Research ArticlePreparation and Photocatalytic Performance ofTi3C2TiO2CuO Ternary Nanocomposites
Yang Lu1 Meihuan Yao2 Aiguo Zhou1 Qianku Hu1 and LiboWang1
1School of Materials Science and Engineering Henan Polytechnic University Jiaozuo Henan 454000 China2School of Chemistry and Chemical Engineering Henan Normal University Xinxiang 453007 China
Correspondence should be addressed to Libo Wang wanglibo537hpueducn
Received 6 January 2017 Accepted 7 March 2017 Published 3 April 2017
Academic Editor Jim Low
Copyright copy 2017 Yang Lu et al This is an open access article distributed under the Creative Commons Attribution License whichpermits unrestricted use distribution and reproduction in any medium provided the original work is properly cited
Ti3C2TiO2CuO nanocomposites were synthesized via the decomposition of amixture of Ti
3C2(a novel two-dimensional carbide)
and cupric nitrate under an argon atmosphere The morphology and structures of the obtained samples were characterized X-raydiffraction and energy dispersive spectrometer analysis indicate that the sample is composed of Ti
3C2 anatase-TiO
2 and CuO
Scanning electron microscopy images show that CuO and TiO2nanoparticles were evenly distributed on the surface of Ti
3C2
The particles size increased with an increase in the cupric nitrate content Photocatalytic degradation of methyl orange shows thatthe Ti
3C2TiO2CuO nanocomposite has good photocatalytic degradation efficiency A possible photocatalytic mechanism of the
Ti3C2TiO2CuO nanocomposites was proposed The data indicated that CuO and Ti
3C2effectively promote the separation of
photoelectrons from vacancies
1 Introduction
Industrial wastewater has become one of the major factorsin water pollution and in particular wastewater from dyeindustries is difficult to treat Of the various techniques forcleaning the environment photocatalytic degradation hasbeen widely researched to treat pollutants that are difficultto degrade TiO
2and ZnO are the most widely studied pho-
tocatalysts [1 2] To improve the photocatalysis efficiency ofTiO2 binary nanocomposites such as TiO
2metal (Ag [3 4]
Au [5 6] and Pt [7]) TiO2graphene [8ndash10] TiO
2ZnO [11]
TiO2CuO [12] TiO
2(CdSe CdS and CdSeS) [13 14] and
TiO2SnO2[15 16] have been extensively studied and the
results show that the binary nanocomposites perform betterthan the single components Less research has been done onternary nanocomposites [17] than on binary nanocompositesTi3C2is a member of a family of novel two-dimensional
carbides or carbonitrides called MXenes which are synthe-sized by etching an A-group element from the correspondingMAXphase using hydrofluoric acid [18] Because of its speciallaminated structure Ti
3C2has been widely researched in
many fields [19ndash23] However the resistance to oxidization
of Ti3C2is not good Under hydrothermal conditions or in
an oxygen atmosphere the surface of Ti3C2easily oxidizes to
form TiO2at temperatures above 100∘C [18 24 25] Hence
Ti3C2can be used as a precursor for TiO
2and as a carrier for
other oxidesIn this study Ti
3C2TiO2CuO ternary nanocomposites
were successfully fabricated using cupric nitrate decompo-sition with Ti
3C2under an argon atmosphere The pho-
tocatalytic performance of Ti3C2TiO2CuO was studied
using MO as a simulated pollutant The results show thatthe Ti
3C2TiO2CuO ternary composite has good catalytic
activity for MO photodegradation
2 Experimental
In these experiments 0 g 0005 g 001 g 002 g and 004 gof cupric nitrate were each dissolved in 1mL of deionizedwater and then 1 g of Ti
3C2powder (prepared according to
the literature [18]) was added The mixture was kept at roomtemperature for 24 h and then dried at 70∘C in a vacuumThe Ti
3C2TiO2CuO nanocomposites were synthesized by
annealing the mixture under an argon atmosphere at 500∘C
HindawiJournal of NanomaterialsVolume 2017 Article ID 1978764 5 pageshttpsdoiorg10115520171978764
2 Journal of Nanomaterials
MXeneDeco
CuO
mposition
Ti3C2 + O2 㨀rarr TiO2 + CO2 uarr
Cu(NO3)2
Cu(NO3)2
Cu(NO3)2
㨀rarr + NO2 uarr + O2 uarr
CuO
TiO2
Figure 1 Procedure for synthesizing the Ti3C2TiO2CuO nanocomposite
for 30minThe heating rate was set at 10∘CminThe obtainedsamples were denoted as sample a sample b sample csample d and sample e according to cupric nitrate massesrespectively
The detailed procedure is represented schematically inFigure 1 In this process the chemical reaction for theformation of Ti
3C2TiO2CuO may be expressed as follows
Cu (NO3)2997888rarr CuO +NO
2uarr +O
2uarr (1)
Ti3C2+O2997888rarr TiO
2+ CO2uarr (2)
The crystal structure of the obtained samples was char-acterized using powder X-ray diffraction (XRD PhilipsXrsquoPert-MPD system Cu K120572 radiation) The morphologyand microstructures of the samples were examined using aQuanta 250 field emission gun scanning electronmicroscope(FEI Quanta 250 FEG-SEM) equipped with a Bruker NanoGmbHwith an X-Max 30mm2 detector energy dispersive X-ray spectrometer (Bruker Quantax 200 XFlash 6 | 30 EDS)
The photocatalytic activity of the samples was evaluatedfor the photodegradation of MO (20mgL) under UV illu-mination First the obtained powder catalyst (100mg) wasdispersed in a solution ofMO (100mL) and was magneticallystirred in the dark for 30min to establish the adsorption equi-librium The whole photocatalytic reaction was carried outat 10∘C The solution was then irradiated with a 175W mer-cury lamp light (GGZ175 Shanghai Jiguang Special LightingElectrical Appliance Factory China) 50mL of solution wastransferred every 10min centrifuged to remove the catalystand then analyzed using a UV-vis spectrophotometer (TU-1900 Beijing Purkinje General Instrument Co Ltd China)
3 Results and Discussion
XRD results of the samples are shown in Figure 2 The peaksdetected at 2120579 = 902∘ 182∘ and 275∘ were assigned as thediffraction peaks of Ti
3C2[20] The peaks at 2534∘ 3790∘
4817∘ 5402∘ and 5516∘ were indexed to the (101) (004)(200) (105) and (211) planes respectively of anatase-TiO
2
(JCPDF Number 21-1272) This means Ti3C2was partially
oxidized to TiO2after treatment at 500∘C for 30min The
10 20 30 40 50 60 70 80 90
(e)
(d)
(c)
(b)
(a)
Inte
nsity
clubsclubs clubs
clubs
clubs
⧫
⧫
⧫
⧫
⧫
Ti3C2
TiO2
2휃 (degree)
Figure 2 XRD patterns of the as-prepared samples
oxygen came from the adsorbed water and the thermal-decomposition of cupric nitrate Because of the low contentand the small crystalline size of CuO in the nanocompositesthe XRD signal was weak and may have been covered by therobust signal of TiO
2and Ti
3C2 Thus the diffraction peaks
of CuO were not observedSEM images of samples andashe are shown in Figures
3(a)ndash3(e) Figure 3(a) is the SEM image of the sample whichwas obtained by Ti
3C2that was kept at 500∘C for 30min
under an argon atmosphere It can be observed that thesample had a smooth surface with small nanoparticles whichmay be TiO
2 Figures 3(b)ndash3(e) show the SEM image of
the Ti3C2TiO2CuO ternary nanocomposites From these
figures it can be seen that a large number of CuO andTiO2nanoparticles were densely connected to one another
on the surface of the Ti3C2nanosheets With an increase in
the cupric nitrate content the density of the particulates onTi3C2increased The increase of the size of the nanoparticles
(see Figures 3(d) and 3(e)) indicates an agglomeration ofnanoparticles It can be also observed that the thickness of
Journal of Nanomaterials 3
(a) (b) (c)
(d) (e)
1 2 3 4 5 6 7 8 9(keV)
00020406081012141618
(cps
eV
)
Ti Ti F O C
Al Cu
Ti C O
Cu Al F
Ti-KA C-K O-K
Cu-L Al-K F-K
(f)
Figure 3 SEM images of the samples (a) Ti3C2 (bndashe) Ti
3C2TiO2CuO (samples andashd) and (f) EDS spectra and mapping of the marked
domain in (f)
the layer increased In order to observe the distribution ofdifferent elements sample c was further identified using EDSmapping analysis of Ti C O Cu Al and F in SEM from theselected areas in Figure 3(f) The results show that CuO wasdistributed evenly on the surface of Ti
3C2
The photocatalytic activities of the samples were mea-sured and the results are shown in Figure 4 It can beseen that the Ti
3C2TiO2CuO nanocomposites have good
photocatalytic activity The MO quickly degraded to about99 in 80 minutes with sample c as the catalyst Thephotocatalytic activity of the nanocomposites was enhancedwith an increase in the cupric nitrate content and was bestwhen 001 g of cupric nitrate was added After that with anincrease in themass of cupric nitrate agglomeration occurredand led to a decrease in the photocatalytic performance
A possible photocatalytic mechanism of the Ti3C2TiO2
CuO nanocomposites is shown in Figure 5 The band gapbetween the TiO
2valance band (VB) and the conduction
band (CB) is 32 eV Under UV radiation an electron and
hole are generated on the surface of TiO2and CuO Because
the CB of CuO is situated below that of TiO2 the electrons
in the CB of TiO2are easily transferred to the CB of CuO
On the other hand the photoelectrons of TiO2and CuO are
transferred promptly by Ti3C2because of its good electron
conductivity which lowers the electron-hole recombinationrate Analysis indicates that Ti
3C2TiO2CuO exhibited a
more effective electron-hole separation under UV radiationThus the surface redox process by photogenerated electronsand holes occurs more easily and correspondingly thephotocatalytic activity of the samples significantly improved
4 Conclusion
Ti3C2TiO2CuO ternary nanocomposites were fabricated
via cupric nitrate decomposition on the surface of Ti3C2
Analysis indicates that the samples were composed of Ti3C2
degradation experiments showed that the Ti3C2TiO2CuO
4 Journal of Nanomaterials
0 30 60 90 12000
02
04
06
08
10
Time (min)
(a)(b)(c)
(d)(e)
minus30
CC
0
Figure 4 Curves of 1198621198620versus time for the photodegradation of
MO with samples andashe
eminus
eminus
eminus
TiO2
h+ h
+
CuO
H2O
H2O
T3C2
TiO2
CuO
MO
CO2
O2O2∙minus
OH∙
Figure 5 Schematic illustration of a possible photocatalytic mech-anism of the Ti
3C2TiO2CuO nanocomposites
nanocomposite has a better efficiency of electron-hole sepa-ration than TiO
2 and this significantly improved the photo-
catalytic activity of the nanocomposites
Conflicts of Interest
The authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
The authors gratefully acknowledge the National NatureScience Foundation of China (51205111 51472075) thePlan for Scientific Innovation Talent of Henan Province(134100510008) the Program for Innovative Research Team
of Henan Polytechnic University (T2013-4) and Key Projectof Henan Educational Committee (15A440006)
References
[1] A Kubacka M Fernandez-Garcıa and G Colon ldquoAdvancednanoarchitectures for solar photocatalytic applicationsrdquo Chem-ical Reviews vol 112 no 3 pp 1555ndash1614 2012
[2] M N Chong B Jin C W K Chow and C Saint ldquoRecentdevelopments in photocatalytic water treatment technology areviewrdquoWater Research vol 44 no 10 pp 2997ndash3027 2010
[3] H Y Chuang and D H Chen ldquoFabrication and photocatalyticactivities in visible and UV light regions of AgTiO
2and
NiAgTiO2nanoparticlesrdquo Nanotechnology vol 20 no 10
Article ID 105704 2009[4] P D Cozzoli E Fanizza R Comparelli M L Curri A
Agostiano and D Laub ldquoRole of metal nanoparticles in TiO2Ag nanocomposite-based microheterogeneous photocatalysisrdquoJournal of Physical Chemistry B vol 108 no 28 pp 9623ndash96302004
[5] H Li Z Bian J Zhu Y Huo H Li and Y Lu ldquoMesoporousAuTiO2 nanocomposites with enhanced photocatalytic activ-ityrdquo Journal of the American Chemical Society vol 129 no 15pp 4538ndash4539 2007
[6] X-F Wu H-Y Song J-M Yoon Y-T Yu and Y-F ChenldquoSynthesis of core-shell AuTiO2 nanopartides with truncatedwedge-shaped morphology and their photocatalytic proper-tiesrdquo Langmuir vol 25 no 11 pp 6438ndash6447 2009
[7] J Yu L Qi and M Jaroniec ldquoHydrogen production by photo-catalytic water splitting over PtTiO
2nanosheets with exposed
(001) facetsrdquo The Journal of Physical Chemistry C vol 114 no30 pp 13118ndash13125 2010
[8] Y H Zhang Z-R Tang X Z Fu and Y-J Xu ldquoTiO2-graphene
nanocomposites for gas-phase photocatalytic degradation ofvolatile aromatic pollutant is TiO
2-graphene truly different
from other TiO2-carbon composite materialsrdquo ACS Nano vol
4 no 12 pp 7303ndash7314 2010[9] Y Liang H Wang H S Casalongue Z Chen and H Dai
ldquoTiO2 nanocrystals grown on graphene as advanced photocat-alytic hybrid materialsrdquo Nano Research vol 3 no 10 pp 701ndash705 2010
[10] D Zhang Y Wang W Zhang J Pan and J Cai ldquoEnlargementof diatom frustules pores by hydrofluoric acid etching at roomtemperaturerdquo Journal of Materials Science vol 46 no 17 pp5665ndash5671 2011
[11] P Bansal N Bhullar and D Sud ldquoStudies on photodegradationof malachite green using TiO
2ZnO photocatalystrdquo Desalina-
tion and Water Treatment vol 12 no 1ndash3 pp 108ndash113 2009[12] A Manivel S Naveenraj P S Sathish Kumar and S Anandan
ldquoCuO-TiO2nanocatalyst for photodegradation of acid Red 88
in aqueous solutionrdquo Science of Advanced Materials vol 2 no1 pp 51ndash57 2010
[13] J Luo L Ma T He et al ldquoTiO2(CdS CdSe CdSeS) nanorod
heterostructures and photoelectrochemical propertiesrdquo TheJournal of Physical Chemistry C vol 116 no 22 pp 11956ndash119632012
[14] J H Zhu D Yang J Q Geng D M Chen and Z Y JiangldquoSynthesis and characterization of bamboo-like CdSTiO
2nan-
otubes composites with enhanced visible-light photocatalyticactivityrdquo Journal of Nanoparticle Research vol 10 no 5 pp 729ndash736 2008
Journal of Nanomaterials 5
[15] C Wang C Shao X Zhang and Y Liu ldquoSnO2nanostructures-
TiO2nanofibers heterostructures controlled fabrication and
[16] Z Liu D D Sun P Guo and J O Leckie ldquoAn efficientbicomponent TiO2SnO2 nanofiber photocatalyst fabricated byelectrospinning with a side-by-side dual spinneret methodrdquoNano Letters vol 7 no 4 pp 1081ndash1085 2007
[17] H-I Kim J Kim W Kim and W Choi ldquoEnhanced photocat-alytic and photoelectrochemical activity in the ternary hybrid ofCdSTiO2WO3 through the cascadal electron transferrdquo Journalof Physical Chemistry C vol 115 no 19 pp 9797ndash9805 2011
[18] Z Y Li L B Wang D D Sun et al ldquoSynthesis and thermalstability of two-dimensional carbide MXene Ti
3C2rdquo Materials
Science and Engineering B vol 191 pp 33ndash40 2015[19] M Naguib J Come B Dyatkin et al ldquoMXene a promising
transition metal carbide anode for lithium-ion batteriesrdquo Elec-trochemistry Communications vol 16 no 1 pp 61ndash64 2012
[20] M R Lukatskaya O Mashtalir C E Ren et al ldquoCation inter-calation and high volumetric capacitance of two-dimensionaltitanium carbiderdquo Science vol 341 no 6153 pp 1502ndash1505 2013
[21] Q M Peng J X Guo Q R Zhang et al ldquoUnique lead adsorp-tion behavior of activated hydroxyl group in two-dimensionaltitanium carbiderdquo Journal of the American Chemical Society vol136 no 11 pp 4113ndash4116 2014
[22] OMashtalir KMCook VNMochalinMCroweMW Bar-soum and Y Gogotsi ldquoDye adsorption and decomposition ontwo-dimensional titanium carbide in aqueous mediardquo Journalof Materials Chemistry A vol 2 no 35 pp 14334ndash14338 2014
[23] J Yang B B Chen H J Song H Tang and C S LildquoSynthesis characterization and tribological properties of two-dimensional Ti
3C2rdquo Crystal Research and Technology vol 49
no 11 pp 926ndash932 2014[24] M Naguib O Mashtalir M R Lukatskaya et al ldquoOne-step
synthesis of nanocrystalline transition metal oxides on thinsheets of disordered graphitic carbon by oxidation of MXenesrdquoChemical Communications vol 50 no 56 pp 7420ndash7423 2014
[25] Y P Gao L BWang A G Zhou et al ldquoHydrothermal synthesisof TiO
Figure 1 Procedure for synthesizing the Ti3C2TiO2CuO nanocomposite
for 30minThe heating rate was set at 10∘CminThe obtainedsamples were denoted as sample a sample b sample csample d and sample e according to cupric nitrate massesrespectively
The detailed procedure is represented schematically inFigure 1 In this process the chemical reaction for theformation of Ti
3C2TiO2CuO may be expressed as follows
Cu (NO3)2997888rarr CuO +NO
2uarr +O
2uarr (1)
Ti3C2+O2997888rarr TiO
2+ CO2uarr (2)
The crystal structure of the obtained samples was char-acterized using powder X-ray diffraction (XRD PhilipsXrsquoPert-MPD system Cu K120572 radiation) The morphologyand microstructures of the samples were examined using aQuanta 250 field emission gun scanning electronmicroscope(FEI Quanta 250 FEG-SEM) equipped with a Bruker NanoGmbHwith an X-Max 30mm2 detector energy dispersive X-ray spectrometer (Bruker Quantax 200 XFlash 6 | 30 EDS)
The photocatalytic activity of the samples was evaluatedfor the photodegradation of MO (20mgL) under UV illu-mination First the obtained powder catalyst (100mg) wasdispersed in a solution ofMO (100mL) and was magneticallystirred in the dark for 30min to establish the adsorption equi-librium The whole photocatalytic reaction was carried outat 10∘C The solution was then irradiated with a 175W mer-cury lamp light (GGZ175 Shanghai Jiguang Special LightingElectrical Appliance Factory China) 50mL of solution wastransferred every 10min centrifuged to remove the catalystand then analyzed using a UV-vis spectrophotometer (TU-1900 Beijing Purkinje General Instrument Co Ltd China)
3 Results and Discussion
XRD results of the samples are shown in Figure 2 The peaksdetected at 2120579 = 902∘ 182∘ and 275∘ were assigned as thediffraction peaks of Ti
3C2[20] The peaks at 2534∘ 3790∘
4817∘ 5402∘ and 5516∘ were indexed to the (101) (004)(200) (105) and (211) planes respectively of anatase-TiO
2
(JCPDF Number 21-1272) This means Ti3C2was partially
oxidized to TiO2after treatment at 500∘C for 30min The
10 20 30 40 50 60 70 80 90
(e)
(d)
(c)
(b)
(a)
Inte
nsity
clubsclubs clubs
clubs
clubs
⧫
⧫
⧫
⧫
⧫
Ti3C2
TiO2
2휃 (degree)
Figure 2 XRD patterns of the as-prepared samples
oxygen came from the adsorbed water and the thermal-decomposition of cupric nitrate Because of the low contentand the small crystalline size of CuO in the nanocompositesthe XRD signal was weak and may have been covered by therobust signal of TiO
2and Ti
3C2 Thus the diffraction peaks
of CuO were not observedSEM images of samples andashe are shown in Figures
3(a)ndash3(e) Figure 3(a) is the SEM image of the sample whichwas obtained by Ti
3C2that was kept at 500∘C for 30min
under an argon atmosphere It can be observed that thesample had a smooth surface with small nanoparticles whichmay be TiO
2 Figures 3(b)ndash3(e) show the SEM image of
the Ti3C2TiO2CuO ternary nanocomposites From these
figures it can be seen that a large number of CuO andTiO2nanoparticles were densely connected to one another
on the surface of the Ti3C2nanosheets With an increase in
the cupric nitrate content the density of the particulates onTi3C2increased The increase of the size of the nanoparticles
(see Figures 3(d) and 3(e)) indicates an agglomeration ofnanoparticles It can be also observed that the thickness of
Journal of Nanomaterials 3
(a) (b) (c)
(d) (e)
1 2 3 4 5 6 7 8 9(keV)
00020406081012141618
(cps
eV
)
Ti Ti F O C
Al Cu
Ti C O
Cu Al F
Ti-KA C-K O-K
Cu-L Al-K F-K
(f)
Figure 3 SEM images of the samples (a) Ti3C2 (bndashe) Ti
3C2TiO2CuO (samples andashd) and (f) EDS spectra and mapping of the marked
domain in (f)
the layer increased In order to observe the distribution ofdifferent elements sample c was further identified using EDSmapping analysis of Ti C O Cu Al and F in SEM from theselected areas in Figure 3(f) The results show that CuO wasdistributed evenly on the surface of Ti
3C2
The photocatalytic activities of the samples were mea-sured and the results are shown in Figure 4 It can beseen that the Ti
3C2TiO2CuO nanocomposites have good
photocatalytic activity The MO quickly degraded to about99 in 80 minutes with sample c as the catalyst Thephotocatalytic activity of the nanocomposites was enhancedwith an increase in the cupric nitrate content and was bestwhen 001 g of cupric nitrate was added After that with anincrease in themass of cupric nitrate agglomeration occurredand led to a decrease in the photocatalytic performance
A possible photocatalytic mechanism of the Ti3C2TiO2
CuO nanocomposites is shown in Figure 5 The band gapbetween the TiO
2valance band (VB) and the conduction
band (CB) is 32 eV Under UV radiation an electron and
hole are generated on the surface of TiO2and CuO Because
the CB of CuO is situated below that of TiO2 the electrons
in the CB of TiO2are easily transferred to the CB of CuO
On the other hand the photoelectrons of TiO2and CuO are
transferred promptly by Ti3C2because of its good electron
conductivity which lowers the electron-hole recombinationrate Analysis indicates that Ti
3C2TiO2CuO exhibited a
more effective electron-hole separation under UV radiationThus the surface redox process by photogenerated electronsand holes occurs more easily and correspondingly thephotocatalytic activity of the samples significantly improved
4 Conclusion
Ti3C2TiO2CuO ternary nanocomposites were fabricated
via cupric nitrate decomposition on the surface of Ti3C2
Analysis indicates that the samples were composed of Ti3C2
degradation experiments showed that the Ti3C2TiO2CuO
4 Journal of Nanomaterials
0 30 60 90 12000
02
04
06
08
10
Time (min)
(a)(b)(c)
(d)(e)
minus30
CC
0
Figure 4 Curves of 1198621198620versus time for the photodegradation of
MO with samples andashe
eminus
eminus
eminus
TiO2
h+ h
+
CuO
H2O
H2O
T3C2
TiO2
CuO
MO
CO2
O2O2∙minus
OH∙
Figure 5 Schematic illustration of a possible photocatalytic mech-anism of the Ti
3C2TiO2CuO nanocomposites
nanocomposite has a better efficiency of electron-hole sepa-ration than TiO
2 and this significantly improved the photo-
catalytic activity of the nanocomposites
Conflicts of Interest
The authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
The authors gratefully acknowledge the National NatureScience Foundation of China (51205111 51472075) thePlan for Scientific Innovation Talent of Henan Province(134100510008) the Program for Innovative Research Team
of Henan Polytechnic University (T2013-4) and Key Projectof Henan Educational Committee (15A440006)
References
[1] A Kubacka M Fernandez-Garcıa and G Colon ldquoAdvancednanoarchitectures for solar photocatalytic applicationsrdquo Chem-ical Reviews vol 112 no 3 pp 1555ndash1614 2012
[2] M N Chong B Jin C W K Chow and C Saint ldquoRecentdevelopments in photocatalytic water treatment technology areviewrdquoWater Research vol 44 no 10 pp 2997ndash3027 2010
[3] H Y Chuang and D H Chen ldquoFabrication and photocatalyticactivities in visible and UV light regions of AgTiO
2and
NiAgTiO2nanoparticlesrdquo Nanotechnology vol 20 no 10
Article ID 105704 2009[4] P D Cozzoli E Fanizza R Comparelli M L Curri A
Agostiano and D Laub ldquoRole of metal nanoparticles in TiO2Ag nanocomposite-based microheterogeneous photocatalysisrdquoJournal of Physical Chemistry B vol 108 no 28 pp 9623ndash96302004
[5] H Li Z Bian J Zhu Y Huo H Li and Y Lu ldquoMesoporousAuTiO2 nanocomposites with enhanced photocatalytic activ-ityrdquo Journal of the American Chemical Society vol 129 no 15pp 4538ndash4539 2007
[6] X-F Wu H-Y Song J-M Yoon Y-T Yu and Y-F ChenldquoSynthesis of core-shell AuTiO2 nanopartides with truncatedwedge-shaped morphology and their photocatalytic proper-tiesrdquo Langmuir vol 25 no 11 pp 6438ndash6447 2009
[7] J Yu L Qi and M Jaroniec ldquoHydrogen production by photo-catalytic water splitting over PtTiO
2nanosheets with exposed
(001) facetsrdquo The Journal of Physical Chemistry C vol 114 no30 pp 13118ndash13125 2010
[8] Y H Zhang Z-R Tang X Z Fu and Y-J Xu ldquoTiO2-graphene
nanocomposites for gas-phase photocatalytic degradation ofvolatile aromatic pollutant is TiO
2-graphene truly different
from other TiO2-carbon composite materialsrdquo ACS Nano vol
4 no 12 pp 7303ndash7314 2010[9] Y Liang H Wang H S Casalongue Z Chen and H Dai
ldquoTiO2 nanocrystals grown on graphene as advanced photocat-alytic hybrid materialsrdquo Nano Research vol 3 no 10 pp 701ndash705 2010
[10] D Zhang Y Wang W Zhang J Pan and J Cai ldquoEnlargementof diatom frustules pores by hydrofluoric acid etching at roomtemperaturerdquo Journal of Materials Science vol 46 no 17 pp5665ndash5671 2011
[11] P Bansal N Bhullar and D Sud ldquoStudies on photodegradationof malachite green using TiO
2ZnO photocatalystrdquo Desalina-
tion and Water Treatment vol 12 no 1ndash3 pp 108ndash113 2009[12] A Manivel S Naveenraj P S Sathish Kumar and S Anandan
ldquoCuO-TiO2nanocatalyst for photodegradation of acid Red 88
in aqueous solutionrdquo Science of Advanced Materials vol 2 no1 pp 51ndash57 2010
[13] J Luo L Ma T He et al ldquoTiO2(CdS CdSe CdSeS) nanorod
heterostructures and photoelectrochemical propertiesrdquo TheJournal of Physical Chemistry C vol 116 no 22 pp 11956ndash119632012
[14] J H Zhu D Yang J Q Geng D M Chen and Z Y JiangldquoSynthesis and characterization of bamboo-like CdSTiO
2nan-
otubes composites with enhanced visible-light photocatalyticactivityrdquo Journal of Nanoparticle Research vol 10 no 5 pp 729ndash736 2008
Journal of Nanomaterials 5
[15] C Wang C Shao X Zhang and Y Liu ldquoSnO2nanostructures-
TiO2nanofibers heterostructures controlled fabrication and
[16] Z Liu D D Sun P Guo and J O Leckie ldquoAn efficientbicomponent TiO2SnO2 nanofiber photocatalyst fabricated byelectrospinning with a side-by-side dual spinneret methodrdquoNano Letters vol 7 no 4 pp 1081ndash1085 2007
[17] H-I Kim J Kim W Kim and W Choi ldquoEnhanced photocat-alytic and photoelectrochemical activity in the ternary hybrid ofCdSTiO2WO3 through the cascadal electron transferrdquo Journalof Physical Chemistry C vol 115 no 19 pp 9797ndash9805 2011
[18] Z Y Li L B Wang D D Sun et al ldquoSynthesis and thermalstability of two-dimensional carbide MXene Ti
3C2rdquo Materials
Science and Engineering B vol 191 pp 33ndash40 2015[19] M Naguib J Come B Dyatkin et al ldquoMXene a promising
transition metal carbide anode for lithium-ion batteriesrdquo Elec-trochemistry Communications vol 16 no 1 pp 61ndash64 2012
[20] M R Lukatskaya O Mashtalir C E Ren et al ldquoCation inter-calation and high volumetric capacitance of two-dimensionaltitanium carbiderdquo Science vol 341 no 6153 pp 1502ndash1505 2013
[21] Q M Peng J X Guo Q R Zhang et al ldquoUnique lead adsorp-tion behavior of activated hydroxyl group in two-dimensionaltitanium carbiderdquo Journal of the American Chemical Society vol136 no 11 pp 4113ndash4116 2014
[22] OMashtalir KMCook VNMochalinMCroweMW Bar-soum and Y Gogotsi ldquoDye adsorption and decomposition ontwo-dimensional titanium carbide in aqueous mediardquo Journalof Materials Chemistry A vol 2 no 35 pp 14334ndash14338 2014
[23] J Yang B B Chen H J Song H Tang and C S LildquoSynthesis characterization and tribological properties of two-dimensional Ti
3C2rdquo Crystal Research and Technology vol 49
no 11 pp 926ndash932 2014[24] M Naguib O Mashtalir M R Lukatskaya et al ldquoOne-step
synthesis of nanocrystalline transition metal oxides on thinsheets of disordered graphitic carbon by oxidation of MXenesrdquoChemical Communications vol 50 no 56 pp 7420ndash7423 2014
[25] Y P Gao L BWang A G Zhou et al ldquoHydrothermal synthesisof TiO
Figure 3 SEM images of the samples (a) Ti3C2 (bndashe) Ti
3C2TiO2CuO (samples andashd) and (f) EDS spectra and mapping of the marked
domain in (f)
the layer increased In order to observe the distribution ofdifferent elements sample c was further identified using EDSmapping analysis of Ti C O Cu Al and F in SEM from theselected areas in Figure 3(f) The results show that CuO wasdistributed evenly on the surface of Ti
3C2
The photocatalytic activities of the samples were mea-sured and the results are shown in Figure 4 It can beseen that the Ti
3C2TiO2CuO nanocomposites have good
photocatalytic activity The MO quickly degraded to about99 in 80 minutes with sample c as the catalyst Thephotocatalytic activity of the nanocomposites was enhancedwith an increase in the cupric nitrate content and was bestwhen 001 g of cupric nitrate was added After that with anincrease in themass of cupric nitrate agglomeration occurredand led to a decrease in the photocatalytic performance
A possible photocatalytic mechanism of the Ti3C2TiO2
CuO nanocomposites is shown in Figure 5 The band gapbetween the TiO
2valance band (VB) and the conduction
band (CB) is 32 eV Under UV radiation an electron and
hole are generated on the surface of TiO2and CuO Because
the CB of CuO is situated below that of TiO2 the electrons
in the CB of TiO2are easily transferred to the CB of CuO
On the other hand the photoelectrons of TiO2and CuO are
transferred promptly by Ti3C2because of its good electron
conductivity which lowers the electron-hole recombinationrate Analysis indicates that Ti
3C2TiO2CuO exhibited a
more effective electron-hole separation under UV radiationThus the surface redox process by photogenerated electronsand holes occurs more easily and correspondingly thephotocatalytic activity of the samples significantly improved
4 Conclusion
Ti3C2TiO2CuO ternary nanocomposites were fabricated
via cupric nitrate decomposition on the surface of Ti3C2
Analysis indicates that the samples were composed of Ti3C2
degradation experiments showed that the Ti3C2TiO2CuO
4 Journal of Nanomaterials
0 30 60 90 12000
02
04
06
08
10
Time (min)
(a)(b)(c)
(d)(e)
minus30
CC
0
Figure 4 Curves of 1198621198620versus time for the photodegradation of
MO with samples andashe
eminus
eminus
eminus
TiO2
h+ h
+
CuO
H2O
H2O
T3C2
TiO2
CuO
MO
CO2
O2O2∙minus
OH∙
Figure 5 Schematic illustration of a possible photocatalytic mech-anism of the Ti
3C2TiO2CuO nanocomposites
nanocomposite has a better efficiency of electron-hole sepa-ration than TiO
2 and this significantly improved the photo-
catalytic activity of the nanocomposites
Conflicts of Interest
The authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
The authors gratefully acknowledge the National NatureScience Foundation of China (51205111 51472075) thePlan for Scientific Innovation Talent of Henan Province(134100510008) the Program for Innovative Research Team
of Henan Polytechnic University (T2013-4) and Key Projectof Henan Educational Committee (15A440006)
References
[1] A Kubacka M Fernandez-Garcıa and G Colon ldquoAdvancednanoarchitectures for solar photocatalytic applicationsrdquo Chem-ical Reviews vol 112 no 3 pp 1555ndash1614 2012
[2] M N Chong B Jin C W K Chow and C Saint ldquoRecentdevelopments in photocatalytic water treatment technology areviewrdquoWater Research vol 44 no 10 pp 2997ndash3027 2010
[3] H Y Chuang and D H Chen ldquoFabrication and photocatalyticactivities in visible and UV light regions of AgTiO
2and
NiAgTiO2nanoparticlesrdquo Nanotechnology vol 20 no 10
Article ID 105704 2009[4] P D Cozzoli E Fanizza R Comparelli M L Curri A
Agostiano and D Laub ldquoRole of metal nanoparticles in TiO2Ag nanocomposite-based microheterogeneous photocatalysisrdquoJournal of Physical Chemistry B vol 108 no 28 pp 9623ndash96302004
[5] H Li Z Bian J Zhu Y Huo H Li and Y Lu ldquoMesoporousAuTiO2 nanocomposites with enhanced photocatalytic activ-ityrdquo Journal of the American Chemical Society vol 129 no 15pp 4538ndash4539 2007
[6] X-F Wu H-Y Song J-M Yoon Y-T Yu and Y-F ChenldquoSynthesis of core-shell AuTiO2 nanopartides with truncatedwedge-shaped morphology and their photocatalytic proper-tiesrdquo Langmuir vol 25 no 11 pp 6438ndash6447 2009
[7] J Yu L Qi and M Jaroniec ldquoHydrogen production by photo-catalytic water splitting over PtTiO
2nanosheets with exposed
(001) facetsrdquo The Journal of Physical Chemistry C vol 114 no30 pp 13118ndash13125 2010
[8] Y H Zhang Z-R Tang X Z Fu and Y-J Xu ldquoTiO2-graphene
nanocomposites for gas-phase photocatalytic degradation ofvolatile aromatic pollutant is TiO
2-graphene truly different
from other TiO2-carbon composite materialsrdquo ACS Nano vol
4 no 12 pp 7303ndash7314 2010[9] Y Liang H Wang H S Casalongue Z Chen and H Dai
ldquoTiO2 nanocrystals grown on graphene as advanced photocat-alytic hybrid materialsrdquo Nano Research vol 3 no 10 pp 701ndash705 2010
[10] D Zhang Y Wang W Zhang J Pan and J Cai ldquoEnlargementof diatom frustules pores by hydrofluoric acid etching at roomtemperaturerdquo Journal of Materials Science vol 46 no 17 pp5665ndash5671 2011
[11] P Bansal N Bhullar and D Sud ldquoStudies on photodegradationof malachite green using TiO
2ZnO photocatalystrdquo Desalina-
tion and Water Treatment vol 12 no 1ndash3 pp 108ndash113 2009[12] A Manivel S Naveenraj P S Sathish Kumar and S Anandan
ldquoCuO-TiO2nanocatalyst for photodegradation of acid Red 88
in aqueous solutionrdquo Science of Advanced Materials vol 2 no1 pp 51ndash57 2010
[13] J Luo L Ma T He et al ldquoTiO2(CdS CdSe CdSeS) nanorod
heterostructures and photoelectrochemical propertiesrdquo TheJournal of Physical Chemistry C vol 116 no 22 pp 11956ndash119632012
[14] J H Zhu D Yang J Q Geng D M Chen and Z Y JiangldquoSynthesis and characterization of bamboo-like CdSTiO
2nan-
otubes composites with enhanced visible-light photocatalyticactivityrdquo Journal of Nanoparticle Research vol 10 no 5 pp 729ndash736 2008
Journal of Nanomaterials 5
[15] C Wang C Shao X Zhang and Y Liu ldquoSnO2nanostructures-
TiO2nanofibers heterostructures controlled fabrication and
[16] Z Liu D D Sun P Guo and J O Leckie ldquoAn efficientbicomponent TiO2SnO2 nanofiber photocatalyst fabricated byelectrospinning with a side-by-side dual spinneret methodrdquoNano Letters vol 7 no 4 pp 1081ndash1085 2007
[17] H-I Kim J Kim W Kim and W Choi ldquoEnhanced photocat-alytic and photoelectrochemical activity in the ternary hybrid ofCdSTiO2WO3 through the cascadal electron transferrdquo Journalof Physical Chemistry C vol 115 no 19 pp 9797ndash9805 2011
[18] Z Y Li L B Wang D D Sun et al ldquoSynthesis and thermalstability of two-dimensional carbide MXene Ti
3C2rdquo Materials
Science and Engineering B vol 191 pp 33ndash40 2015[19] M Naguib J Come B Dyatkin et al ldquoMXene a promising
transition metal carbide anode for lithium-ion batteriesrdquo Elec-trochemistry Communications vol 16 no 1 pp 61ndash64 2012
[20] M R Lukatskaya O Mashtalir C E Ren et al ldquoCation inter-calation and high volumetric capacitance of two-dimensionaltitanium carbiderdquo Science vol 341 no 6153 pp 1502ndash1505 2013
[21] Q M Peng J X Guo Q R Zhang et al ldquoUnique lead adsorp-tion behavior of activated hydroxyl group in two-dimensionaltitanium carbiderdquo Journal of the American Chemical Society vol136 no 11 pp 4113ndash4116 2014
[22] OMashtalir KMCook VNMochalinMCroweMW Bar-soum and Y Gogotsi ldquoDye adsorption and decomposition ontwo-dimensional titanium carbide in aqueous mediardquo Journalof Materials Chemistry A vol 2 no 35 pp 14334ndash14338 2014
[23] J Yang B B Chen H J Song H Tang and C S LildquoSynthesis characterization and tribological properties of two-dimensional Ti
3C2rdquo Crystal Research and Technology vol 49
no 11 pp 926ndash932 2014[24] M Naguib O Mashtalir M R Lukatskaya et al ldquoOne-step
synthesis of nanocrystalline transition metal oxides on thinsheets of disordered graphitic carbon by oxidation of MXenesrdquoChemical Communications vol 50 no 56 pp 7420ndash7423 2014
[25] Y P Gao L BWang A G Zhou et al ldquoHydrothermal synthesisof TiO
Figure 4 Curves of 1198621198620versus time for the photodegradation of
MO with samples andashe
eminus
eminus
eminus
TiO2
h+ h
+
CuO
H2O
H2O
T3C2
TiO2
CuO
MO
CO2
O2O2∙minus
OH∙
Figure 5 Schematic illustration of a possible photocatalytic mech-anism of the Ti
3C2TiO2CuO nanocomposites
nanocomposite has a better efficiency of electron-hole sepa-ration than TiO
2 and this significantly improved the photo-
catalytic activity of the nanocomposites
Conflicts of Interest
The authors declare that there are no conflicts of interestregarding the publication of this paper
Acknowledgments
The authors gratefully acknowledge the National NatureScience Foundation of China (51205111 51472075) thePlan for Scientific Innovation Talent of Henan Province(134100510008) the Program for Innovative Research Team
of Henan Polytechnic University (T2013-4) and Key Projectof Henan Educational Committee (15A440006)
References
[1] A Kubacka M Fernandez-Garcıa and G Colon ldquoAdvancednanoarchitectures for solar photocatalytic applicationsrdquo Chem-ical Reviews vol 112 no 3 pp 1555ndash1614 2012
[2] M N Chong B Jin C W K Chow and C Saint ldquoRecentdevelopments in photocatalytic water treatment technology areviewrdquoWater Research vol 44 no 10 pp 2997ndash3027 2010
[3] H Y Chuang and D H Chen ldquoFabrication and photocatalyticactivities in visible and UV light regions of AgTiO
2and
NiAgTiO2nanoparticlesrdquo Nanotechnology vol 20 no 10
Article ID 105704 2009[4] P D Cozzoli E Fanizza R Comparelli M L Curri A
Agostiano and D Laub ldquoRole of metal nanoparticles in TiO2Ag nanocomposite-based microheterogeneous photocatalysisrdquoJournal of Physical Chemistry B vol 108 no 28 pp 9623ndash96302004
[5] H Li Z Bian J Zhu Y Huo H Li and Y Lu ldquoMesoporousAuTiO2 nanocomposites with enhanced photocatalytic activ-ityrdquo Journal of the American Chemical Society vol 129 no 15pp 4538ndash4539 2007
[6] X-F Wu H-Y Song J-M Yoon Y-T Yu and Y-F ChenldquoSynthesis of core-shell AuTiO2 nanopartides with truncatedwedge-shaped morphology and their photocatalytic proper-tiesrdquo Langmuir vol 25 no 11 pp 6438ndash6447 2009
[7] J Yu L Qi and M Jaroniec ldquoHydrogen production by photo-catalytic water splitting over PtTiO
2nanosheets with exposed
(001) facetsrdquo The Journal of Physical Chemistry C vol 114 no30 pp 13118ndash13125 2010
[8] Y H Zhang Z-R Tang X Z Fu and Y-J Xu ldquoTiO2-graphene
nanocomposites for gas-phase photocatalytic degradation ofvolatile aromatic pollutant is TiO
2-graphene truly different
from other TiO2-carbon composite materialsrdquo ACS Nano vol
4 no 12 pp 7303ndash7314 2010[9] Y Liang H Wang H S Casalongue Z Chen and H Dai
ldquoTiO2 nanocrystals grown on graphene as advanced photocat-alytic hybrid materialsrdquo Nano Research vol 3 no 10 pp 701ndash705 2010
[10] D Zhang Y Wang W Zhang J Pan and J Cai ldquoEnlargementof diatom frustules pores by hydrofluoric acid etching at roomtemperaturerdquo Journal of Materials Science vol 46 no 17 pp5665ndash5671 2011
[11] P Bansal N Bhullar and D Sud ldquoStudies on photodegradationof malachite green using TiO
2ZnO photocatalystrdquo Desalina-
tion and Water Treatment vol 12 no 1ndash3 pp 108ndash113 2009[12] A Manivel S Naveenraj P S Sathish Kumar and S Anandan
ldquoCuO-TiO2nanocatalyst for photodegradation of acid Red 88
in aqueous solutionrdquo Science of Advanced Materials vol 2 no1 pp 51ndash57 2010
[13] J Luo L Ma T He et al ldquoTiO2(CdS CdSe CdSeS) nanorod
heterostructures and photoelectrochemical propertiesrdquo TheJournal of Physical Chemistry C vol 116 no 22 pp 11956ndash119632012
[14] J H Zhu D Yang J Q Geng D M Chen and Z Y JiangldquoSynthesis and characterization of bamboo-like CdSTiO
2nan-
otubes composites with enhanced visible-light photocatalyticactivityrdquo Journal of Nanoparticle Research vol 10 no 5 pp 729ndash736 2008
Journal of Nanomaterials 5
[15] C Wang C Shao X Zhang and Y Liu ldquoSnO2nanostructures-
TiO2nanofibers heterostructures controlled fabrication and
[16] Z Liu D D Sun P Guo and J O Leckie ldquoAn efficientbicomponent TiO2SnO2 nanofiber photocatalyst fabricated byelectrospinning with a side-by-side dual spinneret methodrdquoNano Letters vol 7 no 4 pp 1081ndash1085 2007
[17] H-I Kim J Kim W Kim and W Choi ldquoEnhanced photocat-alytic and photoelectrochemical activity in the ternary hybrid ofCdSTiO2WO3 through the cascadal electron transferrdquo Journalof Physical Chemistry C vol 115 no 19 pp 9797ndash9805 2011
[18] Z Y Li L B Wang D D Sun et al ldquoSynthesis and thermalstability of two-dimensional carbide MXene Ti
3C2rdquo Materials
Science and Engineering B vol 191 pp 33ndash40 2015[19] M Naguib J Come B Dyatkin et al ldquoMXene a promising
transition metal carbide anode for lithium-ion batteriesrdquo Elec-trochemistry Communications vol 16 no 1 pp 61ndash64 2012
[20] M R Lukatskaya O Mashtalir C E Ren et al ldquoCation inter-calation and high volumetric capacitance of two-dimensionaltitanium carbiderdquo Science vol 341 no 6153 pp 1502ndash1505 2013
[21] Q M Peng J X Guo Q R Zhang et al ldquoUnique lead adsorp-tion behavior of activated hydroxyl group in two-dimensionaltitanium carbiderdquo Journal of the American Chemical Society vol136 no 11 pp 4113ndash4116 2014
[22] OMashtalir KMCook VNMochalinMCroweMW Bar-soum and Y Gogotsi ldquoDye adsorption and decomposition ontwo-dimensional titanium carbide in aqueous mediardquo Journalof Materials Chemistry A vol 2 no 35 pp 14334ndash14338 2014
[23] J Yang B B Chen H J Song H Tang and C S LildquoSynthesis characterization and tribological properties of two-dimensional Ti
3C2rdquo Crystal Research and Technology vol 49
no 11 pp 926ndash932 2014[24] M Naguib O Mashtalir M R Lukatskaya et al ldquoOne-step
synthesis of nanocrystalline transition metal oxides on thinsheets of disordered graphitic carbon by oxidation of MXenesrdquoChemical Communications vol 50 no 56 pp 7420ndash7423 2014
[25] Y P Gao L BWang A G Zhou et al ldquoHydrothermal synthesisof TiO
[16] Z Liu D D Sun P Guo and J O Leckie ldquoAn efficientbicomponent TiO2SnO2 nanofiber photocatalyst fabricated byelectrospinning with a side-by-side dual spinneret methodrdquoNano Letters vol 7 no 4 pp 1081ndash1085 2007
[17] H-I Kim J Kim W Kim and W Choi ldquoEnhanced photocat-alytic and photoelectrochemical activity in the ternary hybrid ofCdSTiO2WO3 through the cascadal electron transferrdquo Journalof Physical Chemistry C vol 115 no 19 pp 9797ndash9805 2011
[18] Z Y Li L B Wang D D Sun et al ldquoSynthesis and thermalstability of two-dimensional carbide MXene Ti
3C2rdquo Materials
Science and Engineering B vol 191 pp 33ndash40 2015[19] M Naguib J Come B Dyatkin et al ldquoMXene a promising
transition metal carbide anode for lithium-ion batteriesrdquo Elec-trochemistry Communications vol 16 no 1 pp 61ndash64 2012
[20] M R Lukatskaya O Mashtalir C E Ren et al ldquoCation inter-calation and high volumetric capacitance of two-dimensionaltitanium carbiderdquo Science vol 341 no 6153 pp 1502ndash1505 2013
[21] Q M Peng J X Guo Q R Zhang et al ldquoUnique lead adsorp-tion behavior of activated hydroxyl group in two-dimensionaltitanium carbiderdquo Journal of the American Chemical Society vol136 no 11 pp 4113ndash4116 2014
[22] OMashtalir KMCook VNMochalinMCroweMW Bar-soum and Y Gogotsi ldquoDye adsorption and decomposition ontwo-dimensional titanium carbide in aqueous mediardquo Journalof Materials Chemistry A vol 2 no 35 pp 14334ndash14338 2014
[23] J Yang B B Chen H J Song H Tang and C S LildquoSynthesis characterization and tribological properties of two-dimensional Ti
3C2rdquo Crystal Research and Technology vol 49
no 11 pp 926ndash932 2014[24] M Naguib O Mashtalir M R Lukatskaya et al ldquoOne-step
synthesis of nanocrystalline transition metal oxides on thinsheets of disordered graphitic carbon by oxidation of MXenesrdquoChemical Communications vol 50 no 56 pp 7420ndash7423 2014
[25] Y P Gao L BWang A G Zhou et al ldquoHydrothermal synthesisof TiO
