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Materials Chemistry and Physics 189 (2017) 111e117

Contents lists available at ScienceDirect

Materials Chemistry and Physics


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

Waved graphene: Unique structure for the adsorption of small


molecules
Hui Pan
Institute of Applied Physics and Materials Engineering, University of Macau, Macao

h i g h l i g h t s

 Adsorption of small molecules on waved graphene is greatly enhanced.


 Strong physical adsorption in the trough of waved graphene can be achieved by tuning the curvature.
 Chemical adsorption is on the crest of waved graphene.
 Exothermic dissociation of H2 and O2 can be realized on waved graphene under high compression.
 Wave graphene can be candidates as catalysts and gas storage/sensor.

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

Article history: We propose waved graphenes for the strong adsorption of molecules and investigate their potential
Received 30 June 2016 applications. We nd that the physical adsorption of molecules on waved graphene is greatly enhanced
Received in revised form by compression. At optimal compression, the physical adsorption energies of H2, N2, NO, and CO are
7 December 2016
increased by 6e9 times, and that for O2 is more than 2 times. We show that the energy for their chemical
Accepted 28 December 2016
Available online 29 December 2016
adsorption on waved graphene decreases dramatically with the increment of compression. The energy of
dissociation of H2 on at graphene is 1.63 eV and reduced to 0.06 eV (96% reduction) on waved graphene
at a compression of 50%, respectively. The energy for chemical adsorption of O2 on waved graphenes is
Keywords:
Molecule adsorption and dissociation
extremely reduced from 0.98 eV to 0.57 eV as with compression increasing from 0 to 50%, indicating
Waved graphenes the transition of endothermic chemical adsorption to exothermic. We further show that the electronic
Catalysis properties of waved graphenes are modied, leading to the change of electrical characters. We see that
First-principles calculation the waved graphenes may nd applications in gas storage, sensor and catalyst because of enhanced
physical and chemical adsorption and the induced change of electronic properties.
2016 Elsevier B.V. All rights reserved.

1. Introduction its applications in sensors, energy storage, and catalysts have


attracted increasing attention [10e13,16,20,22e24,28e39]. To
Since its discovery [1], graphene has triggered extensive enhance its sensitivity and catalytic activity, creating defects (such
research activities in all of science and engineering elds because of as vacancy and edge states), doping (such as nitrogen), and deco-
its intriguing physical and chemical properties and encouraging rating metal clusters have been employed because at graphene is
applications in diverse disciplines, ranging from nanodevices, cat- inert to chemical reaction and molecule adsorption. For example,
alysts, to medicines [2e10]. Its potential applications can be hydrogen storage on graphene can be improved by decorating
extensively broadened by surface modication/functionalization metallic nanoparticles [11,14,38]. Doping can enhance its reactivity
such as doping [11e14], adsorption of molecules [15e21], and in oxygen reduction reaction [12,13,30,31,34]. Although these
decoration of nanoparticles [22e28]. The functionalization can methods made great progress in applications to sensor and catalyst,
efciently tune its physical and chemical properties, leading not the fabrication is complicated and expensive, which limits their
only to multi-functional electronic devices, but to sensors to detect practical applications. Is it possible to utilize as-grown or pure
and catalysts to dissociate particular molecules [11e26]. Recently, graphene to realize these purposes? According to the p-orbital
axis vector (POAV) theory [40e44], the chemical properties of
carbon nanostructure can be tuned by geometry/structure engi-
E-mail address: huipan@umac.mo. neering, because carbon atoms at edges, defects, or regions with

http://dx.doi.org/10.1016/j.matchemphys.2016.12.061
0254-0584/ 2016 Elsevier B.V. All rights reserved.
112 H. Pan / Materials Chemistry and Physics 189 (2017) 111e117

high local curvature are more active than those at at regions starting wavelength (c0) is about 25.7 (referring to the supercell's
[20,29,32,40e43]. The elevated chemical potential and strain en- length of the at graphene along armchair direction), which is
ergy at those locations can strongly accelerate activity in chemical constructed based on the optimized lattice parameter of graphene
reactions (such as catalytic performance) and promote sensitivity (CeC bond length is 1.427 ) [48]. Waved graphenes with shrunk
in molecule adsorption. Recently, we reported that waved graphene wavelength (c), dened as c c0  1  , are realized by com-
showed excellent mechanic, electronic and chemical properties pressing, where ( c0cc
0
 100%) is compression percentage. The
[48]. The wave graphene with periodic ripples showed controllable width of these graphenes is about 12.6 . To investigate the
chemical reactivity under compression, which may nd applica- adsorption of molecule on the waved graphene, all of possible sites
tions in molecule adsorption and dissociation. Experimentally, the to attract molecule are considered, focusing on crest and trough
waved graphene can be easily fabricated by releasing pre-strained because of the strong local chemical potential because other sites
polymer with at graphene [49]. In this work, we investigate the are unfavorable to hold molecules. (Fig. 1). Five kinds of molecules,
adsorption of molecules, including H2, O2, N2, NO, and CO, on wave including H2, O2, N2, NO, and CO, are studied. All of possible
graphenes. We nd that strong physical-adsorption of these mol- adsorption congurations with the consideration of molecule
ecules on waved graphenes can be achieved by tuning compression. orientation to adsorption site on each waved graphene are sys-
We show that hydrogen molecule can be dissociated on waved tematically calculated, for example, NO normal to adsorption site
graphene under moderate conditions and oxygen molecule with by N or O atom. These molecules can be either physically or
extended bond length can chemically adsorb to wave graphene chemically adsorbed on waved graphenes, strongly depending on
through exothermic process, indicating the application of waved the wavelength of waved graphenes.
graphene in catalytic reactions. We further show that the electronic
structures of wave graphene are modied by adsorbed molecule, 3.1. Physical adsorption
leading to its application in gas detectors.
After systematically investigated all of possible adsorption
2. Methods congurations on each waved graphene (wG), the most stable
physical adsorption site is found out by calculating the adsorption
We carry out rst-principles calculations to investigate the energy based on following formula:
physical and chemical adsorption of molecules on waved graphenes
on the basis of the density functional theory (DFT) [50] and the Ead EwG Molecule  EwG  EMolecule (1)
Perdew-Burke-Eznerhof generalized gradient approximation (PBE-
where E(wG Molecule) and E(wG) are the total energies of waved
GGA) [51]. The Vienna ab initio simulation package (VASP) [52]
graphenes with and without molecule, respectively. E(Molecule) is
incorporated with projector augmented wave (PAW) scheme
the energy of the molecule, including H2, O2, N2, NO, and CO, which
[53,54] is used to perform the calculations. k point sampling for
is calculated for an isolated molecule in a supercell. Our calculations
integration over the rst Brillouin zone is based on the Monkhorst
show that the physical adsorption energies of molecules (Ead),
and Pack scheme [55]. A 3  3  1 grid for k-point sampling for
including H2, N2, NO, and CO, on at graphene (0% in compression)
geometry optimization and calculations of density of states,
is very weak (about 10 meV) (Fig. 2), and the physical adsorption
respectively, and an energy cut-off of 500 eV are consistently used
energy of O2 on at graphene is much stronger than others
for the nanoribbons in our calculations. Good convergence is ob-
(about 45 meV). Considering the thermal energy (kBT 25 meV),
tained with these parameters and the total energy was converged
we see that intrinsic at graphene is not ideal for the adsorption of
to 2.0  105 eV/atom.
most of molecules and only O2 can adsorb on at graphene at room
temperature, which is consistent with literature [56]. Interestingly,
3. Results and discussion we nd that the adsorption energy (negative) initially decreases as
the compression increases and reaches an energy minimum
The waved graphenes with various wavelengths (Fig. 1) are (negative) at 10% (Fig. 2). The energies for physical adsorption of
constructed by compressing at graphene under various mechanic
strengths [48], which could be experimentally realized by releasing
pre-strained substrates with at graphenes on top [49]. The

Fig. 1. Representative structure of waved graphene (wG) (a) tilted view and (b) top Fig. 2. Calculated physical adsorption energies of molecules on waved graphenes as a
view with indication of possible adsorption sites. function of compression or wavelength.
H. Pan / Materials Chemistry and Physics 189 (2017) 111e117 113

H2, N2, NO, and CO on waved graphenes at 10% are 70 Table 1
to 80 meV, which are 6e9 times higher than those at 0%, and Physically binding distances of molecules on waved graphene under a compression
of 10% and the bond lengths in adsorbed molecules. Distance: the shortest distance
that for O2 is about 110 meV, which is more than 2 times higher. from molecule to the bottom of the trough.
Then, Ead increases with further increasing compression (Fig. 2). At
50%, Ead for O2 is about 55 meV and those for other molecules H2 O2 N2 NO CO

are 30 to 40 meV. Clearly, we see that physical adsorption of Distance () 3.3 3.4 3.6 3.5 3.7
molecule strongly depends on the wavelength of waved graphene. Bond length () 0.75 1.25 1.11 1.17 1.14

Controllable adsorption of molecule on waved graphene can be


easily achieved by adjusting its wavelength via compression.
graphene. To realize the aim, we purposely put the diatom mole-
The fully relaxed geometries of waved graphenes with physi-
cules directly on the top of CeC bond in parallel or vertically on the
cally adsorbed molecules at 10% (wG-10) show that these
top of C atom at the crest of waved graphene within the distance to
molecules prefer to the troughs of waved graphenes (Fig. 3). Except
form chemical bond. Then, the system is fully relaxed to nd the
O2, the hole site at trough (6 in Fig. 1b) is more possible to stably
energy for chemical adsorption and study its effect on the elec-
hold other molecules (H2, N2, NO, and CO). The top view shows that
tronic property of waved graphene. After the geometry relaxation
there has an angle of about 70 between OeO and CeC bonds on
of waved graphenes with chemically absorbed molecules (wG-
O2-adsorbed wG-10 (Fig. 3c). The calculated adsorption distance
chem-Mo, Mo H2, O2, N2, NO, and CO), we nd that only parallel
and bond length of molecule upon adsorption further conrm their
chemical adsorption is possible, while the molecules in vertical
physical adsorption character (Table 1). For example, the bond
cases move far away from the waved graphenes. The optimized
length of H2 on wG-10 is equal to that calculated in free space. It is
structures show the two atoms in the diatom molecules form
noted that the stable adsorption site is also dependent on the
chemical bonds with C atoms on waved graphenes at a compres-
wavelength of waved graphene. The trough is better than crest
sion ranging from 0 to 50% (Fig. 4 and Fig. S-1 in supporting in-
when < 50%. At 50%, the crest is stable to hold these molecules.
formation). Interestingly, we see that hydrogen molecules are
The calculated adsorption distance may reveal the mechanism on
dissociated with HeH distance increased to 2.12 when chemically
wavelength-dependent physical adsorption. For example, the
adsorbed on waved graphenes (Fig. 4a and Fig. S-1a). The HeC bond
physical-adsorption distance of H2 to graphene is ~3.3 . In the
length is about 1.1 in all of the considered systems. The CeC
trough of waved graphene, the attractive interaction between H2
distance on wG-chem-H2, where C is bonded to H, is extended to
and curved graphene is initially enhanced as the wavelength de-
1.559 at 0% and further increases with the compression
creases and the magnitude increases under compression because
increasing (Fig. 5). The OeO distance in O2 is extended to 1.503
the interaction area within optimal and uniform adsorption dis-
upon its chemical adsorption on graphene and increases as the
tance is increased. Further increasing compression or reducing
compression increases (Fig. 6a). The OeC bond length on wG-
wavelength of waved graphene, the repulsive interaction increases
chem-O2 (Fig. 4b and Fig. S-1b) is 1.499 at 0% and decreases
because the adsorption distance is uneven to the curved graphene,
with the increment of compression (Fig. 6a), and CeC bond upon
leading to reduction of physical-adsorption energy. For example,
O2-adsorption increases from 1.546 to 1.721 with increasing
the half wavelength of waved graphene under 50% is about
from 0 to 50% (Fig. 5). Different from O2, the NeN distance of
6.1 . It is difcult for molecules to stay in trough with adsorption
chemically-adsorbed N2 on waved graphene at 0% is 1.267 ,
distance less than 3.3 due to strong repulsion. Therefore, mole-
keeps unchanged up to 30%, and then decreases to 1.246
cules prefer to crest sites on these waved graphenes under high
when > 30% (inset Fig. 6b). Accordingly, the NeC bond length
compression. Our calculations also show that high gas storage can
decreases from 1.536 to 1.513 with increasing from 0 to 30%,
be achieved by optimal design of the channels in waved graphene.
and jumps down to 1.453 at 40% (Fig. 6b). Closely examining
For example, nanostructured materials possessing pore sizes be-
the optimized structures of wG-chem-N2, we see that CeC bond,
tween 0.7 nm and 1.2 nm may show great potential for hydrogen
where N2 is bonded, increases with the increase of compression
storage [57e59]. The size of channel in waved graphene can simply
and breaks when > 30% (Fig. 4c, inset in Fig. 5, and Fig. S-1c). The
be realized to satisfy the requirement, leading to potential appli-
NeO and CeO bonds in NO and CO on waved graphenes are about
cation in hydrogen storage with enhanced performance. The effects
1.398 and 1.327 , respectively, and are independent of the
of physically-adsorbed molecules on the electronic properties of
compression (Fig. 4d , e and Fig. S-1d, e). The trends of adsorption
waved graphenes should be negligible because of the long binding
distances and CeC bonds on waved graphenes are similar to those
distances and weak physical adsorption energy. Therefore, the
in wG-chem-O2 (Figs. 5, 6c and 6d). Fine views of the optimized
mechanism of physical adsorption is not applicable to gas sensors.
structures of waved graphenes with chemically absorbed mole-
cules show that the C atoms on waved graphenes at 0% with
3.2. Chemical adsorption molecule bonded are dragged up because of sp3 hybridization (S-1).
The effect of hybridization on the local structure in waved graphene
To apply waved graphene in gas sensor and catalysts, it is reduces with the increased compression (decreased wavelength)
necessary to investigate the possibility of chemical adsorption of due to the curvature-enhanced tolerance (S-1). The calculated
molecule and its effect on the electronic property of waved structural parameters on bond lengths and binding distances, and

Fig. 3. The relaxed structures with physical-adsorbed molecules: (a) H2, (b) O2, (c) N2, (d) NO, and (e) CO at the most stable sites on waved graphenes under a compression of 10%.
Up: side view; down: top view.
114 H. Pan / Materials Chemistry and Physics 189 (2017) 111e117

Fig. 4. Optimized structures of waved graphenes with the chemical adsorption of (a) H2, (b) O2, (c) N2, (d) NO, and (e) CO at 40%.

optimized structures of waved graphenes with chemically-


adsorbed molecules clearly indicate that energies need to be
absorbed for the realization of chemical adsorption.
To quantify the chemical adsorption, the chemical adsorption
energy (Echem-ad) is calculated using Eq. (1) based on the optimized
structure, as discussed above (Figs. 4e6 and Fig. S-1). The calculated
energies show that the chemical adsorption for all of considered
molecules on graphene at 0% are endothermic, indicating that
chemical adsorption on at graphene is difcult and even impos-
sible for certain molecules, such as N2 and CO, because of huge
positive chemical adsorption energies (Fig. 7). The Echem-ad on
waved graphene is dramatically reduced and decrease with the
increment of compression (or the reduction of wavelength),
revealing that chemical adsorption on waved graphene may be
realized with less efforts. The chemical adsorption of H2 on at
graphene needs to overcome an energy of 1.63 eV which is reduced
to only 0.06 eV on waved graphene at 50% (96% reduction)
(Fig. 7a). Considering the dissociation of H2 on graphene (Fig. 4a
and Fig. S-1a), we see that waved graphene can split hydrogen
Fig. 5. Calculated C-C distance on waved graphenes with chemically-adsorbed mole- molecules into atoms under moderate conditions, such as room
cules, including H2, O2, NO, and CO at 0, 10, 20, 30, 40, and 50%. The inset shows the temperature. Interestingly, the Echem-ad of O2 is reduced from
C-C distance on waved graphenes with chemically-adsorbed N2.

Fig. 6. Calculated adsorption distance between waved graphene and molecule (a) O2, (b) N2, (c) NO, and (d) CO at 0, 10, 20, 30, 40, and 50%. Inset in (b) shows the N-N distance
upon chemical adsorption.
H. Pan / Materials Chemistry and Physics 189 (2017) 111e117 115

Fig. 7. Calculated chemical adsorption energies of molecules on waved graphenes as a function of compression or wavelength: (a) H2 and O2, and (b) N2, NO, and CO.

Fig. 8. Calculated band structures of waved graphenes with chemically-adsorbed molecules: (a) H2, (b) O2, and (c) NO at 40%.

0.95 eV on at graphene to 0.62 eV on waved graphene with conducting characters of waved graphenes are modied by chem-
50% (Fig. 8a). The negative adsorption energy starts on waved ically adsorbed molecules (Fig. 8). We see that the Dirac cones are
graphene at 30%, indicating that the chemical adsorption of O2 not observable on the band structures of wG-Chem-Mo. Although
is exothermic and the transition of physical adsorption to chemical the conduction band bottom (VBB) and valence band top (VBT)
adsorption occurs. Its large adsorption energy (negative) on waved slightly overlap cross the Fermi level, the conductivity of wG-
graphene at 50% shows that the chemical adsorption of O2 is Chem-Mo is reduced, comparing with pure waved graphene,
favored than physical adsorption on waved graphenes under high where Dirac cone keeps [48]. It is, therefore, predicted that waved
compression. Compared to H2 and O2, N2, NO, and CO are more graphenes under high compression can be used as sensor to detect
difcult to be chemically adsorbed on waved graphenes even under the presence of molecules, such as H2, O2, and NO, because of their
huge compression because of high chemical adsorption energies possible chemical adsorption and induced change in conductivity
(Fig. 7b). The chemical adsorption energies of N2 and CO on at accordingly.
graphenes are about 4.5 eV, and reduced by 30 and 45%, respec-
tively, on waved graphenes at 50%. The chemical adsorption 4. Conclusions
energies of NO is reduced from 2.79 eV on at graphene to 1.38 eV
on waved graphenes at 50%, indicating the chemical adsorption In summary, we report a rst-principles study on the physical
of NO on waved graphene is more possible than N2 and CO under and chemical adsorption of molecules on waved graphenes. We
suitable conditions. The calculated chemical adsorption energy of nd that the physical adsorption on at graphene is very weak and
molecule on waved graphene is more or less reduced with the greatly enhanced on waved graphene, where the enhancement is
increment of compression because of enhanced local chemical dependent on its wavelength. We show that strongest physical
potential at high curvature [40e48]. The enhanced chemical adsorption of molecules on waved graphene can be achieved by
adsorption of molecules on waved graphenes demonstrates that tuning the compression (or wavelength) due to the competition
certain applications can be realized by engineering the geometry of between van der Waals and repulsive forces, demonstrating
graphene. For example, the extension of chemical bond in H2 and possible application for gas storage. We further show that chemical
O2 and their easy chemical adsorption indicate the potential adsorption of molecules on at graphene is impossible or needs to
application of waved graphenes, pure carbon nanostructures, as absorb huge energy, but can be easily realized on waved graphene
catalysts in oxygen reduction reactions (ORR) or hydrogen evolu- under high compression, where the positive chemical adsorption
tion reaction (HER). Furthermore, the chemical adsorption may energy is greatly reduced, even the chemical adsorption becomes
strongly affect the electronic properties of waved graphenes, exothermic. Hydrogen molecule can be dissociated into atoms on
leading to their application in sensor. waved graphene under high compression by overcoming a weak
The calculated electronic structures clearly show that their chemical adsorption energy as small as of 0.06 eV. The positive
116 H. Pan / Materials Chemistry and Physics 189 (2017) 111e117

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