Inner-sphere Electron Transfer Research Articles

Tuning the inner- and outer-sphere electron transfer behavior of aqueous {CoW12} polyoxometalate clusters for redox flow batteries exceeding 1.5V

Redox active species as the key component of redox flow batteries (RFBs) directly determine battery performance. Herein, we report a unique redox active specie, {CoW12}, exhibits both outer-sphere electron transfer of the {CoO4} core and inner-sphere electron transfer of the {W12O36} shell in one cluster, which is capable of constructing a symmetric {CoW12}-based RFB with pH-controlled operating voltage output. The DFT calculation discloses the proton-coupled electron transfer process of the {W12O36} shell in thermodynamically and kinetically, explaining the negative shift of the redox potential of {W12O36} shell as the pH increasing from 1 to 4. Interestingly, the redox potential of outer-sphere controlled {CoO4} core is unchanged, which leads to an extension of voltage window from 1.31 to 1.56 V. Consequently, the cycling measurement of the symmetrical battery proves that low capacity decay rate of 0.009 % and high Coulombic efficiency over 99 % can be retained in 400 cycles at pH 4.

Photoinduced copper-catalyzed C–N coupling with trifluoromethylated arenes

Selective defluorinative functionalization of trifluoromethyl group (–CF3) is an attractive synthetic route to the pharmaceutically privileged fluorine-containing moiety. Herein, we report a strategy based on photoexcited copper catalysis to activate the C–F bond of di- or trifluoromethylated arenes for divergent radical C–N coupling with carbazoles and aromatic amines. The use of different ligands can tune the reaction products diversity. A range of substituted, structurally diverse α,α-difluoromethylamines can be obtained from trifluoromethylated arenes via defluorinative C-N coupling with carbazoles, while an interesting double defluorinative C-N coupling is ready for difluoromethylated arenes. Based on this success, a carbazole-centered PNP ligand is designed to be an optimal ligand, enabling a copper-catalyzed C–N coupling for the construction of imidoyl fluorides from aromatic amines through double C-F bond functionalization. Interestingly, a 1,2-difluoroalkylamination strategy of styrenes is also developed, delivering γ,γ-difluoroalkylamines, a bioisostere to β-aminoketones, in synthetically useful yields. The DFT studies reveal an inner-sphere electron transfer mechanism for Cu-catalyzed selective activation of C(sp3)–F bonds.

Cation-induced changes in the inner- and outer-sphere mechanisms of electrocatalytic CO2 reduction

The underlying mechanism of cation effects on CO2RR remains debated. Herein, we study cation effects by simulating both outer-sphere electron transfer (OS-ET) and inner-sphere electron transfer (IS-ET) pathways during CO2RR via constrained density functional theory molecular dynamics (cDFT-MD) and slow-growth DFT-MD (SG-DFT-MD), respectively. Our results show without any cations, only OS-ET is feasible with a barrier of 1.21 eV. In the presence of K+ (Li+), OS-ET shows a very high barrier of 2.93 eV (4.15 eV) thus being prohibited. However, cations promote CO2 activation through IS-ET with the barrier of only 0.61 eV (K+) and 0.91 eV (Li+), generating the key intermediate (adsorbed CO{}_{2}^{delta -}). Without cations, CO2-to-CO{}_{2}^{delta -}(ads) conversion cannot proceed. Our findings reveal cation effects arise from short-range Coulomb interactions with reaction intermediates. These results disclose that cations modulate the inner- and outer-sphere pathways of CO2RR, offering substantial insights on the cation specificity in the initial CO2RR steps.

Unravelling the Effect of Acid-Driven Electron Transfer in High-Valent FeIV =O/MnIV =O Species and Its Implications for Reactivity.

The electron transfer (ET) step is one of the crucial processes in biochemical redox reactions that occur in nature and has been established as a key step in dictating the reactivity of high-valent metal-oxo species. Although metalloenzymes possessing metal-oxo units at their active site are typically associated with outer-sphere electron transfer (OSET) processes, biomimetic models, in contrast, have been found to manifest either an inner-sphere electron transfer (ISET) or OSET mechanism. This distinction is clearly illustrated through the behaviour of [(N4Py)MnIV (O)]2+ (1) and [(N4Py)FeIV (O)]2+ (2) complexes, where complex 1 showcases an OSET mechanism, while complex 2 exhibits an ISET mechanism, especially evident in their reactions involving C-H bond activation and oxygen atom transfer reactions in the presence of a Lewis/Bronsted acid. However, the precise reason for this puzzling difference remains elusive. This work unveils the origin of the perplexing inner-sphere vs outer-sphere electron transfer process (ISET vs OSET) in [(N4Py)MnIV (O)]2+ (1) and [(N4Py)FeIV (O)]2+ (2) species in the presence of Bronsted acid. The calculations indicate that when the substrate (toluene) approaches both 1 and 2 that is hydrogen bonded with two HOTf molecules (denoted as 1-HOTf and 2-HOTf, respectively), proton transfer from one of the HOTf molecules to the metal-oxo unit is triggered and a simultaneous electron transfer occurs from toluene to the metal centre. Interestingly, the preference for OSET by 1-HOTf is found to originate from the choice of MnIV =O centre to abstract spin-down (β) electron from toluene to its δ(dxy ) orbital. On the other hand, in 2-HOTf, a spin state inversion from triplet to quintet state takes place during the proton (from HOTf) coupled electron transfer (from toluene) preferring a spin-up (α) electron abstraction to its σ* (dz 2 ) orbital mediated by HOTf giving rise to ISET. In addition, 2-HOTf was calculated to possess a larger reorganisation energy, which facilitates the ISET process via the acid. The absence of spin-inversion and smaller reorganisation energy switch the mechanism to OSET for 1-HOTf. Therefore, for the first time, the significance of spin-state and spin-inversion in the electron transfer process has been identified and demonstrated within the realm of high-valent metal-oxo chemistry. This discovery holds implications for the potential involvement of high-valent Mn-oxo species in performing similar transformative processes within Photosystem II.

The Critical Role of Ligand Flexibility on the Activity of Free and Immobilized Mn Superoxide Dismutase Mimics

In low-molecular-weight Mn superoxide dismutase (SOD) mimics, the ligand plays a key role in tuning the reactivity of the metal center with O2•−. We used three ligands differing in their donor sites, flexibility and/or charge, to compare the redox properties and SOD activity of the resulting Mn complexes: 1,3-bis[(pyridin-2-ylmethyl)(propargyl)amino]propane (pypapn), 1,3-bis(pyridin-2-ylmethyleneamino)propane (py2pn) and 1,4-bis(salicylidenamino)butane (H2salbn). These ligands afford Mn complexes that, in aqueous solution, exist as mononuclear species [Mn(II)(pypapn)(H2O)2]2+, [Mn(II)(py2pn)(H2O)2]2+ and [Mn(III)(salbn)(H2O)2]+. The relative reactivity of these compounds with O2•− at pH 7.8, [Mn(pypapn)(H2O)2]2+ > [Mn(salbn)(H2O)2]+ > [Mn(py2pn)(H2O)2]2+, is independent of the redox potential but strongly depends on the ligand flexibility which becomes a critical feature when the reaction occurs through an inner-sphere electron-transfer mechanism. Immobilization was used to isolate and protect the catalyst from dissociation or dimerization during catalysis. [Mn(pypapn)(H2O)2]2+, with the alkyne group, was covalently grafted to azide functionalized mesoporous silica through click chemistry, while [Mn(py2pn)(solv)2]2+ and [Mn(salbn)(solv)2]+ were encapsulated in SBA-15 mesoporous silica through ionic exchange. The retention or enhancement of the SOD activity and the improved stability of the covalently attached catalyst and the doubly charged complex encapsulated in the silica pores, make them suitable for use in aqueous media.

Insight into the Mechanism Underlying Dehalococcoides mccartyi Strain CBDB1-Mediated B12-Dependent Aromatic Reductive Dehalogenation.

Anaerobic bacteria transform aromatic halides through reductive dehalogenation. This dehalorespiration is catalyzed by the supernucleophilic coenzyme vitamin B12, cob(I)alamin, in reductive dehalogenases. So far, the underlying inner-sphere electron transfer (ET) mechanism has been discussed controversially. In the present study, all 36 chloro-, bromo-, and fluorobenzenes and full-size cobalamin are analyzed at the quantum chemical density functional theory level with respect to a wide range of theoretically possible inner-sphere ET mechanisms. The calculated reaction free energies within the framework of CoI···X (X = F, Cl, and Br) attack rule out most of the inner-sphere pathways. The only route with feasible energetics is a proton-coupled two-ET mechanism that involves a B12 side-chain tyrosine (modeled by phenol) as a proton donor. For 12 chlorobenzenes and 9 bromobenzenes with experimental data from Dehalococcoides mccartyi strain CBDB1, the newly proposed PC-TET mechanism successfully discriminates 16 of 17 active from 4 inactive substrates and correctly predicts the observed regiospecificity to 100%. Moreover, fluorobenzenes are predicted to be recalcitrant in agreement with experimental findings. Conceptually, based on the Bell-Evans-Polanyi principle, the computational approach provides novel mechanistic insights and may serve as a tool for predicting the energetic feasibility of reductive aromatic dehalogenation.

Trinuclear Gold-Catalyzed 1,2-Difunctionalization of Alkenes.

Activated alkyl halides have been extensively explored to generate alkyl radicals with Ru- and Ir- photocatalysts for 1,2-difunctionalization of alkenes, but unactivated alkyl bromides remain challenging substrates due to their strong reduction potential. Here we report a three-component 1,2-difunctionalization reaction of alkenes, unactivated alkyl bromides and nucleophiles (e.g., amines and indoles) using a trinuclear gold catalyst [Au3 (tppm)2 ](OTf)3 . It can achieve the 1,2-aminoalkylation and 1,2-alkylarylation readily. This protocol has a broad reaction scope and excellent functional group compatibility (>100 examples with up to 96 % yield). It also affords a robust formal [2+2+1] cyclization strategy for the concise construction of pyrrolidine skeletons under mild reaction conditions. Mechanistic studies support an inner-sphere single electron transfer pathway for the successful cleavage of inert C-Br bonds.

Theoretical Study of the Catalytic Mechanism of the Cu-Only Superoxide Dismutase.

The catalytic mechanisms for the wild-type and the mutated Cu-only superoxide dismutase were studied using the hybrid density functional B3LYP and a quantum chemical cluster approach. Optimal protonation states of the active site were examined for each stage of the catalytic cycle. For both the reductive and the oxidative half-reactions, the arrival of the substrate was found to be accompanied by a charge-compensating H+ with exergonicities of -15.4 kcal·mol and -4.7 kcal·mol, respectively. The second-sphere Glu-110 and first-sphere His-93 were suggested to be the transient protonation site for the reductive and the oxidative half-reactions, respectively, which collaborates with the hydrogen bonding water chain to position the substrate near the redox-active copper center. For the reductive half-reaction, the rate-limiting step was found to be the inner-sphere electron transfer from the partially coordinated to CuII with a barrier of 8.1 kcal·mol. The formed O2 is released from the active site with an exergonicity of -14.9 kcal·mol. For the oxidative half-reaction, the inner-sphere electron transfer from CuI to the partially coordinated was found to be accompanied by the proton transfer from the protonated His-93 and barrierless. The rate-limiting step was found to be the second proton transfer from the protonated Glu-110 to with a barrier of 7.3 kcal·mol. The barriers are reasonably consistent with experimental activities, and a proton-transfer rate-limiting step in the oxidative half-reaction could explain the experimentally observed pH-dependence. For the E110Q CuSOD, Asp-113 was suggested to be likely to serve as the transient protonation site in the reductive half-reaction. The rate-limiting barriers were found to be 8.0 and 8.6 kcal·mol, respectively, which could explain the slightly lower performance of E110X mutants. The results were found to be stable, with respect to the percentage of exact exchange in B3LYP.

Close-Shell Reductive Elimination versus Open-Shell Radical Coupling for Site-Selective Ruthenium-Catalyzed C-H Activations by Computation and Experiments.

Ruthenium-catalyzed σ-bond activation-assisted meta-C-H functionalization has emerged as a useful tool to forge distal C-C bonds. However, given the limited number of mechanistic studies, a clear understanding of the origin of the site-selectivity and the complete reaction pattern is not available. Here, we present systematic computational studies on ruthenium-catalyzed C-H functionalization with primary, secondary, tertiary alkyl bromides and aryl bromides. The C-H scission and the C-C formation were carefully examined. Monocyclometalated ruthenium(II) complexes were identified as the active species, which then underwent inner-sphere single electron transfer (ISET) to activate the organic bromides. The site-selectivity results from the competition between the close-shell reductive elimination and the open-shell radical coupling. Based on this mechanistic understanding, a multilinear regression model was built to predict the site-selectivity, which was further validated by experiments.

Electronic Effect on Phenoxide Migration at a Nickel(II) Center Supported by a Tridentate Bis(phosphinophenyl)phosphido Ligand.

A phosphide nickel(II) phenoxide pincer complex (2) reacts with CO(g) to give a pseudo-tetrahedral nickel(0) monocarbonyl complex (3) possessing a phosphinite moiety. This metal-ligand cooperative (MLC) transformation occurs with a (PPP)Ni scaffold (PPP- = P[2-PiPr2-C6H4]2-), which can accommodate both square planar and tetrahedral geometries. The 2-electron reduction of a nickel(II) species induced by CO coordination involves group transfer to generate a P-O bond. For better mechanistic understanding, a series of nickel(II) phenolate complexes (2a-2e, XC6H4O- (X = OMe, Me, H, and CF3) and pentafluorophenolate) were prepared. Kinetic experimental data reveal that a phenolate species with an electron-withdrawing group reacts faster than those with electron-donating groups. The reaction kinetic experiments were conducted in pseudo-first order conditions at room temperature monitored by UV-vis spectroscopy. A pentafluorophenolate nickel(II) complex (2e) reveals instantaneous reactions even at -40 °C to give a nickel(0) monocarbonyl species (3e) and the reverse reaction is also possible. According to kinetic experiments, the rate determining step (RDS) would be the formation of a 5-coordinate intermediate 4 with a negative entropy value (ΔS‡ < 0), and a positive ρ value based on the Hammett plot indicates that the electron-deficient phenolate leads to a faster CO association. Furthermore, scramble experiments suggest that phenolate de-coordinates from the intermediate 4, which gives a (PPP)Ni-CO species 6. The cationic nickel monocarbonyl intermediate can possess a P--Ni(II), P•-Ni(I), or even a P+-Ni(0) character. Such an inner-sphere electron transfer is suggested when a π-acidic ligand such as CO coordinates to a metal ion. Another possible reaction is homolysis of a Ni-O bond to give P--Ni(I) or P•-Ni(0), when a phenoxyl radical is liberated. Considering the P-O bond formation, closed-shell nucleophilic and open-shell radical pathways are suggested. A phenolate pathway reveals a lower energy state for 2e relative to other complexes (2c and 2d), while its radical pathway undergoes via a higher energy state. Therefore, the formation of a P-O bond may occur with the binding of a closed-shell phenolate to the electron-deficient P center.

Investigating the mechanism of Ni-mediated trifluoromethylthiolation of aryl halides using AgSCF3.

The mechanism of the Ni-catalysed trifluoromethylthiolation of aryl chlorides using AgSCF3 is studied herein. A variety of IPr NiII complexes were synthesized via oxidative addition of Ni0 to 2-(2-chloro)phenylpyridines. Their reactivity with AgSCF3 was tested by performing stoichiometric experiments, cyclic voltammetry, and NMR spectroscopic studies. CuSCF3 was shown to behave similarly to AgSCF3, while reactions with NMe4SCF3 revealed a major stoichiometric side reaction that forms a nickel fluoride complex. NMR kinetic studies revealed there is little correlation between the electron-withdrawing/donating nature of the para substituents on either the phenyl or pyridyl groups with the formation of the corresponding products. Cyclic voltammetry (CV) indicated the feasibilty of NiI/NiIII transitions, and an increased rate of formation of product was observed with increased solvent polarity. Evidence suggests that the mechanism proceeds via inner-sphere electron transfer (ET) from AgSCF3 to NiII, ultimately leading to the formation of the trifluoromethylthiolated product.

Photoinduced Ion-Pair Inner-Sphere Electron Transfer-Reversible Addition-Fragmentation Chain Transfer Polymerization.

Photoredox-mediated reversible deactivation radical polymerization (RDRP) is a promising method of precise synthesis of polymers with diverse structures and properties. However, its mechanism mainly based on the outer-sphere electron transfer (OSET) leads to stringent requirements for an efficient photocatalyst. In this paper, the zwitterionic organoboranes [L2B]+X- are prepared and applied in reversible addition-fragmentation chain transfer (RAFT) polymerization with the photoinduced ion-pair inner-sphere electron transfer (IP-ISET) mechanism. The ion-pair electron transfer mechanism and the formation of the radical [L2B]• are supported by electron paramagnetic resonance (EPR) radical capture experiments, 1H/11B NMR spectroscopy, spectroelectrochemical spectroscopy, transient absorption spectroscopy, theoretical calculation, and photoluminescence quenching experiments. Photoluminescence quenching experiments show that when [CTA]/[[L2B]+] ≥ 0.6, it is static quenching because of the in situ formation of [L2B]+[ZCS2]-, the real catalytic species. [L2B]+[C3H7SCS2]- is synthesized, and its photoluminescence lifetime is the same as the lifetime in the static quenching experiment, indicating the formation of [L2B]+[ZCS2]- in polymerization and the IP-ISET mechanism. The matrix-assisted laser desorption ionization time-of-flight mass (MALDI-TOF MS) spectra show that the structure of [C3H7SCS2] was incorporated into the polymer, indicating that ion-pair electron transfer occurs in catalytic species. The polymerization shows high catalytic activity at ppb catalyst loading, a wide range of monomers, excellent tolerance in the presence of 5 mol % phenolic inhibitors, and the synthesis of ultrahigh-molecular-weight polymers. This protocol with the IP-ISET mechanism exhibits a value in the development of new organic transformations and polymerization methods.

Inner-Sphere Electron Transfer Induced Reversible Electron Reservoir Feature of Azoheteroarene Bridged Diruthenium Frameworks.

This article demonstrates the stabilization of ground- and redox-induced metal-to-ligand charge transfer excited states on coordination of azo-coupled bmpd(L4) [bmpd = (E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene; L4 = -N═N-] to the electron-rich {Ru(acac)2} (acac = acetylacetonate) unit in mononuclear RuII(acac)2(L4) (1) and diastereomeric dinuclear (acac)2Ru2.5(μ-L4•-)Ru2.5(acac)2 [rac, ΔΔ/ΛΛ (2a)/meso, ΔΛ (2b)] complexes, respectively. It also develops further one-step intramolecular electron transfer induced L4•- bridged isovalent higher analogue [(acac)2RuIII(μ-L4•-)RuIII(acac)2]ClO4 in diastereomeric forms, rac-[2a]ClO4/meso-[2b]ClO4. On the contrary, under identical reaction conditions electronically and sterically permuted bimpd [L5, (E)-1,2-bis(4-iodo-1-methyl-1H-pyrazol-3-yl)diazene)] delivered mononuclear RuII(acac)2(L5) (3) as an exclusive product. Further, the generation of unprecedented heterotrinuclear complex [(acac)2RuII(μ-L4)AgI(μ-L4)RuII(acac)2]ClO4 ([4]ClO4) involving unreduced L4 via the reaction of 1 and AgClO4 revealed the absence of any inner-sphere electron transfer (IET) as in precursor 1, which in turn reaffirmed an IET (at the interface of electron-rich Ru(acac)2 and acceptor L4) mediated stabilization of 2. Structural authentication of the complexes with special reference to the tunable azo distance (N═N, N-N•-, N-N2-) of L and their spectro-electrochemical events in accessible redox states including the reversible electron reservoir feature of 2 → 2+/2+ → 2 were evaluated in conjunction with density functional theory/time-dependent density functional theory calculations. The varying extent of IET as a function of heteroaromatics appended to the azo group of L (L1 = abpy = 2,2'-azobipyridine, L2 = abbt = 2,2'-azobis(benzothiazole), L3 = abim = azobis(1-methylbenzimidazole), L4 and L5, Schemes 1 & 2) in the Ru(acac)2-derived respective molecular setup has been addressed.

Boosting peroxymonosulfate activation by porous single-atom catalysts with FeN4O1 configuration for efficient organic pollutants degradation

The construction of single Fe atoms with favorable electron structures is highly desired to boost peroxymonosulfate (PMS) activation for organics degradation. Herein, this study embedded isolated Fe atoms on N, O co-doped porous carbon substrate (FeSA-N/OC), and first found the constructed FeN4O1 configuration can realize efficient PMS activation via electron transfer by inner-sphere complexation, instead of the usual reactive oxygen species (ROS) as a major role. Structural investigation showed that the FeN4O1 moieties possess high content of high spin (HS) Fe(II), resulting in the delocalization of unpaired electrons around Fe centers, which is benefit to transfer electrons when reacted with PMS. EIS and LSV curves further certified the electron transfer process. Density functional theory (DFT) calculations unveiled that the FeN4O1 configuration can directly adsorb OO bond of PMS, leading to electron accumulation around Fe-O2 bond, and then ulteriorly trigger the electron shuttling in organics degradation. Consequently, the optimized FeSA-N/OC/PMS system exhibited superior oxidation ability for various organic pollutants, and was not affected by initial pH variation (3.19 ∼ 10.89), inorganic anions (ClO4−, Cl− and H2PO4−) and natural organic matter (NOM) interference. Importantly, the developed system presented certain applicability in the treatment of actual water from Taihu Lake basin, China. Hence, this study not only elucidates the inner-sphere complexation-oriented electron transfer mechanism between unique FeN4O1 configuration and PMS, but provides new insights into engineered single atom catalysts for wastewater purification.

Electro-polymerization rates of diazonium salts are dependent on the crystal orientation of the surface

Electro-polymerization of diazonium salts is widely used for modifying surfaces with thin organic films. Initially this method was primarily applied to carbon, then to metals, and more recently to semiconducting Si. Unlike on other surfaces, electrochemical reduction of diazonium salts on Si, which is one of the most industrially dominant material, is not well understood. Here, we report the electrochemical reduction of diazonium salts on a range of silicon electrodes of different crystal orientations (111, 211, 311, 411, and 100). We show that the kinetics of surface reaction and the reduction potential is Si crystal-facet dependent and is more favorable in the hierarchical order (111) > (211) > (311) > (411) > (100), a finding that offers control over the surface chemistry of diazonium salts on Si. The dependence of the surface reaction kinetics on the crystal orientation was found to be directly related to differences in the potential of zero charge (PZC) of each crystal orientation, which in turn controls the adsorption of the diazonium cations prior to reduction. Another consequence of the effect of PZC on the adsorption of diazonium cations, is that molecules terminated by distal diazonium moieties form a compact film in less time and requires less reduction potentials compared to that formed from diazonium molecules terminated by only one diazo moiety. In addition, at higher concentrations of diazonium cations, the mechanism of electrochemical polymerization on the surface becomes PZC-controlled adsorption-dominated inner-sphere electron transfer while at lower concentrations, diffusion-based outer-sphere electron transfer dominates. These findings help understanding the electro-polymerization reaction of diazonium salts on Si en route towards an integrated molecular and Si electronics technology.

Electroprecipitation of Nanometer-Thick Films of Ln(OH)3 [Ln = La, Ce, and Lu] at Pt Microelectrodes and Their Effect on Electron-Transfer Reactions.

We report investigations of the deposition of nanometer-thick Ln(OH)3 films (Ln = La, Ce, and Lu) and their effect on outer-sphere and inner-sphere electron-transfer reactions. Insoluble Ln(OH)3 films are deposited from aqueous solutions of LaCl3 onto the surface of 12.5 μm radius Pt microdisk electrodes during water or oxygen reduction. Both reactions produce interfacial OH-, which complexes with Ln3+, resulting in the precipitation of Ln(OH)3. Surface analyses by scanning electron microscopy (SEM), SEM-energy-dispersive X-ray spectroscopy, and atomic force microscopy indicate the formation of a 1-2 nm thick uniform film. Outer-sphere electron-transfer reactions (Ru(NH3)63+ reduction, FcMeOH oxidation, and Fe(CN)64-/3- oxidation/reduction) were investigated at Ln(OH)3-modified electrodes of different film thicknesses. The results demonstrate that the steady-state transport-limited current for these reactions decreases with an increase in the film thickness. Moreover, the degree of blockage depends upon the redox species, suggesting that the Ln(OH)3 films are free from pinholes greater than the size of the redox molecules. This suggests that the films are either ionically conducting or that electron tunneling occurs across these thin layers. A similar blocking effect was observed for the inner-sphere reductions of H2O and O2. We further demonstrate that the thickness of La(OH)3 films can be controlled by anodic dissolution. Additionally, we show that La3+ lowers the supersaturation of dissolved H2 required to nucleate a stable nanobubble.

Voltammetric Mapping of Hydrogen Evolution Reaction on Pt Locally via Scanning Electrochemical Cell Microscopy.

The advancement in nanoscale electrochemical tools has offered the opportunity to better understand heterogeneity at electrochemical interfaces. Scanning electrochemical cell microscopy (SECCM) has been increasingly used for revealing local kinetics and the distribution of active sites in electrocatalysis. Constant-contact scanning and hopping scanning are the two commonly used modes. The former is intrinsically faster, whereas the latter enables full voltammetry at individual locations. Herein, we revisit a less used mode that combines the advantages of hopping and constant-contact scan, resulting in a faster voltammetric mapping. In this mode, the nanodroplet cell in SECCM maintains contact with the surface during the scanning and makes intermittent pauses for local voltammetry. The elimination of frequent retraction and approach greatly increases the speed of mapping. In addition, iR correction can be readily applied to the voltammetry, resulting in more accurate measurements of the electrode kinetics. This scanning mode is demonstrated in the oxidation of a ferrocene derivative on HOPG and hydrogen evolution reaction (HER) on polycrystalline Pt, serving as model systems for outer-sphere and inner-sphere electron transfer reactions, respectively. While the kinetics of the inner-sphere reaction is consistent spatially, heterogeneity is observed for the kinetics of HER, which is correlated with the crystal orientation of Pt.

Critical Roles of Exchange and Superexchange Interactions in Dictating Electron Transfer and Reactivity in Metalloenzymes.

Electron transfer (ET) is a fundamental process in transition-metal-dependent metalloenzymes. In these enzymes, the spin-spin interactions within the same metal center and/or between different metal sites can play a pivotal role in the catalytic cycle and reactivity. This Perspective highlights that the exchange and/or superexchange interactions can intrinsically modulate the inner-sphere and long-range electron transfer, thus controlling the mechanism and activity of metalloenzymes. For mixed-valence diiron oxygenases, the spin-regulated inner-sphere ET can be dictated by exchange interactions, leading to efficient O-O bond activations. Likewise, the spin-regulated inner-sphere ET can be enhanced by both exchange and superexchange interactions in [Fe4S4]-dependent SAM enzymes, which enable the efficient cleavage of the S─C(γ) or S─C5' bond of SAM. In addition to inner-sphere ET, superexchange interactions may modulate the long-range ET between metalloenzymes. We anticipate that the exchange and superexchange enhanced reactivity could be applicable in other important metalloenzymes, such as Photosystem II and nitrogenases.

Self-Assembled TMD Nanoparticles on N-Doped Carbon Nanostructures for Oxygen Reduction Reaction and Electrochemical Oxygen Sensing Thereof

Here, we report on a universal carbothermal reduction strategy for the synthesis of well-dispersed WS2 nanoparticles (∼1.7 nm) supported on a N-doped carbon (NxC) nanostructure and the electrocatalytic activity toward oxygen reduction reaction (ORR). Bulk WS2 powder (2 μm) is the source for WS2 nanoparticles, and dicyandiamide is the source for NxC and carbothermal reduction. Interestingly, WS2/NxC serves the purpose of innovative and robust active sites for ORR through an efficient four-electron transfer process with excellent durability. Remarkably, WS2/NxC suppresses the peroxide generation due to the dominating inner-sphere electron transfer mechanism where the direct adsorption of the desolvated O2 molecule on the electroactive centers takes place. The mass activity (at 0.4 and 0.85 V vs RHE) of WS2/NxC outperforms the previously reported transition metal based electrocatalysts. The study further establishes a correlation between the work function and the ORR activity. We have also exploited WS2/NxC for electrochemical oxygen sensing, and there exists a direct correlation between oxygen sensing and ORR as both depend on the oxygen adsorption ability. Finally, the carbothermal reduction strategy has been extended for the synthesis of other TMDs/NxC such as MoS2/NxC, MoSe2/NxC, and WSe2/NxC.

Inverse potential scaling in co-electrocatalytic activity for CO2 reduction through redox mediator tuning and catalyst design.

Electrocatalytic CO2 reduction is an attractive strategy to mitigate the continuous rise in atmospheric CO2 concentrations and generate value-added chemical products. A possible strategy to increase the activity of molecular systems for these reactions is the co-catalytic use of redox mediators (RMs), which direct reducing equivalents from the electrode surface to the active site. Recently, we demonstrated that a sulfone-based RM could trigger co-electrocatalytic CO2 reduction via an inner-sphere mechanism under aprotic conditions. Here, we provide support for inner-sphere cooperativity under protic conditions by synthetically modulating the mediator to increase activity at lower overpotentials (inverse potential scaling). Furthermore, we show that both the intrinsic and co-catalytic performance of the Cr-centered catalyst can be enhanced by ligand design. By tuning both the Cr-centered catalyst and RM appropriately, an optimized co-electrocatalytic system with quantitative selectivity for CO at an overpotential (η) of 280 mV and turnover frequency (TOF) of 194 s−1 is obtained, representing a three-fold increase in co-catalytic activity at 130 mV lower overpotential than our original report. Importantly, this work lays the foundation of a powerful tool for developing co-catalytic systems for homogeneous electrochemical reactions.