James
Malloy
a,
Erin
Marlowe
a,
Christopher J.
Jensen
a,
Isaac S.
Liu
ab,
Thomas
Hulse
ac,
Anne F.
Murray
d,
Daniel
Bryan
d,
Thomas G.
Denes
d,
Dustin A.
Gilbert
e,
Gen
Yin
a and
Kai
Liu
*a
aDepartment of Physics, Georgetown University, Washington, DC 20057, USA. E-mail: kai.liu@georgetown.edu
bDepartment of Computer Science, Vanderbilt University, Nashville, TN 37235, USA
cDepartment of Physics, University of Louisville, Louisville, KY 40292, USA
dDepartment of Food Science, University of Tennessee, Knoxville, TN 37996, USA
eDepartment of Materials Science and Engineering, University of Tennessee, Knoxville, TN 37996, USA
First published on 17th July 2024
The COVID-19 pandemic has shown the urgent need for the development of efficient, durable, reusable and recyclable filtration media for the deep-submicron size range. Here we demonstrate a multifunctional filtration platform using porous metallic nanowire foams that are efficient, robust, antimicrobial, and reusable, with the potential to further guard against multiple hazards. We have investigated the foam microstructures, detailing how the growth parameters influence the overall surface area and characteristic feature size, as well as the effects of the microstructures on the filtration performance. Nanogranules deposited on the nanowires during electrodeposition are found to greatly increase the surface area, up to 20 m2 g−1. Surprisingly, in the high surface area regime, the overall surface area gained from the nanogranules has little correlation with the improvement in capture efficiency. However, nanowire density and diameter play a significant role in the capture efficiency of PM0.3 particles, as do the surface roughness of the nanowire fibers and their characteristic feature sizes. Antimicrobial tests on the Cu foams show a >99.9995% inactivation efficiency after contacting the foams for 30 seconds. These results demonstrate promising directions to achieve a highly efficient multifunctional filtration platform with optimized microstructures.
Many novel filter materials have been studied in light of the COVID-19 pandemic, including electrostatically charged Polyvinylidene fluoride (PVDF) nanofibers,13 nanoparticle imbedded protein nanofibrils,14 Ag-imbedded polymers,15–17 porous metal–organic frameworks (MOFs),18–21 and carbon nanotubes.22–24 Metallic filtraton media with no polymer components are particularly promising, as they can withstand high temperatures, ionizing radiation, and exposure to oils, all of which cause polymers to rapidly degrade.25–27 Conventional porous metal foams often utilize sizable building blocks, with micron-scale dimensions and larger, which are inefficient against deep-submicron particulates that are the hardest to capture.28,29 Recently advances in metallic nanowire networks and foams offer a promising new platform for explorations in catalysis, gas storage, nanomagnetics and neuromorphic computing.30–35 However, most such metallic monoliths are not mechanically robust enough to be useful as practical filters. It is challenging to realize nanoporous metallic foams that maintain nanoscale dimensions, which are essential for deep micron particulate filtration, and are also mechanically robust.
Previously, we have demonstrated that nanowire-based low-density metal foams, synthesized by electrodeposition and sintering, are robust enough to withstand air speeds of over 20 m s−1 and pressure differentials of over several atmospheres without showing any sign of deformation or degradation.36 Further, they also exhibit extremely large surface areas as well as outstanding filtration efficiencies (>96.6%) in the PM0.3 regime with breathability comparable to N-95 respirators.36 They can also be easily cleaned36 and decontaminated37 to allow sustained use, and eventually recycled at the end of their useful lifetime.38
Despite the promising initial results on such nanoporous metallic foams, a quantitative understanding of how the synthesis conditions and foam microstructures affect the filtration performance is still lacking. To enhance the foam mechanical stability, a second electrodeposition process was used to reinforce the intersections of the Cu foams.36 An accompanying effect is a significant change in the foam surface areas and morphology due to nanogranule growths along the nanowires. In such 3D interconnected foams, it is critical to understand the correlation between the foam microstructures and the filtration performance.
In this study we have quantitatively investigated how the nanoporous foam microstructures impact the filtration performance, particularly against particulates that are around 0.3 μm in size used in standardized filtration efficiency tests.28,29 We distinguish the effects of surface area enhancement vs. the density of nanoscale feature sizes comparable to the particulates being filtered. Interestingly, while foam surface areas are generally important for filtration efficiency, for high surface areas in the range of 1 m2 g−1 and beyond, the sizes of the foam surface features play a more prominent role. These results demonstrate nanoporous metallic nanowire foams as a multi-functional platform for deep submicron particulate filtration that is efficient, robust, antimicrobial, and reusable, with the potential to further guard against multiple hazards.
Subsequently, the foams were strengthened further using a secondary electrodeposition (2ED) step to achieve a final density ρf, in a bath of copper sulfate along with a mixture of leveler, accelerator, and suppressor compounds to ensure even and homogeneous plating.36 The resulting foams were significantly stronger and more durable due to increased bonding areas at intersections of nanowires, while still retaining a high surface area and an excellent filtration efficiency.36
The morphology of the foams varied widely depending on the amount of secondary electroplating as well as other factors (Fig. 1). As the 2ED process began, small nanogranules started to deposit along the surface of the NWs (Fig. 1a, for a ρf = 2.2% density foam). As the amount of copper plated increased, these nanogranules began to increase in size (Fig. 1b, for a ρf = 5% density foam). With enough plating, e.g., for a foam with a ρf = 30% density, the nanogranules eventually coalesced together, enclosing multiple nanowires into larger filaments with smoother surfaces (Fig. 1c). The foam microstructures could be further tuned by the electrolyte conditions, e.g., lowering the pH value of the solution reduced the nanograin feature size deposited on the nanowire surface and increased the overall surface smoothness (see ESI†). Final optimized foams exhibit both low density and strong mechanical strength that are essential for filtration media applications (Fig. 2a and b).
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Fig. 2 Robust and breathable light-weight foam. (a) A 120 mg 15% bulk density foam 9 mm in diameter resting on the tip of a feather. (b) The same foam supporting a 1.8 kg weight. (c) Comparison of measured (blue) vs. calculated (red) breathability for foam samples with various initial density ρi (%), final density ρf (%), and thickness t (mm). A 15% bulk density foam (sample 7) similar to the one pictured in panels (a) and (b) has a comparable breathability to an N-95 respirator (purple line). Panels (a) and (b) adapted with permission of ASM International, from Ref. 41. |
Sample ID | ρ i (%) | ρ f (%) | t (mm) | ΔP/v (kPa m−1 s) | Efficiency (%) (measured) | F QE | F QC | F QC error (%) | F QSF | Q Measured | Q Calcu. |
---|---|---|---|---|---|---|---|---|---|---|---|
a Including ![]() |
|||||||||||
1 | 2.0 | 3.5 | 0.9 | 0.48 ± 0.04 | 91.0 ± 0.1 | 2.41 ± 0.01 | 2.59 | 7.5 | 2.43 | 5.02 ± 0.41 | 4.87 |
2 | 2.0 | 5.0 | 0.9 | 0.58 ± 0.03 | 84.2 ± 3.0 | 1.85 ± 0.19 | 1.98 | 7.0 | 1.87 | 3.19 ± 0.36 | 3.47 |
3 | 2.5 | 5.4 | 1.0 | — | 92.5 ± 0.1 | 2.59 ± 0.01 | 2.92 | 13 | — | — | — |
4 | 3.2 | 5.0 | 0.9 | 1.88 ± 0.12 | 99.0 ± 0.1 | 4.61 ± 0.10 | 3.95 | −14 | 4.56 | 2.45 ± 0.15 | 2.68 |
5 | 2.5 | 6.8 | 1.0 | — | 89.1 ± 0.1 | 2.22 ± 0.09 | 2.60 | 17 | — | — | — |
6 | 2.0 | 9.0 | 1.0 | 0.73 ± 0.03 | 81.1 ± 0.5 | 1.67 ± 0.02 | 1.62 | −3.0 | 1.71 | 2.29 ± 0.10 | 2.31 |
7 | 2.0 | 15 | 1.0 | 0.97 ± 0.11 | 76.8 ± 1.3 | 1.46 ± 0.05 | 1.25 | −14 | 1.41 | 1.51 ± 0.18 | 1.22 |
8 | 2.0 | 15 | 2.5 | 2.76 ± 0.21 | 96.6 ± 2.0 | 3.38 ± 0.67 | 3.13 | −7.4 | — | — | — |
9 | 2.0 | 30 | 1.0 | 4.67 ± 0.24 | 54.2 ± 0.5 | 0.78 ± 0.01 | 0.88 | 13 | 0.77 | 0.17 ± 0.01 | 0.18 |
For comparison, an N-95 respirator has a pressure drop coefficient of around 1.0 kPa m−1 s.36 Our ρf = 15% foams (sample 7, ΔP/v = 0.97 ± 0.11 kPa m−1 s) were found to have breathability comparable to an N-95, while also being light-weight enough to rest comfortably on the tip of a feather (Fig. 2a) and structurally robust enough to support a 1.8 kg weight without collapse or deformation (Fig. 2b). Most of our 1 mm thick foams with ρf ≤ 15% (samples 1–7) exhibit excellent breathability, which improves as foam thickness and packing density decrease, with the ultra-low density ρf = 3.5% foam (Table 1, sample 1, ΔP/v = 0.48 ± 0.04 kPa m−1 s) being over twice as breathable as an N-95 (ΔP/v = 1.02 ± 0.02 kPa m−1 s). This overall trend is also illustrated in Fig. 2 (blue bins), which reveal a few trends: (1) an inverse proportionality between breathability and filter thickness is clearly seen for foams with the same initial and final densities (sample 7 vs. 8). (2) For foams with the same initial density ρi and thickness (sample #1 vs. 2, #6 vs. 7 and 9), the higher the final density ρf, the larger the ΔP/v, indicating that the additional Cu deposited during the 2ED process is generally impeding the air flow. (3) Interestingly, for foams with the same final density ρf and thickness, sample 4 with ρi of 3.2% has a ΔP/v that is more than 3 times that of sample 2 with ρi of 2.0%. Both samples were made with the same starting 200 nm diameter Cu nanowires, however sample 4 was fabricated with a greater number density of nanowires which results in a significantly increased nanowire length density compared to sample 2. Further, the amount of Cu plated onto sample 4 per nanowire during the 2ED stage is significantly less than in sample 2, which results in smaller final diameter nanowires. Both the increased nanowire length density and the decreased nanowire diameter in sample 4 contribute to a higher pressure drop due to the increased surface area per filter volume which induces more drag.44
To gain a quantitative understanding of the exact relationship between breathability and nanowire diameter and foam initial/final densities, as a crude first approximation, we may consider the foams as a simple compilation of isolated cylindrical fibers with smooth surfaces, even though the actual foams are more complex interconnected 3D nanowire networks with various surface details. Single fiber theory for the pressure drop,44 combined with the Miyagi model45 for the pressure drop across an array of fibers allows us to express the linear pressure drop coefficient as (derivation in ESI†):
![]() | (1) |
Remarkably, with this substantial simplification, the calculated pressure drop is quite comparable to the measured results (Fig. 2c). This agreement suggests that pressure drop scales linearly with filter thickness (t) and increases substantially as the initial nanowire number density (∝ρi) and final density (ρf) go up. By fitting eqn (1) across a range of foam samples, the scaling factor C is determined to be 3.64 × 106 kPa m−2 s.
To evaluate the correlation between the foam microstructure and filtration efficiency, we will first model the capture efficiency using basic air filtration theory for a perfectly smooth fiber. The filtration quality of a material is defined as a dimensionless quantity FQ ≡ −log(1 − E), where E is the filtration efficiency.2,44 An N-95 respirator is certified to have a FQ of at least 3.0 for particles in every size range, while an N-99 respirator has a FQ of at least 4.6.46 Using the smooth fiber model,3,44 the filtration quality can be written as (see ESI†):
![]() | (2) |
As shown in Table 1, the smooth fiber model alone can be used to describe the filtration quality of the foam filters to within an error of ±17%. With a theoretical baseline for how well perfectly smooth fibers capture particles, we can now determine to what extent surface features contribute towards particulate filtration. It is well established that a rougher fiber surface improves filtration capture efficiency,47–49 which is intimately coupled with an increase in surface area and the foam microstructure. Initially the nanowires which comprise the foam have a relatively smooth surface structure as they were grown in an anodized aluminum oxide mold. However, during the 2ED process the deposition of Cu nanogranules on the surface of the nanowires begin to dramatically increase the surface area. Surface area was measured to high accuracy (<0.5% error) with a BET krypton adsorption isotherm. It was found that foams that were initially ∼3% bulk density pre-2ED exhibit a maximal surface area of 20 m2 g−1 for a 13% bulk density after 2ED. The surface area was found to initially increase as the relative density increases, with the percentage density increase being measured in coulombs of copper deposited during the 2ED process per mg of 1ED foam (Fig. 3a). In foams with an even higher density, the deposited nanogranules begin to coalesce into a smoother surface structure and the surface area decreases.
Previously we have observed a substantial drop in filtration efficiency in the ρf = 30% foam, whose surface area is more than an order of magnitude smaller than other foams with a lower ρf. It is interesting to examine any direct correlation between surface area and filtration efficiency. With the 2ED process, it was found that the deposited surface features increase the internal surface area of the foam substantially, some by over a factor of 10 higher than what is predicted by the smooth fiber model, e.g., the aforementioned sample with a 20 m2 g−1 surface area. To determine how much the increased surface area from the foam's surface features might influence capture efficiency, additional surface area from 2ED is compared with the smooth fiber filtration quality model, as illustrated in Fig. 3b.
Image analysis on SEM micrographs was performed on foam samples of various densities to determine the feature size distribution across samples. After preprocessing to remove the blurry background, an auto-local-threshold filter is applied to extract and measure the size and frequency of the nanogranule deposits along the nanowire surface (more details in ESI†). From this we can determine the feature size distribution across various samples, as illustrated in Fig. 4.
The increased particle capture due to nesting is maximized when surface features along the nanowires are similar in size to the particles being captured, and becomes diminished as the surface features become too large or too small relative to the particles. While the theoretical smooth fiber model provides a good fit to the experimental results (Fig. 5a), there are still appreciable differences due to surface features. To determine what the capture efficiency contribution is from the surface features, we can cross-reference the percentage of surface features in the 200–400 nm size range (Fig. 5b) with the filtration quality deviation between our measured results and the smooth fiber model (Fig. 5a).
By directly comparing the deviation in filtration quality for 300 nm sized particles between our measured results and the calculated smooth fiber model to the percentage of surface area that has surface features between 200–400 nm in size, we find that there is a very high correlation with the r2 value of 0.96 in a simple linear regression model, as shown in Fig. 5b. This suggests that the size of the surface structure plays a prominent role in increasing filtration efficiency, with some samples showing over a 30% increase in filtration quality compared to smooth fibers. Furthermore, the filtration efficiency dependence on feature size provides an explanation for why rough surfaces and high surface area do not necessarily result in an increase to capture efficiency. This can be understood as much of the added surface area from the 2ED process is primarily from ultrasmall surface features that are simply too small relative to the 300 nm sized particles to enhance particle capture efficiency via nesting, and also too small to change the geometry of the fiber to increase capture through diffusion or interception.
By approximating a linear relationship with the percentage increase in filtration quality and percentage of surface structures in the 200–400 nm range, a surface feature adjusted filtration quality can be derived as
![]() | (3) |
![]() | (4) |
This allows us to optimize the quality factor of the foam by tuning the initial and final densities of the foam. This can be seen in Table 1 where an ultra-low density 3.5% density foam (sample 1) was able to achieve a quality factor of 5.02, over 50% better than a standard N-95 respirator which has a quality factor of around 3.20.36
Note that our study has mostly focused on studying the effects of the nanowire length density, plating ratio during the 2ED stage, and surface features. There are a number of other parameters that can also influence both breathability as well as filtration efficiency that remained constant throughout the range of samples measured. As such, their contributions to filtration efficiency and breathability could be absorbed into the fitted proportionality constant. For instance, the spacing geometry of the NWs is important. When the NWs bundle together such that they create large pockets absent of NWs, the breathability increases dramatically. However, this benefit is offset by the significant drop in filtration efficiency. Similarly, the studies were carried out on samples that were in the density range of being structurally stable and NWs being relatively inflexible. While the derived equations would suggest that ultra-low-density foams would have an extremely high breathability and quality factor, it was found experimentally that at densities below 3% the NWs begin to collapse, limiting both breathability and filtration efficiency. Additionally, while the derived quality factor equation suggests that extremely high-quality factors can be achieved by reducing the NW density, realistically at these limits, the heavily diminished structural integrity and changes to NW spacing begins to play a non-negligible role which causes the quality factor to decrease. Additionally, the choice of NW materials may affect both the sticking coefficient of airborne particles and the rigidity of the foams, which are relevant to the pressure drop as well as filtration quality, which is of interest for future studies.
Another important functionality of the foams is its antimicrobial characteristics. Once captured, conventional filter materials sequester the live pathogens, which can survive in the respirator. This makes the used filter material a potential hazard as the pathogens can be released from the filter through rough handling.51 Copper, being a bioactive metal with antimicrobial properties achieved through surface contact,52 is expected to be self-sterilizing, killing captured bacteria and inactivating captured viruses.15,53 Antimicrobial testing was performed on our Cu foams using a contact assay described previously.52 In these tests, 10 μL of a concentrated solution containing the bacteriophage Phi6 was deposited on the surface of the foam, then a glass slide was set on top of the droplet to disperse the solution across a 6.4 cm2 area. After 30 seconds, the slide was removed and the solution was washed from the foam using 990 μL of phosphate buffer solution, which was collected in a Petri dish. The solution was then enumerated by double-layer agar plating using its host bacteria Pseudomonas syringae. The bacteriophage Phi6 has a similar structure to SARS-CoV 2, including a double capsid lipid–protein envelope and protruding spike proteins. Bioactivity from a stainless steel coupon was also measured as a negative control. Each test was performed in triplicate.
The copper foam resulted in a 6.7 ± 1.3 log-reduction of the active bacteriophage, corresponding to a >99.9995% inactivation efficiency in the 30 seconds test. These results are consistent with the strong bioactivity of copper and demonstrate that this bioactivity extends to the nanostructured material. Functionally, these results confirm that captured pathogens will become inactivated soon after contacting the Cu superstructure.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d4nr02368d |
This journal is © The Royal Society of Chemistry 2024 |