Copper/Polyaniline Interfaces Confined CO2 Electroreduction for Selective Hydrocarbon Production.

Polyaniline (PANI) provides an attractive organic platform for CO2 electrochemical reduction due to the ability to adsorb CO2 molecules and in providing means to interact with metal nanostructures. In this work, a novel PANI supported copper catalyst has been developed by coupling the interfacial polymerization of PANI and Cu. The hybrid catalyst demonstrates excellent activity towards production of hydrocarbon products including CH4 and C2H4, compared with the use of bare Cu. A Faradaic efficiency of 71.8 % and a current density of 16.9 mA/cm2 were achieved at -0.86 V vs. RHE, in contrast to only 22.2 % and 1.0 mA/cm2 from the counterpart Cu catalysts. The remarkably enhanced catalytic performance of the hybrid PANI/Cu catalyst can be attributed to the synergistic interaction between the PANI underlayer and copper. The PANI favours the adsorption and binding of CO2 molecules via its nitrogen sites to form *CO intermediates, while the Cu/PANI interfaces confine the diffusion or desorption of the *CO intermediates favouring their further hydrogenation or carbon-carbon coupling to form hydrocarbon products. This work provides insights into the formation of hydrocarbon products on PANI-modified Cu catalysts, which may guide the development of conducting polymer-metal catalysts for CO2 electroreduction.

A high-performance capillary-fed electrolysis cell promises more cost-competitive renewable hydrogen.

Renewable, or green, hydrogen will play a critical role in the decarbonisation of hard-to-abate sectors and will therefore be important in limiting global warming. However, renewable hydrogen is not cost-competitive with fossil fuels, due to the moderate energy efficiency and high capital costs of traditional water electrolysers. Here a unique concept of water electrolysis is introduced, wherein water is supplied to hydrogen- and oxygen-evolving electrodes via capillary-induced transport along a porous inter-electrode separator, leading to inherently bubble-free operation at the electrodes. An alkaline capillary-fed electrolysis cell of this type demonstrates water electrolysis performance exceeding commercial electrolysis cells, with a cell voltage at 0.5 A cm-2 and 85 °C of only 1.51 V, equating to 98% energy efficiency, with an energy consumption of 40.4 kWh/kg hydrogen (vs. ~47.5 kWh/kg in commercial electrolysis cells). High energy efficiency, combined with the promise of a simplified balance-of-plant, brings cost-competitive renewable hydrogen closer to reality.

Boosting Formate Production from CO2 at High Current Densities Over a Wide Electrochemical Potential Window on a SnS Catalyst.

The flow-cell design offers prospect for transition to commercial-relevant high current density CO2 electrolysis. However, it remains to understand the fundamental interplay between the catalyst, and the electrolyte in such configuration toward CO2 reduction performance. Herein, the dramatic influence of electrolyte alkalinity in widening potential window for CO2 electroreduction in a flow-cell system based on SnS nanosheets is reported. The optimized SnS catalyst operated in 1 m KOH achieves a maximum formate Faradaic efficiency of 88 ± 2% at -1.3 V vs reversible hydrogen electrode (RHE) with the current density of ≈120 mA cm-2 . Alkaline electrolyte is found suppressing the hydrogen evolution across all potentials which is particularly dominant at the less negative potentials, as well as CO evolution at more negative potentials. This in turn widens the potential window for formate conversion (>70% across -0.5 to -1.5 V vs RHE). A comparative study to SnOx counterpart indicates sulfur also acts to suppress hydrogen evolution, although electrolyte alkalinity resulting in a greater suppression. The boosting of the electrochemical potential window, along with high current densities in SnS derived catalytic system offers a highly attractive and promising route toward industrial-relevant electrocatalytic production of formate from CO2 .

A Self-Assembled CO2 Reduction Electrocatalyst: Posy-Bouquet-Shaped Gold-Polyaniline Core-Shell Nanocomposite.

Here it was demonstrated that the decoration of gold (Au) with polyaniline is an effective approach in increasing its electrocatalytic reduction of CO2 to CO. The core-shell-structured gold-polyaniline (Au-PANI) nanocomposite delivered a CO2 -to-CO conversion efficiency of 85 % with a high current density of 11.6 mA cm-2 . The polyaniline shell facilitated CO2 adsorption, and the subsequent formation of reaction intermediates on the gold core contributed to the high efficiency observed.

Reversible and Selective Interconversion of Hydrogen and Carbon Dioxide into Formate by a Semiartificial Formate Hydrogenlyase Mimic.

The biological formate hydrogenlyase (FHL) complex links a formate dehydrogenase (FDH) to a hydrogenase (H2ase) and produces H2 and CO2 from formate via mixed-acid fermentation in Escherichia coli. Here, we describe an electrochemical and a colloidal semiartificial FHL system that consists of an FDH and a H2ase immobilized on conductive indium tin oxide (ITO) as an electron relay. These in vitro systems benefit from the efficient wiring of a highly active enzyme pair and allow for the reversible conversion of formate to H2 and CO2 under ambient temperature and pressure. The hybrid systems provide a template for the design of synthetic catalysts and surpass the FHL complex in vivo by storing and releasing H2 on demand by interconverting CO2/H2 and formate with minimal bias in either direction.

Human Neural Tissues from Neural Stem Cells Using Conductive Biogel and Printed Polymer Microelectrode Arrays for 3D Electrical Stimulation.

Electricity is important in the physiology and development of human tissues such as embryonic and fetal development, and tissue regeneration for wound healing. Accordingly, electrical stimulation (ES) is increasingly being applied to influence cell behavior and function for a biomimetic approach to in vitro cell culture and tissue engineering. Here, the application of conductive polymer (CP) poly(3,4-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT:PSS) pillars is described, direct-write printed in an array format, for 3D ES of maturing neural tissues that are derived from human neural stem cells (NSCs). NSCs are initially encapsulated within a conductive polysaccharide-based biogel interfaced with the CP pillar microelectrode arrays (MEAs), followed by differentiation in situ to neurons and supporting neuroglia during stimulation. Electrochemical properties of the pillar electrodes and the biogel support their electrical performance. Remarkably, stimulated constructs are characterized by widespread tracts of high-density mature neurons and enhanced maturation of functional neural networks. Formation of tissues using the 3D MEAs substantiates the platform for advanced clinically relevant neural tissue induction, with the system likely amendable to diverse cell types to create other neural and non-neural tissues. The platform may be useful for both research and translation, including modeling tissue development, function and dysfunction, electroceuticals, drug screening, and regenerative medicine.

Facile electrochemical synthesis of ultrathin iron oxyhydroxide nanosheets for the oxygen evolution reaction.

We propose a facile approach to synthesise ultrathin iron oxyhydroxide nanosheets for use in catalysing the electrochemical oxygen evolution reaction. This two dimensional material lowers the overpotential and provides a platform for further performance enhancement via integration of species such as nickel into an ultrathin nanosheet structure.

Photoelectrochemical H2 Evolution with a Hydrogenase Immobilized on a TiO2-Protected Silicon Electrode.

The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron-transfer processes at highly active and well-defined catalytic sites on a light-harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO2-coated p-Si photocathode for the photo-reduction of protons to H2. The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO2 layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p-Si|TiO2|hydrogenase photocathode displays visible-light driven production of H2 at an energy-storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p-type semiconductor photocathode through the engineering of the enzyme-materials interface.

A decahaem cytochrome as an electron conduit in protein-enzyme redox processes.

The decahaem cytochrome MtrC from Shewanella oneidensis MR-1 was employed as a protein electron conduit between a porous indium tin oxide electrode and redox enzymes. Using a hydrogenase and a fumarate reductase, MtrC was shown as a suitable and efficient diode to shuttle electrons to and from the electrode with the MtrC redox activity regulating the direction of the enzymatic reactions.

Photoelectrochemical H2 Evolution with a Hydrogenase Immobilized on a TiO2 -Protected Silicon Electrode.

The combination of enzymes with semiconductors enables the photoelectrochemical characterization of electron-transfer processes at highly active and well-defined catalytic sites on a light-harvesting electrode surface. Herein, we report the integration of a hydrogenase on a TiO2 -coated p-Si photocathode for the photo-reduction of protons to H2 . The immobilized hydrogenase exhibits activity on Si attributable to a bifunctional TiO2 layer, which protects the Si electrode from oxidation and acts as a biocompatible support layer for the productive adsorption of the enzyme. The p-Si|TiO2 |hydrogenase photocathode displays visible-light driven production of H2 at an energy-storing, positive electrochemical potential and an essentially quantitative faradaic efficiency. We have thus established a widely applicable platform to wire redox enzymes in an active configuration on a p-type semiconductor photocathode through the engineering of the enzyme-materials interface.

A Decaheme Cytochrome as a Molecular Electron Conduit in Dye-Sensitized Photoanodes.

In nature, charge recombination in light-harvesting reaction centers is minimized by efficient charge separation. Here, it is aimed to mimic this by coupling dye-sensitized TiO2 nanocrystals to a decaheme protein, MtrC from Shewanella oneidensis MR-1, where the 10 hemes of MtrC form a ≈7-nm-long molecular wire between the TiO2 and the underlying electrode. The system is assembled by forming a densely packed MtrC film on an ultra-flat gold electrode, followed by the adsorption of approximately 7 nm TiO2 nanocrystals that are modified with a phosphonated bipyridine Ru(II) dye (RuP). The step-by-step construction of the MtrC/TiO2 system is monitored with (photo)electrochemistry, quartz-crystal microbalance with dissipation (QCM-D), and atomic force microscopy (AFM). Photocurrents are dependent on the redox state of the MtrC, confirming that electrons are transferred from the TiO2 nanocrystals to the surface via the MtrC conduit. In other words, in these TiO2/MtrC hybrid photodiodes, MtrC traps the conduction-band electrons from TiO2 before transferring them to the electrode, creating a photobioelectrochemical system in which a redox protein is used to mimic the efficient charge separation found in biological photosystems.

Wiring of Photosystem II to Hydrogenase for Photoelectrochemical Water Splitting.

In natural photosynthesis, light is used for the production of chemical energy carriers to fuel biological activity. The re-engineering of natural photosynthetic pathways can provide inspiration for sustainable fuel production and insights for understanding the process itself. Here, we employ a semiartificial approach to study photobiological water splitting via a pathway unavailable to nature: the direct coupling of the water oxidation enzyme, photosystem II, to the H2 evolving enzyme, hydrogenase. Essential to this approach is the integration of the isolated enzymes into the artificial circuit of a photoelectrochemical cell. We therefore developed a tailor-made hierarchically structured indium-tin oxide electrode that gives rise to the excellent integration of both photosystem II and hydrogenase for performing the anodic and cathodic half-reactions, respectively. When connected together with the aid of an applied bias, the semiartificial cell demonstrated quantitative electron flow from photosystem II to the hydrogenase with the production of H2 and O2 being in the expected two-to-one ratio and a light-to-hydrogen conversion efficiency of 5.4% under low-intensity red-light irradiation. We thereby demonstrate efficient light-driven water splitting using a pathway inaccessible to biology and report on a widely applicable in vitro platform for the controlled coupling of enzymatic redox processes to meaningfully study photocatalytic reactions.

Photoelectrochemical reduction of aqueous protons with a CuO|CuBi2O4 heterojunction under visible light irradiation.

A p-type heterojunction photoelectrode consisting of platinized CuBi2O4 layered on a CuO film was prepared. The CuO|CuBi2O4|Pt electrode photo-generates H2 in pH neutral aqueous solution during visible light irradiation and exhibits a substantially enhanced photocurrent compared to CuO|Pt and CuBi2O4|Pt electrodes. Reduced electron-hole recombination by the band offsets in the heterostructure is responsible for the improved photoelectrochemical performance of CuO|CuBi2O4 with a small band-gap of approximately 1.5 eV.

Mediator enhanced water oxidation using Rb4[Ru(II)(bpy)3]5[{Ru(III)4O4(OH)2(H2O)4}(γ-SiW10O36)2] film modified electrodes.

The water insoluble complex Rb4[Ru(II)(bpy)3]5[{Ru(III)4O4(OH)2(H2O)4}(γ-SiW10O36)2], ([Ru(II)bpy]5[Ru(III)4POM]), was synthesized from Rb8K2[{Ru(IV)4O4(OH)2(H2O)4}(γ-SiW10O36)2] and used for electrocatalytic water oxidation under both thin- and thick-film electrode conditions. Results demonstrate that the [Ru(II)bpy]5[Ru(III)4POM] modified electrode enables efficient water oxidation to be achieved at neutral pH using thin-film conditions, with [Ru(bpy)3](3+)([Ru(III)bpy]) acting as the electron transfer mediator and [Ru(V)4POM] as the species releasing O2. The rotating ring disc electrode (RRDE) method was used to quantitatively determine the turnover frequency (TOF) of the catalyst, and a value of 0.35 s(-1) was obtained at a low overpotential of 0.49 V (1.10 V vs Ag/AgCl) at pH 7.0. The postulated mechanism for the mediator enhanced catalytic water process in a pH 7 buffer containing 0.1 M LiClO4 as an additional electrolyte includes the following reactions (ion transfer for maintaining charge neutrality is omitted for simplicity): [Ru(II)bpy]5[Ru(III)4POM] → [Ru(III)bpy]5[Ru(V)4POM] + 13 e(-) and [Ru(III)bpy]5[Ru(V)4POM] + 2H2O → [Ru(III)bpy]5[Ru(IV)4POM] + O2 + 4H(+). The voltammetry of related water insoluble [Ru(II)bpy]2[S2M18O62] (M = W and Mo) and [Fe(II)Phen]x[Ru(III)4POM] materials has also been studied, and the lack of electrocatalytic water oxidation in these cases supports the hypothesis that [Ru(III)bpy] is the electron transfer mediator and [Ru(V)4POM] is the species responsible for oxygen evolution.

Self-organized cobalt fluoride nanochannel layers used as a pseudocapacitor material.

Aligned CoF2 nanochannel layers have been formed by self-ordering electrochemical anodization. In voltammograms these layers provide multiple oxidation states, an almost ideal rectangular pseudocapacitive behavior, a high specific capacitance and good capacitance retention. These layers may thus be promising for supercapacitor applications.

Anodic nanotubular/porous hematite photoanode for solar water splitting: substantial effect of iron substrate purity.

Anodization of iron substrates is one of the most simple and effective ways to fabricate nanotubular (and porous) structures that could be directly used as a photoanode for solar water splitting. Up to now, all studies in this field focused on achieving a better geometry of the hematite nanostructures for a higher efficiency. The present study, however, highlights that the purity of the iron substrate used for any anodic-hematite-formation approach is extremely important in view of the water-splitting performance. Herein, anodic self-organized oxide morphologies (nanotubular and nanoporous) are grown on different iron substrates under a range of anodization conditions, including elevated temperatures and anodization supported by ultrasonication. Substrate purity has not only a significant effect on oxide-layer growth rate and tube morphology, but also gives rise to a ninefold increase in the photoelectrochemical water-splitting performance (0.250 vs. 0.028 mA cm−2 at 1.40 V vs. reversible hydrogen electrode under AM 1.5 100 mW cm−2 illumination) for 99.99 % versus 99.5 % purity iron substrates of similar oxide geometry. Elemental analysis and model alloys show that particularly manganese impurities have a strong detrimental effect on the water-splitting performance.

Enhancing the water splitting efficiency of Sn-doped hematite nanoflakes by flame annealing.

The effect of flame annealing on the water-splitting properties of Sn decorated hematite (α-Fe2O3) nanoflakes has been investigated. It is shown that flame annealing can yield a considerable enhancement in the maximum photocurrent under AM 1.5 (100 mW cm(-2)) conditions compared to classic furnace annealing treatments. Optimizing the annealing time (10 s at 1000 °C) leads to a photocurrent of 1.1 mA cm(-2) at 1.23 V (vs. RHE) with a maximum value 1.6 mA cm(-2) at 1.6 V (vs. RHE) in 1 M KOH. The improvement in photocurrent can be attributed to the fast direct heating that maintains the nanoscale morphology, leads to optimized Sn decoration, and minimizes detrimental substrate effects.