Enhanced CO2 capture in Fe3O4-graphene nanocomposite by physicochemical

adsorption
A. K. Mishra and S. Ramaprabhu

Citation: Journal of Applied Physics 116, 064306 (2014); doi: 10.1063/1.4892458

View online: http://dx.doi.org/10.1063/1.4892458
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/116/6?ver=pdfcov
Published by the AIP Publishing

Articles you may be interested in

Synthesis and characterization of Fe3O4–TiO2 core-shell nanoparticles
J. Appl. Phys. 116, 114312 (2014); 10.1063/1.4896070

Effects of graphene oxide concentration on optical properties of ZnO/RGO nanocomposites and their application
to photocurrent generation
J. Appl. Phys. 116, 084307 (2014); 10.1063/1.4894141

Optical and dielectric properties of TiO 2 doped PVA - CN / LiClO 4 composite electrolyte
AIP Conf. Proc. 1512, 1278 (2013); 10.1063/1.4791519

PLLA- Fe3O4 nanocomposites

AIP Conf. Proc. 1459, 238 (2012); 10.1063/1.4738455

Carbon dioxide adsorption in graphene sheets

AIP Advances 1, 032152 (2011); 10.1063/1.3638178

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
130.191.17.38 On: Sun, 09 Nov 2014 17:22:59
 JOURNAL OF APPLIED PHYSICS 116, 064306 (2014)

Enhanced CO2 capture in Fe3O4-graphene nanocomposite by

physicochemical adsorption
A. K. Mishra and S. Ramaprabhua)
Alternative Energy and Nanotechnology Laboratory (AENL), Nano Functional Materials Technology Centre
(NFMTC), Department of Physics, Indian Institute of Technology Madras, Chennai – 600036, India
(Received 17 June 2014; accepted 26 July 2014; published online 13 August 2014)
Cost effective and efficient methods for CO2 capture are the need of the hour to render the clean
environment in the era of rising energy demand. Here, we report the physicochemical adsorption of
carbon dioxide (CO2) in iron oxide decorated graphene nanocomposite at elevated pressures and
temperatures. Nanocomposite was prepared by scalable and cost effective technique and its
suitability for CO2 capture was studied at elevated pressures (3–13 bar) and temperatures
(25–100  C) using Sieverts apparatus. The higher CO2 capture capacities of 60, 35, and
24 mmol g1 were observed at 11 bar pressure and 25, 50, and 100  C, respectively, compared to
other studied porous materials. Nature of interaction (Physicochemical adsorption) of CO2 with
nanocomposite was identified using Fourier transform infrared spectroscopy. Degassing was
performed to examine the recovery of nanocomposite. V C 2014 AIP Publishing LLC.

[http://dx.doi.org/10.1063/1.4892458]

I. INTRODUCTION carbon nanotubes and its nanocomposites.22,23 We have also

shown the better CO2 capture performance of graphene com-
Increasing usage of carbonaceous fuels for meeting the
pared to nanotubes.24 However, carbon nanotubes based
current energy demand has resulted in excess carbon dioxide
nanocomposite are costly and adsorption capacity of gra-
(CO2) emission and it is expected that its atmospheric con-
phene largely depends on surface area and pore size distribu-
centration may cross 550 ppm by 2035.1 Efficient carbon
tion and hence, synthesis process.
capture and sequestration (CCS) technology can be achieved
Capture capacity of graphene decreases sharply at
by improving CO2 capture efficiency and reducing its cost.
higher temperatures due to easier desorption of physically
The CCS technology attempts to prevent the release of large
adsorbed gas. As the exhaust of industries, such as automo-
quantities of CO2 into the atmosphere from fossil fuel use in
bile, steel and cement industries, thermal power plants may
power generation and other industries.2 Among the conven-
exist at high temperatures, sustainability of CO2 capture
tional methods including cryogenic distillation, chemical sol-
capacity is one of the major concerns. Graphene based nano-
vent scrubbing, adsorption and separation, adsorption in
composites can be worthy candidates to overcome such
porous sorbents is considered to be one of the most economi-
problem. In this regard, we have decorated the surface of
cal and efficient approaches. Activated carbons (ACs), zeo-
graphene sheets with nanocrystalline iron oxide (Fe3O4) par-
lites, molecular sieves, metal organic frameworks (MOFs)
ticles and demonstrated the higher adsorption capacity of
and templated carbon adsorbents along with their surface
resulted nanocomposite even at elevated temperatures. In the
modifications are widely reported for CO2 capture from dif-
present work, high pressure CO2 adsorption study is per-
ferent process streams.3–9 ACs generally show higher
formed with Sieverts apparatus at three different tempera-
capacity than zeolites at pressures above atmospheric pres-
tures 25, 50, and 100  C and the nature of interaction is
sure and are often preferred over zeolites because of their
confirmed using Fourier transform infrared (FTIR) spectros-
relatively moderate strengths of adsorption for gases, which
copy. Recovery of material has been examined by degassing
facilitates easier desorption.10–12
the adsorbed CO2 from nanocomposite at 150  C in a vac-
ACs indicate CO2 adsorption in the range 5–25 mmol
uum of 109 bar.
g1 at room temperature and 12–35 bar pressures.13,14 Under
similar pressure and temperature conditions, zeolites and
other porous materials shows low adsorption capacity in the II. EXPERIMENTAL SECTION
range 3–5 mmol g1.11,15,16 Chemical interaction of CO2 A. Nanocomposite synthesis and characterization
with metal oxides (CaO, MgO, etc.), lithium zirconates,
hydrotalcites, barium and strontium titanates, etc. has also Iron oxide decorated graphene (Fe3O4-HEG) nanocom-
been examined.17–19 Carbon based nanostructures like car- posite was prepared in two steps. In initial step, graphene
bon nanotubes, graphene can act as adsorbents for CO2 due was synthesized by hydrogen induced thermal exfoliation of
to their high surface area and porosity.20,21 Our earlier graphite oxide at 200  C,24 prepared by oxidation of graphite
reports indicates high degree of CO2 capture in multiwalled (Sigma Aldrich, USA) using Hummer’s method.25 As pre-
pared graphene sheets was named as hydrogen exfoliated
a)
Telephone: þ91-44-22574862. Fax: þ91-44-22570509. Electronic mail: graphene (HEG). In second step, nanocrystalline Fe3O4 par-
ramp@iitm.ac.in. ticles were decorated over HEG by chemical route using

0021-8979/2014/116(6)/064306/5/$30.00 116, 064306-1 C 2014 AIP Publishing LLC

V

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
130.191.17.38 On: Sun, 09 Nov 2014 17:22:59
 064306-2 A. K. Mishra and S. Ramaprabhu
FeCl3.6H2O, FeSO4.7H2O and ammonia solution (Across
Organics) as published elswhere.26
Surface morphology was studied using FEI Quanta 200
Scanning Electron Microscope (SEM) with energy disper-
sive X-ray (EDX) system, while structural morphology by
Technai G20 Transmission Electron Microscope (TEM) at
the voltage of 200 kV in high vacuum of 1011 bar. The crys-
talline nature of Fe3O4-HEG was examined by X-ray diffrac-
tion (XRD) using X’pert PRO, PANalytical diffractometer
with nickel-filtered Cu Ka radiation (k ¼ 1.54 Å). X-ray pho-
toelectron spectroscopy (XPS) analysis was performed to
confirm the magnetite phase in nanocomposite using an
Omicrometer nanotechnology X-ray photoelectron spec-
trometer. Vibrational characteristic was examined by Perkin
Elmer Spectrum1 FTIR instrument. Porous nature of nano-
composite was studied using Micromeritics ASAP 2020 ana-
lyser by out gassing the sample at 150  C for 12 h.
B. Adsorption-desorption experiment
Measurement of CO2 capture capacity of Fe3O4-HEG
was studied using high pressure Sieverts apparatus.22
Capture capacity was measured by pressure reduction in con-
stant volume using van der Waals gas equations. The adsorp-
tion experiments were performed in the pressure range of
3–13 bar at 25, 50, and 100  C. In each cycle, first evacuation
of chamber was performed using rotary and diffusion pump
and CO2 gas was allowed at particular pressure and tempera-
ture. The pressure reduction was observed in the chamber
due to the adsorption of CO2 in nanocomposite and the sys-
tem was allowed to reach equilibrium. Each cycle of adsorp-
tion experiment was followed by degassing of CO2 at 150  C
under the vacuum of 109 bar. Following to desorption,
adsorption experiments were repeatedly performed to ensure
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
130.191.17.38 On: Sun, 09 Nov 2014 17:22:59
J. Appl. Phys. 116, 064306 (2014)
the reversibility of CO2 capture capacity and recovery of
nanocomposite.
III. RESULTS AND DISCUSSION
A. Morphology study
SEM and TEM images of Fe3O4-HEG nanocomposite
are given in Figs. 1(a) and 1(b), respectively. Figure 1(a)
shows the surface morphology of the nanocomposite indicat-
ing differently oriented graphene sheets decorated with
Fe3O4 nanoparticles over the surface. Figure 1(b) shows the
structural morphology indicating nearly uniform distribution
of Fe3O4 nanoparticles over graphene sheets. Figure 1(c)
shows the EDX analysis indicating the presence of Fe, C,
and O elements suggesting the purity of Fe3O4-HEG. Figure
1(d) depicts the histogram of EDX analysis suggesting the
average loading of Fe3O4 nanoparticles around 25 wt. % in
nanocomposite.
B. X-ray diffraction and XPS analysis
Figure 2(a) shows the XRD pattern for graphite oxide,
HEG and Fe3O4-HEG. XRD pattern of graphite oxide
shows peak at 10.6 , corresponding to the (001) diffraction
peak. Oxidation of graphite leads to the increase in
d-spacing. XRD pattern of HEG shows a very low intense
peak around 24.4 , indicates the distorted graphite structure
and hence suggests the formation of graphene sheets.24
XRD pattern of Fe3O4-HEG depicts the peaks at 2h values
of 30.5 , 36 , 43.5 , 53.8 , 57.5 , 63.1 , and 74.6 , corre-
sponding to the different planes of face centred cubic struc-
ture of Fe3O4 nanoparticles.26–28 Average size of Fe3O4
nanoparticles is found around 15 nm using Scherer’s for-
mula. Formation of Fe3O4 phase in nanocomposite was also
FIG. 1. (a) SEM, (b) TEM, and (c)
EDX images of Fe3O4-HEG, (d)
Histogram of loading in different
regions of Fe3O4-HEG.
 064306-3 A. K. Mishra and S. Ramaprabhu
confirmed with XPS analysis. Magnesium K alpha radiation
was used for X-ray generation. Figure 2(b) shows the wide
scan spectrum of the hybrid material. The photoelectron
lines at binding energy of about 284, 530, 713, and 727 eV
are attributed to the C 1s, O 1s, Fe 2p3/2, and Fe 2p1/2,
respectively. These lines clearly suggest the Fe3O4 phase in
Fe3O4-HEG nanocomposite.22
C. Surface area analysis
Figure 3 shows the N2 adsorption-desorption isotherm
for nanocomposite. Surface area is calculated using
Brunauer-Emmett-Teller (BET) equation. The specific sur-
face area of the material is observed around 98.2 m2 g1
using BET equation. The inset image in Figure 3 shows
the pore size distribution in Fe3O4-HEG nanocomposite.
The Barrett, Joyner, and Halenda (BJH) method was
used to calculate the pore size distribution. The pore vol-
ume was found to be 0.31056 cm3 g1 using BJH method
with the major number of pores having average diameter
around 3.8 nm, indicating the mesoporous nature of
nanocomposite.
FIG. 3. N2 adsorption-desorption isotherm for Fe3O4-HEG nanocomposite,
inset image shows its pore size distribution.
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
130.191.17.38 On: Sun, 09 Nov 2014 17:22:59
J. Appl. Phys. 116, 064306 (2014)
FIG. 2. (a) XRD pattern of Graphite
oxide, HEG and Fe3O4-HEG (b) XPS
analysis of Fe3O4-HEG.
D. Adsorption isotherms and temperature variation
Number of moles of adsorbed CO2 was measured by
calculating the number of moles of gas in the system before
and after adsorption process using van der Waals gas equa-
tion.22–24 Amount of CO2 adsorbed in moles was measured
by following equations:
Dnadsorbed ¼ ni  ðn0 þ n00 Þ; (1)
where “ni” is the number of mole of CO2 in the initial vol-
ume “Vi” at the known initial pressure “Pi”. n0 is the number
of moles in “Vi” at equilibrium pressure “Peq” and n00 is the
number of moles in cell volume Vc at equilibrium pressure
Peq. The gas constants a ¼ 3.67  101 J m3 mol2 and
b ¼ 4.32  105 m3 mole1 were used in van der Waals gas
equation for CO2.
Figure 4 shows the adsorption isotherms for CO2 capture
in nanocomposite. It clearly depicts the increase in CO2 cap-
ture capacity with pressure at each temperature. Increase in
capture capacity with pressure may be attributed to the mul-
tilayer adsorption of CO2 and its improved interaction with
nanocomposite at higher pressures. Adsorption capacities of
nearly 60, 35, and 24 mmol g1 were observed at 11 bar
FIG. 4. CO2 adsorption isotherms for Fe3O4-HEG nanocomposite at differ-
ent temperatures.
 064306-4 A. K. Mishra and S. Ramaprabhu J. Appl. Phys. 116, 064306 (2014)

TABLE I. Comparison of other solid sorbents for CO2 capture capacity. clearly shows that at each pressure, CO2 capture capacity
decreases with increase in temperature. This decrease in cap-
Pressure (bar)/ Capture capacity
ture capacity is directly associated with larger kinetic energy
Material temperature (  C) (mmol g1) Reference
of CO2 molecules at higher temperature. At higher tempera-
Molecular Seive 13X 12/25 4–4.5 11 ture, CO2 molecules hold high rate of mobility due to their
Maxsorb AC 35/25 25 13 increased kinetic energy. This results in the lower interaction
ACs 12/25 10–15 14 of CO2 molecules with porous surface of nanocomposite and
13X Zeolite 12/25 3.2 15 Fe3O4 nanoparticles and hence in lower CO2 capture.30 It
MCM Silica 12/25 5 16
shows the CO2 capture capacity of 69.1 mmol g1 at 12 bar
MWNTs 11/25 14.3 22
and 25  C. This capacity decreases to 30.6 mmol g1 at
Fe3O4-MWNTs 11/25 49 22
Graphene 11/25 11.7 23
100  C equivalent to 56% reduction in capture capacity. At
Fe3O4-Graphene 11/25 60 Present work the pressure of 4 bar, CO2 capture capacity is found to be
11.5 and 6.9 mmol g1 at 25 and 100  C, respectively. It is
equivalent to 40% reduction in capture capacity.
pressure and 25, 50, and 100  C, respectively. These adsorp-
tion capacities were found higher than that of pure HEG as
E. FTIR Spectroscopy Analysis
reported earlier.24 Adsorption capacities of 21.6, 18, and
12 mmol g1 were observed for pure HEG at 11 bar pressure FTIR spectroscopy was performed for Fe3O4-HEG with
and 25, 50, and 100  C temperatures, respectively.24 and without CO2 capture to confirm the nature of interaction.
Although the specific surface area of Fe3O4-HEG (98.2 m2 Figure 6 shows the FTIR spectra of as prepared Fe3O4-HEG
g1) was lower than that of HEG (443 m2 g1),24 it shows nanocomposite and CO2 captured Fe3O4-HEG nanocompo-
higher sorption capacity compared to pure HEG. This clearly site. FTIR study of Fe3O4-HEG nanocomposite confirms the
indicates that the physical adsorption of CO2 is not the only presence of ¼CH- (1578 cm1), >C¼C (1729 cm1), -CH2
mechanism for CO2 capture in Fe3O4-HEG nanocomposite, (2850, 2918 cm1), and –OH (3433 cm1) functional groups
as it depends on surface area and porosity. This suggests that over its surface.31 A broad band is observed in the range
an additional mechanism is involved which results in higher 1000–1200 cm1, which may be associated with the vibra-
CO2 capture capacity of nanocomposite. This additional tions of >C¼O. Along with these functional groups, a peak
mechanism is related to the chemical interaction of CO2 with occurs around 598 cm1, which may corresponds to the
Fe3O4 nanoparticles in nanocomposite.29 Thus, Fe3O4-HEG stretching vibration of Fe-O-Fe in Fe3O4.32
nanocomposite shows the physical as well as chemical inter- In case of CO2 captured Fe3O4-HEG nanocomposite,
action with CO2 and hence physicochemical adsorption of additional peaks were observed corresponding to the asym-
CO2 is responsible for high CO2 capture in nanocomposite. metric stretching of CO2 molecules (2332 cm1), (O-C-O)
This mechanism is further confirmed using spectroscopy symmetric vibrational mode of bicarbonates (1384 cm1)
studies. Capture capacity of Fe3O4-HEG nanocomposite is and (C-O) symmetric vibrational mode of carbonates (1044,
found higher than other solid sorbents under similar condi- 1094 cm1). Enlarged spectrum of CO2 captured Fe3O4-
tions as summarized in Table I. HEG is shown as inset in Figure 6. Asymmetric stretching of
Figure 5 shows the variation in CO2 capture capacity of
Fe3O4-HEG with temperature at different pressures. It

FIG. 6. FTIR spectra of Fe3O4-HEG nanocomposite with and without CO2

FIG. 5. Variation in CO2 captures capacity of Fe3O4-HEG nanocomposite capture, inset image shows the enlarged peaks in the range 1200–2900 cm1
with temperature. for CO2 captured nanocomposite.

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
130.191.17.38 On: Sun, 09 Nov 2014 17:22:59
 064306-5 A. K. Mishra and S. Ramaprabhu J. Appl. Phys. 116, 064306 (2014)

CO2 confirms the physical adsorption of CO2,33,34 while

5
vibrational modes of bicarbonates and carbonates confirm
6
the chemical interaction of CO2 with Fe3O4 nanoparticles.35
Formation of bicarbonates may be due to the strong interac- 7
8
tion of CO2 with the hydroxyl groups attached to the Fe3O4
nanoparticles. Addition to these extra peaks, shifts were 9
observed in other peaks of Fe3O4-HEG and large shift was 10
11
observed stretching vibration of Fe-O-Fe (now at
578 cm1). Large shift in stretching vibration of Fe-O-Fe 12
and presence of vibrational modes of bicarbonates and car-
bonates suggest the high degree of interaction of CO2 with 13
Fe3O4 nanoparticles in nanocomposite. Thus, FTIR spectros-
14
copy confirms the physicochemical adsorption of CO2 in
15
Fe3O4-HEG nanocomposite.
16
IV. CONCLUSION
17
High CO2 capture capacity of Fe3O4-HEG nanocompo-
18
site at high pressures and temperatures is reported. In best of
our knowledge, this is the first study demonstrating the phys- 19
icochemical interaction of CO2 with Fe3O4-HEG nanocom-
posite at elevated pressures and temperatures. The nature of
20
the CO2 interaction with nanocomposite was confirmed
using FTIR spectroscopy. The chemical interaction of CO2 21
with Fe3O4 nanoparticles along with physical adsorption
22
leads to the higher CO2 capture capacity of Fe3O4-HEG
23
nanocomposite compared to the other metal oxide and car-
24
bon materials reported earlier. Additionally, facile synthesis 25
of nanocomposite and desorption of CO2 for repeated use of
26
nanocomposite makes it commercially attractive.
27
28
ACKNOWLEDGMENTS
29
The authors acknowledge the supports of IITM, Office
of Alumini affairs IITM and DST, India. One of the authors 30
(A. K. Mishra) is thankful to DST, India for providing the
31
financial support during the work. Authors are also thankful
to Department of chemistry and SAIF, IIT Madras for 32
helping in surface area, XPS and FTIR analysis.
33
1
B. Hileman, Chem Eng News 84, 7 (2006).
2 34
A. Hui, F. Bo, and S. Shi, Carbon 47, 2396 (2009).
3
G. P. Hao, W. C. Li, and A. H. Lu, J. Mater. Chem. 21, 6447 (2011).
4 35
P. D. Jadhav, S. S. Rayalu, R. B. Biniwale, and S. Devotta, Curr. Sci. 92,
724 (2007).
P. D. Jadhav, R. V. Chatti, R. B. Biniwale, N. K. Labshetwar, S. Devotta,
and S. S. Rayalu, Energy Fuels 21, 3555 (2007).
X. Xu, C. Song, J. M. Anderson, B. G. Miller, and A. W. Scaroni,
Micropor. Mesopor. Mater. 62, 29 (2003).
J. R. Karra and K. S. Walton, J. Phys. Chem. C 114, 15735 (2010).
B. Mu, P. M. Schoenecker, and K. S. Walton, J. Phys. Chem. C 114, 6464
(2010).
L. Wang and R. T. Yang, J. Phys. Chem. C 116, 1099 (2012).
S. Sircar, T. C. Golden, and M. B. Rao, Carbon 34, 1 (1996).
R. V. Siriwardane, M. Shen, E. P. Fisher, and J. Poston, Energy Fuels 15,
279 (2001).
T. D. Burchell, R. R. Judkins, M. R. Rogers, and A. M. Williams, Carbon
35, 1279 (1997).
S. Himeno, T. Komatsu, and S. Fujita, J. Chem. Eng. Data 50, 369
(2005).
Z. Zhang, M. Xu, H. Wang, and Z. Li, Chem. Eng. J. 160, 571 (2010).
S. Cavenati, C. A. Grande, and A. E. Rodrigues, J. Chem. Eng. Data 49,
1095 (2004).
Y. Belmabkhout, R. S. Guerrero, and A. Sayari, Chem. Eng. Sci. 64, 3721
(2009).
G. Pacchioni, J. M. Ricart, and F. Illas, J. Am. Chem. Soc. 116, 10152
(1994).
Q. Wang, J. Luo, Z. Zhong, and A. Borgna, Energy Environ. Sci. 4, 42
(2011).
J. D. Baniecki, M. Ishii, K. Kurihara, K. Yamanaka, T. Yano, K.
Shinozaki, T. Imada, and Y. Kobayashi, J. Appl. Phys. 106, 054109
(2009).
M. Cinke, J. Li, C. W. Bauschlicher, Jr., A. Ricca, and M. Meyyappan,
Chem. Phys. Lett. 376, 761 (2003).
A. Ghosh, K. S. Subrahmanyam, K. Sai Krishna, S. Datta, A. Govindaraj,
S. K. Pati, and C. N. R. Rao, J. Phys. Chem. C 112, 15704 (2008).
A. K. Mishra and S. Ramaprabhu, Energy Environ. Sci. 4, 889 (2011).
A. K. Mishra and S. Ramaprabhu, RSC Adv. 2, 1746 (2012).
A. K. Mishra and S. Ramaprabhu, AIP Adv. 1, 032152 (2011).
W. Hummers, Jr. and R. E. Offeman, J. Am. Chem. Soc. 80, 1339
(1958).
A. K. Mishra and S. Ramaprabhu, J. Phys. Chem. C 114, 2583 (2010).
Z. Shu and S. Wang, J. Nanomater. 2009, 340217.
T. Missana, C. Maffiotte, and M. Garcıa-Gutierrez, J. Colloid Interface
Sci. 261, 154 (2003).
S. G. Wang, X. Y. Liao, D. B. Cao, C. F. Huo, Y. W. Li, J. Wang, and H.
Jiao, J. Phys. Chem. C 111, 16934 (2007).
X. Xu, C. Song, J. M. Anderson, B. G. Miller, and A. W. Scaroni, Energy
Fuel 16, 1463 (2002).
U. J. Kim, C. A. Furtado, X. Liu, G. Chen, and P. C. Eklund, J. Am.
Chem. Soc. 127, 15437 (2005).
Y. Liu, W. Jiang, Y. Wang, X. J. Zhang, D. Song, and F. S. Li, J. Magn.
Magn. Mater. 321, 408 (2009).
W. M. Hlaing Oo, M. D. McCluskey, A. D. Lalonde, and M. G. Norton,
Appl. Phys. Lett. 86, 073111 (2005).
W. L. Yim, O. Byl, J. T. Yates, and J. K. Johnson, J. Chem. Phys. 120,
5377 (2004).
J. Baltrusaitis, J. H. Jensen, and V. H. Grassian, J. Phys. Chem. B 110,
12005 (2006).

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
130.191.17.38 On: Sun, 09 Nov 2014 17:22:59