Chelation-directed interface engineering of in-place self-cleaning membranes.

Water-energy sustainability will depend upon the rapid development of advanced pressure-driven separation membranes. Although energy-efficient, water-treatment membranes are constrained by ubiquitous fouling, which may be alleviated by engineering self-cleaning membrane interfaces. In this study, a metal-polyphenol network was designed to direct the armorization of catalytic nanofilms (ca. 18 nm) on inert polymeric membranes. The chelation-directed mineralized coating exhibits high polarity, superhydrophilicity, and ultralow adhesion to crude oil, enabling cyclable crude oil-in-water emulsion separation. The in-place flux recovery rate exceeded 99.9%, alleviating the need for traditional ex situ cleaning. The chelation-directed nanoarmored membrane exhibited 48-fold and 6.8-fold figures of merit for in-place self-cleaning regeneration compared to the control membrane and simple hydraulic cleaning, respectively. Precursor interaction mechanisms were identified by density functional theory calculations. Chelation-directed armorization offers promise for sustainable applications in catalysis, biomedicine, environmental remediation, and beyond.

Advanced Materials for Energy-Water Systems: The Central Role of Water/Solid Interfaces in Adsorption, Reactivity, and Transport.

The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the water-and often the water molecules themselves-to detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena. Despite the importance of these interfaces, much remains to be learned about their multiscale interactions. Developing a deeper understanding of the molecular- and mesoscale phenomena at water/solid interfaces will be essential to driving innovation to address grand challenges in supplying sufficient fit-for-purpose water in the future. In this Review, we examine the current state of knowledge surrounding adsorption, reactivity, and transport in several key classes of water/solid interfaces, drawing on a synergistic combination of theory, simulation, and experiments, and provide an outlook for prioritizing strategic research directions.

Molecular interactions in short-chain perfluoroalkyl carboxylic acids and aqueous solutions.

The presence of short-chain per- and polyfluoroalkyl substances in water poses a major health and environmental challenge. Here, we have performed high-energy small- and wide-angle X-ray scattering measurements on CF3[CF2]nCOOH (where n = 1, 2, 3 represents the chain length) and their aqueous solutions at 10% mole concentrations to characterize their molecular interactions at the atomic and nanometer length scales. The experimental wide-angle structure factors have been modelled using Empirical Potential Structural Refinement. The oxygen-oxygen partial X-ray pair distribution functions show that the coordination number between the hydroxyl oxygen on the acid and surrounding oxygen water molecules increases significantly with acid chain length, rising from 3.2 for n = 1 to 4.1 for n = 3. The small-angle scattering is dominated by a sharp, high-intensity peak at Q1 ∼ 0.2 Å-1 and a smaller peak at Q2 = 1.2 Å-1 for n = 3, both of which decrease with decreasing chain length. The Q2 peak is attributed to groups of adjacent non-bonded acid molecules, and Q1 has contributions from both correlations between acid molecules and water-water interactions. In all cases, the models show nanoscale aggregation occurs in the form of denser channels of winding hydrogen-bonded chains, approximately 20 water molecules in length, surrounding clusters of acid molecules. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Surface Zeta Potential of ALD-Grown Metal-Oxide Films.

Membranes are among the most promising technologies for energy-efficient and highly selective separations, and the surface-charge property of membranes plays a critical role in their broad applications. Atomic layer deposition (ALD) can deposit materials uniformly and with high precision and controllability on arbitrarily complex and large substrates, which renders it a promising method to tune the electrostatics of water/solid interfaces. However, a systematic study of surface-charge properties of ALD-grown films in aqueous environments is still lacking. In this work, 17 ALD-grown metal-oxide films are synthesized, and a comprehensive study of their water stability, wetting properties, and surface-charge properties is provided. This work represents a resource guide for researchers and ultimately for materials and process engineers, seeking to tailor interfacial charge properties of membranes and other porous water treatment components.

Enrichment and Distribution of Pb2+ Ions in Zwitterionic Poly(cysteine methacrylate) Brushes at the Solid-Liquid Interface.

Cysteine-based polyzwitterionic brushes have been prepared via a two-step route. First, poly(allyl methacrylate) (PAMA) brushes have been grown from the surface of silicon substrates using surface-initiated atom transfer radical polymerization. The obtained PAMA brushes with free pendant vinyl groups were further modified via radical thiol-ene addition reaction to attach l-cysteine moieties. Surface ζ potential investigations on pH-responsiveness of these poly(cysteine methacrylate) (PCysMA) brushes confirm their zwitterionic character at intermediate pH range, while at pH values either below pH 3.50 or above pH 8.59, they exhibit polyelectrolyte character. Under acid (pH < 3.50) or base (pH > 8.59) conditions, they possess either cationic or anionic character, respectively. In the zwitterionic region, these PCysMA brushes show positive surface ζ potential in the presence of Pb(CH3COO)2 solutions of various concentrations. The results are in line with microscopic investigations using anomalous X-ray reflectivity (AXRR) carried out along the absorption edge of Pb2+ ions. When the photon energies were varied around the absorption L3 edge of lead (13037 eV), the Pb2+ concentration normal to the silicon substrates, as a function of depth inside PCysMA brushes, could be revealed at the nanoscale. Both ζ potential and AXRR measurements confirm the enrichment of Pb2+ ions inside PCysMA brushes, indicating the potential of PCysMA to be used as a water purification material.

The chemical physics of sequential infiltration synthesis-A thermodynamic and kinetic perspective.

Sequential infiltration synthesis (SIS) is an emerging materials growth method by which inorganic metal oxides are nucleated and grown within the free volume of polymers in association with chemical functional groups in the polymer. SIS enables the growth of novel polymer-inorganic hybrid materials, porous inorganic materials, and spatially templated nanoscale devices of relevance to a host of technological applications. Although SIS borrows from the precursors and equipment of atomic layer deposition (ALD), the chemistry and physics of SIS differ in important ways. These differences arise from the permeable three-dimensional distribution of functional groups in polymers in SIS, which contrast to the typically impermeable two-dimensional distribution of active sites on solid surfaces in ALD. In SIS, metal-organic vapor-phase precursors dissolve and diffuse into polymers and interact with these functional groups through reversible complex formation and/or irreversible chemical reactions. In this perspective, we describe the thermodynamics and kinetics of SIS and attempt to disentangle the tightly coupled physical and chemical processes that underlie this method. We discuss the various experimental, computational, and theoretical efforts that provide insight into SIS mechanisms and identify approaches that may fill out current gaps in knowledge and expand the utilization of SIS.

Effect of Nanostructured Domains in Self-Assembled Block Copolymer Films on Sequential Infiltration Synthesis.

There are broad interests in selective and localized synthesis in nanodomains of self-assembled block copolymers (BCPs) for a variety of applications. Sequential infiltration synthesis (SIS) shows promise to selectively grow a controllable amount of materials in one type of nanodomain of a self-assembled BCP film. However, the effects of nanostructured domains in a BCP film and SIS cycles on the material growth behavior of SIS are rarely studied. In this work, we investigated the growth behavior of TiO2 SIS within self-assembled polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films and the two corresponding pure homopolymer films (PS and PMMA) by using in situ quartz crystal microbalance (QCM). According to the experimental results, reactant purge steps are essential to enable a high selectivity of SIS in PMMA nanodomains in the BCP films by eliminating the undesired homogeneous reactions. The continuous PS nanodomain acts as the main channel in transporting reactants to PMMA nanodomains in the self-assembled PS-b-PMMA BCP films. The segregated nanoscale PMMA nanodomains in the BCP films show dramatically different TiCl4 diffusion/reaction behavior than a continuous PMMA film. The mass gain per SIS cycle within PMMA nanodomains decreases quickly with increasing cycle number. After 7 TiO2 SIS cycles, TiO2 SIS can only take place at the interface between PS and PMMA nanodomains in the BCP film. The TiO2 SIS process can uniformly modify PMMA nanodomains throughout a self-assembled PS-b-PMMA film up to the diffusion depth owing to the unique nanostructure-enabled diffusion. SIS cycle number and chemistry of a BCP will strongly affect the material growth behavior of a SIS chemistry on the BCP film and, therefore, the final morphology of the resulting nanomaterial. Detailed studies are warranted for a SIS process on a self-assembled BCP film of different chemistry.

L-Tryptophan on Cu(111): engineering a molecular labyrinth driven by indole groups.

The present article investigates the adsorption and molecular orientation of L-Tryptophan, which is both an essential amino acid important for protein synthesis and of particular interest for the development of chiral molecular electronics and biocompatible processes and devices, on Cu(111) using scanning tunneling microscopy and spectroscopy at 55 K and at room temperature. The arrangement of chemisorbed L-Tryptophan on the copper surface varies with both temperature and surface coverage. At low coverage, small clusters form on the surface irrespective of temperature, while at high coverage an ordered chain structure emerges at room temperature, and a tightly packed structure forms a molecular labyrinth at low temperature. The dominating superstructure of the adsorbates arises from intermolecular hydrogen bonding, and π-bonding interactions between the indole groups of neighboring molecules and the Cu surface.

Kinetically Enhanced Approach for Rapid and Tunable Self-Assembly of Rod-Coil Block Copolymers.

A facile approach is reported to process rod-coil block copolymers (BCPs) into highly ordered nanostructures in a rapid, low-energy process. By introducing a selective plasticizer into the rod-coil BCPs during annealing, both the annealing temperature and time to achieve thermodynamic equilibrium and highly ordered structures can be decreased. This process improvement is attributed to enhanced chain mobility, reduced rod-rod interaction, and decreased rod-coil interaction from the additive. The novel method is based on kinetically facilitating thermodynamic equilibrium. The process requires no modification of polymer structure, indicating that a wide variety of desired polymer functionalities can be designed into BCPs for specific applications.

Exciton size and quantum transport in nanoplatelets.

Two-dimensional nanoplatelets (NPLs) are an exciting class of materials with promising optical and energy transport properties. The possibility of efficient energy transport between nanoplatelets raises questions regarding the nature of energy transfer in these thin, laterally extended systems. A challenge in understanding exciton transport is the uncertainty regarding the size of the exciton. Depending on the material and defects in the nanoplatelet, an exciton could plausibly extend over an entire plate or localize to a small region. The variation in possible exciton sizes raises the question how exciton size impacts the efficiency of transport between nanoplatelet structures. Here, we explore this issue using a quantum master equation approach. This method goes beyond the assumptions of Förster theory to allow for quantum mechanical effects that could increase energy transfer efficiency. The model is extremely flexible in describing different systems, allowing us to test the effect of varying the spatial extent of the exciton. We first discuss qualitative aspects of the relationship between exciton size and transport and then conduct simulations of exciton transport between NPLs for a range of exciton sizes and environmental conditions. Our results reveal that exciton size has a strong effect on energy transfer efficiency and suggest that manipulation of exciton size may be useful in designing NPLs for energy transport.

Process-controlled multiscale morphologies in metal-containing block copolymer thin films.

Poly(styrene-block-ferrocenyldimethylsilane) (PS-b-PFS) is a metal-containing block copolymer that exhibits certain advantages as a scaffold for nanoporous membranes and as a mask for lithographic applications. These advantages include compatibility with a wide range of substrates, ease of control over domain morphologies and remarkable stability, which aid in the development of robust nanoporous networks or high-aspect-ratio patterns. An asymmetric cylinder-forming PS-b-PFS copolymer is subjected to different processing to manipulate the morphology of the phase-separated domains. Control of film structure and domain morphology is achieved by adjusting the film thickness, mode of annealing, and/or annealing time. Changing the process from thermal or solvent annealing to hybrid annealing (thermal and then solvent annealing in sequence) leads to the formation of mesoscale spherulitic and dendritic morphologies. In this communication, we show that reversing the order of the hybrid annealing (solvent annealing first and then thermal annealing) of relatively thick films (> 100 nm) on homogeneously thick substrates develops a discontinuous lamellar structure. Furthermore, the same processing applied on a substrate with a thin, mechanically flexible window in the center leads to the formation of sub-micron scale concentric ring patterns. Enhanced material mobility in the thick film during hybrid annealing along with dynamic rippling effects that may arise from the vibration of the thin window during spin casting are likely causes for these morphologies.

Visualization of hierarchical nanodomains in polymer/fullerene bulk heterojunction solar cells.

Traditional electron microscopy techniques such as bright-field imaging provide poor contrast for organic films and identification of structures in amorphous material can be problematic, particularly in high-performance organic solar cells. By combining energy-filtered corrected transmission electron microscopy, together with electron energy loss and X-ray energy-dispersive hyperspectral imaging, we have imaged PTB7/PC61BM blended polymer optical photovoltaic films, and were able to identify domains ranging in size from several hundred nanometers to several nanometers in extent. This work verifies that microstructural domains exist in bulk heterojunctions in PTB7/PC61BM polymeric solar cells at multiple length scales and expands our understanding of optimal device performance providing insight for the design of even higher performance cells.

The brine of the times.

New processes directly extract lithium from dilute sources.

Influence of the Dielectric Constant on the Ionic Current Rectification of Bipolar Nanopores.

In this paper, we investigate how the dielectric constant, ϵ, of an electrolyte solvent influences the current rectification characteristics of bipolar nanopores. It is well recognized that bipolar nanopores with two oppositely charged regions rectify current when exposed to an alternating electric potential difference. Here, we consider dilute electrolytes with NaCl only and with a mixture of NaCl and charged nanoparticles. These systems are studied using two levels of description, all-atom explicit water molecular dynamics (MD) simulations and coarse-grained implicit solvent MD simulations. The charge density and electric potential profiles and current-voltage relationship predicted by the implicit solvent simulations with ϵ = 11.3 show good agreement with the predictions from the explicit water simulations. Under nonequilibrium conditions, the predictions of the implicit solvent simulations with a dielectric constant closer to the one of bulk water are significantly different from the predictions obtained with the explicit water model. These findings are closely aligned with experimental data on the dielectric constant of water when confined to nanometric spaces, which suggests that ϵ decreases significantly compared to its value in the bulk. Moreover, the largest electric current rectification is observed in systems containing nanoparticles when ϵ = 78.8. Using enhanced sampling, we have shown that this larger rectification arises from the presence of a significantly deeper minimum in the free energy of the system with a larger ϵ, and when a negative voltage bias is applied. Since implicit solvent models and mean-field continuum theories are often used to design Janus membranes based on bipolar nanopores, this work highlights the importance of properly accounting for the effects of confinement on the dielectric constant of the electrolyte solvent. The results presented here indicate that the dielectric constant in implicit solvent simulations may be used as an adjustable parameter to approximately account for the effects of nanometric confinement on aqueous electrolyte solvents.

Protein-activated atomic layer deposition for robust crude-oil-repellent hierarchical nano-armored membranes.

Atomic layer deposition (ALD) offers unique capabilities to fabricate atomically engineered porous materials with precise pore tuning and multi-functionalization for diverse applications like advanced membrane separations towards sustainable energy-water systems. However, current ALD technique is inhibited on most non-polar polymeric membranes due to lack of accessible nucleation sites. Here, we report a facile method to efficiently promote ALD coating on hydrophobic surface of polymeric membranes via novel protein activation/sensitization. As a proof of concept, TiO2 ALD-coated membranes activated by bovine serum albumin exhibit remarkable superhydrophilicity, ultralow underwater crude oil adhesion, and robust tolerance to rigorous environments including acid, alkali, saline, and ethanol. Most importantly, excellent cyclable crude oil-in-water emulsion separation performance can be achieved. The mechanism for activation/sensitization is rooted in reactivity for a particular set of amino acids. Furthermore, the universality of protein-sensitized ALD is demonstrated using common egg white, promising numerous potential usages in biomedical engineering, environmental remediation, low-carbon manufacturing, catalysis, and beyond.

Thiol-Functionalized Adsorbents through Atomic Layer Deposition and Vapor-Phase Silanization for Heavy Metal Ion Removal.

The removal of toxic heavy metal ions from water resources is crucial for environmental protection and public health. In this study, we address this challenge by developing a surface functionalization technique for the selective adsorption of these contaminants. Our approach involves atomic layer deposition (ALD) followed by vapor-phase silanization of porous substrates. We utilized porous silica gel powder (∼100 µm particles, 89 m2/g surface area, ∼30 nm pores) as an initial substrate. This powder was first coated with ∼0.5 nm ALD Al2O3, followed by vapor-phase grafting of a thiol-functional silane. The modified powder, particularly in acidic conditions (pH = 4), showed high selectivity in adsorbing Cd(II), As(V), Pb(II), Hg(II), and Cu(II) heavy metal ions in mixed ion solutions over common benign ions (e.g., Na, K, Ca, and Mg). Langmuir adsorption isotherms and breakthrough adsorption studies were conducted to assess heavy metal binding affinity and revealed the order of Cd(II) < Pb(II) < Cu(II) < As(V) < Hg(II), with a significantly higher affinity for As(V) and Hg(II) ions. Time-dependent uptake studies demonstrated rapid removal of heavy metal ions from aqueous environments, with Hg(II) exhibiting the fastest adsorption kinetics on thiol-modified surfaces. These findings highlight the potential of ALD and vapor-phase silanization to create effective adsorbents for the targeted removal of hazardous contaminants from water.

Lanthanides: new metallic cathode materials for organic photovoltaic cells.

Organic photovoltaics (OPVs) are compliant with inexpensive, scalable, and environmentally benign manufacturing technologies. While substantial attention has been focused on optimization of active layer chemistry, morphology, and processing, far less research has been directed to understanding charge transport at the interfaces between the electrodes and the active layer. Electrical properties of these interfaces not only impact efficiency, but also play a central role in stability of organic solar cells. Low work function metals are the most widely used materials for the electron transport layer with Ca being the most common material. In bulk heterojunction OPV devices, low work function metals are believed to mirror the role they play in OLEDs, where such metals are used to control carrier selectivity, transport, extraction, and blocking, as well as interface band bending. Despite their advantages, low work function materials are generally prone to reactions with water, oxygen, nitrogen, and carbon dioxide from air leading to rapid device degradation. Here we discuss the search for a new metallic cathode interlayer material that increases device stability and still provides device efficiency similar to that achieved with a Ca interlayer.

Nanofluidic computing makes a splash.

Ionic computing raises the possibility of devices that operate similarly to the human brain.

Engineering In Situ Catalytic Cleaning Membrane Via Prebiotic-Chemistry-Inspired Mineralization.

Pressure-driven membrane separation promises a sustainable energy-water nexus but is hindered by ubiquitous fouling. Natural systems evolved from prebiotic chemistry offer a glimpse of creative solutions. Herein, a prebiotic-chemistry-inspired aminomalononitrile (AMN)/Mn2+ -mediated mineralization method is reported for universally engineering a superhydrophilic hierarchical MnO2 nanocoating to endow hydrophobic polymeric membranes with exceptional catalytic cleaning ability. Green hydrogen peroxide catalytically triggered in-situ cleaning of the mineralized membrane and enabled operando flux recovery to reach 99.8%. The mineralized membrane exhibited a 9-fold higher recovery compared to the unmineralized membrane, which is attributed to active catalytic antifouling coupled with passive hydration antifouling. Electron density differences derived from the precursor interaction during mediated mineralization unveiled an electron-rich bell-like structure with an inner electron-deficient Mn core. This work paves the way to construct multifunctional engineered materials for energy-efficient water treatment as well as for diverse promising applications in catalysis, solar steam generation, biomedicine, and beyond.

Material Design Strategies for Recovery of Critical Resources from Water.

Population growth, urbanization, and decarbonization efforts are collectively straining the supply of limited resources that are necessary to produce batteries, electronics, chemicals, fertilizers, and other important products. Securing the supply chains of these critical resources via the development of separation technologies for their recovery represents a major global challenge to ensure stability and security. Surface water, groundwater, and wastewater are emerging as potential new sources to bolster these supply chains. Recently, a variety of material-based technologies have been developed and employed for separations and resource recovery in water. Judicious selection and design of these materials to tune their properties for targeting specific solutes is central to realizing the potential of water as a source for critical resources. Here, the materials that are developed for membranes, sorbents, catalysts, electrodes, and interfacial solar steam generators that demonstrate promise for applications in critical resource recovery are reviewed. In addition, a critical perspective is offered on the grand challenges and key research directions that need to be addressed to improve their practical viability.