pubs.acs.

org/journal/ascecg Research Article

Inherently Functionalized Carbon from Algae to Adsorb Precursors

of Secondary Organic Aerosols in Noncombustion Sources
Masoumeh Mousavi, Vladimir Martis, and Elham H. Fini*

Cite This: ACS Sustainable Chem. Eng. 2021, 9, 14375−14384 Read Online

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ABSTRACT: Recent findings have opened a new window on a hidden

source of volatile and semivolatile organic compounds that are released
into the atmosphere in the form of gas or aerosol. Asphalt pavement and
Downloaded via PURDUE UNIV on December 9, 2021 at 18:56:58 (UTC).

bituminous composites in general have been found to be noncombustion

sources that emit gas-phase precursors of submicron atmospheric aerosols
that have serious impacts on human health as well as the climate. This
study highlights the merits of using an inherently functionalized carbon
(IFC) derived from an algal feedstock to selectively adsorb some
potentially hazardous bitumen emissions, alleviating the side effects of
intense sun exposure and high temperatures on air quality. With the use of
density functional theory (DFT), six organic compounds emitted from
bitumen that are precursors to secondary organic aerosols were modeled,
then their adsorption to the active zones of a model surface of the IFC
containing N-functional groups of amide, amine, pyrrole, and pyridine was measured. In a laboratory experiment, the adsorption
properties of the functionalized carbon were also evaluated by a vapor sorption analyzer, supporting the DFT results that indicate the
IFC’s potential to retain these volatile compounds in the matrix of bitumen. Of the organic molecules studied, benzofuran showed
the least interaction with functional groups of the IFC surface (ΔE = −8.3 kcal/mol) and the most total adsorption uptake (2.443 wt
%) by the IFC. Dibenzo-thiophene showed the most surface adsorption (ΔE = −18.1 kcal/mol) and the least total adsorption
uptake (0.018 wt %) by the IFC. This could be explained by the extent of mobility and penetration of target volatile organic
molecules into the IFC’s pores. The strong interactions of the IFC’s functional groups with organic molecules limit their penetration
into the IFC’s pores, leading to a decreased total adsorption and vice versa.
KEYWORDS: sustainability, secondary organic aerosols, functionalized carbon, air quality, noncombustion emissions

■ INTRODUCTION
The identification, chemistry, and depletion of atmospheric
aerosols (also known as particulate matter) are important due
to their serious impact on many aspects of life, from human
health to climate and atmospheric reactivity. Airborne
particulates represent a complex mixture of inorganic and
organic substances; the organic fraction accounts for 20%−
90% of the total fine aerosol mass. Primary organic aerosols
(POAs) are directly emitted from natural (biogenic) sources
and human-made (anthropogenic) sources. Examples of
biogenic sources are volcanic eruptions, vegetation, and
micro-organisms; examples of anthropogenic sources are
industrial activities, combustion of fossil fuels, and open
biomass burnings such as agricultural straw burning and forest
fires.1,2 In contrast to POAs, which originate directly from
biogenic or anthropogenic sources, secondary organic aerosols
(SOAs) are formed from the condensation of vapors on pre-
existing particles or homogenous nucleation through the
successive atmospheric oxidation of gas-phase precursors
(gas-phase organic compounds).3 The main source of gas-
phase precursors could be either biogenic or anthropogenic
emissions of volatile organic compounds.4,5 The size and
chemical composition of the aerosols evolve with time through
coagulation, condensation, and chemical reactions.
Recent findings have opened a window on noncombustion
sources of emissions of volatile organic compounds. These
active organic compounds function as precursors to ozone and
SOAs.6,7 Asphalt pavement and asphalt binder (bitumen; a
petroleum-derived substance) have been identified as a
potential missing source of volatile and semivolatile organic
compounds that are released into the atmosphere in the form
of gas or aerosol.8 Bitumen emissions include thousands of
individual chemical compounds that eventually form particles
Received: June 7, 2021
Revised: September 27, 2021
Published: October 18, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c03827

14375 ACS Sustainable Chem. Eng. 2021, 9, 14375−14384
ACS Sustainable Chemistry & Engineering
with varying aerodynamic diameters (from nm to μm) and
different toxicological properties that can be a potential hazard
for human health9 and climate.10,11 These emissions are
temperature-dependent compounds that are doubled in a
temperature rise from 40 to 60 °C; they reach the maximum
level at temperatures over 140 °C, indicating that SOA
precursors are released into the air more significantly in
summer months.8 Exposure to ultraviolet is also an influential
factor accelerating the emission of volatile and semivolatile
organic compounds from areas surfaced with bitumen.
Here, it is hypothesized that inherently functionalized
carbon made from algal biomass adsorbs undesirable chemical
compounds that are normally emitted from bitumen. This
hypothesis can also be viewed from another perspective: a
tailored functionalized carbon could increase a bituminous
composite’s retention time of some compounds that would
otherwise be released to the atmosphere in the form of gaseous
emissions (SOA precursors) in a process exacerbated by heat
and solar radiation. Considering the efficacy and abundance of
functional groups in carbonaceous materials such as biochar,
the targeted inherently functionalized carbon could be
developed from a feedstock of pure algae or a balanced
mixture of algae feedstock with other feedstocks, tailored to the
adsorption of bitumen emissions to alleviate the side effects of
intense sun exposure on both air quality and construction
durability. It is worth noting that “biochar” is mostly atributed
to the charcoal produced by pyrolysis of biomass in the
absence of oxygen. The carbonaceous material used in our
studies is made from hydrothermal liquefaction of algae and is
referred to as inherently functionalized carbon (IFC) in this
study.
Considering the urgent need for the development of
alternative and renewable resources, algae are among the
promising biomasses for energy production and other
environmental applications.12−16 In addition to algae’s
capability in energy production, algae have a good record as
a promising appropriate sorbent for CO2 fixation.17−21 The
recent studies on an IFC derived from the thermochemical
liquefaction of a blend of algae (rich in protein and nucleic
acids) and swine manure (rich in lipids) indicated the merits of
the newly made carbonaceous material as a free-radical
scavenger that significantly reduces the aging of bitumen
exposed to ultraviolet irradiation.22 On the basis of the study
results, the IFC made from algae alone performs even better
than hybrid IFC made from algae and swine manure. The
efficacy of algae IFC as a free-radical scavenger and ultraviolet
blocker was attributed to the rather high surface area and rich
phenol functional groups (C6H5-OH) in algal IFC.
Apart from the role of O-containing functional groups such
as phenols, alcohols, ketones, lactones, and carboxylic acids
that are normally abundant in IFCs, the role of N-containing
functionals in algae IFC cannot be overlooked. The O-
containing functional groups and N-containing functional
groups have been shown to be the factors most influencing
the acidity or basicity of the carbon’s surface.23−26 The N-
containing functional groups mainly demonstrate the basic
characteristic. The good performance of N-containing func-
tional groups has been shown through extensive studies
performed on N-grafted activated carbons used to adsorb some
primary greenhouse gas-phase molecules such as CO2.27−31
Amine-grafted surfaces have also shown high efficiency in the
adsorption of CO2 molecules.32−34
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An important difference between algae biomass and
terrestrial biomass is the higher protein content of algae
biomass. The hydrolysis of protein produces amino acids
(containing a −NH2 group) and carboxylic acids (containing a
−COOH group), so deamination and decarboxylation are the
main pathways for the decomposition of amino acids. The
nitrogen compounds of biochar are not limited to high-protein
biomasses such as algae. Analysis of the chars prepared from
high-temperature coal pyrolysis (>750 °C) has shown the
super thermal stability of some N-containing compounds such
as pyridinic-N, pyrrolic-N, and quaternary-N.35−37 Unlike coal,
the dominant nitrogen form in algae is protein-N, which has a
lower thermal stability. Thus, algae pyrolysis is usually
performed at lower temperature ranges (500−600 °C) that
could be considered as a green chemistry of algae, minimizing
the generation of hazardous chemical compounds.38,39
In this study, an inherently functionalized carbon derived
from the hydrothermal liquefaction of an algal biomass was
used to investigate the efficacy of this carbon in the adsorption
of a series of air-polluting chemical compounds (precursors of
secondary organic aerosols in the atmosphere) normally
emitted from bitumen at elevated temperatures. With the use
of quantum-based computational modeling performed in the
framework of density functional theory, the molecular
interactions of six of bitumen’s emitted chemical compounds
with the targeted active sites of the algal IFC were studied. The
adsorbate molecules were three O-containing compounds
(benzoic acid, benzofuran, and hexanal) and three S-containing
compounds (dibenzo-thiophene, 3-pentylthiophene, and hex-
anethiol). In a comparative study, the average adsorption
energy of each compound on the IFC surface was calculated to
estimate the adsorption strength of each compound.
Laboratory experiments were performed using dynamic vapor
sorption analysis under vacuum to measure the extent of
adsorption of select gas-phase compounds by functionalized
carbon.
■
MATERIALS AND METHODS
The neat bitumen used in this study was graded as PG 64-16 and
supplied by HollyFrontier Corporation in Arizona (Table 1). The
Table 1. Properties of PG 64-16 Bitumen
specific gravity @ 15.6 °C 1.025
flashpoint °C 300
absolute viscosity, P @ 60 °C 2,005
G*/sin δ, kPa @ 64 °Ca 1.23
mass change after −0.210%
RTFO (rolling thin-film oven)
G*/sin δ, kPa @ 64 °Ca 3.33
G*/sin δ, kPa @ 28 °Ca 2,87
stiffness (MPa) @ 60 s, @ −6 °C 90.4
m value @ 60 s, @ −6 °C 0.384
a
G* is a symbol commonly used for the complex shear modulus.
functionalized carbon was made from the thermochemical conversion
of algae (Cyanidioschyzon merolae).40 Adsorbents used for measure-
ments were 2,3-benzofuran (99%, Sigma-Aldrich), dibenzo-thiophene
(analytical standard, Supelco Inc.), and benzoic acid (99.5%, Sigma-
Aldrich). In this study, functionalized carbon was directly mixed into
the bitumen at 10% concentration based on the weight of the
bitumen.
To prepare samples, the IFC was preheated to 50 °C and held at
this temperature under vacuum (<1 × 105 Torr) for 300 min, to
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ensure that residual species were removed from the sample pores.
Then, the sample was slowly cooled under vacuum to the desired
temperature for isotherm measurements, and the above-mentioned
adsorbents were introduced for measurement.
Dynamic Vapor Sorption Method. The adsorption/desorption
properties of functionalized carbon were measured by an automated
vacuum vapor/gas gravimetric sorption analyzer (DVS Vacuum)41
from Surface Measurement Systems Ltd. During the test, the weight
of the sample was measured directly and continuously using the SMS
UltraBalance with a resolution of 0.1 μg throughout the experiment. A
set partial pressure of solvent was introduced under vacuum using a
mass flow controller connected to a flask filled with solvent, whereby a
saturated vapor pressure of solvent at the desired temperature was
generated. The pressure control inside the vacuum chamber was done
via a closed-loop PID control between the butterfly valve, pressure
transducers, and mass flow controllers. The sorption measurements
were done in a mass-equilibrium mode, in which the mass-equilibrium
criteria were set as a change in mass per minute (dm/dt). The control
software automatically calculates and checks the dm/dt criteria against
the set dm/dt value. When the sample’s mass reaches equilibrium at a
certain partial pressure (P/Po) of sorbate molecules within the set
dm/dt tolerance, the control software makes the test proceed to the
next partial-pressure step.
DFT-Based Computational Methodology. Designing the
model of the functionalized carbon’s surface is the first step in
tracking the molecular interactions between the IFC surface
(adsorbent) and our target gas molecules (adsorbates). It is worth
noting the term “surface of alga IFC” that is used for the solid sorbent
related to the alga in this study. However, this sorbent could be a
macromolecule rather than a surface of a crystal. Since the term
“adsorption” is mostly associated with a “surface”, this term is used
throughout this study. As for the biochar surface, a very limited
number of molecular representations of biochar have been proposed
in the literature. A typical biochar is quite dependent on its initial
precursor (biomass), so a molecular model of a typical biochar is
commonly designed based on the biochar’s empirical formula and
FTIR results. In contrast to graphene with its apparent crystalline
properties, it is not easy to detect aromatic clusters in biochars derived
at high temperature. However, there is sufficient evidence indicating
degrees of crystallinity in biochars.42,43 Even in amorphous biochars,
poorly ordered graphene stacks are expected.42 In our case study, the
peaks at 26.426° and 43.019° (2θ) of X-ray powder diffraction spectra
indicated the presence of graphite-like carbon in the IFC derived by
hydrothermal liquefaction of algae.40 In addition, at the temperature
range (300−350 °C) used in the production of IFC in this study, the
presence of randomly oriented polyaromatic clusters is expected. This
is supported by the findings that the carbonaceous material prepared
at a temperature range of 280−350 °C contained small polyaromatic
rings connected through polyphosphate bridges.43
The characteristics of the functional groups surrounding the central
aromatic zone of our IFC model molecule are determined based on
the analytical and spectroscopic studies performed on our target alga.
The FTIR adsorption peaks indicate the presence of alcoholic OHs
and other O-containing functional groups such as phenols, carboxyl,
carbonyl, and ketene.43 The presence of N-containing compounds in
our algal IFC is evidenced by the bands at 2100−2270 cm−1
corresponding to diimides and azides and by the bands at 1600−
1670 cm−1 corresponding to N−H stretching of cyclic amides.
Figure 1 shows a schematic representation of the IFC model
molecule used in this study. This IFC model molecule contains four
N-functional groups: amide, amine, pyrrole, and pyridine. Since the
focus of the present study is on the interactions of specific parts of the
IFC surface, not the entire surface, the central aromatic zone of the
biochar model molecule (dashed lines in Figure 1) is designed just for
connecting the four targeted zones. In this figure, the four active zones
containing N-functional groups are 1-amide zone, 2-amine zone, 3-
pyrrole zone, and 4-pyridine zone. As specified in Figure 1, to simulate
the chemical environment near the targeted N-functional groups
(amide, amine, pyrrole, and pyridine), a part of the aromatic zone
coordinated to that N-functional group was considered as the targeted
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Figure 1. Schematic representation of the IFC molecular model.
Active zones containing N-functionals are circled.
zone. Each IFC zone was optimized to its minimum energy before
introducing the gas molecules for interaction.
The targeted gas molecules chosen for adsorption on the model
surface are six potentially hazardous chemical compounds: three
contain S functional groups (dibenzo-thiophene, 3-pentylthiophene,
and hexanethiol), and three contain O functional groups (benzoic
acid, benzofuran, and hexanal). Although S-containing hydrocarbon
compounds and O-containing hydrocarbon compounds make up only
5% to 15% of emissions at temperatures relevant to the life cycles of
asphalt materials, their contribution to the total emissions under solar
irradiation is significant: under sun exposure, S-containing com-
pounds show a 700% increase, and O-containing compounds show a
400% increase.8
Given the limited information about the exact chemical
composition of the S-containing compounds and O-containing
compounds of bitumen emissions, here we use a group of chemical
compounds recently introduced as asphalt-related emissions.8 The
highly aromatic S-containing compounds chosen for this study
include formulas representing benzothiophenes and dibenzothio-
phenes, a selection of which have been previously observed as
individual compounds in petroleum and coal. The complex mixture of
O-containing compounds includes formulas representing benzofurans
and dibenzofurans that are often observed in complex petroleum-
related mixtures.
All energy optimizations on the four biochar sections, the gas
adsorbate molecules, and their corresponding adsorption complexes
were performed via the DMol3 module44,45 implemented in the
Accelrys Materials Studio program package (version 6.0). The PBE
(Perdew−Burke−Ernzerhof)46 formulation of generalized gradient
approximation (GGA) was used as the functional for all calculations.
Due to the high polarizability of the algal biochar surface, the long-
range van der Waals interactions need to be included in the
calculations to accurately estimate the thermodynamic stability and
strength of adsorbent−adsorbate interactions. The dispersion terms
defined by Grimme et al. (DFT-D2 or DFT-D3) have been shown to
provide a quite accurate thermochemistry for the systems dominated
by covalence as well as dispersion forces.47 So, the Grimme’s long-
range dispersion correction48 (PBE-D) was included, as implemented
in the DMol3 module of the Accelrys Materials Studio program
package. All-electron double numerical basis sets augmented by
polarization functions (DNP) were defined for the optimization
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Figure 2. (a) Adsorption/desorption kinetics of inherently functionalized carbon (IFC) at 25 °C for benzofuran. The red line (mass) corresponds
to the y-axis on the left, and the blue line partial pressure (P/P0) corresponds to the y-axis on the right. The mass loss during the first 300 min is
due to outgassing of the IFC at 50 °C under high vacuum and subsequent cooling to the sorption temperature of 25 °C under high vacuum for 120
min. (b) Adsorption isotherm of inherently functionalized carbon for benzofuran at 25 °C.

Figure 3. Selected adsorbate molecules (left) to interact with four N-containing zones of an algal biochar (right).

process. “Fine” grid was specified for the matrix numerical
integrations. At this level of integration, the tolerances for energy,
maximum force, and displacement convergence were 1.0 × 10−5
Hartree, 2.0 × 10−3 Hartree/Å, and 5.0 × 10−3 Å, respectively.
During the adsorption of gas molecules on each part of the IFC
surface, the thermodynamic stability of the adsorption complex
formed was expressed through the adsorption energy (Eads). Eads is the
energy difference between the adsorption complex formed and its
constituents, a gas molecule and the IFC zone, when they are in their
lowest energy state.
to as adsorbents) was used. Figure 2 shows the adsorption/
desorption kinetics for benzofuran as well as the total
adsorption uptake versus partial pressure. Measurement of
other adsorbents followed the same procedure. It was found
that IFC is able to retain the adsorbents; the adsorption of
benzofuran was the highest among the three (2.443 wt %),
followed by benzoic acid (0.519 wt %) and dibenzo-thiophene
(0.018 wt %). Variation in the extent of adsorption indicates
that IFC could selectively adsorb some potentially hazardous

■
RESULTS AND DISCUSSION
It has been documented that IFC made from algal biomass
significantly delays the aging of bituminous composites.22
Here, it is hypothesized that the observed delay in aging is
partly due to a delayed loss of volatile oxygenated compounds
of bitumen in the form of emissions. Among those volatiles are
benzofuran, dibenzo-thiophene, and benzoic acid.8 To evaluate
the capability of IFC to retain these gas molecules, a dynamic
sorption method using the above three gas molecules (referred
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bitumen emissions that would otherwise be emitted from
bitumen. This can explain part of the delayed progress of aging
observed in our recent study.22 The following section explains
the molecular modeling used to quantify the binding energy
between the typical volatile compounds emitted from bitumen
and the functionalized carbon.
DFT-Based Modeling Results. For a solid sorbent such as
a biochar, the ideal features are not limited to a large surface
area and a high free volume; also required are appropriate
interactions between the adsorbate molecules and the solid
sorbent. Adsorption of the target organic compounds on the
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Figure 4. Typical intercations between dibenzo-thiophene and four N-containing active zones (pyrrole, pyridine, amine, and amide). In each
interaction, the inactive portion of the surface is shown in white.
biochar is partly a thermodynamic process based on differences
in the adsorption energies of different compounds. Therefore,
energy-based data can clarify the adsorption strength for
different adsorbate molecules, indicating the capability of the
biochar to adsorb the gas-phase molecules before they are
released to the atmosphere.
The results for our case study discussed below indicate how
a quantum-based density functional approach can be used to
show the adsorption behavior of a selected group of gas
molecules, normally emitted from the bitumen surface, on the
N-rich surface of our algal IFC. Figure 3 shows the selected
group of six adsorbate molecules (three O-containing
compounds and three S-containing compounds) supposed to
interact with four active zones of the IFC surface containing N-
functionals of amide, amine, pyridine, and pyrrole. The O-
containing compounds are benzoic acid, benzofuran, and
hexanal (an aldehyde molecule). The S-containing compounds
are dibenzo-thiophene, 3-pentylthiophene, and hexanethiol.
The reason behind this selection is the significant role of polar
molecules including sulfur or oxygen elements as precursors of
secondary organic aerosols.8 At temperatures relevant to the
life cycle of bitumen materials, hydrocarbons constitute a great
fraction of bitumen emissions. However, O-containing
emissions and S-containing emissions, contributing 1%−14%
and 5%−30% of the total emissions, respectively, constitute a
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greater fraction at high temperatures.8 On the basis of recent
findings,8 solar exposure results in a 700% increase in the
emission of S-containing compounds, a 400% increase in the
emission of O-containing compounds and a 300% increase in
hydrocarbons.
The highly aromatic S-containing compounds in bitumen
emissions include chemical structures representing benzo-
thiophenes and dibenzo-thiophenes.9 The complex mixture of
O-containing emissions includes chemical structures represent-
ing benzofurans and dibenzofurans, commonly found in
complex petroleum-based mixtures.
A biochar surface generally includes many O-containing
functional groups, including phenols, alcohols, ketones,
lactones, and carboxylic acids. However, the active zones
targeted in this study mostly contain N-containing functional
groups (Figure 1). It should be noted that the distinctive
performance of the algae IFC compared to other function-
alized carbons is attributed to the N-compounds in IFC made
from algae. As stated earlier, in this study, the area of each
active zone is not limited to an individual N-functional group
but also contains a small portion of the biochar surface
coordinated to the N-functional group, to simulate the
chemical environment around the functional. This is of
particular importance, because the nature of substituents
(e.g., electron-withdrawing or electron-donating character-
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istics) near the N-functional group may impact the eventual depending on the nature of interactions and thermodynamic
performance of the N-functional group and its subsequent stability of the newly formed complexes, our target IFC may
interactions with gas molecules. selectively function as the sorbent for a specific group of
Figure 4 shows a typical physical adsorption of dibenzo- organic compounds. In the following, the interactions between
thiophene on four active zones of the IFC surface containing the N-components of the surface and the gas molecules with
amide, amine, pyridine, and pyrrole functional groups. In this the most adsorption strength and the least adsorption strength
figure, the gas molecule (dibenzo-thiophene) and the active are investigated.
zone that are supposed to interact are in their normal colors, Interaction of Benzoic Acid and Dibenzo-Thiophene
and the inactive portion of the surface is in white. In this figure, with N-Components of the Biochar Surface. Benzoic acid
the priority of polar interactions of H. . .N and H. . .S in total is one of the most common organic acids in the Earth’s
interactions is shown. atmosphere; it is an important organic aerosol that reacts with
The results of interactions between the six gas molecules and OH, NO3, and SO4 radicals in the atmosphere.49 This simple
the four active zones of biochar are shown in Table 2. To have aromatic acid is a weak acid (pKa = 4.2) with irritating fumes at
elevated temperatures. Benzoic acid is released to the
Table 2. Range of Adsorption Energy (In kcal/mol) for environment in various ways,50−52 including biomass combus-
Interaction of Six Chemical Compounds, Normally Emitted tion53 and hot bitumen.54
from a Bitumen Surface, With Four Active Zones of an Algal The adsorption reaction of benzoic acid by our N-rich
IFC Surface Containing N-Functional Groupsa carbon was investigated by tracking the molecular interactions
between this organic aerosol and four active zones containing
adsorbate pyridine pyrrole
molecules amide zone amine zone zone zone N functional groups. On the basis of the energy results shown
in Figure 6a,b, the pyrrole zone (here, in the form of indole)
benzoic acid 16.9−17.2 8.6−14.8 13.0−20.6 14.8−20.1
and the pyridine zone (here, in the form of quinoline) have the
benzofuran 5.6−6.03 2.6−8.4 4.5−7.3 6.2−11.5
best interaction with benzoic acid, evidenced by an Eads of ∼20
hexanal 9.4−11.5 5.2−10.3 5.3−8.9 9.2−15.5
kcal/mol, followed by the amide and amine zones at 17.2 and
dibenzo- 9.4−16.4 18.3−21.8 9.0−13.5 11.5−20.7
thiophene 14.8 kcal/mol (not shown here), respectively.
3-pentyl- 14.3−15.8 12.0−18.6 8.6−11.2 10.4−17.8 Even for the best interactions (associated with the highest
thiophene adsorption energies), no H-transfer or ionic interaction (e.g.,
hexanethiol 14.3−18.5 13.8−18.3 8.8−9.8 12.7−17.3 between benzoic acid and the pyridine zone, C6H5-COO−. .
a
The range of energy covers different orientations of each chemical .+HN-Ar) was observed between benzoic acid and N-
compound toward the target active zone. All the negative numbers of containing zones. As shown in Figure 6a, the maximum
energy are written as positive. adsorption energies for benzoic acid and the pyrrole zone and
pyridine zone concern H-bonding and other intermolecular
a better evaluation of adsorption strength of each gas molecule, forces, including dipole−dipole and dispersion.
the average adsorption of each gas molecule on four N- Due to the chemical nature of benzoic acid and amine (as a
containing zones is plotted in Figure 5. This figure clearly base), two possible chemical reactions between two
confirms the low adsorption of benzofuran, with E = 8.3 kcal/ components were investigated: a simple ion-pair reaction
mol, and hexanal, with E = 11.5 kcal/mol, compared to other (C6H5-COO−. . .+H3N-R), and an amidization reaction that
compounds. occurs as the following reaction 1 to produce R-NH-CO-Ar +
H2O.
carboxylic acid + amine → amide + H 2O (1)

However, neither of these two reactions were performed

Figure 5. Comparison of average adsorptions (in kcal/mol) of six gas
compounds on four N-containing active zones of an algal IFC. All the
negative numbers of energy are written as positive.
Dibenzo-thiophene and benzoic acid are two other identified
chemical compounds that are normally emitted from a
bitumen surface. On the basis of our DFT results, dibenzo-
thiophene and benzoic acid with an average adsorption energy
of 18.1 kcal/mol have the most interaction with the IFC
surface. The discrepancy in adsorption strength between
benzofuran and dibenzo-thiophene/benzoic acid implies that
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successfully, indicating that the interactions between this weak
acid and base are dominated by the physical interactions rather
than the chemical reactions. In the amidization reaction, the
energy released from this reaction (−7.8 kcal/mol) is less than
the physical interactions between the two components (−8.6
to −14.8 kcal/mol).
Dibenzo-thiophene, a sulfur-containing polycyclic aromatic
compound consisting of a thiophene ring flanked by two
benzene rings (Figure 3), belongs to the intermediate-volatile
organic compounds that have been recognized as contributors
to secondary organic aerosols.55 As one of the most abundant
S-containing compounds in the atmosphere, dibenzo-thio-
phene is emitted from burning wood,56 incomplete combus-
tion,57 and noncombustion resources such as bitumen.8
Dibenzo-thiophene is also found in crude oil and petroleum,
from which it is removed before further use.58,59
In this work, along with benzoic acid, dibenzo-thiophene
shows the maximum adsorption on the biochar model surface,
with average adsorption energy of −18.1 kcal/mol. The best
performance of this polycyclic aromatic compound is related to
its interactions with the amine zone (Eads = −21.8 kcal/mol)
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Figure 6. Adsorption complexes of the benzoic acid, dibenzo-thiophene, and benzofuran gas molecules.
and the pyrrole zone (Eads = −20.7 kcal/mol) (Figure 6c,d). In
either complex, the S atom of dibenzo-thiophene takes
advantage of an H-bonding interaction with the NH part of
the amine or pyrrole group that brings a good thermodynamic
stabilization for the newly formed adsorption complex. In
addition, good adsorption for dibenzo-thiophene is provided
by its polyaromatic nature and the relatively high electron
density that it carries due to its large size. In Figure 6d, the
binding (relative) distance, defined based on the two centers of
mass of the targeted compounds, is 4.2 Å, which is a common
range for the binding distance of aromatic planes. In this case,
two polyaromatic compounds are arranged in a displaced-
parallel (offset) orientation, which is a favorable arrangement
in which the π-electron repulsion of quadrupole/quadrupole
interactions between two aromatic planes is minimized and the
complex becomes stabilized.
Interaction of Benzofuran with N-Components of the
Biochar Surface. Benzofuran and dibenzofuran are precur-
sors to secondary organic aerosols; these precursors are often
found in complex petroleum-based mixtures. Among the three
O-containing gas molecules chosen for this study (benzoic
acid, benzofuran, and hexanal), benzofuran has the least
adsorption on the model surface of algae biochar. The best
performance of benzofuran is related to its adsorption on the
pyrrole zone (a substituted indole) with a stabilization energy
of −11.5 kcal/mol (Figure 6e). Next best is its adsorption on
the amine zone with a stabilization energy of −8.4 kcal/mol
(Figure 6e,f). Comparison of the adsorption complexes of the
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dibenzo-thiophene-pyrrole zone (Figure 6d) with the
benzofuran-pyrrole zone (Figure 6e) shows that while both
structures benefit from a displaced-parallel arrangement with
an H-bonding interaction, the former complex is stabilized
much better than the latter complex, Eads = −20.7 kcal/mol
compared to Eads = −11.5 kcal/mol. This energy difference
highlights the importance of the number of aromatic rings in a
polyaromatic compound (with the consequent electron density
carried by those rings) on its π−π electron interactions.
Also, comparison of the arrangements and stabilization
energies for the two adsorption complexes benzoic acid-pyrrole
zone (Figure 6a) and benzofuran-pyrrole zone (Figure 6e)
further supports this hypothesis that the most effective
nonbonding interactions in the benzoic acid complex
compared to the benzofuran complex provide a higher stability
for the former complex (Eads = −20.1 kcal/mol) compared to
the latter one (Eads = −11.5 kcal/mol). Therefore, despite the
smaller electron density of benzoic acid, due to its smaller size
compared to benzofuran, the functional groups of benzoic acid
perform better than those of benzofuran in adsorption on the
surface of algal biochar.
Final Adsorption Behavior of IFC. A comparison of the
results of the dynamic vapor sorption experiment and the
molecular modeling shows that while benzofuran and dibenzo-
thiophene respectively show the least and the most interaction
with the IFC surface, the total adsorption uptake of benzofuran
molecules (2.448 wt %) by IFC is noticeably higher than that
of dibenzo-thiophene (0.018 wt %). The specific surface area
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ACS Sustainable Chem. Eng. 2021, 9, 14375−14384
ACS Sustainable Chemistry & Engineering
and the pore size of carbonaceous materials are two key factors
in their adsorption behaviors. Biochars, in general, have a
smaller specific surface area and are more porous compared to
other functionalized carbons. The low interaction of
benzofuran with functional groups of the IFC surface increases
its mobility and its penetration to the pores. In contrast, the
stronger interaction of dibenzo-thiophene with the IFC surface
compared to the benzofuran limits the free mobility and
penetration of dibenzo-thiophene to the pores, leading to the
lower total adsorption for this molecule.
■
CONCLUSION
This study highlights the merits of applying functionalized
carbon in bituminous composites used in outdoor construction
elements, to reduce the bituminous composites’ emissions
especially when exposed to ultraviolet exposure and hot
weather. Exposure to ultraviolet and high temperatures have
recently been shown to be two influential factors accelerating
the emission of volatile and semivolatile organic compounds
from areas surfaced with bitumen. The compounds emitted are
potential precursors to ozone and to secondary organic
aerosols, which are submicron (<2.5 μm) atmospheric aerosols
with serious impacts on human health and the environment. In
addition, the loss of such compounds from bituminous
composites that are used in built environments such as
roads, bridges, airports, and roofs, etc. accelerate their
degradation, shortening their service life. This study focused
on an inherently functionalized carbon from algal feedstock,
rich in N compounds due to a high content of protein and
nucleic acids. The study’s results indicate the merits of the
newly made functionalized carbon as an appropriate solid
sorbent for a specific group of atmospheric aerosols.
The proper features of an ideal solid sorbent are not limited
to a large surface area and a high free volume; the surface
interactions between the adsorbate molecules and the solid
sorbent strongly affect the adsorption process. Adsorption of
the target organic compounds on the functionalized carbon is
partly a thermodynamic process based on differences in the
adsorption energies of different compounds.
On the basis of our DFT results measuring adsorption of six
molecules (benzoic acid, benzofuran, hexanal, dibenzo-
thiophene, 3-pentylthiophene, and hexanethiol) toward the
N-rich surface of biochar, benzoic acid and dibenzo-thiophene
showed the greatest average adsorption energy of 18.1 kcal/
mol, and benzofuran showed the lowest average adsorption
energy of 8.3 kcal/mol. Even for the best interaction, there
were no H-transfers, no simple ion-pair reactions, and no
amidization reactions during the interaction, indicating that the
interactions between this N-rich surface and the targeted air-
pollutant emissions are dominated by the physical interactions
(H-bonding, dipole−dipole, and dispersion forces) rather than
the chemical reactions.
The adsorption properties of our functionalized carbon were
also evaluated by an automated vacuum vapor/gas gravimetric
sorption analyzer (DVS vacuum). The DVS vacuum showed a
good total adsorption uptake by IFC for benzofuran (2.443 wt
%), while DFT found a weak interaction between this
compound and functional groups of the IFC surface. A similar
trend was observed for dibenzo-thiophene: the lowest surface
adsorption and the highest total adsorption uptake (0.018 wt
%) were for this compound. This could be explained by the
extent of mobility and penetration of target volatile organic
molecules to IFC’s pores. Although strong interactions of
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IFC’s functional groups with organic molecules increase their
surface adsorption, they limit penetration of the organic
molecules into IFC’s pores, leading to a decrease in total
adsorption. Weak interactions of IFC’s functional groups with
organic molecules decrease their surface adsorption, facilitating
penetration of the organic molecules into IFC’s pores, leading
to an increase in total adsorption, with active zones targeted.
■ AUTHOR INFORMATION
Corresponding Author
Elham H. Fini − Arizona State University, Tempe, Arizona
85287-3005, United States; orcid.org/0000-0002-3658-
0006; Phone: 480-965-4273; Email: efini@asu.edu
Authors
Masoumeh Mousavi − Arizona State University, Tempe,
Arizona 85287-3005, United States; orcid.org/0000-
0003-4750-8154
Vladimir Martis − Surface Measurement System, London HA0
4PE, United Kingdom
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.1c03827
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This research was sponsored by the National Science
Foundation (Award no. 1935723). The authors greatly
appreciate Kodanda Phani Raj Dandamudi with Arizona
State University for providing the functionalized carbon and
Daniel Burnett and Peter Gibson with Surface Measurement
Systems for assisting with the conduct of laboratory experi-
ments.
■
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