Critical Review

pubs.acs.org/est

Carbon-Based Adsorbents for Postcombustion CO2 Capture: A

Critical Review
Anne Elise Creamer and Bin Gao*
Department of Agricultural and Biological Engineering, University of Florida, Gainesville, Florida 32611, United States

ABSTRACT: The persistent increase in atmospheric CO2 from

anthropogenic sources makes research directed toward carbon capture
and storage imperative. Current liquid amine absorption technology has
several drawbacks including hazardous byproducts and a high-energy
requirement for regeneration; therefore, research is ongoing to develop
more practical methods for capturing CO2 in postcombustion scenarios.
The unique properties of carbon-based materials make them specifically
promising for CO2 adsorption at low temperature and moderate to high
partial pressure. This critical review aims to highlight the development of
carbon-based solid sorbents for postcombustion CO2 capture. Specifically,
it provides an overview of postcombustion CO2 capture processes with
solid adsorbents and discusses a variety of carbon-based materials that
could be used. This review focuses on low-cost pyrogenic carbon, activated
carbon (AC), and metal−carbon composites for CO2 capture. Further, it touches upon the recent progress made to develop
metal organic frameworks (MOFs) and carbon nanomaterials and their general CO2 sorption potential.

■ INTRODUCTION
There is a continued rise in greenhouse gas concentrations in
Table 1. State of Postcombustion CO2 Capture
Developmenta
the atmosphere, which causes severe problems, such as absorbent adsorbent membrane
increases in the frequency of extreme weather events.1 These commercialization high moderate low
phenomena are greatly due to the increased release of CO2 operational confidence high high low/moderate
through human activities. Research that aims to reduce CO2 primary source of energy regeneration regeneration compression
release is imperative, as it accounted for 82% of all penalty
anthropogenic greenhouse gas emissions in the US in 2013.2 a
Adapted from ref 12.
There are numerous ways to reduce anthropogenic carbon
footprint, from increasing household energy efficiency to
sequestering carbon in soils;3 some studies even focus on CO2 capture materials. Out of the 120 postcombustion CO2
capturing CO2 from ambient air.4 Because the combustion of capture technologies they assessed, the majority are absorption
fossil fuels to produce electricity contributes to 37% of all processes (60%).12 It is necessary to utilize regenerative
anthropogenic CO2 released, power plants have been proposed materials, rather than chemicals that must be disposed of, as
as important locations for CO2 capture.2 the global supply of sorbent chemicals would be depleted;
Currently, chemical absorption is the most applicable hence, the biggest challenge in applying absorption processes
technology for CO2 capture in power plants, but has several for postcombustion CO2 capture is to reduce the heat of
drawbacks (i.e., corrosion rate and high energy regeneration regeneration. 12−14 In addition to the high energy of
requirements).5−7 Alternative technologies using other absorb- regeneration associated with chemical absorbents, another
ents, adsorbents, and membranes have been studied for their problem is the release of hazardous byproducts.15,16 For these
ability to capture postcombustion CO2.8−10 Because flue gas reasons, solid adsorbents are considered promising for the
has different properties, such as CO2 concentration, temper- capture of postcombustion CO2.5,17−20
ature, and pressure, it is important to be able to design sorbents CO2 capture by solid adsorbents typically relies on the
with a variety of applications.11 Four main characteristics are mechanism of physical adsorption, or weak bonding between
considered when evaluating postcombustion CO2 capture CO2 and the adsorbent surface, which in turn results in lower
materials: capture efficiency, sorption rate, energy required regeneration energy. Numerous promising solid adsorbents
for regeneration, and volume of sorbent.5,11 have been developed that possess desirable characteristics, such
Bhown et al.12 evaluated a diversity of postcombustion CO2
capture technologies and assigned them a “Technology Received: February 9, 2016
Readiness Level”, similar to that developed originally by Revised: May 27, 2016
NASA. Table 1 gives an overview of the progress that has Accepted: June 3, 2016
been made in developing three categories of postcombustion Published: June 3, 2016

© 2016 American Chemical Society 7276 DOI: 10.1021/acs.est.6b00627

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Figure 1. CO2 sorption process using a fluidized bed reactor.29

as high adsorption capacity, insensitivity to moisture,21 property pressure and vacuum swing adsorption (PSA and VSA,
variability, low cost, 13 good selectivity for CO2 , easy respectively) are possible designs for CO2 capture from flue gas.
regeneration, and good reusability.22 Some examples of solid In temperature swing adsorption, CO2 is adsorbed at low
physical adsorbents include metal−organic frameworks, zeo- temperature and desorbed by raising the temperature.28 Figure
lites, and carbonaceous materials such as activated carbon23 and 1 illustrates a postcombustion CO2 capture system using
engineered carbon nanomaterials.11,24,25 When evaluating solid temperature swing adsorption. The flow gas is propelled by a
physical adsorbents, it is important to consider their surface blower, cooled, and bubbled through one or more fluidized
area, density, pore size and volume, feasibility of regeneration, beds. The adsorbent is circulated through the cooling reactor;
production method, stability, and abundance and sustain- when it becomes rich with CO2, the adsorbent is pumped into a
ability.26 Studies based on carbonaceous adsorbents focus on separate tank, where the CO2 can be desorbed at higher
high partial pressure CO2 capture scenarios, as the extent of temperature and rise into an overhead baghouse. The
physical adsorption usually increases with increase in gas adsorbent then recirculates through the initial fluidized
pressure.27 reactor.29
The general focus of this review is to summarize the Krutka et al.29 considered process designs that would capture
progresses made in developing carbon-based solid sorbents for 90% CO2 from flue gas in a coal-fired power plant at low CO2
postcombustion CO2 capture. Specifically, this work will partial pressure, using temperature swing adsorption. They
provide overviews of (1) postcombustion CO2 capture chose a bubbling fluidized bed reactor to be the optimal design,
processes with solid adsorbents, (2) low-cost pyrogenic carbon as this design had the most efficient heat and mass transfer, and
in CO2 capture, (3) activated carbon (AC) in capturing CO2, therefore provided the optimal configuration for effective CO2
(4) the development and applications of metal−carbon capture. The optimal CO2 adsorbent was chosen to be an
composites for CO2 capture, (5) recent progress made to amine-based solid adsorbent, as it provided high CO2 working
develop metal organic frameworks (MOFs) for CO2 capture,
capacity under the influence H2O vapor.29 Nevertheless, other
and (6) carbon nanomaterials and their general CO2 sorption
solid adsorbents are promising for thermal swing adsorption
potential.

■
processes and will be discussed further in later sections of this
review. Because CO2 sorbents need to be recycled, when
CO2 CAPTURE PROCESS WITH SOLID SORBENTS assessing potential CO2 sorbents for large-scale applications, it
Temperature swing adsorption, pressure swing adsorption, and is important to consider the regeneration temperature.29,22
vacuum swing adsorption are three processes considered for Hasan et al.,30 who assessed the suitability for zeolite 13X in
CO2 capture. Different infrastructure and different adsorbent VSA, found that when the CO2 concentration makes up more
materials would be required depending on the type of than 15−20% of gas in the stream, it is more cost-effective to
adsorption cycle. Temperature swing adsorption (TSA) and use VSA than traditional MEA-based absorption. Pressure
7277 DOI: 10.1021/acs.est.6b00627
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swing adsorption (PSA) and vacuum swing adsorption (VSA) technology and process, and power plant engineers, who can
use pressure change, within an adiabatic system, to remove CO2 integrate these materials into postcombustion infrastructure,
from the flue gas stream. Typically, PSA and VSA are carried work alongside each other in order to reach a technology
out in parallel vessels. While one adsorbs, the other desorbs. breakthrough in postcombustion CO2 capture.12
The cost of pressure swing adsorption using solid adsorbents is
comparable to that of conventional MEA absorption
technologies; however, at this time, the purity is lower.31 A
■ LOW-COST PYROGENIC CARBON
Low-cost pyrogenic carbon materials, such as charcoal, biochar,
PSA cycle involves the use of several vessels to compress and agrichar, carbonized biomass, and other labels of pyrogenic
cool gas. Although it is beneficial to remove impurities such as carbon materials have been used frequently in environmental
SOx, water vapor, and NOx prior to the PSA/VSA process (via remediation,36−38 for carbon sequestration,39,40 and as soil
dehydration, desulfurization steps, and molecular sieves),31 amendment.41,42 The diversity of names assigned to pyrogenic
Chaffee et al.32 found that the most important parameter for carbon reflects not only the diversity of characteristics upon the
VSA, in determining the amount of CO2 captured, is the spectrum of pyrolysis but also their diversity of applications,
ultimate vacuum pressure, rather than the purity of the gas from energy to agriculture.43 Bird and Ascough43 have shown
stream. the progression of the characteristics of pyrogenic carbon as it
A few example PSA and VSA methods include the Skarstrom progresses from partly charred biomass to black carbon (Figure
cycle, Gemini Process, and Seven-step PSA cycle,31 but these 3).
are difficult to evaluate due to their complexity. For this reason,
Chung et al.33 developed the “short-cut” method to model
more easily the PSA process (Figure 2). In this model, PSA

Figure 3. Pyrogenic carbon continuum; diagram based on Bird and

Ascough.43

As the carbonization/pyrolysis temperature increases, so

does the porosity and carbon content of the pyrogenic carbon
and the product becomes less subject to demineralization from
environmental influences.43,44 Figure 4 depicts the process of
biochar production through slow pyrolysis, in which wet
biomass is dried and the pyrolysis temperature is raised slowly
(less than 100 K/min) under oxygen-starved conditions.45
Figure 2. Short-cut method of VSA/PSA process.31
The peak temperature at which pyrolysis is performed also
affects the properties of the pyrogenic carbon, and therefore the
systems rely on batch sorption vessels with a fixed volume. The subsequent application.46−48 The products of pyrolysis include
processes of pressurization and adsorption and the processes of syngas, bio-oil, and solid char.49,50 Fast pyrolysis to 808 °C of
depressurization and desorption are combined. CO2 is lignite, or “brown carbon” produces pyrogenic carbon with
adsorbed at higher pressure and desorbed at lower pressure, higher open-pore volume than that of slow pyrolysis.51,52 Fast
under adiabatic conditions. The adsorption and desorption can pyrolysis produces chars of larger N2 and CO2 surface area;
be modeled by the Langmuir isotherm. however, very little carbon is produced and the yield is made up
When designing the system, the feed temperature and almost entirely of volatiles.51,53 On the other hand, with slow
concentration of gas in the stream must be considered. In pyrolysis, there is a much higher yield of carbon and the
regards to the apparatus, working parameters include the bed properties of this product are dependent on the starting carbon-
length, effective working length, internal diameter, wall based material.51,53,54 Low heating rates tend to produce
thickness, and adsorbent load in each bed. When assessing biochar that largely consists of micropores; whereas, rapid
adsorbents for pressure or vacuum swing adsorption, the heating produces macropores in the material.55 Another major
adsorbent properties that are often considered include: bulk limitation of producing char through rapid heating is its
density, micropore volume, particle density, and skeletal tendency to rapidly chemi-sorb to large amounts of O2 when
density.34 For this reason, carbonaceous materials, like AC the char comes in contact with air, which would reduce the
are promising adsorbents for PSA and VSA systems.35 surface area and active sites for sorption.51
It is suggested that chemists, who can design and produce the When the material is undergoes carbonization/pyrolysis, the
materials, process engineers, who can model the separation carbon content increases and the oxygen content decreases
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Figure 4. Pyrolysis of biomass to biochar and bioenergy; diagram based on Brown, Wright, and Brown.45

Table 2. Chemical Analysis of a Selection of Low Cost Pyrogenic Carbon Materials

pH BET SA C H O N source
raw olive stones 6.2 na 51.6 6 41.7 0.2 56
pyrolyzed olive stones 8.7 na 93 2.2 4.5 0.3 56
BC300 8.28 0.56 68.48 5.5 25.71 0.31 153
BC500 9.49 181 86.66 3.2 9.74 0.4 153
BC600 10.05 381.5 90.71 2.26 6.7 0.33 153
raw sludge 4.42 na 32.3 4.47 18.36 3.27 154
sludge300 5.32 na 25.6 2.55 8.33 3.32 154
sludge500 7.72 na 20.3 0.88 0.65 2.13 154
sludge700 12 na 20.4 0.51 0 1.2 154
digested bagasse char 10.9 17.66 73.55 2.41 24.04 na 155
bagasse char 7.7 14.07 76.45 2.93 19.83 0.79 155
digested SB tailing na na 33.94 4.53 46.89 2.35 156
raw SB tailing na na 36.06 3.43 55.82 1.23 156
digested SBT char 9.95 336 30.81 1.38 39.87 2.74 156
SBT char 9.45 2.6 50.78 2.08 36.7 1.83 156
raw hickory wood 5.8 0.1 45.51 6.17 47.83 0.15 46
raw bagasse 6 0.4 45.82 6.25 47.18 0.36 46
raw bamboo 6.6 na 46.52 6.11 46.89 0.2 46
hydrochar HW 6 2.5 53.52 6.13 39.84 0.25 46
HW300 7.1 na 69.13 4.85 24.36 0.39 46
HW600 8.4 401 81.81 2.17 14.03 0.73 46
hydrochar bagasse 5.7 3.8 53.32 6.23 39.93 0.44 46
BG300 7.3 5.2 69.5 4.2 24.36 0.9 46
BG600 7.5 388.3 76.45 2.93 18.33 0.79 46
hydrochar bamboo 6.3 1.3 55.27 6.18 38.27 0.21 46
BB300 7.9 1.3 66.2 4.7 27.72 0.4 46
BB600 9.2 375.5 80.89 2.43 14.87 0.15 46

significantly.46,49 This transformation produces a material with There are a few other ways of producing pyrolyzed-carbon at
higher surface area and higher pH.56,57 Just like with the a low cost and zero net emissions, including microwave-assisted
pyrolysis of other biomass materials, as the temperature of pyrolysis and hydrothermal carbonization. It was found that
pyrolysis increases, some functional groups are removed as biochar produced by microwave-assisted pyrolysis has similar
volatile matter.49,51,57 Table 2 shows the chemical breakdown of properties to conventionally produced biochar.64 Another way
the char material from the raw biomass. The abundant minerals, that biomass can be converted into pyrogenic carbon is by
surface functional groups, and high surface area of pyrogenic hydrothermal carbonization (HTC), or the production of raw
carbon enable its sorption of contaminants, such as heavy HTC biochar or “hydrochar”.65 In this process, the biomass
metals.37,58 Similar properties and sorption mechanisms are feedstock (e.g., bamboo, peat, cellulose, coconut, wood, etc.) is
desirable in a CO2 capture material. hydrolyzed and then is carbonized at temperatures less than
Variations in feedstock materials correspond to variations in
that of dry pyrolysis.66−68 The benefit of this process is that
the properties of the pyrogenic carbon. It is important to
there are less energy inputs because the drying process is
develop materials that provide minimal diffusional resistance for
the adsorbate, until adsorption in the meso or micropores. For eliminated.69 Plasma-assisted pyrolysis of biomass is another
example, coal chars have a tree system where macropores method of pyrogenic-carbon production, but not well studied
branch into many super micropores.59,60 Before carbon-based in the literature. The resulting carbon has high surface area and
materials are subjected to gasification or pyrolysis, materials micropore volume, making it promising for CO2 capture.70
tend to have very narrow pores. Under this condition, Even without activation, pyrogenic biomass has been found
adsorption is based on activated diffusion, where activation to be highly effective in carbon dioxide capture.71−74 Studies
energy is required so that the gas can diffuse. After pyrolysis, indicate that the main mechanism for the capture of CO2 in
the pore diameter increases and sorption follows Knudsen (or biomass-derived pyrogenic carbon (i.e., biochar) is physical
bulk) diffusion principles. Here, the rate of gas transport is adsorption; they express the importance of high surface area on
limited by diffusion into and out of a feeder pore system of sorption capacity.75 The production of the biochar material,
larger pores (i.e., mesopores).61−63 which uses agricultural, forestry, and waste biomass, produces
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more hydrogen than it consumes, making it a net energy Shihong77 developed biochar by pyrolyzing cotton stalk
producer for the power plant.76 biomass at 600 °C and reported that it has a CO2 adsorption
Plaza and Pevida56 developed low-cost solid CO2 sorbents capacity of about 58 mg g−1 at 20 °C; however, when the
out of olive stones. The biomass was pyrolyzed at 600 °C to temperature was raised to 120 °C, the capacity is less than 20
increase surface area and carbon fraction. The pyrolyzed mg g−1. The physical adsorption mechanism is highly desirable
product (GKOS) has CO2 capture capacities that are for postcombustion CO2 capture because of the requirement of
comparable to the activated samples at 25 °C and is reported relatively low temperature desorption of the CO2, which
to be higher that other commercial ACs. The significant regenerates the material.13,27,78
sorption capacities are attributed to the effect that the When assessing the usefulness of char for CO2 adsorption
formation of basic sites and favorable pore size distribution applications, it is also important to consider porosity. As the
that are formed during the carbonization process.56 Creamer et carbon precursor is carbonized and further activated, the
al.71 produced biochar from sugarcane bagasse and hickory surface area increases; however, if the pore size is also enlarged,
wood that was pyrolyzed under N2 flow at temperatures the result is a reduction in the interactions between the walls of
between 300 and 600 °C to capture CO2. The biochar the pores and the CO2 molecules. In this case, increases in
produced from sugarcane bagasse feedstock at 600 °C had the surface area may correspond less with increases in CO2
highest CO2 capture capacity (73.55 mg g−1 at 25 °C and 101 uptake,79 as a pore diameter of 0.5 to 0.8 nm is optimal for
kPa). Even when the feedstock was pyrolyzed at 300 °C, it still CO2 sorption at atmospheric pressure and room temper-
was able to capture 38.72 and 34 mg g−1 (for the bagasse and ature.80,81 Because the materials rely on physical adsorption, it
hickory-based biochar, respectively). A major benefit of using is pivotal that the pyrogenic biomass has sufficiently high
adsorbents produced simply by slow pyrolysis of biomass is the surface area, appropriate pore size and high pore volume.13,27,78
ease of regeneration. Figure 5 indicates the relationship For example, Tan and Ani82 carbonized palm shell waste from
palm oil production to produce a CO2 adsorbing material. The
carbon precursor was crushed and dried at 120 °C and then
pyrolyzed at 600−1000 °C under nitrogen flow; no further
activation was performed. The material was then evaluated on
its effectiveness as a carbon molecular sieve, rather than for
adsorption capacity; nevertheless, the samples showed high
selectivity and capacity for CO2 capture. When the material was
pyrolyzed at 600 °C, the micropore surface area was 753 m2/g;
it shows CO2 capture at 0.02 P/P0 to be near 100 mg/g at 298
K. When the pyrolysis temperature increased to 1000 °C, the
micropore surface area and the pore volume decreased;
however, the selectivity toward CO2 increased.82
To increase the CO2 sorption capacity, pyrogenic biomass
can be modified with nitrogenous functional groups. For
example, Xiong and Shihong77 modified the biochar with NH3.
When the NH3 modified biochar was pyrolyzed at 600 °C, the
material captured more CO2 than the unmodified one at 120
°C. This could be due to the introduction of nitrogen-
containing functional groups that improve the capture of CO2
at higher temperature. On the other hand, at a CO2 flow of only
20 °C, the unmodified biochar performed better than the NH3
modified one.77
Hydrochar has also had success in CO2 capture. Recently,
Figure 5. Temperature dependence of CO2 adsorption for sugarcane
Sevilla and Fuertes83 produced porous carbon CO2 capture
bagasse biochar.71
materials through hydrothermally treating polysaccharides and
biomass. Although the pristine hydrochar showed low sorption
between temperature and CO2 adsorption for biochar produced ability to CO2, they found that chemically activating the
from sugarcane bagasse.71 Because of the physical adsorption material with KOH significantly increased the amount of
mechanism, CO2 is captured at low temperatures and desorbed micropores and therefore its CO2 capture capacity.83
at higher temperatures. Figure 5 also shows that the biochar In summary, low-cost pyrogenic carbon derived from
produced by sugarcane bagasse releases CO2 by 92% when the biomass, itself, has substantial potential as a CO2 capture
temperature is raised to 120 °C (Figure 5).71 Day et al.73 material. It has been shown that biochar and other pyrogenic
demonstrated that a novel, nitrogen-rich, biochar material carbon materials can be produced to have high enough surface
produced through pyrolysis that is capable of capturing CO2 area for the employment of CO2 physisorption, as well as
within its pore structures. Similar to the biochar produced by natural basic surface properties and adequate pore size that
allow for selectivity of CO2.13,71,72,84

■
Creamer et al., this sustainable material can even play the role
of a carbon-sequestering, slow-release fertilizer.
The mechanism of physical adsorption, or the weak bonding ACTIVATED CARBON
of CO2 to the surface of the material, is based on Henry’s law, Activated carbon (AC) can also be derived from biomass
which indicates that molecules are adsorbed under low through pyrolysis, but requires either physical or chemical
temperature and high pressure and are desorbed at high activation. The feedstock of AC production can range from
temperature and low pressure. For example, Xiong and waste biomass, such as spent coffee grounds,85 to nitrogen-rich
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chitosan,86 to synthetic organic polymers,87 to chicken

feathers.23 To prepare chemically activated carbon, it is
necessary to introduce chemicals, such as acid, base, or salt to
treat the feedstock biomass. Preparing physically active carbon
usually involves two steps: (1) convert biomass into pyrogenic
carbon at relatively low temperature conditions, and (2)
activate the carbon with steam, CO2, O2, or other gases at high
temperature conditions.88−90 AC can also be made from natural
charcoal materials such as coal and lignite.91,92 Numerous
studies focus on AC production using a diversity of activation
techniques to optimize the capacity for CO2 sorption.93−95 The Figure 6. Production of activated carbon from biomass with KOH
activation.103
sorption affinity of AC is comparable to that of other proposed
CO2 capture materials, such as zeolites. The benefit of AC for
postcombustion CO2 capture tends to be its low heat of surface of the AC. The material can be oxidized with gas or
adsorption and lower relative cost.96−98 aqueous solution; high temperature leads to the incorporation
Physical activation can be performed using steam/water of weak acid groups, such as phenol. Acid digestion, with
vapor, air, or CO2. For example, A.S. Gonzalez used olive HNO3, HCl, and HF, is also used in order to remove ash from
stones (OS) and almond shells (AS) that were subjected to samples and to concentrate any unburned carbon.105 Low
single-step activation at 800 °C with CO2 to capture CO2. temperature activation produces strong acid groups, such as
Under 101 kPa, the OS-based carbon was able to adsorb 4.8, carboxylic acid. By this treatment, hydrophilic groups on the
3.0, and 0.7 mmol CO2 g−1 at the temperatures of 0, 25, and material are removed.100,102
100 °C, respectively. At 25 °C and 15 kPa, the capture is CO2 is an acidic molecule, so acid activated carbon is less
reduced to 1.1 mmol g−1, demonstrating the importance of effective for CO2 capture. Interactions between AC and CO2,
temperature and pressure on physical CO2 adsorption. Plaza et including H−H bonding, dipole−dipole interactions, and
al. also used almond shells and olive stones as a basis for the covalent bonding, are enhanced with the incorporation of
production of a stable CO2 trapper; however, rather than basic surface groups. The carbon structure itself acts a lewis
activating the biomass with CO2, the biomass was heated under base and can absorb protons from solution. Further, the
a mixture of gaseous N2 and O2 (3%) at 650 °C. The ACs introduction of nitrogenous groups onto AC surfaces is known
derived from almond shells and olive stones were able to to increase the basicity of the material, and therefore increase
adsorb 2.11 and 2.02 mmol g−1, respectively.99 AC produced its ability to sorb CO2.100,102
from olive stones has been shown to not only preferentially Although nonactivated celtuce leaf porous carbon is able to
capture CO2 but also water vapor, over N2 and O2. Fortunately, capture efficiently CO2, when the carbon was activated with
when water vapor is incorporated into the gas stream, H2O KOH at 600 °C, its CO2 adsorption capacity became
coadsorbs with CO2 and there is no significant reduction in the significantly higher. The CO2 capture at 0 and 25 °C are
AC’s capacity for CO2. Regeneration of both CO2 and H2O can shown in Figure 7. The material is also highly selective for CO2
be accomplished by raising the temperature to 150 °C.100 over N2.103
Carbon can also be chemically activated by various chemicals The AC produced by Sevilla et al.83 showed high CO2
to increase the surface area as well as add (or remove) specific capture ability (4.8 mmol g−1) due to the prevalence of weak
surface functional groups. When carbon is activated with interactions between the CO2 and the carbon surface. These
ammonia at high temperatures, nitrogenous groups are added weak bonds make it possible for efficient regeneration.83 As the
and acidic oxygen groups are removed, which significantly bond strength (measured by heat of sorption) between the AC
improves basicity.101 Functional groups, such as amide, imide, surface and CO2 increases, so does the energy needed to
pyrrolic, pyridinic, and lactame groups are formed through regenerate the adsorbent. Although chemically activated
reaction with nitrogen-containing reagents, such as NH3, nitric carbons tend to have higher heat of sorption than nonactivated
acids, and amines.100,102 Acidic functional groups can be porous carbons (Figure 8), it still tends to be lower than that of
removed by heat treatment, as oxygen-containing functional other adsorbents, such as zeolites.106
groups will decompose at 800−1000 °C.101 An assortment of AC materials for CO2 capture are
Although most of the chemically activated carbons are represented in Table 3. Activation with KOH appears to
produced from feedstock pretreated with various chemical enhance greatly capture, whereas activation with HCl is less
agents, several studies have also explored the activation of effective. Fan et al.106 optimized the mixture ratio of
pyrogenic carbons with chemicals. Wang et al.103 prepared AC chitosan:K2O3 and the activation temperature with amines.
from celtuce leaves with KOH as the activation agent at 600 °C. Zhao et al.107 showed that the addition of p-diaminobenzene to
The activation process is shown in Figure 6. The dry feedstock furfural alcohol enhances the capture of CO2. Most of these lab-
is carbonized and then activated with KOH. This produces a produced ACs are significantly more effective than the
product capable of efficient ion exchange. Sevilla et al. produced commercial ones (such as that produced by Alfa Aesar
a chemically activated carbon by hydrothermally carbonizing Co.),108 which capture about 2.1 mol CO2 per gram adsorbent.
polysaccharides and biomass at 600 °C and then activating this The table also shows that higher activation temperature does
precursor with KOH. This led to an extensive production of the not always correspond with higher CO2 sorption capacity, and
narrow micropores in the carbon material.83 the choice of activation agent is important.
It is also common to activate the surface of carbon with acids, In summary, when producing an AC for CO2 capture, many
such as nitric or hydrochloric acid, especially when the goal is to conditions must be considered. The feedstock, activation agent
adsorb a basic contaminant (i.e., NH3).104 Oxygen groups, such and conditions, as well as the addition of extra solvents and
as carboxyl, lactone, and phenol, can be incorporated on the chemicals can be optimized. The extensive diversity of AC
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metal organic frameworks (MOFs), which are typically

developed from pure, high-cost materials.
Most synthesis methods for metal oxyhydroxide carbon are
designed to produce a composite with high surface area and
good dispersion of nanosized or colloidal oxide or hydroxide on
the surface within the porous carbon network. When used for
CO2 capture, the mechanisms of both chemisorption (from the
addition of some metal oxyhydroxides) and physisorption
(from increased surface area of the structure) may be involved
in the process. Typically, samples with added metals, such as
Ca, Mg, Al, Fe oxides and hydroxides, will have capacities for
CO2 that are higher than those of the unmodified samples.
Nevertheless, it was found that there is typically an optimal
metal content to incorporate, as too much will decrease the
surface area,112 and therefore active sites for bonding.
Metal oxyhydroxides, themselves, have been shown to be
effective CO2 trappers. For example, Pierre-Louis et al. studied
the ability of Al/Fe oxyhydroxide to capture CO2.111 There is
an optimal ratio of the metal oxyhydroxides in the composite;
the addition of AlOOH to the composite enhanced the CO2
sorption until the ratio of Al to Fe reached 30%. In this study,
both physical adsorption (from the high surface area and basic
nature of mesoporous carbon and metal oxyhydroxides), and
chemical adsorption (from the presence of metal oxyhydroxides
that chemically bind with CO2) are present within the
composite and contribute to CO2 sorption.111
Figure 7. CO2 capture by celtuce leaf porous carbon.103
Creamer et al.78 produced carbon−aluminum, magnesium,
and iron oxyhydroxide composites from hickory wood biomass.
The ratio of metal to biomass was varied to determine the
concentration to lead to the highest sorption of CO2. The
materials were produced in solution, dried, and pyrolyzed at
600 °C. It was found that the aluminum hydroxide−hickory
composite with a AlCl3:cottonwood (CW) biomass ratio of 4:1
captured 71 mg g−1 CO2, which was higher than the other
metal composites and the unmodified hickory biochar (58 mg
g−1). The results of the kinetics experiment, performed at 25 °C
are displayed in Figure 9.78 The capture of CO2 by the
composites follows second-order kinetics. It can be seen that
the represented metal-composites (FeCW, MgCW, AlCW) are
all more effective at capturing CO2 than the unmodified
cottonwood sample (CW(0)); however, even the unmodified
sample had comparable adsorbent capacity.78 SEM-EDS
imaging showed the presence of the metal particles on the
surface of the carbon. When the surface area and metal
concentration of the metal hydroxide composite was compared
to the sorption capacity, it was elucidated that both the metal
Figure 8. Heat of adsorption for AC-2-635 as CO2 is adsorbed.106 concentration in the composite and the surface area impact the
CO2 sorption capacity.78
Several studies have focused on producing MgO/C
materials available for evaluation is valuable, as the material composites to capture CO2 at both high and low temper-
properties can be decisively altered to fit a specific application atures.109,117−119 Bhagiyalakshmi110 carbonized a mixture of
scenario.

■
magnesium nitrate along with other solvents (HCl, sucrose,
H2SO4, H2O) after evaporation. This led to the production of a
METAL OXYHYDROXIDE−CARBON COMPOSITES thermally stable mesoporous supported MgO that is capable of
The addition of metal oxides and/or hydroxides (i.e., sorbing up to 92 mg g−1 CO2 at 25 °C. Only a low
oxyhydroxides) to the surface of porous carbon adsorbents concentration of metal was required; the material could be fully
has been shown to enhance CO2 capture ability by increasing regenerated at low temperature (200 °C).110
surface area, increasing the basicity of the material, and even Liu et al.120 developed MgO nanoparticles that were
promoting the production of carbonates with the reaction of stabilized by mesoporous carbon. MgCl2 was obtained in low
CO2.109−111 These composite materials can be derived from the concentrations from seawater, mixed in solution with biomass,
pyrolysis of either biomass feedstock along with a metal oxide and pyrolyzed to produce an efficient CO2 capture material.
or hydroxide,112,113 or biomass pretreated with precursors of The excellent CO2 capture is attributed to the porous structure
metal oxyhydroxides,38,114−116 making them lower cost than along with the presence of basic −OH groups. The high surface
7282 DOI: 10.1021/acs.est.6b00627
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Table 3. AC Adsorbents for CO2 Capture

moles gas/kg activation
name sorbent feedstock and carbonization method activation temperature agent source
celtuce leaf AC 4.36 celtuce leaf at 600 °C 600 °C KOH 103
3C-1000N 3.25 nitrogen doped OMCs at 1000 °C 1000 °C NH3 157
H-600 1.73 nitrogen doped OMCs at 600 °C 600 °C HCl 157
AC-2-635 3.86 chitosan/K2CO3 = 2 635 °C amines 106
AC-2-800 3.08 chitosan/K2CO3 = 2 800 °C amines 106
IBN9-NC 2.21 p-diaminobenzene none none 107
IBN9-NC-A 3.68 p-diaminobenzene 600 °C KOH 107
IBN9-NC1-A 4.5 p-diaminobenzene, with furfural alcohol 600 °C KOH 107
AC-1-600 3.57 chitosan/K2CO3 = 1 600 °C amines 106
AC-1-800 2.78 chitosan/K2CO3 = 1 800 °C amines 106
nitrogen rich porous carbon 3.2 terephthalaldeyde and amine polymer pyrolyzed at 180 °C prior to pyrolysis amines 158
600 °C

Figure 9. CO2 sorption kinetics of metal oxyhydroxide biochar.78

area is said to result from the dehydration and decomposition

of MgCl2, which enhances the release of volatile matter in the
■ METAL ORGANIC FRAMEWORKS
MOFs are promising adsorbents in the field of CO2 capture for
pyrolysis process. Lastly, the presence of the MgO crystal postcombustion scenarios. Because of their huge potentials in
facilitates the formation of carbonate (MgCO3), indicating both various applications, several review papers discuss their
physical and chemical mechanisms of adsorption.120 synthesis14 and CO2 capture applications.14,121,122 This review,
Li et al.118 used carbon as a support for the dispersion of fine therefore, only provides a brief overview of the potential
application of MOFs in CO2 capture.
MgO particles. The carbon-based composite was capable of
With the use of pristine components, it is possible to select
high temperature (150 °C) CO2 capture that was higher than for specific structural and chemical characteristics of MOFs. In
MgO−SiO2 composites. The high sorption is attributed to the other words, it is possible to “tune” or alter MOF properties to
basicity of the samples and hierarchal structure of the carbon, fit a specific CO2 capture scenario.123 Altering the pore
which led to large surface area. Desorption was possible at dimension and surface chemistry can help optimize the capture
temperatures around 230 °C.118 CO2 or other gases.124−128 For example, isoreticular metal
In summary, the biggest benefit of using carbon-based organic frameworks (IRMOF) have a tunable pore size and are
made up of bridging metal-based nodes (i.e., Al3+, Cr3+, Cu2+,
oxyhydroxide composites is that the material can call upon the Zn2+) with organic linking groups (i.e., carboxylate and pyridyl)
use of not only enhanced physical adsorption but also, in some through strong coordination bonds to produce a 3D organic−
cases, the mechanism of chemical adsorption. When the inorganic network.
biomass feedstock is pyrolyzed with the metal oxyhydroxides The structure of an example metal organic framework is
or the precursors, not only is the surface area increased but also depicted in Figure 10.129 The fully assembled MOF-14 (Figure
10E) is broken into 5 different components of the framework
additional functional groups may be added to the carbon
(Figure 10A−D) for clarity.
surface, which contributes to enhanced physical adsorption. For all MOFs, it is necessary to optimize the production
Further, chemical sorption, from the interaction of the metal conditions to fit the necessary situation. Altering the
oxyhydroxides and CO2, is an added benefit. concentration of the reactants, pH of the solution, the ratio
7283 DOI: 10.1021/acs.est.6b00627
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Figure 10. Metal organic framework structure.129 Single-crystal structure of Cu3(BTB)2(H2O)3·(DMF)9(H2O)2(MOF-14) composed of (A) square
paddle-wheel and triangular BTB SBUs, which assemble into (B and C) a pair of augmented Pt3O4 nets that are held together by (D) numerous π−π
and C−H···π interactions to yield (E) a pair of interwoven three-dimensional porous frameworks. Cu, red; C, gray or blue atoms not linked directly
to Cu; O, gray atoms linked directly to Cu.129

of the metal-to-ligand, reaction temperature, and reaction times mechanical, and chemical properties. They are typically
can provide the necessary changes in the properties of the produced through self-assembly or polymerization followed
material. The production of these MOFs, which includes by direct carbonization. Self-assembly relies on hydrogen-
sonication-assisted synthesis,130 microwave heating,131 mecha- bonding interactions between the carbon precursors and block
nochemical procedures,132 photochemical133 or electrochemical copolymer surfactants.135 Dai et al. showed that using
synthesis,134 is difficult and costly at large scale. Because of the phenolresorcinol-/phloroglucinol-based phenolic resins allows
low stability of MOFs, slight perturbations to the chemical or the synthesis of monoliths, fibers or particles. Nanospheres can
structural properties, which might occur in a densely packed be functionalized easily in bulk or on the surface through
adsorbent bed or under mechanical pressure, can considerably template or self-assembly.137 The synthesis of porous carbon
impact its performance in CO2 capture scenarios.14 Regardless, nanofilms requires a monomer-block copolymer film casting,
MOFs have potential to be used in numerous applications, structure refining through solvent annealing, polymerization of
including postcombustion CO2 capture, so current research is the carbon precursor, and carbonization.135
working to develop and synthesize a huge diversity of these Carbon nanocomposites are carbon-containing nanoparticles
adsorbents.13 that are functionalized to enhance their properties, such as

■ CARBON NANOMATERIALS
Carbon nanomaterials, or carbon materials with one or more
conductivity.138 They are typically produced through heat
treatment after heat impregnation onto a silica or metal oxide
matrix. Another typical way to produce these carbon nanoma-
dimensions less than 100 nm, can take on many different forms. terials is through “nanocasting”. This is when a nanosized mold
They possess a large diversity of properties, leading to their use is filled with a carbon precursor that, when the template is
in many applications, including catalyst supports, energy removed, is left with pores where the template once was and
conversion and storage, filtration, and sorption.135 This review results in a porous carbon framework.139 Silica is frequently
will only touch upon the specifics of carbon nanomaterials as a studied as a hard template for the preparation of mesoporous
CO2 capture material. carbon. First, the porous template is prepared with a controlled
Carbon nanomaterials can be synthesized in bulk and possess porosity, then the carbon precursor undergoes wet impregna-
a hierarchical porous structure and contain both macropores tion, polymerization, and pyrolysis of the precursor to generate
and micropores, which is important for CO2 capture as the the composite. Lastly, the inorganic template is removed.
macropores allow for low resistance pathways and high surface Porous carbons can also be replicated from MgO nano-
area to access micropores.135 The challenge of synthesizing particles.135 Carbon composites are shown to be efficient in the
carbon nanomaterials through polymerization is preventing capture of CO2 from flue gas.140 A study by Meng and Park
aggregation.136 used spherical nanosilica templates to produce carbon materials
Individual carbon nanomaterials, including fullerenes, carbon with enhanced capacity for CO2 capture. Increasing the ratio of
nanotubes, graphene, and carbon nanofilms or nanofibers have silica to polystyrene-based resin increased the pore volume and
been highly studied because of their unique thermal, electrical, surface area, which yielded higher CO2 capture.141
7284 DOI: 10.1021/acs.est.6b00627
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Environmental Science & Technology Critical Review

3D carbon nanomaterials, including carbon-gels and other zeolites, as well as other pristine solid and chemical sorbents.
porous structures, can be used for numerous applications in Metal−carbon composites have enhanced CO2 capture ability,
adsorption. To produce carbon aerogels, the sol−gel process is while being less expensive to produce than MOFs. The addition
typically used. Here, molecular precursors are transformed into of metal oxides and/or hydroxides gives them increased
high cross-linked organic gels. Another way to produce these functionality and surface area. Extensive research has also
structures is through direct transformation, which can be been done toward developing synthesized metal organic
performed through carbonization of crystalline polymers or frameworks (MOFs) and carbon nanomaterials for CO2
MOFs.135 Alhwaige et al. produced biobased chitosan hybrid capture. These materials, although more intensive to produce,
aerogels decorated with graphene oxide nanosheets that were have relatively high capacities for CO2. Overall, research on
able to capture between 1.92 and 4.14 mmol g−1 CO2 with high carbon-based adsorbents for postcombustion CO2 capture is
stability.142 still in its infancy. To promote this technology, further
Carbon nanomaterials, although they might be more investigations are needed in many areas, such as (1) Improving
intensive and expensive to produce than other carbon materials, the adsorption ability of pyrogenic carbon: pyrogenic carbon
can be produced precisely for optimal CO2 capture with high materials are typically renewable, inexpensive to produce, have
selectivity and capacity. As shown in Table 4, carbon low heat of regeneration,71 and hydrophobic properties.143,144
Research should be conducted to optimize their production
Table 4. Carbon Nanomaterials for CO2 Capture processes and to understand further the interaction mecha-
nisms for optimal CO2 capture, particularly at the field scale.
CO2 capture
material (mmol g−1) conditions source (2) Develop novel composites: adsorption ability of pyrogenic
carbon can be improved by impregnating metal oxyhydroxides
TiO2/GO nanocomposite 1.88 25 °C, 1 atm 25
or other CO2 capture agents. Further research is needed to
CTS-GO-15 (chitosan GO 3.96 25 °C, 1 atm 142
composite) prepare novel carbon-based composites, particularly carbon
PEI/graphene/silica sheets 3.9 75 °C, 1 atm 159 nanocomposites for CO2 capture. (3) Development of
GODC4-600 (graphene oxide 8.9 27 °C, 20 atm 160 nanotechnology: the properties associated with carbon nano-
derived carbon) materials enhance reactions associated with CO2 adsorption,
N-HCS (hollow carbon 2.67 25 °C, 1 atm 148 conversion, and binding;145 however, relatively few studies have
nanosphere) been performed to assess the ability of carbon-based nanoma-
carbon nanotube 2.2 25 °C, 0.5 atm 90 terials.22,146−150 It is necessary that future studies consider the
CNT (APTS) (modified carbon 2.6 20 °C, 0.5 atm 161 unique properties of carbon-based nanomaterials and expand
nanotube)
polypyrrole functionalized 4.3 25 °C, 1 atm 162
their applications into the field of CO2 capture and storage. (4)
graphene sheets Regeneration and reuse of CO2: with the increase in CO2
CS3-6A (nitrogen enriched 4.1 25 °C, 1 atm 163 capture, it is critical to develop new technologies to store
porous carbon spheres) CO2151 or convert it to useable materials, such as methane.152

■
CS3-6A (nitrogen enriched 6.2 0 °C, 1 atm 163
porous carbon spheres)
N-doped carbon aerogel 3.6 25 °C, 1 atm 164
AUTHOR INFORMATION
N-doped carbon aerogel 4.5 273 K, 1 atm 164 Corresponding Author
14ACA-900 carbon aerogel 3 25 °C, 1 atm 165 *B. Gao. Phone: (352) 392-1864 ext. 285. Email: bg55@ufl.
edu.
nanostructures have very high CO2 capture ability (e.g., Notes
functionalized graphene sheets capture 4.3 mmol g−1 at 25 The authors declare no competing financial interest.
°C, 1 atm), high thermal stability, and good regeneration.

■ CONCLUSIONS AND FUTURE DIRECTIONS

■ ACKNOWLEDGMENTS
This research was partially supported by the NSF through
Flue gas from power production results in the emission of Grant CBET-1054405.

■
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