The influence of electrolyte identity upon the electro-reduction of CO2

AbstractThe influence of supporting electrolyte cations on the voltammetric behaviour and product distribution in N-methylpyrrolidone-based carbon dioxide electroreduction systems is investigated. The reduction potentials associated with TBABF4 (0.1M) and corresponding alkali metal (M+) electrolytes; LiBF4, NaBF4 and RbBF4 (focussing mainly on the reduction of the widely employed Li+ species) were established in both the presence and absence of CO2 at polycrystalline noble metal working electrodes. In situ and ex situ Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and qualitative element identification via flame testing were used to aid the assignment of reduction processes. It was established that CO2 reduction products in the metal cationic systems were formed at a much less negative potential than those found with the non-metal cation (−1.5V vs. Ferrocene, c.f. −2.2V), however the resultant alteration of the surface environment was found to deactivate the electrode to further CO2 reduction. The presence of CO2 in solution was found to affect the potential required for the bulk deposition of metal from the electrolyte through the same process. Where TBA+ and M+ were employed simultaneously in the system, the resultant voltammetry shared the majority of features with the pure M+ system with CO2 reduction suppressed at more negative potentials therefore supporting the conclusion that any ‘catalytic effect’ associated with TBA+ is in fact a lack of deactivation given by the M+ system, rather than any enhancement offered by the former

Au Electrodeposition at the Liquid-Liquid Interface: mechanistic aspects

The deposition mechanism of metallic gold was investigated based on charge transfer voltammetry at the water/1,2-dichloroethane (W/DCE) interface, and the corresponding redox voltammetry of the metal precursor in W and the reductant, triphenylamine (TPA), in DCE. The metal precursor was present as Au(III) (AuCl_4^[−]), or Au(I) (AuCl_2^[−]) in W or DCE. Electron transfer could be observed voltammetrically at the interface between W containing both Au precursors and DCE containing TPA. Au particles, formed by constant potential electrolysis at the W/DCE interface, were examined by transmission electron microscopy. It was shown that deposit size could be controlled via the applied potential and time, with specific conditions to form particles of less than 10 nm identified

Use of voltammetry for in vitro equilibrium and transport studies of ionisable drugs

In this review, we will briefly outline the voltammetric investigations of the transfer of ionisable drugs at the interface between two immiscible electrolyte solutions. The voltammetric techniques enable the determination of some key in vitro properties of ionisable drugs, including partition coefficient, diffusion coefficient and membrane permeability. Some successful applications will be highlighted, together with the background methodologies

On the controlled electrochemical preparation of R4N+ graphite intercalation compounds and their host structural deformation effects

AbstractWe present electrochemical studies of tetraalkylammonium (R4N+) reduction chemistry at Highly Orientated Pyrolytic Graphite (HOPG) and glassy carbon (GC) electrodes. We show that by electrochemically controlled intercalation and formation of a graphite intercalation complex (GIC) into layered HOPG, the irreversible reduction of the tetraalkylammonium cation can be prevented and subsequent de-intercalation of the GIC via the use of potentiostatic control is achievable. R4N+ cations with varying alkyl chain lengths (methyl, ethyl and butyl) have been shown to exhibit excellent charge recovery effects during charge/discharge studies. Finally the effects of electrode expansion on the degree of recovered charge have been investigated and the observed effects of R4N+ intercalation on the graphite cathode have been probed by scanning electron microscopy (SEM) and X-ray diffraction (XRD)

Anodic dissolution growth of metal-organic framework HKUST-1 monitored:Via in situ electrochemical atomic force microscopy

In situ electrochemical atomic force microscopy (ec-AFM) is utilised for the first time to probe the initial stages of metal-organic framework (MOF) coating growth via anodic dissolution. Using the example of the Cu MOF HKUST-1, real time surface analysis is obtained that supports and verifies many of the reaction steps in a previously proposed mechanism for this type of coating growth. No evidence is observed however for the presence or formation of Cu2O, which has previously been suggested to be both key for the formation of the coating and a potential explanation for the anomalously high adhesion strength of coatings obtained via this methodology. Supporting in situ electrochemical Raman spectroscopy also fails to detect the presence of any significant amount of Cu2O before or during the coating's growth process

Electron Paramagnetic Resonance as a Structural Tool to Study Graphene Oxide: Potential-Dependence of the EPR Response

Electron paramagnetic resonance (EPR) spectroscopy is reported as a tool to probe the behavior of graphene oxide (GO). The potential-dependent response of GO is reported for the first time and correlated with the observed electrochemical response. The EPR signal, deconvoluted into two constituent parts, was used along with lineshape simulations and the temperature dependence to probe the electrochemical processes. The EPR signal is found to be well described by two components. The narrower one is associated with unpaired electrons on localized functional groups and shows a reversible increase as GO is biased to positive potentials. The Curie behavior of this component suggests that it increases because of the formation of stable radical species, such as semiquinones, derived from quinones and other carbonyl functional groups found on GO. A stronger dependence of the narrow component with potential, and an elevated g value over 2.0034, is found in alkaline conditions compared to neutral electrolytes, reflecting the greater stability of seminquinone-like species at higher pH. By contrast, the second, broader component of the EPR signal was found to be potential-independent. The EPR approach described here offers a solution phase alternative, which can be employed under electrochemical control, to techniques such as X-ray photoelectron spectroscopy and Raman spectroscopy, as a means to probe the structure of GO and related materials

Single stage electrochemical exfoliation method for the production of few-layer graphene via intercalation of tetraalkylammonium cations

We present a non-oxidative production route to few layer graphene via the electrochemical intercalation of tetraalkylammonium cations into pristine graphite. Two forms of graphite have been studied as the source material with each yielding a slightly different result. Highly orientated pyrolytic graphite (HOPG) offers greater advantages in terms of the exfoliate size but the source electrode set up introduces difficulties to the procedure and requires the use of sonication. Using a graphite rod electrode, few layer graphene flakes (2 nm thickness) are formed directly although the flake diameters from this source are typically small (ca. 100–200 nm). Significantly, for a solvent based route, the graphite rod does not require ultrasonication or any secondary physical processing of the resulting dispersion. Flakes have been characterized using Raman spectroscopy, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS)

Metal-organic framework templated electrodeposition of functional gold nanostructures

Utilizing a pair of quick, scalable electrochemical processes, the permanently porous MOF HKUST-1 was electrochemically grown on a copper electrode and this HKUST-1-coated electrode was used to template electrodeposition of a gold nanostructure within the pore network of the MOF. Transmission electron microscopy demonstrates that a proportion of the gold nanostructures exhibit structural features replicating the pore space of this ∼1.4 nm maximum pore diameter MOF, as well as regions that are larger in size. Scanning electron microscopy shows that the electrodeposited gold nanostructure, produced under certain conditions of synthesis and template removal, is sufficiently inter-grown and mechanically robust to retain the octahedral morphology of the HKUST-1 template crystals. The functionality of the gold nanostructure within the crystalline HKUST-1 was demonstrated through the surface enhanced Raman spectroscopic (SERS) detection of 4-fluorothiophenol at concentrations as low as 1 μM. The reported process is confirmed as a viable electrodeposition method for obtaining functional, accessible metal nanostructures encapsulated within MOF crystals

Electrochemical deposition of zeolitic imidazolate framework electrode coatings for supercapacitor electrodes

Zn and Co electrodes have been successfully coated with five different zeolitic imidazolate frameworks ZIFs (ZIF-4, ZIF-7, ZIF-8, ZIF-14 and ZIF-67) via the anodic dissolution method. Careful control of the reaction conditions allows for electrode coating growth; in contrast to previous reports of electrochemical ZIF growth, which have not succeeded in obtaining ZIF electrode coatings. Coating crystallinity is also shown to be heavily dependent upon reaction conditions, with amorphous rather than crystalline material generated at shorter reaction times and lower linker concentrations. Electrochemical applications for ZIF-coated electrodes are highlighted with the observation of an areal capacitance of 10.45 mF cm−2 at 0.01 V s−1 for additive-free ZIF-67 coated Co electrodes. This is superior to many reported metal organic framework (MOF)/graphene composites and to capacitance values previously reported for additive-free MOFs

Redox and Ligand Exchange during the Reaction of Tetrachloroaurate with Hexacyanoferrate(II) at a Liquid-Liquid Interface: Voltammetry and X-ray Absorption Fine-Structure Studies

AbstractVoltammetry for charge (ion and electron) transfer at two immiscible electrolyte solutions (VCTIES) has been used to provide insight into the ligand exchange and redox processes taking place during the interfacial reaction of aqueous hexacyanoferrate(II) with tetrachloroaurate ([AuCl4]−) in 1,2-dichloroethane (DCE). VCTIES permitted the detection of the reactants, intermediates and products at the liquid/liquid interface. A model for the sequence of interfacial processes was established with the support of speciation analysis of the key elementary reactions by X-ray absorption spectroscopy (XAS). The potential-driven transfer of [AuCl4]− from the organic into the aqueous phase is followed by reduction and ligand exchange by the aqueous hexacyanoferrate(II) to form dicyanoaurate ([Au(CN)2]−). Inferences from the reactions point to the likely formation of [AuCl2]− during the reduction sequence. The reaction is influenced by ligand exchange equilibria between [AuCl4]−, [AuCl3(OH)]– and [AuCl2(OH)2]– which are shown to be dependent on the chloride ion concentration and pH of the solution. The difference between the Gibbs energy of transfer at the water | DCE interface (ΔGDCEW°)of AuCl4– and [AuCl3(OH)]–, and the difference between [AuCl3(OH)]– and [AuCl2(OH)2]– were found to change by a value close to the difference between ΔGDCEW° of Cl– and that of OH–. The intermediate Au(I) species, [AuCl2]−, was seen to decompose at neutral pH and in the absence of Cl– in water to form metallic Au, although it was stable in >10mM HCl for an hour. Time-dependent VCTIES and X-ray absorption fine structure (XAFS) speciation analysis of the homogeneous aqueous phase indicate that reaction between [AuCl4]− and hexacyanoferrate(II) is accompanied by the formation of an intermediate ionic species, formed when the concentration of [AuCl4]− is close to that of hexacyanoferrate(II). This species, whose identity was not precisely determined, was also generated by reaction between [AuCl2]− and hexacyanoferrate(III). The species is shown by VCTIES to be more hydrophilic than [Au(CN)2]−, [AuCl2]− and [AuCl4]−