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*

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

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with varying aerodynamic diameters (from nm to μm) and An important difference between algae biomass and
different toxicological properties that can be a potential hazard terrestrial biomass is the higher protein content of algae
for human health9 and climate.10,11 These emissions are biomass. The hydrolysis of protein produces amino acids
temperature-dependent compounds that are doubled in a (containing a −NH2 group) and carboxylic acids (containing a
temperature rise from 40 to 60 °C; they reach the maximum −COOH group), so deamination and decarboxylation are the
level at temperatures over 140 °C, indicating that SOA main pathways for the decomposition of amino acids. The
precursors are released into the air more significantly in nitrogen compounds of biochar are not limited to high-protein
summer months.8 Exposure to ultraviolet is also an influential biomasses such as algae. Analysis of the chars prepared from
factor accelerating the emission of volatile and semivolatile high-temperature coal pyrolysis (>750 °C) has shown the
organic compounds from areas surfaced with bitumen. super thermal stability of some N-containing compounds such
Here, it is hypothesized that inherently functionalized as pyridinic-N, pyrrolic-N, and quaternary-N.35−37 Unlike coal,
carbon made from algal biomass adsorbs undesirable chemical the dominant nitrogen form in algae is protein-N, which has a
compounds that are normally emitted from bitumen. This lower thermal stability. Thus, algae pyrolysis is usually
hypothesis can also be viewed from another perspective: a performed at lower temperature ranges (500−600 °C) that
tailored functionalized carbon could increase a bituminous could be considered as a green chemistry of algae, minimizing
composite’s retention time of some compounds that would the generation of hazardous chemical compounds.38,39
otherwise be released to the atmosphere in the form of gaseous In this study, an inherently functionalized carbon derived
emissions (SOA precursors) in a process exacerbated by heat from the hydrothermal liquefaction of an algal biomass was
and solar radiation. Considering the efficacy and abundance of used to investigate the efficacy of this carbon in the adsorption
functional groups in carbonaceous materials such as biochar, of a series of air-polluting chemical compounds (precursors of
the targeted inherently functionalized carbon could be secondary organic aerosols in the atmosphere) normally
developed from a feedstock of pure algae or a balanced emitted from bitumen at elevated temperatures. With the use
of quantum-based computational modeling performed in the
mixture of algae feedstock with other feedstocks, tailored to the
framework of density functional theory, the molecular
adsorption of bitumen emissions to alleviate the side effects of
interactions of six of bitumen’s emitted chemical compounds
intense sun exposure on both air quality and construction
with the targeted active sites of the algal IFC were studied. The
durability. It is worth noting that “biochar” is mostly atributed
adsorbate molecules were three O-containing compounds
to the charcoal produced by pyrolysis of biomass in the (benzoic acid, benzofuran, and hexanal) and three S-containing
absence of oxygen. The carbonaceous material used in our compounds (dibenzo-thiophene, 3-pentylthiophene, and hex-
studies is made from hydrothermal liquefaction of algae and is anethiol). In a comparative study, the average adsorption
referred to as inherently functionalized carbon (IFC) in this energy of each compound on the IFC surface was calculated to
study. estimate the adsorption strength of each compound.
Considering the urgent need for the development of Laboratory experiments were performed using dynamic vapor
alternative and renewable resources, algae are among the sorption analysis under vacuum to measure the extent of
promising biomasses for energy production and other adsorption of select gas-phase compounds by functionalized
environmental applications.12−16 In addition to algae’s carbon.

■
capability in energy production, algae have a good record as
a promising appropriate sorbent for CO2 fixation.17−21 The MATERIALS AND METHODS
recent studies on an IFC derived from the thermochemical The neat bitumen used in this study was graded as PG 64-16 and
liquefaction of a blend of algae (rich in protein and nucleic supplied by HollyFrontier Corporation in Arizona (Table 1). The
acids) and swine manure (rich in lipids) indicated the merits of
the newly made carbonaceous material as a free-radical Table 1. Properties of PG 64-16 Bitumen
scavenger that significantly reduces the aging of bitumen
exposed to ultraviolet irradiation.22 On the basis of the study specific gravity @ 15.6 °C 1.025
results, the IFC made from algae alone performs even better flashpoint °C 300
than hybrid IFC made from algae and swine manure. The absolute viscosity, P @ 60 °C 2,005
efficacy of algae IFC as a free-radical scavenger and ultraviolet G*/sin δ, kPa @ 64 °Ca 1.23
blocker was attributed to the rather high surface area and rich mass change after −0.210%
phenol functional groups (C6H5-OH) in algal IFC. RTFO (rolling thin-film oven)
Apart from the role of O-containing functional groups such G*/sin δ, kPa @ 64 °Ca 3.33
as phenols, alcohols, ketones, lactones, and carboxylic acids G*/sin δ, kPa @ 28 °Ca 2,87
that are normally abundant in IFCs, the role of N-containing stiffness (MPa) @ 60 s, @ −6 °C 90.4
functionals in algae IFC cannot be overlooked. The O- m value @ 60 s, @ −6 °C 0.384
a
containing functional groups and N-containing functional G* is a symbol commonly used for the complex shear modulus.
groups have been shown to be the factors most influencing
the acidity or basicity of the carbon’s surface.23−26 The N- functionalized carbon was made from the thermochemical conversion
containing functional groups mainly demonstrate the basic of algae (Cyanidioschyzon merolae).40 Adsorbents used for measure-
characteristic. The good performance of N-containing func- ments were 2,3-benzofuran (99%, Sigma-Aldrich), dibenzo-thiophene
(analytical standard, Supelco Inc.), and benzoic acid (99.5%, Sigma-
tional groups has been shown through extensive studies
Aldrich). In this study, functionalized carbon was directly mixed into
performed on N-grafted activated carbons used to adsorb some the bitumen at 10% concentration based on the weight of the
primary greenhouse gas-phase molecules such as CO2.27−31 bitumen.
Amine-grafted surfaces have also shown high efficiency in the To prepare samples, the IFC was preheated to 50 °C and held at
adsorption of CO2 molecules.32−34 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 Figure 1. Schematic representation of the IFC molecular model.
(adsorbent) and our target gas molecules (adsorbates). It is worth Active zones containing N-functionals are circled.
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 zone. Each IFC zone was optimized to its minimum energy before
“adsorption” is mostly associated with a “surface”, this term is used introducing the gas molecules for interaction.
throughout this study. As for the biochar surface, a very limited The targeted gas molecules chosen for adsorption on the model
number of molecular representations of biochar have been proposed surface are six potentially hazardous chemical compounds: three
in the literature. A typical biochar is quite dependent on its initial contain S functional groups (dibenzo-thiophene, 3-pentylthiophene,
precursor (biomass), so a molecular model of a typical biochar is and hexanethiol), and three contain O functional groups (benzoic
commonly designed based on the biochar’s empirical formula and acid, benzofuran, and hexanal). Although S-containing hydrocarbon
FTIR results. In contrast to graphene with its apparent crystalline compounds and O-containing hydrocarbon compounds make up only
properties, it is not easy to detect aromatic clusters in biochars derived 5% to 15% of emissions at temperatures relevant to the life cycles of
at high temperature. However, there is sufficient evidence indicating asphalt materials, their contribution to the total emissions under solar
degrees of crystallinity in biochars.42,43 Even in amorphous biochars, irradiation is significant: under sun exposure, S-containing com-
poorly ordered graphene stacks are expected.42 In our case study, the pounds show a 700% increase, and O-containing compounds show a
peaks at 26.426° and 43.019° (2θ) of X-ray powder diffraction spectra 400% increase.8
indicated the presence of graphite-like carbon in the IFC derived by Given the limited information about the exact chemical
hydrothermal liquefaction of algae.40 In addition, at the temperature composition of the S-containing compounds and O-containing
range (300−350 °C) used in the production of IFC in this study, the compounds of bitumen emissions, here we use a group of chemical
presence of randomly oriented polyaromatic clusters is expected. This compounds recently introduced as asphalt-related emissions.8 The
is supported by the findings that the carbonaceous material prepared highly aromatic S-containing compounds chosen for this study
at a temperature range of 280−350 °C contained small polyaromatic include formulas representing benzothiophenes and dibenzothio-
rings connected through polyphosphate bridges.43 phenes, a selection of which have been previously observed as
The characteristics of the functional groups surrounding the central individual compounds in petroleum and coal. The complex mixture of
aromatic zone of our IFC model molecule are determined based on O-containing compounds includes formulas representing benzofurans
the analytical and spectroscopic studies performed on our target alga. and dibenzofurans that are often observed in complex petroleum-
The FTIR adsorption peaks indicate the presence of alcoholic OHs related mixtures.
and other O-containing functional groups such as phenols, carboxyl, All energy optimizations on the four biochar sections, the gas
carbonyl, and ketene.43 The presence of N-containing compounds in adsorbate molecules, and their corresponding adsorption complexes
our algal IFC is evidenced by the bands at 2100−2270 cm−1 were performed via the DMol3 module44,45 implemented in the
corresponding to diimides and azides and by the bands at 1600− Accelrys Materials Studio program package (version 6.0). The PBE
1670 cm−1 corresponding to N−H stretching of cyclic amides. (Perdew−Burke−Ernzerhof)46 formulation of generalized gradient
Figure 1 shows a schematic representation of the IFC model approximation (GGA) was used as the functional for all calculations.
molecule used in this study. This IFC model molecule contains four Due to the high polarizability of the algal biochar surface, the long-
N-functional groups: amide, amine, pyrrole, and pyridine. Since the range van der Waals interactions need to be included in the
focus of the present study is on the interactions of specific parts of the calculations to accurately estimate the thermodynamic stability and
IFC surface, not the entire surface, the central aromatic zone of the strength of adsorbent−adsorbate interactions. The dispersion terms
biochar model molecule (dashed lines in Figure 1) is designed just for defined by Grimme et al. (DFT-D2 or DFT-D3) have been shown to
connecting the four targeted zones. In this figure, the four active zones provide a quite accurate thermochemistry for the systems dominated
containing N-functional groups are 1-amide zone, 2-amine zone, 3- by covalence as well as dispersion forces.47 So, the Grimme’s long-
pyrrole zone, and 4-pyridine zone. As specified in Figure 1, to simulate range dispersion correction48 (PBE-D) was included, as implemented
the chemical environment near the targeted N-functional groups in the DMol3 module of the Accelrys Materials Studio program
(amide, amine, pyrrole, and pyridine), a part of the aromatic zone package. All-electron double numerical basis sets augmented by
coordinated to that N-functional group was considered as the targeted 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 to as adsorbents) was used. Figure 2 shows the adsorption/
integrations. At this level of integration, the tolerances for energy, desorption kinetics for benzofuran as well as the total
maximum force, and displacement convergence were 1.0 × 10−5 adsorption uptake versus partial pressure. Measurement of
Hartree, 2.0 × 10−3 Hartree/Å, and 5.0 × 10−3 Å, respectively. other adsorbents followed the same procedure. It was found
During the adsorption of gas molecules on each part of the IFC
that IFC is able to retain the adsorbents; the adsorption of
surface, the thermodynamic stability of the adsorption complex
formed was expressed through the adsorption energy (Eads). Eads is the
benzofuran was the highest among the three (2.443 wt %),
energy difference between the adsorption complex formed and its followed by benzoic acid (0.519 wt %) and dibenzo-thiophene
constituents, a gas molecule and the IFC zone, when they are in their (0.018 wt %). Variation in the extent of adsorption indicates
lowest energy state. that IFC could selectively adsorb some potentially hazardous

■
bitumen emissions that would otherwise be emitted from
RESULTS AND DISCUSSION bitumen. This can explain part of the delayed progress of aging
observed in our recent study.22 The following section explains
It has been documented that IFC made from algal biomass the molecular modeling used to quantify the binding energy
significantly delays the aging of bituminous composites.22 between the typical volatile compounds emitted from bitumen
Here, it is hypothesized that the observed delay in aging is and the functionalized carbon.
partly due to a delayed loss of volatile oxygenated compounds DFT-Based Modeling Results. For a solid sorbent such as
of bitumen in the form of emissions. Among those volatiles are a biochar, the ideal features are not limited to a large surface
benzofuran, dibenzo-thiophene, and benzoic acid.8 To evaluate area and a high free volume; also required are appropriate
the capability of IFC to retain these gas molecules, a dynamic interactions between the adsorbate molecules and the solid
sorption method using the above three gas molecules (referred 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 greater fraction at high temperatures.8 On the basis of recent
in the adsorption energies of different compounds. Therefore, findings,8 solar exposure results in a 700% increase in the
energy-based data can clarify the adsorption strength for emission of S-containing compounds, a 400% increase in the
different adsorbate molecules, indicating the capability of the emission of O-containing compounds and a 300% increase in
biochar to adsorb the gas-phase molecules before they are hydrocarbons.
released to the atmosphere. The highly aromatic S-containing compounds in bitumen
The results for our case study discussed below indicate how emissions include chemical structures representing benzo-
a quantum-based density functional approach can be used to thiophenes and dibenzo-thiophenes.9 The complex mixture of
show the adsorption behavior of a selected group of gas O-containing emissions includes chemical structures represent-
molecules, normally emitted from the bitumen surface, on the ing benzofurans and dibenzofurans, commonly found in
N-rich surface of our algal IFC. Figure 3 shows the selected complex petroleum-based mixtures.
group of six adsorbate molecules (three O-containing A biochar surface generally includes many O-containing
compounds and three S-containing compounds) supposed to functional groups, including phenols, alcohols, ketones,
interact with four active zones of the IFC surface containing N- lactones, and carboxylic acids. However, the active zones
functionals of amide, amine, pyridine, and pyrrole. The O- targeted in this study mostly contain N-containing functional
containing compounds are benzoic acid, benzofuran, and groups (Figure 1). It should be noted that the distinctive
hexanal (an aldehyde molecule). The S-containing compounds performance of the algae IFC compared to other function-
are dibenzo-thiophene, 3-pentylthiophene, and hexanethiol. alized carbons is attributed to the N-compounds in IFC made
The reason behind this selection is the significant role of polar from algae. As stated earlier, in this study, the area of each
molecules including sulfur or oxygen elements as precursors of active zone is not limited to an individual N-functional group
secondary organic aerosols.8 At temperatures relevant to the but also contains a small portion of the biochar surface
life cycle of bitumen materials, hydrocarbons constitute a great coordinated to the N-functional group, to simulate the
fraction of bitumen emissions. However, O-containing chemical environment around the functional. This is of
emissions and S-containing emissions, contributing 1%−14% particular importance, because the nature of substituents
and 5%−30% of the total emissions, respectively, constitute a (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

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
Figure 5. Comparison of average adsorptions (in kcal/mol) of six gas to secondary organic aerosols.55 As one of the most abundant
compounds on four N-containing active zones of an algal IFC. All the S-containing compounds in the atmosphere, dibenzo-thio-
negative numbers of energy are written as positive. phene is emitted from burning wood,56 incomplete combus-
tion,57 and noncombustion resources such as bitumen.8
Dibenzo-thiophene and benzoic acid are two other identified Dibenzo-thiophene is also found in crude oil and petroleum,
chemical compounds that are normally emitted from a from which it is removed before further use.58,59
bitumen surface. On the basis of our DFT results, dibenzo- In this work, along with benzoic acid, dibenzo-thiophene
thiophene and benzoic acid with an average adsorption energy shows the maximum adsorption on the biochar model surface,
of 18.1 kcal/mol have the most interaction with the IFC with average adsorption energy of −18.1 kcal/mol. The best
surface. The discrepancy in adsorption strength between performance of this polycyclic aromatic compound is related to
benzofuran and dibenzo-thiophene/benzoic acid implies that 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 dibenzo-thiophene-pyrrole zone (Figure 6d) with the
either complex, the S atom of dibenzo-thiophene takes benzofuran-pyrrole zone (Figure 6e) shows that while both
advantage of an H-bonding interaction with the NH part of structures benefit from a displaced-parallel arrangement with
the amine or pyrrole group that brings a good thermodynamic an H-bonding interaction, the former complex is stabilized
stabilization for the newly formed adsorption complex. In much better than the latter complex, Eads = −20.7 kcal/mol
addition, good adsorption for dibenzo-thiophene is provided compared to Eads = −11.5 kcal/mol. This energy difference
by its polyaromatic nature and the relatively high electron highlights the importance of the number of aromatic rings in a
density that it carries due to its large size. In Figure 6d, the polyaromatic compound (with the consequent electron density
binding (relative) distance, defined based on the two centers of carried by those rings) on its π−π electron interactions.
mass of the targeted compounds, is 4.2 Å, which is a common Also, comparison of the arrangements and stabilization
range for the binding distance of aromatic planes. In this case, energies for the two adsorption complexes benzoic acid-pyrrole
two polyaromatic compounds are arranged in a displaced- zone (Figure 6a) and benzofuran-pyrrole zone (Figure 6e)
parallel (offset) orientation, which is a favorable arrangement further supports this hypothesis that the most effective
in which the π-electron repulsion of quadrupole/quadrupole nonbonding interactions in the benzoic acid complex
interactions between two aromatic planes is minimized and the compared to the benzofuran complex provide a higher stability
complex becomes stabilized. for the former complex (Eads = −20.1 kcal/mol) compared to
Interaction of Benzofuran with N-Components of the the latter one (Eads = −11.5 kcal/mol). Therefore, despite the
Biochar Surface. Benzofuran and dibenzofuran are precur- smaller electron density of benzoic acid, due to its smaller size
sors to secondary organic aerosols; these precursors are often compared to benzofuran, the functional groups of benzoic acid
found in complex petroleum-based mixtures. Among the three perform better than those of benzofuran in adsorption on the
O-containing gas molecules chosen for this study (benzoic surface of algal biochar.
acid, benzofuran, and hexanal), benzofuran has the least Final Adsorption Behavior of IFC. A comparison of the
adsorption on the model surface of algae biochar. The best results of the dynamic vapor sorption experiment and the
performance of benzofuran is related to its adsorption on the molecular modeling shows that while benzofuran and dibenzo-
pyrrole zone (a substituted indole) with a stabilization energy thiophene respectively show the least and the most interaction
of −11.5 kcal/mol (Figure 6e). Next best is its adsorption on with the IFC surface, the total adsorption uptake of benzofuran
the amine zone with a stabilization energy of −8.4 kcal/mol molecules (2.448 wt %) by IFC is noticeably higher than that
(Figure 6e,f). Comparison of the adsorption complexes of the of dibenzo-thiophene (0.018 wt %). The specific surface area
14381 https://doi.org/10.1021/acssuschemeng.1c03827
ACS Sustainable Chem. Eng. 2021, 9, 14375−14384
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

and the pore size of carbonaceous materials are two key factors IFC’s functional groups with organic molecules increase their
in their adsorption behaviors. Biochars, in general, have a surface adsorption, they limit penetration of the organic
smaller specific surface area and are more porous compared to molecules into IFC’s pores, leading to a decrease in total
other functionalized carbons. The low interaction of adsorption. Weak interactions of IFC’s functional groups with
benzofuran with functional groups of the IFC surface increases organic molecules decrease their surface adsorption, facilitating
its mobility and its penetration to the pores. In contrast, the penetration of the organic molecules into IFC’s pores, leading
stronger interaction of dibenzo-thiophene with the IFC surface to an increase in total adsorption, with active zones targeted.
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.
■ AUTHOR INFORMATION

■
Corresponding Author
Elham H. Fini − Arizona State University, Tempe, Arizona
CONCLUSION 85287-3005, United States; orcid.org/0000-0002-3658-
This study highlights the merits of applying functionalized 0006; Phone: 480-965-4273; Email: efi[email protected]
carbon in bituminous composites used in outdoor construction
elements, to reduce the bituminous composites’ emissions Authors
especially when exposed to ultraviolet exposure and hot Masoumeh Mousavi − Arizona State University, Tempe,
weather. Exposure to ultraviolet and high temperatures have Arizona 85287-3005, United States; orcid.org/0000-
recently been shown to be two influential factors accelerating 0003-4750-8154
the emission of volatile and semivolatile organic compounds Vladimir Martis − Surface Measurement System, London HA0
from areas surfaced with bitumen. The compounds emitted are 4PE, United Kingdom
potential precursors to ozone and to secondary organic Complete contact information is available at:
aerosols, which are submicron (<2.5 μm) atmospheric aerosols https://pubs.acs.org/10.1021/acssuschemeng.1c03827
with serious impacts on human health and the environment. In
addition, the loss of such compounds from bituminous Notes
composites that are used in built environments such as The authors declare no competing financial interest.
roads, bridges, airports, and roofs, etc. accelerate their
degradation, shortening their service life. This study focused
on an inherently functionalized carbon from algal feedstock,
■ ACKNOWLEDGMENTS
This research was sponsored by the National Science
rich in N compounds due to a high content of protein and Foundation (Award no. 1935723). The authors greatly
nucleic acids. The study’s results indicate the merits of the appreciate Kodanda Phani Raj Dandamudi with Arizona
newly made functionalized carbon as an appropriate solid State University for providing the functionalized carbon and
sorbent for a specific group of atmospheric aerosols. Daniel Burnett and Peter Gibson with Surface Measurement
The proper features of an ideal solid sorbent are not limited Systems for assisting with the conduct of laboratory experi-
to a large surface area and a high free volume; the surface ments.

■
interactions between the adsorbate molecules and the solid
sorbent strongly affect the adsorption process. Adsorption of REFERENCES
the target organic compounds on the functionalized carbon is
(1) Kanellopoulos, P. G.; Verouti, E.; Chrysochou, E.; Koukoulakis,
partly a thermodynamic process based on differences in the K.; Bakeas, E. Primary and secondary organic aerosol in an urban/
adsorption energies of different compounds. industrial site: Sources, health implications and the role of plastic
On the basis of our DFT results measuring adsorption of six enriched waste burning. J. Environ. Sci. 2021, 99, 222−238.
molecules (benzoic acid, benzofuran, hexanal, dibenzo- (2) Ghosh, S.; Rabha, R.; Chowdhury, M.; Padhy, P. K. Source and
thiophene, 3-pentylthiophene, and hexanethiol) toward the chemical species characterization of PM10 and human health risk
N-rich surface of biochar, benzoic acid and dibenzo-thiophene assessment of semi-urban, urban and industrial areas of West Bengal,
showed the greatest average adsorption energy of 18.1 kcal/ India. Chemosphere 2018, 207, 626−636.
mol, and benzofuran showed the lowest average adsorption (3) Ervens, B.; Turpin, B.; Weber, R. Secondary organic aerosol
energy of 8.3 kcal/mol. Even for the best interaction, there formation in cloud droplets and aqueous particles (aqSOA): a review
were no H-transfers, no simple ion-pair reactions, and no of laboratory, field and model studies. Atmos. Chem. Phys. 2011, 11
(21), 11069−11102.
amidization reactions during the interaction, indicating that the
(4) Heald, C. L.; Henze, D. K.; Horowitz, L. W.; Feddema, J.;
interactions between this N-rich surface and the targeted air- Lamarque, J.-F.; Guenther, A.; Hess, P. G.; Vitt, F.; Seinfeld, J. H.;
pollutant emissions are dominated by the physical interactions Goldstein, A. H.; Fung, I. Predicted change in global secondary
(H-bonding, dipole−dipole, and dispersion forces) rather than organic aerosol concentrations in response to future climate,
the chemical reactions. emissions, and land use change. Journal of Geophysical Research:
The adsorption properties of our functionalized carbon were Atmospheres 2008, 113 (D5), 1−16.
also evaluated by an automated vacuum vapor/gas gravimetric (5) Jimenez, J. L.; Canagaratna, M.; Donahue, N.; Prevot, A.; Zhang,
sorption analyzer (DVS vacuum). The DVS vacuum showed a Q.; Kroll, J. H.; DeCarlo, P. F.; Allan, J. D.; Coe, H.; Ng, N. Evolution
good total adsorption uptake by IFC for benzofuran (2.443 wt of organic aerosols in the atmosphere. Science 2009, 326 (5959),
%), while DFT found a weak interaction between this 1525−1529.
(6) Khare, P.; Gentner, D. R. Considering the future of
compound and functional groups of the IFC surface. A similar
anthropogenic gas-phase organic compound emissions and the
trend was observed for dibenzo-thiophene: the lowest surface increasing influence of non-combustion sources on urban air quality.
adsorption and the highest total adsorption uptake (0.018 wt Atmos. Chem. Phys. 2018, 18 (8), 5391−5413.
%) were for this compound. This could be explained by the (7) McDonald, B. C.; De Gouw, J. A.; Gilman, J. B.; Jathar, S. H.;
extent of mobility and penetration of target volatile organic Akherati, A.; Cappa, C. D.; Jimenez, J. L.; Lee-Taylor, J.; Hayes, P. L.;
molecules to IFC’s pores. Although strong interactions of McKeen, S. A.; et al. Volatile chemical products emerging as largest

14382 https://doi.org/10.1021/acssuschemeng.1c03827
ACS Sustainable Chem. Eng. 2021, 9, 14375−14384
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

petrochemical source of urban organic emissions. Science 2018, 359 (29) Drage, T. C.; Arenillas, A.; Smith, K. M.; Pevida, C.; Piippo, S.;
(6377), 760−764. Snape, C. E. Preparation of carbon dioxide adsorbents from the
(8) Khare, P.; Machesky, J.; Soto, R.; He, M.; Presto, A. A.; Gentner, chemical activation of urea−formaldehyde and melamine−form-
D. R. Asphalt-related emissions are a major missing nontraditional aldehyde resins. Fuel 2007, 86 (1−2), 22−31.
source of secondary organic aerosol precursors. Science Advances (30) El-Sayed, Y.; Bandosz, T. J. A study of acetaldehyde adsorption
2020, 6 (36), No. eabb9785. on activated carbons. J. Colloid Interface Sci. 2001, 242 (1), 44−51.
(9) Kriech, A. J.; Schreiner, C. A.; Osborn, L. V.; Riley, A. J. (31) Maroto-Valer, M. M.; Tang, Z.; Zhang, Y. CO2 capture by
Assessing cancer hazards of bitumen emissions−a case study for activated and impregnated anthracites. Fuel Process. Technol. 2005, 86
complex petroleum substances. Crit. Rev. Toxicol. 2018, 48 (2), 121− (14−15), 1487−1502.
142. (32) Harlick, P.; Sayari, A. Amine Grafted, Pore-Expanded MCM−
(10) Lohmann, U.; Feichter, J. Global indirect aerosol effects: a 41 for Acid Gas Removal: Effect of Grafting Temperature, Water, And
review. Atmos. Chem. Phys. 2005, 5 (3), 715−737. Amine Type on Performance. In Studies in Surface Science and
(11) Rosenfeld, D.; Sherwood, S.; Wood, R.; Donner, L. Climate Catalysis; Elsevier: 2005; Vol. 158, pp 987−994.
effects of aerosol-cloud interactions. Science 2014, 343 (6169), 379− (33) Hiyoshi, N.; Yogo, K.; Yashima, T. Adsorption of carbon
380. dioxide on modified mesoporous materials in the presence of water
(12) Guo, Y.; Yeh, T.; Song, W.; Xu, D.; Wang, S. A review of bio-oil vapor. In Studies in Surface Science and Catalysis; Elsevier: 2004; Vol.
production from hydrothermal liquefaction of algae. Renewable 154, pp 2995−3002, DOI: 10.1016/S0167-2991(04)80583-4.
Sustainable Energy Rev. 2015, 48, 776−790. (34) Knowles, G. P.; Graham, J. V.; Delaney, S. W.; Chaffee, A. L.
(13) Amin, S. Review on biofuel oil and gas production processes Aminopropyl-functionalized mesoporous silicas as CO2 adsorbents.
from microalgae. Energy Convers. Manage. 2009, 50 (7), 1834−1840. Fuel Process. Technol. 2005, 86, 1435−1448.
(14) Cole, A.; Dinburg, Y.; Haynes, B. S.; He, Y.; Herskowitz, M.; (35) Liu, H.; Zhang, Q.; Hu, H.; Liu, P.; Hu, X.; Li, A.; Yao, H.
Jazrawi, C.; Landau, M.; Liang, X.; Magnusson, M.; Maschmeyer, T.; Catalytic role of conditioner CaO in nitrogen transformation during
et al. From macroalgae to liquid fuel via waste-water remediation, sewage sludge pyrolysis. Proc. Combust. Inst. 2015, 35 (3), 2759−
hydrothermal upgrading, carbon dioxide hydrogenation and hydro- 2766.
treating. Energy Environmental Science 2016, 9 (5), 1828−1840. (36) Friebel, J.; Köpsel, R. The fate of nitrogen during pyrolysis of
(15) Ruiz, J.; Olivieri, G.; De Vree, J.; Bosma, R.; Willems, P.; Reith, German low rank coalsa parameter study. Fuel 1999, 78 (8), 923−
J. H.; Eppink, M. H.; Kleinegris, D. M.; Wijffels, R. H.; Barbosa, M. J. 932.
Towards industrial products from microalgae. Energy Environ. Sci. (37) Kelemen, S.; Gorbaty, M.; Kwiatek, P.; Fletcher, T.; Watt, M.;
2016, 9 (10), 3036−3043. Solum, M.; Pugmire, R. Nitrogen transformations in coal during
(16) Demirbas, A.; Fatih Demirbas, M. Importance of algae oil as a
pyrolysis. Energy Fuels 1998, 12 (1), 159−173.
source of biodiesel. Energy Convers. Manage. 2011, 52 (1), 163−170. (38) Chen, W.; Yang, H.; Chen, Y.; Xia, M.; Yang, Z.; Wang, X.;
(17) Tian, Z.; Qiu, Y.; Zhou, J.; Zhao, X.; Cai, J. The direct
Chen, H. Algae pyrolytic poly-generation: Influence of component
carbonization of algae biomass to hierarchical porous carbons and
difference and temperature on products characteristics. Energy 2017,
CO2 adsorption properties. Mater. Lett. 2016, 180, 162−165.
131, 1−12.
(18) Saha, D.; Thorpe, R.; Van Bramer, S. E.; Alexander, N.;
(39) Chen, W.; Yang, H.; Chen, Y.; Xia, M.; Chen, X.; Chen, H.
Hensley, D. K.; Orkoulas, G.; Chen, J. Synthesis of nitrogen and sulfur
Transformation of nitrogen and evolution of N-containing species
codoped nanoporous carbons from algae: role in CO2 separation. ACS
during algae pyrolysis. Environ. Sci. Technol. 2017, 51 (11), 6570−
Omega 2018, 3 (12), 18592−18602.
(19) Sevilla, M.; Falco, C.; Titirici, M.-M.; Fuertes, A. B. High- 6579.
performance CO2 sorbents from algae. RSC Adv. 2012, 2 (33), (40) Dandamudi, K. P. R.; Murdock, T.; Lammers, P. J.; Deng, S.;
12792−12797. Fini, E. H. Production of functionalized carbon from synergistic
(20) Wang, H.; Wang, H.; Liu, G.; Yan, Q. In-situ pyrolysis of Taihu hydrothermal liquefaction of microalgae and swine manure. Resources,
blue algae biomass as appealing porous carbon adsorbent for CO2 Conservation Recycling 2021, 170 (1−11), 105564.
capture: Role of the intrinsic N. Sci. Total Environ. 2021, 771, 145424. (41) Dynamic Vapor Sorption (DVS). https://www.
(21) Moreira, D.; Pires, J. C. Atmospheric CO2 capture by algae: surfacemeasurementsystems.com/solutions/dynamic_vapor_
negative carbon dioxide emission path. Bioresour. Technol. 2016, 215, sorption/ (accessed October 5, 2021).
371−379. (42) Keiluweit, M.; Nico, P. S.; Johnson, M. G.; Kleber, M. Dynamic
(22) Rajib, A.; Fini, E. H. Inherently Functionalized Carbon from molecular structure of plant biomass-derived black carbon (biochar).
Lipid and Protein-Rich Biomass to Reduce Ultraviolet-Induced Environ. Sci. Technol. 2010, 44 (4), 1247−1253.
Damages in Bituminous Materials. ACS Omega 2020, 5 (39), (43) Sajjadi, B.; Zubatiuk, T.; Leszczynska, D.; Leszczynski, J.; Chen,
25273−25280. W. Y. Chemical activation of biochar for energy and environmental
(23) Boehm, H. P. Chemical Identification of Surface Groups. In applications: a comprehensive review. Rev. Chem. Eng. 2019, 35 (7),
Advances in Catalysis; Elsevier: 1966; Vol. 16, pp 179−274, 777−815.
DOI: 10.1016/S0360-0564(08)60354-5. (44) Delley, B. An all-electron numerical method for solving the
(24) Boehm, H. P. Surface oxides on carbon and their analysis: a local density functional for polyatomic molecules. J. Chem. Phys. 1990,
critical assessment. Carbon 2002, 40 (2), 145−149. 92 (1), 508−517.
(25) Montes-Morán, M.; Suárez, D.; Menéndez, J.; Fuente, E. On (45) Delley, B. From molecules to solids with the DMol3 approach.
the nature of basic sites on carbon surfaces: an overview. Carbon J. Chem. Phys. 2000, 113 (18), 7756−7764.
2004, 42 (7), 1219−1225. (46) Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient
(26) Radovic, L. R.; Moreno-Castilla, C.; Rivera-Utrilla, J. Carbon approximation made simple. Phys. Rev. Lett. 1996, 77 (18), 3865−
materials as adsorbents in aqueous solutions. Chemistry and Physics of 3868.
Carbon 2001, 27, 227−406. (47) Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and
(27) Houshmand, A.; Daud, W. M. A. W.; Lee, M.-G.; Shafeeyan, M. accurate ab initio parametrization of density functional dispersion
S. Carbon dioxide capture with amine-grafted activated carbon. Water, correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010,
Air, Soil Pollut. 2012, 223 (2), 827−835. 132 (15), 154104.
(28) Arenillas, A.; Rubiera, F.; Parra, J.; Ania, C.; Pis, J. Surface (48) Grimme, S. Density functional theory with London dispersion
modification of low cost carbons for their application in the corrections. Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2011, 1 (2),
environmental protection. Appl. Surf. Sci. 2005, 252 (3), 619−624. 211−228.

14383 https://doi.org/10.1021/acssuschemeng.1c03827
ACS Sustainable Chem. Eng. 2021, 9, 14375−14384
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

(49) Zhang, X.; Zhang, C.; Sun, X.; Yang, J.; Zhu, C. Mechanism and
kinetic study of the reaction of benzoic acid with OH, NO3 and SO4−
radicals in the atmosphere. RSC Adv. 2019, 9 (33), 18971−18977.
(50) Rogge, W. F.; Hildemann, L. M.; Mazurek, M. A.; Cass, G. R.;
Simoneit, B. R. Sources of fine organic aerosol. 2. Noncatalyst and
catalyst-equipped automobiles and heavy-duty diesel trucks. Environ.
Sci. Technol. 1993, 27 (4), 636−651.
(51) Rogge, W. F.; Hildemann, L. M.; Mazurek, M. A.; Cass, G. R.;
Simoneit, B. R. Sources of fine organic aerosol. 3. Road dust, tire
debris, and organometallic brake lining dust: roads as sources and
sinks. Environ. Sci. Technol. 1993, 27 (9), 1892−1904.
(52) Payne, J. R.; Phillips, C. R. Photochemistry of petroleum in
water. Environ. Sci. Technol. 1985, 19 (7), 569−579.
(53) Iinuma, Y.; Herrmann, H. Method development for the analysis
of particle phase substituted methoxy phenols and aromatic acids
from biomass burning using capillary electrophoresis/electrospray
ionization mass spectrometry (CE/ESI-MS). Journal of Chromatog-
raphy A 2003, 1018 (1), 105−115.
(54) Rogge, W. F.; Hildemann, L. M.; Mazurek, M. A.; Cass, G. R.;
Simoneit, B. R. Sources of fine organic aerosol. 7. Hot asphalt roofing
tar pot fumes. Environ. Sci. Technol. 1997, 31 (10), 2726−2730.
(55) Liu, Y.; Lu, J.; Chen, Y.; Liu, Y.; Ye, Z.; Ge, X. Aqueous-phase
production of secondary organic aerosols from oxidation of
dibenzothiophene (DBT). Atmosphere 2020, 11 (2), 151 (1−13).
(56) Hays, M. D.; Smith, N. D.; Dong, Y. Nature of unresolved
complex mixture in size-distributed emissions from residential wood
combustion as measured by thermal desorption-gas chromatography-
mass spectrometry. J. Geophys. Res. 2004, 109 (D16), 1−13.
(57) Chan, A.; Kreisberg, N.; Hohaus, T.; Campuzano-Jost, P.;
Zhao, Y.; Day, D.; Kaser, L.; Karl, T.; Hansel, A.; Teng, A.; et al.
Speciated measurements of semivolatile and intermediate volatility
organic compounds (S/IVOCs) in a pine forest during BEACHON-
RoMBAS 2011. Atmospheric Chemistry Physics 2016, 16 (2), 1187−
1205.
(58) Craven, J.; Yee, L.; Ng, N.; Canagaratna, M.; Loza, C.; Schilling,
K.; Yatavelli, R.; Thornton, J.; Ziemann, P.; Flagan, R.; et al. Analysis
of secondary organic aerosol formation and aging using positive
matrix factorization of high-resolution aerosol mass spectra:
application to the dodecane low-NO x system. Atmospheric Chemistry
Physics 2012, 12 (24), 11795−11817.
(59) Ho, T. C. Deep HDS of diesel fuel: chemistry and catalysis.
Catal. Today 2004, 98 (1−2), 3−18.

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