Effect of the Cu2+/1+ Redox Potential of Non-Macrocyclic Cu Complexes on Electrochemical CO2 Reduction.

Cu2+/1+ complexes facilitate the reduction of CO2 to valuable chemicals. The catalytic conversion likely involves the binding of CO2 and/or reduction intermediates to Cu2+/1+, which in turn could be influenced by the electron density on the Cu2+/1+ ion. Herein we investigated whether modulating the redox potential of Cu2+/1+ complexes by changing their ligand structures influenced their CO2 reduction performance significantly. We synthesised new heteroleptic Cu2/1+ complexes, and for the first time, studied a (Cu-bis(8-quinolinolato) complex, covering a Cu2+/1+ redox potential range of 1.3 V. We have found that the redox potential influenced the Faradaic efficiency of CO2 reduction to CO. However, no correlation between the redox potential and the Faradaic efficiency for methane was found. The lack of correlation could be attributed to the presence of a Cu-complex-derived catalyst deposited on the electrodes leading to a heterogeneous catalytic mechanism, which is controlled by the structure of the in situ deposited catalyst and not the redox potential of the pre-cursor Cu2+/1+ complexes.

When "Donor-Acceptor" Dyes Delocalize: A Spectroscopic and Computational Study of D-A Dyes Using "Michler's Base".

In this study, we show that the "Michler's base" motif can be combined in a donor-acceptor arrangement with a range of acceptor units (indandione, indandione with cyano substituents, barbituric acid, or rhodanine) to give photophysical properties that are dominated by delocalized excited states. By changing the acceptor unit and by altering the planarity of this system, it is possible to tune the low-energy absorption feature in terms of intensity from 23 000 to 67 000 M-1 cm-1 and energy between 500 and 700 nm. Resonance Raman spectroscopy and time-dependent density functional theory indicate that this absorption feature has two underlying transitions: a weaker charge-transfer transition around 500 nm and a strong mixed or delocalized transition between 550 and 700 nm. Generally, these compounds are not strongly emissive; however, dual emission is observed, and the relative intensity of the two states can be modulated by solvent polarity. The energy of these emissive states does not correlate with the Lippert-Mataga analysis in which the Stokes shift is related to the solvent polarity (Δf).

Flexible Tuning of Unsaturated ß-Substituents on Zn Porphyrins: A Synthetic, Spectroscopic and Computational Study.

A series of zinc porphyrins substituted at adjacent ß-positions with a CN group and para-substituted ethenyl/ethynyl-phenyl group have been studied using electronic absorption spectroscopy, resonance Raman spectroscopy and DFT calculations. The oxidative nucleophilic substitution of hydrogen was utilized for the introduction of a cyano substituent on the porphyrin ring. This modification has a remarkable electronic effect on the ring. The resulting porphyrin cyanoaldehyde was further modified in Wittig condensations to give series of arylalkene- and arylalkyne-substituted derivatives. This substitution pattern caused significant redshifting and broadening of the B band, tuning from 433-446 nm. Additionally the Q/B band intensity ratios show much higher values than observed for the parent porphyrin ZnTPP (0.20 vs. 0.03). Careful analysis of the electronic transitions using DFT and resonance Raman spectroscopy reveal that the substituent does not significantly perturb the electronic structure of the porphyrin core, which is still well described by Gouterman's four-orbital model. However, the substituents do play a role in elongating the conjugation length and this results in the observed spectral changes.

Organic Mixed Ionic-Electronic Conductors Based on Tunable and Functional Poly(3,4-ethylenedioxythiophene) Copolymers.

Organic mixed ionic-electronic conductors (OMIECs) are being explored in applications such as bioelectronics, biosensors, energy conversion and storage, and optoelectronics. OMIECs are largely composed of conjugated polymers that couple ionic and electronic transport in their structure as well as synthetic flexibility. Despite extensive research, previous studies have mainly focused on either enhancing ion conduction or enabling synthetic modification. This limited the number of OMIECs that excel in both domains. Here, a series of OMIECs based on functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) copolymers that combine efficient ion/electron transport with the versatility of post-functionalization were developed. EDOT monomers bearing sulfonic (EDOTS) and carboxylic acid (EDOTCOOH) groups were electrochemically copolymerized in different ratios on oxygen plasma-treated conductive substrates. The plasma treatment enabled the synthesis of copolymers containing high ratios of EDOTS (up to 68%), otherwise not possible with untreated substrates. This flexibility in synthesis resulted in the fabrication of copolymers with tunable properties in terms of conductivity (2-0.0019 S/cm) and ion/electron transport, for example, as revealed by their volumetric capacitances (122-11 F/cm3). The importance of the organic nature of the OMIECs that are amenable to synthetic modification was also demonstrated. EDOTCOOH was successfully post-functionalized without influencing the ionic and electronic transport of the copolymers. This opens a new way to tailor the properties of the OMIECs to specific applications, especially in the field of bioelectronics.

A PEDOT based graft copolymer with enhanced electronic stability.

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) remains the most investigated conjugated polymer in bioelectronics, due to its biocompatibility, high conductivity, and commercial availability. Despite these advantages, it suffers from structural and electronic instability, associated with the PSS component. Here, a graft copolymer based on ionised sulfonic modified PEDOT, poly(EDOTS-g-EDOT), was electrochemically synthesised with demonstrated structural and electronic stability and enhanced electrochemical performance. The graft copolymer was insoluble in water without crosslinking, and exhibited enhanced ion diffusion upon electrochemical switching, as revealed by its volumetric capacitance (159 ± 8 F cm-3), which was significantly higher than that of spin-coated PEDOT:PSS films (41 ± 5 F cm-3). Similarly, its performance as an active channel material in organic electrochemical transistors (OECTs) was superior to the spin-coated PEDOT:PSS, as shown for instance by its high normalised transconductance (273 ± 79 S cm-1) and a significantly high ION/IOFF ratio (19 345 ± 1205). Its short- and long-term electronic stability were also confirmed with no drop in its output drain current, despite its high swelling degree. In contrast, the spin-coated PEDOT:PSS experienced a significant deterioration in its performance over the same operational time. The facile synthesis and improved performance of poly(EDOTS-g-EDOT) highlight the importance of innovative material design in overcoming existing operational shortcomings in electronic devices.

Catalytic Decomposition of an Organic Electrolyte to Methane by a Cu Complex-Derived In Situ CO2 Reduction Catalyst.

Metal complexes are often transformed to metal complex-derived catalysts during electrochemical CO2 reduction, enhancing the catalytic performance of CO2 reduction or changing product selectivity. To date, it has not been investigated whether metal-complex derived catalysts also enhance the decomposition of the solvent/electrolyte components as compared to an uncoated electrode. Here, we tested the electrochemical stability of five organic solvent-based electrolytes with and without a Cu complex-derived catalyst on carbon paper in an inert atmosphere. The amount of methane and hydrogen produced was monitored using gas chromatography. Importantly, the onset potential for methane production was reduced by 300 mV in the presence of a Cu complex-derived catalyst leading to a significant amount of methane (417.7 ppm) produced at -2.17 V vs Fc/Fc+ in acetonitrile. This suggests that the Cu complex-derived catalyst accelerated not only CO2 reduction but also the reduction of the electrolyte components. This means that Faradaic efficiency (FE) measurements under CO2 in acetonitrile may significantly overestimate the amount of CH4. Only 28.8 ppm of methane was produced in dimethylformamide under an inert atmosphere, much lower than that produced under CO2 (506 ppm under CO2) at the same potential, suggesting that dimethylformamide is a more suitable solvent. Measurements in propylene carbonate produced mostly hydrogen gas while in dimethyl sulfoxide and 3-methoxypropionitrile neither methane nor hydrogen was detected. A strong linear correlation between the measured current and the amount of methane produced with and without the Cu complex-derived catalyst confirmed that the origin of methane production is solvent/electrolyte decomposition and not the decomposition of the catalyst itself. The study highlights that in a nonaqueous system, highly active catalyst in situ deposited during electrochemical testing can significantly influence background measurements as compared to uncoated electrodes, therefore the choice of solvent is paramount for reliable testing.

Edge-Functionalized Graphene/Polydimethylsiloxane Composite Films for Flexible Neural Cuff Electrodes.

The design of neural electrodes has changed in the past decade, driven mainly by the development of new materials that open the possibility of manufacturing electrodes with adaptable mechanical properties and promising electrical properties. In this paper, we report on the mechanical and electrochemical properties of a polydimethylsiloxane (PDMS) composite with edge-functionalized graphene (EFG) and demonstrate its potential for use in neural implants with the fabrication of a novel neural cuff electrode. We have shown that a 200 µm thick 1:1 EFG/PDMS composite film has a stretchability of up to 20%, a Young's modulus of 2.52 MPa, and a lifetime of more than 10000 mechanical cycles, making it highly suitable for interfacing with soft tissue. Electrochemical characterization of the EFG/PDMS composite film showed that the capacitance of the composite increased up to 35 times after electrochemical reduction, widening the electrochemical water window and remaining stable after soaking for 5 weeks in phosphate buffered saline. The electrochemically activated EFG/PDMS electrode had a 3 times increase in the charge injection capacity, which is more than double that of a commercial platinum-based neural cuff. Electrochemical and spectrochemical investigations supported the conclusion that this effect originated from the stable chemisorption of hydrogen on the graphene surface. The biocompatibility of the composite was confirmed with an in vitro cell culture study using mouse spinal cord cells. Finally, the potential of the EFG/PDMS composite was demonstrated with the fabrication of a novel neural cuff electrode, whose double-layered and open structured design increased the cuff stretchability up to 140%, well beyond that required for an operational neural cuff. In addition, the cuff design offers better integration with neural tissue and simpler nerve fiber installation and locking.

Physicochemical study of spiropyran-terthiophene derivatives: photochemistry and thermodynamics.

The photochemistry and thermodynamics of two terthiophene (TTh) derivatives bearing benzospiropyran (BSP) moieties, 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-acetate (BSP-2) and 1-(3,3″-dimethylindoline-6'-nitrobenzospiropyranyl)-2-ethyl 4,4″-didecyloxy-2,2':5',2″-terthiophene-3'-carboxylate (BSP-3), differing only by a single methylene spacer unit, have been studied. The kinetics of photogeneration of the equivalent merocyanine (MC) isomers (MC-2 and MC-3, respectively), the isomerisation properties of MC-2 and MC-3, and the thermodynamic parameters have been studied in acetonitrile, and compared to the parent, non-TTh-functionalised, benzospiropyran derivative, BSP-1. Despite the close structural similarity of BSP-2 and BSP-3, their physicochemical properties were found to differ significantly; examples include activation energies (E(a(MC-2)) = 75.05 kJ mol(-1), E(a(MC-3)) = 100.39 kJ mol(-1)) and entropies of activation (ΔS = 43.38 J K(-1) mol(-1), ΔS = 37.78 J K(-1) mol(-1)) for the thermal relaxation from MC to BSP, with the MC-3 value much closer to the unmodified MC-1 value (46.48 J K(-1) mol(-1)) for this latter quantity. The thermal relaxation kinetics and solvatochromic behaviour of the derivatives in a range of solvents of differing polarity (ethanol, dichloromethane, acetone, toluene and diethyl ether) are also presented. Differences in the estimated values of these thermodynamic and kinetic parameters are discussed with reference to the molecular structure of the derivatives.

Cu-THQ-EFG Composite for Highly Selective Electrochemical CO2 Reduction to Formate at Low Overpotentials.

Metal organic framework (MOFs) are promising materials for electrocatalysis. However, the active sites of bulk MOFs crystal normally cannot be fully utilized because of the slow reagent penetration of pores and blockage of active sites. Herein, we report a facile way to deposit copper-benzoquinoid (Cu-THQ) on the edge-functionalized graphene (EFG) which prevented material's aggregation. EFG used as a substrate provides higher electrical conductivity and stability in water than previously utilized graphene oxide (GO). Besides, the plate-like morphology of EFG proved to be more beneficial to support the MOF, because of the functional groups on its edge regions and much lower resistance compared to the sheet GO. Therefore, EFG can boost the resultant material's catalytic activity for CO2 electroreduction (CO2RR). Furthermore, Cu-THQ exhibits high selectivity for formate formation in CO2RR. Representing as the only CO2 reduced liquid product, formate can be separated from gaseous products and further extracted from the electrolyte for practical use. The electrocatalytic results of Cu-THQ-EFG indicate the composite exhibits a higher current density of -3 mA/cm2 and faradaic efficiency of -0.25 V vs. RHE, corresponding to 50 mV of overpotential. Moreover, it features a less negative on-set potential of -0.22 V vs. RHE, which is close to the equilibrium potential of CO2RR (-0.2 V vs. RHE) and is 0.16 V more positive than the on-set potential of Cu-THQ-GO (-0.38 V vs. RHE).

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.

A multiswitchable poly(terthiophene) bearing a spiropyran functionality: understanding photo- and electrochemical control.

An electroactive nitrospiropyran-substituted polyterthiophene, poly(2-(3,3''-dimethylindoline-6'-nitrobenzospiropyranyl)ethyl 4,4''-didecyloxy-2,2':5',2''-terthiophene-3'-acetate), has been synthesized for the first time. The spiropyran, incorporated into the polymer backbone by covalent attachment to the alkoxyterthiophene monomer units, leads to multiple colored states as a result of both photochemical and electrochemical isomerization of the spiropyran moiety to merocyanine forms as well as electrochemical oxidation of the polyterthiophene backbone and the merocyanine substituents. While electrochemical polymerization of the terthiophene monomer can take place without oxidation of the spiropyran, increasing the oxidation potential leads to complex electrochemistry that clearly involves this substituent. To understand this complex behavior, the first detailed electrochemical study of the oxidation of the precursor spiropyran, 1-(2-hydroxyethyl)-3,3-dimethylindoline-6'-nitrobenzospiropyran, was undertaken, showing that, in solution, an irreversible electrochemical oxidation of the spiropyran occurs leading to reversible redox behavior of at least two merocyanine isomers. With these insights, an extensive electrochemical and spectroelectrochemical study of the nitrospiropyran-substituted polyterthiophene films reveals an initial irreversible electrochemical oxidative ring-opening of the spiropyran to oxidized merocyanine. Subsequent reduction and cyclic voltammetry of the resulting nitromerocyanine-substituted polyterthiophene film gives rise to the formation of both merocyanine π-dimers or oligomers and π-radical cation dimers, between polymer chains. Although merocyanine formation is not electrochemically reversible, the spiropyran can be photochemically regenerated, through irradiation with visible light. Subsequent electrochemical oxidation of the nitrospiropyran-substituted polymer reduces the efficiency of the spiropyran to merocyanine isomerization, providing electrochemical control over the polymer properties. SEM and AFM images support the conclusion that the bulky spiropyran substituent is electrochemically isomerized to the planar merocyanine moiety, affording a smoother polymer film. The conductivity of the freestanding polymer film was found to be 0.4 S cm(-1).

Multisample Correlation Reveals the Origin of the Photocurrent of an Unstable Cu2O Photocathode during CO2 Reduction.

The reliable characterization of the photoelectrochemical (PEC) performance of unstable photoelectrodes, often the simplest devices used as a baseline, is a huge challenge. By performing a correlation analysis of more than 100 parameters of Cu2O photocathodes electrodeposited under the same conditions, we discovered a strong positive correlation (R = 0.866) between the photocurrent in argon and the deposition current peak magnitude during electrodeposition, while a strong negative correlation (R = -0.787) was found in CO2. In argon, a positive correlation between the photocurrent during PEC tests and the post-PEC dark current suggests the dominance of photodegradation. In CO2, the higher photocurrent in PEC tests correlates well with the lower post-PEC dark current, revealing the dominance of photocatalytic CO2 reduction during the rapid PEC tests. Correlation analysis provides statistically robust insights into the operation of unstable electrodes based on routinely measured parameters and thus constitutes a simple yet previously unexplored methodology for characterizing photoelectrodes within the first minutes of operation.

Rapid spatially-resolved post-synthetic patterning of metal-organic framework films.

Reactive inkjet printing was used for fast and facile spatially-controlled post-synthetic patterning of metal-organic framework films. Here, we report use of the reactive inkjet printing technique to rapidly produce patterned electroactive MOF films by covalent attachment of redox-responsive ferrocenyl groups to UiO-66-NH2 on FTO glass. This study paves the way for the wide applicability of reactive printing to MOF film modification.

Dual Droplet Functionality: Phototaxis and Photopolymerization.

The use of phototaxis to move droplets in liquids offers the opportunity to emulate natural processes such as the controlled transport of materials in fluidic environments and to undertake chemistry at specific locations. We have developed a photoactive organic droplet, whose movement in aqueous solution is driven by a photoinitiator, as a result of a light-induced reaction within the droplet generating a Marangoni flow. The photoinitiator not only drives the droplet motion but can also be used to initiate polymerization following transfer of the droplet to a specific location and its merging with a monomer-containing droplet. The same light is used to control the transport of the droplet and the polymerization. The efficacy of this droplet transport and reactor system has been demonstrated by the site-specific underwater polymerization of N-isopropylacrylamide to repair a leaking vessel and the adhesion of two materials together.

Efficient and Stable Solid-State Dye-Sensitized Solar Cells by the Combination of Phosphonium Organic Ionic Plastic Crystals with Silica.

Remarkably efficient quasi-solid-state dye-sensitized solar cells (DSSCs) have been fabricated using organic ionic plastic crystal electrolytes based on a small triethyl(methyl)phosphonium [P1222] cation and two types of sulfonamide anions, bis(fluorosulfonyl)amide (FSA) and bis(trifluoromethanesulfonyl)amide (TFSA), in combination with varying amounts of silica (SiO2). Solar cell efficiencies of up to 7.4% were obtained, which is comparable to our benchmark efficiencies of liquid (acetonitrile) electrolyte-based devices. Such a high efficiency for DSSCs using quasi-solid-state electrolytes is attributed to improved ionic conductivity, enhanced redox couple transport, improved interfacial interaction between the electrolyte and the electrode as well as decreased resistance at both electrode interfaces. Notably, the devices with the silica-containing electrolytes displayed excellent stability after 5 months of storage, with the most stable devices, formed with either plastic crystal electrolyte containing 2% silica, showing no decrease in efficiency.

Moving Droplets in 3D Using Light.

The emulation of the complex cellular and bacterial vesicles used to transport materials through fluids has the potential to add revolutionary capabilities to fluidic platforms. Although a number of artificial motile vesicles or microdroplets have been demonstrated previously, control over their movement in liquid in 3D has not been achieved. Here it is shown that by adding a chemical "fuel," a photoactive material, to the droplet, it can be moved in any direction (3D) in water using simple light sources without the need for additives in the water. The droplets can be made up of a range of solvents and move with speeds as high as 10.4 mm s-1 toward or away from the irradiation source as a result of a light-induced isothermal change in interfacial tension (Marangoni flow). It is further demonstrated that more complex functions can be accomplished by merging a photoactive droplet with a droplet carrying a "cargo" and moving the new larger droplet to a "reactor" droplet where the cargo undergoes a chemical reaction. The control and versatility of this light-activated, motile droplet system will open up new possibilities for fluidic chemical transport and applications.

Application of terpyridyl ligands to tune the optical and electrochemical properties of a conducting polymer.

We present a simple and effective way of using metal and metal-ligand modifications to tune the electrochemical and optical properties of conducting polymers. To that end, a polyterthiophene functionalized with terpyridine moieties was synthesized and then the resulting film's surface or bulk was modified with different metal ions, namely Fe2+, Zn2+ and Cu2+ and terpyridine. The modification of the terpyridine functionalized polyterthiophene film by Fe2+ increased the absorptivity and electrochemical capacitance of the conducting polymer, and improved its conjugation. Further modification by Zn2+ and Cu2+ resulted in dramatically different spectroelectrochemical properties of the film. Moreover, the influence of the solvents (ACN and 1 : 1 ACN : H2O) in conjunction with the metal ion applied for the modification was found crucial for the electrochemical and optical properties of the films.

Poly(3,4-ethylenedioxythiophene):dextran sulfate (PEDOT:DS) - a highly processable conductive organic biopolymer.

A novel water-dispersible conducting polymer analogous to poly(3,4-dioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been chemically synthesized in a single reaction in high yield. PEDOT:DS, a new member of the polythiophene family, is composed of a complex between PEDOT and the sulfonated polysaccharide polyanion dextran sulfate. Drop-cast films of aqueous suspensions of the material display a native conductivity of up to 7 ± 1 S cm(-1), increasing to 20 ± 2 S cm(-1) after treatment with ethylene glycol and thermal annealing. Mass ratios of the precursors NaDS and EDOT were varied from 5:1 to 2:1 and a decrease in the NaDS:EDOT ratio produces tougher, less hygroscopic films of higher conductivity. Ultraviolet-visible spectroelectrochemistry yields spectra typical of PEDOT complexes. Cyclic voltammetry reveals that PEDOT:DS is electrochemically active from -1.0 to 0.8 V vs. Ag/Ag(+) in acetonitrile, with similar characteristics to PEDOT:PSS. Water dispersions of PEDOT:DS are successfully processed by drop casting, spray coating, inkjet printing and extrusion printing. Furthermore, laser etching of dried films allows the creation of patterns with excellent definition. To assess the cytotoxicity of PEDOT:DS, L-929 cells were cultured with a polymer complex concentration range of 0.002 to 0.2 g l(-1) in cell culture medium. No significant difference is found between the proliferation rates of L-929 cells exposed to PEDOT:DS and those in plain medium after 96h. However, PEDOT:PSS shows around 25% less cell growth after 4 days, even at the lowest concentration. Taken together, these results suggest PEDOT:DS has exceptional potential as an electromaterial for the biointerface.

Photo-chemopropulsion--light-stimulated movement of microdroplets.

The controlled movement of a chemical container by the light-activated expulsion of a chemical fuel, named here "photo-chemopropulsion", is an exciting new development in the array of mechanisms employed for controlling the movement of microvehicles, herein represented by lipid-based microdroplets. This "chemopropulsion" effect can be switched on and off, and is fully reversible.