Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry.

Carbon corrosion at high anodic potentials is a major source of instability, especially in acidic electrolytes and impairs the long-term functionality of electrodes. In-depth investigation of carbon corrosion in alkaline environment by means of differential electrochemical mass spectrometry (DEMS) is prevented by the conversion of CO2 into CO3 2- . We report the adaptation of a DEMS system for online CO2 detection as the product of carbon corrosion in alkaline electrolytes. A new cell design allows for in situ acidification of the electrolyte to release initially dissolved CO3 2- as CO2 in front of the DEMS membrane and its subsequent detection by mass spectrometry. DEMS studies of a carbon-supported nickel boride (Nix B/C) catalyst and Vulcan XC 72 at high anodic potentials suggest protection of carbon in the presence of highly active oxygen evolution electrocatalysts. Most importantly, carbon corrosion is decreased in alkaline solution.

On the Theory of Electrolytic Dissociation, the Greenhouse Effect, and Activation Energy in (Electro)Catalysis: A Tribute to Svante Augustus Arrhenius.

Svante Augustus Arrhenius (1859, Vik - 1927, Stockholm) received the Nobel Prize for Chemistry in 1903 "in recognition of the extraordinary services he rendered to the advancement of chemistry by his electrolytic theory of dissociation". Arrhenius was a physicist, and he received his PhD from the University of Uppsala, where he later became a professor for phyiscal chemistry, the first in the country for this subject. He was offered several positions as professor abroad, but decided to remain in Sweden and to build a Nobel Institute for physical chemistry using the Nobel funds. He remained director of the Institute until his death. There are powerful lessons to take from Svante August Arrhenius' journey leading to a Nobel laureate as there are from his tremendous contributions to chemistry and science in general, including climate science, immunochemistry and cosmology. The theory of electrolytic dissociation for which Arrhenius received the 1903 Nobel Prize in Chemistry has had a profound impact on our understanding of the chemistry of solutions, chemical reactivity, mechanisms underlying chemical transformations as well as physiological processes. As a tribute to Arrhenius, we present a brief historical perspective and present status of the theory of electrolytic dissociation, its relevance and role to the development of electrochemistry, as well as some perspectives on the possible role of the theory to future advancements in electroanalysis, electrocatalysis and electrochemical energy storage. The review briefly highlights Arrhenius' contribution to climate science owing to his studies on the potential effects of increased anthropogenic CO2 emissions on the global climate. These studies were far ahead of their time and revealed a daunting global dilemma, global warming, that we are faced with today. Efforts to abate or reverse CO2 accumulation constitute one of the most pressing scientific problems of our time, "man's urgent strive to save self from the adverse effects of his self-orchestrated change on the climate". Finally, we review the application of the Arrhenius equation that correlates reaction rate constants (k) and temperature (T); k = A e ( - E a / R T ) , in determining reaction barriers in catalysis with a particular focus on recent modifications of the equation to account for reactions exhibiting non-linear Arrhenius behavior with concave curvature due to prevalence of quantum mechanical tunneling, as well as infrequent convexity of Arrhenius plots due to decrease of the microcanonical rate coefficient with energy as observed for some enzyme catalyzed reactions.

Enhancing Electrocatalytic Activity through Liquid-Phase Exfoliation of NiFe Layered Double Hydroxide Intercalated with Metal Phthalocyanines in the Presence of Graphene.

Earth-abundant transition-metal-based catalysts are attractive for alkaline water electrolysis. However, their catalytic properties are often limited by their poor electrical conductivity. Here, we present a strategy for enhancing the electrical conductivity of NiFe layered double hydroxide (LDH) in order to further improve its properties as an electrocatalyst for the oxygen evolution reaction (OER) in alkaline media. We show that NiFe LDH containing metal tetrasulfonate phthalocyanine in the interlayers between the NiFe oxide galleries can be coupled with graphene during liquid-phase exfoliation by taking advantage of their π-π stacking capabilities. A substantial enhancement in the electrocatalytic activity of NiFe LDH with respect to the OER was observed. Moreover, the activity and selectivity of the catalyst materials towards the oxygen reduction reaction were investigated, demonstrating that both the metal hydroxide layer and the interlayer species contribute to the electrocatalytic performance of the composite material.

Oxygen Evolution Catalysis with Mössbauerite-A Trivalent Iron-Only Layered Double Hydroxide.

Mössbauerite is investigated for the first time as an "iron-only" mineral for the electrocatalytic oxygen evolution reaction in alkaline media. The synthesis proceeds via intermediate mixed-valence green rust that is rapidly oxidized in situ while conserving the layered double hydroxide structure. The material catalyzes the oxygen evolution reaction on a glassy carbon electrode with a current density of 10 mA cm-2 at 1.63 V versus the reversible hydrogen electrode. Stability measurements, as well as post-electrolysis characterization are presented. This work demonstrates the applicability of iron-only layered double hydroxides as earth-abundant oxygen evolution electrocatalysts. Mössbauerite is of fundamental importance since as an all Fe3+ material its performance has no contributions from unknown synergistic effects as encountered for mixed valence Co/Ni/Fe LDH.

Influence of Temperature and Electrolyte Concentration on the Structure and Catalytic Oxygen Evolution Activity of Nickel-Iron Layered Double Hydroxide.

NiFe layered double hydroxide (LDH) is inarguably the most active contemporary catalyst for the oxygen evolution reaction under alkaline conditions. However, the ability to sustain unattenuated performance under challenging industrial conditions entailing high corrosivity of the electrolyte (≈30 wt. % KOH), high temperature (>80 °C) and high current densities (>500 mA cm-2 ) is the ultimate criterion for practical viability. This work evaluates the chemical and structural stability of NiFe LDH at conditions akin to practical electrolysis, in 30 % KOH at 80 °C, however, without electrochemical polarization, and the resulting impact on the OER performance of the catalyst. Post-analysis of the catalyst by means of XRD, TEM, FT-IR, and Raman spectroscopy after its immersion into 7.5 m KOH at 80 °C for 60 h revealed a transformation of the structure from NiFe LDH to a mixture of crystalline ß-Ni(OH)2 and discrete predominantly amorphous FeOOH containing minor non-homogeneously distributed crystalline domains. These structural and compositional changes led to a drastic loss of the OER activity. It is therefore recommended to study catalyst stability at industrially relevant conditions.

Electrocatalytic Oxidation of 5-(Hydroxymethyl)furfural Using High-Surface-Area Nickel Boride.

The electrochemical oxidation of the biorefinery product 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA), an important platform chemical for the polymer industry, is receiving increasing interest. FDCA-based polymers such as polyethylene 2,5-furandicarboxylate (PEF) are sustainable candidates for replacing polyethylene terephthalate (PET). Herein, we report the highly efficient electrocatalytic oxidation of HMF to FDCA, using Ni foam modified with high-surface-area nickel boride (Nix B) as the electrode. Constant potential electrolysis in combination with HPLC revealed a high faradaic efficiency of close to 100 % towards the production of FDCA with a yield of 98.5 %. Operando electrochemistry coupled to ATR-IR spectroscopy indicated that HMF is oxidized preferentially via 5-hydroxymethyl-2-furancarboxylic acid rather than via 2,5-diformylfuran, which is in agreement with HPLC results. This study not only reports a low-cost active electrocatalyst material for the electrochemical oxidation of HMF to FDCA, but additionally provides insight into the reaction pathway.

Cobalt-metalloid alloys for electrochemical oxidation of 5-hydroxymethylfurfural as an alternative anode reaction in lieu of oxygen evolution during water splitting.

The electrochemical water splitting commonly involves the cathodic hydrogen and anodic oxygen evolution reactions (OER). The oxygen evolution reaction is more energetically demanding and kinetically sluggish and represents the bottleneck for a commercial competitiveness of electrochemical hydrogen production from water. Moreover, oxygen is essentially a waste product of low commercial value since the primary interest is to convert electrical energy into hydrogen as a storable energy carrier. We report on the anodic oxidation of 5-hydroxymethylfurfural (HMF) to afford the more valuable product 2,5-furandicarboxylic acid (FDCA) as a suitable alternative to the oxygen evolution reaction. Notably, HMF oxidation is thermodynamically more favorable than water oxidation and hence leads to an overall improved energy efficiency for H2 production. In addition, contrary to the "waste product O2", FDCA can be further utilized, e.g., for production of polyethylene 2,5-furandicarboxylate (PEF), a sustainable polymer analog to polyethylene terephthalate (PET) and thus represents a valuable product for the chemical industry with potential large scale use. Various cobalt-metalloid alloys (CoX; X = B, Si, P, Te, As) were investigated as potential catalysts for HMF oxidation. In this series, CoB required 180 mV less overpotential to reach a current density of 55 mA cm-2 relative to OER with the same electrode. Electrolysis of HMF using a CoB modified nickel foam electrode at 1.45 V vs RHE achieved close to 100% selective conversion of HMF to FDCA at 100% faradaic efficiency.

Overcoming the Instability of Nanoparticle-Based Catalyst Films in Alkaline Electrolyzers by using Self-Assembling and Self-Healing Films.

Engineering stable electrodes using highly active catalyst nanopowders for electrochemical water splitting remains a challenge. We report an innovative and general approach for attaining highly stable catalyst films with self-healing capability based on the in situ self-assembly of catalyst particles during electrolysis. The catalyst particles are added to the electrolyte forming a suspension that is pumped through the electrolyzer. Particles with negatively charged surfaces stick onto the anode, while particles with positively charged surfaces stick to the cathode. The self-assembled catalyst films have self-healing properties as long as sufficient catalyst particles are present in the electrolyte. The proof-of-concept was demonstrated in a non-zero gap alkaline electrolyzer using NiFe-LDH and Nix B catalyst nanopowders for anode and cathode, respectively. Steady cell voltages were maintained for at least three weeks during continuous electrolysis at 50-100 mA cm-2 .

Powder Catalyst Fixation for Post-Electrolysis Structural Characterization of NiFe Layered Double Hydroxide Based Oxygen Evolution Reaction Electrocatalysts.

Highly active electrocatalysts for the oxygen evolution (OER) reaction are in most cases powder nanomaterials, which undergo substantial changes upon applying the high potentials required for high-current-density oxygen evolution. Owing to the vigorous gas evolution, the durability under OER conditions is disappointingly low for most powder electrocatalysts as there are no strategies to securely fix powder catalysts onto electrode surfaces. Thus reliable studies of catalysts during or after the OER are often impaired. Herein, we propose the use of composites made from precursors of polybenzoxazines and organophilically modified NiFe layered double hydroxides (LDHs) to form a stable and highly conducting catalyst layer, which allows the study of the catalyst before and after electrocatalysis. Characterization of the material by XRD, SEM, and TEM before and after 100 h electrolysis in 5 m KOH at 60 °C and a current density of 200 mA cm-2 revealed previously not observed structural changes.

Bipolar Electrochemistry for Concurrently Evaluating the Stability of Anode and Cathode Electrocatalysts and the Overall Cell Performance during Long-Term Water Electrolysis.

Electrochemical efficiency and stability are among the most important characteristics of electrocatalysts. These parameters are usually evaluated separately for the anodic and cathodic half-cell reactions in a three-electrode system or by measuring the overall cell voltage between the anode and cathode as a function of current or time. Here, we demonstrate how bipolar electrochemistry can be exploited to evaluate the efficiency of electrocatalysts for full electrochemical water splitting while simultaneously and independently monitoring the individual performance and stability of the half-cell electrocatalysts. Using a closed bipolar electrochemistry setup, all important parameters such as overvoltage, half-cell potential, and catalyst stability can be derived from a single galvanostatic experiment. In the proposed experiment, none of the half-reactions is limiting on the other, making it possible to precisely monitor the contribution of the individual half-cell reactions on the durability of the cell performance. The proposed approach was successfully employed to investigate the long-term performance of a bifunctional water splitting catalyst, specifically amorphous cobalt boride (Co2B), and the durability of the electrocatalyst at the anode and cathode during water electrolysis. Additionally, by periodically alternating the polarization applied to the bipolar electrode (BE) modified with a bifunctional oxygen electrocatalyst, it was possible to explicitly follow the contributions of the oxygen reduction (ORR) and the oxygen evolution (OER) half-reactions on the overall long-term durability of the bifunctional OER/ORR electrocatalyst.

Renewable Syngas Generation via Low-Temperature Electrolysis: Opportunities and Challenges.

The production of syngas (i.e., a mixture of CO and H2) via the electrochemical reduction of CO2 and water can contribute to the green transition of various industrial sectors. Here we provide a joint academic-industrial perspective on the key technical and economical differences of the concurrent (i.e., CO and H2 are generated in the same electrolyzer cell) and separated (i.e., CO and H2 are electrogenerated in different electrolyzers) production of syngas. Using a combination of literature analysis, experimental data, and techno-economic analysis, we demonstrate that the production of synthesis gas is notably less expensive if we operate a CO2 electrolyzer in a CO-selective mode and combine it with a separate PEM electrolyzer for H2 generation. We also conclude that by the further decrease of the cost of renewable electricity and the increase of CO2 emission taxes, such prepared renewable syngas will become cost competitive.

Catalytic Reactivation of Industrial Oxygen Depolarized Cathodes by in†situ Generation of Atomic Hydrogen.

Electrocatalytically active materials on the industrial as well as on the laboratory scale may suffer from chemical instability during operation, air exposure, or storage in the electrolyte. A strategy to recover the loss of electrocatalytic activity is presented. Oxygen-depolarized cathodes (ODC), analogous to those that are utilized in industrial brine electrolysis, are analyzed: the catalytic activity of the electrodes upon storage (4 weeks) under industrial process conditions (30 wt % NaOH, without operation) diminishes. This phenomenon occurs as a consequence of surface oxidation and pore blockage, as revealed by scanning electron microscopy, focused ion beam milling, X-ray photoelectron spectroscopy, and Raman spectroscopy. Potentiodynamic cycling of the oxidized electrodes to highly reductive potentials and the formation of "nascent" hydrogen re-reduces the electrode material, ultimately recovering the former catalytic activity.

Polybenzoxazine-Derived N-doped Carbon as Matrix for Powder-Based Electrocatalysts.

In addition to catalytic activity, intrinsic stability, tight immobilization on a suitable electrode surface, and sufficient electronic conductivity are fundamental prerequisites for the long-term operation of particle- and especially powder-based electrocatalysts. We present a novel approach to concurrently address these challenges by using the unique properties of polybenzoxazine (pBO) polymers, namely near-zero shrinkage and high residual-char yield even after pyrolysis at high temperatures. Pyrolysis of a nanocubic prussian blue analogue precursor (Km Mnx [Co(CN)6 ]y ⋅n H2 O) embedded in a bisphenol A and aniline-based pBO led to the formation of a N-doped carbon matrix modified with Mnx Coy Oz nanocubes. The obtained electrocatalyst exhibits high efficiency toward the oxygen evolution reaction (OER) and more importantly a stable performance for at least 65 h.

Poly(benzoxazine)s Modified with Osmium Complexes as a Class of Redox Polymers for Wiring of Enzymes to Electrode Surfaces.

Benzoxazine-based redox polymers bearing Os complexes are synthesized and used as an immobilization matrix for glucose oxidase (GOx) as a model system for a reagentless biosensor. The polymers are formed by electrochemically induced anodic polymerization of the corresponding benzoxazine monomers modified with Os complexes. The precursors are synthesized in a Mannich-type reaction between bisphenol A, formaldehyde, and the corresponding Os complexes or ligands, which contain free amino groups. The Os complexes are redox active within the polymer films, and thus, can be used as redox relays for the electron transfer between the electrode surface and the prosthetic group within the enzyme. Entrapment of GOx within the poly(benzoxazine) film is achieved successfully, as shown by the biocatalytic activity of the poly(benzoxazine)/GOx films upon the addition of glucose.

Doping Level of Boron-Doped Diamond Electrodes Controls the Grafting Density of Functional Groups for DNA Assays.

The impact of different doping levels of boron-doped diamond on the surface functionalization was investigated by means of electrochemical reduction of aryldiazonium salts. The grafting efficiency of 4-nitrophenyl groups increased with the boron levels (B/C ratio from 0 to 20,000 ppm). Controlled grafting of nitrophenyldiazonium was used to adjust the amount of immobilized single-stranded DNA strands at the surface and further on the hybridization yield in dependence on the boron doping level. The grafted nitro functions were electrochemically reduced to the amine moieties. Subsequent functionalization with a succinic acid introduced carboxyl groups for subsequent binding of an amino-terminated DNA probe. DNA hybridization significantly depends on the probe density which is in turn dependent on the boron doping level. The proposed approach opens new insights for the design and control of doped diamond surface functionalization for the construction of DNA hybridization assays.

Thermoresponsive amperometric glucose biosensor.

The authors report on the fabrication of a thermoresponsive biosensor for the amperometric detection of glucose. Screen printed electrodes with heatable gold working electrodes were modified by a thermoresponsive statistical copolymer [polymer I: poly(ω-ethoxytriethylenglycol methacrylate-co-3-(N,N-dimethyl-N-2-methacryloyloxyethyl ammonio) propanesulfonate-co-ω-butoxydiethylenglycol methacrylate-co-2-(4-benzoyl-phenoxy)ethyl methacrylate)] with a lower critical solution temperature of around 28 °C in aqueous solution via electrochemically induced codeposition with a pH-responsive redox-polymer [polymer II: poly(glycidyl methacrylate-co-allyl methacrylate-co-poly(ethylene glycol)methacrylate-co-butyl acrylate-co-2-(dimethylamino)ethyl methacrylate)-[Os(bpy)2(4-(((2-(2-(2-aminoethoxy)ethoxy)ethyl)amino)methyl)-N,N-dimethylpicolinamide)](2+)] and pyrroloquinoline quinone-soluble glucose dehydrogenase acting as biological recognition element. Polymer II bears covalently bound Os-complexes that act as redox mediators for shuttling electrons between the enzyme and the electrode surface. Polymer I acts as a temperature triggered immobilization matrix. Probing the catalytic current as a function of the working electrode temperature shows that the activity of the biosensor is dramatically reduced above the phase transition temperature of polymer I. Thus, the local modulation of the temperature at the interphase between the electrode and the bioactive layer allows switching the biosensor from an on- to an off-state without heating of the surrounding analyte solution.