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M. Thandavarayan and A. Manthiram, J. Mater. Chem. A, 2016, DOI: 10.1039/C6TA01349J.
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ARTICLE
Received00thJanuary20xx,
Accepted00thJanuary20xx
CobaltOxidecoatedNandBdopedGrapheneHollowSpheresas
aBifunctionalElectrocatalystforOxygenReductionandOxygen
EvolutionReactions
DOI:10.1039/x0xx00000x
ZhongqingJiang,a,bZhongJieJiang,*cThandavarayanMaiyalaganbandArumugamManthiram*b
www.rsc.org/
A simple and scalable method has been developed for the synthesis of Co3O4coated N and Bdoped graphene hollow
spheres (Co3O4/NBGHSs). These Co3O4/NBGHSs are highly active for both oxygen reduction and evolution reactions and
can exhibit higher electrocatalytic activities and better durability than the commercial Pt/C and RuO2/C, respectively,
demonstratingthemtobeefficientbifunctionalelectrocatalysts.IndepthanalysisshowsthatthecouplingbetweenCo3O4
andNBGHSs,thestronginteractionwithadsorbedO2,thehighelectricconductivity,andthespecifichollowstructureplay
important roles in imparting the higher electrocatalytic activities to the Co3O4/NBGHSs. When tested as the cathode
catalystsforZnairbattery,theCo3O4/NBGHSsexhibitbetterperformanceandhigherstabilitythanthePt/Ccatalystand
other catalysts reported previously. This strongly suggests that the Co3O4/NBGHSs could be used as the efficient
electrocatalysts for metalair batteries with great potential to replace the precious metal/carbon based materials.
Introduction
Broadercontext
Electrochemicalenergyconversionandstoragedevicesrequire
electrode materials that are both highly active for the energy
conversion/storage reactions and electrically conductive to
achieve high power densities.13 The traditional single
componentmaterials,duetotheirinherentlimitations,cannot
meetwellthisrequirementfortheseapplications.Forexample,
although some transitionmetal oxides (TMOs) have been
identifiedaspromisingelectrodematerials,theirpracticaluses
haveindeedbeenlimitedduetotheirintrinsicallylowelectric
conductivity.46 Composite materials, which integrate
components that are electrochemically active for energy
conversion/storage reactions with those that are highly
electrically conductive, have therefore attracted particular
a.
DepartmentofChemicalEngineering,NingboUniversityofTechnology,Ningbo,
Zhejiang315016,P.R.China.
b.
ElectrochemicalEnergyLaboratory&MaterialsScienceandEngineering
Program,TheUniversityofTexasatAustin,Austin,Texas78712,UnitedStates.
*Email:manth@austin.utexas.edu
c.
NewEnergyResearchInstitute,CollegeofEnvironmentandEnergy,SouthChina
UniversityofTechnology,Guangzhou,Guangdong510006,P.R.China.
*Email:eszjiang@scut.edu.cn,andzhongjiejiang1978@hotmail.com
Electronic Supplementary Information (ESI) available: [Details of experimental
procedures;RamanspectrumofpureCo3O4hollowmicrospheres,Co3O4/NBGHSs,
andNBGHSs;TGAanalysisofCo3O4/NBGHSs;SEMandTEMimagesofpureCo3O4
hollowmicrospheres,Co3O4/GHSs,Co3O4/NGHSs,andCo3O4/BGHSs;SEMandTEM
images of NBGHSs fabricated by the removal of the Co3O4 hollow microspheres
from Co3O4/NBGHSs with a 1.0 M HCl solution; Nitrogen adsorption/desorption
isothermsofCo3O4hollowmicrospheresandCo3O4/NBGHSs;LSVcurvesatvarious
rotation rates for the ORR and corresponding KL plots for Co3O4, Co3O4/GHSs,
Co3O4/NGHSs, Co3O4/BGHSs, NBGHSs and Pt/C in O2saturated 0.1 M KOH
solution;TEMandSEMimagesoftheCo3O4/NBGHSsafterORRandOERstability
test; OER electrochemical stability of Co3O4, Co3O4/GHSs, Co3O4/NGHSs,
Co3O4/BGHSs, the Pt/C, and RuO2/C catalysts for 500 cycles]. See
DOI:10.1039/x0xx00000x
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Resultsanddiscussion
Figure 1 schematically illustrates the procedure used for the
fabrication of the Co3O4/NBGHSs (the detailed procedure for
the synthesis of the Co3O4/NBGHSs is given in the
experimental section and Supplementary Information).
Specifically,sphericalsilicaMCM41particleswereusedasthe
templates, which were first functionalized with NH2groups
through their reaction with 3aminopropyltrimethoxysilane,
makingthempositivelychargedinthesolutionwithapHvalue
of <10.50,51Thenegativelychargedgrapheneoxide(GO)was
then adsorbed onto the surface of the NH2MCM41 spheres
to form GO/NH2MCM41 with a core/shell structure through
an electrostatic interaction (the GO is negatively charged due
tothepresenceofoxygengroups52,53).ThecodopingofNand
B in the graphene hollow shell could be accomplished by a
hydrothermal reaction of the GO/NH2MCM41 in the
presence of NH3BF3 similar to that previously reported,54, 55
whichledtotheformationofNandBdopedgraphenecoated
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Figure1.SchematicallyillustratingthefabricationoftheCo3O4/NBGHSs.
Figure2.(a)TEMand(b)SEMimagesofCo3O4/NBGHSs.(c)SEMimageofacollapsedCo3O4/NBGHS.ThewallthicknessofCo3O4/NBGHSsis
markedinthefigure.(d)BlowupoftheoutermostwalloftheCo3O4/NBGHSs.
NH2MCM41(NBG/NH2MCM41).ThedepositionofCo3O4on
the surface of the NBG/NH2MCM41 was achieved through
agingasolutionofCo(NO3)3inthepresenceoftheNBG/NH2
MCM41. The Co3O4/NBGHSs were then obtained after the
removal of the NH2MCM41 core from the Co3O4/NBG/NH2
MCM41throughaNaOHetching.
Figure2ashowsatypicalTEMimageoftheCo3O4/NBGHSs,
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(d)
220
511
400
10
20
30
40
422
50
2degree
60
440
622
533
70
80
Figure 3. (a) and (b) magnified TEM images of the Co3O4/NBGHSs. (c) HRTEM image of a Co3O4 nanoplate corresponding to the region
markedinFigure3b(theinsetisaselectedareaelectrondiffractionpattern).(d)XRDpatternofCo3O4/NBGHSs.
Co3O4 deposited on the free NBG that was uncoated on NH2
MCM41. The collapse of some Co3O4/NBGHSs could also be
observedintheSEMimageshowninFigure2b,suggestingthat
the highly pliable nature of the NBGHSs and the ultrathin
characteristics of the Co3O4 wall could not well support the
specific hollow structure of these Co3O4/NBGHSs, which are
destroyed by the ultrasonication and mechanical stirring
duringthewashingandsamplepreparationforSEMandTEM
imaging.ThemeasurementofthecollapsedCo3O4/NBGHSsin
Figure2cshowsthattheobtainedCo3O4/NBGHSshaveawall
thickness of 30 nm. The blowup of the outermost wall of
theCo3O4/NBGHSsrevealsthatthewalloftheCo3O4/NBGHSs
mainly consists of the platelike materials as shown in Figure
2d. The magnified TEM images in Figure 3a and b further
confirm the hollow nature of Co3O4/NBGHSs with uniform
platelikeCo3O4depositedontheexternalsurfacesofNBGHSs.
Theseplatelikematerialsarewellcrystallizedwiththelattice
fringes clearly observable in their highresolution TEM image
shown in Figure 3c. The 0.285 nm crystal plane spacing
matches well the (220) crystal spacing of the facecentered
cubic (FCC) spinel Co3O4.56 Selected area electron diffraction
(SAED) pattern, displayed in the inset of Figure 3c, further
demonstrates the obtained Co3O4 is well crystallized with the
FCCstructure.
TheXPSsurveyspectrumoftheCo3O4/NBGHSs(Figure4a)
showspeaksattributabletoCo,O,N,C,andB.Thepresenceof
Co3O4couldbedemonstratedbythetwopeaksat780.0eVfor
Co2p3/2and795.1eVforCo2p1/2inthehighresolutionCo2p
spectruminFigure4bandthedistinctOlatticepeakat529.88eV
inthedeconvolutedO1speaksinFigure4c.Thiscouldfurther
besupportedbyfourdistinctpeaksat677.1,517.1,470.4and
193.5cm1intheRamanspectraoftheCo3O4/NBGHSs(Figure
S1), corresponding to the A1g, F2g1, Eg, and F2g2 modes of
Co3O4,57,58respectively.ThespectraldeconvolutionoftheC1s
peakinFigure4dshowsthepresenceofeightdistinguishable
peaks,whichcouldbeassignedtothechemicalenvironments
of carbon atoms bonded to carbon, oxygen, nitrogen, and
boroningrapheneandthe*shakeupsatellitepeak.54,5961
ThisisanalogoustothedeconvolutedN1sspectruminFigure
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311
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400
200
0.25
0.00
778
780
Co3O4
780
790
800
810
(d) C 1s
C sp
Intensity / a.u.
Intensity / a.u.
Olattice
O-C-O/C-O-B
/N-O
NBGHSs
adsorbed O2
H2O(adsorbed)/C=O
3
O-C=O/C-O-B
sp C/C-N
/N-C=O
C=O C-O
532
530
528
526
(e) N 1s
sp C/C-N
294
292
290
(f)
NBGHSs
Pyrrolic N
Graphitic N
Pyridinic N
B-N
Oxidized N
B4C
286
284
282
280
Co3O4/NBGHSs
CBO/C-BN
2
B-C(sp )
B-doped carbon
B4C
C-BNO
Intensity / a.u.
B-N
288
B-C sp
B 1s
Pyridinic N
Pyrrolic N
C sp
Binding energy / eV
Co3O4/NBGHSs
Graphitic N
Oxidized N
B4C
O-C=O/C-O-B
/N-C=O
C=O C-O
Binding energy / eV
B-C sp
NBGHSs
O-C-O/C-O-B
/N-O
534
Co3O4/NBGHSs
adsorbed O2
536
784
Binding energy / eV
H2O(adsorbed)/C=O
538
782
Binding energy / eV
Co3O4/NBGHSs
Co3O4/NBGHSs
O 1s
0.50
2p1/2
Binding energy / eV
(c)
0.75
C-BO2
NBGHSs
CBO/C-BN
2
B-C(sp )
B-doped carbon
C-BNO
C-BO2
B4C
406
404
402
400
398
396
394
Binding energy / eV
196
194
192
190
Binding energy / eV
188
186
Figure 4. (a) XPS survey spectra of Co3O4/NBGHSs and NBGHSs fabricated by the removal of Co3O4 hollow microspheres from
Co3O4/NBGHSswiththe1.0MHClsolution.(b)HighresolutionCo2pspectraofCo3O4/NBGHSsandCo3O4hollowmicrospheres.Theinset
shows a comparison of the normalized Co 2p spectra of Co3O4/NBGHSs and Co3O4 hollow microspheres. (c) Deconvoluted O 1s, (d)
deconvolutedC1s,(e)deconvolutedN1s,and(f)deconvolutedB1sspectraoftheCo3O4/NBGHSsbeforeandaftertheetchingwiththe1.0
MHClsolution.
featurelessvoltammetriccurrent,whiletheircorrespondingCV
obtainedintheO2saturatedsolutionexhibitsacathodicpeak
corresponding to the reduction of O2. This clearly indicates
that the Co3O4/NBGHSs are electrochemically active for the
ORR. The linear sweeping voltammograms (LSVs) in Figure 5b
show that the Co3O4/NBGHSs could exhibit an ORR halfwave
potential E1/2 of 0.862 V vs. RHE (the potential at which the
currentishalfofthelimitingcurrent),whichis~20mVmore
postivethanthatofthePt/C(E1/2=0.842Vvs.RHE).This,along
with their relatively higher ORR current density than that of
thePt/C(Figure5b),stronglysuggeststhattheCo3O4/NBGHSs
are efficient electrocatalysts for the ORR with higher activity
thanthePt/Cwith20wt.%Pt.
To understand the origin of the higher electrocatalytic
activity of Co3O4/NBGHSs, the electrocatalytic properties of
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2p3/2
DOI: 10.1039/C6TA01349J
Co 2p3/2
1.00
O 2s
B 1s
N 1s
C 1s
O 1s
800
Co 2p
Intensity / a.u.
Co 3s
Co3p1/2 & 3/2
O 2s
C 1s
B 1s
N 1s
O 1s
Co 2p1/2
Co 2p3/2
Co LMM
OKLL
Co 2s
OKLL
Intensity / a.u.
NBGHSs
1000
Intensity / a.u.
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(b)
Co3O4/NBGHSs
Normalized intensity
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Assignment
Co3O4/NBGHSs
NBGHSs
529.88
Olattice
O1s
531.50
531.26
adsorbedO2
532.35
532.72
H2O(adsorbed)/C=O
533.12
534.14
OCO/COB/NO
282.66
282.75
B4C
283.65
283.70
BCsp2
284.58
284.73
Csp2
3
285.34
285.50
sp C/CN
C1s
286.07
286.75
CO
287.30
288.10
C=O
288.70
289.31
OC=O/COB/NC=O
290.52
290.80
*
397.60
398.04
BN
398.38
399.24
pyridinicN
N1s
400.00
400.19
pyrrolicN
401.21
402.52
graphiticN
403.40
404.11
oxidizedN
187.83
188.22
B4C
188.81
189.20
Bdopedcarbon
189.59
190.25
BC(sp2)
B1s
190.51
191.30
CBN/CBO
191.92
192.45
CBNO
193.19
193.60
CBO2
addition of the GHSs and the NBGHSs could increase the the boron doped graphene hollow microspheres
electrocatalytic activity of the Co3O4 hollow spheres. Prior (Co3O4/BGHSs), as demonstrated in Figure 5b, suggests that
studies have demonstrated the strong electronic coupling the doping of B and N into the graphitic structure of the
between TMO and the graphene substrate,4,9,33 which could NBGHSs both improves the electrocatalytic activity of the
improve electrocatalytic activity of the graphenesupported Co3O4/NBGHSs (the procedures for the synthesis of the
TMO nanoparticles.9,15,33 The coupling between NBGHSs and Co3O4/NGHSs and the Co3O4/BGHSs are given in the
Co3O4 might be enhanced due to the strong interaction Supplementary Information, and their SEM and TEM images
between Co and N/B, leading to the higher electrocatalytic aregiveninFigureS3).
activityoftheCo3O4/NBGHSsthanthatoftheCo3O4/GHSs,as To exactly demonstrate that there exists the electronic
observed in Figure 5b. Indeed, the enhancement in the coupling between NBGHSs and Co3O4, the XPS spectra of the
electrocatalytic activity of Co3O4/NBGHSs by the strong NBGHSsfabricatedbytheetchingoftheCo3O4/NBGHSswitha
coupling between NBGHSs and Co3O4 could also be 1.0 M HCl solution were measured. The XPS survey spectrum
demonstratedbytheobservationsthattheLSVoftheNBGHSs of the NBGHSs in Figure 4a shows the absence of the peaks
fabricated by the etching of the Co3O4/NBGHSs with a 1.0 M assignabletoCo,indicatingthatCo3O4haswellbeenremoved
HClsolution(theSEMandTEMimageoftheNBGHSsshowsa fromtheCo3O4/NBGHSsthroughtheiretchinginthe1.0MHCl
microspherical hollow structure, indicating their good solution. This is consistent with the lack of the Olattice peak in
morphology retention property during the acidic etching, as the deconvoluted O 1s spectrum of the NBGHSs. The high
showninFigureS4intheSupplementaryInformation)andthe resolutionXPSspectrainFigure4dfshowthattheC1s,N1s
combined LSV of the NBGHSs and the pure Co3O4 hollow and B 1s peaks of the NBGHSs exhibit the shapes greatly
microspheres both exhibit less positive halfwave potentials different from those of the Co3O4/NBGHSs. This is in good
andlowercurrentdensitiesthanthose of theCo3O4/NBGHSs, agreement with the fact that the removal of Co3O4 would
as shown in Figure 5b. This indicates that the higher make the NBGHSs, which are initially covered by the Co3O4
electrocatalyticactivityofCo3O4/NBGHSsdoesnotsimplyarise shell, well accessible to the xray beams. The spectra
from the NBGHSs or the physical mixing of the Co3O4 hollow deconvolution of the C 1s, N 1s and B 1s peaks shows the
microspheres and the NBGHSs. The fact that the presence of theC, Nand Bcontainingcomponents withthe
electrocatalytic activity of the Co3O4/NBGHSs is higher than numbers and types similar to those of the Co3O4/NBGHSs
those of Co3O4 deposited on the nitrogendoped graphene (Figure 4d, e and f), but with the corresponding positions
hollow microspheres (Co3O4/NGHSs) and Co3O4 deposited on appearingattherelativelyhigherbindingenergies(Table1).
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Co3O4
(a)
Current density / mA cm
Co3O4/BGHSs
Co3O4/NBGHSs
NBGHSs
0.4
0.6
0.8
Co3O4/NGHSs
-1
Co3O4/BGHSs
-2
Co3O4/NBGHSs
-3
Pt/C
NBGHSs
Co3O4+NBGHSs
-4
(c)
Co3O4/NBGHSs
E1/2=0.862V
0.4
(d)
0.40
0.6
E / V vs. RHE
0.8
1.0
Co3O4/NBGHSs
-1
0.35
2
-2
400 rpm
625 rpm
900 rpm
1225 rpm
1600 rpm
2025 rpm
-5
-6
0.2
4.0
0.4
0.6
E / V vs.RHE
0.8
-1
-4
0.30
-1
-3
j / mA cm
Current Density / mA cm
-2
E1/2=0.842V
-5
-6
1.0
(b)
Co3O4/GHSs
E/ V vs. RHE
0.25
0.642 V
0.542 V
0.442 V
0.342 V
0.242 V
0.20
0.15
0.021
1.0
0.028
0.035
0.042
100
(e)
(f)
Co3O4
Co3O4/GHSs
80
3.5
jk / mA cm
Co3O4/NGHSs
Co3O4/BGHSs
2.5
2.0
1.5
0.2
Co3O4/NGHSs
Co3O4
Co3O4/GHSs
3.0
Co3O4/NBGHSs
Pt/C
NBGHSs
0.3
0.049
/ rpm-0.5
Co3O4/BGHSs
-2
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Current
Co3O4/NGHSs
DOI: 10.1039/C6TA01349J
Co3O4
-2
Co3O4/GHSs
0.2
Co3O4/NBGHSs
60
Pt/C
NBGHSs
40
20
0.4
0.5
E / V vs. RHE
0.6
0.7
0
0.2
0.3
0.4
0.5
E / V vs.RHE
0.6
0.7
Figure5.(a)CVcurvesofpureCo3O4hollowmicrospheres,Co3O4/GHSs,Co3O4/NGHSs,Co3O4/BGHSs,Co3O4/NBGHSs,andNBGHSs,inO2
(solid) or N2 (dash) saturated 0.1 M KOH solution at a scan rate of 5 mV s1. (b) LSVs for the ORR on pure Co3O4 hollow microspheres,
Co3O4/GHSs,Co3O4/NGHSs,Co3O4/BGHSs,NBGHSs,Co3O4/NBGHSs,andPt/CelectrodesinanO2saturated0.1MKOHsolutionatascan
rateof5mVs1andarotationrateof1600rpm.Thecombinedcurve,whichconsistsoftheLSVsofpureCo3O4hollowmicrospheresand
NBGHSs, is also shown in Figure (Co3O4+NBGHSs). The weighing of the LSVs of pure Co3O4 hollow microspheres and NBGHSs in the
combined LSV is similar to the weight percentage of Co3O4 and NBGHSs in the Co3O4/NBGHSs. (c) Rotating disk electrode LSVs of
Co3O4/NBGHSsinO2saturated0.1MKOHatvariousdifferentrotationrates.Thescanratewas5mVs1.(d)KouteckyLevichplotsofthe
ORRatCo3O4/NBGHSsobtainedbasedonthedataextractedfromFigure5c.Thedotsaretheexperimentalresultsandthestraightlines
aretheircorrespondingfittingsusingEquation1.(e)ComparisonoftheelectrontransfernumberinvolvedintheORRattheelectrodesof
thepureCo3O4hollowmicrospheres,Co3O4/GHSs,Co3O4/NGHSs,Co3O4/BGHSs,NBGHSs,andCo3O4/NBGHSsandPt/CintheO2saturated
0.1 M KOH. (f) Calculated kinetic current densities of the ORR at the electrodes of pure Co3O4 hollow microspheres, Co3O4/GHSs,
Co3O4/NGHSs,Co3O4/BGHSs,NBGHSs,Co3O4/NBGHSsandPt/CinO2saturated0.1MKOH.
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0.95
34
62
.6
mV
.4
.4
5
de
mV
mV 6.5
c
d
de - mV
c 1
de - ec -1
c 1
48.
9m
0.90
-1
(b)
0.8
0.7
91.
0.6
1m
V d -1
ec
0.5
-2.0
-1.5
V d -1
ec
-1.0
-0.5
0.0
-2
log|Ik/Am cm |
Co3O4
Co3O4/GHSs
Co3O4/NGHSs
0.85
DOI: 10.1039/C6TA01349J
100
Co3O4/BGHSs
6%
80
29%
Pt/C
60
Co3O4/NBGHSs
0.80
-2.0
40
-1.6
-1.2
-0.8
-0.4
0.0
0.4
0.8
10
(d)
Pt/C
Co3O4/NBGHSs
80
Addition of
0.3 M methanol
40
Relative Current / %
(b)
100
60
Time / h
-2
log|I /Am cm |
Relative Current / %
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Co3O4/NBGHSs
Pt/C
100
Pt/C
Co3O4/NBGHSs
80
Addition of CO
60
40
20
20
0
200
400
600
800
200
Time / s
400
600
Time / s
800
Figure6.(a)TafelplotsofCo3O4/GHSs,Co3O4/NGHSs,Co3O4/BGHSs,Co3O4/NBGHSs,andPt/C,derivedbythemasstransportcorrectionof
their corresponding RDE data (see the Supplementary Informa on for details). The inset is a Tafel plot of the pure Co3O4 hollow
microspheres.TheTafelslopeofthecatalystsatthelowcurrentdensityregionisgiven.(b)DurabilityevaluationoftheCo3O4/NBGHSsand
thePt/Celectrodesfor10hat0.642Vvs.RHEandarotationrateof1600rpm.(c)ChronoamperometricresponseofCo3O4/NBGHSsand
1
Pt/Cat0.642VinO2saturated0.1molL KOHsolution.Thearrowsindicatetheadditionofmethanol.(d)Chronoamperometricresponse
1
ofCo3O4/NBGHSsandPt/Cat0.642VinO2saturated0.1molL KOHsolution.ThearrowsindicatetheadditionofCO.
This indicates the existence of the strong electronic coupling
between Co3O4 and NBGHSs with a possible electron transfer
from Co3O4 to NBGHSs, while the removal of Co3O4 from the
Co3O4/NBGHSs would not change the molecular structure of
the NBGHSs, but removes the coupling between Co3O4 and
NBGHSs. Indeed, the electronic coupling between Co3O4 and
NBGHSscouldalsobedemonstratedbytheappearanceofthe
Co2pXPSpeakofCo3O4intheCo3O4/NBGHSsattherelatively
higher binding energy and the emergence of the A1g, F2g1, Eg,
and F2g2 Raman modes of Co3O4 in the Co3O4/NBGHSs at the
higher wavenumbers in comparison to those in the Co3O4
hollow spheres, as shown in Figure 4b and S1, respectively.
The appearance of all the B and N containing components in
the Co3O4/NBGHSs at the lower binding energies relative to
those in the NBGHSs may suggest that Co3O4 could interact
with both N and B doped structures, which is in good
agreement with the observations that the electrocatalytic
activityoftheCo3O4/NBGHSsishigherthantheCo3O4/NGHSs
andtheCo3O4/BGHSs,asdemonstratedinFigure5b.
The most interesting is that although the components of
H2O(adsorbed)/C=O
and
OCO/OCB/NO
in
the
deconvoluted O 1s spectrum of the Co3O4/NBGHSs appear at
the positions with the relatively lower binding energies in
comparison to those of the NBGHSs, indicating the possible
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1 1
1
1
1
(1)
J J K J L J K B1/2
where J is the measured current density, JK and JL are the kinetic
anddiffusionlimitingcurrentdensities,istheelectroderotating
rate,andBistheLevichconstant.Figure5dandFigureS7showthat
1
0.5
there exist linear relationships between J and at a range of
potentials,indicatingthattheelectrocatalyticreductionreactionof
O2 by these catalysts is of first order with respect to the
concentration of dissolved O2. The linear fitting of the KL plots
yieldstheLevichconstants,whichcanthenbeusedtoextract the
electrontransfernumbers(n)involvedineachORRwiththeLevich
Equationshownbelow:
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JournalName
Co3O4
DOI: 10.1039/C6TA01349J
(b)
1.4
1.5
1.7
0.0
m
V
.9
68
-1
de
c
0.5
Co3O4/BGHSs
Co3O4/NBGHSs
Pt/C
NBGHSs
RuO2/C
1.0
1.5
2.0
lg |i/mA cm |
(d)
Current densitygeo / mA cm
-2
-2
(c)
10
0
0
-0.5
c
de
-2
Potential / V vs RHE
15
1.60
-1.0
1.8
de
c
-1
1.6
95
.0
de
V
m
.2
98
69.9 mV dec
1.3
m
V
-1
dec -1
mV
277.1
-1
1.2
Co3O4/NGHSs
-1
V
m
.0
63
mV
1.65
Co3O4
Co3O4/GHSs
15
2 .8
10
1.70
-1
15
Pt/C
NBGHSs
RuO2/C
de
c
Co3O4/NBGHSs
m
V
20
1.75
.7
Co3O4/BGHSs
70
Co3O4/NGHSs
25
de
c
-1
Co3O4/GHSs
2000
4000
6000
8000
10000
30
First scan
th
500 scan
20
10
0
1.2
12000
1.4
1.6
1.8
2.0
Time / s
Figure7.(a)LSVsofpureCo3O4hollowmicrospheres,Co3O4/GHSs,Co3O4/NGHSs,Co3O4/BGHSs,Co3O4/NBGHSs,NBGHSs,Pt/C,andRuO2/C
loaded onto glassy carbon electrodes measured in 0.1 M KOH. (b) Tafel plots of pure Co3O4 hollow microspheres, Co3O4/GHSs,
Co3O4/NGHSs,Co3O4/BGHSs,Co3O4/NBGHSs,NBGHSs,Pt/C,andRuO2/CforOER.(c) DurabilityevaluationofCo3O4/NBGHSscatalystsfor
10800sat1.7Vvs.RHE.(d)PolarizationcurvesfortheCo3O4/NBGHSsbeforeandafter500cycles.
to their catalytic activity. This is in contrast to Pt/C, in which
the loss of more than 29% of their original activity could be
observedafter10hoftheORR,duetothedissociationofthe
Ptnanoparticlesfromthecarbonsubstrateortheaggregation
71,
ofthePtnanoparticlesduringtheelectrochemicalprocesses.
72
The introduction of methanol and CO causes even higher
lossesoftheiractivities,duetotheblockageofactivesiteson
the Pt nanoparticles by the adsorption of the methanol
7375
These results clearly indicate
oxidation products or CO.
thattheCo3O4/NBGHSsaremorestablecatalystsfortheORR
than the commercial Pt/C. Figure S8a and b show that the
Co3O4/NBGHSs could maintain their microspherical hollow
structurewithnodetectablemorphologicalchangesafter10h
oftheORR.
To demonstrate the electrocatalytic activity of the
Co3O4/NBGHSsfortheOER,theirLSVatthevoltagerangefrom
1.20to1.78VinanO2saturated0.1MKOHsolutionatascan
rate of 20 mV s1 was measured. Figure 7a shows an abrupt
increase in the voltammetric current at the relatively high
potential range, suggesting the electrocatalytic activity of the
Co3O4/NBGHSsfortheOER.TheonsetpotentialoftheOERfor
theCo3O4/NBGHSsis~1.6V,whichislesspositivethanthose
of the pure Co3O4 hollow microspheres, the Co3O4/GHSs, the
Co3O4/NGHSs, the Co3O4/BGHSs, the NBGHSs, and the Pt/C,
indicating the higher electrocatalytic activity of the
Co3O4/NBGHSs for the OER than the other catalysts. This
suggeststhatthepresenceoftheNBGHSscouldalsoincrease
the OER activity of the Co3O4/NBGHSs. Worthnoting is that
although the OER onset potential of the Co3O4/NBGHSs is
more positive than that of the conventional RuO2/C, their
2
overpotentialthatreachestoacurrentdensityof10mAcm is
smallerthanthatoftheRuO2/C,~0.47Vvs.~0.52V(Figure7a).
This further demonstrates that the Co3O4/NBGHSs are the
efficient catalysts for the OER. The Tafel plots derived from
Figure 7b show that the Co3O4/NBGHSs possess a OER Tafel
1
slopeof63mVdec ,whichismuchsmallerthanthoseofthe
pure Co3O4 hollow microspheres (95 mV dec1), the
1
1
Co3O4/GHSs(71mVdec ),theCo3O4/NGHSs(70mVdec ),the
1
1
Co3O4/BGHSs (69 mV dec ), the NBGHSs (277 mV dec ), the
1
1
Pt/C (98 mV dec ), the RuO2/C (152.8 mV dec ), and the
9,15
catalysts reported in the literature, intrinsically explaining
thereasonthattheCo3O4/NBGHSscouldexhibithigher
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1.80
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1.50
1.5
(b)
0.1
0.6
Pt/C
Co3O4/NBGHSs
0.4
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0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.0
-2
j=50 mA cm
1.20
1.2
1.1
1.0
1.05
0.90
-2
10 mA cm
-2
100 mA cm
1.3
Voltage / V
0.2
0.8
1.35
Voltage / V
Voltage / V
1.0
Power density / W cm
0.3
1.2
(c)
1.4
-2
j=5 mA cm
Pt/C
Co3O4/NBGHSs
0
10
15
20
25
Time / h
-2
Current density / A cm
0.9
0.8
100
200
300
400
500
600
-1
700
Figure 8. (a) Polarization curves (V~i) and corresponding power density plots of the Znair batteries usingthe Co3O4/NBGHSs and the
commercialPt/Ccatalystasthecathodecatalyst.(b)LongtimedischargecurvesoftheprimarybatteriesusingtheCo3O4/NBGHSsandthe
commercialPt/Ccatalyst at two different current densities. (c) Typical discharge curves of the primary Znair batteries withthe
Co3O4/NBGHSs as the cathode catalyst under continuous discharge until complete consumption ofZnat two different current densities.
SpecificcapacitywasnormalizedtothemassofconsumedZn.
electrocatalytic activity for the OER. The stability tests show
that the Co3O4/NBGHSs can remain highly active for the OER
duringcycling,althoughalargecurrentdensitydropcouldbe
observedintheinitialcyclesduetotheblockageoftheactive
sites on the catalyst by the gradual accumulation of the
evolved O2bubbles, as showninFigure7c. Thiscould alsobe
demonstrated by the results in Figure 7d which shows that
after 500 cycles the polarization curve of the Co3O4/NBGHSs
exhibits an onset potential comparable to that of the initial
cycle with only a very slightly positive shift to the higher
potential. TEM and SEM show no detactable morphological
changesintheCo3O4/NBGHSsafter10800softheOERat1.7V
vs.RHE,asshowninFigureS8candd.FigureS9showsthatthe
stabilityoftheCo3O4/NBGHSsfortheOERismuchhigherthan
thatofthepureCo3O4hollowmicrospheres,theCo3O4/GHSs,
the Co3O4/NGHSs, the Co3O4/BGHSs, the Pt/C, and RuO2/C,
indicating that the stronger coupling between Co3O4 and
NBGHSs could make the Co3O4/NBGHSs highly stable for the
OER. These results clearly suggests that the Co3O4/NBGHSs
couldbeusedastheefficientandstablecatalystsfortheOER.
TopracticallyverifythattheCo3O4/NBGHSscouldbeused
astheelectrocatalystsformetalairbatteries,weassembleda
primaryZnairbatterywiththeuseoftheCo3O4/NBGHSsanda
Zn foil as the respective cathode and anode (the detailed
assembling procedure of the Znair battery is given in the
Supplementary Information). Figure 8a shows that in the
presence of 6.0 M KOH the battery could deliver an open
circuit voltage of ~1.40 V. At a voltage of 1.0 V, it shows a
current density of ~ 240 mA cm2. A peak power density of
2
~330 mW cm could be obtained when the battery works at
0.62 V. Both the current density at 1.0 V and peak power
densityofthebatterywiththeCo3O4/NBGHSsarehigherthan
thoseofthebatterymadewiththePt/C(Figure8a),indicating
thatthetheCo3O4/NBGHSscouldbeusedasthebifunctional
cathode catalysts for the metalair batteries. Indeed, the
currentdensityat1.0Vandpeakpowerdensityofthebattery
with the Co3O4/NBGHSs are also higher than those of the
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Conclusions
The Co3O4/NBGHSs electrocatalysts, consisting of the NBG
arranged in a microspherical hollow structure with the Co3O4
shell grown onto their surface, have been synthesized with a
simpleprocedureinvolvingthesynthesisoftheGO/NH2MCM
41 composites, the deposition of Co3O4, and the subsequent
removal of the NH2MCM41 core. These Co3O4/NBGHSs are
highlyefficientforboththeORRandtheOERandcouldexhibit
higheractivityandbetterdurabilityfortheORRandtheOERin
alkaline solutions than the commercial Pt/C and RuO2/C,
respectively. The enhanced electrochemical performance of
theCo3O4/NBGHSscouldbeattributed tothestrong coupling
between Co3O4 and NBGHSs, the strong interaction between
the Co3O4/NBGHSs and adsorbed O2, and their high electric
conductivity and specific hollow structure. The Znair battery
assembled with Co3O4/NBGHSs could also exhibit higher
electrochemical performance and better stability than those
with the commerical Pt/C and RuO2/C and other
electrocatalysts reported previoulsy. This makes us believe
that the Co3O4/NBGHSs could be used as the efficient
electrocatalystsformetalairbatterieswithgreatpotentialto
replace the precious metal/carbon based materials.
Additionally,thepresentmethodisalsosuitableforlargescale
production of the Co3O4/NBGHSs, making it particularly
attractivefortheproductionofbifunctionalelectrocatalystfor
both the ORR and the OER with low cost, but higher
electrocatalyticactivity.
ExperimentalSection
FabricationofaminomodifiedsilicaMCM41spheres(NH2MCM
41)
ThemesoporousMCM41sphereswithsizesrangingfrom450
to 800 nm were synthesized from an alkaline solution
containing nhexade cyltrimethylammonium bromide
(C16TMABr), tetraethyl orthosilicate (TEOS), and NH3H2O
accordingtoaprocedurereportedintheliterature.81Fortheir
aminofunctionalization,~1gofMCM41wasdispersedin300
mL of dry toluene by ultrasonication. After the addition of 3
mLof3Aminopropyltrimethoxysilane,themixturewasheated
to65Cunderstirringandkeptatthattemperaturefor12h.
The obtained NH2MCM41 spheres were washed through
centrifugationandredispersedinwater.
FabricationofNBGHSs/NH2MCM41core/shellspheres
For the fabrication of the NBGHSs/NH2MCM41 composites,
0.3 g of NH2MCM41 obtained above was dispersed in 30.0
mL of distilled water. The pH value of the solution was then
adjusted to 2.5 by adding drops of 1.0 M HCl solution, which
made the NH2MCM41 spheres positively charged. To this
solution, 20 mL of 2.0 mg mL1 negatively charged GO
suspension(synthesizedfromthenaturalgraphiteflakesusing
a modified Hummers method described elsewhere82, 83) was
added.Theobtainedmixturewasstirredatroomtemperature
View Article Online
DOI: 10.1039/C6TA01349J
for24h,whichledtothedepositionofGOontothesurfaceof
NH2MCM41 through an electrostatic interaction. 18 mmol
ammonia boron trifluoride (NH3BF3) was then added under
stirring.TheresultingstablesuspensionwassealedinaTelfon
linedautoclaveandhydrothermallytreatedat180Cfor12h.
After freezedrying overnight and vacuumdrying at 60 C for
several hours, the obtained products were calcined in Ar
atmosphereat420Cfor2handat800Cfor30min,which
led to the formation of NBGHSs/NH2MCM41 with a
core/shellstructure.
FabricationofcobaltoxidecoatedNBGHSs(Co3O4/NBGHSs)
For the fabrication of the Co3O4/NBGHSs, the core/shell
NBGHSs/NH2MCM41 synthesized above was soaked in a
solutionofconcentratedHClfor3hat150Candthenwashed
by centrifugation. The obtained product was redispersed in
200mLof0.3molCo(NO3)2solutionandultrasonicatedfor15
min.Themixturewasthenagedfor7daystoallowthecoating
ofNBGHSs/NH2MCM41withCo3O4.Thecoatedsphereswere
thensubjectedto four cycles ofcentrifugationwater washing
to remove impurities and unreacted cobalt precursors,
followed by drying at 60 C for 5 h in a vacuum oven. The
Co3O4coated NBGHSs/NH2MCM41 spheres were then
calcinedinAratmosphereat450 oCfor2handredispersedin
1 M NaOH to remove the NH2MCM41 cores. The resulting
Co3O4/NBGHSs were washed with deionized water and
vacuumdried.
Electrochemicalmeasurements
Electrochemical measurements were performed with a
computercontrolled potentiostat (CHI 760C, CH Instrument,
USA) with a typical threeelectrode cell. The threeelectrode
cell consisted of a saturated calomel electrode (SCE) as the
referenceelectrode,aplatinumwireasthecounterelectrode,
and a glassy carbon electrode/rotating disk electrode (RDE)
loadedwithvariouscatalystsastheworkingelectrode.Allthe
experiments were carried out in 0.1 M KOH at room
1
temperature (25 C). The scan rate was 5 mV s for cyclic
voltammetry measurements and RDE measurements and 20
1
mVs forOERmeasurements.Thepotentialsreportedinthis
work were referenced to the reversible hydrogen electrode
(RHE) through the RHE calibration. In 0.1 M KOH, E (RHE) = E
(SCE) + 0.992 V. See Supplementary Information for detailed
experimentalprocedures.
Characterization
An environmental scanning electron microscope (Model
Quanta650FEG)atanoperationvoltageof20.0kVwasused
to record the morphology of the obtained samples. TEM
measurements were conducted on a JEM2100F high
resolution transmission electron microscope with an
accelerating voltage of 200 kV. The chemical compositions of
the samples were determined by Xray photoelectron
spectroscopy (XPS) on a VG ESCALAB 250 spectrometer
(ThermoElectron,U.K.),usinganAlKXraysource(1486eV).
Xray diffraction patterns of samples were performed on a
Scintag XDS 2000 Xray powder diffractometer with
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monochromatizedCuKaradiation(=1.5418).Thedatawere
collected between scattering angles (2) of 10 and 80o.
Thermogravimetric analysis (TGA) was performed on a
METTLERinstrumentsunderaO2atmosphereataheatingrate
of5C/min.
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Acknowledgements
Thesmallscalesynthesisandelectrochemicalcharacterization
workwassupportedbytheU.S.DepartmentofEnergy,Office
of Basic Energy Sciences, Division of Materials Sciences and
Engineering under the award number DESC0005397. The
detailed stability measurements and largescale synthesis of
the samples were supported by the Chinese National Natural
Science Foundation (No. 11474101, and U1532139), the
Zhejiang Provincial Natural Science Foundation (No.
LY14B030001), and the Ningbo Natural Science Foundation
(No.2014A610035).
Notesandreferences
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Co3O4-coated N- and B-doped graphene hollow spheres synthesized from a simple and scalable
method have been used as an electrocatalyst for the ORR and the OER, demonstrating higher
electrochemical performance and better durability than the commercial Pt/C and RuO2/C,
respectively.
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