Unifying the Conversation: Membrane Separation Performance in Energy, Water, and Industrial Applications.

Dense polymer membranes enable a diverse range of separations and clean energy technologies, including gas separation, water treatment, and renewable fuel production or conversion. The transport of small molecular and ionic solutes in the majority of these membranes is described by the same solution-diffusion mechanism, yet a comparison of membrane separation performance across applications is rare. A better understanding of how structure-property relationships and driving forces compare among applications would drive innovation in membrane development by identifying opportunities for cross-disciplinary knowledge transfer. Here, we aim to inspire such cross-pollination by evaluating the selectivity and electrochemical driving forces for 29 separations across nine different applications using a common framework grounded in the physicochemical characteristics of the permeating and rejected solutes. Our analysis shows that highly selective membranes usually exhibit high solute rejection, rather than fast solute permeation, and often exploit contrasts in the size and charge of solutes rather than a nonelectrostatic chemical property, polarizability. We also highlight the power of selective driving forces (e.g., the fact that applied electric potential acts on charged solutes but not on neutral ones) to enable effective separation processes, even when the membrane itself has poor selectivity. We conclude by proposing several research opportunities that are likely to impact multiple areas of membrane science. The high-level perspective of membrane separation across fields presented herein aims to promote cross-pollination and innovation by enabling comparisons of solute transport and driving forces among membrane separation applications.

Enabling selective zinc-ion intercalation by a eutectic electrolyte for practical anodeless zinc batteries.

Two major challenges hinder the advance of aqueous zinc metal batteries for sustainable stationary storage: (1) achieving predominant Zn-ion (de)intercalation at the oxide cathode by suppressing adventitious proton co-intercalation and dissolution, and (2) simultaneously overcoming Zn dendrite growth at the anode that triggers parasitic electrolyte reactions. Here, we reveal the competition between Zn2+ vs proton intercalation chemistry of a typical oxide cathode using ex-situ/operando techniques, and alleviate side reactions by developing a cost-effective and non-flammable hybrid eutectic electrolyte. A fully hydrated Zn2+ solvation structure facilitates fast charge transfer at the solid/electrolyte interface, enabling dendrite-free Zn plating/stripping with a remarkably high average coulombic efficiency of 99.8% at commercially relevant areal capacities of 4 mAh cm-2 and function up to 1600 h at 8 mAh cm-2. By concurrently stabilizing Zn redox at both electrodes, we achieve a new benchmark in Zn-ion battery performance of 4 mAh cm-2 anode-free cells that retain 85% capacity over 100 cycles at 25 °C. Using this eutectic-design electrolyte, Zn | |Iodine full cells are further realized with 86% capacity retention over 2500 cycles. The approach represents a new avenue for long-duration energy storage.

A reverse-selective ion exchange membrane for the selective transport of phosphates via an outer-sphere complexation-diffusion pathway.

Specific-ion selectivity is a highly desirable feature for the next generation of membranes. However, existing membranes rely on differences in charge, size and hydration energy, which limits their ability to target individual ion species. Here we demonstrate a nanocomposite ion-exchange membrane material that enables a reverse-selective transport mechanism that can selectively pass a single ion species. We demonstrate this transport mechanism with phosphate ions selectively transporting across negatively charged cation exchange membranes. Selective transport is enabled by the in situ growth of hydrous manganese oxide nanoparticles throughout a cation exchange membrane that provide a diffusion pathway via phosphate-specific, reversible outer-sphere interactions. On incorporating the hydrous manganese oxide nanoparticles, the membrane's phosphate flux increased by a factor of 27 over an unmodified cation exchange membrane, and the selectivity of phosphorous over sulfate, nitrate and chloride reaches 47, 100 and 20, respectively. By pairing ion-specific outer-sphere interactions between the target ions and appropriate nanoparticles, these nanocomposite ion-exchange materials can, in principle, achieve selective transport for a range of ions.

Screening of bimetallic electrocatalysts for water purification with machine learning.

Electrocatalysis provides a potential solution to NO3 - pollution in wastewater by converting it to innocuous N2 gas. However, materials with excellent catalytic activity are typically limited to expensive precious metals, hindering their commercial viability. In response to this challenge, we have conducted the most extensive computational search to date for electrocatalysts that can facilitate NO3 - reduction reaction, starting with 59 390 candidate bimetallic alloys from the Materials Project and Automatic-Flow databases. Using a joint machine learning- and computation-based screening strategy, we evaluated our candidates based on corrosion resistance, catalytic activity, N2 selectivity, cost, and the ability to synthesize. We found that only 20 materials will satisfy all criteria in our screening strategy, all of which contain varying amounts of Cu. Our proposed list of candidates is consistent with previous materials investigated in the literature, with the exception of Cu-Co and Cu-Ag based compounds that merit further investigation.

Zinc Titanium Nitride Semiconductor toward Durable Photoelectrochemical Applications.

Photoelectrochemical fuel generation is a promising route to sustainable liquid fuels produced from water and captured carbon dioxide with sunlight as the energy input. Development of these technologies requires photoelectrode materials that are both photocatalytically active and operationally stable in harsh oxidative and/or reductive electrochemical environments. Such photocatalysts can be discovered based on co-design principles, wherein design for stability is based on the propensity for the photocatalyst to self-passivate under operating conditions and design for photoactivity is based on the ability to integrate the photocatalyst with established semiconductor substrates. Here, we report on the synthesis and characterization of zinc titanium nitride (ZnTiN2) that follows these design rules by having a wurtzite-derived crystal structure and showing self-passivating surface oxides created by electrochemical polarization. The sputtered ZnTiN2 thin films have optical absorption onsets below 2 eV and n-type electrical conduction of 3 S/cm. The band gap of this material is reduced from the 3.36 eV theoretical value by cation-site disorder, and the impact of cation antisites on the band structure of ZnTiN2 is explored using density functional theory. Under electrochemical polarization, the ZnTiN2 surfaces have TiO2- or ZnO-like character, consistent with Materials Project Pourbaix calculations predicting the formation of stable solid phases under near-neutral pH. These results show that ZnTiN2 is a promising candidate for photoelectrochemical liquid fuel generation and demonstrate a new materials design approach to other photoelectrodes with self-passivating native operational surface chemistry.

Effect of osmotic ballast properties on the performance of a concentration gradient battery.

A concentration gradient battery (CGB) is an energy storage system comprised of a series of concentrated and dilute salt solution compartments, separated by ion exchange membranes (IEMs). The battery is charged by electrodialysis (ED), which increases the concentration gradient between these solutions, and discharged by reverse electrodialysis (RED), which allows these solutions to mix. In both ED and RED, water moves by osmosis from dilute to concentrated compartments, reducing the CGB faradaic and energy efficiency. A promising approach to mitigate osmosis is to use an osmotic ballast in the dilute solution to balance the osmotic pressure and reduce faradaic energy losses. The objective of this study was to investigate the impact of ballast properties (i.e., size, structure, end-group) on the faradaic and round-trip efficiency of the CGB. To accomplish this objective, we tested seven sugar and five glycol compounds as osmotic ballasts in a closed-loop cell. Results show that ballasts with high molecular weight generally resulted in higher faradaic efficiency and lower water transport compared with low molecular weight ballasts. Data also indicates that ballast with a cyclic structure (instead of linear), non-planar structure (instead of planar), and lower number of methyl end-groups led to lower water transport. Of all ballasts tested, sucrose performed best in terms of reducing non-ideal water transport (by 109%) and enhancing both faradaic and round-trip efficiencies (from 47.4% to 77.7% and 25.5% to 38.1%, respectively) compared with the non-ballasted CGB. Our results contribute to fundamental understanding of the impact of solute properties on water and small organic molecule transport in ion exchange membranes and indicate that ballasted CGBs can be further improved through development of optimized ballasts and selection of optimum membrane-ballast pairs. The improved understanding of ballast impact on CGB performance could be used for evaluation of potential ballast benefits in other membrane-based systems that may be impacted by osmosis such as the acid-base flow battery, waste heat recovery using RED, ED purification processes, osmotically assisted processes, and redox flow batteries.

Tunable Anion Exchange Membrane Conductivity and Permselectivity via Non-Covalent, Hydrogen Bond Cross-Linking.

Ion exchange membranes (IEMs) are a key component of electrochemical processes that purify water, generate clean energy, and treat waste. Most conventional polymer IEMs are covalently cross-linked, which results in a challenging tradeoff relationship between two desirable properties─high permselectivity and high conductivity─in which one property cannot be changed without negatively affecting the other. In an attempt to overcome this limitation, in this work we synthesized a series of anion exchange membranes containing non-covalent cross-links formed by a hydrogen bond donor (methacrylic acid) and a hydrogen bond acceptor (dimethylacrylamide). We show that these monomers act synergistically to improve both membrane permselectivity and conductivity relative to a control membrane without non-covalent cross-links. Furthermore, we show that the hydrogen bond donor and acceptor loading can be used to tune permselectivity and conductivity relatively independently of one another, escaping the tradeoff observed in conventional membranes.

Aqueous Stability of Zirconium Clusters, Including the Zr(IV) Hexanuclear Hydrolysis Complex [Zr6O4(OH)4(H2O)24]12+, from Density Functional Theory.

Framework materials constitute a broad family of solids that range from zeolites and metal-organic frameworks (MOFs) to coordination polymers. The synthesis of such network structures typically rely on precursor molecular building blocks. As an example, the UiO-66 MOF series is constructed of hexanuclear [Zr6O4(OH)4(CO2)12] cluster nodes and linear carboxylate linkers. Unfortunately, these Zr MOF cluster nodes cannot currently be manufactured in a sustainable way, motivating a search for "green" alternative synthesis methods. Stabilizing the hexanuclear Zr(IV) cluster (i.e., the hexamer, {Zr612+}) without the use of organic ligation would enable the use of environmentally friendly solvents such as water. The Zr(IV) tetranuclear cluster (i.e., the tetramer, {Zr48+}) can be stabilized in solution with or without organic ligands, yet the hexamer has yet to be synthesized without supporting ligands. The reasons why certain zirconium clusters are favored in aqueous solution over others are not well understood. This study reports the relative thermodynamic instability of the hypothetical hexamer {Zr612+} compared to the ubiquitous {Zr48+} tetramer. Density functional theory calculations were performed to obtain the hydrolysis Gibbs free energy of these species and used to construct Zr Pourbaix diagrams that illustrate the effects of electrochemical potential, pH, and Zr(IV) concentration. It was found that the aqueous {Zr612+} hexamer is ∼17.8 kcal/mol less stable than the aqueous {Zr48+} tetramer at pH = 0, V = 0, and [Zr(IV)] = 1 M, which is an energy difference on the order of counterion interactions. Electronic structure analyses were used to explore trends in the highest occupied molecular orbital-lowest unoccupied molecular orbital gap, frontier molecular orbitals, and electrostatic potential distribution of these clusters. The evidence suggests that the aqueous {Zr612+} hexamer may be promoted with more strategic syntheses incorporating minimal ligands and counterions.

A framework for quantifying uncertainty in DFT energy corrections.

In this work, we demonstrate a method to quantify uncertainty in corrections to density functional theory (DFT) energies based on empirical results. Such corrections are commonly used to improve the accuracy of computational enthalpies of formation, phase stability predictions, and other energy-derived properties, for example. We incorporate this method into a new DFT energy correction scheme comprising a mixture of oxidation-state and composition-dependent corrections and show that many chemical systems contain unstable polymorphs that may actually be predicted stable when uncertainty is taken into account. We then illustrate how these uncertainties can be used to estimate the probability that a compound is stable on a compositional phase diagram, thus enabling better-informed assessments of compound stability.

Junction Potentials Bias Measurements of Ion Exchange Membrane Permselectivity.

Ion exchange membranes (IEMs) are versatile materials relevant to a variety of water and waste treatment, energy production, and industrial separation processes. The defining characteristic of IEMs is their ability to selectively allow positive or negative ions to permeate, which is referred to as permselectivity. Measured values of permselectivity that equal unity (corresponding to a perfectly selective membrane) or exceed unity (theoretically impossible) have been reported for cation exchange membranes (CEMs). Such nonphysical results call into question our ability to correctly measure this crucial membrane property. Because weighing errors, temperature, and measurement uncertainty have been shown to not explain these anomalous permselectivity results, we hypothesized that a possible explanation are junction potentials that occur at the tips of reference electrodes. In this work, we tested this hypothesis by comparing permselectivity values obtained from bare Ag/AgCl wire electrodes (which have no junction) to values obtained from single-junction reference electrodes containing two different electrolytes. We show that permselectivity values obtained using reference electrodes with junctions were greater than unity for CEMs. In contrast, electrodes without junctions always produced permselectivities lower than unity. Electrodes with junctions also resulted in artificially low permselectivity values for AEMs compared to electrodes without junctions. Thus, we conclude that junctions in reference electrodes introduce two biases into results in the IEM literature: (i) permselectivity values larger than unity for CEMs and (ii) lower permselectivity values for AEMs compared to those for CEMs. These biases can be avoided by using electrodes without a junction.

Partitioning of Alkali Metal Salts and Boric Acid from Aqueous Phase into the Polyamide Active Layers of Reverse Osmosis Membranes.

The partition coefficient of solutes into the polyamide active layer of reverse osmosis (RO) membranes is one of the three membrane properties (together with solute diffusion coefficient and active layer thickness) that determine solute permeation. However, no well-established method exists to measure solute partition coefficients into polyamide active layers. Further, the few studies that measured partition coefficients for inorganic salts report values significantly higher than one (∼3-8), which is contrary to expectations from Donnan theory and the observed high rejection of salts. As such, we developed a benchtop method to determine solute partition coefficients into the polyamide active layers of RO membranes. The method uses a quartz crystal microbalance (QCM) to measure the change in the mass of the active layer caused by the uptake of the partitioned solutes. The method was evaluated using several inorganic salts (alkali metal salts of chloride) and a weak acid of common concern in water desalination (boric acid). All partition coefficients were found to be lower than 1, in general agreement with expectations from Donnan theory. Results reported in this study advance the fundamental understanding of contaminant transport through RO membranes, and can be used in future studies to decouple the contributions of contaminant partitioning and diffusion to contaminant permeation.

Osmotic Ballasts Enhance Faradaic Efficiency in Closed-Loop, Membrane-Based Energy Systems.

Aqueous processes for energy storage and conversion based on reverse electrodialysis (RED) require a significant concentration difference across ion exchange membranes, creating both an electrochemical potential and an osmotic pressure difference. In closed-loop RED, which we recently demonstrated as a new means of energy storage, the transport of water by osmosis has a very significant negative impact on the faradaic efficiency of the system. In this work, we use neutral, nonpermeating solutes as "osmotic ballasts" in a closed-loop concentration battery based on RED. We present experimental results comparing two proof-of-concept ballast molecules, and show that the ballasts reduce, eliminate, or reverse the net transport of water through the membranes when cycling the battery. By mitigating osmosis, faradaic and round-trip energy efficiency are more than doubled, from 18% to 50%, and 7% to 15%, respectively in this nonoptimized system. However, the presence of the ballasts has a slightly negative impact on the open circuit voltage. Our results suggest that balancing osmotic pressure using noncharged solutes is a promising approach for significantly reducing faradaic energy losses in closed-loop RED systems.

Effect of magnetic ion exchange and ozonation on disinfection by-product formation.

The purpose of this research was to investigate the performance of treatment with magnetic ion exchange (MIEX) resin followed by ozonation in achieving disinfection goals while controlling bromate and chlorinated disinfection by-product (DBP) formation. Three water samples were collected from raw water supplies impacted by the San Francisco Bay Delta to represent the varying levels of bromide and total organic carbon (TOC) that occur throughout the year. A fourth water was prepared by spiking bromide into a portion of one of the samples. Samples of each water were pre-treated with alum or virgin MIEX resin, and the raw and treated waters were subsequently ozonated under semi-batch conditions to assess the impact of treatment on ozone demand, ozone exposure for disinfection ("CT"), and bromate formation. Finally, aliquots of raw, coagulated, resin-treated, and ozonated waters were chlorinated in order to measure trihalomethane formation potential (THMFP). In the waters studied, MIEX resin removed 41-68% of raw water TOC, compared to 12-44% for alum. MIEX resin also reduced the bromide concentration by 20-50%. The removal of TOC by alum and MIEX resin significantly reduced the ozone demand of all waters studied, resulting in higher dissolved ozone concentrations and CT values for a given amount of ozone transferred into solution. For a given level of disinfection (CT), the amount of bromate produced by ozonation of MIEX-treated waters was similar to or slightly less than that of raw water and significantly less than that of alum-treated water. MIEX resin removed 39-85% of THMFP compared to 16-56% removal by alum. Ozonation reduced THMFP by 35-45% in all cases. This work indicates that in bromide-rich waters in which ozone disinfection is used, MIEX resin is a more appropriate treatment than alum for the removal of organic carbon, as it achieves superior TOC and THM precursor removal and decreases the production of bromate from ozone.