An official website of the United States government
Bio-based compostable starch aerogels have significant potential as a sustainable alternative to traditional polymer aerogels across various applications. However, they suffer from very significant shrinkage, shown in published work as 40–50% using existing processes. We hypothesized that the shrinkage is largely caused by pore collapse through the solvent exchange process, during which the water used to fabricate the starch matrix is replaced with ethanol. To mitigate this issue, this work introduces two strategies: (1) implementing a deep-freezing protocol (DFP) prior to the solvent exchange, followed by pure ethanol solvent exchanges instead of water/ethanol mixtures, and (2) incorporating chitin as a structural additive. As a baseline, we fabricated potato starch aerogels (PSAs) using conventional processes of mixing, heating, and retrogradation. By applying a DFP before pure ethanol exchanges, shrinkage was reduced from 44% to 10% in pure PSA samples. Furthermore, the addition of chitin reduced shrinkage to 8% in potato starch-chitin aerogels. Porosity, density, surface area, pore size distribution, thermal decomposition temperature, thermal conductivities, and scanning electron microscopy images demonstrate a correlation between reduced shrinkage and desired thermal material properties.
more »
« less
Structural Formation and Pore Control of Freeze-Cast Directional Graphene Aerogel (DGA)
Directional graphene aerogels (DGAs) are proposed as electrode materials to alleviate ionic and mass transport issues in organic redox flow batteries (ORFBs). DGAs with high pore directionality would provide low resistance channels for effective ionic charge and liquid electrolyte transport in these devices. DGAs’ porous and directional characteristics can be controlled by the growth of ice crystals during freeze casting, which is influenced by the self-diffusivity of water, phase change driving forces, water−ice graphene interactions, and convection in the water−graphene media. It is found that mass transport-related properties of DGAs, including pore size and directionality, show a significant dependence on freezing temperature, graphene oxide (GO) loadings, and synthesis vessel diameter-to-height ratio (D/H). For the freezing temperature change from −20 to −115 °C, the average pore size progressively decreased from 120 to 20 μm, and the pore directionality transitioned from lamellar to ill-defined structures. When GO loadings were increased from 2 to 10 mg/mL at a fixed freezing temperature, pore size reduction was observed with less defined directionality. Furthermore, the pore directionality diminished with an increased width-to-height aspect ratio of DGA samples due to the buoyancy-driven convective circulation, which interfered with the directional ice/pore growth. Understanding the comprehensive effects of these mechanisms enables the controlled growth of ice crystals, leading to graphene aerogels with highly directional microstructures.
more »
« less
- Award ID(s):
- 1933800
- PAR ID:
- 10492643
- Publisher / Repository:
- ACS Publications
- Date Published:
- Journal Name:
- ACS Applied Materials & Interfaces
- Volume:
- 16
- Issue:
- 1
- ISSN:
- 1944-8244
- Page Range / eLocation ID:
- 425-434
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract All cloud and climate models assume ice crystals grow as if they were formed from pure water, even though cloud and haze droplets are solutions. The freezing process of a solution droplet is different than that of a pure water droplet, as shown in prior work. This difference can potentially affect the particle’s subsequent growth as an ice crystal. We present measurements of ice crystal growth from frozen sodium chloride (NaCl) solution droplets in the button electrode levitation diffusion chamber at temperatures between −61° and −40°C. Measured scattering patterns show that concentrated solution droplets remain unfrozen with classical scattering fringes until the droplets freeze. Upon freezing, the scattering patterns become complex within 0.1 s, which is in contrast with frozen pure water particles that retain liquid-like scattering patterns for about a minute. We show that after freezing, solution particles initially grow as spherical-like crystals and then transition to faster growth indicative of a morphological transformation. The measurements indicate that ice formed from solution droplets grows differently and has higher growth rates than ice formed from pure water droplets. We use these results to develop a power-law-based parameterization that captures the supersaturation and mass dependencies.more » « less
-
Abstract The transport of water through nanoscale capillaries/pores plays a prominent role in biology, ionic/molecular separations, water treatment and protective applications. However, the mechanisms of water and vapor transport through nanoscale confinements remain to be fully understood. Angstrom-scale pores (~2.8–6.6 Å) introduced into the atomically thin graphene lattice represent ideal model systems to probe water transport at the molecular-length scale with short pores (aspect ratio ~1–1.9) i.e., pore diameters approach the pore length (~3.4 Å) at the theoretical limit of material thickness. Here, we report on orders of magnitude differences (~80×) between transport of water vapor (~44.2–52.4 g m −2 day −1 Pa −1 ) and liquid water (0.6–2 g m −2 day −1 Pa −1 ) through nanopores (~2.8–6.6 Å in diameter) in monolayer graphene and rationalize this difference via a flow resistance model in which liquid water permeation occurs near the continuum regime whereas water vapor transport occurs in the free molecular flow regime. We demonstrate centimeter-scale atomically thin graphene membranes with up to an order of magnitude higher water vapor transport rate (~5.4–6.1 × 10 4 g m −2 day −1 ) than most commercially available ultra-breathable protective materials while effectively blocking even sub-nanometer (>0.66 nm) model ions/molecules.more » « less
-
Layer-stacked graphene oxide (GO) membranes, in which unique two-dimensional (2D) water channels are formed between two neighboring GO nanosheets, have demonstrated great potential for aqueous phase separation. Subjects of crucial importance are to fundamentally understand the interlayer spacing ( i.e. channel height) of GO membranes in an aqueous environment, elucidate the mechanisms for water transport within such 2D channels, and precisely control the interlayer spacing to tune the membrane separation capability for targeted applications. In this investigation, we used an integrated quartz crystal mass balance (QCM-D) and ellipsometry to experimentally monitor the interlayer spacing of GO, reduced GO and crosslinked GO in aqueous solution and found that crosslinking can effectively prevent GO from swelling and precisely control the interlayer spacing. We then used molecular dynamics simulations to study the mass transport inside the 2D channels and proved that the chemical functional groups on the GO plane dramatically slow down water transport in the channels. Our findings on GO structure and water transport provide a necessary basis for further tailoring and optimizing the design and fabrication of GO membranes in various separation applications.more » « less
-
Acidic oxygen evolution reaction (OER) electrocatalysts that provide high activity, lower costs, and long-term stability are needed for the wide-scale adoption of proton-exchange membrane (PEM) water electrolyzers for generating hydrogen through electrochemical water splitting. We report the effects of chromium substitution and temperature treatments on the structure, OER activity, and electrochemical stability of ruthenium oxide (RuO2) aerogel OER electrocatalysts. RuO2 and Cr-substituted RuO2 aerogels (Ru0.6Cr0.4O2) were synthesized using sol–gel chemistry and then thermally treated at different temperatures. Introducing chromium into the synthesis increased the surface area (7–11 times higher) and pore volume (5–6 times higher) relative to RuO2 aerogels. X-ray diffraction analysis is consistent with s that Cr was substituted into the rutile RuO2 structure. X-ray photoelectron spectroscopy showed that trivalent Cr substitution altered the surface electronic structure and ratio of surface hydroxides. The specific capacitance values of Cr-substituted RuO2 aerogels were consistent with charge storage within a hydrous surface. Cr-substituted RuO2 aerogels exhibited 26 times the OER mass activity and 3.5 times the OER specific activity of RuO2 aerogels. Electrochemical stability tests show that Cr-substituted RuO2 aerogels exhibit similar stability to commercial RuO2. Understanding how metal substituents can be used to alter OER activity and stability furthers our ability to obtain highly active, durable, and lower-cost OER electrocatalysts for PEM electrolyzers.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript
- Journal Article:
- https://doi.org/10.1021/acsami.3c10998
