VOL 23 NO 1

Carbon Dioxide Characterization of Carbons with the TriStar II 3020

Andrew D. D’Amico and Yundi Jiang
Micromeritics Instrument Corporation

Introduction
The use of carbon dioxide allows
for rapid, high-resolution charac-
terization of microporous materi-
als. The Micromeritics TriStar II
3020 can be used to characterize
micropores below 10 angstroms
within 8 hours using CO2 as the
adsorptive gas and an ice bath
(273 K) for the analysis bath.
Isotherms from CO2 adsorption
were compared with N2 adsorp-
tion isotherms at 77.3 K. Density
functional theory (DFT) models
for nitrogen and carbon dioxide on
slit-pore carbon were used for the
pore-size-distribution calculations.
Slow diffusion (equilibration)
rates—on the order of hours to
days—may be observed during
adsorption at cryogenic tem-
peratures on materials with small
carbon dioxide, prepurified nitro- stroms, of the Carboxen 1012 carbon
gen, and ultra-high purity helium are not shown for clarity.
were used during the analyses. The resolution of the micropore
Results and Discussion distributions is shown in Figure 2.
When compared to nitrogen physi-
Figure 1 shows the nitrogen and sorption, features of the pore size
carbon dioxide isotherms of the
distribution are captured in much
Carboxen 1012 and MAST synthet- greater detail with DFT calcula-
ic carbon. Nitrogen adsorption on
tions from carbon dioxide sorp-
Carboxen 1012 displays type I iso- tion, and pore filling below 7 Å is
therm behavior, while the MAST
observed.
carbon displays type IV isotherm
Figure 3 shows the isotherms of
behavior. The trend of enhanced
carbon dioxide up to 760 torr com-
gas uptake by the Carboxen 1012
pared with the measurements up
is observed with the carbon dioxide
to 7600 torr—demonstrating the
sorption as well. Mesopores of the
agreement of high-pressure and
MAST carbon and larger micro-
“low-pressure” adsorption.
pores, between 10 and 20 ang-
500 500
N2 @ 77.35K CO2 @ 273K
450 450

pores. Strong adsorption potentials 400 400

Volume Adsorbed (cm3 g-1)

Volume Adsorbed (cm3 g-1)

in confined pores result in high 350 350

uptake of adsorptives, such as 300 300

nitrogen, which corresponds to the 250 250
filling of micropores at very low 200
200
pressures that can challenge the 150
lower sensitivity limits of one-torr 150

pressure transducers. Analysis 100 100

Carbonxen 1012
with carbon dioxide addresses 50 Carbonxen 1012 50
MAST
MAST
both of these issues by having 0 0
0.2 0.3
0.0 0.1
faster equilibration rates, due to 0.0 0.2 0.4
P/Po
0.6 0.8 1.0
P/Po
increased temperature, and gas
uptake at much higher pressures. Figure 1. N2 and CO2 adsorption isotherms for the Carboxen 1012 and MAST synthetic car-
bon analyzed in this study.
Experimental
Two readily available carbon sam-
ples, Carboxen® 1012 from Supelco 2.0 4.5 1.4
and a sample of MAST synthetic N2 @ 77.35K N2 @ 77.3K

CO2 Differemtial Pore Volume (cm3 g-1)

1.8 4.0
N2 Differemtial Pore Volume (cm3 g-1)

CO2@ 273K
carbon, were used. A Micromeritics 1.6
CO2@ 273K 1.2
3.5
Differential Pore Volume (cm3 g-1)

TriStar II 3020 was the principle 1.0

1.4
instrument used for CO2 analyses 3.0

up to 760 torr (relative pressure 1.2

2.5 0.8
of 0.03). A Micromeritics ASAP 1.0
2.0 0.6
2050 high-pressure sorption ana- 0.8
1.5
lyzer was used to measure CO2 0.6 0.4
isotherms up to 7600 torr, and 0.4 1.0

a Micromeritics ASAP 2020 was 0.2 0.5

0.2

used to verify micropore sizes 0.0 0.0 0.0

using DFT calculations from nitro- 4 6 8 10 4 6 8 10

gen isotherms at 77 K. Bone-dry Pore width (A) Pore width (A)

Figure 2. Pore size distribution calculated by N2 adsorption at 77 K and CO2 adsorption

at 273 K on MAST carbon (left) and Carboxen 1012 (right).

1
 VOL 23 NO 1

350
TriStar 3020 (10 torr)
ASAP 2050
300

250

Volume Adsorbed (cm3 g-1)

Table 1. Surface areas for CO2 and N2 physisorption

200
Langmuir (CO2) BET (N2)
Carboxen 1660 1692 100
150
MAST 945 940 75
50
100
25
Table 1 shows the surface area
50 0
calculations from carbon dioxide
0.00 0.01 0.02 0.03
sorption compared with calcula-
tions from nitrogen sorption. BET
surface area calculations were 0.00 0.05 0.10 0.15 0.20 0.25 0.30
performed below 0.1 relative pres- P/Po
sure in order to make the results
physically meaningful, a common Figure 3. CO2 adsorption isotherm at 273 K at 760 torr and 7600 torr for Carboxen 1012.
procedure for microporous materi-
Conclusions
als. The Langmuir surface areas
from CO2 adsorption were calcu- From the data presented, it can be 273 K can be extended to high pres-
lated over an absolute pressure concluded that the TriStar II 3020, sure, allowing for Langmuir and BET
range of 600-3000 torr. Langmuir as well as other Micromeritics surface areas to be calculated. For the
surface areas (not shown) from N2 physisorption instruments, can be two materials analyzed in this work,
adsorption, calculated using pres- used to obtain rapid, high-resolu- the Langmuir surface areas calculated
sures up to an absolute pressure tion characterization of micro- from CO2 adsorption at 273 K are
of 50 torr, agreed within 6% with pores in carbons. The technique comparable to BET surface areas calcu-
the nitrogen BET surface areas. of carbon dioxide physisorption at lated from N2 adsorption at 77.3 K.