Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources. De-centralized production of hydrogen peroxide (H2O2) from water and oxygen of air is highly desirable for daily life and industry. We report an effective electrochemical refinery (e-refinery) for H2O2 by means of electrocatalysis-controlled comproportionation reaction (2(H)O + O -> 2(HO)), feeding pure water and oxygen only. Mesoporous nickel (II) oxide (NiO) was used as electrocatalyst for oxygen evolution reaction (OER), producing oxygen at the anode. Conducting polymer poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) drove the oxygen reduction reaction (ORR), forming H2O2 on the cathode. The reactions were evaluated in both half-cell and device configurations. The performance of the H2O2 e-refinery, assembled on anion-exchange solid electrolyte and fed with pure water, was limited by the unbalanced ionic transport. Optimization of the operation conditions allowed a conversion efficiency of 80%.

Sustainable production of hydrogen gas, a green energy carrier of high density, is possible only by electrolysis of water based on the hydrogen evolution reaction (HER). Here, we report the effect of oxygen poisoning on the efficiency of hydrogen production and the consumption by the HER and the hydrogen oxidation reaction (HOR), respectively, on the interface of platinum group metal-free electrocatalyst TaS2 in pristine form and intercalated by the organic Lewis base hexylamine. The state of the surface probed by photoelectron spectroscopy was significantly altered by both Lewis base doping and oxygen poisoning. This alteration dramatically affects the hydrogen production efficiency in the HER, while the back process by the HOR was less sensitive to the changes in the surface states of the electrocatalysts. The oxygenated and intercalated electrocatalyst shows more than 2 x 105 times lower exchange current density of the HER compared to pristine oxygenated materials.

On-site electrosynthesis of hydrogen peroxide (H2O2) is a promising alternative technology to the conversional centralized anthraquinone oxidation process. Here, we report a platinum group metal (PGM)-free H2O2 electrogenerator with mesoporous Cr2O3 and NiCo2O4 used as electrocatalysts for oxygen reduction and evolution reactions (ORR and OER), respectively. The catalysts were synthesized via a hydrothermal synthesis route and had pore sizes of 3 and 7 nm and specific surface areas of 112 and 62 m(2) g(-1), respectively. Mesoporous Cr2O3 was evaluated in a half cell with 0.1 M KOH for electrocatalytic oxygen reduction, which shows 2.2 transferred electrons per oxygen and an in situ H2O2 yield of 70%. This enables the electrosynthesis of hydrogen peroxide in alkaline medium using Cr2O3 as a 2e-ORR-H2O2 electrocatalyst, with oxygen evolution as an auxiliary reaction on NiCo2O4. The effect of electrolyte flow on the H2O2 electrogenerator was investigated. It is observed that one-way feeding of the catholyte suppresses deterioration of the electrocatalyst and allows a faradic conversion up to similar to 90% with a production rate of similar to 0.36 [g (h<middle dot>g(cat))(-1)], operating within the cell voltage of 1.2 V. This work demonstrates both a viable method for electrosynthesis of H2O2 production using PGM-free electrocatalysts and the possibility to obtain a high faradic efficiency by mitigating the effect from catalyst degradation.

Seamless integration between biological systems and electrical components is essential for enabling a twinned biochemical–electrical recording and therapy approach to understand and combat neurological disorders. Employing bioelectronic systems made up of conjugated polymers, which have an innate ability to transport both electronic and ionic charges, provides the possibility of such integration. In particular, translating enzymatically polymerized conductive wires, recently demonstrated in plants and simple organism systems, into mammalian models, is of particular interest for the development of next-generation devices that can monitor and modulate neural signals. As a first step toward achieving this goal, enzyme-mediated polymerization of two thiophene-based monomers is demonstrated on a synthetic lipid bilayer supported on a Au surface. Microgravimetric studies of conducting films polymerized in situ provide insights into their interactions with a lipid bilayer model that mimics the cell membrane. Moreover, the resulting electrical and viscoelastic properties of these self-organizing conducting polymers suggest their potential as materials to form the basis for novel approaches to in vivo neural therapeutics.

Direct electrification of oxygen-associated reactionscontributesto large-scale electrical storage and the launch of the green hydrogeneconomy. The design of the involved catalysts can mitigate the electricalenergy losses and improve the control of the reaction products. Weevaluate the effect of the interface composition of electrocatalystson the efficiency and productivity of the oxygen reduction reaction(ORR) and oxygen evolution reaction (OER), both mechanistically andat device levels. The ORR and OER were benchmarked on mesoporous nickel-(II)oxide and nickel cobaltite (NiO and NiCo2O4,respectively) obtained by a facile template-free hydrothermal synthesis.Physicochemical characterization showed that both NiO and NiCo2O4 are mesoporous and have a cubic crystal structurewith abundant surface hydroxyl species. NiCo2O4 showed higher electrocatalytic activity in OER and selectivity towater as the terminal product of ORR. On the contrary, ORR over NiOyielded hydroxyl radicals as products of a Fenton-like reaction ofH(2)O(2). The product selectivity in ORR was usedto construct two electrolyzers for electrified purification of oxygenand generation of hydroxyl radicals.

Operational stability is essential for the success of organic electrochemical transistors (OECTs) in bioelectronics. The oxygen reduction reaction (ORR) is a common electrochemical side reaction that can compromise the stability of OECTs, but the relationship between ORR and materials degradation is poorly understood. In this study, the impact of ORR on the stability and degradation mechanisms of thiophene-based OECTs is investigated. The findings show that an increase in pH during ORR leads to the degradation of the polymer backbone. By using a protective polymer glue layer between the semiconductor channel and the aqueous electrolyte, ORR is effectively suppressed and the stability of the OECTs is significantly improved, resulting in current retention of nearly 90% for & AP;2 h cycling in the saturation regime.

Hydrogen technology, as a future breakthrough for the energy industry, has been defined as an environmentally friendly, renewable, and high-power energy carrier. The green production of hydrogen, which mainly relies on electrocatalysts, is limited by the high cost and/ or the performance of the catalytic system. Recently, studies have been conducted in search of bifunctional electrocatalysts accelerating both the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR). Herein, we report the investigation of the high efficiency bifunctional electrocatalyst TaS2 for both the HER and the HOR along with the asymmetric effect of inhibition by organic intercalation. The linear organic agent, to boost the electron donor property and to ease the process of intercalation, provides a higher interlayer gap in the tandem structure of utilized nanosheets. XRD and XPS data reveal an increase in the interlayer distance of 22%. The HER and the HOR were characterized in a Pt group metal-free electrochemical system. The pristine sample shows a low overpotential of -0.016 Vat the onset. The intercalated sample demonstrates a large shift in its performance for the HER. It is revealed that the intercalation is a potential key strategy for tuning the performance of this family of catalysts. The inhibition of the HER by intercalation is considered as the increase in the operational window of a water-based electrolyte on a negative electrode, which is relevant to technologies of electrochemical energy storage.

The climate change due to human activities stimulates the research on new energy resources. Hydrogen has attracted interest as a green carrier of high energy density. The sustainable production of hydrogen is achievable only by water electrolysis based on the hydrogen evolution reaction (HER). Graphitic materials are widely utilized in this technology in the role of conductive catalyst supports. Herein, by performing dynamic and steady-state electrochemical measurements in acidic and alkaline media, we investigated the bidirectional electrocatalysis of the HER and hydrogen oxidation reaction (HOR) on metal- and defect-free epigraphene (EG) grown on 4H silicon carbide (4HSiC) as a ground level of structural organization of general graphitic materials. The absence of any signal degradation illustrates the high stability of EG. The experimental and theoretical investigations yield the coherent conclusion on the dominant HER pathway following the Volmer-Tafel mechanism. We ascribe the observed reactivity of EG to its interaction with the underlying SiC substrate that induces strain and electronic doping. The computed high activation energy for breaking the O-H bond is linked to the high negative overpotential of the HER. The estimated exchange current of HER/HOR on EG can be used in the evaluation of complex electrocatalytic systems based on graphite as a conducing support.

Bifunctional electrocatalysts with both accelerated oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) enable high-power density electricity storage and decentralized extraction of pure oxygen from air for usage in health care. Herein, a hydrothermal synthesis employing the anionic surfactant sodium dodecyl sulfate as structure-directing agent is developed to fabricate a family of crystalline mesoporous metal oxides (meso-MO X , M = Cr, Fe, Co, Ni, Ce). The pore size and specific surface area depend on the metal used and they range from 3 to 6 nm and 60 to 200 m(2) g(-1), respectively. NiO and Co3O4 show a higher catalytic efficiency in alkaline media in comparison with the other oxides studied, and their activities are comparable with the values reported for platinum group metal (PGM)-based electrocatalysts. This stems from lower voltage losses and by the presence of specific hydroxide adsorbates on the surface. Both ORR and OER driven on Co3O4 show the unified rate-determining chemical step (|OO-|(center dot) (ads) + H2O <-> |OOH|(center dot) (ads) + OH-, where | X | ads are the species adsorbed on active sites). The bifunctional ORR/OER electrocatalysis obtained on mesoporous NiO is utilized for the first symmetrical PGM-free oxygen pump fed by air and water only.

Producing thick films of conducting polymers by a low-cost manufacturing technique would enable new applications. However, removing huge solvent volume from diluted suspension or dispersion (1-3 wt%) in which conducting polymers are typically obtained is a true manufacturing challenge. In this work, a procedure is proposed to quickly remove water from the conducting polymer poly(3,4-ethylenedioxythiophene:poly(4-styrene sulfonate) (PEDOT:PSS) suspension. The PEDOT:PSS suspension is first flocculated with 1 m H2SO4 transforming PEDOT nanoparticles (approximate to 50-500 nm) into soft microparticles. A filtration process inspired by pulp dewatering in a paper machine on a wire mesh with apertures dimension between 60 mu m and 0.5 mm leads to thick free-standing films (approximate to 0.5 mm). Wire mesh clogging that hinders dewatering (known as dead-end filtration) is overcome by adding to the flocculated PEDOT: PSS dispersion carbon fibers that aggregate and form efficient water channels. Moreover, this enables fast formation of thick layers under simple atmospheric pressure filtration, thus making the process truly scalable. Thick freestanding PEDOT films thus obtained are used as electrocatalysts for efficient reduction of oxygen to hydrogen peroxide, a promising green chemical and fuel. The inhomogeneity of the films does not affect their electrochemical function.

Oxygen evolution reaction (OER) is critical for producing high purity hydrogen and oxygen via electrocatalytic water splitting. In this work, single crystalline, nanoporous nickel oxide (NiO) was prepared using a hydro thermal, soft-templated synthesis route followed by calcination at different temperatures. It is shown that the NiO crystals have a cubic lattice, and the pore size can be tuned from similar to 1 to similar to 70 nm by varying the calcination temperature, i.e. variation from micro to macroporosity. The NiOs catalytic performance as electrocatalysts was evaluated in OER, both thermodynamically and kinetically. Mesoporous NiO with calcination temperature of 400 degrees C had the lowest overpotential (335 mV) required @ 10 mA/cm(2) accompanied with the highest turnover frequency value and mass activity among of the obtained NiO electrocatalysts. The study shows that the electrocatalytic activity of nanoporous NiO outperforms that of commercial catalyst Ir/C (similar to 360 mV @ 10 mA/cm(2)). Microporous NiO possess the highest specific surface area and electrical double layer capacitance, while the nonporous NiO particles have the highest specific activity and BET activity of the catalysts. It is concluded that the minimization of voltage losses by the nanoscale enlargement of the electrocatalyst surface area shows the coherence between gas adsorption and electrocapacitive measurements. Conversely, the OER kinetics showed deterioration with surface area maximization due to the impediment of ionic transport inside the micropores. This work demonstrates the importance of morphology optimization to obtain an efficient OER electrocatalyst with low required overpotential and kinetic loss.

The Dawson-type sulfate polyoxometalate (POM) [S2W18O62]4- has successfully been entrapped in polypyrrole (PPy) films on glassy carbon electrode (GCE) surfaces through pyrrole electropolymerization. Films of varying POM loadings (i.e., thickness) were grown by chronocoulometry. Film-coated electrodes were then characterized using voltammetry, revealing POM surface coverages ranging from 1.9 to 11.7 x 10-9 mol center dot cm-2, and were stable over 100 redox cycles. Typical film morphology and composition were revealed to be porous using atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy, and the effects of this porosity on POM redox activity were probed using AC impedance. The hybrid organic- inorganic films exhibited a good electrocatalytic response toward the reduction of iodate with a sensitivity of 0.769 mu A center dot cm-2 center dot mu M-1.

The precursors have significant influence on the catalytic activity of nonprecious electrocatalysts for effective water splitting. Herein, we report active electrocatalysts based on cobalt oxide (Co3O4) hierarchical nanostructures derived from four different precursors of cobalt (acetate, nitrate, chloride, and sulfate salts) using the low-temperature aqueous chemical growth method. It has been found that the effect of precursor on the morphology of nanostructured material depends on the synthetic method. The Co3O4 nanostructures exhibited cubic phase derived from these four precursors. The Co3O4 nanostructures obtained from chloride precursor have demonstrated improved oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) compared to other precursors due relatively higher content of Co3O4 nanostructures at the surface of material. An overpotential of 400 mV versus reversible hydrogen electrode (RHE) at 10 mA cm(-2) was observed for HER. The Co3O4 nanostructures derived from the chloride precursor have shown favorable reaction kinetics via 34 mV dec(-1) value of the Tafel slope for HER reaction. The Co3O4 nanostructures derived from chloride precursor have also shown an excellent HER durability for 15 hr in alkaline media. Furthermore, the OER functional characterization was carried out onto Co3O4 nanostructures derived from chloride precursor exhibited 220 mV overpotential at 10 mA cm(-2) and Tafel slope of 56 mV dec(-1). Importantly, the reason behind the favorable catalytic activity of Co3O4 nanostructures derived from chloride precursor was linked to one order of magnitude smaller charge transfer resistance and higher amount of Co3O4 content at the surface of nanostructures than the Co3O4 nanostructures derived from other precursors. The performance of Co3O4 nanostructures derived from chloride precursor via the wet chemical method suggests that cobalt chloride precursor could be of great interest for the development of efficient, stable, nonprecious, and environmentally friendly electrocatalysts for the chemical energy conversion and storage devices.

The drawbacks of current state-of-the-art selective membranes, such as poor barrier properties, high cost, and poor recyclability, limit the large-scale deployment of electrochemical energy devices such as redox flow batteries (RFBs) and fuel cells. In recent years, cellulosic nanomaterials have been proposed as a low-cost and green raw material for such membranes, but their performance in RFBs and fuel cells is typically poorer than that of the sulfonated fluoropolymer ionomer membranes such as Nafion. Herein, sulfonated cellulose nanofibrils densely cross-linked to form a compact sulfonated cellulose membrane with limited swelling and good stability in water are used. The membranes possess low porosity and excellent ionic transport properties. A model aqueous organic redox flow battery (AORFB) with alizarin red S as negolyte and tiron as posolyte is assembled with the sulfonated cellulose membrane. The performance of the nanocellulose-based battery is superior in terms of cyclability in comparison to that displayed by the battery assembled with commercially available Nafion 115 due to the mitigation of crossover of the redox-active components. This finding paves the way to new green organic materials for fully sustainable AORFB solutions.

The next generation of green ion selective membranes is foreseen to be based on cellulosic nanomaterials with controllable properties. The introduction of ionic groups into the cellulose structure via chemical modification is one strategy to obtain desired functionalities. In this work, bleached softwood fibers are oxidatively sulfonated and thereafter homogenized to liberate the cellulose nanofibrils (CNFs) from the fiber walls. The liberated CNFs are subsequently used to prepare and characterize novel cellulose membranes. It is found that the degree of sulfonation collectively affects several important properties of the membranes via the density of fixed charged groups on the surfaces of the CNFs, in particular the membrane morphology, water uptake and swelling, and correspondingly the ionic transport. Both ionic conductivity and cation transport increase with the increased level of sulfonation of the starting material. Thus, it is shown that the chemical modification of the CNFs can be used as a tool for precise and rational design of green ion selective membranes that can replace expensive conventional fluorinated ionomer membranes.

Ion selective membranes are at the heart of energy conversion and harvesting, water treatment, and biotechnologies. The currently available membranes are mostly based on expensive and non-biodegradable polymers. Here, we report a cation-selective and low-cost membrane prepared from renewable nanocellulose and 1,2,3,4-butanetetracarboxylic acid which simultaneously serves as crosslinker and source of anionic surface groups. Charge density and structure of the membranes are studied. By using different degrees of crosslinking, simultaneous control over both the nanochannel structure and surface charge concentration is achieved, which in turn determines the resulting ion transport properties. Increasing negative charge concentration via higher crosslinker content, the obtained ion conductivity reaches up to 8 mS/cm (0.1 M KCl). Optimal ion selectivity, also influenced by the solution pH, is achieved at 20 wt% crosslinker addition (with ion conductivity of 1.6 mS/cm). As regular similar to 1.4 nm nanochannels were formed at this composition, nanofluidic contribution to ion transport is likely.

Recent research and few pilot deployments have demonstrated promising aqueous organic redox flow battery (RFB) systems. However, the claim that these organic RFB systems are eco-friendlier energy storage than Lithium-ion batteries and aqueous inorganic metallic RFB counterparts needs reinforcement, primarily if cell components other than redox-active species are still based on unsustainable materials. This thesis of the present work presents the prospects of achieving future eco-friendly RFBs with higher consideration for sustainability by adopting significant amounts of abundant bio-sourced/based materials for all main cell components. As we highlight the promising sources of the energy materials from a review of previous studies, we infer that plant derived quinones and other organic polymers may continue to dominate the organic redox-active species space. Furthermore, a candidate methodology to accomplish porous electrodes and membranes/separators of the eco-friendly RFBs is to apply stand-alone bio-based/sourced fibrils derived from cellulose, lignin, chitin, among other materials. These materials can be combined with (un)carbonised biomass or food wastes & residues to impart conductivity, catalytic activity, and ion selectivity. We explore symmetric chemistry as an ideal system for the eco-friendly RFBs of the discourse, given interplay between the electrolyte, electrode material and membrane dictates energy efficiency and cycling stability. These strategies also need to be coupled with further improvements to achieve reliability.

Green hydrogen is identified as one of the prime clean energy carriers due to its high energy density and a zero emission of CO2. A possible solution for the transport of H2 in a safe and low-cost way is in the form of liquid organic hydrogen carriers (LOHCs). As an alternative to loading LOHC with H2 via a two-step procedure involving preliminary electrolytic production of H2 and subsequent chemical hydrogenation of the LOHC, we explore here the possibility of electrochemical hydrogen storage (EHS) via conversion of proton of a proton donor into a hydrogen atom involved in covalent bonds with the LOHC (R) via a protoncoupled electron transfer (PCET) reaction: . We chose 9-fluorenone/ fluorenol (Fnone/Fnol) conversion as such a model PCET reaction. The electrochemical activation of Fnone via two sequential electron transfers was monitored with in-situ and operando spectroscopies in absence and in presence of different alcohols as proton donors of different reactivity, which enabled us to both quantify and get the mechanistic insight on PCET. The possibility of hydrogen extraction from the loaded carrier molecule was illustrated by chemical activation.

Novel two-dimensional materials (2DMs) with balanced electrical conductivity and lithium (Li) storage capacity are desirable for next-generation rechargeable batteries as they may serve as high-performance anodes, improving output battery characteristics. Gaining an advanced understanding of the electrochemical behavior of lithium at the electrode surface and the changes in interior structure of 2DM-based electrodes caused by lithiation is a key component in the long-term process of the implementation of new electrodes into to a realistic device. Here, we showcase the advantages of bilayer-patched epitaxial graphene on 4H-SiC (0001) as a possible anode material in lithium-ion batteries. The presence of bilayer graphene patches is beneficial for the overall lithiation process because it results in enhanced quantum capacitance of the electrode and provides extra intercalation paths. By performing cyclic voltammetry and chronoamperometry measurements, we shed light on the redox behavior of lithium at the bilayer-patched epitaxial graphene electrode and find that the early-stage growth of lithium is governed by the instantaneous nucleation mechanism. The results also demonstrate the fast lithium-ion transport (similar to 4.7-5.6 x 10(-7) cm(2).s(-1)) to the bilayer-patched epitaxial graphene electrode. Raman measurements complemented by in-depth statistical analysis and density functional theory calculations enable us to comprehend the lithiation effect on the properties of bilayer-patched epitaxial graphene and ascribe the lithium intercalation-induced Raman G peak splitting to the disparity between graphene layers. The current results are helpful for further advancement of the design of graphene-based electrodes with targeted performance.

Catalysts capable of improving the performance of oxygen evolution reaction (OER) and oxygen reduction reactions (ORR) are essential for the advancement of renewable energy technologies. Herein, Ag-decorated vertically aligned MoS2 nanoflakes are developed via magnetron co-sputtering and investigated as electrocatalyst towards OER and ORR. Due to the presence of silver, the catalyst shows more than 1.5 times an increase in the roughness-normalized rate of OER, featuring a very low Tafel slope (58.6 mv dec(-1)), thus suggesting that the catalyst surface favors the thermodynamics of hydroxyl radical (OH center dot) adsorption with the deprotonation steps being the rate-determining steps. The improved performance is attributed to the strong interactions between OOH intermediates and the Ag surface which reduces the activation energy. Rotating ring disk electrode (RRDE) analysis shows that the net disk currents on the Ag-MoS2 sample are two times higher at 0.65 V compared to MoS2, demonstrating the co-catalysis effect of silver doping. Based on the rate constant values, Ag-MoS2 proceeds through a mixed 4 electron and a 2 + 2 serial route reduction mechanism, in which the ionized hydrogen peroxide is formed as a mobile intermediate. The presence of silver decreases the electron transfer number and increases the peroxide yield due to the interplay of a 2 + 2 electron reduction pathway. A 2.5-6 times faster conversion rate of peroxide to OH- observed due to the presence of silver, indicating its effective cocatalyst nature. This strategy can help in designing a highly active bifunctional catalyst that has great potential as a viable alternative to precious-metal-based catalysts.

Polymer-based ion exchange membranes (IEMs) are utilized for many applications such as in water desalination, energy storage, fuel cells and in electrophoretic drug delivery devices, exemplified by the organic electronic ion pump (OEIP). The bulk of current research is primarily focused on finding highly conductive and stable IEM materials. Even though great progress has been made, a lack of fundamental understanding of how specific polymer properties affect ionic transport capabilities still remains. This leads to uncertainty in how to proceed with synthetic approaches for designing better IEM materials. In this study, an investigation of the structure-property relationship between polymer size and ionic conductivity was performed by comparing a series of membranes, based on ionically charged hyperbranched polyglycerol of different polymer sizes. Observing an increase in ionic conductivity associated with increasing polymer size and greater electrolyte exclusion, indi-cating an ionic transportation phenomenon not exclusively based on membrane electrolyte uptake. These findings further our understanding of ion transport phenomena in semi-permeable membranes and indicate a strong starting point for future design and synthesis of IEM polymers to achieve broader capabilities for a variety of ion transport-based applications.

The oxygen reduction reaction (ORR) limits the efficiency of oxygen-associated energy conversion in fuel cells and air-metal batteries. Today, expensive noble metal catalysts are often utilized to enhance the ORR and the resulting conversion efficiency in those devices. Hence, there is an intensive research to find efficient electrodes, exhibiting a favorable electronic structure, for ORR based on abundant materials that can be manufactured using low cost processes. In that context, metal-free carbon-based nanostructures and conducting polymers have been actively investigated. The negatively doped poly(benzimidazobenzophenanthroline) (BBL) as an efficient and stable oxygen cathode material is reported here. Compared to the benchmark p-doped conducting polymer poly(3,4-ethylendioxythiophene) (PEDOT), the BBL provides electrocatalysis that fully reduces dioxygen into water, via a (2 + 2)-electron transfer pathway with hydrogen peroxide (H2O2) as an intermediate; while PEDOT limits the ORR to H2O2. It is demonstrated that n-doped BBL is a promising air electrode material for low-cost and ecofriendly model fuel cells, without the need of any co-catalysts, and its performance is found to be superior to p-doped PEDOT air electrodes.

In recent years, there has been an upsurge in the study of novel and alternative energy storage devices beyond lithium-based systems due to the exponential increase in price of lithium. Sodium (Na) metal-based batteries can be a possible alternative to lithium-based batteries due to the similar electrochemical voltage of Na and Li together with the thousand times higher natural abundance of Na compared to Li. Though two different kinds of Na-O-2 batteries have been studied specifically based on electrolytes until now, very recently, a hybrid Na-air cell has shown distinctive advantage over nonaqueous cell systems. Hybrid Na-air batteries provide a fundamental advantage due to the formation of highly soluble discharge product (sodium hydroxide) which leads to low overpotentials for charge and discharge processes, high electrical energy efficiency, and good cyclic stability. Herein, the current status and challenges associated with hybrid Na-air batteries are reported. Also, a brief description of nonaqueous Na-O-2 batteries and its close competition with hybrid Na-air batteries are provided.

The mass implementation of renewable energies is limited by the absence of efficient and affordable technology to store electrical energy. Thus, the development of new materials is needed to improve the performance of actual devices such as batteries or supercapacitors. Herein, the facile consecutive chemically oxidative polymerization of poly(1-amino-5-chloroanthraquinone) (PACA) and poly(3,4-ethylenedioxythiophene (PEDOT) resulting in a water dispersible material PACA-PEDOT is shown. The water-based slurry made of PACA-PEDOT nanoparticles can be processed as film coated in ambient atmosphere, a critical feature for scaling up the electrode manufacturing. The novel redox polymer electrode is a nanocomposite that withstands rapid charging (16 A g−1) and delivers high power (5000 W kg−1). At lower current density its storage capacity is high (198 mAh g−1) and displays improved cycling stability (60% after 5000 cycles). Its great electrochemical performance results from the combination of the redox reversibility of the quinone groups in PACA that allows a high amount of charge storage via Faradaic reactions and the high electronic conductivity of PEDOT to access to the redox-active sites. These promising results demonstrate the potential of PACA-PEDOT to make easily organic electrodes from a water-coating process, without toxic metals, and operating in non-flammable aqueous electrolyte for large scale pseudocapacitors. 

Understanding the mechanism of metal electrodeposition on graphene as the simplest building block of all graphitic materials is important for electrocatalysis and the creation of metal contacts in electronics. The present work investigates copper electrodeposition onto epitaxial graphene on 4H-SiC by experimental and computational techniques. The two subsequent single-electron transfer steps were coherently quantified by electrochemistry and density functional theory (DFT). The kinetic measurements revealed the instantaneous nucleation mechanism of copper (Cu) electrodeposition, controlled by the convergent diffusion of reactant to the limited number of nucleation sites. Cu can freely migrate across the electrode surface. These findings provide fundamental insights into the nature of copper reduction and nucleation mechanisms and can be used as a starting point for performing more sophisticated investigations and developing real applications.

The selective ion transport characteristics of a conducting polymer electrode, based on poly(3,4-ethylenedioxythiophene) (PEDOT), is evaluated with respect to its electrocatalytic performance, specifically targeting redox switching of quinone couples. Employing model organic redox quinones, here, the novel phenomenon of ion-selective electrocatalysis (ISEC) is conceptualized. The effect of ISEC is studied and evaluated using two forms of PEDOT electrodes, which differ in their ion-exchange characteristics, by comparing the redox transformations of catechol and tiron. It is rationalized that the choice of the specific redox couple and the ion selectivity characteristics of the conducting polymer electrode impacts the activation losses in aqueous organic redox-flow batteries. By carefully selecting and designing the conducting polymer electrodes, high conversion efficiency on acid-resistant electrodes is obtained. As far as it is known, this is the first redox flow battery to include conducting polymer electrodes operating in both the posolyte and negolyte configurations, thus the first "all-organic" RFBs.

The integration of epitaxial graphene on 4H-SiC with different metals may allow tunability of electronic and optical properties of graphene, enabling novel high-performance devices. Here we present a Raman spectroscopy study on epitaxial graphene decorated with electrodeposited Pb and Li adatoms and with magnetron sputtered 5 nm-thick Ag nano-island films. We find that the presence of metals on the epitaxial graphene surface generates defects and induces n-type doping, which is evidenced by the observation of the defect related Raman modes (namely D, D and D + G) and systematic red-shift of the main characteristic modes of graphene. In-depth statistical analysis of the Raman data before and after metal deposition complemented by density functional theory (DFT) calculations allowed to link the interaction strength between the three selected metals and graphene with the metal-induced changes in the vibrational/electronic properties of graphene. Large-area uniform electron doping of epitaxial graphene and surface-enhanced Raman scattering (SERS) effect are reached by room temperature deposition of Ag nano-island films. Very promising results have been obtained from graphene subjected to electrochemical intercalation by Li, which can serve as prerequisites of the construction of Li batteries. The strong interaction between Li or Pb with graphene implies the possibility to exploit the epitaxial graphene as an efficient material for energy storage or for heavy metal sensing, while predominant van der Waals interaction between Ag and graphene favors the formation of extremely thin silver coatings towards two-dimensional metal systems. The present results give better understanding of the nature of epitaxial graphene response to metal deposition and can be useful to design high-performance energy storage devices, optical sensors and heavy metal detection systems. (C) 2019 Elsevier Ltd. All rights reserved.

Molecular oxygen requires activation in order to be reduced, which prompts extensive searching for efficient and sustainable electrode materials to drive electrochemical oxygen reduction reaction (ORR), of primary importance for energy production and storage. A conjugated polymer PEDOT is a metal-free material for which promising ORR experimental results have been obtained. However, sound theoretical understanding of this reaction at an organic electrode is insufficient, as the concepts inherited from electrocatalysis at transition metals are not necessarily relevant for a molecular organic material. In this work, we critically analyze the basics of electrochemical ORR and build a model for our DFT calculations of the reaction thermodynamics based on this analysis. Altogether, this work leads to a conclusion that outer sphere electron transfer that currently attracts increasing attention in the context of ORR is a viable mechanism at a conducting polymer electrode.

The oxygen reduction reaction (ORR) is an essential process in electrocatalysis limiting the commercialization of sustainable energy conversion technologies, such as fuel cells. The use of conducting polymers as molecular porous and conducting catalysts obtained from the high abundance elements enables the route towards low cost and high-throughput fabrication of disposable plastic electrodes of fuel cells. Poly(3,4-ethylenedioxythiophene) (PEDOT) is a 2-electron ORR electrocatalyst yielding specifically hydrogen peroxide that limits the full utilization of chemical energy of oxygen. Here, we demonstrated an innovative product-to-intermediate relay approach achieving complete oxygen reduction reaction (cORR) with Prussian blue (PB) integrated microporous PEDOT cathode in fuel cells. The microporous structured PEDOT electrode prepared via a simple cryosynthesis allows the bulk integration and stabilization of the poor conducting PB co-catalyst into the PEDOT ion-electron conductor, while the microporous PEDOT allows effective oxygen diffusion into the matrix. We evaluated systematically the effect of sequential PEDOT 2-electron ORR followed by PB co-catalysis launching hydrogen peroxide reduction reaction (HPRR) into H2O. This resulted in the establishment of electronic and ionic transport between PEDOT and PB catalyst enabling the combination of enhanced ORR electrocatalysis by means of the ORR course extension from 2to 4-electron reduction to achieve cORR. The cORR performance delivered by the product-to-intermediate relay between microporous PEDOT and PB co-catalysis led to a four times increase in power density of model proton-exchange membrane fuel cell (PEMFC) assembled from the polymer-based air breathing cathode.

Energy harvesting from photosynthetic membranes, proteins, or bacteria through bio-photovoltaic or bio-electrochemical approaches has been proposed as a new route to clean energy. A major shortcoming of these and solar cell technologies is the underutilization of solar irradiation wavelengths in the IR region, especially those in the far IR region. Here, a biohybrid energy-harvesting device is demonstrated that exploits IR radiation, via convection and thermoelectric effects, to improve the resulting energy conversion performance. A composite of nanocellulose and the conducting polymer system poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is used as the anode in biohybrid cells that includes thylakoid membranes (TMs) and redox mediators (RMs) in solution. By irradiating the conducting polymer electrode by an IR light-emitting diode, a sixfold enhancement in the harvested bio-photovoltaic power is achieved, without compromising stability of operation. Investigation of the output currents reveals that IR irradiation generates convective heat transfer in the electrolyte bulk, which enhances the redox reactions of RMs at the anode by suppressing diffusion limitations. In addition, a fast-transient thermoelectric component, originating from the PEDOT:PSS-nanocellulose-electrolyte interphase, further increases the bio-photocurrent. These results pave the way for the development of energy-harvesting biohybrids that make use of heat, via IR absorption, to enhance energy conversion efficiency.

Hydrogen production as alternative energy source is still a challenge due to the lack of efficient and inexpensive catalysts, alternative to platinum. Thus, stable, earth abundant, and inexpensive catalysts are of prime need for hydrogen production via hydrogen evolution reaction (HER). Herein, we present an efficient and stable electrocatalyst composed of earth abundant TiO2 nanorods decorated with molybdenum disulfide thin nanosheets, a few nanometers thick. We grew rutile TiO2 nanorods via the hydrothermal method on conducting glass substrate, and then we nucleated the molybdenum disulfide nanosheets as the top layer. This composite possesses excellent hydrogen evolution activity in both acidic and alkaline media at considerably low overpotentials (350 mV and 700 mV in acidic and alkaline media, respectively) and small Tafel slopes (48 and 60 mV/dec in acidic and alkaline conditions, respectively), which are better than several transition metal dichalcogenides, such as pure molybdenum disulfide and cobalt diselenide. A good stability in acidic and alkaline media is reported here for the new MoS2/TiO2 electrocatalyst. These results demonstrate the potential of composite electrocatalysts for HER based on earth abundant, cost-effective, and environmentally friendly materials, which can also be of interest for a broader range of scalable applications in renewable energies, such as lithium sulfur batteries, solar cells, and fuel cells.

Developing highly active nonprecious metal and binder free bifunctional electrocatalysts for water splitting is a challenging task. In this study, we used a simple strategy to deposit a nickel iron layered double hydroxide (NiFeLDH) onto cobalt oxide (Co3O4) nanowires. The cobalt oxide nanowires are covered with thin nanosheets of NiFeLDH forming a core shell structure. The Co3O4 nanowires contain the mixed oxidation states of Co2+ and Co3+, and the surface modification of Co3O4 nanowires has shown synergetic effects due to there being more oxygen defects, catalytic sites, and enhanced electronic conductivity. Further, the core shell structure of Co3O4 nanowires demonstrated a bifunctional activity for water splitting in 1 M KOH aqueous solution. From the hydrogen evolution reaction (HER), a current density of 10 mA cm - 2 is achieved at a potential of - 0.303 V vs. reversible hydrogen electrode (RHE). Meanwhile for the case of the oxygen evolution reaction (OER), a current density of 40 mA cm - 2 is measured at a potential of 1.49 V vs. RHE. Also, this electrocatalyst has shown a considerable long- term stability of 15 h for both the HER and the OER. Importantly, electrochemical impedance spectroscopy has shown that the NiFeLDH integration onto cobalt oxide exhibited around 3 fold decrease of charge transfer resistance for both the HER and the OER in comparison with pristine cobalt oxide films, which reveals an excellent electrocatalytic activity for both faradaic processes. All these results confirm that the proposed electrocatalyst can be integrated into an efficient water splitting system.

The photoemission electron microscopy and x-ray photoemission spectroscopy were utilized for the study of anodized epitaxial graphene (EG) on silicon carbide as a fundamental aspect of the oxygen evolution reaction on graphitic materials. The high-resolution analysis of surface morphology and composition quantified the material transformation during the anodization. We investigated the surface with lateral resolution amp;lt;150 nm, revealing significant transformations on the EG and the role of multilayer edges in increasing the film capacitance.

Graphitic materials exhibit significant anisotropy due to the difference in conductivity in a single layer and between adjacent layers. This anisotropy is manifested on epitaxial graphene (EG), which can be manipulated on the nanoscale in order to provide tailor-made properties. Insertion of defects into the EG lattice was utilized here for controllable surface modification with a model biocatalyst and the properties were quantified by both electrochemical and optical methods. A comparative evaluation of the electrode reaction kinetics on the enzyme-modified 2D material vs conventional carbon electrode materials revealed a significant enhancement of mediated bioelectrocatalysis at the nanoscale.

Electrocatalysis for energy‐efficient chemical transformations is a central concept behind sustainable technologies. Numerous efforts focus on synthesizing hydrogen peroxide, a major industrial chemical and potential fuel, using simple and green methods. Electrochemical synthesis of peroxide is a promising route. Herein it is demonstrated that the conducting polymer poly(3,4‐ethylenedioxythiophene), PEDOT, is an efficient and selective heterogeneous catalyst for the direct reduction of oxygen to hydrogen peroxide. While many metallic catalysts are known to generate peroxide, they subsequently catalyze decomposition of peroxide to water. PEDOT electrodes can support continuous generation of high concentrations of peroxide with Faraday efficiency remaining close to 100%. The mechanisms of PEDOT‐catalyzed reduction of O2 to H2O2 using in situ spectroscopic techniques and theoretical calculations, which both corroborate the existence of a chemisorbed reactive intermediate on the polymer chains that kinetically favors the selective reduction reaction to H2O2, are explored. These results offer a viable method for peroxide electrosynthesis and open new possibilities for intrinsic catalytic properties of conducting polymers.

The exploration for true electrocatalytic reactions at organic conducting polymer electrodes, including chemisorption of a reactant and desorption of a product, is receiving renewed interest due to the profound implications it could have on low-cost large area electrochemical energy technology. Here, we finalize the debate about the ability of an organic electrode, more specifically poly(3,4-ethylenedioxythiophene) (PEDOT), to be an electrocatalyst for hydrogen production. This paper proves and covers fundamental studies of the hydrogen evolution reaction (HER) on PEDOT films. Both theory based on DFT (Density Functional Theory) and experimental studies using electrochemical techniques and operando mass spectrometry suggest a Volmer-Heyrovsky mechanism for the actual HER on PEDOT. It is shown that PEDOT reaches an exchange current density comparable to that of metals (i.e. Cu, Ni, and Au) and in addition does not form passivating oxide layers or suffer from chemical corrosion in acidic media. Finally, an electrolyzer stack using the organic polymer electrode demonstrates HER performance in real applications.

In this work, we investigated the sensing performance of epitaxial graphene on Si-face 4H-SiC (EG/SiC) for liquid-phase detection of heavy metals (e.g., Pb and Cd), showing fast and stable response and low detection limit. The sensing platform proposed includes 3D-printed microfluidic devices, which incorporate all features required to connect and execute lab-on-chip (LOC) functions. The obtained results indicate that EG exhibits excellent sensing activity towards Pb and Cd ions. Several concentrations of Pb2+ solutions, ranging from 125 nM to 500 mu M, were analyzed showing Langmuir correlation between signal and Pb2+ concentrations, good stability, and reproducibility over time. Upon the simultaneous presence of both metals, sensor response is dominated by Pb2+ rather than Cd2+ ions. To explain the sensing mechanisms and difference in adsorption behavior of Pb2+ and Cd2+ ions on EG in water-based solutions, we performed van-der-Waals (vdW)-corrected density functional theory (DFT) calculations and non-covalent interaction (NCI) analysis, extended charge decomposition analysis (ECDA), and topological analysis. We demonstrated that Pb2+ and Cd2+ ions act as electron-acceptors, enhancing hole conductivity of EG, due to charge transfer from graphene to metal ions, and Pb2+ ions have preferential ability to binding with graphene over cadmium. Electrochemical measurements confirmed the conductometric results, which additionally indicate that EG is more sensitive to lead than to cadmium.

Two experimental methods to estimate the electrochemically active surface area (EASA) of microelectrodes are investigated. One method is based on electrocapacitive measurements and depends significantly on the surface roughness as well as on other parameters. The other method is based on faradaic current measurements and depends on the geometric surface area. The experimental results are supplemented with numerical modeling of electrodes with different surface roughness. A systematic study reveals a strong influence of the scale and arrangement of the surface roughness, the measurement potential and the electrolyte concentration on the EASA of microelectrodes estimated from the electrocapacitive measurements. The results show that electrocapacitive measurements should not be used to estimate the faradaic EASA of microelectrodes with a non-negligible surface roughness.

Fast and real time detection of Mercury (Hg) in aqueous solutions is a great challenge due to its bio-accumulative character and the detrimental effect on human health of this toxic element. Therefore, development of reliable sensing platforms is highly desirable. Current research is aiming at deep understanding of the electrochemical response of epitaxial graphene to Mercury exposure. By performing cyclic voltammetry and chronoamperometry measurements as well as density functional theory calculations, we elucidate the nature of Hg-involved oxidation-reduction reactions at the graphene electrode and shed light on the early stages of Hg electrodeposition. The obtained critical information of Hg behavior will be helpful for the design and processing of novel graphene-based sensors.

The design of the earth-abundant, nonprecious, efficient, and stable electrocatalysts for efficient hydrogen evolution reaction (HER) in alkaline media is a hot research topic in the field of renewable energies. A heterostructured system composed of MoSx deposited on NiO nanostructures (MoSx@NiO) as a robust catalyst for water splitting is proposed here. NiO nanosponges are applied as cocatalyst for MoS2 in alkaline media. Both NiO and MoS2@NiO composites are prepared by a hydrothermal method. The NiO nanostructures exhibit sponge-like morphology and are completely covered by the sheet-like MoS2. The NiO and MoS2 exhibit cubic and hexagonal phases, respectively. In the MoSx@NiO composite, the HER experiment in 1 m KOH electrolyte results in a low overpotential (406 mV) to produce 10 mA cm(-2) current density. The Tafel slope for that case is 43 mV per decade, which is the lowest ever achieved for MoS2-based electrocatalyst in alkaline media. The catalyst is highly stable for at least 13 h, with no decrease in the current density. This simple, cost-effective, and environmentally friendly methodology can pave the way for exploitation of MoSx@NiO composite catalysts not only for water splitting, but also for other applications such as lithium ion batteries, and fuel cells.

Counterion exchange strategies are used to modify the hydrophilic character of the self-doped conjugated polyelectrolyte PEDOTS. The supramolecular complexes, soluble in organic solvents, are suitable to fabricate finely performing thin active layers in organic electrochemical transistors (OECTs). We demonstrate that ionic transport in these PEDOTS based complexes, thus their performance in OECT devices, is governed by a delicate balance among degree of doping, wettability and porosity, which can be controlled by a precise tuning of the polyelectrolyte/hydrophobic counterion ratio. We also show that the device operation can be modulated by varying the composition of the aqueous electrolyte in a range compatible with biological processes, making these materials suitable candidates to be interfaced with living cells.

Abstract Lignosulfonate (LS) is a large-scale surplus product of the forest and paper industries, and has primarily been utilized as a low-cost plasticizer in making concrete for the construction industry. LS is an anionic redox-active polyelectrolyte and is a promising candidate to boost the charge capacity of the positive electrode (positrode) in redox-supercapacitors. Here, the physical-chemical investigation of how this biopolymer incorporates into the conducting polymer PEDOT matrix, of the positrode, by means of counter-ion exchange is reported. Upon successful incorporation, an optimal access to redox moieties is achieved, which provides a 63% increase of the resulting stored electrical charge by reversible redox interconversion. The effects of pH, ionic strength, and concentrations, of included components, on the polymer?polymer interactions are optimized to exploit the biopolymer-associated redox currents. Further, the explored LS-conducting polymer incorporation strategy, via aqueous synthesis, is evaluated in an up-scaling effort toward large-scale electrical energy storage technology. By using an up-scaled production protocol, integration of the biopolymer within the conducting polymer matrix by counter-ion exchange is confirmed and the PEDOT-LS synthesized through optimized strategy reaches an improved charge capacity of 44.6 mAh g?1.

Electrochemistry is an old but still flourishing field of research due to the importance of the efficiency and kinetics of electrochemical reactions in industrial processes and (bio-)electrochemical devices. The heterogeneous electron transfer from an electrode to a reactant in the solution has been well studied for metal, semiconductor, metal oxide, and carbon electrodes. For those electrode materials, there is little correlation between the electronic transport within the electrode material and the electron transfer occurring at the interface between the electrode and the solution. Here, we investigate the heterogeneous electron transfer between a conducting polymer electrode and a redox couple in an electrolyte. As a benchmark system, we use poly(3,4-ethylenedioxythiophene) (PEDOT) and the Ferro/ferricyanide redox couple in an aqueous electrolyte. We discovered a strong correlation between the electronic transport within the PEDOT electrode and the rate of electron transfer to the organometallic molecules in solution. We attribute this to a percolation-based charge transport within the polymer electrode directly involved in the electron transfer. We show the impact of this finding by optimizing an electrochemical thermogalvanic cell that transforms a heat flux into electrical power. The power generated by the cell increased by four orders of magnitude on changing the morphology and conductivity of the polymer electrode. As all conducting polymers are recognized to have percolation transport, we believe that this is a general phenomenon for this family of conductors.

Organic electrochemical transistors (OECTs) have been the subject of intense research in recent years. To date, however, most of the reported OECTs rely entirely on p-type (hole transport) operation, while electron transporting (n-type) OECTs are rare. The combination of efficient and stable p-type and n-type OECTs would allow for the development of complementary circuits, dramatically advancing the sophistication of OECT-based technologies. Poor stability in air and aqueous electrolyte media, low electron mobility, and/or a lack of electrochemical reversibility, of available high-electron affinity conjugated polymers, has made the development of n-type OECTs troublesome. Here, it is shown that ladder-type polymers such as poly(benzimidazobenzophenanthroline) (BBL) can successfully work as stable and efficient n-channel material for OECTs. These devices can be easily fabricated by means of facile spray-coating techniques. BBL-based OECTs show high transconductance (up to 9.7 mS) and excellent stability in ambient and aqueous media. It is demonstrated that BBL-based n-type OECTs can be successfully integrated with p-type OECTs to form electrochemical complementary inverters. The latter show high gains and large worst-case noise margin at a supply voltage below 0.6 V.

Lignin is one of the most abundant biopolymers, constituting 25% of plants. The pulp and paper industries extract lignin in their process and today seek new applications for this by-product. Here, it is reported that the aromatic alcohols obtained from lignin depolymerization can be used as fuel in high power density electrical power sources. This study shows that the conducting polymer poly(3,4-ethylenedioxythiophene), fabricated from abundant ele-ments via low temperature synthesis, enables efficient, direct, and reversible chemical-to-electrical energy conversion of aromatic alcohols such as lignin residues in aqueous media. A material operation principle related to the rela-tively high molecular diffusion and ionic conductivity within the conducting polymer matrix, ensuring efficient uptake of protons in the course of proton-coupled electron transfers between organic molecules is proposed.

In this work, water dispersed electrochromic polymer nanoparticles (WDENs) prepared with miniemulsion process are introduced into electrochromic polymer (ECP) electrode for the first time. The poly [2, 3-bis-(3-octyloxyphenyl) quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl]) nanoparticle (NP) electrode shows much faster switching speed than the compacted electrode (e.g. 2.10 s vs. 24.15 s for coloring, 8.65 s vs. 25.95 s for bleaching @ 0.4 V; 1.30 s vs. 9.20 s coloring and 1.7 s vs. 2.90 s for bleaching @ 1.0 V). Moreover, the potentiality of WDENs for universal ECPs is demonstrated. The microelectrochemical measurement indicates much more efficient counter-ion diffusion between the electrolyte and the NP films than the compacted films, which results in much faster electrochromic switching. Besides the facile and eco-friendly processing of the WDENs, all solution and low cost fabrication of ECP NP films suggest their broad applications in commercial production of polymer electrochromic display and great potential for other polymer electrochemical electronics.

Here, we report the electrochemical deposition of lead (Pb) as a model metal on epitaxial graphene fabricated on silicon carbide (Gr/SiC). The kinetics of electrodeposition and morphological characteristics of the deposits were evaluated by complementary electrochemical, physical and computational methods. The use of Gr/SiC as an electrode allowed the tracking of lead-associated redox conversions. The analysis of current transients passed during the deposition revealed an instantaneous nucleation mechanism controlled by convergent mass transport on the nuclei locally randomly distributed on epitaxial graphene. This key observation of the deposit topology was confirmed by low values of the experimentally-estimated apparent diffusion coefficient, Raman spectroscopy and scanning electron microscopy (SEM) studies. First principles calculations showed that the nucleation of Pb clusters on the graphene surface leads to weakening of the interaction strength of the metal-graphene complex, and only spatially separated Pb adatoms adsorbed on bridge and/or edge-plane sites can affect the vibrational properties of graphene. We expect that the lead adatoms can merge in large metallic clusters only at defect sites that reinforce the metal-graphene interactions. Our findings provide valuable insights into both heavy metal ion electrochemical analysis and metal electroplating on graphene interfaces that are important for designing effective detectors of toxic heavy metals.

Solar-to-chemical conversion of sunlight into hydrogen peroxide as a chemical fuel is an emerging carbon-free sustainable energy strategy. The process is based on the reduction of dissolved oxygen to hydrogen peroxide. Only limited amounts of photoelectrode materials have been successfully explored for photoelectrochemical production of hydrogen peroxide. Herein we detail approaches to produce robust organic semiconductor photocathodes for peroxide evolution. They are based on evaporated donor-acceptor heterojunctions between phthalocyanine and tetracarboxylic perylenediimide, respectively. These small molecules form nanocrystalline films with good operational stability and high surface area. We discuss critical parameters which allow fabrication of efficient devices. These photocathodes can support continuous generation of high concentrations of peroxide with faradaic efficiency remaining at around 70%. We find that an advantage of the evaporated heterojunctions is that they can be readily vertically stacked to produce tandem cells which produce higher voltages. This feature is desirable for fabricating two-electrode photoelectrochemical cells. Overall, the photocathodes presented here have the highest performance reported to date in terms of photocurrent for peroxide production. These results offer a viable method for peroxide photosynthesis and provide a roadmap of strategies that can be used to produce photoelectrodes with even higher efficiency and productivity.

Dawson-type 18-molybdodisulphate anion [S2Mo18O62](4-) has been immobilized within polypyrrole film by means of electrochemical polymerization. The polymer modified electrodes have been characterized with voltammetry and surface based techniques. The noticeable change in electrochemical properties of [S2Mo18O62](4-) has been observed with immobilization, which is favours its electrocatalytic performance. Hydrogen peroxide reduction in neutral pH as a standard system for electrocatalytic properties assessment has been studied on composite film-modified electrodes and showed the sensitivity of 127 mAM(-1) cm(-2). Developed system showed high stabilities towards redox switching and peroxide reduction. (C) 2018 Published by Elsevier Ltd.

The surface immobilization of the parent Dawson polyoxometalate (POM) as a counter-ion for the electropolymerization of polypyrrole (PPy) or as an electrode-adhered solid was utilized for voltammetric studies of the surface adhered POM in room temperature ionic liquids (RTIL). Illustrating the efficiency of intermediate stabilization, voltammetry at POM-modified electrodes in a PF6-based RTIL revealed richer redox behaviour and higher stabilization in comparison with aqueous electrolytes and with BF4-based RTIL, respectively. High stability of the POM-doped PPy towards continuous charge-discharge voltammetric redox cycles was confirmed by minor changes in film morphology observed after the cycling in RTILs. (c) 2017 Elsevier Ltd. All rights reserved.