In situ IR spectroscopy is used to monitor electrolyte composition and acid protonation state at the interface of graphene nanoflake electrodes. Deprotonation of both electrode-immobilised and solution acids is driven by a local increase in cation activity at the electrode surface on application of a negative electrode potential.

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(I) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO2 saturated KHCO3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO2. On cycling to negative potentials, larger reduction currents were observed in the presence of CO2; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO2 CuO underwent reduction to Cu2O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials.

•ATR IR spectroscopy used to study interaction between ethanol and nanodiamond.•Loss in ν(OH) and δ(OH) bands indicates preferential binding of ethanol –OH with ND.•Spectral changes indicate ordering of surface ethanol and confinement within pores.In situ Attenuated Total reflectance infrared (ATR IR) spectroscopy is used to study the interaction between ethanol vapour and oxidised nanodiamond (ND) surfaces. On initial exposure an amorphous multilayer of adsorbed ethanol is observed, but over ca. 30 min a loss in intensity of ν(OH) and δ(OH) bands indicates a preferential binding of the ethanol –OH with the ND surface. Other spectral changes indicate ordering of the ethanol molecules on the surface and their confinement within the pores of the ND structure in specific conformations. Changes in the IR spectrum also suggest that vibrational frequencies of carbonyl groups on the ND surface are affected by the adsorption of ethanol and that surface-bound water is either displaced or involved in hydrogen-bonding with ethanol.Figure optionsDownload full-size imageDownload as PowerPoint slide

Cyclic voltammetry (CV) of polystyrene nanospheres was carried out after immobilisation onto boron-doped diamond electrodes. Although the polystyrene is insulating, a voltammetric response was obtained. This was attributed to the high surface area of the nanospheres, allowing the redox chemistry of the polystyrene surface to be probed despite the non-conducting nature of the bulk. The polystyrene redox response was found to be strongly dependent on prior mechanical agitation. Centrifuged, sonicated and vortexed polystyrene nanospheres all exhibited significantly higher oxidation currents than the non-agitated polystyrene. Mechanical treatment by sonication and centrifugation was found to bring about changes to surface chemistry of the polystyrene spheres, in particular the introduction of oxygen functionalities. For these samples the CV response is attributed to the presence of surface phenol functionalities. On the non-agitated and vortex treated polystyrene surfaces X-ray photoelectron spectroscopy revealed an absence of oxygen functionalities that could explain the redox response. Repetition of the CV experiment in the presence of a solution spin trap suggests that radical species play a role in the observed response. For the vortexed sample the increased oxidation currents were attributed to significant surface roughening and deformation, as revealed by Transmission Electron Microscopy.

The mixed-valence triiron complexes [Fe3(CO)7–x(PPh3)x(μ-edt)2] (x = 0–2; edt = SCH2CH2S) and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2] (diphosphine = dppv, dppe, dppb, dppn) have been prepared and structurally characterized. All adopt an anti arrangement of the dithiolate bridges, and PPh3 substitution occurs at the apical positions of the outer iron atoms, while the diphosphine complexes exist only in the dibasal form in both the solid state and solution. The carbonyl on the central iron atom is semibridging, and this leads to a rotated structure between the bridged diiron center. IR studies reveal that all complexes are inert to protonation by HBF4·Et2O, but addition of acid to the pentacarbonyl complexes results in one-electron oxidation to yield the moderately stable cations [Fe3(CO)5(PPh3)2(μ-edt)2]+ and [Fe3(CO)5(κ2-diphosphine)(μ-edt)2]+, species which also result upon oxidation by [Cp2Fe][PF6]. The electrochemistry of the formally Fe(I)–Fe(II)–Fe(I) complexes has been investigated. Each undergoes a quasi-reversible oxidation, the potential of which is sensitive to phosphine substitution, generally occurring between 0.15 and 0.50 V, although [Fe3(CO)5(PPh3)2(μ-edt)2] is oxidized at −0.05 V. Reduction of all complexes is irreversible and is again sensitive to phosphine substitution, varying between −1.47 V for [Fe3(CO)7(μ-edt)2] and around −1.7 V for phosphine-substituted complexes. In their one-electron-reduced states, all complexes are catalysts for the reduction of protons to hydrogen, the catalytic overpotential being increased upon successive phosphine substitution. In comparison to the diiron complex [Fe2(CO)6(μ-edt)], [Fe3(CO)7(μ-edt)2] catalyzes proton reduction at 0.36 V less negative potentials. Electronic structure calculations have been carried out in order to fully elucidate the nature of the oxidation and reduction processes. In all complexes, the HOMO comprises an iron–iron bonding orbital localized between the two iron atoms not ligated by the semibridging carbonyl, while the LUMO is highly delocalized in nature and is antibonding between both pairs of iron atoms but also contains an antibonding dithiolate interaction.

Reactions of Fe2(CO)6(μ-pdt) (pdt = SCH2CH2CH2S) with aminodiphosphines Ph2PN(R)PPh2 (R = allyl, iPr, iBu, p-tolyl, H) have been carried out under different conditions. At room temperature in MeCN with added Me3NO·2H2O, dibasal chelate complexes Fe2(CO)4{κ2-Ph2PN(R)PPh2}(μ-pdt) are formed, while in refluxing toluene bridge isomers Fe2(CO)4{μ-Ph2PN(R)PPh2}(μ-pdt) are the major products. Separate studies have shown that chelate complexes convert to the bridge isomers at higher temperatures. Two pairs of bridge and chelate isomers (R = allyl, iPr) have been crystallographically characterised together with Fe2(CO)4{μ-Ph2PN(H)PPh2}(μ-pdt). Chelate complexes adopt the dibasal diphosphine arrangement in the solid state and exhibit very small P–Fe–P bite-angles, while the bridge complexes adopt the expected cisoid dibasal geometry. Density functional calculations have been carried out on the chelate and bridge isomers of the model compound Fe2(CO)4{Ph2PN(Me)PPh2}(μ-pdt) and reveal that the bridge isomer is thermodynamically favourable relative to the chelate isomers that are isoenergetic. The HOMO in each of the three isomers exhibits significant metal–metal bonding character, supporting a site-specific protonation of the iron–iron bond upon treatment with acid. Addition of HBF4·Et2O to the Fe2(CO)4{κ2-Ph2PN(allyl)PPh2}(μ-pdt) results in the clean formation of the corresponding dibasal hydride complex [Fe2(CO)4{κ2-Ph2PN(allyl)PPh2}(μ-H)(μ-pdt)][BF4], with spectroscopic measurements revealing the intermediate formation of a basal–apical isomer. A crystallographic study reveals that there are only very small metric changes upon protonation. In contrast, the bridge isomers react more slowly to form unstable species that cannot be isolated. Electrochemical and electrocatalysis studies have been carried out on the isomers of Fe2(CO)4{Ph2PN(allyl)PPh2}(μ-pdt). Electron accession is predicted to occur at an orbital that is anti-bonding with respect to the two metal centres based on the DFT calculations. The LUMO in the isomeric model compounds is similar in nature and is best described as an antibonding Fe–Fe interaction that contains differing amounts of aryl π* contributions from the ancillary PNP ligand. The proton reduction catalysis observed under electrochemical conditions at ca. −1.55 V is discussed as a function of the initial isomer and a mechanism that involves an initial protonation step involving the iron–iron bond. The measured CV currents were higher at this potential for the chelating complex, indicating faster turnover. Digital simulations showed that the faster rate of catalysis of the chelating complex can be traced to its greater propensity for protonation. This supports the theory that asymmetric distribution of electron density along the iron–iron bond leads to faster catalysis for models of the Fe–Fe hydrogenase active site.

•A fluorinated model of the iron-only hydrogenase is introduced.•Lower electron density at Fe–Fe bond leads to less negative reduction potential.•Proton reduction catalysis takes place at the reduction potential of the complex.•Simulations reveal the rate-limiting step is H2 elimination.•Phosphine substitution does not result in improved catalytic performance.Here we report the synthesis, electrochemistry and electrocatalytic activity of Fe2(CO)6(μ-SC6F5)2 (1) where the highly fluorinated bridge is electron-withdrawing, resulting in decreased electron-density at the iron–iron bond. Additionally we discuss the related substituted complexes Fe2(CO)5(PPh3)(μ-SC6F5)2 (2) and Fe2(CO)4(μ-Ph2PCH2PPh2)(μ-SC6F5)2 (3). As none of the complexes could be protonated in their neutral form it was found that proton reduction catalysis in the presence of strong acid (HBF4) took place at the potential of the first reduction of complex 1 and 3, following an EC mechanism. Complex 2 was unstable in the presence of strong acid. For 1 the potential at which proton reduction took place represented a relatively mild reduction potential (−1.15 V vs. Fc/Fc+ in acetonitrile) that was comparable to examples of similar complexes in the literature. Complex 1 generated a small concentration of a highly catalytic species after electrochemical reduction, which we attribute to cleavage of the Fe–Fe bond and formation of a mono-nuclear iron species or to Fe–S bond breakage generating a vacant coordination site. The contributions to the catalytic currents were simulated using DigiSim, where it was found that the rate limiting step for 3 was the elimination of H2. It was also found that the highly catalytic species generated after reduction of 1 was more basic than 1− and also that protonation of this species was faster.

Attenuated total reflectance infrared spectroscopy is used to monitor nanodiamond surface group transformations in the presence of aqueous IrCl62−. Electron transfer between the nanoparticle surface and the solution redox species results in oxidation of ∼8.5% of surface alcohol groups, with concomitant formation of unsaturated ketone or quinone-like moieties.

This article discusses some of our recent work on the origins of redox activity of undoped nanodiamond (ND) powders, as well as reviewing some properties and applications of this material. The electrochemical activity is attributed to unsaturated bonding at the ND particle surface; hence the most recent understanding of the surface chemistry of these materials is discussed. The implications of the observed redox activity, especially for use in biological applications, are highlighted, along with future avenues of research.

The electrochemical response of an electrode-immobilized layer of undoped, insulating diamond nanoparticles is reported, which we attribute to the oxidation and reduction of surface states. The potentials of these surface states are pH-dependent; moreover they are able to interact with solution redox species. The voltammetric response of redox couples Fe(CN)63−/4− and IrCl63−/2− are compared at bare boron-doped diamond electrodes and electrodes modified with a layer of nanodiamond (ND). In all cases the presence of ND modifies the CV response at slow scan rates if low concentrations of redox couple are used. Enhancements of oxidation currents are noted at potentials at which the ND surface states can also undergo oxidation, and enhancements of reduction currents are likewise observed where ND is also reducible. We attribute these observations to electron transfer occurring between the species generated at the underlying electrode during CV and the ND immobilized in the interfacial region, leading to regeneration of the starting species and hence enhancement in currents due to a feedback mechanism. The magnitude of current enhancement thus depends on the standard potential of the redox couple relative to those of the ND surface states.

The redox behavior of an undoped nanodiamond (ND) film grown by chemical vapor deposition was investigated using cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM) and redox mediators Fe(CN)63−, Fe(CN)64−, ferrocenemethanol (FcOH), and Ru(NH3)63+. CV showed extremely sluggish kinetics for all redox couples, but the reduction of Fe(CN)63- was found to be especially slow when compared to the oxidation of Fe(CN)64−. SECM confirmed this trend, with experimental heterogeneous rate constants, obtained by fitting approach curves to theory, being of the magnitude of 10−3 cm s−1. The oxidation of Fe(CN)64− at an overpotential, |η|, of 0.6 V was found to occur 5 times faster than the reduction of Fe(CN)63− at the same |η|. The results are explained by assuming conduction takes place through extended sp2 (graphitic and defect sites) through the film. The nondiamond component of the film introduces impurity bands into the band gap that allows limited metallic type conductivity. The slow electron transfer was attributed to the very small percentage of the surface that was electrochemically active and hence relatively narrow impurity bands and limited carrier numbers. About 2% of the surface was calculated to be active in the potential range −0.4 to 0.5 V vs Ag/AgCl. At >0.5 V, the active area was found to increase with applied potential up to about 10% at 0.8 V. This increase in active electrode area explains the faster rate constants obtained for the oxidation of Fe(CN)64− at these potentials. It is postulated that the increase in active area is due to oxidation of defect sites of the film to form electron deficient, hence redox active, centers. This results in the widening of the impurity bands in the band gap and hence an increased density of states. Approach curves to a layer of 5 nm ND powder using the same redox couples exhibited a similar trend, with reduction of Fe(CN)63− taking place much slower than oxidation of Fe(CN)64−. Overall, rate constants were about 10 times faster at the powder interface than the film. It is believed that electron transfer at the ND nanoparticle surface takes place at similar sites as on the ND film but that they are present at higher relative concentrations due to the higher surface to bulk atom ratio of the nanoparticles.

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH3)63+/2+ and Fe(CN)64–/3– was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp3diamond core with a surface that has significant delocalised π character due to unsatisfied surface atoms and CO bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.

This paper demonstrates the promoting effects of 5 nm undoped detonation diamond nanoparticles on redox reactions in solution. An enhancement in faradaic current for the redox couples Ru(NH3)63+/2+ and Fe(CN)64–/3– was observed for a gold electrode modified with a drop-coated layer of nanodiamond (ND), in comparison to the bare gold electrode. The ND layer was also found to promote oxygen reduction. Surface modification of the ND powders by heating in air or in a hydrogen flow resulted in oxygenated and hydrogenated forms of the ND, respectively. Oxygenated ND was found to exhibit the greatest electrochemical activity and hydrogenated ND the least. Differential pulse voltammetry of electrode-immobilised ND layers in the absence of solution redox species revealed oxidation and reduction peaks that could be attributed to direct electron transfer (ET) reactions of the ND particles themselves. It is hypothesised that ND consists of an insulating sp3diamond core with a surface that has significant delocalised π character due to unsatisfied surface atoms and CO bond formation. At the nanoscale surface properties of the particles dominate over those of the bulk, allowing ET to occur between these essentially insulating particles and a redox species in solution or an underlying electrode. We speculate that reversible reduction of the ND may occur via electron injection into available surface states at well-defined reduction potentials and allow the ND particles to act as a source and sink of electrons for the promotion of solution redox reactions.

In situ IR spectroscopy is used to monitor electrolyte composition and acid protonation state at the interface of graphene nanoflake electrodes. Deprotonation of both electrode-immobilised and solution acids is driven by a local increase in cation activity at the electrode surface on application of a negative electrode potential.

This article discusses some of our recent work on the origins of redox activity of undoped nanodiamond (ND) powders, as well as reviewing some properties and applications of this material. The electrochemical activity is attributed to unsaturated bonding at the ND particle surface; hence the most recent understanding of the surface chemistry of these materials is discussed. The implications of the observed redox activity, especially for use in biological applications, are highlighted, along with future avenues of research.

Attenuated total reflectance infrared spectroscopy is used to monitor nanodiamond surface group transformations in the presence of aqueous IrCl62−. Electron transfer between the nanoparticle surface and the solution redox species results in oxidation of ∼8.5% of surface alcohol groups, with concomitant formation of unsaturated ketone or quinone-like moieties.

Reactions of Fe2(CO)6(μ-pdt) (pdt = SCH2CH2CH2S) with aminodiphosphines Ph2PN(R)PPh2 (R = allyl, iPr, iBu, p-tolyl, H) have been carried out under different conditions. At room temperature in MeCN with added Me3NO·2H2O, dibasal chelate complexes Fe2(CO)4{κ2-Ph2PN(R)PPh2}(μ-pdt) are formed, while in refluxing toluene bridge isomers Fe2(CO)4{μ-Ph2PN(R)PPh2}(μ-pdt) are the major products. Separate studies have shown that chelate complexes convert to the bridge isomers at higher temperatures. Two pairs of bridge and chelate isomers (R = allyl, iPr) have been crystallographically characterised together with Fe2(CO)4{μ-Ph2PN(H)PPh2}(μ-pdt). Chelate complexes adopt the dibasal diphosphine arrangement in the solid state and exhibit very small P–Fe–P bite-angles, while the bridge complexes adopt the expected cisoid dibasal geometry. Density functional calculations have been carried out on the chelate and bridge isomers of the model compound Fe2(CO)4{Ph2PN(Me)PPh2}(μ-pdt) and reveal that the bridge isomer is thermodynamically favourable relative to the chelate isomers that are isoenergetic. The HOMO in each of the three isomers exhibits significant metal–metal bonding character, supporting a site-specific protonation of the iron–iron bond upon treatment with acid. Addition of HBF4·Et2O to the Fe2(CO)4{κ2-Ph2PN(allyl)PPh2}(μ-pdt) results in the clean formation of the corresponding dibasal hydride complex [Fe2(CO)4{κ2-Ph2PN(allyl)PPh2}(μ-H)(μ-pdt)][BF4], with spectroscopic measurements revealing the intermediate formation of a basal–apical isomer. A crystallographic study reveals that there are only very small metric changes upon protonation. In contrast, the bridge isomers react more slowly to form unstable species that cannot be isolated. Electrochemical and electrocatalysis studies have been carried out on the isomers of Fe2(CO)4{Ph2PN(allyl)PPh2}(μ-pdt). Electron accession is predicted to occur at an orbital that is anti-bonding with respect to the two metal centres based on the DFT calculations. The LUMO in the isomeric model compounds is similar in nature and is best described as an antibonding Fe–Fe interaction that contains differing amounts of aryl π* contributions from the ancillary PNP ligand. The proton reduction catalysis observed under electrochemical conditions at ca. −1.55 V is discussed as a function of the initial isomer and a mechanism that involves an initial protonation step involving the iron–iron bond. The measured CV currents were higher at this potential for the chelating complex, indicating faster turnover. Digital simulations showed that the faster rate of catalysis of the chelating complex can be traced to its greater propensity for protonation. This supports the theory that asymmetric distribution of electron density along the iron–iron bond leads to faster catalysis for models of the Fe–Fe hydrogenase active site.

Cyclic voltammetry (CV) of polystyrene nanospheres was carried out after immobilisation onto boron-doped diamond electrodes. Although the polystyrene is insulating, a voltammetric response was obtained. This was attributed to the high surface area of the nanospheres, allowing the redox chemistry of the polystyrene surface to be probed despite the non-conducting nature of the bulk. The polystyrene redox response was found to be strongly dependent on prior mechanical agitation. Centrifuged, sonicated and vortexed polystyrene nanospheres all exhibited significantly higher oxidation currents than the non-agitated polystyrene. Mechanical treatment by sonication and centrifugation was found to bring about changes to surface chemistry of the polystyrene spheres, in particular the introduction of oxygen functionalities. For these samples the CV response is attributed to the presence of surface phenol functionalities. On the non-agitated and vortex treated polystyrene surfaces X-ray photoelectron spectroscopy revealed an absence of oxygen functionalities that could explain the redox response. Repetition of the CV experiment in the presence of a solution spin trap suggests that radical species play a role in the observed response. For the vortexed sample the increased oxidation currents were attributed to significant surface roughening and deformation, as revealed by Transmission Electron Microscopy.