Cobalt Oxide Coated N and B Doped Graphene Hollow Spheres As

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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
Bifunctional electrocatalysts for both oxygen reduction

reaction (ORR) and oxygen evolution reaction (OER) are
crucial components of energy conversion and storage
devices, such as metalair batteries. Fabrication of highly
efficientelectrocatalystsforboththeORRandtheOERis,
therefore, an effective way to improve the electrochemical
performance of metalair batteries. Herein, 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
boththeORRandtheOERandexhibithigherelectrochemical
performance and better durability than the commercial Pt/C
and RuO2/C, demonstrating them to be an efficient bi
functional electrocatalyst. Indepth analysis shows that the
interaction between Co3O4 and NBGHSs plays an important
role in the higher electrocatalytic activities of Co3O4/NBGHSs.
Additionally, the present method is also demonstrated to be
suitable for largescale production of the Co3O4/NBGHSs.
These results are therefore helpful to design and develop
othercatalystsofhighefficiencyandarealsoattractiveforthe
production of bifunctional electrocatalysts with low cost, but
higheractivity.
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
attention in recent years.1, 79 Such materials could not only

combine the properties of individual components but also
generate new fascinating properties that are favorable for
energy conversion/storage reactions through their collective
interactionsbetweenconstituents.Studieshavedemonstrated
that the composite materials comprising TMOs and electron
conducting carbonaceous materials or polymers exhibit
significantly enhanced electrochemical performance when
ThisjournalisTheRoyalSocietyofChemistry20xx
J.Name.,2013,00,13|1
Journal of Materials Chemistry A Accepted Manuscript
DOI: 10.1039/C6TA01349J
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used as electrode materials in energy conversion and storage

devices.1012
Recently,developmentofelectrocatalyststhatareactivefor
both oxygen reduction reaction (ORR) and oxygen evolution
reaction (OER) have received tremendous attention for their
potential uses in rechargeable metalair batteries.9, 1316 An
aqueous rechargeable metalair battery delivers an electric
current when oxygen is reduced to OH in the presence of
waterandisrechargedwhenOHisoxidizedwiththerelease
of oxygen and water.1719 Exploiting bifunctional catalysts
efficientforboththeORRandtheOERis,therefore,desiredto
improve the electrochemical performance of the metalair
batteries. Although the ORR and OER processes both involve
multiple electron transfer, their associated reaction
mechanismsaregreatlydifferent,20,21whichmakesthedesign
of catalysts that are effective for the both processes rather
difficult. For example, although precious metals such as
platinum(Pt)anditsalloysarewellknownelectrocatalystsfor
theORR,theiractivitiestowardOERarelow,whileiridium(Ir)
and ruthenium(Ru) oxidebased electrocatalystsare reported
to be highly active for the OER, but they exhibit low ORR
activity.22,23 This, together with their high costs and scarcity,
has greatly hindered the widespread uses of Pt, Ir, and Ru
basedmaterialsinmetalairbatteries.15,24,25Recentefforthas,
therefore, been devoted to the development of nonprecious
metal based materials.15, 16, 2628 Among various materials
reported to date, TMOs have attracted particular attention
duetotheirlowcostandpotentialasbifunctionalcatalystsfor
both the ORR and the OER.9, 2933 The practical uses of the
TMOs as a bifunctional catalyst for the ORR and the OER,
however,haveshownthatthebareTMOparticlesexhibitlow
electrocatalytic activities due to their intrinsically low electric
conductivity.34,35 Although their electrochemical performance
mightbeimprovedthroughtheircombinationwithelectrically
conductingmaterials,suchasgrapheneandcarbonnanotubes
(CNTs),theircatalyticactivitiesarestilllowerthanthoseofthe
commercial Pt/C catalysts.31,33,35,36 This suggests that efforts
arestillneededtofurtherincrease theactivitiesof theTMOs
for the ORR and the OER to promote their practical use in
metalairbatteries.
Compared with the conventional materials, those with a
hollow structure are of particular interest due to their high
surfacetovolume ratio, low density, as well as high
permeability for gases and liquids. It has been demonstrated
thathollowstructuredTMObasedmaterialscouldbeusedas
excellent catalysts for many applications and as anode
materials to improve the electrochemical performance of
lithium ion batteries.3741 However, the pure TMObased
hollow particles might not be desirable as bifunctional
catalystsfortheORRandtheOERduetotheirlimitedelectric
conductivity. To make the TMObased hollow particles highly
active for both the ORR and the OER, materials with high
electric conductivity should be introduced. Growing TMO
hollowmaterialsonthesurfaceofconductivehollowspheres
(CHSs)toformTMOcoatedCHSs(TMO/CHSs) isanattractive
way to improve their electrocatalytic activity. In such a
composite,theCHSsaretheinnerwalloftheTMO/CHSswith
the TMOs grown on their surface, which would not

block
the
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DOI: 10.1039/C6TA01349J
access of the TMOs to the dissolved oxygen
during the ORR
andthereleaseofoxygentothesolutionduringtheOER,but
increase the electric conductivity of the TMO/CHSs through
the high electric conductivity of the CHSs. Unlike the
conventional conducting material coated TMOs (CM/TMOs)
reported previously,4245 in which the electrochemical
reactions can only take place when the reactants diffuse
throughtheshelloftheconductingmaterialtotheTMOs,such
TMO/CHSs might be usable as efficient electrocatalysts for
boththeORRandtheOER.
We report herein the synthesis of Co3O4 hollow
microspheres grown onto the surface of N and Bdoped
graphene hollow microspheres (Co3O4/NBGHSs) through a
simple and scalable method and their uses as bifunctional
catalysts for both the ORR and the OER. Previous work has
demonstrated that Co3O4 and Ndoped graphene are both
electrocatalytically active for the ORR and the OER,15, 4649
which makes the Co3O4/NBGHSs particularly attractive, since
theelectrocatalyticactivitiesoftheCo3O4/NBGHSsfortheORR
and the OER may be enhanced through the collective
interactions between Co3O4 and NBGHSs. The electrochemical
resultsdemonstratethattheCo3O4/NBGHSscanexhibithigher
activity for both the ORR and the OER and better durability
than the commercial carbonsupported Pt catalyst (the
Johnson Matthey (JM) Pt/C with 20 wt. % Pt loading on the
carbonblack),andRuO2/Cwith20wt.%RuO2loadingonthe
carbon black, respectively, indicating that the Co3O4/NBGHSs
could be used as efficient bifunctional catalysts for both ORR
andtheOER.ThestongcouplingbetweenCo3O4andNBGHSsis
found to play an important role in the high electrocatalytic
activitiesoftheCo3O4/NBGHSs.Additionally,thepotentialuse
oftheCo3O4/NBGHSsinthemetalairbatterisisdemonstrated
by assembling them into a Znair battery which shows the
significantly higher electrochemical performance and better
stability.
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,
which appear as translucent pancakes with opaque

peripheries, clearly demonstrating their specific hollow
structure. Most of the Co3O4/NBGHSs could maintain their
microspherical hollow morphology although some sheetlike
materials could also be observed in the TEM image of the
Co3O4/NBGHSs, as marked with a red box in Figure 2a. These
sheetlikematerialscouldbeattributedtotheCo3O4deposited
NBG,whicharisesfromthecollapsedCo3O4/NBGHSsorthe
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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
4e, where five peaks corresponding to the BN, pyridinic N,

pyrrolicN,graphiticN,andoxidizedNcanbeclearlyidentified,
54, 59, 6264
and the deconvoluted B 1s spectrum in Figure 4f,
which shows the presence of six peaks corresponding to B4C,
Bdopedcarbon,BC(sp2),CBN/CBO,CBNO,andCBO2.54,59,
60,65
TheassignmentsofthepeaksforthevariousC,NandB
containing components in the Co3O4/NBGHSs and their
corresponding binding energies are summerized in Table 1.
Thedominationofsp2C,asindicatedinFigure4dandTable1,
suggeststhepresenceofthegraphiticstructure.Thisisingood
agreement with the Raman spectrum of the Co3O4/NBGHSs
shown in Figure S1, where two prominent peaks
corresponding to the D band (~1362 cm1,arising from the
disordered sp2 hybridized graphitic carbon66) and G band
(~1594cm1,associatedwiththetangentialstretchingmodeof
highly ordered pyrolytic graphitic carbon63) of the graphitic
stucture could be clearly observed. These results are well
consistent with the XPS spectra of NBG reported in the
literature,54, 55, 67 suggesting the presence of NBG in the
Co3O4/NBGHSs. The presence of a large percentage of the
oxygen component assignable to the physically adsorbed
oxygen, as shown in Figure 4c, might indicate the high
adsorbabilityoftheCo3O4/NBGHSstooxygen.
Figure3dshowsthexraydiffraction(XRD)patternofthe
Co3O4/NBGHSs, which exhibits the diffraction peaks
attributable to the FCC structured Co3O4 (JCPDS card no. 43
1467),ingoodagreementwiththeresultshownbytheHRTEM
image in Figure 3c. The lack of diffraction peaks ascribable to
impuritiessuggeststhestoichiometricpurityoftheFCCCo3O4.
The absence of welldefined diffraction peaks that could be
attributedtoNBGHSsindicatesthelackofwelldefinedlayered
structure for the NBGHSs. The thermogravimetric analysis
(TGA)demonstratesa64wt.%ofCo3O4intheCo3O4/NBGHSs,
asshowninFigureS2.
The electrocatalytic activity of the Co3O4/NBGHSs for the
ORR could be demonstrated by comparing their cyclic
voltammograms (CVs) in 0.1 M KOH aqueous solution
saturatedwithN2orO2.AsshowninFigure5a,theCVofthe
Co3O4/NBGHSsobtainedinN2satruratedsolutionshowsa
4|J.Name.,2012,00,13
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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
the Co3O4 hollow spheres and the Co3O4 deposited on

graphenehollowmicrospheres(Co3O4/GHSs)fortheORRwere
alsoinvestigated(theproceduresofthesynthesisofthepure
Co3O4 hollow spheres and the Co3O4/GHSs are given in the
Supplementary Information, and their SEM and TEM images
are given in Figure S3). The CVs and LSVs in Figure 5a and b
show that although the Co3O4 hollow spheres are also
electrocatalytically active for the ORR (the electrocatalytic
activity of the Co3O4 hollow spheres for the ORR is similar to
those of the Co3O4 materials reported previously23, 36), their
activity is much lower than that of the Co3O4/NBGHSs, as
demonstrated by their significantly lower current density and
less positive onset potential. The greatly improved current
densities and more positive onset potentials for the ORR on
theCo3O4/GHSsandtheCo3O4/NBGHSssuggestthatthe
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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.
(b)
Co3O4/NBGHSs
Normalized intensity
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(a)
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JournalName
Bindingenergy/eV
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).
Peak
6|J.Name.,2012,00,13
View Article Online

10.1039/C6TA01349J
Table 1. Peak assignments for the O, C, N, and Bcontaining components in Co3O4/NBGHSs and NBGHSsDOI:
based
on the spectra
deconvolutionshowninFigure4.
Journal
Page 7 of 15
JournalName
ARTICLE
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
Electron Transfer Number
Current
Co3O4/NGHSs
DOI: 10.1039/C6TA01349J
Co3O4
-2
Co3O4/GHSs
0.2
View Article Online
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.
J.Name.,2013,00,13|7
Journal
Page 8 of 15
JournalName
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
View Article Online
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 |
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
electron transfer from Co3O4 to NBGHSs, the component of

adsorbedO2appearsatthepositionwiththerelativelyhigher
binding energy. This clearly suggests a stronger interaction of
adsorbed O2with Co3O4/NBGHSs than that with NBGHSs. This
mightbeduetothefactthattheelectrontransferfromCo3O4
to NBGHSs because of their strong coupling creates suitable
environments at the surface of Co3O4 for the oxygen
adsorption,whichwouldleadtoaneasieradsorptionofO2to
the surface of the Co3O4/NBGHSs, facilitating the subsequent
dissociation of O2 through a chargetransfer reaction. The
diffusioncorrected Tafel plots in Figure 6a (see the
SupplementaryInformationfordetails)showthattheORRon
theCo3O4/NBGHSsatthelowcurrentdensityregionexhibitsa
Tafel slope (34.4 mV dec1), which is much lower than of the
ORR on the Co3O4 hollow microspheres(91.1 mV dec1), the
Co3O4/GHSs(48.9mVdec1), theCo3O4/NGHSs(44.4mVdec1),
theCo3O4/BGHSs(56.5mVdec1),andthePt/C(62.6mVdec1),
clearly suggesting that O2 is much easily adsorbed and
activatedatthesurfaceoftheCo3O4/NBGHSs.ThelowerTafel
slope makes the ORR overpotential increase slowly with
currentdensity,resultinginarelativelyhigherelectrocatalytic
activity of Co3O4/NBGHSs than that of the Co3O4 hollow
microspheres, the Co3O4/GHSs, the Co3O4/NGHSs, the
Co3O4/BGHSs,thePt/C,asdemonstratedinFigure5b.
8|J.Name.,2012,00,13
(a)
44
Potential / V vs. RHE
1.00
potential / V vs. RHE
ARTICLE
Journal
JournalName
ARTICLE
Indeed, the introduction of NBGHSs could not only

facilitate the strong electronic coupling between Co3O4 and
NBGHSs and promote an easier adsorption of O2, but also
increase the electric conductivity of the Co3O4/NBGHSs. The
electric conductivity measurements (see the Supplementary
Information for details) have shown that the Co3O4/NBGHSs
have conductivity of 70.3 S/m, which is much higher than
thatofthepureCo3O4hollowmicrospheres(2.7S/m)andis
close to the Pt/C ( 69.6 S/m). This indicates that the
introductionofNBGHSswouldmaketheCo3O4/NBGHSshighly
conductive, which is an important feature for their
applications on the ORR, since it facilitates the transfer of
electrongeneratedduringtheORR.
Previous studies has proposed a possible contribution of
the high electrocatalytic activities of some catalyst systems
fromactivesitessuchasCoNxandCoBx.24,68Suchactivesites
could also lead to the higher electrocatalytic activity of the
Co3O4/NBGHSs.However,theabsenceoftheCoNxandCoBx
peaksintheXPSspectraoftheCo3O4/NBGHSsandtheNBGHSs
(the CoNx and CoBx bonds are relatively stable in the acidic
solutions24)clearlyexcludesthecontributionofCoNxandCo
BxtothehigherelectrocatalyticactivityoftheCo3O4/NBGHSs.
Additionally, the nitrogen adsorption/desorption analysis in
Figure S5 has demonstrated that the Co3O4/NBGHSs have a
BrunauerEmme Teller (BET) specific area of 377 m2 g1,
higherthanthoseoftheCo3O4hollowspheres(163m2g1)and
the Co3O4 based materials reported previously.69,70 The pore
sizedistributioncalculatedusingaslit/cylindricalNLDFTmodel
in Figure S5b shows that the Co3O4/NBGHSs have a uniform
porosityandnarrowporesizedistributionattherangeof37
nm. These pores are formed from the stacking of the Co3O4
platesinitshollowshell,whichcouldbedemonstratedbythe
similarity in the pore size distribution of the Co3O4 hollow
microspheres and the Co3O4/NBGHSs. The presence of these
pores, along with their microspherical hollow strucrture,
would make the active materials of the Co3O4/NBGHSs well
accessbile to the ORR. The CVs in the Fe(CN)63/Fe(CN)64
solution show that the Co3O4/NBGHSs have an electroactive
surface area higher than those of the Co3O4 hollow
microspheres, the Co3O4/GHSs, the Co3O4/NGHSs, the
Co3O4/BGHSs, and the Pt/C 20 wt.%, as shown in Figure S6.
This could be an additional reason leading to the higher
electrocatalyticactivityoftheCo3O4/NBGHSs.Based on these
results, we wouldattributethehigher electrocatalyticactivity
of the Co3O4/NBGHSs to the following reasons: (1) stong
couplingbetweenCo3O4andNBGHSs;(2)stronginteractionof
adsorbed O2 with the Co3O4/NBGHSs; (3) high electric
conductivity of the Co3O4/NBGHSs, and (4) specific hollow
structureoftheCo3O4/NBGHSs.
Togaininsightinto the electrontransferkinetics involved
intheORR,theLSVsofthecatalystsinO2saturated0.1MKOH
solutions under various rotating rates were measured. Figure
5c and Figure S7 show that the voltammetric profiles of the
LSVsforallthecatalystsexhibitanincreasedcurrentintensity
with increasing rotating rate due to the enhancement of the
electrolyte diffusion. The ORR performance in the diffusion
and kinetically limited regions is then analyzed

withOnline
the
View Article
DOI: 10.1039/C6TA01349J
KouteckyLevich(KL)equation,
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:
Page 9 of 15
B 0.62nFC0 D0 2/3 1/6 (2)

wherenistheoverallnumberofelectronstransferredintheORR,F
isFaradicconstant(F=96486Cmol1),C0isthebulkconcentrationof
6
3
O2 (1.210 mol cm ), D0 is the diffusion coefficient of O2 in the
5
2 1
electrolytesolution(D0=1.910 cm s ),iskinematicviscosityof
2 1
theelectrolyte(0.01cm s for0.1MKOH).
Figure5eshowsthattheelectrontransfernumberforthe
ORR on the Co3O4/NBGHSs is larger than 3.85 over the
potential range covered from 0.25 to 0.65 V (vs. RHE),
indicating that the ORR mainly proceeds via a fourelectron
process. The electrontransfer number for ORR on
Co3O4/NBGHSsisalwayshigherthanthoseonthepureCo3O4
hollow spheres, the Co3O4/GHSs, the Co3O4/NGHSs, the
Co3O4/BGHSs, and the NBGHSs, further suggesting that
Co3O4/NBGHSs are more efficient catalysts for the ORR. This
could also be demonstrated by their relatively higher kinetic
current density, Jk, for the ORR with respect to those of the
pureCo3O4hollowspheres,theCo3O4/GHSs,theCo3O4/NGHSs,
the Co3O4/BGHSs, and the NBGHSs (Figure 5f). Although the
ORR on the Pt/C also proceeds via the fourelectron process,
as demonstrated by its electrontransfer number (close to 4)
shown in Figure 5e, its kinetic current density is much lower
than that on the Co3O4/NBGHSs, indicating that the
Co3O4/NBGHSs is more kinetically facile toward ORR than the
Pt/C.ThisiswellconsistentwiththeresultsinFigure5b,which
shows that the Co3O4/NBGHSs could exhibit higher current
density and more positive halfwave potential for the ORR
than the Pt/C. These results strongly suggest that the
Co3O4/NBGHSscouldbeusedasefficientcatalystsfortheORR
withgreatpotentialtoreplacethenoblemetalbasedcatalysts.
The potential use of the Co3O4/NBGHSs as efficient
electrocatalysts could further be supported by their relatively
higherstabilityandbettertolerancetomethanolandCOthan
those of Pt/C. As shown in Figure 6b, the Co3O4/NBGHSs can
remain highly efficient for the ORR with only ~ 6% of their
original activity loss observable over 10 h of the ORR. The
introductionofCOormethanolshowsnonoticeablechanges
J.Name.,2013,00,13|9
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JournalName
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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
10|J.Name.,2012,00,13
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1.80
-2
35
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DOI: 10.1039/C6TA01349J
1.50
1.5
(b)
0.1
0.6
Pt/C
Co3O4/NBGHSs
0.4
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
Specific capacity / mAh g
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
batteries assembled with other catalysts reported in the

7679
which stongly suggests the great potential of
literature,
using the Co3O4/NBGHSs as the cathode for the metalair
batteries. Indeed, the potential use of the Co3O4/NBGHSs for
the metalair batteries could further be demonstrated by the
highperformancestabilityoftheCo3O4/NBGHSsbasedbattery.
As shown in Figure 8b, the Co3O4/NBGHSs assembled battery
could remain highly efficient with no voltage drop observed
2
whengalvanostaticallydischargedat5mAcm for25horat
2
50 mA cm for 15 h. This is contrast to the battery with the
Pt/Cinwhichdistinctvoltagedropcouldbeobservedwhenit
isdischargedforalongtime,especiallyattherelativelyhigher
current density. As the galvanostatic discharge continues, the
Zn metal will undergo a depletion. The battery would stop
functioning when all the Zn metal is consumed. Figure 8c
shows the specific capacity normalized to the mass of the
1
consumed Zn is 705 mAh gZn (corresponding to an energy
1
2
density of 909 Wh kgZn ) at a current density of 10 mA cm ,
whichindicates86%utilizationofthetheoreticalcapaciy(~820
1
2
mAhgZn ).Evenatthehighercurrentdensityof100mAcm ,
1
the specific capacity of the battery is 681 mAh gZn ,
corresponding to the energy density of 768 Wh kgZn1. These
values are also higher than those of Znair batteries using
76, 78, 80
further
other catalysts reported in the literature,
demonstratingthepotentialuseoftheCo3O4/NBGHSsforthe
metalairbatteries.
The results shown above clearly demonstrate that the
Co3O4/NBGHSs are highly active electrocatalysts for both the
ORR andthe OERand can be usedinmetalairbatteries with
great potential to replace the precious metal/carbon based
materials. Largescale production showed that up to 10 g of
Co3O4/NBGHSscouldbeproducedinonecycleofthereaction
process if the volume of the reactions is increased by 100
times with the relative mole ratio of the reaction precursors
remainingconstant.Theobtainedproductsshow morphology
andelectrochemicalpropertiessimilartothoseobtainedwith
the smallscale production process. This suggests a great
J.Name.,2013,00,13|11
0.4
(a)
-2
1.4
Journal
JournalName
potential of the scalability of the present technique for the

massproductionoftheCo3O4/NBGHSs.
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
12|J.Name.,2012,00,13
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ARTICLE
monochromatizedCuKaradiation(=1.5418).Thedatawere
collected between scattering angles (2) of 10 and 80o.
Thermogravimetric analysis (TGA) was performed on a
METTLERinstrumentsunderaO2atmosphereataheatingrate
of5C/min.
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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Journal of Materials Chemistry A

View Article Online
DOI: 10.1039/C6TA01349J
Cobalt Oxide-coated N- and B-doped Graphene Hollow Spheres

as a Bifunctional Electrocatalyst for Oxygen Reduction and
Oxygen Evolution Reactions
Zhongqing Jiang,a,b Zhong-Jie Jiang,*c Thandavarayan Maiyalaganb and Arumugam
Manthiram*b
a
Department of Chemical Engineering, Ningbo University of Technology, Ningbo,
Zhejiang 315016, P. R. China.
b
Electrochemical Energy Laboratory & Materials Science and Engineering
Program, The University of Texas at Austin, Austin, Texas 78712, United States.
*E-mail: manth@austin.utexas.edu
c
New Energy Research Institute, College of Environment and Energy, South China
University of Technology, Guangzhou, Guangdong 510006, P. R. China.
*E-mail: eszjiang@scut.edu.cn, and zhongjiejiang1978@hotmail.com
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.
Table of Content

Cobalt Oxide Coated N and B Doped Graphene Hollow Spheres As

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Cobalt Oxide Coated N and B Doped Graphene Hollow Spheres As

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This is an Accepted Manuscript, which has been through the

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Bifunctional electrocatalysts for both oxygen reduction

attention in recent years.1, 79 Such materials could not only

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used as electrode materials in energy conversion and storage

the TMOs grown on their surface, which would not

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which appear as translucent pancakes with opaque

Journal of Materials Chemistry A Accepted Manuscript

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4e, where five peaks corresponding to the BN, pyridinic N,

Journal of Materials Chemistry A Accepted Manuscript

the Co3O4 hollow spheres and the Co3O4 deposited on

Journal of Materials Chemistry A Accepted Manuscript

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Electron Transfer Number

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Journal of Materials Chemistry A Accepted Manuscript

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electron transfer from Co3O4 to NBGHSs, the component of

Journal of Materials Chemistry A Accepted Manuscript

Potential / V vs. RHE

potential / V vs. RHE

Indeed, the introduction of NBGHSs could not only

and kinetically limited regions is then analyzed

Journal of Materials Chemistry A Accepted Manuscript

B 0.62nFC0 D0 2/3 1/6 (2)

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Potential / V vs. RHE

Journal of Materials Chemistry A Accepted Manuscript

Potential / V vs. RHE

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Specific capacity / mAh g

batteries assembled with other catalysts reported in the

Journal of Materials Chemistry A Accepted Manuscript

potential of the scalability of the present technique for the

Journal of Materials Chemistry A Accepted Manuscript

G. H. Yu, L. B. Hu, N. A. Liu, H. L. Wang, M. Vosgueritchian, Y.

Journal of Materials Chemistry A Accepted Manuscript

83 Z. Jiang, X. Zhao and A. Manthiram, Int. J. Hydrogen

Journal of Materials Chemistry A Accepted Manuscript

Journal of Materials Chemistry A

Cobalt Oxide-coated N- and B-doped Graphene Hollow Spheres

Journal of Materials Chemistry A Accepted Manuscript

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