Journal of Nuclear Materials 511 (2018) 328e340

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Journal of Nuclear Materials

journal homepage: www.elsevier.com/locate/jnucmat

Modeling and predicting total hydrogen adsorption in nanoporous

carbon materials for advanced nuclear systems
Stephen T. Lam*, Ronald Ballinger, Charles Forsberg
Massachusetts Institute of Technology, Cambridge, MA, 02139, United States

h i g h l i g h t s

High hydrogen adsorption found in carbon enabling tritium capture in salt reactors.

Retention is a strong function of surface area, pore volume and microporosity.

Modeling isotherms with Sips equation yields best prediction.

Hydrogen undergoes dissociative adsorption and trapping in nanoporous carbon.

a r t i c l e i n f o a b s t r a c t

Article history: The retention of hydrogen in a variety of disordered carbon materials including graphene nanoplatelets
Received 15 April 2018 and amorphous carbon was measured by volumetric adsorption and modeled using thermodynamic
Received in revised form methods. To date, high temperature hydrogen adsorption research in carbon has predominately focused
6 September 2018
on graphite used as plasma-facing materials in fusion systems, moderators in high temperature gas
Accepted 6 September 2018
Available online 7 September 2018
reactors, and fuel components in molten-salt cooled reactors. Tritium, a hydrogen isotope that is pro-
duced in these systems, adsorbs on carbon surfaces that could be used effectively as sinks to remove
tritium. Since hydrogen has chemical similarity to tritium, it can be used as a surrogate to simplify
Keywords:
Hydrogen chemisorption
experimental studies, greatly expediting materials exploration. Thus, an understanding and prediction of
Activated carbon hydrogen behavior on carbon materials is essential for evaluation of performance and safety of present
Nanoporous carbon and future reactor designs. Chemisorption experiments were conducted on 9 different materials with a
Surface area range of surface areas, pore volumes, and pore size distributions. The results showed that carbons with
Pore volume higher surface area and pore volume exhibit higher hydrogen adsorption, which is attributed to larger
Langmuir quantities of active sites. Further, hydrogen adsorption was found to increase in materials with greater
Temkin micropore (<10 Å) surface area, which was interpreted as being a result of in-pore trapping. In contrast to
Freundlich
previous studies that assumed a single isotherm, four isotherms were examined including two- and
Sips
three-parameter methods and homo- and heterogeneous surface methodsdthe Langmuir, Temkin,
Isotherm
Freundlich and Sips isotherms. Analyses of non-linear models by ordinary least squares and Marquardt's
percent standard deviation minimization were performed. It was found that constant order homoge-
neous models that have been used in the past lack the ability to describe pathways and reactions steps
that occur. Further, it was found that Sips isotherm consistently provided the best minimization of error
and most accurate prediction.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction [1,2]. In next-generation advanced fission reactors, including solid-

Carbon materials in nuclear applications have been found in the
past to exhibit high hydrogen retention even at high temperatures
* Corresponding author.
E-mail address: stlam@mit.edu (S.T. Lam).
fuel fluoride salt-cooled high temperature reactors (FHRs) [3],
dissolved fuel molten salt reactors (MSRs) [4] and high temperature
gas-cooled reactors (HTGRs) [5], carbon materials have been pro-
posed as moderating and structural materials, where they have or
will interact with significant quantities of produced tritium. The
extent of this interaction can greatly influence the corrosion po-
tential in salt-systems that form tritium halides [6], and the control

https://doi.org/10.1016/j.jnucmat.2018.09.009
0022-3115/© 2018 Elsevier B.V. All rights reserved.
 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340
of radioactive release from tritium gas diffusion [7]. In fusion sys-
tems, efforts have been made to quantify the behavior of tritium on
graphite and carbon fiber composites (CFCs) due to their potential
to be used as a heat-resistant, low Z, highly heat-conductive, first-
wall materials [8,9]. Various studies have attempted to analyze the
hydrogen behavior in these materials above 1273K for fusion re-
actors [10e12].
At high temperatures, it is generally believed that hydrogen
chemisorbs onto graphitic material via chemical bonding. However,
the general mechanism suggested has been inconsistent amongst
different studies and different grades [13e15]. Analyzing IG-110U
and POCO AXF-5QBG graphite materials at 700e1000  C and
pressures below 20 kPa, Shirasu found that the adsorption isotherm
followed Sievert's law with a square root dependence on pressure
which suggested a simple dissociative adsorption process [16]. This
result is confirmed by Strehlow who analyzed A681, CGB, POCO
AXF-5QBG [17]. In contrast, Atsumi analyzed 18 different graphite
materials under similar conditions and found that the square root
dependence was not always followed [18]. Atsumi suggested that
multiple adsorption and desorption modes could co-exist based on
findings from temperature programmed desorption studies [12].
He proposed a hydrogen transport and adsorption model which
accounts for porous diffusion and dissociative trapping shown in
shown Fig. 1a. In this model, the edges of the graphite sheets pre-
sent under-coordinated carbon atoms that have high hydrogen
reactivity [18e20], which are shown in Fig. 1b.
The model proposed by Atsumi follows the dissociative Lang-
muir equation, which converges to Strehlow and Shirasu's obser-
vations at low pressure [2]. Hence, differences in the model
interpretation can be attributed to large differences in hydrogen
retention amongst different types of carbon material. Macroscopi-
cally, the combination of these adsorption and trapping mecha-
nisms for any carbon material theoretically follows the overall
reaction stoichiometry:
H2 þ nC 42H$nC
Where C is a reactive site on the carbon surface and n is the order,
which refers to the number of sites occupied by an adsorbed
hydrogen molecule. Depending on the reaction order, inter-
molecular interaction between adsorbates, and activation energy
Fig. 1. a) Hydrogen permeation, diffusion and trapping model [12] and b) Two stacked graphene sheets with reactive ‘zig-zag’ type edge site [46].
329
shift during hydrogen loading, the isotherms of the above reaction
are modeled differently [21].
Several authors have previously proposed the use of carbon
materials in advanced fission systems for in-situ tritium capture at
high temperature due to their high tritium-retention, chemical
stability, and ability to be structurally modified for purpose-driven
designs [22,23]. To date, the only experience under thermody-
namically similar conditions, is in the Molten Salt Reactor Experi-
ment (MSRE) of Oak Ridge National Laboratory (ORNL), where
tritium was unexpectedly produced and found after-the-fact to be
captured on graphite surfaces [24e26]. However, targeted study
and detailed investigation is still lacking for proposed conditions in
nuclear systems such as the MSR and FHR where tritium is pro-
duced by salt irradiation or the HTGR where tritium is generated by
irradiation of the helium coolant and Li-6 impurities in graphite
moderators [27]. In this research, knowledge on hydrogen
adsorption behavior has been extended to amorphous carbons and
retention measurements have been made within the high tem-
perature and low partial H2 pressure conditions that exist in FHRs,
MSRs and HTGRs. Thermodynamic models have been applied to
eight materials. Further, the relationships between morphological
aspects such as pore size distribution and hydrogen retention have
been investigated to probe the underlying mechanisms of
adsorption.
2. Experimental
The experiments conducted in this study consist of low and high
temperature adsorption. Low temperature adsorption was used for
physical characterization of the material surface to determine the
surface area, pore volume and pore size distribution. High tem-
perature chemisorption was performed to collect the volumetric
hydrogen isotherms.
2.1. Experimental methods
(1)
An Autosorb IQ-C (QuantaChrome Corp.) analyzer was used for
volumetric measurements at sub-atmospheric pressures. Ultra-low
pressures for micropore analysis were achieved using a turbo-
molecular drag pump with an ultimate vacuum of 5  108 Pa,
and three pressure transducers of 10, 1 and 0.1 torr, with reading
330 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340
accuracy of 0.15% as per manufacturers specification [28].
For characterization experiments, N2 adsorption at 77K was
performed using a liquid nitrogen bath for surface area, pore vol-
ume of open pores under 350 nm and pore size distribution from 1
to 40 nm. A reference cell was used to determine the saturation
pressure P0, the cross sectional area was set to 16.2 Å2/mol, and a
non-ideality correction of 6.58  105 mmHg1 was used for N2. For
each adsorption data point, the cell was equilibrated for a minimum
of 8 min to meet a pressure set point. At the end of the equilibra-
tion, the cell pressure was checked to ensure that it did not deviate
by the set point by more than P/P0 ¼ 2.56E-6 for pressures P/
P0 ¼ 1E-5 to 0.01, P/P0 ¼ 3E-5 for pressures P/P0 ¼ 0.01 to 0.25 and
P/P0 ¼ 0.003 for pressures P/P0 ¼ 0.025 to 1. If the pressure toler-
ance is exceeded, gas is added or removed as needed and the
equilibration is restarted. The equilibration time is chosen such that
pressure equilibrium can be reached, and the calculated adsorption
volume stays constant. Generally, experiments at lower tempera-
tures require longer equilibration times. The surface area was
calculated using the Brunauer-Emmett-Teller (BET) method [29].
The pore volume was calculated by using the adsorbed STP volume
at the plateau near the end of the physisorption isotherm, which
occurred close to P/P0 ¼ 0.95 for all materials tested. The condensed
liquid nitrogen volume inside a pore was calculated by assuming a
constant molar volume of 34.7 cm3/mol [30]. The pore size distri-
bution was calculated using quenched solid density functional
theory (QSDFT) assuming a slit pore geometry, in which the pore
walls are defined by two parallel infinite planes less than 2 nm
apart and cylindrical pore geometry with circular diameter ranging
from 2 to 40 nm [31e33]. The choice of pore geometry in carbon
materials is motivated by molecular probe studies and simulation
[34e37]. The pore size distribution from 0.35 to 1 nm was deter-
mined using CO2 adsorption at 273K, which achieves higher reso-
lution than N2 for narrow micropores (<0.7 nm) [38]. Non-local
density functional theory (NLDFT) was used to calculate the pore
size distribution, with a saturation pressure of 26, 141 torr, a CO2
cross sectional area of 21 Å2/mol and a non-ideality correction
factor of 9.1  106 mmHg1 [39,40]. At each data point, an equil-
ibration time of 5 min was used along with a pressure tolerance of
0.25 Pa for pressures 1 Pa to 1 kPa, 3 Pa for pressures 1 kPae2.5 kPa,
and 30 Pa for pressures 2.5 kPae100 kPa.
For determining the hydrogen adsorption isotherms, high
temperature gas adsorption was conducted at 973K and pressures
below 5 kPa to match expected conditions of advanced reactors
such as the FHR [41,42]. Ultra-high purity (99.9995%) hydrogen was
used. At each data point, an equilibration time of 3 min was used
along with a pressure tolerance of 0.25 Pa for pressures 1 Pa to
1 kPa, 3 Pa for pressures 1 kPae2.5 kPa, and 30 Pa for pressures
2.5 kPae100 kPa. Prior to analysis, the samples of mass 0.5e1.0 g
were cleaned with acetone under ultra-sonication, purged with
pure helium at 1273K for 1 h and held under ultimate vacuum for at
least 2 h to remove volatile impurities.
2.2. Materials
Seven specimens from three morphologies of activated carbon
(AC) materials were tested in this study, which can be grouped into
three categories: 1) Granular activated carbon (GAC), 2) Powder
activated carbon (PAC) and 3) Extruded activated carbon (EAC).
These are typically composed of 90% elemental carbon with a bal-
ance of oxygen, nitrogen, and hydrogen, which form various surface
functional groups such as carboxyls, hydroxyls or phenols. The
properties of these materials depend on many parameters
including raw material, pre-treatment, and manufacturing condi-
tions (time, temperature and heating rate), resulting in a great di-
versity amongst ACs [43e45]. Four GACs were studied: OVC 4  8
(CalgonCarbon), NV612 (Cabot Corporation), CAL TR 12  40 (CTR
12  40 CalgonCarbon), and OLC 12  40 (CalgonCarbon), which
had bulk densities between 0.45 and 0.54 g/mL, iodine numbers
between 920 and 1100 mg/g (indicator of surface area) and mesh
sizes 4  8, 6  12, and 12  40 as indicated by their respective
names. These materials were chosen for their robust form, hardness
numbers of 75e97, and industrial applicability.
Two PAC materials were studied: Norit PAC 200 (Cabot Corpo-
ration) and Maxsorb MSC-30 (Kansai Coke and Chemicals Co. Ltd.).
PAC 200 has a particle size D50 (size by diameter that 50% of par-
ticles are smaller than) of 45 mm and an iodine number of 900 mg/g.
MSC-30 is a chemically super-activated carbon with a published
surface area greater than 3000 m2/g and D50 of 6e50 mm: Due to
the small particle size, PAC materials are typically used in batch
processing. These materials were chosen for their high expected
surface area and porosity.
One EAC material was studied: Norit RB 40M (NRB 40M Cabot
Corporation), which consists of pebbles of diameter 4 mm. The
physical properties are similar to the GACs with iodine number
900e1000 mg/g, apparent density of 0.51 g/mL and hardness of 95.
This material was chosen for it's typical application in the removal
of low concentration contaminates in gases and relatively small
pressure drop when used in an adsorption column or filter.
One graphitic carbon, IG-110U (Toyo Tanso) and graphene
nanoplatelets Graphenit-OX (Nanoinnova Technologies) were
studied. IG-110U is an ultra-purified, fine-grained grade of graphite
that has been used extensively in HTGRs as a moderator [46], and
has been proposed for FHRs as structural material due to its
isotropic behavior and structural stability under irradiation [47].
IG-110U has a bulk density of 1770 kg/m3 and flexural strength of
39 MPa. In comparison to other materials studied, IG-110U was
treated at a much higher temperature during its manufacturing
process, between 2500 and 3000  C, resulting in a more ordered
structure of crystallographic planes. Graphite materials are
composed of individual crystallites of stacked graphene sheets with
small porosity between crystallites [48]. Graphenit-OX has a bulk
density of 0.2 g/mL and has an elemental composition of 96.45 %C,
2.28 %O, 0.43 %N, 0.34 %H, and <0.01% S. It was chosen for analysis
due to their expected high reactive edge density.
3. Data analysis and reduction
3.1. Characterization with physisorption
The reduction of physisorption data for the purposes of calcu-
lating the BET surface area, pore volume and pore size distribution
was performed with ASIQWin 4.01 software using calculation pa-
rameters described in section 2.1. For BET surface area, Rouquerel's
criteria for standardizing data analysis [49] and ISO standard
9277:2010 [50] was used to ensure model validity and consistent
calculation. For pore size distribution with NLDFT and QSDFT, the
model errors from least squares fitting were checked to validate
original assumptions regarding the pore geometry where large
errors (>10%) suggest inaccurate models.
3.2. Chemisorption modeling
Four models were compared with respect to their predictive and
explanatory capability: Langmuir, Temkin, Fruendlich, and Sips
[51], in which regression is performed by non-linear least squares
minimization using a combination SciPy optimization libraries [52]
and classes within the LMFIT toolkit [53]. Two objective error
functions were used: sum of squared errors (ERRSQ) and Mar-
quardt's percent standard deviation (MPSD) defined by Eqns. (2)
and (3) respectively:
 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340 331

model is failure at the low and high pressure extremes due the
n 
X 2
logarithmic dependence.
ERRSQ ¼ qe;meas  qe;calc (2)
i¼1
3.2.3. Freundlich isotherm
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
!2
u In contrast to the Temkin models, the Freundlich model at-
u 1 X n
qe;meas  qe;calc
MPSD ¼ 100 t
tempts to account for surface heterogeneity with a logarithmic
(3)
n  p i¼1 qe;meas energy distribution function where the heat of adsorption is
expressed as DHads ¼  DH oads ln q, from which the isotherm can be
Where qe;meas is the measured volume, qe;calc is the volume calcu- derived as [56]:
lated by the model, n is the number of data points used, and p is the RT RT
degree of freedom of each model. V ¼ Vm K0DHm P DHm ¼ CP 1=nF (9)

3.2.1. Langmuir isotherm
The Langmuir equation assumes energetically homogeneous
monolayer adsorption and is derived from thermodynamic equi-
librium where the forward and backward reaction rates are
assumed to be equal [54]:
ka Pð1  qÞ ¼ kd q
Where ka is the adsorption reaction coefficient, P is the gas phase
pressure of adsorbate, kd is the desorption coefficient, and q is the
surface coverage equal to V=Vm where V is the adsorbed volume
and Vm is volume required to saturate the active sites for a first
order reaction. The non-linear first order Langmuir isotherm can
then be expressed as:
RT
Where the regression coefficients are C ¼ Vm K0DHm and nF ¼ DRT Hm
.
Thus, dissociation occurs if the nF is found experimentally to be
near 2 at low pressure [17].
3.2.4. Sips model
The Sips model was originally derived assuming a Gaussian-like
(4)
energy distribution of active sites and is also commonly referred to
as the Freundlich-Langmuir combined isotherm or the generalized
Langmuir isotherm [57]. This is due to the overall mathematical
form of the model, which represents classical Langmuir depen-
dence except with reaction order generalized by the parameter n as
shown in Eqn. (10). Unlike other isotherms, the Sips model there-
fore contains an additional regression parameter.

K1 P Kn P 1\n
V ¼ Vm1 (5) V ¼ Vmn (10)
1 þ K1 P 1 þ Kn P 1\n

Where K1 ¼ ka =kd . Similarly, a second order equation can be

derived where each hydrogen molecule dissociates and occupies
4. Results and discussion
two sites giving Equation (6):
4.1. Chemisorption modeling
K2 P 1\2
V ¼ Vm2 (6)
1 þ K2 P 1\2
While the classical Langmuir equation and second order
Note that the monolayer volume Vm and equilibrium co- Freundlich model (i.e. Sievert's law) have been used to predict
efficients Km have different numerical values in the first (Eqn. (5)) isotherms in graphite materials with relatively good accuracy, they
and second order (Eqn. (6)) models and thus have been respectively have been best applied over relatively narrow ranges of pressures
subscripted. and temperatures to suit specific applications [2,17]. This small
range of application is due to the fact that the adsorption pathways
are complex and difficult to de-convolute, with several possible
3.2.2. Temkin isotherm
reactions that occur at different rates depending on the operating
In contrast to Langmuir models, the Temkin model allows for a
temperature [58]. Thus, while modeling adsorption with equilib-
non-constant equilibrium coefficient K ¼ ka =kd that describes an
rium isotherms generally lends limited ability to extrapolate, it can
energetically heterogeneous surface whereby the heat of adsorp-
encompass the effects of various elementary steps within relevant
tion DHads varies linearly as the surface is covered by adsorbate
thermodynamic conditions. This remains the most practical
[55]:
approach that can be applied to the design and selection of reactor
  materials under new conditions. Here, the model choice is the
DHoads ð1  lqÞ
K ¼ K0 exp (7) primary consideration in improving predictability in design, and
RT
potentially in inferring reaction mechanisms.
This theory captures effects of inter-adsorbate interaction on the To compare the accuracy of different models, we examine each
surface and change in local electronic structure as adsorbates models ability to effectively minimize an objective error function.
chemically bond to the surface. The adsorption isotherm for the In adsorption, it has been found that the preferred objective func-
Temkin model is therefore written as: tion depends on the type of model used, and the homoscedasticity
  (homogeneity of variance) of experimental data [59,60]. For ho-
RT RT 1 moscedastic data, ordinary least squares minimizing the sum of
V ¼ Vm lnðPÞ þ Vm lnK0 þ ¼ A ln P þ B (8)
DHads l
o
DHads l
o
l square errors (ERRSQ) has been recommended by Markovic et al., is
most widely used in modeling adsorption isotherms, and is hence
Where l is the proportional decay constant, DH oads is the standard used in the comparison below [59,61]. Less common in literature,
enthalpy of adsorption, T is the temperature, and R is the ideal gas Marquardt's percent standard deviation (MPSD) has been found to
constant. The constant regression terms are simply A ¼ Vm DHRTo l be preferred where the experimental noise is heteroscedastic [60],
  ads
which may be expected in this case, given that the measured
and B ¼ Vm DHRTo l lnK0 þ 1l . The primary weakness of the Temkin adsorption at each point of the isotherm is the aggregate of
ads
332 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340

Fig. 2. Adsorption isotherms measured for 8 different materials measured at 973K with a) fit to the molecular (first order) Langmuir equation and b) the corresponding residuals. Fit
by minimization of sum of squared errors (ERRSQ). Volume units in STP cm3/g.

Fig. 3. Adsorption isotherms measured for 8 different materials measured at 973K with a) fit to the dissociative (second order) Langmuir equation and b) the corresponding
residuals. Fit by minimization of sum of squared errors (ERRSQ). Volume units in STP cm3/g.

previous adsorption steps, resulting in an accumulation of uncer-
tainty with increasing pressure. Hence both error functions were
minimized for all materials except for IG-110U, where the total
adsorption was less than the uncertainty of 0.1 cm3/g.
4.1.1. Chemisorption modeling with ERRSQ minimization
Figs. 2e6 show the result of ERRSQ minimization. While the
residuals of the first order Langmuir equation are relatively low, the
model under predicts total retention at higher pressures for most
materials as shown in Fig. 2. This is especially true for materials
with relatively high adsorption such as OVC 4  8 and NRB 40M,
where the adsorbed volume is near 4.5 cm3/g.
The residual plot shows significant non-random behavior sug-
gesting a systematic error in assuming a first order monolayer. In

Fig. 4. Adsorption isotherms measured for 8 different materials measured at 973K with a) fit to the Temkin equation and b) the corresponding residuals. Fit by minimization of sum
of squared errors (ERRSQ). Volume units in STP cm3/g.
 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340 333

Fig. 5. Adsorption isotherms measured for 8 different materials measured at 973K with a) fit to the Freundlich equation and b) the corresponding residuals. Fit by minimization of
sum of squared errors (ERRSQ). Volume units in STP cm3/g.

Fig. 6. Adsorption isotherms measured for 8 different materials measured at 973K with a) fit to the Sips equation and b) the corresponding residuals. Fit by minimization of sum of
squared errors (ERRSQ). Volume units in STP cm3/g.

contrast, the second order Langmuir model is shown in Fig. 3. overall.

The second order Langmuir model in Fig. 3a and b shows a The heterogeneous surface Temkin model shows a similar fit to
significantly better fit at the higher pressures, while maintaining a the data compared to the dissociative Langmuir equation. The
reasonable prediction in the lower pressure range. The main outlier Temkin fit is shown in Fig. 4 where the outlier is again PAC 200. In
for the second order function was PAC 200, where the initial vol- most isotherms, the model slightly over predicts adsorption vol-
ume was significantly over-predicted by the second order function. ume for pressures below 0.5 kPa. Similar to the Temkin isotherm,
The order of the isotherm characterizes the active site occupation of the Freundlich model is considered empirical due to the non-
the adsorbate, where the first order reaction represents a 1:1 saturating behavior at high pressures. The Freundlich model fit is
occupation between the gaseous adsorbate and the adsorbent shown in Fig. 5.
active site and is commonly referred to as the molecular Langmuir
isotherm. In contrast, the second order reaction represents a
dissociation of H2 with each hydrogen atom occupying an active Table 1
Molecular and dissociative Langmuir models with ERRSQ minimization.
site and is referred to as the dissociative Langmuir isotherm. Thus,
the better fit of the second order equation suggests a more disso- Material Molecular Langmuir Dissociative Langmuir
ciative process, agreeing with previous experience with graphite Vm1 K1 ERRSQ Vm2 K2 ERRSQ
[17]. For the materials examined, the results of Langmuir modeling
OVC 4  8 4.57 3.76 0.225 6.15 1.31 0.070
are summarized by Table 1. NV 612 3.49 5.04 0.078 4.35 1.86 0.045
For the majority of nanoporous materials, the dissociative CTR 12  40 2.90 5.75 0.031 3.51 2.18 0.031
Langmuir equation performs better with lower ERRSQ, with the OLC 12  40 4.00 3.63 0.125 5.42 1.27 0.049
exception of the graphene nanoplatelets Graph-OX, and powdered PAC 200 3.22 3.50 0.078 4.31 1.29 0.177
MSC 30 1.40 8.85 0.009 1.58 3.64 0.023
activated carbons PAC 200 and MSC 30, where the ERRSQs are
NRB 40M 4.13 5.55 0.095 5.05 2.08 0.060
0.001, 0.01 and 0.1 cm3/g greater respectively. Further, the width of Graph-OX 0.60 9.28 0.001 0.67 3.76 0.002
the prediction interval containing 90% of the residuals is 0.134 cm3/
*Volume is in units of cm3 STP/g, pressure in units of kPa, and regression coefficients
g for the molecular model compared to 0.094 cm3/g for the disso- defined in section 3.2. Vm1 and Vm2 are in units of cm3 STP/g, K1 in units of kPa1, and
ciative model, indicating a better fit to the dissociative model K2 in units of kPa1/2.
334 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340

Table 2
Sips, temkin and freundlich models with ERRSQ minimization.

Material Sipsa Temkina Freundlicha

Vmn Kn n ERRSQ A B ERRSQ C nF ERRSQ

OVC 4  8 6.15 1.31 2.0 0.070 0.73 3.48 0.057 3.43 4.85 0.075
NV 612 4.12 2.23 1.8 0.044 0.48 2.81 0.051 2.78 5.96 0.074
CTR 12  40 3.08 3.78 1.3 0.024 0.37 2.38 0.045 2.37 6.64 0.065
OLC 12  40 5.21 1.40 1.9 0.049 0.65 3.02 0.047 2.98 4.77 0.086
PAC 200 3.22 3.50 1.0 0.078 0.53 2.41 0.190 2.39 4.82 0.279
MSC 30 1.40 8.85 1.0 0.009 0.13 1.23 0.034 1.23 9.74 0.039
NRB 40M 4.74 2.60 1.7 0.058 0.54 3.38 0.071 3.36 6.42 0.100
Graph-OX 0.60 9.28 1.0 0.001 0.06 0.53 0.004 0.52 9.87 0.005
a
Volume is in units of cm3 STP/g, pressure in units of kPa, and regression coefficients defined in section 3.2. Vmn is in units of cm3 STP/g, Kn is in units of kPa1/n where n is
the reaction order shown in the table.

The residual plots show non-random behavior with consistent
under prediction of adsorption volume at pressures below 0.5 kPa
followed by over-prediction at pressures between 0.5 and 1.5 kPa.
In comparison to the Temkin model, the Freundlich performs
qualitatively worse overall, with a wider prediction interval.
The Freundlich model cannot represent saturation at high
pressures, violating the assumption of classical chemisorption
where a finite number of sites must become occupied at high
pressures. In order to circumvent these limitations, the Sips model
has been used, which is sometimes referred to as the Freundlich-
Langmuir combined isotherm [62]. The combined isotherm al-
lows for behavior similar to Freundlich isotherm at low pressures,
while maintaining Langmuir-like saturation at high pressure. The
results of fitting to the Sips equation are shown in Fig. 6.
The Sips equation shows the best fit overall with a smaller over-
prediction in the low pressure range while maintaining a close fit
near the end of the isotherms. The summary of results from using
the heterogeneous models is shown in Table 2.
In terms of error minimization, the Temkin model performs
better than the Freundlich model for every material with a decrease
ERRSQ ranging from 0.001 to 0.28 cm3/g, owing to the restriction of
the polynomial function of the Freundlich model requiring a
sharper initial increase to maintain a flattened isotherm at higher
pressures compared to a logarithmic function of the Temkin model.
Further, the significant non-random variation in residuals under
1.5 kPa indicate missing parameters or inadequate representation
within the Freundlich model. The significance can be seen by
examining the 90% prediction interval which is smaller for the
Temkin isotherm at 0.12 cm3/g compared to 0.16 cm3/g for the
Freundlich isotherm. Overall, the Sips model performs the best,
with lowest errors between 0.001 and 0.078 cm3/g and prediction
interval of 0.086 cm3/g amongst all models. The summary of ERRSQ
across different materials is shown by Fig. 7.
The Sips model has the lowest total ERRSQ with the accuracy
being improved most for PAC 200. Physically, the addition of the
parameter n in the Sips model can be interpreted as a variable re-
action order within the Langmuir model, representing an overall
order that accounts for a combination different possible reaction
types without providing information on the specific reactions
themselves. The order was constrained between 1.0 and 2.0, and for
the majority of materials minimized in between these two limits,
suggesting a state between molecular adsorption and dissociation
[63,64]. Alternatively, a value n greater than 1 can be interpreted
and derived as a result of a Gaussian energy distribution in active
sites per Sips original interpretation [57]. While the Sips model
should mathematically produce a lower total residual than the
Langmuir and Freundlich methods since more parameters are
allowed, this does not necessarily indicate a physically informative
model. Hence, while a better average prediction may be achieved,
care should be taken in drawing mechanistic information and
extrapolation of the predicted isotherm.
4.1.2. Chemisorption modeling with MPSD minimization
In addition to ERRSQ, MPSD error minimization was performed
since it is applicable to data in which a constant percent error
structure is relevant. Due to the method of collection of volumetric
data by staged adsorption, the errors are expected to compound
and thus scale with measured adsorption volume. In this case,
MPSD could potentially provide determination of model parame-
ters. The summary of fitting parameters for homogeneous models
are shown in Table 3.
For the molecular (n ¼ 1) Langmuir model, the MPSD varies

Table 3
Molecular and dissociative Langmuir isotherm with MPSD minimization.

Material Molecular Langmuir Dissociative Langmuir

Vm1 K1 MPSD Vm2 K2 MPSD

OVC 4  8 4.49 4.17 3.68 6.12 1.33 2.12

NV 612 3.47 5.29 2.65 4.39 1.80 2.31
CTR 12  40 2.89 5.88 2.02 3.56 2.06 2.40
OLC 12  40 3.94 3.95 3.30 5.46 1.24 2.18
PAC 200 3.26 3.19 3.75 4.80 0.98 6.48
MSC 30 1.41 8.39 2.52 1.62 3.20 4.23
NRB 40M 4.11 5.78 2.47 5.09 2.02 2.21
Graph-OX 0.60 8.90 1.78 0.68 3.39 3.31

*Volume is in units of cm3 STP/g, pressure in units of kPa, and regression coefficients
defined in section 3.2. Vm1 and Vm2 are in units of cm3 STP/g, K1 in units of kPa1, and
Fig. 7. Total sum of squared errors (ERRSQ) for 5 different adsorption models. K2 in units of kPa1/2.
 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340 335

from 1.78 for Graph-OX to 3.75 for PAC 200. In comparison, the Table 4
dissociative (n ¼ 2) Langmuir model shows generally larger errors, Sips, temkin and freundlich model with MPSD minimization.

in particular for the powder activated carbon materials PAC 200 and Material Sipsa Temkina Freundlicha
MSC 30 with MPSD values of 6.48 and 4.23 respectively. Dis- Vmn Kn n MPSD A B MPSD C nF MPSD
agreements between model and experimental data near the end of
OVC 4  8 6.12 1.33 2.0 2.22 0.74 3.47 2.01 3.42 4.68 2.67
the isotherm are penalized less when minimizing MPSD than when
NV 612 3.86 2.83 1.5 2.25 0.50 2.80 2.59 2.77 5.61 3.31
minimizing ERRSQ for the first order Langmuir equation. This re- CTR 12  40 3.01 4.34 1.2 1.97 0.39 2.37 2.94 2.35 6.14 3.65
sults from the fact that the percent error (MPSD) in high adsorption OLC 12  40 4.87 1.67 1.7 2.19 0.66 3.01 2.19 2.96 4.50 3.25
volume range makes a smaller contribution than absolute error PAC 200 3.26 3.19 1.0 3.93 0.61 2.37 6.22 2.31 3.95 8.12
MSC 30 1.30 8.39 1.0 2.67 0.15 1.22 5.20 1.22 8.45 5.68
(ERRSQ) in the overall minimization. Comparison of the molecular
NRB 40M 4.52 3.20 1.5 2.15 0.56 3.37 2.54 3.34 6.06 3.14
and dissociative Langmuir isotherms determined by minimizing Graph-OX 0.60 8.90 1.0 1.89 0.06 0.52 4.20 0.52 8.76 4.61
MPSD is shown in Fig. 8. a
Volume is in units of cm3 STP/g, pressure in units of kPa, and regression co-
While MPSD minimization can find the lowest percent error efficients defined in section 3.2. Vmn is in units of cm3 STP/g, Kn is in units of kPa1/n
solution, the MPSD value can be misleading. Across different ma- where n is the reaction order shown in the table.
terials shown in Fig. 8, the molecular Langmuir model consistently
saturates early compared to the dissociative model indicating an
inaccurate representation. Yet, the total MPSD values for both are stabilization of the adsorbate layer and early condensation at
relatively close. Thus, in order to use the MPSD effectively, it is relative pressure below 0.1 P/P0, potentially outside of the BET
important to quantify the error propagation in experimental applicability range [49]. With these considerations, BET surface
techniques and examine the residuals for error patterns. area should only be referenced for the materials in this study as a
For the heterogeneous surface models (See Table 4), the results relative measure rather than an inherent property. Additionally,
of MPSD minimization were similar to those of ERRSQ minimiza- while standardization methods are used to improve repeatability, it
tion. The Temkin model generally performed better than the has been shown that the measurement of area can vary slightly
Freundlich model with MPSD values ranging from 2.01 to 6.22 depending on the selection of points used in the estimation. In
versus 2.67 to 8.12 respectively, with the errors being consistently
higher for Freundlich model regression. Again, Sips model per-
formed the best across all models with errors ranging from 1.89 to
3.93. The parameters Vmn and Kn determined for the Sips equation
by MPSD minimization were relatively close to those determined
by ERRSQ minimization resulting in a qualitatively similar fit as
well. The MPSD error results are summarized in Fig. 9, which shows
consistently that Sips model is the most appropriate model for the
materials examined.

4.2. Chemisorption and physical characteristics

The total chemisorption near the end of the isotherm pressure

range (3 kPa) is correlated to the surface area, pore volume and pore
size distribution in this section.

4.2.1. Chemisorption versus BET surface area and pore volume

The apparent surface area was measured using standard mul-
tipoint BET. BET theory assumes a flat surface and is therefore
rigorous for only non-porous or mesoporous materials [29]. Fig. 9. Total Marquardt's percent standard deviation (MPSD) for 5 different adsorption
Further, the proximity of adjacent walls in micropores results in models.

Fig. 8. Adsorption isotherms minimizing Marquardt's percent standard deviation (MPSD) for a) molecular Langmuir versus b) dissociative Langmuir.
336 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340

Table 5 volume and adsorbed hydrogen is dependent on 1) the relationship

BET surface area and total pore volumes for various carbon materials. between the active sites and surface area/pore volume and 2) the
Material BET Surface Area (cm2/g) Total Pore Volume (cm3/g) relationship between adsorbed volume and active site concentra-
IG-110U 0.588 0.9909E-3
tion. For example, if active site density scales linearly with surface
OVC 4  8 1153.531 0.5024 area and the adsorption occurs such that 1 adsorbate occupies 1
NV 612 923.641 0.5052 active site, the relationship between surface area and adsorbed
CAL TR 12  40 993.224 0.5022 volume can be expected to be linear. However, given the com-
OLC 12  40 1113.998 0.4601
plexities of identifying active sites (various surface functional
PAC 200 1033.576 0.554
MSC-30 3125.557 1.721 groups, trapping sites, etc.), and determining the order of reaction
RB-40M 1094.006 0.5529 discussed in Section 4.1, the relationship cannot be readily deter-
Graphenit OX 113.041 0.1828 mined a priori. In this case, it is clear only that the concentration of
adsorbing sites generally increases with increasing surface area and
pore volume across all the materials tested.
estimating the total pore volume, the molar quantity is converted to
a volumetric quantity using the Gurvich rule, which assumes a 4.2.2. Chemisorption and pore size
constant density in the pore. This produces a small error in the Fig. 10 shows the relationship between adsorbed hydrogen and
result [65]. Table 5 shows the BET surface area and total pore vol- surface area compared to that of adsorbed volume. These differ-
ume measured for the materials tested. ences are caused primarily by the relationship between pore vol-
The relationship between the BET surface area and total pore ume and surface area. This relationship is dependent on the pore
volume and the total hydrogen adsorption is shown in Fig. 10. Note size distribution (smaller pores means higher surface to volume
that MSC-30 is an outlier. After the analysis of MSC-30, a yellow ratio), which is shown in Fig. 11 for the materials studied. There is a
residue was found on the quartz cell, which was not observed large variety of pore size distributions where most materials have a
during other analyses. Thus, the appearance of the outlier is concentration of pores of width less than 50 Å. The graphite IG-
believed to be due to chemical instability of the super-activated 110U has almost no porosity with only a small amount near the
carbon at test conditions. In such cases, chemical reaction of microporous range at 10 Å. The graphene nanoplatelets (Graph-OX)
MSC-30 forming volatiles would significantly drive down the total have the second lowest porosity overall with a maximum differ-
adsorption. This could occur due to the presence of reactive func- ential volume of 0.015 cm3/g under 10 Å. Further, a small amount of
tional groups on the surface or due to incomplete evacuation of the mesoporosity is observed in the 100 Å or 10 nm range, which is
material during the preparation step and must be further investi- believed to be due to condensation between nanoparticles, which
gated by chemically informative methods such as mass spectrom- can be on the order of a few nm in diameter. The other activated
etry and thermal desorption spectroscopy. carbons show similar profiles with large microporosity, followed by
Overall, it was found that materials with higher measured BET a secondary peak in the mesoporous regime. In the micropore
surface areas and pore volumes exhibited higher hydrogen regime (<2 nm), granular carbon OVC 4  8 exhibited the largest
adsorption. However, predictability within the ACs (the strongest volume while the superactivated carbon MSC-30 exhibited the
adsorbents) is weak based on pore volume alone. Excluding MSC- largest total pore volume overall owing to volume contributions
30, the total adsorption can vary by more than 1.5 cm3/g across over the entire pore range.
AC materials with the same total pore volume at 0.5 cm3/g. The accuracy of the pore size models for the distributions shown
The error bars represented in Figs. 10a and b are the maximum in Fig. 11 can be assessed by examining the fit of experimental data
drift of the instrument and are thus systematic. The BET plot to theoretical DFT kernels. Large errors can occur due to the failure
(Fig. 10a) shows a relatively consistent trend amongst graphite, of the models to represent the physical system. Overall, the
graphene and activated carbon materials, while the pore volume experimental data matches the models where almost all the errors
shows lower predictive capacity in the range of 0.5 cm3/g total pore are less than 1%. For IG-110U, the QSDFT (1e40 nm) error is 2.25%
volume where most of the activated carbon materials are located. and For Graph-OX, the NLDFT (<1 nm) the error is 6.0%. In the case
The exact order of the relationship between surface area/pore of IG-110U, the small error is believed to be caused by a lack of

Fig. 10. Adsorbed hydrogen for various carbon materials at 3 kPa versus a) the BET surface area and b) the estimated total pore volume.
 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340 337

Fig. 11. Pore size distributions for graphite, graphene nanoplatelets and activated carbons evaluated with CO2 at 273K using NLDFT in blue, and N2 at 77K using QSDFT in red. (For
interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

porosity due to the annealing conditions during the manufacturing
process. For graphene nanoplatelets, the errors are believed to be
caused by difficulties in modeling inter-particle porosity, which is
on similar length scales (several nm) to the pore sizes measured by
QSDFT. These types of pores fail the assumption of slit/cylindrical
pore geometry used in calculation. Nonetheless, the differences
between the carbon types are large enough such that comparisons
can be made. A more detailed error analysis and model fitting can
be found in the supplemental materials.
Generally, it was found that materials with micropores of less
than <10 Å in diameter adsorbed larger amounts of hydrogen. For
example, the available surface area of pores 4 Å in diameter is
compared against the total hydrogen retention in Fig. 12a, which
shows a general positive trend with an R-value of 0.86. At a pore

Fig. 12. Pore surface area versus total hydrogen adsorption at 3 kPa at pore size of a) 4 Å and b) 24 Å.
338 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340
diameter of 4 Å, the increased hydrogen adsorption could be caused
by hydrogen entrapment in carbon structures, which is character-
istically similar to intercalation traps speculated by Atsumi [2] or
due to stable hydrogen structures between graphite sheets sug-
gested by ab-initio calculations [66]. In this case, it is clear that only
very small pores would have the capability to retain hydrogen. In a
sufficiently large pore, the potential of adsorbed hydrogen at the
surface of a pore wall is no longer affected by the presence of the
adjacent wall of the same pore. Thus, as expected, the availability of
surface area in a larger pore size, does not influence the total
adsorption as shown in Fig. 12b. Clearly, such trapping mechanisms
involving multiple surfaces cannot be represented accurately using
simple homogeneous surface models.
4.2.3. Making predictions of hydrogen retention in carbon materials
While various physical descriptors have been found previously
for graphitic materials, few of these apply to other types of carbon
materials. Namely, these properties include the degree of graphi-
tization, lattice constant, and graphite edge surface area [67,68]. It
has been found generally that reducing the degree of graphitiza-
tion, increasing lattice constant and increasing the graphite edge
area increases the hydrogen chemisorption at high temperature
due to the presence of active sites formed by free un-bonded car-
bon at the end of each graphene plane where hydrogen has been
shown to dissociate [2,10,18]. The properties cannot be easily
translated to understanding hydrogen chemisorption in amor-
phous carbon material, which include a combination of sp3 and sp2
hybridized structures [69], oxygen functional groups (carboxyl,
hydroxyl, carbonyl, quinone, etc.) [70,71], and pentagonal rings
[72], which can all contribute to the surface reactivity. Further, non-
graphitic carbon materials exhibit a dramatically different micro-
structure than graphite, consisting of an agglomeration of highly
disordered, curved planes forming interconnected, microporous
networks into which hydrogen can diffuse and adsorb [73]. Thus,
the interactions of hydrogen with amorphous carbons may be
substantially more complex and difficult to predict. In comparison
to previous results on ordered graphite materials which exhibited
an extrapolated retention on the order of 0.1 cm3/g at 973K and
5 kPa [1,18], the total hydrogen adsorption for amorphous carbon
has been found to be substantially higher exceeding 4.5 cm3/g. The
difference between graphitic and amorphous carbon is again
confirmed in this study where total adsorption was less than
0.1 cm3/g on IG-110U using the volumetric adsorption technique.
Whiles the exact chemical path of adsorption remains unclear, it
has been shown in this study that chemisorption is reliably
dependent on physical observables that can be readily measured. In
particular, the difference in adsorption amongst amorphous car-
bons is well related to the measurable BET surface area and pore
volume since increasing the available area and volume likely in-
creases the density and availability of active sites. Further, it was
found that the total hydrogen chemisorption increases in the
presence of small pores, which may serve as hydrogen traps.
5. Conclusion
This work involved the thermodynamic measurements of
hydrogen adsorption on amorphous carbon materials and charac-
terization of these materials. The data collected was used to relate
the physical properties to observed chemical phenomena at
advanced reactor conditions. The work on these materials was
driven by the need to develop a tritium capture system for
advanced high temperature reactors requiring tritium manage-
ment including, high temperature gas reactors, fluoride salt-cooled
high temperature reactors, and fusion systems. Previous work
related to tritium adsorption on carbon focused on structural
materials requiring mechanical and irradiation resistance, con-
straints that would not apply to systems built primarily for tritium
capture. To the author's best knowledge, no similar work exists that
probe the interactions of hydrogen on the materials examined in
this work at required conditions. Volumetric chemisorption was
performed at a temperature of 973K and pressures under 5 kPa,
conditions similar to those experienced by advanced fission re-
actors. Remarkably high hydrogen adsorption was found, with
retention greatly exceeding that of other known materials at similar
temperatures. Namely, in comparison to known graphitic hydrogen
adsorbers, it was shown that various granular activated carbons
had over 40 times the uptake at reactor conditions. This is believed
to be due to a combination of differences in electronic structure and
physical characteristics of the material. Amorphous carbons
contain a combination of sp2 and sp3 hybridization, while graphitic
materials are mostly sp2 hybridized, which only allows bonding at
particular types of graphite edge sites. This is confirmed in mea-
surements of hydrogen adsorption on graphene nanopletelets,
which was 10 times less than the adsorption measured on amor-
phous carbons. The physical properties examined were surface area
by BET, total pore volume by N2 physisorption, and pore size dis-
tribution (PSD). The PSD was experimentally determined by using
QSDFT on N2 physisorption isotherms and NLDFT on CO2 isotherms
to survey a pore range of 0.35e40 nm at high resolution. Overall
good positive correlation was found between the hydrogen
adsorption and the surface area and pore volume, which is due to
the increase in available active site density. Further, it was found
that materials with high micropore surface area showed increase
adsorption, from which it was inferred that pore-level trapping of
hydrogen could occur at high temperature. The chemisorption
isotherms were modeled with several two- and three-parameter
isotherms namely the Langmuir, Temkin, Freundlich and Sips
models. Non-linear least squares minimization was performed on
the sum of square errors (ERRSQ) and Marquardt's percent stan-
dard deviation (MPSD). It was found that the second order
Freundlich isotherm, which has been previously used for graphite
materials showed the largest error while Sips model was found to
be best at minimizing the error distribution. For the Sips model, it
was found that the least squares error was minimized with n be-
tween 1.0 and 2.0 for the majority of materials tested, which can be
interpreted as the presence of different adsorption states including
chemical dissociation and trapping. While the model in itself does
not provide direct and immediate insight on the elementary reac-
tion steps, it is nonetheless useful for the purpose of prediction. The
results of this study provide a basis for development of a tritium
mitigation system in advanced nuclear systems by providing
baseline hydrogen uptake information required in the design of
adsorption processes at high temperature and low partial pres-
sures. However, it should be noted that there remain many con-
siderations in assessing the applicability of nanoporous carbons as
tritium scavengers in any particular nuclear system. Such consid-
erations include and are not limited to materials handling, long-
term structural integrity in the operating environment, perfor-
mance degradation over time, and ability to regenerate spent
scavenger, which are all subjects of ongoing research.
Data availability
The data collected in this study are openly available in a pub-
lished Mendeley dataset at https://doi.org/10.17632/vyp4wbhxzr.2,
https://doi.org/10.17632/vyp4wbhxzr.1.
Acknowledgements
The authors like to acknowledge the Shanghai Institute of
 S.T. Lam et al. / Journal of Nuclear Materials 511 (2018) 328e340
Nuclear and Applied Physics of the Chinese Academy of Sciences for
supporting this work and Cabot, CalgonCarbon, and Toyo Tanso for
providing samples that were used.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.jnucmat.2018.09.009.
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