagulant and locally fabricated phosphorylated cellulose nanofiber (PCNF) as a binding agent. Rheological investigation was conducted to anticipate the required shaping and design by means of paste flowability, consistency, and stiffness. XRD and FTIR results confirm the preservation of crystalline structure and the occurrence of amine functionalization associated with the presence of PEI, respectively. The proposed method significantly enhances the CO2 adsorption performance of the produced ZIF-8 monolith in comparison with that reached when using the pristine material, achieving a capacity of 1.25-2 mmol·g-1 at 30 °C under dry conditions in a pressure range of 1-13 bar, respectively. In other words, this work clearly highlights an effective applicability of the ZIF-8 monolith as an innovative sorbent for further designing CO2 capture industrial setups.

Atypical applications of transverse diffusion of laminar flow profiles methodology for in-capillary reactions in capillary electrophoresis.

Capillary electrophoresis (CE) is a powerful separation technique offering quick and efficient analyses in various fields of bioanalytical chemistry. It is characterized by many well-known advantages, but one, which is perhaps the most important for this application field, is somewhat overlooked. It is the possibility to perform chemical and biochemical reactions at the nL scale inside the separation capillary. There are two basic formats applicable for this purpose, heterogeneous and homogeneous. In the former, one reactant is immobilized onto a particle or monolithic support or directly on the capillary wall, and the other is injected. In the latter, the reactant mixing inside a capillary is based on electromigration or diffusion. One of the diffusion-based methodologies, termed Transverse Diffusion of Laminar Flow Profiles, is the subject of this review. Since most studies utilizing in-capillary reactions in CE focus on enzymes, which are being continuously and exhaustively reviewed, this review covers the atypical applications of this methodology, but still in the bioanalytical field. As can be seen from the demonstrated applications, they are not limited to reactions, but can also be utilized for other biochemical systems.

In-situ synthesis of V2AlC@V2O5/TiO2 immobilized over honeycomb support with vanadium oxide electron transfer mediator for stimulating selective CO2 photoreduction through bi-reforming in a monolith reactor

Photocatalytic CO2 reduction to valuable chemicals and fuels is a practical approach for climate action; however, available photocatalysts and photoreactors are less efficient. In this work, well-designed V2AlC@V2O5 supported TiO2 and immobilized over honeycomb support for CO2 photoreduction in a monolith reactor have been investigated. The catalysts were loaded over the monolithic support using the sol-gel dip-coating method and found promising for higher light absorbance and charge separation. The performance of V2AlC@V2O5/TiO2 composite for photocatalytic CO2 reduction with water and bi-reforming of methanol was performed using a fixed bed and monolith photoreactor. Using V2AlC@V2O5/TiO2 with a fixed bed reactor and methanol–water mixture, a CO yield of 13.75 mmol g−1h−1 was produced, 26.39 and 38.19-fold higher than using water and pristine TiO2, respectively. Similarly, CH4 production was 1.97 and 12.33 folds higher than using water and TiO2 only, whereas, using water, production of H2 was not detected. The higher photoactivity of the composite with methanol was due to efficient photo-induced carrier separation due to the synergistic effect of V2AlC/V2O5 and more production of protons. Using a monolith photoreactor, CH4, CO and H2 production rates of 55.44, 35.51 and 1.638 mmol g−1h−1 were obtained, 166.50, 2.58 and 3.05 times more than those produced using a fixed bed reactor. This significantly higher photoactivity with monolith photoreactor was due to higher photon flux utilization with surface reactions, resulting in more production and utilization of photoinduced charge carriers. The highest QY after five consecutive cycles was 48.374, 25.358 and 1.51 % for CH4, CO and H2, which is 200.5, 2.54 and 3.87 folds higher than using the fixed bed, respectively. This work provides a new approach to designing and fabricating higher efficient and stable photocatalytic system for CO2 recycling, and it can be further employed for other energy-related applications.

Modeling and experimental analysis of CO2 methanation reaction using Ni/CeO2 monolithic catalyst

In this study, the effect of the cell density of monolithic catalysts was investigated and further mathematically modeled on cordierite supports used in CO2 methanation. Commercial cordierite monoliths with 200, 400, and 500 cpsi cell densities were coated by immersion into an ethanolic suspension of Ni/CeO2 active phase. SEM–EDS analysis confirmed that, owing to the low porosity of cordierite (surface area < 1 m2 g−1), the Ni/CeO2 diffusion into the walls was limited, especially in the case of low and intermediate cell density monoliths; thus, active phase was predominantly loaded onto the channels’ external surface. Nevertheless, despite the larger exposed surface area in the monolith with high cell density, which would allow for better distribution and accessibility of Ni/CeO2, its higher macro-pore volume resulted in some introduction of the active phase into the walls. As a result, the catalytic evaluation showed that it was more influenced by increments in volumetric flow rates. The low cell density monolith displayed diffusional control at flow rates below 500 mL min−1. In contrast, intermediate and high cell density monoliths presented this behavior up to 300 mL min−1. These findings suggest that the interaction reactants-catalyst is considerably more affected by a forced non-uniform flow when increasing the injection rate. This condition reduced the transport of reactants and products within the catalyst channels and, in turn, increased the minimum temperature required for the reaction. Moreover, a slight diminution of selectivity to CH4 was observed and ascribed to the possible formation of hot spots that activate the reverse water–gas shift reaction. Finally, a mathematical model based on fundamental momentum and mass transfer equations coupled with the kinetics of CO2 methanation was successfully derived and solved to analyze the fluid dynamics of the monolithic support. The results showed a radial profile with maximum fluid velocity located at the center of the channel. A reactive zone close to the inlet was obtained, and maximum methane production (4.5 mol m−3) throughout the monolith was attained at 350 °C. Then, linear streamlines of the chemical species were developed along the channel.

Cryogels and Monoliths: Promising Tools for Chromatographic Purification of Nucleic Acids.

The increasing demand for highly pure biopharmaceuticals has put significant pressure on the biotechnological industry to innovate in production and purification processes. Nucleic acid purification, crucial for gene therapy and vaccine production, presents challenges due to the unique physical and chemical properties of these molecules. Meeting regulatory standards necessitates large quantities of biotherapeutic agents of high purity. While conventional chromatography offers versatility and efficiency, it suffers from drawbacks like low flow rates and binding capacity, as well as high mass transfer resistance. Recent advancements in continuous beds, including monoliths and cryogel-based systems, have emerged as promising solutions to overcome these limitations. This review explores and evaluates the latest progress in chromatography utilizing monolithic and cryogenic supports for nucleic acid purification.

Immobilization of controlled Pu:Am ratio on actinide-specific affinity monolith support developed in capillary and coupled to inductively coupled plasma mass spectrometry.

The objective of this work was to develop an actinide-specific monolithic support in capillary designed to immobilize precise Pu:Am ratios and its coupling to inductively coupled plasma mass spectrometry (ICP-MS) for immobilized metal affinity chromatography applications. This format offers many advantages, such as reducing the sample amount and waste production, which are of prime importance when dealing with highly active radioelements. Four organic phosphorylated-based monoliths were synthesized in situ through UV photo-polymerization in capillary and characterized. The capillary coupling to ICP-MS was set up in conventional laboratory using Th and Sm as chemical analogues of Pu and Am. A dedicated method was developed to quantify online Th and Sm amounts immobilized on the monolithic capillaries, allowing to select the best monolith candidate poly(BMEP-co-EDMA)adp. By precisely adjusting the elemental composition in the loading solutions and applying the developed quantification method, the controlled immobilization of several Th:Sm molar ratios onto the monolith was successful. Finally, the capillary ICP-MS coupling was transposed in a glove box and by applying the strategy developed to design the monolithic support using Th and Sm, the immobilization of a 10.5 ± 0.2 (RSD = 2.3%, n = 3) Pu:Am molar ratio reflecting Pu ageing over 48years was achieved in a controlled manner on poly(BMEP-co-EDMA)adp. Hence, the new affinity capillary monolithic support was validated, with only hundred nanograms or less of engaged radioelements and can be further exploited to precisely determine differential interactions of Pu and Am with targeted biomolecules in order to better anticipate the effect of Am on Pu biodistribution.

SSZ-13 membranes on novel silica carbide monoliths for efficient CO2 separation

The usage of normal alumina supports brings the uncertain and undesirable aluminum transformation to the high-silica zeolite membranes to reduce Si/Al ratio in framework. In this current study, a novel aluminum-free silica carbide (SiC) monolithic support is used for the synthesis of SSZ-13 membranes with enhanced Si/Al ratio for the first time. Moreover, this high-porosity and monolithic SiC support enables membrane to increase gas permeance and surface-to-volume ratio. High-quality SSZ-13 membranes were prepared after rational modification of synthesis parameters such as synthesis temperature and time and support material. The effects of test temperature, pressure drop, feed flow rate and humidity on separation performance of the monolithic membranes were studied. The formation mechanism of SSZ-13 membrane was also investigated. The Si/Al ratio and CO2 permeance of SSZ-13 membranes on SiC monolith were 100% and 60% higher than that of membrane on alumina monolith, respectively. This monolithic membrane had comparable separation performance but about 2.3 times higher surface-to-volume ratios to the reported tubular zeolite membranes. This solution could be suitable to prepare other high-silica and all-silica zeolite membranes.

Structural design and particle size examination on NiO-CeO2 catalysts supported on 3D-printed carbon monoliths for CO2 methanation

3D-printed high-surface carbon monoliths have been fabricated and tested as catalyst supports of CO2 methanation active phases (NiO-CeO2, 12 wt% Ni). The carbon carriers show a developed microporosity and good adherence to the catalytic phases of NiO-CeO2, showing great stability and cyclability. Two monolith designs were used: a conventional parallel-channeled structure (honeycomb) and a complex 3D network of non-linear channels built upon interconnected circular sections (circles), where flow turbulences along the reactant gas path are spurred. The effect of the active phases particle size on the catalyst distribution and the overall performance has been assessed by comparing NiO-CeO2 nanoparticles of 7 nm average (Np), with a reference counterpart of uncontrolled structure (Ref). The improved radial gases diffusion in the circles monolith design is confirmed, and nanoparticles show enhanced CO2 methanation activity than the uncontrolled-size active phase at low temperatures (< 300 ºC). On the contrary, the Ref catalysts achieve higher CH4 production at higher temperatures, where the reaction kinetics is controlled by mass transfer limitations (T > 300 ºC). SEM and Hg porosimetry evidence that nanoparticles are deposited at deeper penetration through the narrow micropores of the carbon matrix of the monolithic supports, which tend to accumulate on the channels surface remaining more accessible to the reactant molecules. Altogether, this study examines the impact of the channel tortuosity and the active phase sizing on the CO2 methanation activity, serving as ground knowledge for the further rational and scalable fabrication of carbon monolith for catalytic applications.

Digital light processing 3D printing of microfluidic devices targeting high-pressure liquid-phase separations.

This paper focuses on 3D printing using digital light processing (DLP) to create microchannel devices with inner diameters of100, 200, and 500 µm and cater flow-through applications within the realm of analytical chemistry, in particular high-pressure liquid chromatographic separations. Effects of layer thickness and exposure time on channel dimensions and surface roughness were systematically investigated. Utilizing a commercially accessible 3D printer and acrylate resin formulation, we fabricated 100-500 µm i.d. squared and circular channel designs minimizing average surface roughness (< 20%) by applying a 20-µm layer thickness and exposure times ranging from 1.1 to 0.7s. Pressure resistance was measured by encasing microdevices in an aluminum chip holder that integrated flat-bottom polyetheretherketon (PEEK)nanoports allowing to establish the micro-to-macro interface to the HPLC instrument. After thermal post-curing and finetuning the clamping force of the chip holder, a maximum pressure resistance of 650bar (1.5% RSD) was reached (n = 3). A polymer monolithic support structure was successfully synthesized in situ with the confines of a 500 µm i.d. 3D printed microchannel. A proof-of-concept of a reversed-phase chromatographic gradient separation of intact proteins is demonstrated using an aqueous-organic mobile-phase with isopropanol as organic modifier.

A bio-inspired, monolithic catalyst support structure for optimized conductive heat removal in catalytic reactors

The performance of catalytic reactors in heterogeneous catalysis is especially dependent on the support structures the catalysts are dispersed on. They determine important properties like the pressure drop as well as the temperature distribution within catalytic reactors. The latter is especially important for reactions like the CO2 methanation, which is highly exothermic, but thermodynamically favored at low temperatures. Here we present a novel monolithic catalyst support structure inspired by the shape of diatom shells. By coupling a genetic algorithm with an FEM solver, a parametric model is optimized towards good radial heat transport. By comparing the optimized structures with honeycombs already used in industry, the beneficial thermal properties are demonstrated both for a pure conductive case as well as for superimposed fluid convection using Computational Fluid Dynamics. The optimized designs give a good basis for honeycomb-like catalyst support structures with good heat removal while preserving very low pressure drops.

Design and performance testing of a monolithic nickel-based SiC catalyst for steam methane reforming

Hydrogen is a highly promoted carbon-free energy carrier that has drawn significant attention recently due to its potential to decarbonise energy sector. More than three-quarters of hydrogen is currently produced via steam methane reforming (SMR), and nickel-based catalysts are used in most applications. Structured catalysts have been reported to be able to further improve catalyst performance as they can optimise heat and mass transfer, as well as prevent coke formation with its structural and textural proprieties. Silicon carbide (SiC) has excellent hardness, thermal conductivity, and chemical inertness, therefore is a promising material to develop structured nickel-based monolithic SiC catalysts for SMR. In this work, a structured monolithic catalyst support has been formed by a modified freeze-gelation method, initially starting from SiC powder, and nickel has been distributed to form a monolithic nickel-based catalyst by wet impregnation. The results showed that the catalysts can achieve thermodynamic equilibrium at 600 °C with a gas hourly space velocity (GHSV) of 10,000 h−1, while reaching a high methane conversion of 86% at 800 °C and GHSV value of 20,000 h−1 during the performance tests using low feeding concentration and low pressure. This is the first time SiC catalytic materials have had their performance demonstrated for SMR under realistic operating conditions.

Photocatalytic NOx removal with TiO2-impregnated 3D-printed PET supports

In this work, we investigated the photocatalytic removal of NOx using 3D-printed supports. Monolithic supports with internal channels were fabricated by Fused Modelling Deposition (FDM) using PET as the filament feedstock. The printing parameters of the supports were optimized to maximize the exposure of the photocatalyst to UV light throughout the monolithic PET printed supports. The removal experiments were carried out in a continuous gas phase flow reactor, which was custom designed in-house incorporating a 3D printed PET support impregnated with TiO2 as photocatalyst. The impregnated and non-impregnated supports were characterized by diffuse reflectance spectrometry, SEM and AFM. The effect of several key-factors on the NOx removal capacity was investigated, including the type of PET filament (native recycled, BPET vs. glycol-modified, PETG), the type of TiO2 (P25 vs. Hombikat UV-100), the UV light source (LED vs. tubular lamps), and the number of deposited TiO2 layers. The highest NO and NOx removal were achieved by using PETG supports coated with a single layer of Hombikat UV-100 and irradiating the flat reactor from both sides using two sets of black light lamps. However, the highest selectivity toward nitrate formation was obtained when using P25 under the same experimental conditions. This work demonstrates that 3D printing is a reliable and powerful technique for fabricating photocatalytic reactive supports that can serve as a versatile platform for evaluating photocatalytic performance.

Extending the Affinity Range of Weak Affinity Chromatography for the Identification of Weak Ligands Targeting Membrane Proteins.

The identification of weak-affinity ligands targeting membrane proteins is of great interest in Fragment-Based Drug Design (FBDD). Recently, miniaturized weak affinity chromatography (WAC) has been proposed as a valuable tool to study interactions between small ligands and wild-type membrane proteins embedded in so-called nanodisc biomimetic membranes immobilized on GMA-co-EDMA monoliths in situ-synthesized in capillary columns (less than one microliter in volume). In this proof-of-concept study, the achievable affinity range was limited to medium affinity (low micromolar range). The present work investigates different strategies to extend the affinity range towards low affinities, either by increasing the density of membrane proteins on the chromatographic support or by reducing non-specific interactions with the monolith. The combination of the use of a new and more hydrophilic monolithic support (poly(DHPMA-co-MBA)) and a multilayer nanodisc grafting process (up to three layers) allows a significant increase in the membrane protein density by a more than three-fold factor (up to 5.4 pmol cm-1). Such an increase in protein density associated with reduced non-specific interactions makes it possible to extend the range of detectable affinity, as demonstrated by the identification and characterization of affinities of very low-affinity ligands (Kd values of several hundred micromolar) for the adenosine receptor AA2AR used as a model protein, which was not possible before. The affinity was confirmed by competition experiments.

Immobilized enzyme microreactors for analysis of tryptic peptides in β-casein and β-lactoglobulin

In this study, our primary objective was to develop an effective analytical method for studying trypsin-digested peptides of two proteins commonly found in cow's milk: β-casein (βCN) and β-lactoglobulin (βLG). To achieve this, we employed two distinct approaches: traditional in-gel protein digestion and protein digestion using immobilized enzyme microreactors (μ-IMER). Both methods utilized ZipTip pipette tips filled with C18 reverse phase media for sample concentration. The μ-IMER was fabricated through a multi-step process that included preconditioning the capillary, modifying its surface, synthesizing a monolithic support, and further surface modification. Its performance was evaluated under HPLC chromatography conditions using a small-molecule trypsin substrate (BAEE). Hydrolysates from both digestion methods were analyzed using MALDI-TOF MS. Our findings indicate that the μ-IMER method demonstrated superior sequence coverage for oxidized molecules in βCN (33 ± 1.5%) and βLG (65 ± 3%) compared to classical in-gel digestion (20 ± 2% for βCN; 49 ± 2% for βLG). The use of ZipTips further improved sequence coverage in both classical in-gel digestion (26 ± 1% for βCN; 60 ± 4% for βLG) and μ-IMER (41 ± 3% for βCN; 80 ± 5% for βLG). Additionally, phosphorylations were identified. For βCN, no phosphorylation was detected using classical digestion, but the use of ZipTips showed a value of 27 ± 4%. With μ-IMER and μ-IMER–ZipTip, the values increased to 30 ± 2% and 33 ± 1%, respectively. For βLG, the use of ZipTip enabled the detection of a higher percentage of modified peptides in both classical (79 ± 2%) and μ-IMER (79 ± 4%) digestions. By providing a comprehensive comparison of traditional in-gel digestion and μ-IMER methods, this study offers valuable insights into the advantages and limitations of each approach, particularly in the context of complex biological samples. The findings set a new benchmark in protein digestion and analysis, highlighting the potential of μ-IMER systems for enhanced sequence coverage and post-translational modification detection.

Rapid and simple determination of organophosphorus pesticides in urine using polydopamine-modified monolithic spin column extraction combined with liquid chromatography–mass spectrometry

The determination of organophosphorus pesticides in urine is useful for evaluating human exposure. In this study, a simple micro-solid-phase extraction method based on a polydopamine-modified monolithic spin column combined with liquid chromatography–mass spectrometry (LC-MS) was developed for the determination of six organophosphorus pesticides (dimethoate, dichlorvos, carbofuran, methidathion, phosalone, and chlorpyrifos) in urine samples. A methacrylate polymer monolithic support was prepared in situ in the spin column, and dopamine solution was repeatedly passed through the monolith matrix via centrifugation to generate a polydopamine layer in the polymeric network. All extraction steps were performed via centrifugation. The monolith exhibited good permeability, which enabled high-flow-rate sample loading and significantly reduced the sample pre-treatment time. The addition of polydopamine significantly improved the extraction efficiency of the monolithic spin column owing to the catechol and amine groups in dopamine, which can enhance hydrogen bonding and π–π stacking. Factors affecting the extraction, including the solution pH, centrifugation speed, and desorption solvent, were investigated to determine the optimal extraction conditions. Under the optimal conditions, the OPP detection limits were 0.02–1.32 µg/L. The relative standard deviations of the single column (n = 5) and column-to-column (n = 3) precision for the extraction method were <11%. The monolithic spin column exhibited high stability and could be used for more than 40 extraction cycles. The recoveries for spiked urine samples were 72.1–109.3% (RSDs: 1.6–7.9%). The developed method was successfully applied to the simple and rapid analysis of organophosphorus pesticides in urine samples.

Influence of Support Structure on Catalytic Performance of Supported Liquid-Phase (SLP) Catalysts in Hydroformylation of 1-Butene

Several supported liquid-phase (SLP) catalysts with immobilized Rh-biphephos complexes on monolithic supports were prepared and applied for continuous gas-phase hydroformylation (HyFo) of 1-butene. The support comprised macroporous monolithic silicon carbide (SiC) with deposited silica nanoparticles (NPs) in order to provide mesopores with enhanced capillary forces to retain the liquid-phase. Variable parameters were examined for the monolithic SiC supports, including size and loading of deposited silica NPs and intermediate calcination between silica deposition steps to obtain the most efficient support configuration for the SLP system. The SLP catalysts with larger deposited silica NPs gave higher catalytic activity (i.e. 1-butene conversion and turnover frequency) compared to the supports with smaller sized silica NPs. However, the selectivity towards the preferred linear aldehyde was higher in the SLP catalysts with supports containing less silica with small silica NPs. Importantly, the prepared SLP catalyst systems showed long-term stability in HyFo with negligible formation of high boiling aldol condensation products.

Comparison of Direct Ink Writing and Binder Jetting for additive manufacturing of Pt/Al2O3 catalysts for the dehydrogenation of perhydro-dibenzyltoluene

Two additive manufacturing (AM) techniques, namely extrusion-based Direct Ink Writing (DIW) and powder-based Binder Jetting (BJ), were thoroughly compared to assess their respective advantages and drawbacks for catalyst shaping. The 3D printed monolithic Al2O3 supports were wet impregnated with H3Pt(SO3)2(OH) and tested for the dehydrogenation of perhydro-dibenzyltoluene (18H-DBT), a liquid organic hydrogen carrier (LOHC). The supports were analyzed regarding their specific surface area, compression strength, shrinkage behavior and pore size distribution with calcination temperatures ranging from 600 - 1200°C as well as 3D print specific characteristics. Benefiting the liquid phase reaction, pore diameters below 26nm were diminished above Tcalc = 1050°C, revealing a BET surface area of 26m2/g for BJ and 11m2/g for DIW printed supports. Furthermore, increasing the impregnation duration from 0.5h to 12h showed increased Pt loading, larger metal particles, and a deeper penetration into the support. Most notably, for BJ the Pt loading is generally higher due to higher meso- and macroporosity of the support. Catalytic 18H-DBT dehydrogenation with powder and monolithic catalysts showed equal dehydrogenation rates with both 3D printing methods, respectively. The achieved Pt productivity was about 4.3gH2gPt−1min−1 for powder tests and 2.7gH2gPt−1min−1 for monolithic pellets.

Fast and selective reversed-phase high performance liquid chromatographic separation of UO2 2+ and Th4+ ions using surface modified C18 silica monolithic supports with target specific ionophoric ligands.

Reprocessing nuclear-spent fuels is highly demanded for enhanced resource efficacy and removal of the associated radiotoxicity. The present work elucidates the rapid separation of UO2 2+ and Th4+ ions using a reversed-phase high-performance liquid chromatographic (RP-HPLC) technique by dynamically modifying the surface of a C18 silica monolith column with target-specific ionophoric ligands. For the dynamic modification, four analogous aromatic amide ligands, N 1,N 1,N 3,N 3,N 5,N 5-hexa(alkyl)benzene-1,3,5-tricarboxamide (alkyl = butyl, hexyl, octyl, and decyl) as column modifiers were synthesized. The complexation properties and retention profiles of the amide-based column modifiers for the selective and sequential separation of UO2 2+ and Th4+ ions were investigated. In addition, the selective separation of UO2 2+ and Th4+ ions among the competitive ions of similar chemical properties were also studied. The ionophore immobilized C18 silica monolith columns demonstrated a varying degree of retention behavior for UO2 2+ and Th4+ ions (UO2 2+ is retained longer than Th4+ under all analytical conditions), eventually leading to rapid separations within a period of ≤5 min. A 0.1 M solution of 2-hydroxyisobutyric acid (HIBA, 1 mL min-1) served as the mobile phase, and the qualitative and quantitative assessment of the sequentially separated 5f metal ions was achieved through post-column derivatization reaction, using arsenazo(iii) as a post-column reagent (PCR; 1.5 mL min-1) prior to analysis using a UV-vis detector, at 665 nm (λ max). The developed technique was further evaluated by standardizing various analytical parameters, including modifier concentration, mobile phase pH, mobile phase flow rate, etc., to yield the best chromatographic separation. Also, the conceptual role of alkyl chain length (in the modifier) on the retention behavior of the studied metal ions was evaluated for cutting-edge future applications.