Insights on the Electrocatalytic Seawater Splitting at Heterogeneous Nickel-Cobalt Based Electrocatalysts Engineered from Oxidative Aniline Polymerization and Calcination.

Given the limited access to freshwater compared to seawater, a growing interest surrounds the direct seawater electrolysis to produce hydrogen. However, we currently lack efficient electrocatalysts to selectively perform the oxygen evolution reaction (OER) over the oxidation of the chloride ions that are the main components of seawater. In this contribution, we report an engineering strategy to synthesize heterogeneous electrocatalysts by the simultaneous formation of separate chalcogenides of nickel (NiSx, x = 0, 2/3, 8/9, and 4/3) and cobalt (CoSx, x = 0 and 8/9) onto a carbon-nitrogen-sulfur nanostructured network. Specifically, the oxidative aniline polymerization in the presence of metallic cations was combined with the calcination to regulate the separate formation of various self-supported phases in order to target the multifunctional applicability as both hydrogen evolution reaction (HER) and OER in a simulated alkaline seawater. The OER's metric current densities of 10 and 100 mA cm-2 were achieved at the bimetallic for only 1.60 and 1.63 VRHE, respectively. This high-performance was maintained in the electrolysis with a starting voltage of 1.6 V and satisfactory stability at 100 mA over 17 h. Our findings validate a high selectivity for OER of ~100%, which outperforms the previously reported data of 87-95%.

Advances in Electrocatalysis for Energy Conversion and Synthesis of Organic Molecules.

Ubiquitous electrochemistry is expected to play a major role for reliable energy supply as well as for production of sustainable fuels and chemicals. The fundamental understanding of organics-based electrocatalysis in alkaline media at the solid-liquid interface involves complex mechanisms and performance descriptors (from the electrolyte and reaction intermediates), which undermine the roads towards advance and breakthroughs. Here, we review and diagnose recently designed strategies for the electrochemical conversion of organics into electricity and/or higher-value chemicals. To tune the mysterious workings of nanocatalysts in electrochemical devices, we examine the guiding principles by which the performance of a particular electrode material is governed, thus highlighting various tactics for the development of synthesis methods for nanomaterials with specific properties. We end by examining the production of chemicals by using electrochemical methods, from selective oxidation to reduction reactions. The intricate relationship between electrode and selectivity encourages both of the communities of electrocatalysis and organic synthesis to move forward together toward the renaissance of electrosynthesis methods.

Enhancing the available specific surface area of carbon supports to boost the electroactivity of nanostructured Pt catalysts.

We report increasing improvements in the available specific surface area of the commonly used Vulcan XC 72R and Ketjenblack EC-600JD carbons by simple thermal pre-treatment. The treated Vulcan and Ketjenblack substrates have a specific surface area of 322 and 1631 m(2) g(-1), respectively, instead of 262 and 1102 m(2) g(-1) for the as-received materials, which is a 23 and 48% improvement. Subsequently, when used as platinum nanoparticle (3 nm) supports, the electrochemical active surface area is enhanced by factors of 2.2 and 1.2 for treated Vulcan and Ketjenblack carbons, respectively. Furthermore, electrochemical investigations have highlighted a surprisingly improved catalytic activity for the pre-treated Vulcan XC 72R and Ketjenblack EC-600JD supported Pt nanoparticles. In fact, the synthesized nanostructures from the so-called "Bromide Anion Exchange" method exhibit good catalytic activity toward glucose electrooxidation, both in the alkaline medium and the phosphate buffered solution at pH 7.4. More importantly, the present catalysts are four times more active than those in the literature prepared under similar conditions for glucose dehydrogenation at low potential (0.27 V vs. Reversible Hydrogen Electrode). Consequently, these remarkable trends uncovered herein provide ample new strategic routes for the pre-treatment of Vulcan XC 72R and Ketjenblack carbons for widespread uses.

Galvanostatic Electroshock Synthesis of Low Loading Au-Pt Nanoalloys onto Gas Diffusion Electrodes as Multifunctional Electrocatalysts for a Glycerol-Fed Electrolyzer.

Water electrolysis is increasingly considered a viable solution for meeting the world's growing energy demands and mitigating environmental issues. An inventive strategy to mitigate the energy requirements involves substituting the energy-intensive oxygen evolution reaction (OER) with biomass-derived glycerol electrooxidation. Nonetheless, the synthesis of electrocatalysts for controlling the selectivity towards added-value chemicals at the anode and efficient H2 generation at the cathode remains a critical bottleneck. Herein, we implemented a galvanostatic electroshock synthesis approach to control the reduction kinetics of Au(III) and Pt(IV) to grow ultra-low amount of gold-platinum alloys on a gas diffusion electrode (12-26 µgmetal cm‒2) for glycerol-fed hydroxide anion exchange membrane based electrolyzer. The symmetric GDE-Au100-xPtx||GDE-Au100-xPtx systems showed a notable improvement in electrolyzer performance (GDE-Au64Pt36 = 201 mA cm-2) as compared to monometallic versions (GDE-Au100Pt0 = 18 mA cm-2, GDE-Au0Pt100 = 81 mA cm-2). Chromatography (HPLC) analysis underscores the critical importance of bulk electrolysis methodology (galvanostatic vs potentiostatic) for the efficient conversion of glycerol into high-value-added products. Regarding the electrical energy required to produce 1 kg of H2 for such an electrolyzer fed at the anode with glycerol, our results confirm a drastic decrease by a factor of at least two compared with conventional water electrolysis.

Radiolysis-Assisted Direct Growth of Gold-Based Electrocatalysts for Glycerol Oxidation.

The electrocatalytic oxidation of glycerol by metal electrocatalysts is an effective method of low-energy-input hydrogen production in membrane reactors in alkaline conditions. The aim of the present study is to examine the proof of concept for the gamma-radiolysis-assisted direct growth of monometallic gold and bimetallic gold-silver nanostructured particles. We revised the gamma radiolysis procedure to generate free-standing Au and Au-Ag nano- and micro-structured particles onto a gas diffusion electrode by the immersion of the substrate in the reaction mixture. The metal particles were synthesized by radiolysis on a flat carbon paper in the presence of capping agents. We have integrated different methods (SEM, EDX, XPS, XRD, ICP-OES, CV, and EIS) to examine in detail the as-synthesized materials and interrogate their electrocatalytic efficiency for glycerol oxidation under baseline conditions to establish a structure-performance relationship. The developed strategy can be easily extended to the synthesis by radiolysis of other types of ready-to-use metal electrocatalysts as advanced electrode materials for heterogeneous catalysis.

Spark plasma sintered catalytic nickel-copper alloy and carbon nanotube electrodes for the hydrogen evolution reaction.

We report the proof-of-concept of spark plasma sintered (SPS) consolidated mesoporous composite catalytic electrodes based on nickel-copper alloys and carbon nanotubes for the electrocatalytic hydrogen evolution reaction (HER) in alkaline media. The optimized electrode (203 m2 g-1, 5 wt% Ni75Cu25) operated at -0.1 A cm-2 (current of -0.15 A) for 24 h with a stable overpotential of about 0.3 V. This newly described freestanding SPS approach allows the rational control of specific surface area, metal loading, and electrocatalytic performance, thus opening a new route to catalytic electrodes with controllable physical and catalytic properties.

Review of the Electrospinning Process and the Electro-Conversion of 5-Hydroxymethylfurfural (HMF) into Added-Value Chemicals.

Electrochemical converters (electrolyzers, fuel cells, and batteries) have gained prominence during the last decade for the unavoidable energy transition and the sustainable synthesis of platform chemicals. One of the key elements of these systems is the electrode material on which the electrochemical reactions occur, and therefore its design will impact their performance. This review focuses on the electrospinning method by examining a number of features of experimental conditions. Electrospinning is a fiber-spinning technology used to produce three-dimensional and ultrafine fibers with tunable diameters and lengths. The thermal treatment and the different analyses are discussed to understand the changes in the polymer to create usable electrode materials. Electrospun fibers have unique properties such as high surface area, high porosity, tunable surface properties, and low cost, among others. Furthermore, a little introduction to the 5-hydroxymethylfurfural (HMF) electrooxidation coupled to H2 production was included to show the benefit of upgrading biomass derivates in electrolyzers. Indeed, environmental and geopolitical constraints lead to shifts towards organic/inorganic electrosynthesis, which allows for one to dispense with polluting, toxic and expensive reagents. The electrooxidation of HMF instead of water (OER, oxygen evolution reaction) in an electrolyzer can be elegantly controlled to electro-synthesize added-value organic chemicals while lowering the required energy for CO2-free H2 production.

Design of three-dimensional electrocatalytic all-in-one electrodes by leveraging electrospinning and calcination approaches.

We report the combination of electrospinning and calcination to synthesize many free-standing electrocatalytic electrodes made of nanostructured nickel particles (active sites) and three-dimensional carbon microfibers (support). Precisely, we have used five different nickel precursors to elucidate the nitrogen origin (polyacrylonitrile or metal salts) and the impact on the electrocatalytic properties.

Probing Oxygen-to-Hydrogen Peroxide Electro-Conversion at Electrocatalysts Derived from Polyaniline.

Hydrogen peroxide (H2O2) is a key chemical for many industrial applications, yet it is primarily produced by the energy-intensive anthraquinone process. As part of the Power-to-X scenario of electrosynthesis, the controlled oxygen reduction reaction (ORR) can enable the decentralized and renewable production of H2O2. We have previously demonstrated that self-supported electrocatalytic materials derived from polyaniline by chemical oxidative polymerization have shown promising activity for the reduction of H2O to H2 in alkaline media. Herein, we interrogate whether such materials could also catalyze the electro-conversion of O2-to-H2O2 in an alkaline medium by means of a selective two-electron pathway of ORR. To probe such a hypothesis, nine sets of polyaniline-based materials were synthesized by controlling the polymerization of aniline in the presence or not of nickel (+II) and cobalt (+II), which was followed by thermal treatment under air and inert gas. The selectivity and faradaic efficiency were evaluated by complementary electroanalytical methods of rotating ring-disk electrode (RRDE) and electrolysis combined with spectrophotometry. It was found that the presence of cobalt species inhibits the performance. The selectivity towards H2O2 was 65-80% for polyaniline and nickel-modified polyaniline. The production rate was 974 ± 83, 1057 ± 64 and 1042 ± 74 µmolH2O2 h-1 for calcined polyaniline, calcined nickel-modified polyaniline and Vulcan XC 72R (state-of-the-art electrocatalyst), respectively, which corresponds to 487 ± 42, 529 ± 32 and 521 ± 37 mol kg-1cat h-1 (122 ± 10, 132 ± 8 and 130 ± 9 mol kg-1cat cm-2) for faradaic efficiencies of 58-78%.

Iridium and Ruthenium Modified Polyaniline Polymer Leads to Nanostructured Electrocatalysts with High Performance Regarding Water Splitting.

The breakthrough in water electrolysis technology for the sustainable production of H2, considered as a future fuel, is currently hampered by the development of tough electrocatalytic materials. We report a new strategy of fabricating conducting polymer-derived nanostructured materials to accelerate the electrocatalytic hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and water splitting. Extended physical (XRD, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX)) and electrochemical (cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS)) methods were merged to precisely characterize the as-synthesized iridium and ruthenium modified polyaniline (PANI) materials and interrogate their efficiency. The presence of Ir(+III) cations during polymerization leads to the formation of Ir metal nanoparticles, while Ru(+III) induces the formation of RuO2 oxide nanoparticles by thermal treatment; they are therefore methods for the on-demand production of oxide or metal nanostructured electrocatalysts. The findings from using 0.5 M H2SO4 highlight an ultrafast electrochemical kinetic of the material PANI-Ir for HER (36 - 0 = 36 mV overpotential to reach 10 mA cm-2 at 21 mV dec-1), and of PANI-Ru for OER (1.47 - 1.23 = 240 mV overpotential to reach 10 mA cm-2 at 47 mV dec-1), resulting in an efficient water splitting exactly at its thermoneutral cell voltage of 1.45 V, and satisfactory durability (96 h).

Nanostructured Carbon-Nitrogen-Sulfur-Nickel Networks Derived From Polyaniline as Bifunctional Catalysts for Water Splitting.

The development of reliable production routes for sustainable hydrogen (H2), which is an essential feedstock for industrial processes and energy carrier for fuel cells, is needed. It appears to be an unavoidable alternative to significantly reduce the dependence on conventional energy sources based on fossil fuels without increasing the atmospheric CO2 levels. Among the different power-to-X scenarios to access high purity H2, the electrochemical approach based on electrolysis looks to be a promising sustainable solution at both the small and large industrial scales. However, the practical realization of this important opportunity faces several challenges, including the efficient design of cost-effective catalytic materials to be used as a cathode with improved intrinsic and durable activity. In this contribution, we report the design and development of efficient nanostructured catalysts for the electrocatalytic hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in aqueous media, whereby noble metal-free elements are embedded in a matrix of a conducting polymer, polyaniline (PANI). To increase the electrical conductivity and further the electrocatalytic ability toward HER of the chemically polymerized PANI in the presence of nickel (II) salt (nitrate), the PANI-based materials have first been stabilized at a mild temperature of 250-350°C in air and then carbonized at 800-1,000°C under nitrogen gas to convert the chemical species into nitrogen, sulfur, nickel, and carbon nanostructured networks (CNNs). Different physicochemical (TGA-DSC, Raman spectroscopy, XRD, SEM, EDX, ICP, CHNS, BET, and XPS) and electrochemical (voltammetry and electrochemical impedance spectrometry) methods have been integrated to characterize the as-synthesized CNNs materials and interrogate the relationship of material-to-performance. It has been found that those synthesis conditions allow for the substantial increase of the electrocatalytic performance toward HER and OER in alkaline media in terms of the onset potential and charge transfer resistance and overpotential at the specific activity of 10 milliamps per square centimeter, thus ranking the present materials among the most efficient noble metal-free catalysts and making them possible candidates for integration in practical low-energy consumption alkaline electrolyzers.

Surfactant- and Binder-Free Hierarchical Platinum Nanoarrays Directly Grown onto a Carbon Felt Electrode for Efficient Electrocatalysis.

The future of fuel cells that convert chemical energy to electricity relies mostly on the efficiency of oxygen reduction reaction (ORR) due to its sluggish kinetics. By effectively bypassing the use of organic surfactants, the postsynthesis steps for immobilization onto electrodes, catalytic ink preparation using binders, and the common problem of nanoparticles (NPs) detachment from the supports involved in traditional methodologies, we demonstrate a versatile electrodeposition method for growing anisotropic microstructures directly onto a three-dimensional (3D) carbon felt electrode, using platinum NPs as the elementary building blocks. The as-synthesized materials were extensively characterized by integrating methods of physical (thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, inductively coupled plasma, and X-ray photoelectron spectroscopy) and electroanalytical (voltammetry, electrochemical impedance spectrometry) chemistry to examine the intricate relationship of material-to-performance and select the best-performing electrocatalyst to be applied in the model reaction of ORR for its practical integration into a microbial fuel cell (MFC). A tightly optimized procedure enables decorating an electrochemically activated carbon felt electrode by 40-60 nm ultrathin 3D-interconnected platinum nanoarrays leading to a hierarchical framework of ca. 500 nm. Half-cell reactions reveal that the highly rough metallic surface exhibits improved activity and stability toward ORR (Eonset ∼ 1.1 V vs reversible hydrogen electrode, p(HO2-) < 0.1%) and the hydrogen evolution reaction (-10 mA cm-2 for only 75 mV overpotential). Owing to its unique features, the developed material showed distinguished performance as an air-breathing cathode in a garden compost MFC, exhibiting better current and faster power generation than those of its equivalent classical double chamber. The enhanced performance of the material obtained herein is explained by the absence of any organic surfactants on the surface of the nanoarrays, the good metal-support interaction, particular morphology of the nanoarrays, and the reduced aggregation/detachment of particles. It promises a radical improvement in current surface reactions and paves a new way toward electrodes with regulated surface roughness, allowing for their successful application in heterogeneous catalysis.

Highly Selective Oxidation of Carbohydrates in an Efficient Electrochemical Energy Converter: Cogenerating Organic Electrosynthesis.

The selective electrochemical conversion of highly functionalized organic molecules into electricity, heat, and added-value chemicals for fine chemistry requires the development of highly selective, durable, and low-cost catalysts. Here, we propose an approach to make catalysts that can convert carbohydrates into chemicals selectively and produce electrical power and recoverable heat. A 100% Faradaic yield was achieved for the selective oxidation of the anomeric carbon of glucose and its related carbohydrates (C1-position) without any function protection. Furthermore, the direct glucose fuel cell (DGFC) enables an open-circuit voltage of 1.1 V in 0.5 m NaOH to be reached, a record. The optimized DGFC delivers an outstanding output power Pmax =2 mW cm(-2) with the selective conversion of 0.3 m glucose, which is of great interest for cogeneration. The purified reaction product will serve as a raw material in various industries, which thereby reduces the cost of the whole sustainable process.

Kinetic model for a threshold filter in an enzymatic system for bioanalytical and biocomputing applications.

A recently experimentally observed biochemical "threshold filtering" mechanism by processes catalyzed by the enzyme malate dehydrogenase is explained in terms of a model that incorporates an unusual mechanism of inhibition of this enzyme that has a reversible mechanism of action. Experimental data for a system in which the output signal is produced by biocatalytic processes of the enzyme glucose dehydrogenase are analyzed to verify the model's validity. We also establish that fast reversible conversion of the output product to another compound, without the additional inhibition, cannot on its own result in filtering.