New insights into the dissolution mechanisms of iron oxides and combusted iron particles in oxalic acid.

The influence of oxidation state and crystalline structure on the dissolution mechanisms of both pure iron oxides and combusted iron particles in aqueous oxalic acid (0.5 mol/l) at 60 °C was systematically investigated. Dissolution experiments were carried out in a temperature-controlled, continuous-flow capillary reactor, allowing for the removal of reaction products and thereby suppressing the autocatalytic reaction mechanism.

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, 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 of the electrode arrangement are less reported.

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.

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.

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.

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.

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.

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 (Hypercarb) for this purpose.

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.

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.

Activated Carbon in the Third Dimension-3D Printing of a Tuned Porous Carbon.

A method for obtaining hierarchically structured porous carbons, employing 3D printing to control the structure down to the lower µm scale, is presented. To successfully 3D print a polymer precursor and transfer it to a highly stable and structurally conformal carbon material, stereolithography 3D printing and photoinduced copolymerization of pentaerythritol tetraacrylate and divinylbenzene are employed. Mechanically stable structures result and a resolution of ≈15 µm is demonstrated.

Paper-based microfluidic aluminum-air batteries: toward next-generation miniaturized power supply.

Paper-based microfluidics (lab on paper) emerges as an innovative platform for building small-scale devices for sensing, diagnosis, and energy storage/conversions due to the power-free fluidic transport capability of paper via capillary action. Herein, we report for the first time that paper-based microfluidic concept can be employed to fabricate high-performing aluminum-air batteries, which entails the use of a thin sheet of fibrous capillary paper sandwiched between an aluminum foil anode and a catalyst coated graphite foil cathode without using any costly air electrode or external pump device for fluid transport. The unique microfluidic configuration can help overcome the major drawbacks of conventional aluminum-air batteries including battery self-discharge, product-induced electrode passivation, and expensive and complex air electrodes which have long been considered as grand obstacles to aluminum-air batteries penetrating the market.

Effect of Ionic Liquid Modification on the ORR Performance and Degradation Mechanism of Trimetallic PtNiMo/C Catalysts.

Ionic liquids (ILs) modification, following the concept of "solid catalyst with ionic liquid layer (SCILL)", has been demonstrated to be an effective approach to improving both activity and stability of Pt-based catalysts for the oxygen reduction reaction. In this work, the SCILL concept has been applied to a trimetallic PtNiMo/C system, which has been documented recently to be significantly advantageous over the benchmark PtNi-based catalysts for oxygen reduction. To achieve this, two hydrophobic ILs ([BMIM][NTF2] and [MTBD][BETI]) were used to modify PtNiMo/C with four IL-loading amounts between 7 and 38 wt %.

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.

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.

Tuning the Electrocatalytic Performance of Ionic Liquid Modified Pt Catalysts for the Oxygen Reduction Reaction via Cationic Chain Engineering.

Modifying Pt catalysts using hydrophobic ionic liquids (ILs) has been demonstrated to be a facile approach for boosting the performance of Pt catalysts for the oxygen reduction reaction (ORR). This work aims to deepen the understanding and initiate a rational molecular tuning of ILs for improved activity and stability. To this end, Pt/C catalysts were modified using a variety of 1-methyl-3-alkylimidazolium bis(trifluoromethanesulfonyl)imide ([C Cim][NTf], = 2-10) ILs with varying alkyl chain lengths in imidazolium cations, and the electrocatalytic properties (e.

Modifier-Free Microfluidic Electrochemical Sensor for Heavy-Metal Detection.

Heavy-metal pollution poses severe threat to ecological systems and presents a great challenge for global sustainability. Portable point-of-care sensing platform for detection/monitoring of heavy-metal pollution in the environment is urgently demanded. Herein, a highly sensitive, robust, and low-cost microfluidic electrochemical carbon-based sensor (μCS) for detection of trace heavy metals is presented.

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.

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.

Boosting performance of low temperature fuel cell catalysts by subtle ionic liquid modification.

High cost and poor stability of the oxygen reduction reaction (ORR) electrocatalysts are the major barriers for broad-based application of polymer electrolyte membrane fuel cells. Here we report a facile and scalable approach to improve Pt/C catalysts for ORR, by modification with small amounts of hydrophobic ionic liquid (IL). The ORR performance of these IL-modified catalysts can be readily manipulated by varying the degree of IL filling, leading to a 3.

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.