Interesting Properties of Strained or Defective Graphene

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Interesting Properties of Strained or Defective Graphene

Acknowledgement to

National Research Foundation, Andrew Wee TS, Antonio Castro Neto, O. Barbaros Contributions by

Lu Jiong (NUS), Su chenliang (NUS) Candy Lim Yixuan (NUS)

Kian Ping LOH

Department of Chemistry, National U of Singapore Graphene Research Centre

ACS NANO 2013 7(10), 8350

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Graphene (dry)

Grown by dry CVD process Planar structure

High π electron density bonding interactions

Governed by -  interactions

Graphene-oxide (wet)

Wet chemistry, from graphite Non-stoichiometric COx

Complex interplay of ionic and non-ionic intercations

Nature Nanotechnology 5, 2010, 574 Science 324, 2009, 1312

Pioneers: Rodney Ruoff, (U Texas) Byung Hee Hung (SKKU)

A giant polyaromatic framework that can mediate multiple interactions

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A consequence of graphene being a soft membrane is that it can be strain-

engineered to become highly corrugated by modifying its adhesion to the

substrate.

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As a soft membrane – Graphene is easily rippled

I. Nanoripples

Nanoripple density ~ 1.5 per um

CVDG/SiO2 with high density nanoripples

Typical Cu surface after growth

Step edges (terrace) density~ 2.5 per um

Zhao wang et. al.

Electron-flexural phonon scattering in such partially suspended graphene devices

introduces anisotropic charge transport and limits charge mobility. Influence of Flexural phonon is reduced under tension. Applying weak strain may be enough

Guangxin Ni, O. Barbaros, ACS NANO, 6(2012) 1158

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1. Periodically Strained Graphene

as a Reaction Breadboard

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RT

1300 K for 3-5 mins

40 nm Single crystal graphene

2 nm

Θ> 1ML C60

 T > 1000 oC

 Annealing 3 mins

Graphene Moire Superstructure on Ruthenium:

A Strained Reaction Breadboard

buckling instability

due to the compressive strain between lattice- mismatched Ru and G

produces moire pattern

One inspiration from looking at the periodic blisters on the Moiré superlattice is the

remarkable resemblance of these blisters to an ordered array of nano-bubbles !!

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d. H adsorption at room temperature, random cluster e. After annealing to 300 deg C, ordered cluster

on bright regions of moire = hump.

f,g: after annealing to cause H desorption

Hump region is a sink for diffusing H atoms Yu Wang and K. P. Loh, ACS NANO, 4, 6146 (2010)

Moire Superlattice as Reaction Breadboad:

Example 1: Selective Hydrogenation Occurs on the Hump Region of the Moire

Superlattice

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C60 in the hump

C60 in the valley

C60 in the rim

In one unit cell,

Rim: hump: valley = 6:1:1 A

B

Reaction Breadboard

Example 2: Contrasting Potential Energy Landscape on the Moire Surface

Rotation of C60 frozen on Moire Valley BUT free Rotation of C60 on Moire Hump Jiong Lu, K. P. Loh, ACS Nano, 2012, 6 (1), pp 944–950

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Using the Graphene Moiré Pattern for the Trapping of C60 and Homoepitaxy of Graphene Jiong Lu, K. P. Loh, ACS Nano, 2012, 6 (1), pp

944–950

C60: electron acceptor

Bonded most favorably to hcp site due to back transfer Of electron from metal to Graphene

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2. Engineering Strain in

Graphene by forming Bubbles

(a) Couple dirac particles to strain via pseudomagnetic field

(b) How to control such strain

patterns at the nanoscale ?

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1. Graphene blisters are formed due to the uniform compressive strain associated with the lattice-mismatched ruthenium and

graphene.

2. Oxidation releases Elastic Strain and Moire Blisters sinter to form bubbles

Engineer Graphene Nanobubble

from the Moire Blisters

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150x150 nm

•Defective Moire Pattrern due to sub-surface defects on metal

•Bubbles are more inclined to appear on defective Moire Site

Transforming Graphene Moire Blisters into Geometric Nanobubbles

Jiong Lu, Antonion C. Neto, Kian Ping Loh*, Nature Communcations, 8;3:823.(2012)

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Bubbles appear on site that has defective

Moire pattern, and these can be seeded by

Ion Beam Irradiation

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L: 3.0 nm Triangular 3-D STM image

Transforming Graphene Moire Blisters into Geometric Nanobubbles Jiong Lu, Antonion C. Neto, Kian Ping Loh*,

Nature Communcations, 8;3:823.(2012)

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Decouple graphene and

merging of 5 blisters

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5.65 ??虠蹽 皐 ?皐?r

0.00 ??虠蹽 皐 ?皐?ü

5.56 Å

0

5.65 ??虠蹽 皐 ?皐?r

0.00 ??虠蹽 皐 ?皐?ü

3.05 Å

0

Merging of 7 blisters to form hexagonal bubbles

(B)

8.26 ??虠蹽 皐 ?皐?(

0.00 ??虠蹽 皐 ?皐?'

8.26 Å

0 Merging Continuous bubbles Bubbles dots

more O2 High T

STS: More-like free-standing graphene

Transforming Graphene Moire Blisters into Geometric Nanobubbles,

Jiong Lu, Antonion C. Neto, Kian Ping Loh*, Nature Communcations, 8;3:823.(2012)

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Sintering the Moire Blisters to Make Geometrically well defined Graphene Bubbles With Giant

Pseudomagnetic Field

pseudo-magnetic fields as large as 650 T and electronic gaps of order of 0.8 eV.

the LL energy expected in graphene scales according to E/B1/2

The electronic gaps associated with these

pseudo-magnetic fields are of the order ΔE(eV)

≈ 0.03 [B(T)]1/2 and hence they vary from 0.3 eV to 0.8 eV

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Strain field higher at the edges of graphene bubble versus the center

This results in shifts of the Landau level peaks in the STS curves towards higher energies for regions of bubbles near the edges

A B C

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3. Observing Chemistry Inside Graphene

Nanobubbles

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A hydrothermal anvil made of graphene bubbles ?

No clear insight into how graphene interfaces with diamond

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GRAPHENE NANOBUBBLE MAT FORMED ON DIAMOND

A hydrothermal Anvil made of Graphene nanobubbles on diamond

Candy Su, Kian Ping Loh*

Nature Communications 4, 1556, (2013)

The pressure that is built up in a typical Graphene nanobubble of 2 nm in height and 10 nm in radius is calculated to be

approximately 1 GPa

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1st order

Diamond phonon

peak G

D 2D

1150 cm-1 (mixed sp2/sp3 and

transpolyacetylene D peak Graphene 1360 cm-1

Red shift upon the formation of bubbles - These

observations suggest that the lattice of graphene is biaxially strained

Before heating

After heating to induce bubble formation

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Cyclic voltammetry of Fe(CN)63-/4- redox couple

• Inner sphere redox couple ,

sensitive to density of electronic states and surface microstructure

• Charge transfer rate calculated follows the order of

GNBs on diamond> Diamond> flat G on diamond

Outward rotation of orbitals enhances local density of states and bestows higher

reactivity on the outer surface of the GNB,

however Inner surface is less reactive pz orbital isosurface wavefunction of flat and curved graphene calculated using density functional theory (DFT, at B3LYP/6-31G*).

Graphene Bubbles are

electrochemically more active than flat surface !!

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Strong hydrogen bonding results in a

weakening of the OH oscillator, a red shift in energy and a broadening of the spectral peak

.

A hydrothermal Anvil made of Graphene nanobubbles on diamond

Candy Su, Kian Ping Loh*

Nature Communications 4, 1556, (2013)

Probing the bonding dynamics of

water trapped within Graphene nanobubbles using FTIR:

Bench top hydrothermal anvil cell

The critical temperature of water is 647 K,, 2 MPa

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A significantly reduced dielectric constantof supercritical water allows it to act as an aggressive solvent for organic material

DIAMOND CAN BE CORRODED

BY SUPERHEATED WATER !

The pressure that is built up in a graphene nanobubble 2 nm in height

and 10 nm in radius is calculated to be approximately 1 GPa

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Calibrating the pressure inside the bubbles using pressure sensing

molecules

IR-active modes in polyphenyl molecules that become inactive upon the phase transition from the twisted to the planar

conformation.

Upon planarization, certain IR-active peaks become IR-forbidden.

We would expect to see 6 modes disappear from the spectrum if p-terphenyl belongs to the C2h group, 29 modes if it belongs to the D2 group, and 51 modes if the

molecule has C2 symmetry. These

‘‘disappearing peaks’’

comprise a special subset of vibrational modes

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Monitoring the vanishing of out-of-plane vibrational modes in P-Terphenyl: “ pressure

induced flatterning of the molecules”

Similarly, by increasing the temperature, certain out-of-plane modes of p-terphenyl were found to disappear. These peaks are indicated by arrows.

The recovery of these peaks are also observed upon cooling of the sample.

100 200 300 400 500 690

695 840 850 860

Wavenumber (cm-1 )

Temperature (oC)

600 800 1000 1200 1400 1600

Transmittance (Arb.)

Wavenumber (cm-1)

25oC 500oC

Cooled (25oC)

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What is the pressure in Graphene Nanobubbles?

Graph plotted based on values that has been reported

Phy. Rev. B 45, 12682-12690.

J. Chem. Phys. 99, 3137-3138.

J. Chem. Phys. 114, 5465-5467.

Phys. Rev. Lett. 82, 3625-3628.

100 200 300 400 500

0.3 0.6 0.9 1.2 1.5

Pressure (GPa)

Beyond temperature (

o

C)

Based on our experiments and with reference from previously reported values, we could draw a correlation between temperature and

pressure.

Using this relationship that we derive, we can heat the sample with C60 and determine the pressure at which it undergoes polymerization.

biphenyl

terphenyl

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Oligomerization/Polymerization of Fullerene: Pressure-driven [2+2] Cycloaddition

[2+2] cycloaddition of C60 is symmetry forbidden due to mismatch of MOs.

-Molecular C60: 4 sharp IR modes

-Intermolecular bonding (lowers symmetry) changes vibrational spectra drastically

-Phase transformation of C60 in GNB under different stages of polymerization

Angewandte Chemie

Candy Lim, Kian Ping Loh*

(Accepted) 2013

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4. Technological Implications of

Graphene Nanobubbles (a) Optical effects

(b) Surface Tension effects

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Part II

• Porous Graphene Oxide

• Highly defective relative to CVD

graphene/mechanically exfoliated graphene

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to improve its catalytic efficiency Study its catalytic origin

Probing the Catalytic Activity

of Graphene Oxide and its origin ,

Chen Liang Su and Kian Ping Loh* et. al., Nature Communications, 3, 1298 (2012)

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K. P. Loh JACS., 2011, 133 (23), pp 8888

K. P. Loh, Nature Chemistry 2, 12, 1015 (2011) K. P. Loh JACS, 2010, 132, 41, pg 14481

K. P. Loh. Angewandte Chemie International Edition, 49 (37), 2010, pp 6549

K. P. Loh JACS., 2012, DOI: 10.1021/ja211433h

K. P. Loh JACS., 2010, 132 (32), pp 10976 K. P. Loh JACS., 2009, 131 (46), pp 16832

K. P. Loh JACS., 2008, 130 (44), pp 14392

GRAPHENE OXIDE MEDIATES MULTIPLE SYNTHETIC TRANSFORMATION

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Seeding Ice Growth At Room temperature

Using Nano Graphene Oxide

Zheng Yi and K. P. Loh

Angewandte Chemie 2013

52, Issue 33, 8708–8712

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Hot spots for catalytic action!

All these “imperfections” help to mediate its catalytic properties!

Perfect Graphene

Solid Acid

Solid base

Oxidative nature

N

B N

N

N

O

O OH

O OH OH HO R2N

Amine

Pyridine

O O

O

O Defective Graphene COOH

SO3H

Spin

Red-ox sites

Su C. and Loh, K. P. Acc. Chem. Res. DOI: 10.1021/ar300118v.

These complex cocktails

of functionalities may act in concert during catalysis via hydrogen bonding, ionic

complexation, radical stabilization etc.

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Isolated debris

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Element Graphite GO ba-GO

Mn 45.085 ppmb 304.6516 ppm < 1.0 ppm

Fe 1050.1785 ppm 204.2784 ppm 96.3118 ppm

Zn 94.8833 ppm 35.71 ppm 2.5735 ppm

Au 3.7233 ppm 1.8551 ppm N. D.

Ru N. D. N. D. N. D.

ICP-MS (Inductively Coupled Plasma-Mass Spectroscopy) Analysis of GO, Graphite and ba-GO.a

a20 mg sample was dissolved by 2 ml of mixture acid (HCl : HNO3 = 3 : 1) and diluted to 10 ml by 5% DI water. bMetal/Sample = 1μg/g.

Before After

Metal impurities were removed.

Su, C. and Loh, K. P. Nat. Commun. 3 : 1298

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Solvent free

ba-GO that is low-cost, non-polluting, reusable Open Air

90 oC, 12 h 5wt%

NH2 N

1 2

ba-GO, O2

Oxidative coupling of benzyl amine as the model reaction

Solvent free (only reactant)

Heterogenous Catalyst that is low-cost, non-polluting, reusable Open Air (safe)

Simply heating Low catalyst-loading

(Efficiency)

An ideal model

Su, C. and Loh, K. P. Nat. Commun. 3 : 1298

N-Benzylbenzaldimines

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Carbocatalyst

ba-GO Nano Au/C

Heterogeneous: self-support

Active catalyst: ba-GO Active catalyst: Au

Heterogeneous: carbon support Total catalyst loading: 5 wt% Total catalyst loading: ~250 wt%

Active catalyst loading: 5 wt% Active catalyst loading: ~2 wt% Au

Reaction Temperature: 363 K Reaction Temperature: 373 K Price of GO/ba-GO: <1 $/g Price of bulk Au: >40$/g

Oxidant: Open Air Oxidant: 5 bar O2

Solvent free Solvent: PhMe

6th reuse: 93% yield 3rd reuse: 68% yield

Therefore, this carbocatalyst can be an ideal replacement for metal catalyst.

Journal of catalysis, 2009, 138-144

Gold catalyst

Vs

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1. Holes could be created and enlarged by the strong base-etching process 2. Some unique functionalities might be introduced in the defects: e. g. spin electron from the non-bonding π electron states are likely to be created at the edges.

The change of morphology before and after base treatment

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0.0 0.2 0.4 0.6 0.8 1.0

Quenched GO

Yield%

ba-GO

a b

c d

Electron Spin Resonance (ESR) measurements confirm the present of unpaired electrons

Edge Spin

This suggests that radical states at the edge sites are important in the catalysis besides carboxylic acid groups

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44% yield

15% yield

89% yield

Controlling the acidic functionalities is important for the reactivity

The significant contribution of the carboxylic acids in this catalysis could be confirmed

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Synergistic effect of acidic groups and spins

H2O2 was detected by the UV- visible absorption spectra (Adding DPD and POD.)

The oxygen radical was trapped by the DMPO spin- trapped EPR spectra

Probing the Catalytic Activity of Graphene Oxide Chen Liang Su and Kian Ping Loh* et. al.,

Nature Communications, 3, 1298 (2012)

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Conclusions

• Strained structures like graphene bubbles afford new energy landscape

• The graphene bubbles can be used as a hydrothermal cell for studying reaction

dynamics at high pressure and temperature

• Defective, porous graphene oxide can be

effective carbocatalyst

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45 1. Face-to-Face Transfer of Graphene Films on Silicon Wafer

Libo Gao, A.H. Castro Neto, Kian Ping Loh*

Nature (2013) Accepted

2. Order-Disorder Transition in a 2-D B-C-N alloy

Jiong Lu, Kai Zhang, Tze Chien Su,, A. H. Castro Neto, Kian Ping Loh*

Nature Communictions (In print, ASAP)

3.Graphene Oxide as a Chemically Tuneable Platform for Optical Applications Kian Ping Loh*, Bao QL, Eda G, Manish Chowalla.

Nature Chemistry, 2, 12, 1015-1024 (2010)

4.Transforming Fullerene Molecules into Graphene Quantum dots, Jiong Lu, Pei Shan Emmeline and Kian Ping Loh*,

Nature Nanotechnology, 6, 247–252, (2011)

5.Graphene as broadband polarizer Q. Bao, Y. Wang, D. Y. Tang, Kian Ping Loh*

Nature Photonics, 5, 411–415 (2011)

6.Transforming Graphene Moire Blisters into Geometric Nanobubbles, Jiong Lu, Antonion C. Neto, Kian Ping Loh*,

Nature Communcations, 8;3:823.(2012)

7. Probing the Catalytic Activity of Graphene Oxide and its origin,

Chen Liang Su and Kian Ping Loh* et. al., Nature Communications, 3, 1298 (2012)

8.A hydrothermal Anvil made of Graphene nanobubbles on diamond Candy Su, Kian Ping Loh*

Nature Communications 4, 1556, (2013)

9. High Yield exfoliation of 2-D chalcogenides using Na Naphthanelide Jian Zheng, Kai Zhang, Kian Ping Loh* et. a. Nature Communications

10. The chemistry of ultra-thin transition metal dichalcogenide nanosheets

Manish Chhowalla, Goki Eda, Kian Ping Loh et. al. Nature Chemistry 5, 263 (2013)

References

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