1900 Corporate Drive

Boynton Beach, Florida 33426

APPNOTE 102
800.989.2476
561.731.4999

GRAPHENE AND GRAPHENE-RELATED MATERIALS:

FUNDAMENTAL TECHNIQUES FOR STRUCTURAL ANALYSIS

Introduction

Graphene and graphene-related materials have, in their relatively short life span, revolutionized many areas of materials science and
technology. Their huge technological success is to a large extent related to their unique structure and properties. This Note briefly
examines graphene structure and some key fundamental properties that lead graphene, and graphene-related materials, to challenge
both fundamental physics and technical frontiers in materials science.

Graphene Structure

Graphene has arguably the largest surface area-to-volume ratio
among novel 2D crystalline layered materials. Being spread as an
atom-thick layer of ring-bound carbon atoms (see Figure 1), all
atoms in graphene sheets are in fact exposed to its surface. This
gives graphene a rich array of unique surface physical, chemical,
and electronic properties, which continue to open doors for new
applications in nanotechnology and condensed matter physics.
Currently the most reliable method to evaluate the surface area of
GMs is by the classical BET method [2]. This method derives the BET
surface area of GMs from nitrogen sorption isotherms collected
at 77 K on suitable equipment [3]. Cryogenic conditions facilitate
the formation of an equivalent monolayer of adsorbed nitrogen
molecules on the exposed GM surfaces. BET surface areas are simply
calculated by multiplying the area covered by a nitrogen molecule
(0.162 nm2) times the number of molecules needed to form the
equivalent monolayer. The BET method, introduced decades ago,
is able to quantify surfaces inaccessible by other means, and is thus
recommended by IUPAC for surface area evaluations [2].

Graphene sheets, if fully exposed and reasonably large, have a

Figure 1. HRTEM Image of a Graphene-Related Material Illustrating
Graphene Sheets with Curved Surfaces and In-Plane Carbon Atoms
Distributed in 5-8 Member Rings (Adapted from Ref. 1).
Graphene Surface Area
Surface area impacts every application of graphenes and graphene-
related materials (such as graphene oxide, graphene-metal oxide
composites, heteroatom-doped graphenes, nanostructured photo-
catalysts, etc.). It is largely the exposed surface of these materials that
interacts with gases, liquids, solids, electrons, ions, photons and
phonons. Therefore, evaluating the surface area of graphene materials
(GMs) is a crucial step in understanding and optimizing their per-
formance.
theoretical surface area of 2,629 m2/g. Surface areas of that
magnitude have indeed been reported following, e.g., activation
of exfoliated graphene oxide [1]. However, graphene sheets tend
to stack on top of each other due to weak but extensive van der
Waals interactions between their surfaces. Graphene layer stacking
reduces their accessible surface area in proportion to their degree
of stacking. That relationship was investigated recently by Guo
et al. [4] using an Autosorb. Table 1 shows the predictions from a
simple scaling law of the form N = At/Am, where N is the number
of stacked layers, At is the theoretical graphene surface area, and
Am is the measured BET surface area, in comparison with N values
derived from other techniques. The good agreement between
theory and experiment is especially noted at higher surface areas,
where more of the graphene surface would be accessible through
pores in bulk graphene particles, as illustrated below.

1
 1900 Corporate Drive
Boynton Beach, Florida 33426
APPNOTE 102
800.989.2476
561.731.4999

GRAPHENE AND GRAPHENE-RELATED MATERIALS:

FUNDAMENTAL TECHNIQUES FOR STRUCTURAL ANALYSIS

For example, hierarchical micro-mesopore structures have been

Table 1. Comparison of Average Number of Stacked Layers (N) of shown to enable the retention of high surface area and reactivity
Commercial Graphene Samples Estimated by Gas Sorption with Reported in the smaller micropores with the faster diffusion and transport
Values [4]. of species through the larger mesopores [10]. Clearly, the gas
sorption technique is ideally suited for the characterization of
Commercial BET Surface Number of Stacked Layers, N micro-mesoporous graphenes and graphene-based materials. This
Graphene Area [m2/g] is also evidenced by the exponentially increasing number of
Reported Calculated
publications that include these essential characterization measure-
G1 675 4 4 ments.
G2 187 10 14
G3 126 20 21
G4 98 N.R. 27
G5 26 25 100

Graphene Pore Sizes

Pores in graphene or graphene-related materials can include holes

within sheets, whose dimensions can be tailored by, e.g., selective
ring removal and nitrogen passivation [6], and spaces between
sheets, with the overall pore dimensions and size distribution
being dictated by the degree of stacking, crumpling, or pillaring
with additives [4]. Representative examples of pore size distri-
butions of graphene-based materials measured on an Autosorb
are shown in Figure 2. In this particular case, chemical activation
of an exfoliated graphene oxide material yielded a graphene- Figure 2. Pore Size Distribution of Activated Graphene Sample
Determined by Nonlocal DFT Modeling of Complementary N2/77K
derived product with 98% sp2 bonds, extremely high BET surface
and CO2/273K Sorption Isotherms, Shown in the Figure Inset, on an
area, and a bimodal pore size distribution. Note that ready access
to the ultramicropores below ~0.7 nm was achieved using CO2 ad- Autosorb (Adapted from Ref. 1).
sorption at 273 K, in order to avoid the slow diffusion of nitrogen
in the smallest nanopores. Reasonable agreement was reported
[1] between observations from High Resolution Transmission
Electron Microscopy (HRTEM) analyses and the pore size
distributions calculated from nonlocal DFT or the more advanced
Quenched Solid DFT (QSDFT) method [7], which takes into account
the surface heterogeneity of the graphene-based samples. These
pore size features have been demonstrated to correlate with the
performance of graphenes and graphene-based materials for a
large an increasing number of applications [1,6,8-11].

2
 1900 Corporate Drive
Boynton Beach, Florida 33426
APPNOTE 102
800.989.2476
561.731.4999

GRAPHENE AND GRAPHENE-RELATED MATERIALS:

FUNDAMENTAL TECHNIQUES FOR STRUCTURAL ANALYSIS

Graphene Density Concluding Remarks

Gas pycnometry provides a fast, clean and nondestructive way to
assess the density of carbon materials in general. The precision
and accuracy of modern gas pycnometers such as the automated
micro-Ultrapyc 1200e (capable of handling sample volumes down
to 0.1 cm3) [12] are adequate to assess the differences in chemical
and physical characteristics of graphene-related materials.
The density of graphene sheets can increase with increasing
stacking order and perfection. Perfectly stacked and aligned
graphene sheets have a density close to that of crystalline graphite
(2.267 g/cm3). However, heteroatoms, stacking imperfections
and defects tend to lower the density to a value that depends on
heteroatom nature and content, and on pore characteristics. In
some cases, pores created during stacking or agglomeration can
remain closed to external gases. Closed porosity in particular tends
to lower measured densities significantly, but can be exposed
by, e.g., subjecting bulk graphene particles to high energy mill-
ing processes [13]. Accordingly, reported densities of graphene-
-related materials (in the form of powders or films) ranging between
~1.6 g/cm3 [14] and ~2.1 g/cm3 [15] are not uncommon.
Graphene and graphene-related materials are currently at the
forefront of materials research and technology. The precise evalua-
tion of their structural characteristics is an essential step towards
optimizing their performance. Specific properties that affect
virtually every application of graphene materials include their
specific surface area, pore size distribution, density and reactivity.
Graphene surface areas can vary by orders of magnitude depend-
ing on their degree of stacking, crumping, pillaring, and their
heteroatom and defect content. Holes and micro-mesopores may
be present within and between layers of graphene materials.
Densities of bulk graphenes measured by gas pycnometry tend
to fall below crystalline densities due in part to some closed or
in accessible pores being present in these materials. Graphene
reactivity is related to the nature and concentration of active
sites, which can be quantified using modern chemisorption and
temperature programming techniques. Much remains to be done
to fully exploit and expand the range of applications of graphene
materials. The techniques described above provide useful and
precise tools to empower users to push the boundaries of graphene
materials to ever-increasing levels.

Graphene Reactivity

Although the surfaces of ideal graphene 2D crystals are uniform,

real graphene materials are often energetically, chemically and
physically heterogeneous. Surface sites that may be more reactive
towards adsorption, ion or electron exchange, mechanical strain,
etc., include graphene sheet edges, Stone-Wales defects, hetero-
atoms, functional groups, impurities, metal catalysts, and so on.
Both chemisorption and temperature-programming techniques
to assess the quantity and quality of the more reactive sites
on graphenes and graphene-related materials by classical [16]
and more modern [17,18] techniques, which are conveniently
automated and readily available using advanced chemisorption
instruments such as the Autosorb or the ChemStar [19].

Quantachrome's Autosorb (ASiQ Model).

3
 1900 Corporate Drive
Boynton Beach, Florida 33426
APPNOTE 102
800.989.2476
561.731.4999
GRAPHENE AND GRAPHENE-RELATED MATERIALS:
FUNDAMENTAL TECHNIQUES FOR STRUCTURAL ANALYSIS
References
1. Y. Zhu, S. Murali, M.D. Stoller, K.J. Ganesh, W. Cai, P.J. Ferreira,
A. Pirkle, R.M. Wallace, K.A. Cychosz, M. Thommes, D. Su,
E.A. Stach and R.S. Ruoff, Carbon-Based Supercapacitors
Produced by Activation of Graphene, Science 332 (2011) 1537.
2. M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier,
F. Rodriguez-Reinoso, J. Rouquerol and K.S.W. Sing,
Physisorption of Gases, with Special Reference to the Evaluation
of Surface Area and Pore Size Distribution, IUPAC Report, Pure
Appl. Chem. 87 (2015) 1051.
3. http://www.quantachrome.com/instruments.html.
4. F. Guo, M. Creighton, Y. Chen, R. Hurt and I. Külaots, Porous
Structures in Stacked, Crumpled and Pillared Graphene-Based 3D
Materials, Carbon 66 (2014) 476.
5. http://www.quantachrome.com/gassorption/autosorb_iq.html
6. A.W. Hauser, J. Schrier and P. Schwerdtfeger, Helium Tunneling
through Nitrogen-Functionalized Graphene Pores: Pressure- and
Temperature-Driven Approaches to Isotope Separation, J. Phys.
Chem. C 116 (2012), 10819.
7. A.V. Neimark, Y. Lin, P.I. Ravikovitch and M. Thommes,
Quenched Solid Density Functional Theory and Pore Size Analysis
of Micro-Mesoporous Carbons, Carbon 47 (2009) 1617.
8. S.J. Park and S.Y. Lee, Adsorption Behaviors of Graphene and
Graphene-Related Materials, in J.M.D. Tascón, Ed., Novel Carbon
Adsorbents, Elsevier, Amsterdam (2012), p. 435.
9. F. Bonaccorso, L. Colombo, G. Yu, M. Stoller, V. Tozzini,
A.C. Ferrari, R.S. Ruoff and V. Pellegrini, Graphene, Related Two-
Dimensional Crystals, and Hybrid Systems for Energy Conversion
and Storage, Science 347 (2015) 41.
10. C. Tang, B.Q. Li, Q. Zhang, L. Zhu, H.F. Wang, J.L. Shi and
F. Wei, CaO-Templated Growth of Hierarchical Porous Graphene
for High-Power Lithium–Sulfur Battery Applications, Adv. Funct.
Mater. 26 (2016) 577.
11. R. Verdejo, M.M. Bernal, L.J. Romasanta and M.A. Lopez-
Manchado, Graphene-Filled Polymer Nanocomposites, J. Mater.
Chem. 21 (2011) 3301.
12. http://www.quantachrome.com/product_listing/density_
analyzers.html
13. http://www.quantachrome.com/millprep/millprep.html
14. Q. Wang, J. Yan and Z. Fan, Reply to Comment on Methods
of Calculating the Volumetric Performance of a Supercapacitor,
Energy Storage Materials, in Press (2016).
15. A.B. Fuertes, G.A. Ferrero, and M. Sevilla, Commentary:
Methods of Calculating the Volumetric Performance of a
Supercapacitor, Energy Storage Materials, in Press (2016).
16. C.A. Leon y Leon, An Improved Method for Evaluating the
Active Surface Area of Solid Carbons, 22nd Biennial Conference
on Carbon, University of California, San Diego (1995), p. 446.
17. H. Aso, K. Matsuoka, A. Sharma and A. Tomita, Evaluation
of Size of Graphene Sheet in Anthracite by a Temperature-
Programmed Oxidation Method, Energy & Fuels 18 (2004) 1309.
18.T. Ishii, S. Kashihara, Y. Hoshikawa, J. Ozaki, N. Kannari, K. Takai,
T. Enoki and T. Kyotani, A Quantitative Analysis of Carbon Edge
Sites and an Estimation of Graphene Sheet Size in High-Tempera-
ture Treated, Non-Porous Carbons, Carbon 80 (2014) 135.
19.http://www.quantachrome.com/chemisorption/chemstar_tpx.
html