Adsorption of per- and poly-fluoroalkyl substances (PFAS) on Ni: A DFT investigation.

Electrocatalytic destruction of per- and polyfluoroalkyl substances (PFAS) is an emerging approach for treatment of PFAS-contaminated water. In this study, a systematic ab initio investigation of PFAS adsorption on Ni, a widely used electrocatalyst, was conducted by means of dispersion-corrected Density Functional Theory (DFT) calculations. The objective of this investigation was to elucidate the adsorption characteristics and charge transfer mechanisms of different PFAS molecules on Ni surfaces. PFAS adsorption on three of the most thermodynamically favorable Ni surface facets, namely (001), (110), and (111), was investigated. Additionally, the role of PFAS chain length and functional group was studied by comparing the adsorption characteristics of different PFAS compounds, namely perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS), and perfluorobutanoic acid (PFBA). For each PFAS molecule-Ni surface facet pair, different adsorption configurations were considered. Further calculations were carried out to reveal the effect of solvation, pre-adsorbed atomic hydrogen (H), and surface defects on the adsorption energy. Overall, the results revealed that the adsorption of PFAS on Ni surfaces is energetically favorable, and that the adsorption is primarily driven by the functional groups. The presence of preadsorbed H and the inclusion of solvation produced less exothermic adsorption energies, while surface vacancy defects showed mixed effects on PFAS adsorption. Taken together, the results of this study suggest that Ni is a promising electrocatalyst for PFAS adsorption and destruction, and that proper control for the exposed facets and surface defects could enhance the adsorption stability.

Small-Molecule Adsorption Energy Predictions for High-Throughput Screening of Electrocatalysts.

Predicting adsorption energies of small molecules (e.g., OH, OOH, CO) on electrocatalysts involved in electrochemical reactions aids in accelerating the design and screening of electrocatalysts. Avoiding computationally expensive electronic structure calculations increases the speed of such predictions. Geometric and electronic descriptors have been reported to characterize the environment around surface active sites and predict adsorption energies. However, these descriptors cannot be used to predict adsorption energies of small molecules on various substrates, e.g., metal-oxide and nonmetal electrocatalysts. We compare the performance of these descriptors in predicting adsorption energies of small molecules on various electrocatalysts with adsorption energies calculated from density functional theory. We show that two recently developed machine learning algorithms, Crystal Graph Convolutional Neural Network (CGCNN) and Atomistic Line Graph Neural Network (ALIGNN), outperform the reported descriptors based on geometric (coordination number of the active site and its nearest neighbors) and electronic (the bond-energy-integrated orbitalwise coordination number, the electronegativity, and the number of valence electrons of the active site) properties in predicting the adsorption energies. Our results suggest that ALIGNN is almost always more accurate than CGCNN in adsorption energy predictions. The improvement ranges from 0.02 to 1.0 eV in the mean absolute errors (MAEs). We also compare the performance of CGCNN and ALIGNN algorithms in predicting the overpotentials of the oxygen evolution reaction occurring on various electrocatalysts with MAEs of 0.06 and 0.05 V, respectively.

Electrocatalytic Perchlorate Reduction Using an Oxorhenium Complex Supported on a Ti4O7 Reactive Electrochemical Membrane.

An organometallic rhenium catalyst was deposited on a Ti4O7 reactive electrochemical membrane (Re/REM) for the electrocatalytic reduction of aqueous ClO4- to Cl-. Results showed increasing ClO4- reduction upon increasing cathodic potential (i.e., -0.4 to-1.7 V/SHE). A 5 mM ClO4- solution was reduced by ∼21% in a single pass (residence time ∼0.2 s) through the Re/REM at a pH of 7, with >99% Cl- selectivity and a current efficiency of ∼100%. Kinetic analysis indicated that the reaction rate constant increased from 3953 to 7128 L h-1 gRe-1 at pH values of 9 to 3, respectively, and was mass transport-limited at pH < 5. The rate constants were 2 orders of magnitude greater than reported values for an analogous catalytic system using hydrogen as an electron donor. A continuous flow Re/REM system reduced 1 ppm ClO4- in a groundwater sample by >99.9% for the first 93.5 h, and concentrations were lower than the EPA ClO4- guideline (56 ppb) for 374 h of treatment. The fast ClO4- reduction kinetics and high chloride selectivity without the need for acidic conditions and a continual hydrogen electron donor supply for catalyst regeneration indicate the promising ability of the Re/REM for aqueous electrocatalytic ClO4- treatment.

Pyrogenic carbon-promoted haloacetic acid decarboxylation to trihalomethanes in drinking water.

Drinking water disinfection by chlorination or chloramination can result in the formation of disinfection byproducts (DBPs) such as haloacetic acids (HAAs) and trihalomethanes (THMs). Pyrogenic carbonaceous matter (PCM), such as activated carbon (AC), is commonly used as an ostensibly inert adsorbent to remove HAAs from water. HAA degradation has been mainly attributed to biological factors. This study, for the first time, revealed that abiotic HAA degradation in the presence of PCM could be important under water treatment conditions. Specifically, we observed complete destruction of Br3AA, a model HAA, in the presence of powder AC at pH 7 within 30 min. To understand the role of PCM and the reaction mechanism, we performed a systematic study using a suite of HAAs and various PCM types. We found that PCM significantly accelerated the transformation of three HAAs (Br3AA, BrCl2AA, Br2ClAA) at pH 7. Product characterization indicated an approximately 1:1 HAA molar transformation into their respective THMs following a decarboxylation pathway with PCM. The Br3AA activation energy (Ea) was measured by kinetic experiments at 15-45 °C with and without a model PCM, wherein a significant decrease in Ea from 25.7 ± 3.2 to 13.6 ± 2.2 kcal•mol-1 was observed. We further demonstrated that oxygenated functional groups on PCM (e.g., -COOH) can accelerate HAA decarboxylation using synthesized polymers to resemble PCM. Density functional theory simulations were performed to determine the enthalpy of activation (ΔH‡) for Br3AA decarboxylation with H3O+ and formic acid (HCOOH). The presence of HCOOH significantly lowered the overall ΔH‡ value for Br3AA decarboxylation, supporting the hypothesis that -COOH catalyzes the C-C bond breaking in Br3AA. Overall, our study demonstrated the importance of a previously overlooked abiotic reaction pathway, where HAAs can be quickly converted to THMs with PCM under water treatment relevant conditions. These findings have substantial implications for DBP mitigation in water quality control, particularly for potable water reuse or pre-chlorinated water that allow direct contact between HAAs and AC during filtration as well as PAC fines traveling with finished water in water distribution systems. As such, the volatilization and relative low toxicity of volatile THMs may be considered as a detoxification process to mitigate adverse DBP effects in drinking water, thereby lowering potential health risks to consumers.

Facing the Challenge of Poly- and Perfluoroalkyl Substances in Water: Is Electrochemical Oxidation the Answer?

Electrochemical treatment systems have the unique ability to completely mineralize poly- and perfluoroalkyl substances (PFASs) through potential-driven electron transfer reactions. In this review, we discuss the state-of-the-art on electrooxidation of PFASs in water, aiming at elucidating the impact of different operational and design parameters, as well as reported mechanisms of PFAS degradation at the anode surface. We have identified several shortcomings of the existing studies that are largely limited to small-scale laboratory batch systems and unrealistic synthetic solutions, which makes extrapolation of the obtained data to real-world applications difficult. PFASs are surfactant molecules, which display significant concentration-dependence on adsorption, electrosorption, and dissociation. Electrooxidation experiments conducted with high initial PFAS concentration and/or in high conductivity supporting electrolytes likely overestimate process performance. In addition, the formation of organohalogen byproducts, chlorate and perchlorate, was seldom considered. Nevertheless, the first step toward advancing from laboratory-scale to industrial-scale applications is recognizing both the strengths and limitations of electrochemical water treatment systems. More comprehensive and rigorous evaluation of novel electrode materials, application of scalable proof-of-concept studies, and acknowledgment of all treatment outputs (not just the positive ones) are imperative. The presence of PFASs in drinking water and in the environment is an urgent global public health issue. Developments made in material science and application of novel three-dimensional, porous electrode materials and nanostructured coatings are forging a path toward more sustainable water treatment technologies and potential chemical-free treatment of PFAS-contaminated water.

Chlorinated Byproduct Formation during the Electrochemical Advanced Oxidation Process at Magnéli Phase Ti4O7 Electrodes.

This research investigated chlorinated byproduct formation at Ti4O7 anodes. Resorcinol was used as a model organic compound representative of reactive phenolic groups in natural organic matter and industrial phenolic contaminants and was oxidized in the presence of NaCl (0-5 mM). Resorcinol mineralization was >68% in the presence and absence of NaCl at 3.1 V/SHE (residence time = 13 s). Results indicated that ∼4.3% of the initial chloride was converted to inorganic byproducts (free Cl2, ClO2-, ClO3-) in the absence of resorcinol, and this value decreased to <0.8% in the presence of resorcinol. Perchlorate formation rates from chlorate oxidation were 115-371 mol m-2 h-1, approximately two orders of magnitude lower than reported values for boron-doped diamond anodes. Liquid chromatography-mass spectroscopy detected two chlorinated organic products. Multichlorinated alcohol compounds (C3H2Cl4O and C3H4Cl4O) at 2.5 V/SHE and a monochlorinated phenolic compound (C8H7O4Cl) at 3.1 V/SHE were proposed as possible structures. Density functional theory calculations estimated that the proposed alcohol products were resistant to direct oxidation at 2.5 V/SHE, and the C8H7O4Cl compound was likely a transient intermediate. Chlorinated byproducts should be carefully monitored during electrochemical advanced oxidation processes, and multibarrier treatment approaches are likely necessary to prevent halogenated byproducts in the treated water.

Modeling electrochemical oxidation and reduction of sulfamethoxazole using electrocatalytic reactive electrochemical membranes.

In this research, degradation of the antibiotic sulfamethoxazole (SMX) was studied using electrochemical reduction and oxidation in single pass, flow-through mode using porous titanium suboxide (Ti4O7) reactive electrochemical membranes (REMs) and Pd-Cu doped Ti4O7 REMs (Pd-Cu/Ti4O7 REMs). Electrochemical reduction of SMX increased from 3.8 ±â€¯0.3% for the Ti4O7 REM to 96.1 ±â€¯3.9% for the Pd-Cu/Ti4O7 REM at -1.14 V/SHE and at a permeate flux of 300 L m-2 h-1 (LMH) (liquid residence time: ∼1.8 s). By contrast, electrochemical oxidation using Ti4O7 REMs achieved 95.7 ±â€¯1.0% removal of SMX at 2.03 V/SHE and a permeate flux of 300 LMH (liquid residence time: ∼9.0 s) without the catalyst addition. We developed a reactive transport mathematical model and calibrated it to the SMX experimental data. The calibrated model predicted SMX permeate concentrations at fixed potentials and as a function of permeate flux. Based on products from SMX reduction, we proposed that SMX was reduced by a hydrogen atom transfer reaction that was mediated by the Pd-Cu/Ti4O7 REM. Toxicity tests indicated that electrochemical oxidation/reduction lowered solution toxicity. The results of this work indicate that a tandem electrochemical reduction/oxidation approach using the REM-based technology is a potential treatment strategy for sulfonamide-contaminated pharmaceutical wastewater.

Mechanistic Investigation of Haloacetic Acid Reduction Using Carbon-Ti4O7 Composite Reactive Electrochemical Membranes.

Carbon-Ti4O7 composite reactive electrochemical membranes (REMs) were studied for adsorption and electrochemical reduction of haloacetic acids (HAAs). Powder activated carbon (PAC) or multiwalled carbon nanotubes (MWCNTs) were used in these composites. Results from flow-through adsorption experiments with dibromoacetic acid (DBAA) as a model HAA were interpreted with a transport model. It was estimated that ∼46% of C in the MWCNT-REM and ∼10% of C in the PAC-REM participated in adsorption reactions. Electrochemical reduction of 1 mg L-1 DBAA in 10 mM KH2PO4/K2HPO4 at -1.5 V/SHE (hydraulic residence time, ∼11 s) resulted in 73, 94, and 96% DBAA reduction for Ti4O7, PAC-Ti4O7, and MWCNT-Ti4O7 REMs, respectively. The reactive-transport model yielded kobs values between 9.16 and 33.3 min-1, which were 2 to 4 orders of magnitude higher than previously reported. PAC-Ti4O7 REM was tested with tap water spiked with 0.11 mg L-1 of nine different HAAs in a similar reduction experiment. The results indicated that all HAAs were reduced to <20 µg L-1. Moreover, the total combined concentration of five regulated HAAs was lower than the regulatory limit (60 µg L-1). Density functional theory simulations suggest that a direct electron transfer reaction was the probable rate-determining step for HAA reduction.

Role of Near-Electrode Solution Chemistry on Bacteria Attachment and Poration at Low Applied Potentials.

This research investigated mechanisms for biofouling control at boron-doped diamond (BDD) electrode surfaces polarized at low applied potentials (e.g., -0.2 to 1.0 V vs Ag/AgCl), using Pseudomonas aeruginosa as a model organism. Results indicated that electrostatic interactions between bacteria and ionic electrode functional groups facilitated bacteria attachment at the open-circuit potential (OCP). However, under polarization, the applied potential governed these electrostatic interactions and electrochemical reactions resulted in surface bubble formation and near-surface pH modulation that decreased surface attachment under anodic conditions. The poration of the attached bacteria occurred at OCP conditions and increased with the applied potential. Scanning electrochemical microscopy (SECM) provided near-surface pH and oxidant formation measurements under anodic and cathodic polarizations. The near-surface pH was 3.1 at 1.0 V vs Ag/AgCl and 8.0 at -0.2 V vs Ag/AgCl and was possibly a contributor to bacteria poration. Interpretation of SECM data using a reactive transport model allowed for a better understanding of the near-electrode chemistry. Under cathodic conditions, the primary oxidant formed was H2O2, and under anodic conditions, a combination of H2O2, Cl•, HO2•, Cl2•-, and Cl2 formations likely contributed to bacteria poration at potentials as low as 0.5 V vs Ag/AgCl.

Electron Transfer Kinetics at Graphene Quantum Dot Assembly Electrodes.

Electrochemical performance of nanostructured carbon electrodes was evaluated using cyclic voltammetry and a simple simulation model. The electrodes were prepared from soluble precursors by anodic electrodeposition of two sizes of graphene quantum dot assemblies (hexabenzocoronene (HBC) and carbon quantum dot (CQD)) onto a conductive support. Experimental and simulated voltammograms enabled the extraction of the following electrode parameters: conductivity of the electrodes (a combination of ionic and electronic contributions), density of available electrode states at different potentials, and tunneling rate constant (Marcus-Gerischer model) for interfacial charge transfer to ferrocene/ferrocenium (Fc/Fc+) couple. The parameters indicate that HBC and CQD have significant density of electronic states at potentials more positive than -0.5 V versus Ag/Ag+. Enabled by these large densities, the electron transfer rates at the Fc/Fc+ thermodynamic potential are several orders of magnitude slower than those commonly observed on other carbon electrodes. This study is expected to accelerate the discovery of improved synthetic carbon electrodes by providing fast screening methodology of their electrochemical behavior.

Charged Layered Boron Nitride-Nanoflake Membranes for Efficient Ion Separation and Water Purification.

2D layered nanomaterials have attracted considerable attention for their potential for highly efficient separations, among other applications. Here, a 2D lamellar membrane synthesized using hexagonal boron nitride nanoflakes (h-BNF) for highly efficient ion separation is reported. The ion-rejection performance and the water permeance of the membrane as a function of the ionic radius, ion valance, and solution pH are investigated. The nonfunctionalized h-BNF membranes show excellent ion rejection for small sized salt ions as well as for anionic dyes (>97%) while maintaining a high water permeability, ≈1.0 × 10-3 L m m-2 h-1 bar-1 ). Experiments show that the ion-rejection performance of the membrane can be tuned by changing the solution pH. The results also suggest that the rejection is influenced by the ionic size and the electrostatic repulsion between fixed negative charges on the BN surface and the mobile ions, and is consistent with the Donnan equilibrium model. These simple-to-fabricate h-BNF membranes show a unique combination of excellent ion selectivity and high permeability compared to other 2D membranes.

Electrochemical Production of Si without Generation of CO2 Based on the Use of a Dimensionally Stable Anode in Molten CaCl2.

The current Si production process is based on the high-temperature (1700 °C) reduction of SiO2 with carbon that produces large amounts of CO2 . We report an alternative low-temperature (850 °C) process based on the reduction of SiO2 in molten CaCl2 that does not produce CO2 . It utilizes an anode material (Ti4 O7 ) capable of sustained oxygen evolution. Two types of this anode material, dense Ti4 O7 and porous Ti4 O7 , were tested. The dense anode showed a better performance. The anode stability is attributed to the formation of a protective TiO2 layer on its surface. In situ periodic current reversal and ex situ H2 reduction could be used for extending the lifetime of the anodes. The findings show that this material can be applied as a recyclable anode in molten CaCl2 . Si wires, films, and particles were deposited with this anode under different cathodic current densities. The prepared Si film exhibited ≈30-40 % of the photocurrent response of a commercial p-type Si wafer, indicating potential use in photovoltaic cells.

The Prospect of Electrochemical Technologies Advancing Worldwide Water Treatment.

Growing worldwide population, climate change, and decaying water infrastructure have all contributed to a need for a better water treatment and conveyance model. Distributed water treatment is one possible solution, which relies on the local treatment of water from various sources to a degree dependent on its intended use and, finally, distribution to local consumers. This distributed, fit-for-purpose water treatment strategy requires the development of new modular point-of-use and point-of-entry technologies to bring this idea to fruition. Electrochemical technologies have the potential to contribute to this vision, as they have several advantages over established water treatment technologies. Electrochemical technologies have the ability to simultaneously treat multiple classes of contaminants through the in situ production of chemicals at the electrode surfaces with low power and energy demands, thereby allowing the construction of compact, modular water treatment technologies that require little maintenance and can be easily automated or remotely controlled. In addition, these technologies offer the opportunity for energy recovery through production of fuels at the cathode, which can further reduce their energy footprint. In spite of these advantages, there are several challenges that need to be overcome before widespread adoption of electrochemical water treatment technologies is possible. This Account will focus primarily on destructive electrolytic technologies that allow for removal of water contaminants without the need for residual treatment or management. Most important to the development of destructive electrochemical technologies is a need to fabricate nontoxic, inexpensive, high-surface-area electrodes that have a long operational life and can operate without the production of unwanted toxic byproducts. Overcoming these barriers will decrease the capital costs of water treatment and allow the development of the point-of-use and point-of-entry technologies that are necessary to promote more sustainable water treatment solutions. However, to accomplish this goal, a reprioritization of research is needed. Current research is primarily focused on investigating individual contaminant transformation pathways and mechanisms. While this research is important for understanding these technologies, additional work is needed in developing inexpensive, high-surface-area, stable electrode materials, minimizing toxic byproduct formation, and determining the life cycle and technoeconomic analyses necessary for commercialization. Better understanding of these critical research areas will allow for strategic deployment of electrochemical water treatment technologies to promote a more sustainable future.

Simultaneous Adsorption and Electrochemical Reduction of N-Nitrosodimethylamine Using Carbon-Ti4O7 Composite Reactive Electrochemical Membranes.

This study focused on synthesis and characterization of Ti4O7 reactive electrochemical membranes (REMs) amended with powder-activated carbon (PAC) or multiwalled carbon nanotubes (MWCNTs). These composite REMs were evaluated for simultaneous adsorption and electrochemical reduction of N-nitrosodimethylamine (NDMA). The carbon-Ti4O7 composite REMs had high electrical conductivities (1832 to 2991 S m-1), where carbon and Ti4O7 were in direct electrical contact. Addition of carbonaceous materials increased the residence times of NDMA in the REMs by a factor of 3.8 to 5.4 and therefore allowed for significant electrochemical NDMA reduction. The treatment of synthetic solutions containing 10 µM NDMA achieved >4-log NDMA removal in a single pass (liquid residence time of 11 to 22 s) through the PAC-REM and MWCNT-REM with the application of a -1.1 V/SHE cathodic potential, with permeate concentrations between 18 and 80 ng L-1. The treatment of a 6.7 nM NDMA-spiked surface water sample, under similar operating conditions (liquid residence time of 22 s), achieved 92 to 97% removal with permeate concentrations between 16 and 40 ng L-1. Density functional theory calculations determined a probable reaction mechanism for NDMA reduction, where the rate-limiting step was a direct electron transfer reaction.

Electrochemical Oxidation of Atrazine and Clothianidin on Bi-doped SnO2-Ti nO2 n-1 Electrocatalytic Reactive Electrochemical Membranes.

This research focused on improving mineralization rates during the advanced electrochemical oxidation treatment of agricultural water contaminants. For the first time, bismuth-doped tin oxide (BDTO) catalysts were deposited on Magnéli phase (Ti nO2 n-1, n = 4-6) reactive electrochemical membranes (REMs). Terephthalic acid (TA) was used as a OH• probe, whereas atrazine (ATZ) and clothianidin (CDN) were chosen as model agricultural water contaminants. The BDTO-deposited REMs (REM/BDTO) showed higher compound removal than the REM, due to enhanced OH• production. At 3.5 V/SHE, complete mineralization of TA, ATZ, and CDN was achieved for the REM/BDTO upon a single pass in the reactor (residence time ∼3.6 s). Energy consumption for REM/BDTO was as much as 31-fold lower than the REM, with minimal values per log removal of <0.53 kWh m-3 for TA (3.5 V/SHE), <0.42 kWh m-3 for ATZ (3.0 V/SHE), and 0.83 kWh m-3 for CDN (3.0 V/SHE). Density functional theory simulations provided potential dependent activation energy profiles for ATZ, CDN, and various oxidation products. Efficient mass transfer and a reaction mechanism involving direct electron transfer and reaction with OH• were responsible for the rapid and complete mineralization of ATZ and CDN at very short residence times.

Electrocatalytic Reduction of Nitrate Using Magnéli Phase TiO2 Reactive Electrochemical Membranes Doped with Pd-Based Catalysts.

This research focused on synthesis, characterization, and application of point-of-use catalytic reactive electrochemical membranes (REMs) for electrocatalytic NO3- reduction. Deposition of Pd-Cu and Pd-In catalysts to the REMs produced catalytic REMs (i.e., Pd-Cu/REM and Pd-In/REM) that were active for NO3- reduction. Optimal performance was achieved with a Pd-Cu/REM and upstream counter electrode, which reduced NO3- from 1.0 mM to below the EPAs regulatory MCL (700 µM) in a single pass through the REM (residence time ∼2 s), obtaining product selectivity of <2% toward NO2-/NH3. Nitrate reduction was not affected by dissolved oxygen and carbonate species and only slightly decreased in a surface water sample due to Ca2+ and Mg2+ scaling. Energy consumption to treat surface water was 1.1 to 1.3 kWh mol-1 for 1 mM NO3- concentrations, and decreased to 0.19 and 0.12 kWh mol-1 for 10 and 100 mM NaNO3 solutions, respectively. Electrocatalytic reduction kinetics were shown to be an order of magnitude higher than catalytic NO3- reduction kinetics. Conversion of up to 67% of NO3-, with low NO2- (0.7-11 µM) and NH3 formation (<10 µM), and low energy consumption obtained in this study suggest that Pd-Cu/REMs are a promising technology for distributed water treatment.

Electro-oxidation of organic pollutants by reactive electrochemical membranes.

Electro-oxidation processes are promising options for the removal of organic pollutants from water. The major appeal of these technologies is the possibility to avoid the addition of chemical reagents. However, a major limitation is associated with slow mass transfer that reduces the efficiency and hinders the potential for large-scale application of these technologies. Therefore, improving the reactor configuration is currently one of the most important areas for research and development. The recent development of a reactive electrochemical membrane (REM) as a flow-through electrode has proven to be a breakthrough innovation, leading to both high electrochemically active surface area and convection-enhanced mass transport of pollutants. This review summarizes the current state of the art on REMs for the electro-oxidation of organic compounds by anodic oxidation. Specific focuses on the electroactive surface area, mass transport, reactivity, fouling and stability of REMs are included. Recent advances in the development of sub-stoichiometric titanium oxide REMs as anodes have been made. These electrodes possess high electrical conductivity, reactivity (generation of •OH), chemical/electrochemical stability, and suitable pore structure that allows for efficient mass transport. Further development of REMs strongly relies on the development of materials with suitable physico-chemical characteristics that produce electrodes with efficient mass transport properties, high electroactive surface area, high reactivity and long-term stability.

Fluorination of Boron-Doped Diamond Film Electrodes for Minimization of Perchlorate Formation.

This research investigated the effects of surface fluorination on both rates of organic compound oxidation (phenol and terephthalic acid (TA)) and ClO4- formation at boron-doped diamond (BDD) film anodes at 22 °C. Different fluorination methods (i.e., electrochemical oxidation with perfluorooctanoic acid (PFOA), radio frequency plasma, and silanization) were used to incorporate fluorinated moieties on the BDD surface, which was confirmed by X-ray photoelectron spectroscopy (XPS). The silanization method was found to be the most effective fluorination method using a 1H,1H,2H,2H-perfluorodecyltrichlorosilane precursor to form a self-assembled monolayer (SAM) on the oxygenated BDD surface. The ClO4- formation decreased from rates of 0.45 ± 0.03 mmol m-2 min-1 during 1 mM NaClO3 oxidation and 0.28 ± 0.01 mmol m-2 min-1 during 10 mM NaCl oxidation on the BDD electrode to below detectable levels (<0.12 µmoles m-2 min-1) for the BDD electrode functionalized by a 1H,1H,2H,2H-perfluorodecyltrichlorosilane SAM. These decreases in rates corresponded to 99.94 and 99.85% decreases in selectivity for ClO4- formation during the electrolysis of 10 mM NaCl and 1 mM NaClO3 electrolytes, respectively. By contrast, the oxidation rates of phenol were reduced by only 16.3% in the NaCl electrolyte and 61% in a nonreactive 0.1 M KH2PO4 electrolyte. Cyclic voltammetry with Fe(CN)63-/4- and Fe3+/2+ redox couples indicated that the long fluorinated chains created a blocking layer on the BDD surface that inhibited charge transfer via steric hindrance and hydrophobic effects. The surface coverages and thicknesses of the fluorinated films controlled the charge transfer rates, which was confirmed by estimates of film thicknesses using XPS and density functional theory simulations. The aliphatic silanized electrode also showed very high stability during OH• production. Perchlorate formation rates were below the detection limit (<0.12 µmoles m-2 min-1) for up to 10 consecutive NaClO3 oxidation experiments.

Mechanistic Study of the Validity of Using Hydroxyl Radical Probes To Characterize Electrochemical Advanced Oxidation Processes.

The detection of hydroxyl radicals (OH•) is typically accomplished by using reactive probe molecules, but prior studies have not thoroughly investigated the suitability of these probes for use in electrochemical advanced oxidation processes (EAOPs), due to the neglect of alternative reaction mechanisms. In this study, we investigated the suitability of four OH• probes (coumarin, p-chlorobenzoic acid, terephthalic acid, and p-benzoquinone) for use in EAOPs. Experimental results indicated that both coumarin and p-chlorobenzoic acid are oxidized via direct electron transfer reactions, while p-benzoquinone and terephthalic acid are not. Coumarin oxidation to form the OH• adduct product 7-hydroxycoumarin was found at anodic potentials lower than that necessary for OH• formation. Density functional theory (DFT) simulations found a thermodynamically favorable and non-OH• mediated pathway for 7-hydroxycoumarin formation, which is activationless at anodic potentials > 2.10 V/SHE. DFT simulations also provided estimates of E° values for a series of OH• probe compounds, which agreed with voltammetry results. Results from this study indicated that terephthalic acid is the most appropriate OH• probe compound for the characterization of electrochemical and catalytic systems.