Screen printed 3D microfluidic paper-based and modifier-free electroanalytical device for clozapine sensing.

The increasing demand in healthcare for accessible and cost-effective analytical tools is driving the development of reliable platforms to the customization of therapy according to individual patient drug serum levels, e.g. of anti-psychotics in schizophrenia. A modifier-free microfluidic paper-based electroanalytical device (µPED) holds promise as a portable, sensitive, and affordable solution. While many studies focus on the working electrode catalysts, improvements by engineering aspects e.g. of the electrode arrangement are less reported. In our study, we demonstrate the enhanced capabilities of the 3D electrode layout of µPED compared to 2D µPED arrangements. We especially show that screen printing can be employed to prepare 3D µPEDs. We conducted a comparison of different 2D and 3D electrode arrangements utilizing cyclic voltammetry in [Fe(CN)6]3-/4-, along with square-wave voltammetry for clozapine (CLZ) sensing. Our findings reveal that the utilization of the 3D µPED leads to an increase in both the electrochemically active surface area and the electron transfer rate. Consequently, this enhancement contributes to improve sensitivity in the CLZ sensing. The 3D µPED clearly outperforms the 2D µPED arrangement in terms of signal strength. With the 3D µPED under the optimized conditions, a linear dose-response for a concentration range from 7.0 to 100 µM was achieved. The limit of detection and sensitivity was determined to be 1.47 µM and 1.69 µA µM-1 cm-2, respectively. This evaluation is conducted in the context of detection and determination of CLZ in a human blood serum sample. These findings underscore the potential of the 3D µPED for future applications in pharmacokinetic analyses and clinical tests to personalize the management of schizophrenia.

Exploring the oxidation behavior of undiluted and diluted iron particles for energy storage: Mössbauer spectroscopic analysis and kinetic modeling.

Iron is an abundant and non-toxic element that holds great potential as energy carrier for large-scale and long-term energy storage. While from a general viewpoint iron oxidation is well-known, the detailed kinetics of oxidation for micrometer sized particles are missing, but required to enable large-scale utilization for energy production. In this work, iron particles are subjected to temperature-programmed oxidation. By dilution with boron nitride a sintering of the particles is prevented enabling to follow single particle effects. The mass fractions of iron and its oxides are determined for different oxidation times using Mössbauer spectroscopy. On the basis of the extracted phase compositions obtained at different times and temperatures (600-700 °C), it can be concluded that also for particles the oxidation follows a parabolic rate law. The parabolic rate constants are determined in this transition region. Knowledge of the particle size distribution and its consideration in modeling the oxidation kinetics of iron powder has proven to be crucial.

Nanoscale Hybrid Amorphous/Graphitic Carbon as Key Towards Next-Generation Carbon-Based Oxidative Dehydrogenation Catalysts.

A new strategy affords "non-nano" carbon materials as dehydrogenation catalysts that perform similarly to nanocarbons. Polymer-based carbon precursors that combine a soft-template approach with ion adsorption and catalytic graphitization are key to this synthesis strategy, thus offering control over macroscopic shape, texture, and crystallinity and resulting in a hybrid amorphous/graphitic carbon after pyrolysis. From this intermediate the active carbon catalyst is prepared by removing the amorphous parts of the hybrid carbon materials via selective oxidation. The oxidative dehydrogenation of ethanol was chosen as test reaction, which shows that fine-tuning the synthesis of the new carbon catalysts allows to obtain a catalytic material with an attractive high selectivity (82 %) similar to a carbon nanotube reference, while achieving 10 times higher space-time yields at 330 °C. This new class of carbon materials is accessible via a technically scalable, reproducible synthetic pathway and exhibits spherical particles with diameters around 100 µm, allowing unproblematic handling similar to classic non-nano catalysts.

Probing CO2 Reduction Pathways for Copper Catalysis Using an Ionic Liquid as a Chemical Trapping Agent.

The key to fully leveraging the potential of the electrochemical CO2 reduction reaction (CO2RR) to achieve a sustainable solar-power-based economy is the development of high-performance electrocatalysts. The development process relies heavily on trial and error methods due to poor mechanistic understanding of the reaction. Demonstrated here is that ionic liquids (ILs) can be employed as a chemical trapping agent to probe CO2RR mechanistic pathways. This method is implemented by introducing a small amount of an IL ([BMIm][NTf2 ]) to a copper foam catalyst, on which a wide range of CO2RR products, including formate, CO, alcohols, and hydrocarbons, can be produced. The IL can selectively suppress the formation of ethylene, ethanol and n-propanol while having little impact on others. Thus, reaction networks leading to various products can be disentangled. The results shed new light on the mechanistic understanding of the CO2RR, and provide guidelines for modulating the CO2RR properties. Chemical trapping using an IL adds to the toolbox to deduce the mechanistic understanding of electrocatalysis and could be applied to other reactions as well.

Photochemistry in a soft-glass single-ring hollow-core photonic crystal fibre.

A hollow-core photonic crystal fibre (HC-PCF), guided by photonic bandgap effects or anti-resonant reflection, offers strong light confinement and long photochemical interaction lengths in a microscale channel filled with a solvent of refractive index lower than that of glass (usually fused silica). These unique advantages have motivated its recent use as a highly efficient and versatile microreactor for liquid-phase photochemistry and catalysis. In this work, we use a single-ring HC-PCF made from a high-index soft glass, thus enabling photochemical experiments in higher index solvents. The optimized light-matter interaction in the fibre is used to strongly enhance the reaction rate in a proof-of-principle photolysis reaction in toluene.

Accelerating Oxygen-Reduction Catalysts through Preventing Poisoning with Non-Reactive Species by Using Hydrophobic Ionic Liquids.

Developing cost-effective electrocatalysts for the oxygen reduction reaction (ORR) is a prerequisite for broad market penetration of low-temperature fuel cells. A major barrier stems from the poisoning of surface sites by nonreactive oxygenated species and the sluggish ORR kinetics on the Pt catalysts. Herein we report a facile approach to accelerating ORR kinetics by using a hydrophobic ionic liquid (IL), which protects Pt sites from surface oxidation, making the IL-modified Pt intrinsically more active than its unmodified counterpart. The mass activity of the catalyst is increased by three times to 1.01 A mg(-1) Pt @0.9 V, representing a new record for pure Pt catalysts. The enhanced performance of the IL-modified catalyst can be stabilized after 30 000 cycles. We anticipate these results will form the basis for an unprecedented perspective in the development of high-performing electrocatalysts for fuel-cell applications.

A feasible way to remove the heat during adsorptive methane storage.

Methane originating from biogas or natural gas is an attractive and environmentally friendly alternative to gasoline. Adsorption is seen as promising storage technology, but the heat released limits fast filling of these systems. Here a lab scale adsorptive methane storage tank, capable to study the temperature increase during fast filling, was realized. A variation of the filling time from 1 h to 31 s, showed a decrease of the storage capacity of 14% and temperature increase of 39.6 °C. The experimental data could be described in good accordance with a finite element simulation solving the transient mass, energy, and impulse balance. The simulation was further used to extrapolate temperature development in real sized car tanks and for different heat pipe scenarios, resulting in temperature rises of approximately 110 °C. It could be clearly shown, that with heat conductivity as solei mechanism the heat cannot be removed in acceptable time. By adding an outlet to the tank a feed flow cooling with methane as heat carrier was realized. This setup was proofed in simulation and lab scale experiments to be a promising technique for fast adsorbent cooling and can be crucial to leverage the full potential of adsorptive methane gas storage.

Photonic crystal fibres for chemical sensing and photochemistry.

In this review, we introduce photonic crystal fibre as a novel optofluidic microdevice that can be employed as both a versatile chemical sensor and a highly efficient microreactor. We demonstrate that it provides an excellent platform in which light and chemical samples can strongly interact for quantitative spectroscopic analysis or photoactivation purposes. The use of photonic crystal fibre in photochemistry and sensing is discussed and recent results on gas and liquid sensing as well as on photochemical and catalytic reactions are reviewed. These developments demonstrate that the tight light confinement, enhanced light-matter interaction and reduced sample volume offered by photonic crystal fibre make it useful in a wide range of chemical applications.

Dynamic sparse x-ray nanotomography reveals ionomer hydration mechanism in polymer electrolyte fuel-cell catalyst.

Tomographic imaging of time-evolving samples is a challenging yet important task for various research fields. At the nanoscale, current approaches face limitations of measurement speed or resolution due to lengthy acquisitions. We developed a dynamic nanotomography technique based on sparse dynamic imaging and 4D tomography modeling. We demonstrated the technique, using ptychographic x-ray computed tomography as its imaging modality, on resolving the in situ hydration process of polymer electrolyte fuel cell (PEFC) catalyst. The technique provides a 40-time increase in temporal resolution compared to conventional approaches, yielding 28 nm half-period spatial and 12 min temporal resolution. The results allow a quantitative characterization of the water intake process inside PEFC catalysts with nanoscale resolution, which is crucial for understanding their electrochemical mechanisms and optimizing their performance. Our technique enables high-speed operando nanotomography studies and paves the way for wider application of dynamic tomography at the nanoscale.

Oxygen Reduction Reaction Activity and Stability of Shaped Metal-Doped PtNi Electrocatalysts Evaluated in Gas Diffusion Electrode Half-Cells.

The synthesis of bimetallic and trimetallic platinum-based octahedral catalysts for the cathode of proton exchange membrane fuel cells (PEMFCs) is a particularly active area aimed at meeting technological requirements in terms of durability and cost. The electrocatalytic activity and stability of these shaped catalysts were tested at relatively high potentials (@0.9 V vs RHE) and at lower current densities using the rotating disk electrode, which is less suitable for assessing their behavior under the operating conditions of PEMFCs. In this work, we use a gas diffusion electrode (GDE) half-cell setup to test the performance of the catalysts under application-oriented conditions, relatively higher current densities, and a square-wave stability test. After the stability test, we analyzed the GDE catalytic layer to study the agglomeration and dissolution of the transition metal under these conditions by using high-resolution scanning electron microscopy and energy-dispersive X-ray spectroscopy. The present results provide valuable guidance for developing next-generation active and durable catalysts for PEMFCs.

Increasing Accessible Active Site Density of Non-Precious Metal Oxygen Reduction Reaction Catalysts through Ionic Liquid Modification.

Non-precious metal catalysts show great promise to replace the state-of-the-art Pt-based catalysts for catalyzing the oxygen reduction reaction (ORR), while their catalytic activity still needs to be greatly improved before their broad-based application. Here, we report a facile approach to improving the performance of zeolitic imidazolate framework-derived carbon (ZDC) toward the ORR by incorporating a small amount of ionic liquid (IL). The IL would preferentially fill the micropores of ZDC and greatly enhance the utilization of the active sites within the micropores, which are initially not accessible due to insufficient surface wetting. It is also disclosed that the ORR activity in terms of kinetic current at 0.85 V depends on the loading amount of the IL, and the maximum activity is obtained at a mass ratio of IL to ZDC at 1.2. The optimum stems from the counterbalance between the enhanced utilization of the active sites within the micropores and the retarded diffusion of the reactants within the IL phase due to its high viscosity.

MXene Aerogel Derived Ultra-Active Vanadia Catalyst for Selective Conversion of Sustainable Alcohols to Base Chemicals.

Selective oxidation reactions are an important class of the current chemical industry and will be highly important for future sustainable chemical production. Especially, the selective oxidation of primary alcohols is expected to be of high future interest, as alcohols can be obtained on technical scales from biomass fermentation. The oxidation of primary alcohols produces aldehydes, which are important intermediates. While selective methanol oxidation is industrially established, the commercial catalyst suffers from deactivation. Ethanol selective oxidation is not commercialized but would give access to sustainable acetaldehyde production when using renewable ethanol. In this work, it is shown that employing 2D MXenes as building blocks allows one to design a nanostructured oxide catalyst composed of mixed valence vanadium oxides, which outperforms on both reactions known materials by nearly an order of magnitude in activity, while showing high selectivity and stability. The study shows that the synthesis route employing 2D materials is key to obtain these attractive catalysts. V4C3Tx MXene structured as an aerogel precursor needs to be employed and mildly oxidized in an alcohol and oxygen atmosphere to result in the aspired nanostructured catalyst composed of mixed valence VO2, V6O13, and V3O7. Very likely, the bulk stable reduced valence state of the material together coupled with the nanorod arrangement allows for unprecedented oxygen mobility as well as active sites and results in an ultra-active catalyst.

Scalable Microreactor Concept for the Continuous Kolbe Electrolysis of Carboxylic Acids Using Aqueous Electrolyte.

The Kolbe electrolysis is a promising reaction to combine the usage of electrons as reagents and the application of renewable generated carboxylic acids as raw materials producing value added chemicals. Within this study, the electrolysis was conducted in a specially developed concept electrochemical microreactor and draws the particular attention to continuous operation and reuse of the aqueous electrolyte as well as of the dissolved unreacted feedstock. The electrolysis was conducted in alkaline aqueous solution using n-octanoic acid as model substance. Platinized titanium as anode material in an undivided cell setup was shown to give Kolbe selectivity above 90 %. During the technically relevant conditions of current densities up to 0.6 A cm-2 and overall electrolysis times of up to 3 h, a high electrode stability was observed. Finally, a proof-of-concept continuous operation and the numbering up potential of the ECMR could be demonstrated.

Avoiding Pitfalls in Comparison of Activity and Selectivity of Solid Catalysts for Electrochemical HMF Oxidation.

Electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) offers a renewable approach to produce the value-added platform chemical 2,5-furandicarboxylic acid (FDCA). The key for the economic viability of this approach is to develop active and selective electrocatalysts. Nevertheless, a reliable catalyst evaluation protocol is still missing, leading to elusive conclusions on criteria for a high-performing catalyst. Herein, we demonstrate that besides the catalyst identity, secondary parameters such as materials of conductive substrates for the working electrode, concentration of the supporting electrolyte, and electrolyzer configurations have profound impact on the catalyst performance and thus need to be optimized before assessing the true activity of a catalyst. Moreover, we highlight the importance of those secondary parameters in suppressing side reactions, which has long been overlooked. The protocol is validated by evaluating the performance of free-standing Cu-foam, and CuCoO modified with NaPO2 H2 and Ni, which were immobilized on boron-doped diamond (BDD) electrodes. Recommended practices and figure of merits in carefully evaluating the catalyst performance are proposed.

An improved method to measure the rate of vaporisation and thermal decomposition of high boiling organic and ionic liquids by thermogravimetrical analysis.

The vapour pressure and the thermal stability of liquids are important material properties. For high boiling organic and ionic liquids (ILs), the determination of these properties is laborious and it is not easy to discriminate between evaporation and thermal decomposition. In this work, a simple but accurate method is presented to determine the parameters of decomposition and evaporation by thermogravimetrical analysis (TGA). The mass transfer coefficient was calculated based on a new correlation for the Sherwood number for cylindrical crucibles in overflow of a carrier gas. This correlation is valid for any diameter-to-height ratio and for any filling degree of the crucible and was derived from numerical simulations and proven by experiments with hexadecane, dodecane, and anthracene. The TGA analysis of two ILs was conducted. [EMIM][EtSO(4)] decomposes at ambient pressure without a measurable contribution of evaporation. To the contrary, [BMIM][NTf(2)] is relatively volatile. The vapour pressure of [BMIM][NTf(2)] and the kinetics of decomposition of both ILs were determined.

Paper-Based Microfluidics for Electrochemical Applications.

Paper-based microfluidics is characteristic of fluid transportation through spontaneous capillary action of paper and has exhibited great promise for a variety of applications especially for sensing. Furthermore, paper-based microfluidics enables the design of miniaturized electrochemical devices to be applied in the energy sector, which is especially attractive for the rapid growing market of small size disposable electronics. This review gives a brief summary on the basics of paper chemistry and capillary-driven microfluidic behavior, and highlights recent advances of paper-based microfluidics in developing electrochemical sensing devices and miniaturized energy storage/conversion devices. Their structural features, working principles and exemplary applications are comprehensively elaborated and discussed. Additionally, this review also points out the existing challenges and future opportunities of paper-based microfluidic electronics.

Porous graphite as stationary phase for the chromatographic separation of polymer additives - determination of adsorption capability by Raman spectroscopy and physisorption.

Additives are added to polymers in small concentration to achieve desired application properties widely used to tailor the properties. The rapid diversification of their molecular structures, with often only minute differences, necessitates the development of adequate chromatographic techniques. While modified silica so far is the workhorse as stationary phase we have probed the potential of porous graphitic carbon (HypercarbTM) for this purpose. The results show that the multitude of physicochemical interactions between analyte molecules and the graphitic surface enables separations of polyolefin stabilizers with unprecedented selectivity. To support the chromatographic results the adsorption capability of HypercarbTM for selected antioxidants and UV absorbers has been determined by Raman spectroscopy and argon physisorption measurements. The shift of the Graphite-band in the Raman spectra of HypercarbTM upon infusion with additives correlates with the changes in the Adsorption Potential Distributions. The results of argon physisorption measurements go hand in hand with the chronology of desorption of the additives in liquid chromatography experiments. The elution sequence can be explained by van der Waals or London forces, π-π-interactions and electron lone pair donor-acceptor interactions between the graphite surface and analyte functional groups.

Methanol conversion on borocarbonitride catalysts: Identification and quantification of active sites.

Borocarbonitrides (BCNs) have emerged as highly selective catalysts for the oxidative dehydrogenation (ODH) reaction. However, there is a lack of in-depth understanding of the catalytic mechanism over BCN catalysts due to the complexity of the surface oxygen functional groups. Here, BCN nanotubes with multiple active sites are synthesized for oxygen-assisted methanol conversion reaction. The catalyst shows a notable activity improvement for methanol conversion (29%) with excellent selectivity to formaldehyde (54%). Kinetic measurements indicate that carboxylic acid groups on BCN are responsible for the formation of dimethyl ether, while the redox catalysis to formaldehyde occurs on both ketonic carbonyl and boron hydroxyl (B─OH) sites. The ODH reaction pathway on the B─OH site is further revealed by in situ infrared, x-ray absorption spectra, and density functional theory. The present work provides physical-chemical insights into the functional mechanism of BCN catalysts, paving the way for further development of the underexplored nonmetallic catalytic systems.

Improving control of carbide-derived carbon microstructure by immobilization of a transition-metal catalyst within the shell of carbide/carbon core-shell structures.

Carbon materials for electrical energy devices, such as battery electrodes or fuel-cell catalysts, require the combination of the contradicting properties of graphitic microstructure and porosity. The usage of graphitization catalysts during the synthesis of carbide-derived carbon materials results in materials that combine the required properties, but controlling the microstructure during synthesis remains a challenge. In this work, the controllability of the synthesis route is enhanced by immobilizing the transition-metal graphitization catalyst on a porous carbon shell covering the carbide precursor prior to conversion of the carbide core to carbon. The catalyst loading was varied and the influence on the final material properties was characterized by using physisorption analysis with nitrogen as well as carbon dioxide, X-ray diffraction, temperature-programmed oxidation (TPO), Raman spectroscopy, SEM and TEM. The results showed that this improved route allows one to greatly vary the crystallinity and pore structure of the resulting carbide-derived carbon materials. In this sense, the content of graphitic carbon could be varied from 10-90 wt % as estimated from TPO measurements and resulting in a specific surface area ranging from 1500 to 300 m2·g-1.

Combining autoclave and LCWM reactor studies to shed light on the kinetics of glucose oxidation catalyzed by doped molybdenum-based heteropoly acids.

In this work we combined kinetic studies for aqueous-phase glucose oxidation in a high-pressure autoclave setup with catalyst reoxidation studies in a liquid-core waveguide membrane reactor. Hereby, we investigated the influence of Nb- and Ta-doping on Mo-based Keggin-polyoxometalates for both reaction steps independently. Most importantly, we could demonstrate a significant increase of glucose oxidation kinetics by Ta- and especially Nb-doping by factors of 1.1 and 1.5 compared to the classical HPA-Mo. Moreover, activation energies for the substrate oxidation step could be significantly reduced from around 80 kJ mol-1 for the classical HPA-Mo to 61 kJ mol-1 for the Ta- and 55 kJ mol-1 for the Nb-doped species, respectively. Regarding catalyst reoxidation kinetics, the doping did not show significant differences between the different catalysts.