Direct Electrochemical Oxidation Research Articles

Multiplexed Fluoro-electrochemical Single-Molecule Counting Enabled by SiC Semiconducting Nanofilm.

A major challenge for ultrasensitive analysis is the high-efficiency determination of different target single molecules in parallel with high accuracy. Herein, we developed a quantitative fluoro-electrochemical imaging approach for direct multiplexed single-molecule counting with a SiC-nanofilm-modified indium tin oxide transparent electrode. The nanofilm could control local pH through proton-coupled electron transfer in a lower potential range and further induce direct electrochemical oxidation of the dye molecules with a higher applied potential. The fluoro-electrochemical responses of immobilized single molecules with different pH values and redox behaviors could thus be distinguished within the same fluorescence channels. This method yields nonamplified direct counting of single molecules, as indicated by excellent linear responses in the picomolar range. The successful distinction of seven different randomly mixed dyes underscores the versatility and efficacy of the proposed method in the highly accurate determination of single dye molecules, paving the way for highly parallel single-molecule detection for diverse applications.

Unveiling Direct Electrochemical Oxidation of Methane at the Ceria/Gas Interface.

Solid oxide fuel cells (SOFCs) stand out in sustainable energy systems for their unique ability to efficiently utilize hydrocarbon fuels, particularly those from carbon-neutral sources. CeO2-δ (ceria) based oxides embedded in SOFCs are recognized for their critical role in managing hydrocarbon activation and carbon coking. However, even for the simplest hydrocarbon molecule, CH4, the mechanism of electrochemical oxidation at the ceria/gas interface is not well understood and the capability of ceria to electrochemically oxidize methane remains a topic of debate. This lack of clarity stems from the intricate design of standard metal/oxide composite electrodes and the complex nature of electrode reactions involving multiple chemical and electrochemical steps. This study presents a Sm-doped ceria thin-film model cell that selectively monitors CH4 direct-electro-oxidation on the ceria surface. Using impedance spectroscopy, operando X-ray photoelectron spectroscopy, and density functional theory, it is unveiled that ceria surfaces facilitate C─H bond cleavage and that H2O formation is key in determining the overall reaction rate at the electrode. These insights effectively address the longstanding debate regarding the direct utilization of CH4 in SOFCs. Moreover, these findings pave the way for an optimized electrode design strategy, essential for developing high-performance, environmentally sustainable fuel cells.

Novel Cu(200)/Ti cathode for the enhancement of N2 selectivity in direct ammonia electrolysis: The controls of Cu cathode facet orientation

Direct electrochemical ammonia oxidation reaction (AOR) using NiCu-based anodes is effective in removing ammonia from wastewater. However, this type of anode frequently produces undesired byproducts NO3−. Here, we investigated three configurations of novel Cu/Ti cathodes (Cu(111)/Ti, Cu(200)/Ti, Cu(220)/Ti) coupled with Cu/Ni foam (Cu/NF) anode to enhance N2 selectivity (SN2) in a direct ammonia electrolysis cell. Cu(200)/Ti cathode improved SN2 from 35 % (bare Ti cathode) to 60 % and it achieved 10–15 % higher SN2 compared to Cu(111)/Ti and Cu(220)/Ti. The improvement of SN2 on Cu(200) facet was ascribed to the high nitrate electroreduction activity and its conversion to N2. In real wastewater, Cu/NF anode-Cu(200)/Ti cathode paired electrolysis system demonstrated its excellent capability of 88 % NH3 removal with 95 % SN2. Our electrolysis system was capable to maintain the residual NH3-N and the NO3-N below 8 mg L−1, meeting effluent discharge standards. Our findings highlighted the importance of the control of Cu cathode facet orientations for an efficient elimination of NO3– and improvement of N2 production during direct ammonia electrolysis.

Tailoring Defects in B, N-Codoped Carbon Nanowalls for Direct Electrochemical Oxidation of Glyphosate and its Metabolites.

Tailoring the defects in graphene and its related carbon allotropes has great potential to exploit their enhanced electrochemical properties for energy applications, environmental remediation, and sensing. Vertical graphene, also known as carbon nanowalls (CNWs), exhibits a large surface area, enhanced charge transfer capability, and high defect density, making it suitable for a wide range of emerging applications. However, precise control and tuning of the defect size, position, and density remain challenging; moreover, due to their characteristic labyrinthine morphology, conventional characterization techniques and widely accepted quality indicators fail or need to be reformulated. This study primarily focuses on examining the impact of boron heterodoping and argon plasma treatment on CNW structures, uncovering complex interplays between specific defect-induced three-dimensional nanostructures and electrochemical performance. Moreover, the study introduces the use of defect-rich CNWs as a label-free electrode for directly oxidizing glyphosate (GLY), a common herbicide, and its metabolites (sarcosine and aminomethylphosphonic acid) for the first time. Crucially, we discovered that the presence of specific boron bonds (BC and BN), coupled with the absence of Lewis-base functional groups such as pyridinic-N, is essential for the oxidation of these analytes. Notably, the D+D* second-order combinational Raman modes at ≈2570 cm-1 emerged as a reliable indicator of the analytes' affinity. Contrary to expectations, the electrochemically active surface area and the presence of oxygen-containing functional groups played a secondary role. Argon-plasma post-treatment was found to adversely affect both the morphology and surface chemistry of CNWs, leading to an increase in sp3-hybridized carbon, the introduction of oxygen, and alterations in the types of nitrogen functional groups. Simulations support that certain defects are functional for GLY rather than AMPA. Sarcosine oxidation is the least affected by defect type.

In situ electro-generated Ni(OH)2 synergistic with Cu cathode to promote direct ammonia oxidation to nitrogen.

To solve the problem of low removal rate and poor N2 selectivity in direct electrochemical ammonia oxidation (EAO), commercial Ni foam and Cu foam were used as anode and cathode of the EAO system, respectively. The coupling effect between the cathode and anode promoted nitrogen cycling during the reaction process, which improved N2 selectivity of the reaction system and promoted it to achieve a high ammonia removal rate. This study showed that the thin Ni(OH)2 with oxygen vacancy formed on the surface of Ni foam anode played an effective role in the dimerization of intermediate products in ammonia oxidation to form N2. This electrochemical system was used to treat real goose wastewater containing 422.5 mg/L NH4+-N and 94.5 mg/L total organic carbon (TOC). After treatment, this electrochemical system achieved good performance with an ammonia removal rate of 87%, N2 selectivity of 77%, and TOC removal rate of 72%. Therefore, this simple and efficient system with Ni foam anode and Cu foam cathode is a promising method for treating ammonia nitrogen wastewater.

Treatment of Organics in Wastewater Using Electrogenerated Gaseous Oxidants.

This work focuses on the comparison of the performance of direct electrochemical oxidation with indirect electrolysis mediated by gaseous oxidants in the treatment of diluted wastewater. To do this, energy consumptions of the electrolysis using mixed metal oxide (MMO) electrodes are compared with those required for the production and use of chlorine dioxide in the degradation of methomyl contained in aqueous solutions. Results demonstrate the feasibility of the mediated oxidation process and that this process is competitive with direct oxidation. The oxidants are produced under optimized conditions using the same anodic material applied for the direct degradation of organics, thus avoiding efficiency losses associated with mass transfer limitations in the degradation of dilute organic solutions. Thus, using the ClO2 gaseous oxidant, a concentration of 0.1 mM of methomyl from a solution containing 500 mL is completely removed with an energy consumption as low as 50 Wh. The application of the same energy to a direct electrolytic process for treating the same wastewater can only reach less than half of this removal. These findings may have a very important application in the use of electrochemical technology to achieve the remediation of persistent pollutants in wastewater, where their low concentrations typically make direct processes very inefficient.

Electrochemical Determination of Fentanyl Using Carbon Nanofiber-Modified Electrodes.

In this work, we report the direct electrochemical oxidation of fentanyl using commercial screen-printed carbon electrodes (SPCEs) modified with carboxyl-functionalized carbon nanofibers (fCNFs). CNFs have surface chemistry and reactivity similar to carbon nanotubes (CNTs), yet they are easier to produce and are of a lower cost than CNTs. By monitoring the current produced during the electrochemical oxidation of fentanyl, variables such as fCNF loading, fentanyl accumulation time, electrolyte pH, and differential pulse voltammetry parameters were optimized. Under an optimized set of conditions, the fCNF/SPCEs responded linearly to fentanyl in the concentration range of 0.125-10 μM, with a limit of detection of 75 nM. The fCNF/SPCEs also demonstrated excellent selectivity against common cutting agents found in illicit drugs (e.g., glucose, sucrose, caffeine, acetaminophen, and theophylline) and interferents found in biological samples (e.g., ascorbic acid, NaCl, urea, creatinine, and uric acid). The performance of the sensor was also successfully tested using fentanyl spiked into an artificial urine sample. The straightforward electrode assembly process, low cost, ease of use, and rapid response make the fCNF/SPCEs prime candidates for the detection of fentanyl in both physiological samples and street drugs.

A Novel Synthesis of Nickel Carbide Modified Glassy Carbon Electrode for Electrochemical Investigation of Archetypal Diabetes Biomarker in Human Serum and Urine Samples

We began with an exploration of a novel method for non-enzymatic glucose sensing through the direct electrochemical oxidation process using an annealed Nickel carbide (Ni3C) modified glassy carbon electrode (GCE). We cover the synthesis and detailed characterization of Ni3C, the modification process of the electrode, and its application in the electrocatalytic detection of glucose in human blood and urine samples. Ni3C, known for its high charge transfer efficiency, exceptional stability in harsh environments, and outstanding electrochemical activity, was prepared through an annealing method. The produced Ni3C, characterized by a nanoplate structure ranging from 20 to 50 nanometers, was applied to a GCE to benefit from its extensive surface area and structural robustness. Electrochemical impedance spectroscopy and cyclic voltammetry confirmed the superior electrocatalytic properties and charge transfer capabilities of Ni3C/GCE over the unmodified GCE. The glucose detection was achieved by the direct electrochemical oxidation of glucose on the modified electrode, showcasing a linear detection range from 0.05 to 2236 μM and an impressively low detection limit of 0.0186 μM. This research underscores the effectiveness of Ni3C/GCE as durable, efficient, and reliable tools for the non-enzymatic electrochemical sensing of glucose, providing new prospects for diabetes monitoring.

Efficient removal of ammonia nitrogen via a coupled system of Ni1Cu0.2-Se-T/CP anode and copper foam cathode

Direct electrochemical oxidation is a green, clean and promising process for the treatment of ammonia nitrogen (NH4+-N) wastewater. Nevertheless, drawbacks of slow reaction kinetics and large overpotential greatly limit the ammonia oxidation reaction. To address the issue, Ni1Cu0.2-Se-T/CP was synthesized by the combination of heteroatom doping and in situ electrochemical oxidation (ISEO). Physical characterization shows that there are homogeneous and dense microscopic nanosphere particles on the electrode surface, which provide good attachment sites for the adsorption of reactants. Electrochemical tests further show that this catalytic electrode exhibits not only a high current density (37.17 mA·cm−2) at 0.65 V vs.Hg/HgO but also has the low Tafel slope (92.25 mV·dec−1) to ammonia oxidation reaction. Then, Ni1Cu0.2-Se-T/CP was applied as anode with copper as cathode to construct a coupled system. The area ratio of cathode/anode was optimized to improve the removal effect of ammonia nitrogen. The NH4+-N conversion efficiency of 100% was obtained at a constant anode potential of 0.65 V vs.Hg/HgO for 15 h when the cathode/anode area was 1:4. The system N2 selectivity up to 77.55%. This work provides a promising process for the green and efficient degradation of ammonia nitrogen wastewater.

Tuning Cu2O morphologies of Cu2O/Ni foam electrodes for the control of reactivity and nitrogen selectivity in direct ammonia electrooxidation reaction

Direct electrochemical oxidation of ammonia (AEO) using non-precious metal catalysts is an energy-efficient and low-carbon-footprint method for ammonia removal from wastewater. In this work, Cu2O with three types of morphologies, including flower, particle, and sheet, were electrodeposited on Ni foam substrates (Cu2O/NF) for direct AEO. The Cu2O flower-deposited NF electrode showed the largest electrochemical surface area (19.6 cm2) and the smallest Cu2O size (200–600 nm) among all Cu2O/NF electrodes. In the ammonia solution, the peak current densities of direct AEO from cyclic voltammograms (CVs) at 10 mVs−1 on the Cu2O flower, Cu2O particle, and Cu2O sheet-deposited NF electrodes reached 4.6, 3.1, and 2.2 mAcm−2, respectively. The result showed that, at an initial pH of 11 and an applied potential of 0.95 V vs. Hg/HgO, the order of three types of Cu2O morphologies with respect to ammonia removal efficiency and rate is: Cu2O flower (52%, 4.1×10−3 min−1) > Cu2O particle (38%, 2.6×10−3 min−1) > Cu2O sheet (30%, 1.8×10−3 min−1). Interestingly, ammonia oxidation to N2 on the Cu2O sheet-deposited NF electrode exhibited the highest selectivity (SN2: 60%), which was much higher than the Cu2O flower-deposited NF electrode (SN2: 31%). The high SN2 of Cu2O sheets was ascribed to the presence of the stable Cu(I) sheet structure during direct AEO, confirmed by X-ray photoelectron spectroscopy analysis. On the other hand, the Cu(II)-rich flower structure facilitated the formation of NO3-. Our findings demonstrate that the surface morphologies of Cu2O deposited on the NF electrode show significant stability difference of Cu(I), which determines reactivity and N selectivity during direct AEO.

Simple and sensitive voltammetric sensor for in‐situ clinical and environmental 17‐β‐estradiol monitoring

AbstractThe direct electrochemical oxidation of 17‐β‐estradiol (E2) at conventional electrodes gives weak current signals making detection at trace levels difficult, as required for clinical and environmental applications. In order to strengthen the electrochemical behavior of E2, a simple and sensitive sensor has been realized based on a graphite screen printed electrode (GSPE) functionalized according to a two‐step procedure: i) drop‐casting deposition of gold nanoparticles (AuNPs); ii) electropolymerization of methylene blue (MB). The final PMB‐AuNPs‐GSPE platform was characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The pH value was optimized in order to obtain the best detection efficiency and the highest peak current response was obtained at pH 7.0. The synergistic contributions of both AuNPs and PMB allowed the proposed sensor to show a wide linear range from 0.5 to 125.0 μmol L−1 with a LOD of 41 nmol L−1, long‐term stability and good reproducibility (RSD=2.9 % for n=10). Moreover, the sensor was able to distinguish E2 from several interfering compounds commonly present in urine and river water as well as from other endocrine‐ disrupting chemicals (EDCs), denoting its high specificity to E2 molecule. Finally, the developed electrode platform was successfully applied to the determination of E2 in both human urine and river water samples without any purification step under the standard addition method.

Comparison of photoinduced and electrochemically induced degradation of venlafaxine.

The European Union requires environmental monitoring of the antidepressant drug venlafaxine. Advanced oxidation processes provide a remedy against the spread of micropollutants. In this study, the photoinduced and electrochemical decompositions of venlafaxine were investigated in terms of mechanism and efficacy using high-performance liquid chromatography coupled to high-resolution multifragmentation mass spectrometry. Kinetic analysis, structure elucidation, matrix variation, and radical scavenging indicated the dominance of a hydroxyl-mediated indirect mechanism during photodegradation and hydroxyl and direct electrochemical oxidation for electrochemical degradation. Oxidants, sulfate, and chloride ions acted as accelerants, which reduced venlafaxine half-lives from 62 to 25 min. Humic acid decelerated degradation during ultra-violet irradiation up to 50%, but accelerated during electrochemical oxidation up to 56%. In silico quantitative structure activity relationship analysis predicted decreased environmental hazard after advanced oxidation process treatment. In general, photoirradiation proved more efficient due to faster decomposition and slightly less toxic transformation products. Yet, matrix effects would have to be carefully evaluated when potential applications as a fourth purification stage were to be considered.

Bielectrode Strategy for Determination of CYP2E1 Catalytic Activity: Electrodes with Bactosomes and Voltammetric Determination of 6-Hydroxychlorzoxazone.

We describe a bielectrode system for evaluation of the electrocatalytic activity of cytochrome P450 2E1 (CYP2E1) towards chlorzoxazone. One electrode of the system was employed to immobilize Bactosomes with human CYP2E1, cytochrome P450 reductase (CPR), and cytochrome b5 (cyt b5). The second electrode was used to quantify CYP2E1-produced 6-hydroxychlorzoxazone by its direct electrochemical oxidation, registered using square-wave voltammetry. Using this system, we determined the steady-state kinetic parameters of chlorzoxazone hydroxylation by CYP2E1 of Bactosomes immobilized on the electrode: the maximal reaction rate (Vmax) was 1.64 ± 0.08 min-1, and the Michaelis constant (KM) was 78 ± 9 μM. We studied the electrochemical characteristics of immobilized Bactosomes and have revealed that electron transfer from the electrode occurs both to the flavin prosthetic groups of CPR and the heme iron ions of CYP2E1 and cyt b5. Additionally, it has been demonstrated that CPR has the capacity to activate CYP2E1 electrocatalytic activity towards chlorzoxazone, likely through intermolecular electron transfer from the electrochemically reduced form of CPR to the CYP2E1 heme iron ion.

A perylene diimide electrochemical probe with persulfate as a signal enhancer for dopamine sensing.

Dopamine (DA) is an important biomarker related to parkinsonism, schizophrenia and renal disease. Traditional electrochemical sensors for DA were based on the direct electrochemical oxidation of DA. In this paper, we report a new sensing strategy using N,N'-di(trimethylaminoethyl)perylene diimide (TMPDI) as an electrochemical probe and K2S2O8 as a signal enhancer for DA detection between 0 and -0.7 V with the DPV technique. MoS2 nanoflowers prepared by the hydrothermal method were used as a nanocarrier to load TMPDI. The reduction current of TMPDI was found to show a stepwise and significant increase at -0.24 V with the increase of concentration of K2S2O8 due to the continuous cycle of TMPDI molecules' electrochemical reduction and chemical oxidation. The presence of DA caused a large decrease of the reduction current of TMPDI due to the synergistic interaction of the competitive consumption of DA for K2S2O8 and the blocking effect of polyDA adhering to the electrode surface. The decreased current exhibited a linear response for DA from 10 pM to 100 μM with a detection limit of 4.1 pM and the proposed sensor showed high selectivity and excellent feasibility in human urine/serum sample detection.

Promoting mass transfer by tri-functional carriers for high performance direct electrochemical oxidation process

Direct electrochemical oxidation process was attractive for selective and low energy consumped removal of pollutant. However, it was lengty and low efficient due to limited mass transferation by the slow two-stage mass transfer in solution and the hydrodynamic boundary layer on electrodes. Here, we introduce an innovative single-stage carrier concept to address the identified bottleneck. The carrier, comprised of magnetic biochar nanoparticles, exhibits high conductivity, magnetic separability, and strong adsorption towards 17β-estradiol. Utilizing this carrier, we were able to transfer 93.23 % of 17β-estradiol in solution to the electrodes within a significantly reduced time of 17 min, compared to 187.82 h via diffusion and 1.73 h via convection, thus demonstrating enhanced mass transfer. Furthermore, we achieved a remarkably low energy consumption of 0.11 Wh/g, a fourfold increase in the net oxidation rate, and a 70.28 % improvement in oxidation efficiency compared to processes without carrier involvement. These results underscore the significant potential of carrier usage in enhancing the performance of direct electrochemical oxidation processes by modulating mass transfer.

Efficient Synthesis of Nitric Acid Under Air Atmosphere with Lattice-Confined Ru Clusters

Nitrate (NO3 -) is an important industrial chemical used as fertilizers in agriculture, as well as oxidizing agents in explosives. Today, NO3 - is manufactured predominantly via an Ostwald process by oxidizing ammonia (NH3), and the ammonia used here comes primarily from the Haber–Bosch (HB) process.However, this process operates at high temperatures (300–500 °C) and pressures (200–300 bar), and requires a coupled steam reforming plant for hydrogen (H2) production. As a result, approximately 1.9 metric tons of CO2 is formed per metric ton of NH3 produced, contributing significantly to climate change. In addition, due to the complexity of the Ostwald and Haber-Bosch processes, it is only economical at large scales, leading to centralized production, which situation is poorly matched with the distributed nature of HNO3 utilization. Therefore, it is highly desirable to bypass the ammonia route and develop a direct and sustainable approach for HNO3 synthesis.Electrochemical synthesis of chemicals has been regarded as an attractive alternative to traditional thermochemical methods. In electrochemical reactions, electric potential can replace high temperature and pressure as the thermodynamic driving force.Therefore, direct electrochemical oxidation of molecular nitrogen appears to be a very potential approach for HNO3 synthesis,which could be sustainable, modular and easily integrated with intermittent renewable electricity. However, due to the lack of natural or artificial electrocatalysts as a reference, the nitrogen oxidation reaction (NOR) remains largely unexplored despite its enormous practical value as a replacement for the fossil fuel-driven two-step HNO3 preparation approach.Until 2019, Zhang et al. reported the first experimental NOR electrocatalyst composed of well-dispersed Pd nanoparticles on MXene nanosheets that can effectively convert N2 into nitrate, which definitely proved the feasibility of using electrochemistry to motivate the endothermic NOR at ambient conditions. Unfortunately, to date, there are still only a few works that reported the electrosynthesis of nitrate from nitrogen, and the proposed electrocatalysts can only achieve limited NOR activity.An in-depth exploration of the NOR process, which consists of two main steps: the first step is a rate-limiting step that converts inert N2 into the active NO* intermediate; the second step is a nonelectrochemical step where NO* reacts with H2O and the generated O* from electrocatalytic water splitting to form nitrate. Therefore, the main factors restricting the development of the electrochemical nitrate synthesis technology can be inferred as follows: (1) the strong N≡N triple bond in the dinitrogen molecule (bond energy: 940.95 kJ mol−1) is highly challenging to oxidate nitrogen to nitrate under mild conditions; (2) the potential window between the NOR and oxidation evolution reaction (OER) is quite narrow, and thus the latter as a competitive reaction can severely restrict the selectively of the nitrogen oxidation synthesis of nitrate; (3) the extremely low solubility and diffusion coefficient of N2 in aqueous electrolytes can significantly inhibit the nitrogen available for the reaction, resulting in unfavorable NOR performance. Therefore, to overcome the above obstacles, extensive studies should focus on designing efficient nitrogen oxidation catalysts and improving electrochemical reaction systems to promote NOR and suppress OER.In the present work, we firstly discovered that synthesizing Ru particles grow along the TiO2 lattice (Ru-TiO2) as the working electrode and can achieve excellent NOR performance by using air as a gas source. Textural analysis sufficiently demonstrates that the matching lattice constants of metal Ru and TiO2 allow the Ru to be confined in the TiO2 lattice, leading to the formation of Ru-Ti bonds and the transfer of electrons from TiO2 to Ru metal. Our results reveal that the electron redistribution of Ru-TiO2 can significantly alter the electronic structure of Ru, leading to the formation of highly occupied Ru 4d bands, which can effectively change the adsorption of surface species and improve the NOR activity. In addition, the Ru confined in TiO2 exhibits particularly high stability towards NOR up to potentials above 1.7 V (versus RHE). As a result, Ru-TiO2 could achieve a record-high NOR performance with a nitric acid yield rate of 18.71 ug h-1 cm-2 (150.2 μmol h-1 g-1) and Faraday efficiency of 25.17% in the air atmosphere. This discovery suggests that the surface oxophilicity and electronic structure of metal particles can be effectively modified by lattice confinement in semiconductors and offers an alternative concept for designing catalysts with unique properties for use in catalysis and beyond. Figure 1

β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations

β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations

Direct Electrochemical Oxidation of Benzylic C–H Bond by La2O3@C/CP Composite Electrode with Water as the Green Oxygen Source

Direct Electrochemical Oxidation of Benzylic C–H Bond by La₂O₃@C/CP Composite Electrode with Water as the Green Oxygen Source

Unraveling Multiple Pathways of Electron Donation from Phenolic Moieties in Natural Organic Matter.

Natural organic matter (NOM) exhibits a distinctive electron-donating capacity (EDC) that serves a pivotal role in the redox reactions of contaminants and minerals through the transformation of electron-donating phenolic moieties. However, the ambiguity of the molecular transformation pathways (MTPs) that engender the EDC during NOM oxidation remains a significant issue. Here, MTPs that contribute to EDC were investigated by identifying the oxidized products of phenolic model compounds and NOM samples in direct or mediated electrochemical oxidation (DEO or MEO, respectively) using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). It was found that the oxidation of newly formed phenolic-OH (ArOH) and the oxidative coupling reaction of the phenoxy radical are the main MTPs that directly contribute to EDC, in addition to the transformation of hydroquinones to quinones. Notably, the oxidative coupling reaction of ArOH contributed at least 22-42% to the EDC. Ferulic acid-like structures can also directly contribute to EDC by incorporating H2O into their acrylic substituents. Furthermore, the opening of C rings can indirectly attenuate the EDC through structural alterations in the electron-donating process of NOM. Decarboxylation can either weaken or enhance the EDC depending on the structure of the phenolic moieties in NOM. These findings suggest that the EDC of NOM is a comprehensive result of multiple NOM MTPs, involving not only ArOH oxidation but also the addition of H2O to olefinic bonds and bond-breaking reactions. Our work provides molecular evidence that aids in the comprehension of the multiple EDC-associated transformation pathways of NOM.

Oxidation Chemistry of Bicarbonate and Peroxybicarbonate: Implications for Carbonate Management in Energy Storage.

Carbonate formation presents a major challenge to energy storage applications based on low-temperature CO2 electrolysis and recyclable metal-air batteries. While direct electrochemical oxidation of (bi)carbonate represents a straightforward route for carbonate management, knowledge of the feasibility and mechanisms of direct oxidation is presently lacking. Herein, we report the isolation and characterization of the bis(triphenylphosphine)iminium salts of bicarbonate and peroxybicarbonate, thus enabling the examination of their oxidation chemistry. Infrared spectroelectrochemistry combined with time-resolved infrared spectroscopy reveals that the photoinduced oxidation of HCO3- by an Ir(III) photoreagent results in the generation of the short-lived bicarbonate radical in less than 50 ns. The highly acidic bicarbonate radical undergoes proton transfer with HCO3- to furnish the carbonate radical anion and H2CO3, leading to the eventual release of CO2 and H2O, thus accounting for the appearance of H2O and CO2 in both electrochemical and photochemical oxidation experiments. The back reaction of the carbonate radical subsequently oxidizes the Ir(II) photoreagent, leading to carbonate. In the absence of this back reaction, dimerization of the carbonate radical provides entry into peroxybicarbonate, which we show undergoes facile oxidation to O2 and CO2. Together, the results reported identify tangible pathways for the design of catalysts for the management of carbonate in energy storage applications.