Vanadium-Containing Keggin-Type Polyoxometalates, [VM12O40]3- and [VVM11O40]4- (M = Mo, W): Structural Characterization and Voltammetric, NMR, and EPR Studies Related to Electrochemical Reduction at Framework and Central Vanadium Sites.

Vanadium is accommodated in both the framework (VoutV) and central positions (VinV) in the Keggin-type polyoxometalates (POMs) [VinVVoutVM11O40]4- (M = Mo, W; VinVVoutVM11) and in the central position in [VinVM12O40]3- (VinVM12). The structures of the VinVVoutVM11 class have been determined by X-ray crystallography and compared to those of VinVM12 reported previously. A major feature of interest with POMs is their capacity for very extensive reduction, particularly when protonation accompanies the electron transfer step. With VinVVoutVM11 and VinVM12 POMs, knowledge as to whether reduction occurs at V or M sites and the concomitant dependence on acidity has been obtained. Frozen solution EPR spectra obtained following bulk electrolysis showed that the one-electron reduction of VinVMo12 occurs at the molybdenum framework site to give VinVMoVMo11. In contrast, EPR spectra of one-electron reduced VinVW12 at <30 K are consistent with the electron being accommodated on the central V atom in a tetrahedral environment to give VinIVW12. In the case of VinVVoutVM11, the initial reduction occurs at the framework VoutV site to give VinVVoutIVM11. The second electron is delocalized over the Mo framework in two-electron reduced VinVVoutIVMoVMo10, whereas it is accommodated on the central V site in VinIVVoutIVW11. The distance between VinIV and VoutIV in VinIVVoutIVW11 estimated as 3.5 ± 0.2 Å from analysis of the EPR spectrum is consistent with that obtained in VinVVoutVW11 from crystallographic data. Simulations of the cyclic voltammograms as a function of CF3SO3H acid concentration for the initial reduction processes provide excellent agreement with experimental data obtained in acetonitrile (0.10 M [n-Bu4N][PF6]) and allowed acid association constants to be estimated and compared with the literature values available for [XVoutVM11O40]n- (X = S (n = 3), P and As (n= 4); M = Mo, W). The interpretation of the voltammetric data is supported by 51V NMR measurements on the oxidized VV forms of the POMs.

Fluorine Substitution of TCNQ Alters the Redox-Driven Catalytic Pathway for the Ferricyanide-Thiosulfate Reaction.

Mechanistic variation in catalysis through substituent-based redox tuning is well established. Fluorination of TCNQ (TCNQ=tetracyanoquinodimethane) provides ~850 mV variation in the redox potentials of the TCNQF n 0 / 1 - ${{{\rm {TCNQF}}}_{{\rm {n}}}^{{\rm {0/1-}}}}$ and TCNQF n 1 - / 2 - ${{{\rm {TCNQF}}}_{{\rm {n}}}^{{\rm {1-/2-}}}}$ (n=0, 2, 4) processes. With TCNQF 4 1 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {1-}}}}$ , catalysis of the kinetically very slow ferrocyanide-thiosulfate redox reaction in aqueous solution occurs via a mechanism in which the catalyst TCNQF 4 1 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {1-}}}}$ is reduced to TCNQF 4 2 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {2-}}}}$ when reacting with S 2 O 3 2 - ${{{\rm {S}}}_{{\rm {2}}}{{\rm {O}}}_{{\rm {3}}}^{{\rm {2-}}}}$ which is oxidised to S 4 O 6 2 - ${{{\rm {S}}}_{{\rm {4}}}{{\rm {O}}}_{{\rm {6}}}^{{\rm {2-}}}}$ . Subsequently, TCNQF 4 2 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {2-}}}}$ reacts with [ Fe ( CN ) 6 ]​ 3 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {3-}}}}$ to form [ Fe ( CN ) 6 ]​ 4 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {4-}}}}$ and reform the TCNQF 4 1 - ${{{\rm {TCNQF}}}_{{\rm {4}}}^{{\rm {1-}}}}$ catalyst, in another thermodynamically favoured process. An analogous mechanism applies with TCNQF 2 1 - ${{{\rm {TCNQF}}}_{{\rm {2}}}^{{\rm {1-}}}}$ as a catalyst. In contrast, since the reaction of S 2 O 3 2 - ${{{\rm {S}}}_{{\rm {2}}}{{\rm {O}}}_{{\rm {3}}}^{{\rm {2-}}}}$ with TCNQ 1 - ${{{\rm {TCNQ}}}^{{\rm {1-}}}}$ is thermodynamically unfavourable, an alternative mechanism is required to explain the catalytic activity observed in this non-fluorinated system. Here, upon addition of TCNQ 1 - ${{{\rm {TCNQ}}}^{{\rm {1-}}}}$ , reduction of [ Fe ( CN ) 6 ]​ 3 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {3-}}}}$ to [ Fe ( CN ) 6 ]​ 4 - ${{{\rm {[Fe(CN)}}}_{{\rm {6}}}{{\rm {]}}}^{{\rm {4-}}}}$ occurs with concomitant oxidation of TCNQ 1 - ${{{\rm {TCNQ}}}^{{\rm {1-}}}}$ to TCNQ 0 ${{{\rm {TCNQ}}}^{{\rm {0}}}}$ , which then acts as the catalyst for S 2 O 3 2 - ${{{\rm {S}}}_{{\rm {2}}}{{\rm {O}}}_{{\rm {3}}}^{{\rm {2-}}}}$ oxidation. Thermodynamic data explain the observed differences in the catalytic mechanisms. CuTCNQF n ${{{\rm {CuTCNQF}}}_{{\rm {n}}}}$ (n=0, 4) also act as catalysts for the ferricyanide-thiosulfate reaction in aqueous solution. The present study shows that homogeneous pathways are available following addition of these dissolved materials. Previously, these CuTCNQF n ${{{\rm {CuTCNQF}}}_{{\rm {n}}}}$ (n=0, 4) coordination polymers have been regarded as insoluble in water and proposed as heterogeneous catalysts for the ferricyanide-thiosulfate reaction. Details and mechanistic differences were established using UV-visible spectrophotometry and cyclic voltammetry.

Oxidation of the Platinum(II) Anticancer Agent [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] to Platinum(IV) Complexes by Hydrogen Peroxide.

PtIV coordination complexes are of interest as prodrugs of PtII anticancer agents, as they can avoid deactivation pathways owing to their inert nature. Here, we report the oxidation of the antitumor agent [PtII(p-BrC6F4)NCH2CH2NEt2}Cl(py)], 1 (py = pyridine) to dihydroxidoplatinum(IV) solvate complexes [PtIV{(p-BrC6F4)NCH2CH2NEt2}Cl(OH)2(py)].H2O, 2·H2O with hydrogen peroxide (H2O2) at room temperature. To optimize the yield, 1 was oxidized in the presence of added lithium chloride with H2O2 in a 1:2 ratio of Pt: H2O2, in CH2Cl2 producing complex 2·H2O in higher yields in both gold and red forms. Despite the color difference, red and yellow 2·H2O have the same structure as determined by single-crystal and X-ray powder diffraction, namely, an octahedral ligand array with a chelating organoamide, pyridine and chloride ligands in the equatorial plane, and axial hydroxido ligands. When tetrabutylammonium chloride was used as a chloride source, in CH2Cl2, another solvate, [PtIV{(p-BrC6F4)NCH2CH2NEt2}Cl(OH)2(py)].0.5CH2Cl2,3·0.5CH2Cl2, was obtained. These PtIV compounds show reductive dehydration into PtII [Pt{(p-BrC6F4)NCH=CHNEt2}Cl(py)], 1H over time in the solid state, as determined by X-ray powder diffraction, and in solution, as determined by 1H and 19F NMR spectroscopy and mass spectrometry. 1H contains an oxidized coordinating ligand and was previously obtained by oxidation of 1 under more vigorous conditions. Experimental data suggest that oxidation of the ligand is favored in the presence of excess H2O2 and elevated temperatures. In contrast, a smaller amount (1Pt:2H2O2) of H2O2 at room temperature favors the oxidation of the metal and yields platinum(IV) complexes.

Revisiting the TCNQF 4 0 / 1 - / 2 - ${{\bf TCNQF}_{\bf 4}

The front cover artwork was done by Michelle Farrelly, a member of the Martin group at Monash University. The image represents a perspective of a cuvette in which the catalysis of the thiosulfate-ferricyanide reaction was achieved by a TCNQF4 -based redox reaction in aqueous solution. The primary method used to monitor these reactions was spectrophotometry. Read the full text of the Research Article at 10.1002/cphc.202200942.

Revisiting the TCNQF4 0/1-/2- Catalysis Mechanism for the [Fe(CN)6 ]3-/4- -S2 O3 2- /S4 O6 2- Redox Reaction.

Published data suggest that sparingly soluble metal complexes of TCNQF n 1 - ${{\rm{TCNQF}}_{\rm{n}}^{{\rm{1 - }}} }$ , where n=0, 1, 2, 4, can act as heterogeneous catalysts for the kinetically very slow [ Fe ( CN ) 6 ]​ 3 - / 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - /4 - }}} }$ - S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ / S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ reaction in aqueous solution. This study shows that the coordination polymer CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ , participates as a homogeneous catalyst via an extremely small concentration of dissolved TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ . This finding suggests that the generally accepted mechanism of catalysis by TCNQF 4 ${{\rm{TCNQF}}_{\rm{4}} }$ based solids needs to be revisited to ascertain the role of homogeneous pathways. In the present study, UV-visible spectrophotometry was used to examine the catalysis of the aqueous redox reaction of [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ (1.0 mM) with S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ (100 mM) in the presence of (i) a precursor catalyst, TCNQF 4 0 ${{\rm{TCNQF}}_{\rm{4}}^{\rm{0}} }$ ; (ii) the catalyst, TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ , as the water soluble Li+ salt; and (iii) CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ . A homogeneous reaction scheme that utilises the TCNQF 4 1 - / 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - /2 - }}} }$ couple is provided. In the case of TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ derived from highly soluble LiTCNQF 4 ${{\rm{LiTCNQF}}_{\rm{4}} }$ , quantitative conversion of 1.0 mM S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ to 0.50 mM S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ occurs with complete reduction of [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ to [ Fe ( CN ) 6 ]​ 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{4 - }}} }$ being rapidly accelerated by sub-micomolar concentrations of TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ . TCNQF 4 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{2 - }}} }$ generated in the catalytic cycle, reacts with [ Fe ( CN ) 6 ]​ 3 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - }}} }$ to reform TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ and produce [ Fe ( CN ) 6 ]​ 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{4 - }}} }$ . Along with the rapid catalytic reaction, the sluggish competing reaction between TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ and S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ occurs to give TCNQF 4 2 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{2 - }}} }$ , which is protonated to HTCNQF 4 1 - ${{\rm{\;HTCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ , along with a trace amount of S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ . On addition of the precursor catalyst, TCNQF 4 0 ${{\rm{TCNQF}}_{\rm{4}}^{\rm{0}} }$ , rapid reduction with S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ occurs to form TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ - the active catalyst. CuTCNQF 4 ${{\rm{CuTCNQF}}_{\rm{4}} }$ added to water is shown to be sufficiently soluble to provide adequate TCNQF 4 1 - ${{\rm{TCNQF}}_{\rm{4}}^{{\rm{1 - }}} }$ to act as the catalyst for the [ Fe ( CN ) 6 ]​ 3 - / 4 - ${{\rm{[Fe(CN)}}_{\rm{6}} {\rm{]}}^{{\rm{3 - /4 - }}} }$ - S 2 O 3 2 - ${{\rm{S}}_{\rm{2}} {\rm{O}}_{\rm{3}}^{{\rm{2 - }}} }$ / S 4 O 6 2 - ${{\rm{S}}_{\rm{4}} {\rm{O}}_{\rm{6}}^{{\rm{2 - }}} }$ reaction.

Alloying strategies for tuning product selectivity during electrochemical CO2 reduction over Cu.

Excessive reliance on fossil fuels has led to the release and accumulation of large quantities of CO2 into the atmosphere which has raised serious concerns related to environmental pollution and global warming. One way to mitigate this problem is to electrochemically recycle CO2 to value-added chemicals or fuels using electricity from renewable energy sources. Cu is the only metallic electrocatalyst that has been shown to produce a wide range of industrially important chemicals at appreciable rates. However, low product selectivity is a fundamental issue limiting commercial applications of electrochemical CO2 reduction over Cu catalysts. Combining copper with other metals that actively contribute to the electrochemical CO2 reduction reaction process can selectively facilitate generation of desirable products. Alloying Cu can alter surface binding strength through electronic and geometric effects, enhancing the availability of surface confined carbon species, and stabilising key reduction intermediates. As a result, significant research has been undertaken to design and fabricate copper-based alloy catalysts with structures that can enhance the selectivity of targeted products. In this article, progress with use of alloying strategies for development of Cu-alloy catalysts are reviewed. Challenges in achieving high selectivity and possible future directions for development of new copper-based alloy catalysts are considered.

Hydrophobicity Graded Gas Diffusion Layer for Stable Electrochemical Reduction of CO2.

To mitigate flooding associated with the gas diffusion layer (GDL) during electroreduction of CO2 , we report a hydrophobicity-graded hydrophobic GDL (HGGDL). Coating uniformly dispersed polytetrafluoroethylene (PTFE) binders on the carbon fiber skeleton of a hydrophilic GDL uniformizes the hydrophobicity of the GDL and also alleviates the gas blockage of pore channels. Further adherence of the PTFE macroporous layer (PMPL) to one side of the hydrophobic carbon fiber skeleton was aided by sintering. The introduced PMPL shows an appropriate pore size and enhanced hydrophobicity. As a result, the HGGDL offers spatial control of the hydrophobicity and hence water and gas transport over the GDL. Using a nickel-single-atom catalyst, the resulting HGGDL electrode provided a CO faradaic efficiency of over 83 % at a constant current density of 75 mA cm-2 for 103 h operation in a membrane electrode assembly, which is more than 16 times that achieved with a commercial GDL.

Unveiling the Impact of the Cations and Anions in Ionic Liquid/Glyme Hybrid Electrolytes for Na-O2 Batteries.

A series of hybrid electrolytes composed of diglyme and ionic liquids (ILs) have been investigated for Na-O2 batteries, as a strategy to control the growth and purity of the discharge products during battery operation. The dependence of chemical composition of the ILs on the size, purity, and distribution of the discharge products has been evaluated using a wide range of experimental and spectroscopic techniques. The morphology and composition of the discharge products found in the Na-O2 cells have a complex dependence on the physicochemical properties of the electrolyte as well as the speciation of the Na+ and superoxide radical anion. All of these factors control the nucleation and growth phenomena as well as electrolyte stability. Smaller discharge particle sizes and largely homogeneous (2.7 ± 0.5 µm) sodium superoxide (NaO2) crystals with only 9% of side products were found in the hybrid electrolyte containing the pyrrolidinium IL with a linear alkyl chain. The long-term cyclability of Na-O2 batteries with high Coulombic efficiency (>90%) was obtained for this electrolyte with fewer side products (20 cycles at 0.5 mA h cm-2). In contrast, rapid failure was observed with the use of the phosphonium-based electrolyte, which strongly stabilizes the superoxide anion. A high discharge capacity (4.46 mA h cm-2) was obtained for the hybrid electrolyte containing the pyrrolidinium-based IL bearing a linear alkyl chain with a slightly lower value (3.11 mA h cm-2) being obtained when the hybrid electrolyte contained similar pyrrolidinium-based IL bearing an alkoxy chain.

Advanced Spatiotemporal Voltammetric Techniques for Kinetic Analysis and Active Site Determination in the Electrochemical Reduction of CO2.

ConspectusElectrochemical reduction of the greenhouse gas CO2 offers prospects for the sustainable generation of fuels and industrially useful chemicals when powered by renewable electricity. However, this electrochemical process requires the use of highly stable, selective, and active catalysts. The development of such catalysts should be based on a detailed kinetic and mechanistic understanding of the electrochemical CO2 reduction reaction (eCO2RR), ideally through the resolution of active catalytic sites in both time (i.e., temporally) and space (i.e., spatially). In this Account, we highlight two advanced spatiotemporal voltammetric techniques for electrocatalytic studies and describe the considerable insights they provide on the eCO2RR. First, Fourier transformed large-amplitude alternating current voltammetry (FT ac voltammetry), as applied by the Monash Electrochemistry Group, enables the resolution of rapid underlying electron-transfer processes in complex reactions, free from competing processes, such as the background double-layer charging current, slow catalytic reactions, and solvent/electrolyte electrolysis, which often mask conventional voltammetric measurements of the eCO2RR. Crucially, FT ac voltammetry allows details of the catalytically active sites or the rate-determining step to be revealed under catalytic turnover conditions. This is well illustrated in investigations of the eCO2RR catalyzed by Bi where formate is the main product. Second, developments in scanning electrochemical cell microscopy (SECCM) by the Warwick Electrochemistry and Interfaces Group provide powerful methods for obtaining high-resolution activity maps and potentiodynamic movies of the heterogeneous surface of a catalyst. For example, by coupling SECCM data with colocated microscopy from electron backscatter diffraction (EBSD) or atomic force microscopy, it is possible to develop compelling correlations of (precatalyst) structure-activity at the nanoscale level. This correlative electrochemical multimicroscopy strategy allows the catalytically more active region of a catalyst, such as the edge plane of two-dimensional materials and the grain boundaries between facets in a polycrystalline metal, to be highlighted. The attributes of SECCM-EBSD are well-illustrated by detailed studies of the eCO2RR on polycrystalline gold, where carbon monoxide is the main product. Comparing SECCM maps and movies with EBSD images of the same region reveals unambiguously that the eCO2RR is enhanced at surface-terminating dislocations, which accumulate at grain boundaries and slip bands. Both FT ac voltammetry and SECCM techniques greatly enhance our understanding of the eCO2RR, significantly boosting the electrochemical toolbox and the information available for the development and testing of theoretical models and rational catalyst design. In the future, it may be possible to further enhance insights provided by both techniques through their integration with in situ and in operando spectroscopy and microscopy methods.

Inclusion of multiple cycling of potential in the deep neural network classification of voltammetric reaction mechanisms.

The use of deep neural networks (DNNs) for the classification of electrochemical mechanisms using simulated voltammograms with one cycle of potential for training has previously been reported. In this paper, it is shown how valuable additional patterns for mechanism distinction become available when a new DNN is trained simultaneously on images obtained from three cycles of potential using tensor inputs. Significant improvements, relative to the single cycle training, in achieving the correct classification of E, EC1st and EC2nd mechanisms (E = electron transfer step and C1st and C2nd are first and second order follow up chemical reactions, respectively) are demonstrated with noisy simulated data for conditions where all mechanisms are close to chemically reversible and hence difficult to distinguish, even by an experienced electrochemist. Challenges anticipated in applying the new DNN to the classification of experimental data are highlighted. Directions for future development are also discussed.

Electron Delocalization in Spectroelectrochemically and Computationally Characterized [Pt{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)]+ Formed by Electrochemical Oxidation of [PtII{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)].

[Pt{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)] (1Cl) is the product of the hydrogen peroxide oxidation of the PtII anticancer agent [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] (1). Insights into electron delocalization and bonding in [Pt{(p-BrC6F4)NCH═C(Cl)NEt2}Cl(py)]+ (1Cl+) obtained by electrochemical oxidation of 1Cl have been gained by spectroscopic and computational studies. The 1Cl/1Cl+ process is chemically and electrochemically reversible on the short time scale of voltammetry in dichloromethane (0.10 M [Bu4N][PF6]). Substantial stability is retained on longer time scales enabling a high yield of 1Cl+ to be generated by bulk electrolysis. In situ IR and visible spectroelectrochemical studies on the oxidation of 1Cl to 1Cl+ and the reduction of 1Cl+ back to 1Cl confirm the long-term chemical reversibility. DFT calculations indicate only a minor contribution to the electron density (13%) resides on the Pt metal center in 1Cl+, indicating that the 1Cl/1Cl+ oxidation process is extensively ligand-based. Published X-ray crystallographic data show that 1Cl is present in only one structural form, while NMR data on the dissolved crystals revealed the presence of two closely related structural forms in an almost equimolar ratio. Solution-phase EPR spectra of 1Cl+ are consistent with two closely related structural forms in a ratio of about 90:10. The average g value for the frozen solution spectra (2.0567 for the major species) is significantly greater than the 2.0023 expected for a free radical. Crystal field analysis of the EPR spectra leads to an estimate of the 5d(xz) character of around 10% in 1Cl+. Analysis of X-ray absorption fine structure derived from 1Cl+ also supports the presence of a delocalized singly occupied metal molecular orbital with a spin density of approximately 17% on Pt. Accordingly, the considerably larger electron density distribution on the ligand framework (diminished PtIII character) is proposed to contribute to the increased stability of 1Cl+ compared to that of 1+.

A Voltammetric Perspective of Multi-Electron and Proton Transfer in Protein Redox Chemistry: Insights From Computational Analysis of Escherichia coli HypD Fourier Transformed Alternating Current Voltammetry.

This paper explores the impact of pH on the mechanism of reversible disulfide bond (CysS-SCys) reductive breaking and oxidative formation in Escherichia coli hydrogenase maturation factor HypD, a protein which forms a highly stable adsorbed film on a graphite electrode. To achieve this, low frequency (8.96 Hz) Fourier transformed alternating current voltammetric (FTACV) experimental data was used in combination with modelling approaches based on Butler-Volmer theory with a dual polynomial capacitance model, utilizing an automated two-step fitting process conducted within a Bayesian framework. We previously showed that at pH 6.0 the protein data is best modelled by a redox reaction of two separate, stepwise one-electron, one-proton transfers with slightly "crossed" apparent reduction potentials that incorporate electron and proton transfer terms ( E app 2 0 > E app 1 0 ). Remarkably, rather than collapsing to a concerted two-electron redox reaction at more extreme pH, the same two-stepwise one-electron transfer model with E app 2 0 > E app 1 0 continues to provide the best fit to FTACV data measured across a proton concentration range from pH 4.0 to pH 9.0. A similar, small level of crossover in reversible potentials is also displayed in overall two-electron transitions in other proteins and enzymes, and this provides access to a small but finite amount of the one electron reduced intermediate state.

CdS-Enhanced Ethanol Selectivity in Electrocatalytic CO2 Reduction at Sulfide-Derived Cu-Cd.

The development of Cu-based catalysts for the electrochemical CO2 reduction reaction (eCO2 RR) is of major interest for generating commercially important C2 liquid products such as ethanol. Cu is exclusive among the eCO2 RR metallic catalysts in that it facilitates the formation of a range of highly reduced C2 products, with a reasonable total faradaic efficiency but poor product selectivity. Here, a series of new sulfide-derived copper-cadmium catalysts (SD-Cux Cdy ) was developed. An excellent faradaic efficiency of around 32 % but with a relatively low current density of 0.6 mA cm-2 for ethanol was obtained using the SD-CuCd2 catalyst at the relatively low overpotential of 0.89 V in a CO2 -saturated aqueous 0.10 m KHCO3 solution with an H-cell. The current density increased by an order of magnitude under similar conditions using a flow cell where the mass transport rate for CO2 was greatly enhanced. Ex situ spectroscopic and microscopic, and voltammetric investigations pointed to the role of abundant phase boundaries between CdS and Cu+ /Cu sites in the SD-CuCd2 catalyst in enhancing the selectivity and efficiency of ethanol formation at low potentials.

Diverse and unexpected outcomes from oxidation of the platinum(II) anticancer agent [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] by hydrogen peroxide.

Oxidation of the anti-tumour agent [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)], 1 (py = pyridine) with hydrogen peroxide under a variety of conditions yields a range of organoenamineamidoplatinum(II) compounds [Pt{(p-BrC6F4)NCH=C(X)NEt2}Cl(py)] (X = H, Cl, Br) as well as species with shared occupancy involving H, Cl and Br. Thus, oxidation of the -CH2-CH2- backbone (dehydrogenation) occurs, often accompanied by substitution. Oxidation of 1 with H2O2 in acetone yielded 1:1 co-crystallized [Pt{(p-BrC6F4)NCH=CHNEt2}Cl(py)], 1H and [Pt{(p-BrC6F4)NCH=C(Cl)NEt2}Cl(py)], 1Cl. The former was obtained pure in low yield from the oxidation of 1 with (NH4)2[Ce(NO3)6] in acetone, and the latter was obtained from 1 and H2O2 in CH2Cl2 at near reflux. From the latter reaction under vigorous refluxing [Pt{(p-BrC6F4)NCH=C(Br)NEt2}Cl(py)], 1Br was isolated. In refluxing acetonitrile, oxidation of 1 with H2O2 yielded [Pt{(p-BrC6F4)NCH=C(H0.25Br0.75)NEt2}Cl(py)], 1H0.25Br0.75, in which the alkene is mainly substituted by Br in a dual occupancy. Treatment of 1 with H2O2 and tetrabutylammonium hydroxide in acetone at room temperature formed [Pt{(p-HC6F4)NCH2CH2NEt2}Cl(py)], 2. Oxidation of [Pt{(p-HC6F4)NCH2CH2NEt2}Br(py)], 3 with H2O2 in boiling acetonitrile gave the ligand oxidation product [Pt{(p-HC6F4)NCH=C(Br)NEt2}Br(py)], 3Br. All major products were identified by X-ray crystallography as well as by 1H and 19F NMR spectra. In cases of mixed crystals or dual occupancy compounds, the 19F and 1H NMR spectra showed dissociation into the components in the solution in the same proportions as in isolated crystalline material.

Recent advances and future perspectives for automated parameterisation, Bayesian inference and machine learning in voltammetry.

Advanced data analysis tools such as mathematical optimisation, Bayesian inference and machine learning have the capability to revolutionise the field of quantitative voltammetry. Nowadays such approaches can be implemented routinely with widely available, user-friendly modern computing languages, algorithms and high speed computing to provide accurate and robust methods for quantitative comparison of experimental data with extensive simulated data sets derived from models proposed to describe complex electrochemical reactions. While the methodology is generic to all forms of dynamic electrochemistry, including the widely used direct current cyclic voltammetry, this review highlights advances achievable in the parameterisation of large amplitude alternating current voltammetry. One significant advantage this technique offers in terms of data analysis is that Fourier transformation provides access to the higher order harmonics that are almost devoid of background current. Perspectives on the technical advances needed to develop intelligent data analysis strategies and make them generally available to users of voltammetry are provided.

Using Purely Sinusoidal Voltammetry for Rapid Inference of Surface-Confined Electrochemical Reaction Parameters.

Alternating current (AC) voltammetric techniques are experimentally powerful as they enable Faradaic current to be isolated from non-Faradaic contributions. Finding the best global fit between experimental voltammetric data and simulations based on reaction models requires searching a substantial parameter space at high resolution. In this paper, we estimate parameters from purely sinusoidal voltammetry (PSV) experiments, investigating the redox reactions of a surface-confined ferrocene derivative. The advantage of PSV is that a complete experiment can be simulated relatively rapidly, compared to other AC voltammetric techniques. In one example involving thermodynamic dispersion, a PSV parameter inference effort requiring 7,500,000 simulations was completed in 7 h, whereas the same process for our previously used technique, ramped Fourier transform AC voltammetry (ramped FTACV), would have taken 4 days. Using both synthetic and experimental data with a surface confined diazonium substituted ferrocene derivative, it is shown that the PSV technique can be used to recover the key chemical and physical parameters. By applying techniques from Bayesian inference and Markov chain Monte Carlo methods, the confidence, distribution, and degree of correlation of the recovered parameters was visualized and quantified.

Impact of the Lithium Cation on the Voltammetry and Spectroscopy of [XVM11O40]n- (X = P, As (n = 4), S (n = 3); M = Mo, W): Influence of Charge and Addenda and Hetero Atoms.

Polyoxometalates (POMs) have been proposed as electromaterials for lithium-based batteries because they provide access to multiple electron transfer reactions coupled to fast lithium ion transport processes and high stability over many redox cycles. Consequently, knowledge of reversible potentials and Li+ cation-POM anion interactions provides a strategic basis for their further development. In this study, detailed cyclic voltammetric studies of a series of [XVVM11O40]n- (XVM11n-) POMs (where X (heteroatom) = P (n = 4), As (n = 4), and S (n = 3) and M (addenda atom) = Mo, W) have been undertaken in CH3CN in the presence of LiClO4, with n-Bu4NPF6 also present when required to keep the ionic strength close to constant value of 0.1 M. An analysis of the data has allowed the impact of the POM charge, and addenda and hetero atoms on the reversible potentials and the interaction between Li+ and the oxidized XVVM11n- and reduced XVIVM11(n+1)- forms of the VV/IV redox couple to be determined. The SVV/IVM113-/4- process is independent of the Li+ concentration, implying the absence of the association of this cation with either SVVM113- or SVIVM114- redox levels. However, lithium-ion association constants for both VV and VIV redox levels were obtained from a comparison of simulated and experimental cyclic voltammograms for the reduction of the more negatively charged XVVM114- (X = P, As; M = Mo, W), since the Li+ interaction with these more negatively charged POMs is much stronger. The interaction between Li+ and the oxidized, XVVM11n-, and reduced, XVIVM11(n+1)-, forms was also investigated by 51V NMR and EPR spectroscopy, respectively, and it was confirmed that, due to their lower charge density, SVVM113- and SVIVM114- interact significantly less strongly with the lithium ion than XVVM114- and XVIVM115- (X = P, As). The lithium-POM association constants are substantially smaller than the corresponding proton association constants reported previously, which is attributed to a smaller surface charge density. The much stronger impact of Li+ on the WVI/V- and MoVI/V-based reductions that occur at more negative potentials than the VV/IV process also has been qualitatively evaluated.

The Origin of the Electrocatalytic Activity for CO2 Reduction Associated with Metal-Organic Frameworks.

There has been a rapid growth in the use of metal-organic framework (MOF) materials as electrocatalysts. However, simple anodic stripping analysis reveals that some well-known previously reported stable MOFs are in fact unstable at the negative potentials used to catalytically reduce CO2 in aqueous electrolyte media. Thus, it is the resulting metal nanoparticles derived from reduction of the MOFs rather than the MOFs themselves that are the electrocatalysts. The results reported herein therefore suggest that stability data and the origin of the activity for MOF electrocatalysts may need careful re-evaluation and that suitable strategies are needed to ensure that stable MOF electrocatalysts have been synthesized. The use of the readily accessible stripping analysis method provides a powerful tool to assess MOF stability under turnover conditions.

Two-Dimensional Electrocatalysts for Efficient Reduction of Carbon Dioxide.

Two-dimensional (2D) materials are attractive catalysts for the electrochemical reduction of carbon dioxide reaction (eCO2 RR) by virtue of their tunable atomic structures, abundant active sites, enhanced conductivity, suitable binding affinity to carbon dioxide and/or reaction intermediates, and intrinsic scalability. Herein, recent advances in 2D catalysts for the eCO2 RR are reviewed. Structural features and properties of 2D materials that contribute to their advanced electrocatalytic properties are summarized, and strategies for enhancing their activity and selectivity for the eCO2 RR are reviewed. Prospects and challenges of applications of 2D catalysts for the eCO2 RR on an industrial scale are highlighted.

Unprecedented Formation of a Binuclear Au(II)-Au(II) Complex through Redox State Cycling: Electrochemical Interconversion of Au(I)-Au(I), Au(II)-Au(II), and Au(I)-Au(III) in Binuclear Complexes Containing the Carbanionic Ligand C6F4PPh2.

The rational design of binuclear Au(I)-Au(I), Au(II)-Au(II), and Au(I)-Au(III) complexes requires an understanding of how the redox states interconvert. Herein, the electrochemical interconversion of the three oxidation states I, II, and III is reported on the voltammetric (cyclic and rotating disk electrode) time scales for binuclear gold complexes containing C6F4PPh2 as a ligand, to demonstrate for the first time formation of a binuclear Au(II)-Au(II) from a Au(I)-Au(III) complex. Results are supported by bulk electrolysis and coulometry with reaction products being identified by 31P NMR and UV-vis spectroscopy. All electrochemical processes involve an overall two-electron charge-transfer process with no one-electron intermediate being detected. Importantly, the kinetically rather than thermodynamically favored isomer [Au2IIX2(µ-2-C6F4PPh2)2] is formed on redox cycling of [XAuI(µ-2-C6F4PPh2)(κ2-2-C6F4PPh2)AuIIIX] (X = Cl, ONO2). Finally, a mechanism is proposed to explain the simultaneous change of coordination of the chelating carbanionic ligand to bridging mode and interconversion of oxidation states in binuclear gold complexes.