skip to main content


This content will become publicly available on May 10, 2024

Title: Nano-SCHeMe: Nanomaterial Sponge Coatings for Heavy Metals, an Environmental Remediation Platform
The presence of heavy metals in our water supply poses an immense global public health burden. Heavy metal consumption is tied to increased mortality and a wide range of insidious health outcomes. In recent years, great strides have been made toward nanotechnological approaches for environmental problems, specifically the design of adsorbents to detoxify water, as well as for a related challenge of recovering valuable metals at low concentrations. However, applying nanomaterials at scale and differentiating which nanomaterials are best suited for particular applications can be challenging. Here, we report a methodology for loading nanomaterial coatings onto adsorbent membranes, testing different coatings against one another, and leveraging these materials under a variety of conditions. Our tailored coating for lead remediation, made from manganese-doped goethite nanoparticles, can filter lead from contaminated water to below detectable levels when coated onto a cellulose membrane, and the coated membrane can be recovered and reused for multiple cycles through mild tuning of pH. The Nano-SCHeMe methodology demonstrates a platform approach for effectively deploying nanomaterials for environmental applications and for direct and fair comparisons among these nanomaterials. Moreover, this approach is flexible and expansive in that our coatings have the potential to be applied to a range of sorbents.  more » « less
Award ID(s):
1929356
NSF-PAR ID:
10432830
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
ACS ES&T Water
ISSN:
2690-0637
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Aqueous phosphate pollution can dramatically impact ecosystems, introducing a variety of environmental, economic, and public health problems. While novel remediation tactics based on nanoparticle binding have shown considerable promise in nutrient recovery from water, they are challenging to deploy at scale. To bridge the gap between the laboratory-scale nature of these nanostructure solutions and the practical benchmarks for deploying an environmental remediation tool, we have developed a nanocomposite material. Here, an economical, readily available, porous substrate is dip coated using scalable, water-based processes with a slurry of nanostructures. These nanomaterials have tailored affinity for specific adsorption of pollutants. Our Phosphate Elimination and Recovery Lightweight (PEARL) membrane can selectively sequester up to 99% of phosphate ions from polluted waters at environmentally relevant concentrations. Moreover, mild tuning of pH promotes at will adsorption and desorption of nutrients. This timed release allows for phosphate recovery and reuse of the PEARL membrane repeatedly for numerous cycles. We combine correlative microscopy and spectroscopy techniques to characterize the complex microstructure of the PEARL membrane and to unravel the mechanism of phosphate sorption. More broadly, through the example of phosphate pollution, this work describes a platform membrane approach based on nanostructures with specific affinity coated on a porous structure. Such a strategy can be tuned to address other environmental remediation challenges through the incorporation of other nanomaterials.

     
    more » « less
  2. Heavy metal contamination is one of the leading causes of water pollution, with known adverse effects on human health and the environment. This work demonstrates a novel custom-made 3D printable eco-friendly hydrogel and fabrication process that produces stable biocompatible adsorbents with the ability to capture and remove heavy metals from aqueous environments quickly and economically. The 3D printable ink contains alginate, gelatin, and polyethyleneimine (PEI), which binds heavy metals through primary and secondary amine side chains favoring heavy metal adsorption. The ink's rheological properties are optimized to create mechanically stable constructs, in the form of 3D-printed tablets, fabricated entirely by printing. The optimized tablets have high porosity and accessible surface area with multiple binding sites for heavy metal ion adsorption while the printing process enables rapid and affordable production with the potential for scale-up. The results demonstrate the contribution of hydrogel composition and rheology in determining the printability, stability, and heavy metal binding characteristics of the hydrogel, and indicate the critical role of the PEI in increasing stability of the printed construct, in addition to its metal binding properties. The highest removal capacity was obtained for copper, followed by cadmium, cobalt, and nickel ions. In the optimized formulation, each hydrogel tablet removed 60% from 100 ppm copper in 5 h and up to 98% in 18 h. For more concentrated solutions (1000 ppm), ∼25% of copper was removed in 18 h. The printed tablets are stable, robust, and can be produced in a single simple step from inexpensive biomaterials. The ink's tunability, excellent printability, and stability offer a universally applicable procedure for creating hydrogel-based structures for environmental remediation. These unique capabilities open new avenues for manufacturing tailor-made constructs with integrated functionality for water treatment and environmental applications. 
    more » « less
  3. null (Ed.)
    Graphene-based 3D macroscopic aerogels with their hierarchical porous structures and mechanical strength have been widely explored for removing contaminants from water. However, their large-scale manufacturing and application in various water treatment processes are limited by their scalability. In this study, we report a proof-of-concept direct ink writing (DIW) 3D printing technique and subsequent freeze-drying to prepare graphene-biopolymer aerogels for water treatment. To provide appropriate rheology for DIW printability, two bio-inspired polymers, polydopamine (PDA) and bovine serum albumin (BSA), were added to the graphene-based ink. The biopolymers also contributed to the contaminant removal capacity of the resultant graphene-polydopamine-bovine serum albumin (G-PDA-BSA) aerogel. The physicochemical properties of the aerogel were thoroughly characterized from the nano- to macroscale. The 3D printed aerogel exhibited excellent water contaminant removal performance for heavy metals (Cr( vi ), Pb( ii )), organic dyes (cationic methylene blue and anionic Evans blue), and organic solvents ( n -hexane, n -heptane, and toluene) in batch adsorption studies. The electrostatic interaction dominated the removal of heavy metals and dyes while the hydrophobic interaction dominated the removal of organic solvents from water. Moreover, the aerogel showed superb regeneration and reuse potential. The aerogel removed 100% organic solvents over 10 cycles of regeneration and reuse; additionally, the removal efficiencies for methylene blue decreased by 2–20% after the third cycle. The fit-for-design 3D printed aerogel was also effectively used as a bottle-cap flow-through filter for dye removal. The potential and vision of the 3D printing approach for graphene-based water treatment presented here can be extended to other functional nanomaterials, can enable shape-specific applications of fit-for-purpose adsorbents/reactors and point-of-use filters, and can materialize the large-scale manufacturing of nano-enabled water treatment devices and technologies. 
    more » « less
  4. Semiconductor InSe 2D nanomaterials have emerged as potential photoresponsive materials for broadly distributed photodetectors and wearable electronics technologies due to their high photoresponsivity and thermal stability. This paper addresses an environmental concern about the fate of InSe 2D nanosheets when disposed and released into the environment after use. Semiconducting materials are potentially reactive and often form environmentally damaging species, for example reactive oxygen and nitrogen species, when degraded. InSe nanosheets are prepared using a semi bottom-up approach which involves a reaction between indium and selenium precursors at elevated temperature in an oxygen-free environment to prevent oxidation. InSe nanosheets are formed as a stable intermediate with micrometer-sized lateral dimensions and a few monolayer thickness. The InSe 2D nanosheets are obtained when the reaction is stopped after 30 minutes by cooling. Keeping the reaction at elevated temperature for a longer period, for example 60 minutes leads to the formation of InSe 3D nanoparticles of about 5 nm in diameter, a thermodynamically more stable form of InSe. The paper focuses on the colloidal stabilization of InSe nanosheets in an aqueous solution that contains epigallocatechin gallate (EGCG), a natural organic matter (NOM) simulant. We show that EGCG coats the surface of the hydrophobic, water-insoluble InSe nanosheets via physisorption. The formed EGCG-coated InSe nanosheets are colloidally stable in aqueous solution. While unmodified semiconducting InSe nanosheets could produce reactive oxygen species (ROS) when illuminated, our study shows low levels of ROS generation by EGCG-coated InSe nanosheets under ambient light, which might be attributed to ROS quenching by EGCG. Growth-based viability (GBV) assays show that the colloidally stable EGCG-coated InSe nanosheets adversely impact the bacterial growth of Shewanella oneidensis MR-1, an environmentally relevant Gram-negative bacterium in aqueous media. The impact on bacterial growth is driven by the EGCG coating of the nanosheets. In addition, live/dead assays show insignificant membrane damage of the Shewanella oneidensis MR-1 cells by InSe nanosheets, suggesting a weak association of EGCG-coated nanosheets with the cells. It is likely that the adverse impact of EGCG-coated nanosheets on bacterial growth is the result of increasing local concentration of EGCG either when adsorbed on the nanosheets when the nanosheets interact with the cells, or when desorbed from the EGCG-coated nanosheets to interact with the bacterial cells. 
    more » « less
  5. Surface patterning of inorganic nanoparticles through site-selective functionalization with mixed-ligand shells or additional inorganic material is an intriguing approach to developing tailored nanomaterials with potentially novel and/or multifunctional properties. The unique physicochemical properties of such nanoparticles are likely to impact their behavior and functionality in biological environments, catalytic systems, and electronics applications, making it vital to understand how we can achieve and characterize such regioselective surface functionalization. This Feature Article will review methods by which chemists have selectively modified the surface of colloidal nanoparticles to obtain both two-sided Janus particles and nanoparticles with patchy or stripey mixed-ligand shells, as well as to achieve directed growth of mesoporous oxide materials and metals onto existing nanoparticle templates in a spatially and compositionally controlled manner. The advantages and drawbacks of various techniques used to characterize the regiospecificity of anisotropic surface coatings are discussed, as well as areas for improvement, and future directions for this field. 
    more » « less