Analysis of Co3 O4/M ildly Oxidized Graphite Oxide(mGO)Nanocomposites of M ild Oxidation Degree for the Removal of Acid Orange 7

WANG Qian(王 倩)，SHIPeng-hui(时鹏辉)，2，ZHU Shao-bo(朱少波)，LIJie-bing(李洁冰)，ASIF Hussain，LIDeng-xin(李登新)*

1 College of Environmental Science and Engineering，Donghua University，Shanghai201620，China

2 College of Environmental and Chemical Engineering，Shanghai University of Electronic Power，Shanghai200090，China

Analysis of Co3O4/M ildly Oxidized Graphite Oxide(mGO)Nanocomposites of M ild Oxidation Degree for the Removal of Acid Orange 7

WANG Qian(王 倩)1，SHIPeng-hui(时鹏辉)1，2，ZHU Shao-bo(朱少波)1，LIJie-bing(李洁冰)1，ASIF Hussain1，LIDeng-xin(李登新)1*

1 College of Environmental Science and Engineering，Donghua University，Shanghai201620，China

2 College of Environmental and Chemical Engineering，Shanghai University of Electronic Power，Shanghai200090，China

In this study，a series of Co3O4/m ild ly oxidized graphite oxide(mGO)nanocatalysts(Co3O4/mGO-1，Co3O4/mGO-2 and Co3O4/mGO-3)were synthesized through solvothermalmethod and used as amediator for the heterogeneous peroxymonosulfate(PMS) activation.The performance of Co3O4/mGO/PMS system was investigated using acid orange 7(AO7).Results showed that Co3O4/mGO-3 had the best degradation efficiency of AO7 and the removal rate was above 90%in about 6 m in.The phenomenon indicated the catalytic activity of Co3O4/mGO com posites was related to the oxidation degree of graphite oxide(GO).In addition，experiments showed the content of Co3O4had an effect on the catalytic activity.The com posites were characterized w ith X-ray powder diffraction(XRD)，FTIR，Raman，X-ray photoelectron spectroscopy(XPS)and transm ission electron m icroscopy(TEM).According to the charactrization and synergistic catalytic mechanism，the generation of Co—OH complexes found to be the initial step to activate PMS in the heterogeneous system of Co3O4/ mGO hybrid.

heterogeneous reaction; synergistic catalysis; mildly oxidized graphite oxide(mGO);Co—OH complexes

Introduction

The Nobel Prize in Physics2010 was awarded to Andre Geim and Konstantin Novoselov“for ground breaking experiments regarding the two-dimensionalmaterial graphene”.The discovery of graphene caused the research upsurge in the world for its extraordinary mechanical and electronic transport properties.However，it is difficult to deposit metal or metal oxide on its surface to synthesize graphene-based hybridmaterialsbecause of its poorly soluble in water and polar organic solvents［1］.

It is well known that graphite oxide(GO)is a hydrophilic material owing to the presence of hydroxylgroups decorated on the surface of carbon sheets and the carboxyl groups located at the edges［2］.In the middle of the 20th century，there were mainly three kinds of classic methods to prepare GO:Brodiemethod［3］，staudenmaier method［4］and Hummers method［5］，respectively.Nevertheless，a conventionally-modified Hummersmethod became most popular for its properties of simpleness，security and time saving.Proportional amounts of oxidants，for instance，potassium permanganate，sodium nitrate and concentrated sulfuric acid are used in the fabrication process.Different from graphene，GO consists of a hexagonal ring based carbon network with both sp2and sp3hybridized carbon atoms.As a starting material，GO has been applied into inorganic or organic hybrid nanocomposite systemsmore and more due to its favorable properties［6-7］.For instance，Gao et al.［8］reported a novel graphite oxide GO-TiO2microsphere hierarchical membrane，which performed well and exhibited promising potential in clean water production field.

As the intermediate product of making graphene，GO has been w idely applied in the preparation of cheap graphene and functionalized graphene［9-10］.Therefore， spectroscopy characterization and structure analysis of the different degree of oxidation of GO and associated catalyst have important theoretical and practical significances for revealing the structural transformation rule in the process of oxidation and the preparation of GO and surfacemodification research.

Recently，there has been a considerable amount of interest in the advanced oxidation processes(AOP)which hydroxyl radicals are themain oxidants involved in detoxification of dyeing wastewater.More lately， sulfate radical based-advanced oxidation technologies were engaged in the area of water treatment and other environmental applications.SO· is a major oxidizing specie with high standard redox potential(2.5-3.1 V)compared with·OH radicals(1.89-2.72 V)［11-12］.Furthermore，the high reactivity of sulfate radicals could remain in the range of pH 3-8［13］.Plenty of studies［14-16］have fully proven the applicability of cobalt ion as an efficient catalyst for the activation of peroxymonosulfate(PMS)to produce sulphate radicals.However，the adverse effectof dissolved cobalt inwater still needs to be disposed.Therefore，it is better to activate PMS via a heterogeneous way that could deal with the problem of leached cobalt.Anipsitakis et al.first reported the hetero-PMS-act employing commercially available Co3O4particles［15］.Lately，well-dispersed nanocrystalline Co3O4particles were immobilized onto GO supporter and had played a good role in the water treatment［17］.As a potential material，the nanoparticles may be further used in dyeing wastewater treatment.Therefore，the interaction betweenmGO and Co3O4would be very critical.

In this study，a series of Co3O4/mildly oxidized graphite oxide(mGO) nanocatalysts were prepared and used as a mediator for the heterogeneous PMSactivation.The performance of Co3O4/mGO/PMS system was investigated using acid orange 7(AO7)，a textile azo-dye，as amodel compound.As a result，along with the increase in hydrophilicity during the oxidation process，GO obtained with the maximum possible degree of oxidation expressed the best efficiency along with more oxygen atoms and hydroxyl groups grafted on both sides of them.The formation of Co—OH complexes at the surface of Co3O4/mGO nanoparticles and the synergistic catalytic mechanism between Co3O4andmGO were discussed.

1 Experimental

1.1 M aterials

Flake graphite(300 mesh)was supplied by Shanghai Yifan Graphite Co.，Ltd.Concentrated sulfuric acid(H2SO4，98%)，potassium permanganate(KMnO4)，sodium nitrate(NaNO3)，hydrogen peroxide(H2O2，30%)，cobalt nitrate hexahydrate［Co(NO3)2·6H2O］，AO7(98%purity)，PMS［2(KHSO5)·KHSO4·K2SO4］，and 4.5%-4.9%active oxygen were manufactured by DuPont.A ll chem icals used in this study are analytical grade.

1.2 Synthesis

In this experiment， three kinds of catalysts were composed.Raw materialmGO were prepared w ith themodified Hummersmethod［5，18］.By changing the dosage of KMnO4(2.5，7.5，and 15 g)，we obtained a series of samples of different oxidation degree which were marked asmGO-1，mGO-2，and mGO-3.To compose the catalysts，mGO(including mGO-1，mGO-2 and mGO-3，200 mg)was dissolved into 120 m L of hexyl alcohol and sonicated for 2 h.Meanwhile，Co(NO3)2·6H2O (1 mmol) was dissolved into another 80 m L of hexyl alcohol.The mixture was heated to 140℃under constantmagnetic stirring for 12 h after stirred for 2 h.The resulted productwas collected by centrifugation and washed w ith ethanol and water for several times.Finally，the sediment was dried in a vacuum oven at60℃ for 24 h.And the product was tagged as Co3O4/mGO (including Co3O4/mGO-1，Co3O4/mGO-2 and Co3O4/mGO-3).

1.3 Characterizations

X-ray powder diffraction(XRD)patternswere obtained on a Rigaku X-ray diffractometer(D/Max-2550PC，Japan)w ith a Cu-Ka radiation source operated at40 kV and 200 mA in the 2θ range 5°-90°.

The nanoscale structures were observed using transmission electron m icroscopy(TEM，JEOL JEM-2100F) with an accelerating voltage of 200 kV.

The Fourier transform infrared spectroscopy (FTIR) spectra of the materials were recorded between 4 000 and 500 cm-1using a Thermo Nicolet NEXUS 670 FTIR spectrometer.

Raman spectra were recorded on the Nicolet Micro-Raman System(NEXUS-670，USA)using a 1 200 lines/mm grating and a 50 objective lens.He:Ne green laser with 633 nm wavelength was used to excite Raman signal w ith the power of 17 mW.

The atomic composition of Co3O4/mGO was detected by X-ray photoelectron spectroscopy(XPS).XPS experiments were carried outon an RBD upgraded PHI-5000C ESCA system (Perkin Elmer)with Al Kαradiation(hυ=1 486.6 eV).Binding energies were calibrated by using the containment carbon(C 1s=284.6 eV).The data analysis was carried out by using XPSPeak 4.1.

1.4 Experimental

Firstly，100 m L dye wastewater(0.2 mmol/L)was put into a 250 m L conical flask.Then，the pH of the solution was adjusted to neutral using sodiumm bicarbonate solution (NaHCO3，0.5 mol/L)after PMS(0.2 mmol/L)was added into it.Finally，0.05 g catalystwas put into them ixture and the vessel was placed in a water-bathing constant-temperature vibrator controlled at 25℃ throughout the process.At given reaction time intervals，sampleswere taken for analysis.

2 Results and Discussion

2.1 Degradation of AO7 performances

The degradation curves of AO7 under the effectof different catalysts are shown in Fig.1，where C/Co represents the residual rate of AO7 in thewater and smaller valuemeans higher removal rate.The removal rate of AO7 depends on the concentration of sulfate radicals generated，and hence it can be used to evaluate the performance of the supported cobalt catalysts as activators of PMS.In order to achieve good efficiency，the experiments were carried in neutral conditions which were adjusted w ith 0.5mol/L sodium bicarbonate buffer.The catalysts(Co3O4/mGO) dosage was 0.05 g/L.All experimentswere conducted at room temperature.And pH was constant in the whole process of reaction［19］.

As shown in Fig.1，the adsorption abilities of PMS，Co3O4and mGO-3 are weaker than that of Co3O4/mGO composites.Catalytic propertiesof Co3O4/mGO compoundsare Co3O4/mGO-3＞Co3O4/mGO-2＞Co3O4/mGO-1，respectively.The cobalt catalyst supports on mGO-3 exhibited a much higher catalytic efficiency than the other two materials.It is remarkable that AO7 with a same starting concentration can be nearly degraded in 6min in a typical run when Co3O4/mGO-3 is used as the catalyst.That was to say the catalytic properties of the compounds increased with the improving oxidation degree.Therefore，we presume that high oxidation degree of mGO supporter with appropriate loading of Co3O4can activate PMS efficiently during the reaction.And the effect resulting from these factors is conjunct.Furthermore，the formation of the surface Co—OH complex played an import role in the whole process［18］.

2.2 Catalyst characterization

Graphite raw material shows obvious diffraction peak(002) at26.5°which reveals that it has good degree of crystallinity.Compared with graphitematerials，mGO samples show wide peak (001)at around 10°and increases interlayer spacings which accesses to the formation of large numbers of oxygen-containing groups.In addition，tests show that the electrical resistivity of mGO samples increases gradually(from 0.04 to 118.6Ω·m) with the increasing dosage of oxidant.And the results indicatethe oxidation dgree of GO increases progressively aswell.These groups helpmGO with strong hydrophilism.As can be seen from Fig.2，with the increasing dosage of oxidant，diffraction peaks (002) of mGO samples turn to weaker and wider.And diffraction peak (001) is shaped.Combining previous studies［20-21］，the phenomenon could be explained that the process of preparation mGO at low temperature stage was amild oxidation of the insertion process.The main effects of oxidant were to oxide layer edge or defect of flake graphite so as to help the polar sulfuric acid molecules and hydrogen sulfate ions smoothly insert into the graphite structure layer，and continue the following formation of oxygen-containing groups.

The spectra of Co3O4/mGO-1 catalyst show distinct peaks at31.2°，36.7°，44.2°，55.6°，59.2°，65.7°and 77.4°.The results are consistent w ith the diffraction peaks of(220)，(311)，(400)，(422)，(511)，(440)and(533)of Co3O4，which proves that the formation and existence of cobalt oxide crystal［22-24］.For Co3O4/mGO-2 and Co3O4/mGO-3，w ith the increasing oxidation degree，the diffraction signal of Co3O4is weak and nearly disappeared.Meanwhile，diffraction peak (001)of mGO samples turn to weaker and w ider.However，w ide peaks at 2θ=20°-27°can be seen.This indicatesmGO layers pile up disorderly and it also proves cobalt oxide is successly loaded on both sides ofmGO layers［25］.

The chem ical structure of the catalysts was investigated by FTIR spectrum.There are a lot of carboxyl，hydroxyl and epoxy groups grow ing on mGO surface.As shown in Fig.4，Co3O4/mGO samples have several obvious diffraction peaks.The peak at 3 437 cm-1attributes to O—H stretching and bending vibration［26］.Peaks at 1 630 and 2 926 cm-1turn to weaker on account of the short absorptions of C ＝C and C—H of graphitew ith the increasing oxidation degree［27］.Peak at874 cm-1is due to the deformation and vibration of N—H.It is important to see that peak at 1 439 cm-1decreases gradually w ith the increased oxidation degree of graphite and finally disappears.This is because w ith the increased dosage of oxidant，the carbon atoms and C—C bond which in the form of sp2hybridization in the structures gradually reduces［28-29］.In addition，compared with Co3O4/mGO-3，Co3O4/mGO-1 and Co3O4/mGO-2 show strong absorptions at654 cm-1because of the large amountof Co3O4.And the result is in linew ith thatof XRD.In conclusion，although the amountof oxygen-containing groups and multi-model active sites in the structure of graphite increase w ith the enhanced oxidation degree，the group species are alike.

The spectra of graphite and Co3O4/mGO are shown in Fig.5.Raman spectroscopy is a w idely used tool for the characterization of carbon products，especially considering the fact that conjugated and C—C bonds lead to high Raman intensities.The spectrum of GO exhibits two regular peaks，corresponding to the D-band line(1 350 cm-1)and the G-band line(1 580 cm-1)［24］which assign to E2gand A1gspecies of the infinite crystal，respectively［23］.A D-band line is observed in the center of graphite raw material and proves the existence of a significant number of defects.Obviously，the D-band tends to sharper and stronger.We can see ID/IGincreased gradually w ith the increased dosage of oxidant during graphite amorphization.Therefore，it is unassailable that oxidation degree of graphite is grow ing.In addition，combined w ith XRD and FTIR analyses，we conclude thatw ith the increasing oxidation degree，the size of the in-plane sp2domain reduces and part of the carbon atoms transforms to sp3hybridization which lead to the formation of its disordered structure degree.Strong peak at 2 717 cm-1which corresponds to 2D-band line is allowed in graphite crystal.Diffraction peak of 2D-band line turns to weaker and nearly disappears along w ith the grow ing oxidation degree of graphite.

XPS spectra of supported cobalt catalysts are obtained to determine the compositions of the catalysts and reveal the nature of carbon and oxygen bonds.The peaks at 286.2，533.6，and 783.9 eV are attributed to the characteristic peaks of C 1s，O 1s and Co 2p，respectively(shown in Fig.6(a)，Co3O4/mGO-1).The spectrum of Co3O4/mGO-3 is similar to the Co3O4/ mGO-1.The O 1s core level spectra collected on Co3O4/mGO are shown in Fig.6(b).All O 1s spectra of Co3O4/mGO are clearly asymmetric，which indicate the existence of different oxygen species at the surface of the supporter.For Fig.6(b)，the main peak at about 532.5 eV corresponds to surfacehydroxyl groups(Co—OH)that is ubiquitous in air-exposed cobaltoxidematerials［30-31］while the peak(Co3O4/mGO-1)at lower binding energy of 530.7 eV is identified to lattice oxygen species from Co3O4［32］.However，the peak is vanished from the spectrum of Co3O4/mGO-3 due to the small amount of Co3O4.This phenomenon is in keeping w ith those of XRD and FTIR.In addition，a resolved peak at around 533.5 eV is attributed to the adsorbed oxygen species such as C—O bonds and surface bound water［33］.Figure 6(c)shows Co 2p XPS spectra of Co3O4/mGO-1 and Co3O4/mGO-3.Twomain peaks at 781.7 eV(Co 2p3/2) and 797.1 eV (Co 2p1/2) are observed.Compared w ith the main peaks of Co3O4/mGO-3，the peaks of Co3O4/mGO-1 are sharper and stronger.A spinorbit splitting of 15.4 eV is also considered.The Co 2p spectrum is well consistent w ith the XPS spectrum of Co3O4［34-35］.And the result is in linew ith the characterizations ahead.

The catalystswere further characterized by TEM.Figures7 (a)and(b)show typical low magnification TEM images of Co3O4/mGO-3 and Co3O4/mGO-1.Co3O4nanoparticles are embedded in the mGO nanosheets，which indicates that the Co3O4nanoparticles are firm ly anchored onto the supporter andthey appear to be a strong interaction between Co3O4and mGO［36］.Obviously，Co3O4particles are dispersed on mGO homogeneously.Itmay be due to the mGO nanosheets in the composite which is helpful to suppress the aggregation and hindering the grow th of nanoparticles to a certain extent［37］.In addition，we can see directly that the quantities of Co3O4loaded on the two kinds of catalysts are different.It is also reasonable to suggest that the homogeneous hybridization between Co3O4nanoparticles and mGO nanosheets is beneficial for the formation of Co—OH complexes and for achieving high rate performances.

2.3 Catalytic activities

Similar to Co3O4/mGO，mCo3O4/GO were composed by using differentdosage of Co(NO3)2·6H2O and the same dosage of GO(the dosage of GO was the same as mGO-3).The products were labeled as Co3O4-1/GO， Co3O4-2/GO，Co3O4-3/GO，Co3O4-4/GO， and Co3O4-5/GO (the Co percentage in the compounds followed the order Co3O4-5/GO＞Co3O4-4/GO＞Co3O4-3/GO＞Co3O4-2/GO＞Co3O4-1/GO).In Fig.8，the degradation efficiency of AO7 in water by using Co3O4/GO composites as catalysts follows the order Co3O4-3/GO ＞Co3O4-2/GO ＞Co3O4-1/GO ＞Co3O4-4/ GO ＞ Co3O4-5/GO.Further increasing the Co3O4loading results in a significant decrease of degradation activity.Co3O4-3/GO has the bestdegradation of AO7，which indicates that this concentration produces the best catalysis.According to the experimental result，although bare Co3O4or GO has a low catalytic activity，their hybrid (Co3O4/GO) exhibits an unexpectedly high catalytic activity in the degradation of AO7 in water by advanced oxidation technology based on sulfate radicals.In addition，the nanocomposite shows different catalytic activities w ith different Co3O4loadings.This phenomenon shows the synergistic catalysis exists between Co3O4and GO.

2.4 Stability of the catalyst

Four recycling runs of the catalystwere conducted，and the catalyst(Co3O4/mGO-3)was recycled under the same reaction conditions.After every run of reaction，the catalyst was collected，washed thoroughly，and dried in a vacuum oven at 60℃ before the next round.As shown in Fig.9，the regenerated catalyst exhibits good performance and stability.The activity of the catalyst dropped slightly compared with the fresh catalyst.The concentration of the dissolved cobalt ions(0.04 mg/L) from Co3O4was almost the same as the fresh catalyst detected through the inductive coupled plasma emission spectrometer (ICP).After four runs，the degradation of AO7 occurred w ithin 40 min.Therefore，the Co3O4/mGO-3 has good catalytic performance，slight ion leaching，and an excellent long-term stability.

2.5 Catalytic mechanism analysis

GO is a hydrophilic material ow ing to the presence of hydroxyl groups decorated on the surface of carbon sheets and the carboxyl groups located at the edges.

Based on Fig.1，although bare GO or pure Co3O4or PMS alone exhibits a low catalytic activity，their hybrid(Co3O4/ GO)exhibits an unexpectedly high catalytic activity in the degradation of AO7 in water by advanced oxidation technology.However，higher Co3O4content in the catalyst does not automatically result in a higher catalytic activity.The highest catalytic activity is observed when the Co3O4loading is about1 mmol in the catalyst(Co3O4-3/GO).As shown in Fig.8，the catalytic activity first increases and then decreases w ith increasing Co3O4loading，which indicates a proportional relation between the Co3O4content of the catalyst and the production of a catalytic active site.

As seen in the XPS spectra and TEM images(Figs.6-7)，although the amount of Co3O4crystal particles on the surface of mGO-3 is lower than that of mGO-1，the catalytic activity of Co3O4/mGO-3 is higher.Research［38］showed that metal loading affected the degree to which the carbon-support surface was covered，which leaded to a decrease in specific surface area and activity.Thus，if the relative amount of Co3O4is higher than the optimal quantity，the GO surface is predominantlycovered by Co3O4so that the area of the exposed GO surface available for H2O dissociation becomes limited.

XRD and FTIR analyses indicate the formation of large amount of oxygen-containing groups on GO layers.Aside from themain peak at530.7 eV that corresponds to the lattice oxygen species from Co3O4，a shoulder at a higher binding energy of 532.5 eV is attributed to Co—OH on the surface from the O 1s pattern(Fig.6).

There are two reasons for the formation of Co—OH complexes.One is that the hydroxyl groups are ubiquitous in air-exposed cobalt oxidematerials.The other is that Co species attach to hydroxyl groups decorated on the surface of GO directly.The relevant equations are as follows:［19，39-40］

Therefore，based on reaction(1)，the generation of Co—OH complexes should be the initial step to activate PMS in the heterogeneous system.

3 Conclusions

We treated graphite with different amount of KMnO4and obtained mGO which were decorated w ith—COOH and—OH groups.Experiments show thathigher degree of oxidation of the graphite w ith proper cobalt loaded on leads to a better performance.According to the charactrization and synergistic catalyticmechanism，the generation of Co—OH complexes are found to be the initial step to activate PMS in the heterogeneous system of Co3O4/mGO hybrid.

［1］Gao Y Y，Pu X P，Zhang D F，et al.Combustion Synthesis of Graphene Oxide-TiO2Hybrid Materials for Photodegradation of Methyl Orange［J］.Carbon，2012，50(11):4093-4101.

［2］He H Y，Riedl T，Lerf A，et al.Solid-State NMR Studies of the Structure of Graphite Oxide［J］.Journal of Physical Chemistry，1996，100(51):19954-19958.

［3］Brodie B.Surle Poids Atom ique du Graphite［J］.Advances in Chemical Physics，1860，59(7):466-472.

［4］Staudenmaier L.Verfahren zur Darstellung der Graphitsäure［J］.Berichte der Deutschen Chemischen Gesellschaft，1898，31(2): 1481-1487.

［5］Hummers W S，Offeman R E.Preparation of Graphitic Oxide［J］.Journal of the American Chemical Society，1958，80(6): 1339-1339.

［6］Pasricha R，Gupta S，Srivastava A K.A Facile and Novel Synthesis of Ag-Graphene-Based Nanocomposites［J］.Small，2009，5(20):2253-2259.

［7］Akhavan O，Ghaderi E.Photocatalytic Reduction of Graphene Oxide Nanosheets on TiO2Thin Film for Photoinactivation of Bacteria in Solar Light Irradiation［J］.Journal of Physical Chemistry C，2009，113(47):20214-20220.

［8］Gao P，Liu Z Y，Tai M H，et al.Multifunctional Graphene Oxide-TiO2M icrosphere Hierarchical Membrane for Clean Water Production［J］.Applied Catalysis B:Environmental，2013，138/139:17-25.

［9］Li D，Mueller M B，Gilje S，et al.Processable Aqueous Dispersions of Graphene Nanosheets［J］.Nature Nanotechnology，2008，3(2):101-105.

［10］Dreyer D R，Park S，Bielawski C W，et al.The Chemistry of Graphene Oxide［J］.Chemical Society Reviews，2010，39(1): 228-240.

［11］Anipsitakis G P，Dionysiou D D.Transition Metal/UV-Based Advanced Oxidation Technologies for Water Decontam ination［J］.Applied Catalysis B:Environmental，2004，54(3):155-163.

［12］Anipsitakis G P，Dionysiou D D，Gonzalez M A.Cobalt-Mediated Activation of Peroxymonosulfate and Sulfate Radical Attack on Phenolic Compounds.Implications of Chloride Ions［J］.Environmental Science＆Technology，2006，40(3):1000-1007.

［13］Fernandez J，Maruthamuthu P，Renken A，et al.Bleaching and Photobleaching of Orange IIw ithin Seconds by the Oxone/Co2+Reagent in Fenton-like Processes［J］.Applied Catalysis B: Environmental，2004，49(3):207-215.

［14］Chan K H，Chu W.Degradation of Atrazine by Cobalt-Mediated Activation of Peroxymonosulfate:Different Cobalt Counteranions in Homogenous Process and Cobalt Oxide Catalysts in Photolytic Heterogeneous Process［J］.Water Research，2009，43(9): 2513-2521.

［15］Anipsitakis G P，Dionysiou D D.Heterogeneous Activation of Oxone Using Co3O4［J］.Journal of Physical Chemistry B，2005，109(27):13052-13055.

［16］Ling SK，Wang S，Peng Y.Oxidative Degradation of Dyes in Water Using Co2+/H2O2and Co2+/Peroxymonosulfate［J］.Journal of Hazardous Materials，2010，178(1/2/3):385-389.

［17］Shi PH，Zhu S B，Su R J，et al.Synthesis of Co3O4/RGO as Catalyst for Degradation of Orange II in Water by Advanced Oxidation Processes Based on Sulfate Radicals［J］.Advanced Materials Research，2012，534:269-272.

［18］Shi PH，Su R J，Zhu S B，et al.Supported Cobalt Oxide on Graphene Oxide:Highly Efficient Catalysts for the Removal of Orange II from Water［J］.Journal of Hazardous Materials，2012，229/230:331-339.

［19］Zhang JL，Yang H J，Shen G X，et al.Reduction of Graphene Oxide via L-Ascorbic Acid［J］.Chemical Communications (Cambridge，England)，2010，46(7):1112-1114.

［20］Zhang W，Tay H L，Lim S S，et al.Supported CobaltOxide on MgO:Highly Efficient Catalysts for Degradation of Organic Dyes in Dilute Solutions［J］.Applied Catalysis B:Environmental，2010，95(1/2):93-99.

［21］Lerf A，Buchsteiner A，Pieper J，et al.Hydration Behavior and Dynamics ofWater Molecules in Graphite Oxide［J］.Journal of Physics and Chemistry of Solids，2006，67(5/6):1106-1110.

［22］Huang Q，Sun H J，Yang Y H.Spectroscopy Characterization and Analysis of Graphite Oxide［J］.Chinese Journal of Inorganic Chemistry，2011，27(9):1721-1726.(in Chinese)

［23］Varghese B，Teo C H，Zhu Y，et al.Co3O4Nanostructuresw ith Different Morphologies and Their Field-Em ission Properties［J］.Advanced Functional Materials，2007，17(12):1932-1939.

［24］Brik Y，Kacim i M，Ziyad M，et al.Titania-Supported Cobalt and Cobalt-Phosphorus Catalysts: Characterization and Performances in Ethane Oxidative Dehydrogenation［J］.Journal of Catalysis，2001，202(1):118-128.

［25］Spinolo G，Ardizzone S，Trasatti S.Surface Characterization of Co3O4Electrodesprepared by the Sol-GelMethod［J］.Journal of Electroanalytical Chemistry，1997，423(1/2):49-57.

［26］Enache D I，Rebours B，Roy-Auberger M，et al.In situ XRD Study of the Influence of Thermal Treatmenton the Characteristics and the Catalytic Properties of Cobalt-Based Fischer-Tropsch Catalysts［J］.Journal of Catalysis，2002，205(2):346-353.

［27］Wang X L，Dou W Q.Preparation of Graphite Oxide(GO)and the Thermal Stability of Silicone Rubber/GO Nanocomposites［J］.Thermochimica Acta，2012，529:25-28.

［28］Matsuo Y，Tabata T，Fukunaga T，et al.Preparation and Characterization of Silylated Graphite Oxide［J］.Carbon，2005，43(14):2875-2882.

［29］Du N，Zhao C Y， Chen Q， et al.Preparation and Characterization of Nylon 6/Graphite Composite［J］.Materials Chemistry and Physics，2010，120(1):167-171.

［30］Hadjiev V G，Iliev M N，Vergilov I V.The Raman-Spectra of Co3O4［J］.Journal of Physics C—Solid State Physics，1988，21 (7):L199-L201.

［31］Mattevi C.Evolution of Electrical，Chem ical，and Structural Properties of Transparent and Conducting Chemically Derived Graphene Thin Films［J］.Advanced FunctionalMaterials，2009，19(16):2577-2583.

［32］Mattevi C，Eda G，Agnoli S，et al.Evolution of Electrical，Chem ical， and Structural Properties of Transparent and Conducting Chemically Derived Graphene Thin Films［J］.Advanced Functional Materials，2009，19(16):2577-2583.

［33］Hagelin-Weaver H A E，Hoflund G B，M inahan D M，et al.Electron Energy Loss Spectroscopic Investigation of Co Metal，CoO，and Co3O4before and after Ar+Bombardment［J］.Applied Surface Science，2004，235(4):420-448.

［34］Moussy JB.From Epitaxial Grow th of Ferrite Thin Films to Spin-Polarized Tunnelling［J］.Journal of Physics D: Applied Physics，2013，46(14):143001.

［35］Sun C，Berg JC.A Review of the Different Techniques for Solid Surface Acid-Base Characterization［J］.Advances in Colloid and Interface Science，2003，105:151-175.

［36］Fan Y，Shao H B，Wang J B，et al.Synthesis of Foam-like Freestanding Co3O4Nanosheets w ith Enhanced Electrochem ical Activities［J］.Chemical Communications (Cambridge，England)，2011，47(12):3469-71.

［37］Williams G， Kamat P V.Graphene-Semiconductor Nanocomposites: Excited-State Interactions between ZnO Nanoparticles and Graphene Oxide［J］.Langmuir，2009，25 (24):13869-13873.

［38］Kim J，Edwards J O.A Study of Cobalt Catalysis and Copper Modification in the Coupled Decompositions of Hydrogen Peroxide and Peroxomonosulfate Ion［J］.Inorganica Chimica Acta，1995，235(1/2):9-13.

［39］Yang Q H，Choi H，Dionysiou D D.Nanocrystalline Cobalt Oxide Immobilized on Titanium Dioxide Nanoparticles for the Heterogeneous Activation of Peroxymonosulfate［J］.Applied Catalysis B:Environmental，2007，74(1/2):170-178.

［40］Bezerra CW B，Zhang L，Lee K，et al.A Review of Fe-N/C and Co-N/C Catalysts for the Oxygen Reduction Reaction［J］.Electrochim Acta，2008，53:4937-4951.

O643 Document code:A

1672-5220(2015)02-0185-07

date:2013-12-26

s:Innovation Program of Shanghai Municipal Education Comm ission，China(No.12ZZ069);Research Fund for the Doctoral Program of Higher Education，China(No.20130075110006)

* Correspondence should be addressed to LIDeng-xin，E-mail:lidengxin@dhu.edu.cn