Green Nano-Filters
Green Nano-Filters
Green Nano-Filters
DOI: 10.1039/c6ra24512a
www.rsc.org/advances
Particulate and chemical pollutants are ubiquitous in polluted air. detrimental to health.3,4 Recent studies have reported a more
However, current air filters using traditional polymers can only remove serious PM pollution problem in developing countries.5 A high
particles from the polluted air. To efficiently filter both particulates and degree of air pollution was responsible for numerous premature
chemical pollutants, development of multi-functional air filter mate- deaths. PM2.5 particles are the critical particulate pollution to be
rials with environmental friendness is critically needed. In this study, ltered due to their ability to penetrate into human lungs and
gelatin is employed as an example to study the potential of natural bronchi.1,2,5–10 Indoor air quality has become an increasing issue
proteins as high-performance air-filtering material. Based on an as well. More and more buildings incorporate air ltration
optimized composition of a “green” solvent, uniform gelatin nanofiber protection in their heating, ventilation, and air conditioning
mats were fabricated via an electrospinning approach. For the first systems, but a signicant amount of energy is required to
time, it is found that the resulting nanofabrics possess extremely high maintain the air exchange process due to a high air-resistance
removal efficiencies for both particle matter (with a broad range of (pressure drop) of the air lters. Therefore, air lters with
size from 0.3 mm to 10 mm) and various toxic chemicals (e.g. HCHO and high-efficiency of removing particles and chemicals simulta-
CO). Moreover, these high efficiencies are realized by the protein neously are critically needed.
nanofabrics with a much lower areal density (3.43 g m2) when Understanding of the composition of polluted-air is critical
compared with that of commercial air filters (e.g. 164 g m2 for high for the development of air ltering materials. In general, the
efficiency particulate air filter (HEPA)). This study reveals that nano- composition of pollutants in polluted-air is extremely compli-
fabrics of natural proteins hold great potential for application in cated due to the complexity of the sources of pollution. PM
“green” and multi-functional air filtering materials. particles can be produced from variety of sources, such as fuel
combustion in vehicles, industrial factory plants, cigarette
smoke, dust, etc. These PM particles behave distinctly due to
Introduction their diverse chemical composition. Most PM2.5 particles are
composed of organic compounds such as carbon derived
Air pollution has been of great concern due to the huge emis- matters (e.g. carbon dioxide and carbon monoxide), inorganic
sion of particulate and chemical pollutions. The release of compounds (e.g. sulfur dioxide (SO22), sulfate (SO42), silicon
chemicals, particulates and biological materials into air can dioxide (SiO2), and nitrate (NO3), etc.), and biological threats
lead to various diseases or discomfort to humans and other (e.g. bacteria and viruses).11–13 These particles are very stable in
living organisms, alongside other serious impacts on the envi- air and have lifetimes between hours to weeks due to their very
ronment. The unknown combination of particles and chemical small sizes. They can scatter visible light and reduce visibility
pollutants makes the polluted air even more harmful. Particle because of the similarity between their particle size and visible
Matter (PM) is usually categorized into two groups, PM2.5 and light wavelengths.14 In addition to PM particles, polluted air
PM10–2.5 which denote particles with aerodynamic diameters includes a wide variety of chemical gases such as carbon
smaller than 2.5 mm and between 2.5–10 mm, respectively.1,2 monoxide (CO), nitrogen dioxide (NO2), methane (CH4),
According to the 2009 and 2012 World Bank report, more than benzene, dioxin, ozone, etc. A large number of chemicals in
60% of Americans live in air quality levels that are potentially polluted air are classied as volatile organic compounds (VOCs)
which are primarily emitted by petrochemical and allied
School of Mechanical and Materials Engineering, Washington State University, industries. VOCs can undergo different kinds of photochemical
Pullman, WA 99164, USA. E-mail: [email protected]; [email protected] reactions in the atmosphere and cause various environmental
† Electronic supplementary information (ESI) available. See DOI: hazards. In gas phase carcinogenic or otherwise toxic VOCs
10.1039/c6ra24512a
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present a danger to humans.15,16 Since the polluted air is usually into nanobers as a lter material. The cationic nature of chi-
composed of pollutants with complicated compositions and tosan was used to achieve more than 70% removal of heavy
physicochemical properties, multi-functional air ltering metal ions.22 Other biomaterials were also studied as air lter
materials that are able to generate various types of interactions materials,23 however, they were usually mixed with conventional
with the pollutions are of great interest for air-ltering polymers to fabricate nanobers. As a result, the potential of
applications. pure protein nanofabrics as high-performance air ltering
Air lters are the most common used device to remove materials has never been studied based on the author's
pollutants from the air. They have been widely used in different knowledge. Of course there are still challenging issues for
areas, e.g. automotive industries, residential, general commer- scaling—up the process using metric tons of natural protein
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cial, and even hospitals, general surgeries and so on. The ltra- materials.
tion function is mainly realized via physical and PM size-based In this study, the potential of pure protein nanofabrics for air
capturing mechanisms. There are four primary mechanisms for ltering application is investigated. It is believed that the
ltration based on the size of the pollutant particles. Sieving is combination of nanomaterials with natural proteins can lead to
one of the most important mechanisms and is only effective for a powerful nanofabric with the ability to trap various kinds of
particles with sizes larger than the pore size of the lter. For pollutants, including particulate and toxic gas. In particular,
particles with sizes smaller than the pore size of the lter, inertial gelatin is employed as an example for that. Gelatin protein is
impaction, interception, and diffusion are the dominant mech- derived from thermal denaturation of collagen, the most abun-
anisms for ltration. In specic, interception occurs when small dant protein in human and animal bodies.24 Fabrication of
particles ow with the air stream and come into contact with the gelatin nanobers has been proved very successful and they are
ber surface. The attractive interactions between the small usually reported as scaffolds for food, energy, pharmaceutical,
particles and bers play a critical role for this mechanism. The environmental, and medical applications,25–27 except as air
diffusion mechanism is effective for even smaller particles with ltering material. Here, to study gelatin nanofabrics for air
aerodynamic size smaller than 100 nm. For these particles, ltration purposes, the fabrication of gelatin nanobers is
movement is dominated by Brownian motion and capturing further improved. Firstly, instead of using toxic solvents (e.g.
occurs via random collision.17 Traditionally, air lters are made 2,2,2-triuoroethanol (TFE) or 1,1,1,3,3,3-hexaouro-2-propanol
of porous lms, such as non-woven brous mats with randomly (HFIP)) which are usually used for the electrospinning of
oriented micron-size bers. These types of air-ltering materials gelatin,28 a non-toxic solvent (mixture of acetic acid and water) is
have several disadvantages as explained below. First, the bers employed. Secondly, the diameter of the gelatin nanobers is
are made of chemically synthesized or petroleum based mate- further reduced to be around 70 nm, which is smaller than the
rials, such as polypropylene and berglass. These conventional typical values (ca. 100 nm) for gelatin nanobers.29–31
materials provide very limited chemical functionality, resulting
in insufficient interactions with pollutants. Secondly, disposing
of used air lters made of these materials can cause further Experimental
environmental pollution as most of them are not environmen-
tally friendly. Finally, microber-based air ltering materials Materials and methods
possess limited surface area, which further deteriorate the Raw materials and solution preparation. Gelatin powder
ltration performance. (type A) produced from porcine skin was supplied from Sigma-
To address the above issues related to conventional air-lter Aldrich (MO, USA). Acetic acid (99.9% purity) was purchased
materials, nanober mats have been of great interest recently.18 from J.T.Baker® (PA, USA). Gelatin was dissolved in mixed
Nanober mats possess several advantages as explained below. solvent (volume ratio, acetic acid : DI water ¼ 80 : 20) with
Firstly, nanobers will tend to absorb substance from the a concentration of 18 wt% at 65 C. The mixed solvent was used
environment due to a high surface energy, which enhances the to achieve a good electrospinning of the gelatin solution. With
interactions between bers and pollutants. Secondly, nano- that ratio between water and acetic acid, it was found that
bers can signicantly increase the surface area of lter mate- a homogenous yellow solution and stable electrospinning of the
rials. In other words, nanobers provide more active sites for solution can be achieved.
trapping pollutants. As a result, nanober mats can realize Preparation of protein lter nanofabrics. Protein nano-
a high ltering efficiency for PM while possess low pressure fabrics were prepared by electrospinning techniques. The
drop or air resistance, which is critical for their practical gelatin solution was loaded in a syringe (Monojet™ Kendall)
application.19,20 Therefore, nanofabrics of polymers rich in with a 21-gauge blunt-tip needle. An operating voltage of 18–20
functional groups represent a promising solution for high- kV was employed for the electrospinning and was controlled by
performance air-ltering materials. In particular, biomate- a high voltage power source (ES50P-5W, Gamma High Voltage
rials, such as natural proteins, are promising candidates as Research). A mono-inject syringe pump (KD Scientic, KDS-100)
high-performance air ltering materials.21 It is well-known that was utilized to pump the gelatin solution. Commercial
proteins are rich in functional groups, that is, the R-groups on aluminum mesh with wire diameter of 0.011 inch and mesh size
the amino acids. These functional groups make proteins an of 18 16 was grounded to collect the gelatin bers. The
ideal material for air ltering application. For example, chito- distance between needle and sample collector was xed to be
san has been mixed with poly(ethylene oxide) and fabricated 10 cm and an average ow rate of 0.6 ml h1 was utilized.31,32
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cadmium (Cd2+)).33 Since the original polluted-air samples were gelatin molecules possess a broad range of functional groups in
so concentrated with PM and chemicals, they were diluted in their multi-level structures. The characteristics of these chem-
a gas bag to a hazardous level which can be measured by the ical structures provide capability for interaction with multiple
analyzer. The diluted polluted-air with detectable level of species of polar molecules, which lead to a great potential to
pollutions was used as the nal polluted-air sample for air- capture many chemicals. Specically, gelatin consists of glycine
ltering testing. Before the air-ltering testing, the initial (21.4%), proline (12.4%), hydroxyproline (11.9%), and glutamic
concentrations of PM with different particle sizes (0.3–10 mm) acid (10.0%) in its amino acid prole.35,36 The amino acids bring
and toxic chemicals (HCHO and CO) in the air samples were gelatin various functional groups (such as carboxylic and
measured by a particle counter (CEM, DT-9881). To perform the hydroxyl, charged groups, and many other polar/nonpolar
air-ltering testing, the pressure difference of both sides of air functional groups). These functional groups can act as active
lter was controlled and measured by a manometer (UEi, sites generating numerous interactions with pollutants,
EM201-B) with a standard air ow velocity of 5 cm s1 to including hydrogen bonding, ionic bonding, and charge–charge
investigate the air ow resistance of the air lter material.34 In interactions and so on.35,36 Combined with electrospinning
all the measurements, a circular lter sample with diameter of technique, gelatin nanobers can be fabricated (Fig. 1). Elec-
37 mm was placed in a home-made sample holder. The ltered trospinning is an effective method for making uniform nano-
air was collected by another clean gas bag which was vacuumed bers with high aspect ratio, and high pore interconnectivity
in advance (the digital image of experimental setup is shown in with size ranging from micron to nanometer scale.
Fig. S1, ESI†). When the air-ltering testing ended at different First of all, an appropriate solvent, in particular a non-toxic
ltering time, the concentrations of the PM and toxic chemicals solvent, needs to be selected for preparing the gelatin solution
inside the clean gas bag with ltered air were measured and effective for making nanobers via electrospinning. Many
recorded. Via the eqn (1), one can determine the removing studies have been reported on the fabrication of gelatin bers
efficiency hp. by using toxic solvents (TFE, HFIP),29,30 which yielded average
ber diameter ranges from 100–600 nm. In this study, gelatin
hp ¼ Cp Cc Cp (1)
nanofabrics were fabricated by employing aqueous acetic acid
where Cp is the concentration of the pollution in the polluted- (AA) as a “green” solvent. In order to achieve efficient molecular
air sample before air-ltering testing, and Cc is the concentra-
tion of the pollution in the ltered air sample.
Characterizations. To study how the particle pollutants were
removed by the protein nanofabrics, SEM (FEI SEM Quanta
200F) was employed to investigate the morphology of the
protein nanofabrics before and aer air ltering testing. The
samples were sputter-coated with 10 nm gold nanolayer in
thickness using Technics Hummer V sputter coater. In order to
study the possible interactions between the protein nanofabrics
and pollutants, FTIR (Nicolet, Thermo Scientic) absorption
spectra was employed. To distinguish the interactions between
nanobers and pollutants from the interactions inside the
fabric or polluted-air themselves, the FTIR spectrum of three
kinds of samples were recorded and compared. These samples
include polluted-air, clean protein nanofabrics before and aer
ltration. All the measurement was repeated at least 3 times and
good repeatability was found for these samples.
Statistical analysis. Data were analysed using one-way anal-
ysis of variance (ANOVA) multiple comparison method. The Fig. 1 Schematics of gelatin solution preparation and nanofibers
fabrication via electrospinning, followed by the schematics of a single
condence interval was set to 95%. The differences among the
gelatin nanofiber with a functional surface due to various functional
data with a p-value < 0.05 were reected to be statistically groups available in its structure. Porous structure and fiber diameter of
signicant (see ESI†). nanofabrics contribute to particulate filtration while the rich functional
groups on the fiber surface provides toxic chemical filtration property.
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dissolution of gelatin, good electrospinability and, as the result, drop.38–40 At the same time, due to the high density of functional
uniform lter mat with nanoscale ber diameter, the solvent groups along the gelatin nanobers, the nanober mats are
composition must be adjusted. More importantly, the unifor- expected to possess multiple ltering functions: toxic chemical
mity of the nanobers in the mat along with smaller ber and particulate ltration. The following air ltering perfor-
diameters can result in high surface area for capturing more mance studies were focused on the gelatin lter nanobers
pollutants, which enables the lter to achieve high ltration produced using the optimal solvent.
efficiencies. Therefore, the effect of AA-to-water ratio on the
resulting nanober diameters and their distribution was
studied. The mixture solvent with optimized composition was Particulate ltration
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determined for spinning out uniform gelatin nanober mats. As shown in Fig. 3a, for the gelatin nanofabrics, the removal
The microstructures of gelatin nanobers prepared in different efficiency is dependent on the PM size as well as the areal
ratios of the solvent and the ber morphology of a commercial density of the nanofabrics. The areal density of the nanofabrics
HEPA lter were compared using scanning electron microscopy was controlled by controlling the volume of the solution that
(SEM) images (Fig. 2). It can be seen that by increasing the ratio was electrospun on the substrate. All of the gelatin nanofabric
of AA to water in the solvent from 60 : 40 to 80 : 20, the size of mats possessed a thickness within the range of 8–20 mm. It can
nanobers was reduced from ca. 470 to ca. 70 nm. Moreover, the be found that with a high areal density (e.g. greater than ca.
nanober uniformity was improved signicantly: the relative 3.43 g m2), the gelatin nanofabrics showed almost similar
deviation of the nanobers reduced from 53% to 25% (see ber removal efficiency of above 99.20% for PM with sizes from 0.3 to
diameter distributions and inserted table showing the statistic 10 mm (see Table S1† for number concentration of particulate
results in Fig. 2 and S2 for the pore size distribution of nano- pollutants before and aer ltration). In particular, the removal
bers in ESI†). These results show that by using the mixed efficiency for the most penetrating particle size (MPPS) of 0.3
solvent with the AA-to-water ratio of 80 : 20, uniform gelatin mm particles was signicantly improved from 77.10 to 99.32%
lter mats with the nanober diameter of 70 nm were by increasing the areal density of the nanofabrics from 2.25 to
successfully fabricated, which is smaller than the reported 3.43 g m2. PM particles with size around 0.3 mm (PM0.3) are
studies showing the ber diameter of few hundred nanome- known as the hardest to capture and a high-performance air
ters,31,37 reduction in the nanober diameter can signicantly lter should give rise to an efficiency above 95% for PM0.3.34 The
improve the air ltration capabilities for both particulate and results indicate that the areal density of the nanofabrics is
toxic chemicals due to their high active surface areas. In critical for the removal efficiency of small particles, but not
general, nanobers with high surface-to-volume ratio and large particles. This result can be explained as the difference in
surface activity will have high particle removal efficiency via the mechanisms for ltering big particles (sieving) and small
interception, diffusion, and other mechanisms while retaining particles (smaller than the pore size). Specically, large particles
very low resistance to air ow which results in low pressure were removed by size effects, while small particles were trapped
Fig. 2 SEM images of gelatin nanofabrics prepared in different ratios of AA-to-water; effect of solvent ratio on morphology and fiber diameters
of gelatin nanofabrics compared with that of commercial HEPA filter; percentages in the table are relative standard deviation.
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surface area, such as activated carbon. For the gelatin nano- provide a promising solution for multi-functional air ltering
fabrics, two kinds of toxic chemicals, formaldehyde (HCHO) materials.
and carbon monoxide (CO) which can be detected by the
analyzer, were chosen as examples to test the chemical removal Pressure drop and gure of merit (quality factor)
capability. Fig. 5a shows the chemical removal efficiency of
In addition to the particulate and chemical removal efficiency,
formaldehyde for gelatin nanofabrics with different areal
air ow resistance (pressure drop) is another critical parameter
densities compared with that of commercial HEPA lter (see
describing the performance of an air lter. High pressure drop
Table S2† for concentration of particulate formaldehyde and
downstream of an air lter will consume a large amount of
carbon monoxide before and aer ltration).
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the gelatin nanofabrics when the areal density is higher than ca.
3.43 g m2, such as 3.80 and 7.67 g m2, the removal efficiency
is improved by less than 0.5% (see Fig. 3b), while the pressure
drop increases by more than 74% (see Fig. 6a). Thus, 3.43 g m2
should be close to the optimal areal density for the gelatin
nanofabrics.
To comprehensively describe the ltration performance, the
pressure drop and removal efficiency is combined into one
parameter, the quality factor (QF), also known as gure of merit
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Fig. 8 (a) Simplified representation of functional-capturing filtration mechanism of gelatin nanofabrics via interactions between gelatin
molecules and pollutants. (b) SEM image of gelatin nanofabrics after filtration (c) FTIR characterization of cigarette smoke PM particles
demonstrating existing functional groups. (d) FTIR characterization of gelatin filter before and after filtration showing the active functional groups
and PM-filter interactions. (e) Functional group peak intensity comparison between gelatin fibers before and after filtration indicating
strengthening of corresponding bonds due to PM-filter interactions.
forming aldimine linkages. This reaction elicits a change in smoke and gelatin bers are covered by those inherently exist-
lter color from white to a yellow color. PM particles and other ing in gelatin nanofabrics. Therefore, the dramatic increase in
pollutants with different compositions can interact with the the peak intensity of these functional groups aer ltration
gelatin nanofabrics through hydrogen bonding, charge–charge testing should be the result of the interactions between gelatin
interactions etc. Fig. 8b shows an SEM image of gelatin nano- nanofabrics and the pollutants, such as hydrogen bonding,
lter that captured numerous pollutants via a combination of ionic bonding, and charge–charge interactions, etc.
interaction-based and size-based mechanisms. This schematic
indicates a new interaction-based mechanism of ltration for
gelatin nanofabrics besides the primary four size-based mech- Conclusions
anisms. To further understand the possible interactions
In summary, the gelatin protein was studied as an example to
between the gelatin nanofabrics and the pollutants (solid
demonstrate the potential of natural proteins to serve as envi-
particles and toxic chemicals), Fourier transform infrared
ronmentally friendly and high-performance air-ltering mate-
spectroscopy (FTIR) and dielectric constant measurement (see
rials. Uniform gelatin nanober mats with very small diameters
Fig. S6, ESI†) were used to identify the functional groups from
were fabricated by employing a “green” solvent with optimized
the pure gelatin nanofabrics, polluted air and nanofabrics with
composition. It has been found that the gelatin nanober mats
trapped pollutants. The FTIR spectra of the cigarette smoke is
with a controlled uniformity and small ber diameters possess
shown in Fig. 8c. The specic peaks of functional groups in the
extremely high particulate removal efficiencies of more than
cigarette smoke are around 3649, 2360, 1653, 1558, 1506, and
99.3% and 99.6% for PM0.3 and PM2.5, respectively. These
1456 cm1 which indicate the existence of O–H, C–H (aldehyde),
results indicate that the gelatin nanobers with a much lower
C]O, and C–O (last three peaks) groups, respectively. All of
areal density (e.g. 3.43 g m2) can efficiently remove a broad
these groups in polluted-air sample may interact with the
range of PM particles similar to one of the most efficient
groups on the surface of gelatin nanobers. The comparison of
particulate air lters, HEPA with areal density of 164 g m2.
the FTIR spectra for the gelatin nanobers before and aer
More signicantly, the combination of the inherent surface
ltration is shown in Fig. 8d (see Fig. S7, ESI†). It can be found
chemistry of gelatin nanobers (i.e., various functional groups
that there is no new peak formed aer ltration. However, there
on the ber surface) and nanober technology enables gelatin
is a signicant change in the intensity at specic groups and
protein nanobers to have high interaction capability with toxic
interactions, including hydroxyl, carboxyl, and amine func-
chemicals present in the air. Particularly, the gelatin nano-
tional groups (see Fig. 8e). These results can be explained as
fabrics possess excellent efficiency of absorbing toxic chemicals
that the types of interactions between the pollutants in the
(e.g. ca. 80% for HCHO; 76% for CO), which has never been
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