Electron Transfer Reduction Research Articles

The Implications of Coupling an Electron Transfer Mediated Oxidation with a Proton Coupled Electron Transfer Reduction in Hybrid Water Electrolysis.

Electrolysis of water is a sustainable route to produce clean hydrogen. Full water-splitting requires a high applied potential, in part because of the pH-dependency of the H2 and O2 evolution reactions (HER and OER), which are proton-coupled electron transfer (PCET) reactions. Therefore, the minimum required potential will not change at different pHs. TEMPO [(2,2,6,6-tetramethyl-1-piperidin-1-yl)oxyl], a stable free-radical that undergoes fast electro-oxidation by a single-electron transfer (ET) process, is pH-independent. Here, we show that the combination of PCET and ET processes enables hydrogen production from water at low cell potentials below the theoretical value for full water-splitting by simple pH adjustment. As a case study, we combined the HER with the oxidation of benzylamine by anodically oxidized TEMPO. The pH-independent electrocatalytic oxidation of TEMPO permits the operation of a hybrid water-splitting cell that shows promise to perform at a low cell potential (≈1 V) and neutral pH conditions.

Nanocomposites of Terbium Sulfide Nanoparticles with a Chitosan Capping Agent for Antibacterial Applications

This study aims to investigate the effect of alkaline pH on the bottom-up synthesis of nanocomposites (NCs) containing terbium sulfide nanoparticles (Tb2S3 NPs), where chitosan (CS) was employed as a capping agent, along with evaluation of the antibacterial activity of these NCs. The NCs were characterized using spectroscopy (FESEM-EDX, Raman, FTIR, XRD, XPS, and DLS), zeta-potential, and TGA. The results of FE-SEM, XPS, Raman, and FTIR characterization support the formation of CS-Tb2S3 NPs. A pH variation from 9 to 11 during composite formation was shown to affect the size and composition of NCs. The antibacterial activity of CS-Tb2S3 NCs was studied by coating onto commercial contact lenses, where the best loading efficiency of NCs was 48%. The NCs prepared at pH 10 (without contact lenses) had greater antibacterial activity against Staphylococcus aureus, with a zone of inhibition diameter of 7.15 mm. The coating of NCs onto commercial contact lenses was less effective for inhibition of Staphylococcus aureus, in contrast with the greater activity observed for tetracycline. CS-Tb2S3 NCs offer promising antimicrobial properties that can be further optimized by control of the surface loading and accessibility of Tb2S3 NPs through further study of the role of the chitosan capping agent, since steric effects due to CS are likely to attenuate antimicrobial activity via reduced electron transfer in such nanocomposite systems.

Superlattice‐based Plasmonic Catalysis: Concentrating Light at the Nanoscale to Drive Efficient Nitrogen‐to‐Ammonia Fixation at Ambient Conditions

AbstractPlasmonic catalysis promises green ammonia synthesis but is limited by the need for co‐catalysts and poor performances due to weak electromagnetic field enhancement. Here, we use two‐dimensional plasmonic superlattices with dense electromagnetic hotspots to boost ambient nitrogen‐to‐ammonia photoconversion without needing co‐catalyst. By organizing Ag octahedra into a square superlattice to concentrate light, the ammonia formation is enhanced by ≈15‐fold and 4‐fold over hexagonal superlattice and disorganized array, respectively. Our unique catalyst achieves superior ammonia formation rate and apparent quantum yield up to ≈15‐fold and ≈103‐fold, respectively, better than traditional designs. Mechanistic investigations reveal the abundance of intense plasmonic hotspots is crucial to promote hot electron generation and transfer for nitrogen reduction. Our work offers valuable insights to design electromagnetically hot plasmonic catalysts for diverse chemical and energy applications.

Superlattice-based Plasmonic Catalysis: Concentrating Light at the Nanoscale to Drive Efficient Nitrogen-to-Ammonia Fixation at Ambient Conditions.

Plasmonic catalysis promises green ammonia synthesis but is limited by the need of co-catalysts and poor performances due to weak electromagnetic field enhancement. Here, we use two-dimensional plasmonic superlattices with dense electromagnetic hotspots to boost ambient nitrogen-to-ammonia photoconversion without needing co-catalyst. By organizing Ag octahedra into a square superlattice to concentrate light, the ammonia formation is enhanced by ~15-fold and 4-fold over hexagonal superlattice and disorganized array, respectively. Our unique catalyst achieves superior ammonia formation rate and apparent quantum yield up to ~15-fold and ~103-fold, respectively, better than traditional designs. Mechanistic investigations reveal the abundance of intense plasmonic hotspots is crucial to promote hot electron generation and transfer for nitrogen reduction. Our work offers valuable insights to design electromagnetically hot plasmonic catalysts for diverse chemical and energy applications.

Effects of different iron minerals on organics removal pathway and end-products during anaerobic digestion

Ferrihydrite and magnetite enhanced anaerobic digestion through dissimilatory iron reduction and direct interspecies electron transfer (DIET), respectively.

Divalent metallocenes of the lanthanides - a guideline to properties and reactivity.

Since the discovery in the early 1980s, the soluble divalent metallocenes of lanthanides have become a steadily growing field in organometallic chemistry. The predominant part of the investigation has been performed with samarium, europium, and ytterbium, whereas only a few reports dealing with other rare earth elements were disclosed. Reactions of these metallocenes can be divided into two major categories: (1) formation of Lewis acid-base complexes, in which the oxidation state remains +II; and (2) single electron transfer (SET) reductions with the ultimate formation of Ln(III) complexes. Due to the increasing reducing character from Eu(II) over Yb(II) to Sm(II), the plethora of literature concerning redox reactions revolves around the metallocenes of Sm and Yb. In addition, a few reactivity studies on Nd(II), Dy(II) and mainly Tm(II) metallocenes were published. These compounds are even stronger reducing agents but significantly more difficult to handle. In most cases, the metals are ligated by the versatile pentamethylcyclopentadienyl ligand: (C5Me5). Other cyclopentadienyl ligands are fully covered but only discussed in detail, if the ligand causes differences in synthesis or reactivity. Thus, the focus lays on three compounds: [(C5Me5)2Sm], [(C5Me5)2Eu] and [(C5Me5)2Yb] and their solvates. We discuss the synthesis and physical properties of divalent lanthanide metallocenes first, followed by an overview of the reactivity rendering the full potential of these versatile reactants.

Cofacial porphyrin organic cages. Metals regulating excitation electron transfer and CO2 reduction electrocatalytic properties.

Herein, we introduce a comprehensive study of the photophysical behaviors and CO2 reduction electrocatalytic properties of a series of cofacial porphyrin organic cages (CPOC-M, M = H2, Co(ii), Ni(ii), Cu(ii), Zn(ii)), which are constructed by the covalent-bonded self-assembly of 5,10,15,20-tetrakis(4-formylphenyl)porphyrin (TFPP) and chiral (2-aminocyclohexyl)-1,4,5,8-naphthalenetetraformyl diimide (ANDI), followed by post-synthetic metalation. Electronic coupling between the TFPP donor and naphthalene-1,4 : 5,8-bis(dicarboximide) (NDI) acceptor in the metal-free cage is revealed to be very weak by UV-vis spectroscopic, electrochemical, and theoretical investigations. Photoexcitation of CPOC-H2, as well as its post-synthetic Zn and Co counterparts, leads to fast energy transfer from the triplet state porphyrin to the NDI unit according to the femtosecond transient absorption spectroscopic results. In addition, CPOC-Co enables much better electrocatalytic activity for CO2 reduction reaction than the other metallic CPOC-M (M = Ni(ii), Cu(ii), Zn(ii)) and monomeric porphyrin cobalt compartment, supplying a partial current density of 18.0 mA cm-2 at -0.90 V with 90% faradaic efficiency of CO.

Kinetic and mechanistic investigations of dioxygen reduction by a molecular Cu(II) catalyst bearing a pentadentate amidate ligand.

A pentadentate Cu(II) complex, [CuII(dpaq)](ClO4) (1), featuring a redox active ligand, H-dpaq (H-dpaq = 2-[bis(pyridine-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate), catalyses four-electron reduction of dioxygen by decamethylferrocene (Fc*) in the presence of trifluoroacetic acid (CF3COOH) in acetone at 298 K. No catalytic oxygen reduction was observed in the presence of stronger Brønsted acids than CF3COOH, such as perchloric acid (HClO4) or trifluoromethanesulphonic acid (HOTf). In contrast, facile catalytic reduction of O2 occurs by Fc* with 1 and HClO4 or HOTf in dimethylformamide (DMF). The use of CF3COOH as the proton source in DMF results in the suppression of O2 reduction under otherwise identical reaction conditions. While the O2 reduction reactions in DMF are linearly dependent on the pKa of Brønsted acids, the acid dependence on catalytic O2-reduction reactivity by 1 in acetone showed complete reversal. Cyclic voltammetry studies using p-chloranil as the probe substrates in the presence of acids in the solvents reveal that the strengths of the protonic acids increase significantly in acetone compared to that in DMF. The amidate-N in [CuII(dpaq)](ClO4) (1) undergoes protonation in the presence of HClO4 or HOTf in DMF to form [CuII(H-dpaq)]2+ (1-H+), but not in the presence of CF3COOH. Enhanced acid strength of CF3COOH in acetone, however, effectively protonates 1 and triggers O2 reduction. Protonation of 1 with HClO4 or HOTf in acetone results in the change of its coordination environment, and this protonated species does not trigger O2 reduction. Detailed kinetic studies indicate that 1-H+ undergoes reduction by two-electrons and the reduced species binds O2 to form a Cu(II)-superoxo intermediate. This is followed by a rate-determining proton-coupled electron-transfer (PCET) reduction to generate the Cu(II)-hydroperoxo intermediate. While catalytic O2 reduction in acetone occurs predominantly via a 4e-/4H+ pathway, product selectivity (H2O vs. H2O2) in DMF depends upon the concentration of the reductant (Fc*). While dioxygen reduction to H2O2 is favoured at low [Fc*], mechanistic studies suggest that O2 reduction with high [Fc*] proceeds via a [2e- + 2e-] mechanism, where the released H2O2 during catalysis is further reduced to water.

SIRT5-related desuccinylation modification of AIFM1 protects against compression-induced intervertebral disc degeneration by regulating mitochondrial homeostasis

Mitochondrial dysfunction plays a major role in the development of intervertebral disc degeneration (IDD). Sirtuin 5 (SIRT5) participates in the maintenance of mitochondrial homeostasis through its desuccinylase activity. However, it is still unclear whether succinylation or SIRT5 is involved in the impairment of mitochondria and development of IDD induced by excessive mechanical stress. Our 4D label-free quantitative proteomic results showed decreased expression of the desuccinylase SIRT5 in rat nucleus pulposus (NP) tissues under mechanical loading. Overexpression of Sirt5 effectively alleviated, whereas knockdown of Sirt5 aggravated, the apoptosis and dysfunction of NP cells under mechanical stress, consistent with the more severe IDD phenotype of Sirt5 KO mice than wild-type mice that underwent lumbar spine instability (LSI) surgery. Moreover, immunoprecipitation-coupled mass spectrometry (IP-MS) results suggested that AIFM1 was a downstream target of SIRT5, which was verified by a Co-IP assay. We further demonstrated that reduced SIRT5 expression resulted in the increased succinylation of AIFM1, which in turn abolished the interaction between AIFM1 and CHCHD4 and thus led to the reduced electron transfer chain (ETC) complex subunits in NP cells. Reduced ETC complex subunits resulted in mitochondrial dysfunction and the subsequent occurrence of IDD under mechanical stress. Finally, we validated the efficacy of treatments targeting disrupted mitochondrial protein importation by upregulating SIRT5 expression or methylene blue (MB) administration in the compression-induced rat IDD model. In conclusion, our study provides new insights into the occurrence and development of IDD and offers promising therapeutic approaches for IDD.

Rational regulation of peroxymonosulfate activation over porous Co3O4 with carbon coating to boost utilization efficiency of peroxymonosulfate and achieve rapid removal of pollutants

It is of great significance to regulate rationally the activation mechanism of persulfate for promoting the development of sulfate radical-based advanced oxidation processes in wastewater treatment. Herein, carbon coated porous Co3O4 with hollow structure was synthesized. Notably, the formation of porous hollow structure improved specific surface area of Co3O4 and offered more redox couples of Co2+/Co3+, thereby reducing electron transfer resistance. Thus, the generation of reactive oxygen species and the role of high-valent transition metal complexes (namely Co3O4Co4+) were improved. The formation of carbon layer on the Co3O4 surface can avoid the release of Co ion during reaction process. Benefiting from the role of carbon layer in electron transport, catalyst-mediated the direct electron transfer from pollutant to PMS was boosted. Radical and nonradical pathways worked in coordination each other and realized the rapid removal of various organic pollutants in the presence of a little PMS. In short, current work revealed that modulating rationally the microstructure of catalyst was an efficient strategy for achieving controllable regulation of PMS activation process. More significantly, whether the direct electron transfer process can occur or not depended on both catalyst structure and electronic density of pollutants.

Beyond Photosynthesis: H2O/H2O2/O2 Self-Circulation-Based Biohybrid Photoelectrochemical Cells for Direct and Sustainable Solar-to-Fuel-to-Electric Power Conversion.

Solar-to-fuel conversion followed by secondary utilization in fuel cells provides an appealing approach to alleviating global energy shortages but is largely restricted by the complex design of power systems and the development of functional catalysts. Herein, we presented a biohybrid photoelectrochemical cell (BPEC) to implement sustainable solar-to-fuel-to-electric power conversion in a single compartment, by ingeniously combining reliable photoelectrochemical H2O2 generation with efficient bioelectrochemical H2O2 consumption. Specifically, the BPEC is composed of a Mo-modified BiVO4 (Mo:BiVO4) photoanode and a horseradish peroxidase (HRP)/pyrene-modified 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (bis-Pyr-ABTS)/carbon nanotubes with an encapsulated Co nanoparticle (Co/CNTs) biocathode. Upon photoexcitation, two-electron H2O oxidation can be carried out at the Mo-BiVO4 photoanode to produce H2O2, followed by electroenzymatic reduction of H2O2 to H2O by HRP with the help of a bis-Pyr-ABTS redox mediator at the biocathode. Besides, in response to the insufficient Faradaic efficiency of H2O2 generation at the photoanode, the functional Co/CNTs catalysts, possessing prominent electrocatalytic selectivity toward two-electron O2 reduction (electron transfer number = 2.6), are modified on the biocathode, thus clearly defining effective H2O/H2O2/O2 self-circulation in this device. This developed BPEC obtains an open-circuit potential of 1.03 ± 0.02 V and a maximum power density of 0.18 ± 0.02 mW cm-2. Moreover, inspired by the particular advantage of enzymatic biofuel cells for easy miniaturization, an enclosed "sandwich-like" BPEC of approximately 1 cm3 size is fabricated and delivers a power output of 0.13 ± 0.03 mW cm-2. Our work represents a controllable approach for meaningful solar energy utilization, beyond traditional artificial photosynthesis, and can further provide a significant paradigm shift in building an energy-sustainable society.

Dissimilatory manganese reduction facilitates synergistic cooperation of hydrolysis, acidogenesis, acetogenesis and methanogenesis via promoting microbial interaction during anaerobic digestion of waste activated sludge

Anaerobic digestion (AD) of waste activated sludge (WAS) is commonly limited to poor synergistic cooperation of four stages including hydrolysis, acidogenesis, acetogenesis and methanogenesis. Dissimilatory metal reduction that induced by metal-based conductive materials is promising strategy to regulate anaerobic metabolism with the higher metabolic driving force. In this study, MnO2 as inducer of dissimilatory manganese reduction (DMnR) was added into WAS-feeding AD system for mediating complicated anaerobic metabolism. The results demonstrated that main operational performances including volatile solid (VS) degradation efficiency and cumulative CH4 production with MnO2 dosage of 60 mg/g·VS reached up to maximum 53.6 ± 3.4% and 248.2 ± 10.1 mL/g·VS while the lowest operational performances in control group (38.5 ± 2.8% and 183.5 ± 8.5 mL/g·VS) was originated from abnormal operation of four stages. Furthermore, high-throughput 16 S rRNA pyrosequencing revealed that enrichment of dissimilatory manganese-reducing contributors and methanogens such as Thermovirga, Christensenellaceae_R_7_group and Methanosaeta performed the crucial role in short-chain fatty acids (SCFAs) oxidation and final methanogenesis, which greatly optimized operational environment of hydrolysis, acidogenesis and acetogenesis. More importantly, analysis of functional genes expression proved that abundances of genes encoding enzymes participated in acetate oxidation, direct interspecies electron transfer (DIET) and CO2 reduction pathway were simultaneously up-regulated with the optimum MnO2 dosage, suggesting that DMnR with SCFAs oxidation as electron sink could benefit stable operation of four stages via triggering effective DIET-based microbial interaction mode.

Atomic H*-mediated electrochemical removal of low concentration antimonite and recovery of antimony from water

Compounds containing antimony (Sb) are broadly used as starting materials for a wide range of industrial products, leading to serious water pollution associated with Sb rock mining as well as Sb leaching. Herein, we proposed an innovative design of an electrified membrane consisted of bimetallic palladium and iron nanoparticles (Pd-Fe NPs) supported on conductive carbon nanotube (CNT) networks. The nanohybrid filter enabled effective generation and retainment of atomic hydrogen (H*) under an electric field, which further contributed to the complete electroreduction of antimonite (Sb(III)). The highest atomic H* yield and Sb(III) removal kinetics were identified once a potential of −1.0 V vs. Ag/AgCl was exerted. Compared to the pristine CNT, Pd-CNT and Fe-CNT filters, the reaction rate constant of the Pd/Fe-CNT filter was increased 5.15-, 2.39-, and 1.76-fold, respectively for electrochemical removal of Sb(III). The results denoted that the superior performance of the Pd/Fe-CNT nanohybrid filter originated from: (1) the flow-through design, which enhanced mass transport, (2) the bimetallic design, which increased the catalytic activity, and (3) the collective contribution from atomic H*-mediated indirect reduction and direct electron transfer reduction mechanisms. The robust system performance occurred over a broad range of pH values, a variety of water matrices and can withstand several cycles of experiments. Our findings highlight an effective electro-filtration strategy to induce atomic H*-mediated electrochemical removal and recovery of Sb from water.

Radical Redox Annulations: A General Light-Driven Method for the Synthesis of Saturated Heterocycles.

We introduce here a two-component annulation strategy that provides access to a diverse collection of five- and six-membered saturated heterocycles from aryl alkenes and a family of redox-active radical precursors bearing tethered nucleophiles. This transformation is mediated by a combination of an Ir(III) photocatalyst and a Brønsted acid under visible-light irradiation. A reductive proton-coupled electron transfer generates a reactive radical which undergoes addition to an alkene. Then, an oxidative radical-polar crossover step leading to carbocation formation is followed by ring closure through cyclization of the tethered nucleophile. A wide range of heterocycles are easily accessible, including pyrrolidines, piperidines, tetrahydrofurans, morpholines, δ-valerolactones, and dioxanones. We demonstrate the scope of this approach through broad structural variation of both reaction components. This method is amenable to gram-scale preparation and to complex fragment coupling.

Advance in remediated of heavy metals by soil microbial fuel cells: Mechanism and application.

In the past decade, studies on the remediation of heavy metals contaminated soil by microbial fuel cells (MFCs) have attracted broad attention because of the self-generated power and their multifield principles such as the extracellular electron transfer (EET) reduction, electromigration for heavy metals removal. However, given the bio electro-motive power from soil MFCs is weak and fluctuated during the remediation, we need to comprehensively understand the origination of driving force in MFC based on the analysis of the fundamental rationale of ion moving in cells and improve the performance via the appropriate configurations and operations. In this review, we first described the structures of soil MFCs for heavy metals remediation and compared the advantages of different types of configurations. Then, based on the theoretical models of heavy metal migration, enrichment, and reduction in soil MFCs, the optimization of soil MFCs including the length of the remediation area, soil conductivity, control of electrode reaction, and modification of electrodes were proposed. Accordingly, this review contributes to the application of bioelectrochemistry to efficiently remove heavy metals from soils.

Iron-based passivator mitigates the coupling process of anaerobic methane oxidation and arsenate reduction in paddy soils

Arsenic (As) is a toxic metalloid that is ubiquitous in paddy soils, where passivation is the most widely used method for remediating As contamination. Recently, anaerobic methane oxidation coupled with arsenate (As(V)) reduction (AOM-AsR) has been shown to act as a critical driver for As release in paddy fields. However, the effect and mechanism of the passivators on the AOM-AsR process remain unclear. In this study, we incubated arsenate-contaminated paddy soils under anaerobic conditions. Using isotopically labelled methane and different passivators, we found that an iron-based passivator containing calcium sulfate and iron oxide (9:1, m/m) named IBP showed a much better performance than the other passivators. Adding IBP decreased the arsenite (As(III)) concentration in the soil solution by 78% and increased the AOM rate by 55%. Furthermore, we employed high-throughput sequencing and real-time quantitative polymerase chain reaction (qPCR) to investigate the ability of IBP to control As release mediated by AOM-AsR in paddy fields, as well as its underlying mechanism. Our results showed that IBP addition significantly increased anaerobic methanotrophic (ANME) archaea (ANME-2a-c, ANME-2d, and ANME-3) by 91%, and increased the methane-oxidizing bacterium Methylobacter by 262%. Similarly, IBP addition significantly increased the Fe(III) concentration in soil solution by 39% and increased the absolute abundance of Fe(III)-reducing bacteria (Geobacteraceae) by 21 times in soil. Adding IBP may significantly promote AOM coupled with Fe(III) reduction, significantly reducing electron transfer from AOM to As(V) reduction. Hence, IBP may be used as an efficient passivator to remediate As-contaminated soil using an active AOM-AsR process. These results provide a novel insight into controlling soil As release by regulating an active and critical As mobilization pathway in the environment.

Enhanced photocatalytic nitrogen fixation on oxygen doped high specific surface area g-C3N4 under simulated sunlight

Oxygen doped high specific surface area g-C3N4 photocatalysts were synthesized by secondary calcination and microwave hydrothermal method. The photocatalytic properties of the catalysts were evaluated by photocatalytic nitrogen fixation under simulated sunlight. The results indicated that the ammonia producing rate of photocatalyst OCN-10 (treated with 10 vol% hydrogen peroxide solution) reached the maximum (3980 μmol·g−1·h−1), which was 6.24 times that of bulk g-C3N4 (BCN, 638 μmol·g−1·h−1) and 2.46 times that of non-doped catalyst (OCN-0, 1620 μmol·g−1·h−1). Obviously, secondary calcination and oxygen doping led to the enhanced photocatalytic nitrogen fixation performance of OCN-10. To be specific, secondary calcination increased the specific surface area of g-C3N4 and the porous structure provided more nitrogen adsorption sites; Oxygen doping promoted the utilization of visible light, thus leading to a great increment in photoelectrons participating in nitrogen reduction reaction. The outcome of DFT calculation revealed an augmented N2 adsorption energy of −97.31 kJ·mol−1 for oxygen doped g-C3N4 in contrast to an initial adsorption energy of −72.59 kJ·mol−1 for g-C3N4. Stronger adsorption bond facilitated subsequent electron transfer and nitrogen reduction. The as-synthesized highly-efficient photocatalyst can serve as a superior option for clean nitrogen fixation.

Coordination-Induced Bond Weakening.

Coordination-induced bond weakening is a phenomenon wherein ligand X-H bond homolysis occurs in concert with the energetically favorable oxidation of a coordinating metal complex. The coupling of these two processes enables thermodynamically favorable proton-coupled electron transfer reductions to form weak bonds upon formal hydrogen atom transfer to substrates. Moreover, systems utilizing coordination-induced bond weakening have been shown to facilitate the dehydrogenation of feedstock molecules including water, ammonia, and primary alcohols under mild conditions. The formation of exceptionally weak substrate X-H bonds via small molecule homolysis is a powerful strategy in synthesis and has been shown to enable nitrogen fixation under mild conditions. Coordination-induced bond weakening has also been identified as an integral process in biophotosynthesis and has promising applications in renewable chemical fuel storage systems. This review presents a discussion of the advances made in the study of coordination-induced bond weakening to date. Because of the broad range of metal and ligand species implicated in coordination-induced bond weakening, each literature report is discussed individually and ordered by the identity of the low-valent metal. We then offer mechanistic insights into the basis of coordination-induced bond weakening and conclude with a discussion of opportunities for further research into the development and applications of coordination-induced bond weakening systems.

Phosphorus(V) Porphyrin: A Reductive Electron Quencher in Donor-Acceptor Systems

Phosphorus(V) porphyrins hold an important place in porphyrin chemistry. The hexacoordinated phosphorus center in these porphyrins has a formal oxidation state of +5 and is, thus, extremely electron deficient. As a result, the midpoint potential for oxidation of the phosphorus(V) porphyrin is shifted to a much higher value (1.66 V for PTPP+) compared to the corresponding free-base porphyrin (1.01 V for H2TPP) or zinc(II) porphyrin (0.79 V for ZnTPP). In addition, the phosphorus center provides two axial sites for the covalently binding of substituents, allowing a greater range of possibilities for attaching donors and acceptors. By exploiting these properties several ‘axial-bonding’ type Donor-Acceptor systems have been prepared consisting of octaethylporphyrinatophosphorus(V) (POEP+) and tertaphenylporphyrinatophosphorus(V) (PTPP+) units. The unique structural topology of the octaethylporphyrinatophosphorus(V) (POEP+) and tertaphenylporphyrinatophosphorus(V) (PTPP+) enabled the construction of mono- and di-substituted phosphorus(V) porphyrin-naphthalene conjugates, respectively. Transient absorption studies revealed rapid deactivation of singlet excited phosphorus(V) porphyrin due to the reductive electron transfer process. I will present some of these examples and discuss their structural, redox, and photophysical properties. Figure 1

Understanding CO2 Electrolysis Reactionmechanisms Via pH and Isotopic Labeling Studies

CO2 electrolysis is a highly useful technique allowing us to upconvert society’s major greenhouse gas into a variety of useful chemicals. However, mechanistically the process is still not totally understood both in 2 electron reduction products (e.g. CO) and in >2e- reduced products (e.g. ethanol/ethylene). This work will discuss using pH variations and deuterium to gain further insight into these mechanisms.One area of debate for 2 electron transfer reduction products such as CO and formate is whether the rate limiting step involves a proton, a water molecule, or is simply due to adsorption of the CO2 onto the surface. This work will show the benefits of using deuterated water to help resolve this mechanism. By focusing on catalysts geared towards 2 electron transfer reactions to either formate or CO, we have a simple system to break down the mechanism into the reaction order in terms of protons and water molecules. Variations in pH from 3-7 allows us to show the influence of protons for CO or formate, with H2 evolution on a given catalysts acting as a benchmark. Using deuterated water allows us to denote the influence of water, again using H2 evolution as a benchmark catalyst. Combining both these influences we can mechanistically break down the reactions to denote the mechanism of the rate limiting step. (Since we have obtained relatively straight Tafel slopes over 3 orders of magnitude in current, this entails mass transfer is not significantly influencing our results.)From our results we show that Au and Ag produce a self-consistent mechanism for CO2 to CO reduction, whereas Sn and In produce a self-consistent mechanism for formate evolution. Pd is unique in that it has the ability to solvate hydrogen and deuterium, thus the combined pH variations and deuterium demonstrates how this effect influences our mechanistic understanding.For greater than 2 electron transfer processes (using Cu) two of the major issues are determining the rate limiting step and the branching point between ethanol and ethylene. We will show how variations in pH and using deuterated water can give insight into both of the aforementioned issues.