In this work, Pt/GMC and Pt/rGO electrocatalysts have been prepared by impregnation reduction method in which Pt precursor is chemically reduced by citric acid, ethanol and Ar-H2 dynamic atmosphere. Graphitic mesoporous carbon (GMC) sample was synthesized via nanocasting process with anhydrous pyrolysis at 1273 K using SBA-15 as hard template and purified sugar as carbon source. SBA-15 was prepared via sol gel using pluronic P-123 as surfactant and TEOS as silica precursor. Reduced graphene oxide (rGO) was synthesized by modified Hummers method using graphite as carbon precursor. The prepared materials were characterized by means of N2 physisorption analysis, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and high resolution transmission electron microscopy (HRTEM). The performance of electrocatalysts for methanol oxidation reaction (MOR) was measured by cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS). The electrochemical characterization techniques revealed that the mass activity of Pt/GMC, Pt/GO and the commercial electrocatalyst Pt/C were 627, 332 and 308 mA/mgPt respectively as well as the carbon monoxide tolerance index ICO for these catalysts were 1.07, 1.04 and 0.63 respectively. Therefore, Pt/GMC and Pt/GO exhibit better electrocatalytic performance and best resistance to carbonaceous intermediates species for the electrooxidation of methanol.

1. XVI International Congress of the Mexican
Hydrogen Society 2016
In honor of Professor Oumarou Savadogo
“Electrochemical Evaluation of Pt/GMC and Pt/rGO
for the Electro-oxidation of Methanol”
By:
M.C. David Macías Ferrer, I.Q., L.P.
José Aarón Melo Banda, José Ysmael Verde Gomez, Ulises Páramo García,
Mayda Lam Maldonado, Rebeca Silva Rodrigo, Iván Alziri Estrada Moreno
QUERÉTARO, QRO., MÉXICO SEPTEMBER 2016

2. XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
INTRODUCTIONINTRODUCTION

3. XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
GOGO GMCGMC
20%20% wtwt PtPt Pt/GMCPt/GMCPt/Pt/rGOrGO
OBJECTIVESOBJECTIVES

4. XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
SYNTHESIS OF MATERIALSSYNTHESIS OF MATERIALS

5. GOGO
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
CARBON
PRECURSOR
• Graphite
• H2SO4
• H2O
• NaNO3
• KMnO4
COMPLETE
OXIDATION WASHING DRYING
OXIDIZING
AGENT
• HCl
• CH3OH
• H2O
• H2O2
1) L. Shahriary, A.A. Athawale, “Graphene Oxide Synthesized by using Modified Hummers Approach,” Int. J. Renewable Energy and Environ. Eng., vol. 2, pp.
58-63, January 2014

6. Pt/Pt/rGOrGO
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
METAL
PRECURSOR
• Pt(acac)2
• C6H8O7
• Acetone
• Ethanol
• GO
SONICATION DRYINGIMPREGNATION
• Ar-H2• 30 min
2) A. Santasalo-Aarnio, M. Borghei, I.V. Anoshkin, A.G. Nasibulin, E.I. Kauppinen, V. Ruiz, T. Kallio, “Durability of Different Carbon Nanomaterial Supports
with PtRu Catalyst in A Direct Methanol Fuel Cell,” Int. J. Hydrogen Energy, vol. 37, pp. 3415-3424, December 2012
HEAT
TREATMENT
• 450 °C
STIR

7. SBASBA--1515
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
DISSOLUTION
• HCl
• EO20PO70O20
• H2O
• Si(OC2H5)4
AGING
WASHING AND
FILTERING DRYINGREACTION
3) D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D. Stucky, “Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to
300 Angstrom Pores,” Science, vol. 279, pp. 548-552, January 1998.

8. SBASBA--1515
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
CALCINATION SBA-15
3) D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D. Stucky, “Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to
300 Angstrom Pores,” Science, vol. 279, pp. 548-552, January 1998.

9. GMCGMC
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
CARBON
PRECURSOR
• SBA-15
• Refined Sugar
• H2O
• H2SO4
HEAT
TREATMENTS PYROLISIS
SILICON
REMOVAL
PRE-PYROLISIS
• 1000°C• 100°C
•160 °C
4) R. Ryoo, S.H. Joo, S. Jun, “Synthesis of Highly Ordered Carbon Molecular Sieves via Template-Mediated Structural Transformation,” J. Phys. Chem. B, vol.
103, pp. 7743-7746, August 1999.

10. GMCGMC
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
GMC
WASHING AND
FILTERING DRYING
4) R. Ryoo, S.H. Joo, S. Jun, “Synthesis of Highly Ordered Carbon Molecular Sieves via Template-Mediated Structural Transformation,” J. Phys. Chem. B, vol.
103, pp. 7743-7746, August 1999.

11. GMC (GMC (FunctionalizationFunctionalization))
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
REFLUX
• GMC
• HNO3
• H2SO4
• H2O
• 150°C
• N2
2) A. Santasalo-Aarnio, M. Borghei, I.V. Anoshkin, A.G. Nasibulin, E.I. Kauppinen, V. Ruiz, T. Kallio, “Durability of Different Carbon Nanomaterial Supports
with PtRu Catalyst in A Direct Methanol Fuel Cell,” Int. J. Hydrogen Energy, vol. 37, pp. 3415-3424, December 2012
FUNCTIONALIZED
GMC
WASHING AND
FILTERING DRYING
• H2O

12. Pt/GMCPt/GMC
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
METAL
PRECURSOR
• Pt(acac)2
• C6H8O7
• Acetone
• Ethanol
• GMC
SONICATION STIR DRYINGIMPREGNATION
• Ar-H2• 30 min
5) A. Santasalo-Aarnio, M. Borghei, I.V. Anoshkin, A.G. Nasibulin, E.I. Kauppinen, V. Ruiz, T. Kallio, “Durability of Different Carbon Nanomaterial Supports
with PtRu Catalyst in A Direct Methanol Fuel Cell,” Int. J. Hydrogen Energy, vol. 37, pp. 3415-3424, December 2012
HEAT
TREATMENTS
• 450 °C

13. CHARACTERIZATION AND MEASUREMENTSCHARACTERIZATION AND MEASUREMENTS
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016

14. XX--Ray DiffractionRay Diffraction
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Instrument: X-ray Diffractometer
Model: Bruker d8 Advance
Conditions. Anode: Cu; Stepsize: 0.068; Range WL: 1.5406; 2θ Range: (10-90)°
GOGO GMCGMC
5) H. Feng, Y. Li, J. Li, “Strong reduced graphene oxide–polymer composites: hydrogels and wires,” RCS Adv., vol. 2, pp. 6988-6993, July 2012
6) H. Shang, Y. Lu, F. Zhao, C. Chao, B. Zhang, “Preparing high surface area porous carbon from biomass by carbonization in molten salt medium,” RCS Adv.,
vol. 5, pp. 75728-75734, August 2015

15. XX--Ray DiffractionRay Diffraction
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Pt/GMCPt/GMC
Instrument: X-ray Diffractometer
Model: Bruker d8 Advance
Conditions. Anode: Cu; Stepsize: 0.068; Range WL: 1.5406; 2θ Range: (10-90)°
Pt/Pt/rGOrGO
7) L. Calvillo, V. Celorrio, R. Moliner, A.B. Garcia, I. Caméan, M.J. Lazaro, “Comparative study of Pt catalysts supported on different high conductive carbon
materials for methanol and ethanol oxidation,”Electrochimica Acta, vol. 102, pp. 19-27, April 2013.
8) J. Park, S. Kim, “Synthesis and electrochemical analysis of Pt-loaded, polypyrroledecorated, graphene-composite electrodes,” Carbon Letters, vol. 14, pp.
117-120, February 2013.

16. 9) Scherrer, P., “Bestimmung der Größe und der inneren Struktur von Kolloidteilchen mittels Röntgenstrahlen, Nachrichten von der Gesellschaft der
Wissenschaften zu Göttingen,” Mathematisch-Physikalische Klasse, vol. 1918, pp. 98-100, July 1918
XX--Ray DiffractionRay Diffraction
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Scherrer Formula
Crystallite Size ≈ 14 nm Crystallite Size ≈ 12 nm
0.94
t
cos 

 

Pt/GMCPt/GMCPt/Pt/rGOrGO

17. Energy Dispersive XEnergy Dispersive X--Ray SpectroscopyRay Spectroscopy
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
GOGO GMCGMC
5) H. Feng, Y. Li, J. Li, “Strong reduced graphene oxide–polymer composites: hydrogels and wires,” RCS Adv., vol. 2, pp. 6988-6993, July 2012
6) H. Shang, Y. Lu, F. Zhao, C. Chao, B. Zhang, “Preparing high surface area porous carbon from biomass by carbonization in molten salt medium,” RCS Adv.,
vol. 5, pp. 75728-75734, August 2015
Instrument: Scanning Electron Microscope with EDS detector
Model: JEOL JSM-7600F
Conditions. Mode: SEM; Mag.: 70000X; WD: 8 mm, AV: 20 keV, Scale: 100 nm
EDS (% wt)
C O S K
GO 66.8 32.77 0.31 0.12
EDS (% wt)
C O Si F
GMC 74.69 24.43 0.10 0.78

18. XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Pt/GMCPt/GMCPt/Pt/rGOrGO
7) L. Calvillo, V. Celorrio, R. Moliner, A.B. Garcia, I. Caméan, M.J. Lazaro, “Comparative study of Pt catalysts supported on different high conductive carbon
materials for methanol and ethanol oxidation,”Electrochimica Acta, vol. 102, pp. 19-27, April 2013.
8) J. Park, S. Kim, “Synthesis and electrochemical analysis of Pt-loaded, polypyrroledecorated, graphene-composite electrodes,” Carbon Letters, vol. 14, pp.
117-120, February 2013.
Energy Dispersive XEnergy Dispersive X--Ray SpectroscopyRay Spectroscopy
Instrument: Scanning Electron Microscope with EDS detector
Model: JEOL JSM-7600F
Conditions. Mode: SEM; Mag.: 70000X; WD: 8 mm, AV: 20 keV, Scale: 100 nm
EDS (% wt)
C O Pt
Pt/rGO 67.68 12.45 19.53
EDS (% wt)
C O Pt
Pt/GMC 62.67 17.97 19.36

19. ScanningScanning ElectronElectron MicroscopyMicroscopy
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
GOGO GMCGMC
Instrument: Scanning Electron Microscope
Model: JEOL JSM-7600F
Conditions. Mode: GB-L, SEM; Mag.: 70000X; AV: 2 keV, 10keV; Scale: 100 nm
10) Sh. Zhou, H. Xu, Q. Yuan, H. Shen, X. Zhu, Y. Liu, W. Gan, “N-Doped Ordered Mesoporous Carbon Originated from a Green Biological Dye for
Electrochemical Sensing and High-Pressure CO2 Storage,” ACS Appl. Mater. Interfaces, vol. 8, pp. 918-926, December 2015
11) S. Gurunathan, J. Han, J.H. Park, J.H. Kim, “An in vitro evaluation of graphene oxide reduced by Ganoderma spp. in human breast cancer cells (MDA-MB-
231),” Int. J. Nanomedicine, vol. 9, pp. 1793-1797, November 2013

20. ScanningScanning ElectronElectron MicroscopyMicroscopy
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Pt/Pt/rGOrGO Pt/GMCPt/GMC
Instrument: Scanning Electron Microscope
Model: JEOL JSM-7600F
Conditions. Mode: GB-L; Mag.: 40000X; AV: 2 keV; Scale: 100 nm
12) A. Liu, S. Huang, “A glucose biosensor based on direct electrochemistry of glucose oxidase immobilized onto platinum nanoparticles modified graphene
electrode,” Sci. China Phys. Mech. Astron., vol. 55, pp. 1163-1167, July 2012.
13) R. Zolfaghari, F.-R. Ahmadun, M.R. Othman, W.R.W. Daud, M. Ismail, “Nonionic surfactant-templated mesoporous carbon as an electrocatalyst support
for methanol oxidation,” Mater. Chem. Phys., vol. 139, pp. 262-269, January 2013

21. Pt/Pt/rGOrGO

22. Pt/GMCPt/GMC

23. ScanningScanning ElectronElectron MicroscopyMicroscopy
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Pt/Pt/rGOrGO
Instrument: Scanning Electron Microscope
Model: JEOL JSM-7600F
Conditions. Mode: GB-L, SEM; Mag.: 70000X; AV: 2 keV, 20 keV; Scale: 100 nm
Pt/GMCPt/GMC
12) A. Liu, S. Huang, “A glucose biosensor based on direct electrochemistry of glucose oxidase immobilized onto platinum nanoparticles modified graphene
electrode,” Sci. China Phys. Mech. Astron., vol. 55, pp. 1163-1167, July 2012.
13) R. Zolfaghari, F.-R. Ahmadun, M.R. Othman, W.R.W. Daud, M. Ismail, “Nonionic surfactant-templated mesoporous carbon as an electrocatalyst support
for methanol oxidation,” Mater. Chem. Phys., vol. 139, pp. 262-269, January 2013

24. Pt/Pt/rGOrGO

25. Pt/GMCPt/GMC

26. ScanningScanning ElectronElectron MicroscopyMicroscopy
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Instrument: Scanning Electron Microscope
Model: JEOL JSM-7600F
Conditions. Mode: GB-L, SEM; Mag.: 70000X; AV: 2 keV, 20 keV; Scale: 100 nm
Pt/GMCPt/GMC
Average Particle Size ≈ 12.4 nm Average Particle Size ≈ 13.8 nm
Pt/Pt/rGOrGO
14) Zh. Liu, X. Duan, H. Cheng, J. Zhou, X. Zhou, “Synthesis of platinum/graphene composites by a polyol method: The role of graphite oxide precursor surface
chemistry,” Carbon, vol. 89, pp. 93-101, March 2015
13) R. Zolfaghari, F.-R. Ahmadun, M.R. Othman, W.R.W. Daud, M. Ismail, “Nonionic surfactant-templated mesoporous carbon as an electrocatalyst support
for methanol oxidation,” Mater. Chem. Phys., vol. 139, pp. 262-269, January 2013

27. ELECTROCHEMICAL MEASUREMENTSELECTROCHEMICAL MEASUREMENTS
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016

28. ELECTROCHEMICAL MEASUREMENTSELECTROCHEMICAL MEASUREMENTS
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
•• TheThe electrocatalyticelectrocatalytic activityactivity givengiven byby massmass activityactivity (the(the currentcurrent densitydensity isis
normalizednormalized toto thethe platinumplatinum loadingloading onon thethe electrodes)electrodes) werewere obtainedobtained byby
cycliccyclic voltammetryvoltammetry inin aa conventionalconventional threethree--electrodeelectrode cellcell..
•• TheThe chemisorbedchemisorbed COCO speciespecie isis consideredconsidered asas aa poisoningpoisoning onon purepure PtPt
surface,surface, andand areare moremore difficultdifficult toto oxidizeoxidize thatthat allall intermediateintermediate
carbonaceouscarbonaceous speciesspecies (ICS)(ICS) formedformed duringduring thethe methanolmethanol oxidationoxidation
reactionreaction (MOR)(MOR)..
•• ItIt hashas beenbeen shownshown thatthat thethe hydroxylhydroxyl andand carboxylcarboxyl functionalfunctional groupsgroups
anchoredanchored toto thethe catalyticcatalytic support,support, cancan dissociatedissociate waterwater moleculesmolecules atat veryvery
lowlow potential,potential, andand contributecontribute toto thethe releaserelease ofof thethe activeactive sitessites ofof PtPt
increasingincreasing thethe electrocatalyticelectrocatalytic activityactivity inin thethe MORMOR.. CurrentlyCurrently thisthis processprocess
isis knownknown asas bifunctionalbifunctional mechanismmechanism theorytheory
15) Ch.-T. Hsieh, J.-Y. Lin, “Fabrication of Bimetallic Pt–M (M=Fe, Co, and Ni) Nanoparticle/Carbon Nanotube Electrocatalysts for Direct Methanol Fuel Cells,” J.
Power Sources, vol. 188, pp. 347–352, 2009
16) A. Hamnett, “Mechanism and Electrocatalysis in the Direct Methanol Fuel Cell,” Catalysis Today, vol. 38, pp. 445-457, 1997

29. ELECTROCHEMICAL MEASUREMENTSELECTROCHEMICAL MEASUREMENTS
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
•• TheThe ratioratio ofof thethe forwardforward anodicanodic peakpeak currentcurrent (I(Iff)) toto thethe reversereverse anodicanodic
peakpeak currentcurrent ((IIbb)) denoteddenoted byby IICOCO,, waswas usedused toto measuremeasure thethe tolerancetolerance ofof
electrocatalystelectrocatalyst toto accumulationaccumulation ofof ICS,ICS, particularlyparticularly COCO;; aa higherhigher ratioratio
indicatesindicates moremore effectiveeffective removalremoval ofof thethe poisoningpoisoning speciesspecies onon thethe catalystcatalyst
surfacesurface..
17) H. Li, D. Kang, H. Wang, R. Wang, “Carbon-Supported Pt-RuCo Nanoparticles with Low-NobleMetal Content and Superior Catalysis for Ethanol Oxidization,”
Int. J. Electrochem. Sci., vol. 6, pp. 1058-1065, 2011

30. Cyclic VoltammetryCyclic Voltammetry
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Instrument: Potenciostat/galvanostat
Model: BASi Epsilon Station
Conditions. S.R.: 30 mV/s; Cycles: 20; Gas Purge: N2; El.: 0.5M H2SO4 + 1M CH3OH
16) A. Hamnett, “Mechanism and Electrocatalysis in the Direct Methanol Fuel Cell,” Catalysis Today, vol. 38, pp. 445-457, 1997
18) J.B. Goodenough, R. Mancharan, “Methanol Oxidation in Acid on Ordered NiTi,” J. Mater. Chem., vol. 2, pp. 875-887, 1992

31. Cyclic VoltammetryCyclic Voltammetry
XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
Instrument: Potenciostat/galvanostat
Model: BASi Epsilon Station
Conditions. S.R.: 30 mV/s; Cycles: 20; Gas Purge: N2; El.: 0.5M H2SO4 + 1M CH3OH
19) M. Watanabe, S. Motoo, “Electrocatalysis by Ad-Atoms: Part III. Enhancement of the Oxidation of Carbon Monoxide on Platinum by Ruthenium Ad-Atoms,”
J. Electroanal. Chem., vol. 60, pp. 275-283, 1975
15) Ch.-T. Hsieh, J.-Y. Lin, “Fabrication of Bimetallic Pt–M (M=Fe, Co, and Ni) Nanoparticle/Carbon Nanotube Electrocatalysts for Direct Methanol Fuel Cells,” J.
Power Sources, vol. 188, pp. 347–352, 2009

32. XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
CONCLUSIONSCONCLUSIONS
Pt/GMCPt/GMC
•• hadhad higherhigher electrocatalyticelectrocatalytic activityactivity ((627627 mAmA//mgPtmgPt))
•• betterbetter antipoisoningantipoisoning abilityability (ICO(ICO == 11..0707))

33. XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
ACKNOWLEDGMENTSACKNOWLEDGMENTS

34. XVI International Congress of the Mexican Hydrogen Society 2016XVI International Congress of the Mexican Hydrogen Society 2016
THANK YOU FOR ATTENTIONTHANK YOU FOR ATTENTION