Redox-Functionalized Semiconductor Interfaces for Photoelectrochemical Separations.

Redox-mediated electrosorption is a promising platform for selective electrochemical (EC) separations, due to its molecular selectivity, high uptake, and tunability for target ions. However, the electrical energy required is mainly generated by non-renewable energy sources, which limits its sustainability and overall impact to decarbonization. Here, a redox-mediated photoelectrochemical (PEC) separation process using polyvinyl ferrocene functionalized TiO2 nanorod electrodes is proposed, which integrates direct solar energy as a driver for the selective electrosorption. The photoelectrochemically-driven oxidation and reduction with both homogeneous and heterogeneous ferrocene-systems is investigated to establish the underlying mechanism. The PEC system can separate heavy metal oxyanions at lower voltages or even without electrical energy. At 0.3 V versus SCE, a 124 mg g-1 uptake for Mo is achieved, which is comparable to the performance of EC cells at 0.75 V versus SCE. Thus, PEC systems not only can generate energy for spontaneous redox-separations, but also can reduce electrical energy consumption by 51.4% compared to EC cells for separation processes when coupled with an external electrical energy.

Desalting Plasma Protein Solutions by Membrane Capacitive Deionization.

Plasma protein therapies are used by millions of people across the globe to treat a litany of diseases and serious medical conditions. One challenge in the manufacture of plasma protein therapies is the removal of salt ions (e.g., sodium, phosphate, and chloride) from the protein solution. The conventional approach to remove salt ions is the use of diafiltration membranes (e.g., tangential flow filtration) and ion-exchange chromatography. However, the ion-exchange resins within the chromatographic column as well as filtration membranes are subject to fouling by the plasma protein. In this work, we investigate the membrane capacitive deionization (MCDI) as an alternative separation platform for removing ions from plasma protein solutions with negligible protein loss. MCDI has been previously deployed for brackish water desalination, nutrient recovery, mineral recovery, and removal of pollutants from water. However, this is the first time this technique has been applied for removing 28% of ions (sodium, chloride, and phosphate) from human serum albumin solutions with less than 3% protein loss from the process stream. Furthermore, the MCDI experiments utilized highly conductive poly(phenylene alkylene)-based ion exchange membranes (IEMs). These IEMs combined with ionomer-coated nylon meshes in the spacer channel ameliorate Ohmic resistances in MCDI improving the energy efficiency. Overall, we envision MCDI as an effective separation platform in biopharmaceutical manufacturing for deionizing plasma protein solutions and other pharmaceutical formulations without a loss of active pharmaceutical ingredients.

Investigating the Electrochemically Driven Capture and Release of Long-Chain PFAS by Redox Metallopolymer Sorbents.

The remediation of perfluoroalkyl substances (PFAS) is an urgent challenge due to their prevalence and persistence in the environment. Electrosorption is a promising approach for wastewater treatment and water purification, especially through the use of redox polymers to control the binding and release of target contaminants without additional external chemical inputs. However, the design of efficient redox electrosorbents for PFAS faces the significant challenge of balancing a high adsorption capacity while maintaining significant electrochemical regeneration. To overcome this challenge, we investigate redox-active metallopolymers as a versatile synthetic platform to enhance both electrochemical reversibility and electrosorption uptake capacity for PFAS removal. We selected and synthesized a series of metallopolymers bearing ferrocene and cobaltocenium units spanning a range of redox potentials to evaluate their performance for the capture and release of perfluorooctanoic acid (PFOA). Our results demonstrate that PFOA uptake and regeneration efficiency increased with more negative formal potential of the redox polymers, indicating possible structural correlations with the electron density of the metallocenes. Poly(2-(methacryloyloxy)ethyl cobaltoceniumcarboxylate hexafluorophosphate) (PMAECoPF6) showed the highest affinity toward PFOA, with an uptake capacity of more than 90 mg PFOA/g adsorbent at 0.0 V vs Ag/AgCl and a regeneration efficiency of more than 85% at -0.4 V vs Ag/AgCl. Kinetics of PFOA release showed that electrochemical bias greatly enhanced the regeneration efficiency when compared to open-circuit desorption. In addition, electrosorption of PFAS from different wastewater matrices and a range of salt concentrations demonstrated the capability of PFAS remediation in complex water sources, even at ppb levels of contaminants. Our work showcases the synthetic tunability of redox metallopolymers for enhanced electrosorption capacity and regeneration of PFAS.

Ultrasound-promoted preparation of polyvinyl ferrocene-based electrodes for selective formate separation: Experimental design and optimization.

The selective separation of ions is a major technological challenge having far-ranging impacts from product separation in electrochemical production of base chemicals from CO2 to water purification. In recent years, ion-selective electrochemical systems leveraging redox-materials emerged as an attractive platform based on their reversibility and remarkable ion selectivity. In the present study, we present an ultrasound-intensified fabrication process for polyvinyl ferrocene (PVF)-functionalized electrodes in a carbon nanotube (CNT) matrix for selective electro-adsorption of formate ions. To this end, a response surface methodology involving the Box-Behnken design with three effective independent variables, namely, PVF to CNT ratio, sonication duration, and ultrasonic amplitude was applied to reach the maximum formate adsorption efficiency. The fabricated electrodes were characterized using cyclic voltammetry, X-ray diffraction, Raman spectroscopy, and scanning electron microscopy (SEM). SEM images revealed that an optimized ultrasonic amplitude and sonication time provided remarkable improvements in electrode morphology. Through a sedimentation study, we qualitatively demonstrate that the main optimized conditions improved PVF/CNT dispersion stability, consequently providing the highest number of active surface sites for adsorption and the highest adsorption efficiency. The highest percentage of active electrode surface sites and the maximum adsorption efficiency were 97.8 and 90.7% respectively at a PVF/CNT ratio of 3, ultrasonication time of one hour, and 50% ultrasonic amplitude.

Building an operational framework for selective nitrogen recovery via electrochemical stripping.

Recovering nitrogen from wastewater can simultaneously fulfill the roles of traditional removal technologies such as nitrification-denitrification and fertilizer production processes such as Haber-Bosch. We have recently demonstrated a proof-of-concept for selective recovery of the fertilizer ammonium sulfate via electrochemical stripping, a combination of electrodialysis and membrane stripping. In this study, we furthered electrochemical stripping from concept to informed practice by investigating the effects of influent concentration (30, 300, and 3000 mg N/L), catholyte temperature (15, 23, and 35 °C), and gas permeable membrane choice on electrochemical nitrogen removal and recovery. We also proposed and validated a nitrogen mass transport model for the experimental results, providing mechanistic rationale behind observed effects of varying operating parameters. While changing operating parameters did affect performance, electrochemical stripping exhibited robust performance over a range of realistic ambient temperatures, three gas permeable membranes, and three orders of magnitude of influent concentrations. Practically, these results demonstrate that electrochemical stripping is viable across a range of waste streams and resilient to fluctuations in temperature and nitrogen concentration; they also establish operational trade-offs between residence time and energy consumption. As a result of this work, electrochemical stripping continues to mature from concept to practice and provides lessons for developing other resource recovery technologies.

Semiconducting Polymer Interfaces for Electrochemically Assisted Mercury Remediation.

Nanostructured polymer interfaces can play a key role in addressing urgent challenges in water purification and advanced separations. Conventional technologies for mercury remediation often necessitate large energetic inputs, produce significant secondary waste, or when electrochemical, lead to strong irreversibility. Here, we propose the reversible, electrochemical capture and release of mercury, by modulating interfacial mercury deposition through a sulfur-containing, semiconducting redox polymer. Electrodeposition/stripping of mercury was carried out with a nanostructured poly(3-hexylthiophene-2,5-diyl)-carbon nanotube composite electrode, coated on titanium (P3HT-CNT/Ti). During electrochemical release, mercury was reversibly stripped in a non-acid electrolyte with 12-fold higher release kinetics compared to nonfunctionalized electrodes. In situ optical microscopy confirmed the rapid, reversible nature of the electrodeposition/stripping process with P3HT-CNT/Ti, indicating the key role of redox processes in mediating the mercury phase transition. The polymer-functionalized system exhibited high mercury removal efficiencies (>97%) in real wastewater matrices while bringing the final mercury concentrations down to <2 µg L-1. Moreover, an energy consumption analysis highlighted a 3-fold increase in efficiency with P3HT-CNT/Ti compared to titanium. Our study demonstrates the effectiveness of semiconducting redox polymers for reversible mercury deposition and points to future applications in mediating electrochemical stripping for various environmental applications.