Electrochemical advanced oxidation processes (EAOPs) have emerged as novel water treatment technologies for the elimination of a broad-range of organic contaminants. Considerable validation of this technology has been performed at both the bench-scale and pilot-scale, which has been facilitated by the development of stable electrode materials that efficiently generate high yields of hydroxyl radicals (OH˙) (e.g., boron-doped diamond (BDD), doped-SnO2, PbO2, and substoichiometic- and doped-TiO2). Although a promising new technology, the mechanisms involved in the oxidation of organic compounds during EAOPs and the corresponding environmental impacts of their use have not been fully addressed. In order to unify the state of knowledge, identify research gaps, and stimulate new research in these areas, this review critically analyses published research pertaining to EAOPs. Specific topics covered in this review include (1) EAOP electrode types, (2) oxidation pathways of select classes of contaminants, (3) rate limitations in applied settings, and (4) long-term sustainability. Key challenges facing EAOP technologies are related to toxic byproduct formation (e.g., ClO4(-) and halogenated organic compounds) and low electro-active surface areas. These challenges must be addressed in future research in order for EAOPs to realize their full potential for water treatment.

Catalytic reduction of water contaminants using palladium (Pd)-based catalysts and hydrogen gas as a reductant has been extensively studied at the bench-scale, but due to technical challenges it has only been limitedly applied at the field-scale. To motivate research that can overcome these technical challenges, this review critically analyzes the published research in the area of Pd-based catalytic reduction of priority drinking water contaminants (i.e., halogenated organics, oxyanions, and nitrosamines), and identifies key research areas that should be addressed. Specifically, the review summarizes the state of knowledge related to (1) proposed reaction pathways for important classes of contaminants, (2) rates of contaminant reduction with different catalyst formulations, (3) long-term sustainability of catalyst activity with respect to natural water foulants and regeneration strategies, and (4) technology applications. Critical barriers hindering implementation of the technology are related to catalyst activity (for some contaminants), stability, fouling, and regeneration. New developments overcoming these limitations will be needed for more extensive field-scale application of this technology.

This research investigates the characterization and testing of an anodic reactive electrochemical membrane (REM) for water treatment. The REM consists of a porous substoichiometric titanium dioxide (Ti4O7) tubular, ceramic electrode operated in cross-flow filtration mode. Advection-enhanced mass transfer rates, on the order of a 10-fold increase, are obtained when the REM is operated in filtration-mode, relative to a traditional flow-through mode. Oxidation experiments with model organic compounds showed that the REM was active for both direct oxidation reactions and formation of hydroxyl radicals (OH(•)). Electrochemical impedance spectroscopy data interpreted by transmission line modeling determined that the electro-active surface area was 619 times the nominal geometric surface area. Results from filtration-mode experiments with p-methoxyphenol indicate that compound removal occurred by electro-assisted adsorption and subsequent oxidation. Electro-assisted adsorption was the primary removal mechanism at potentials where OH(•) did not form. At higher potentials (>2.0 V), where OH(•) concentrations were significant, p-methoxyphenol removal occurred by a combination of electro-assisted adsorption and OH(•) oxidation. These removal mechanisms resulted in 99.9% p-methoxyphenol removal in the permeate, with calculated current efficiencies >73% at applied current densities of 0.5-1.0 mA cm(-2). These results illustrate the extreme promise of the REM for water treatment.

Conspectus 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.

An energy-efficient Magneĺi phase Ti 4 O 7 reactive electrochemical membrane (REM) was applied for the oxidation of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS). Approximately 5-log removal of these compounds was achieved in a single pass through the REM with residence times of ∼11 s at 3.3 V/SHE for PFOA and 3.6 V/SHE for PFOS. The permeate concentrations of PFOA and PFOS were <86 and 35 ng L −1 , from initial concentrations of 4.14 and 5 mg L −1 , respectively. The highest removal rates were 3415 ± 203 μmol m −2 h −1 for PFOA and 2436 ± 106 μmol m −2 h −1 for PFOS at a permeate flux of 720 L m −2 h −1 (residence times of ∼3.8 s). The levels of energy consumption (per log removal) to remove PFOA and PFOS to below the detection limits were 5.1 and 6.7 kWh m −3 , respectively. These values are the lowest reported for electrochemical oxidation and approximately an order of magnitude lower than those reported for other technologies (i.e., ultrasonication, photocatalysis, vacuum ultraviolet photolysis, and microwave−hydrothermal decomposition), demonstrating the promise of the REM technology for water treatment applications.