Ministry of Education, Science and Technological Development

Project type:

Basic Research

Duration

2011-2014

Project Coordinator:

ICTM -  Department of Electrochemistry University of Belgrade

Participants:

• ICTM - Department of Electrochemistry University of Belgrade;
• Faculty of Chemistry, University of Belgrade;
• Technical Faculty in Bor, University of Belgrade

Project Manager:

Dr Amalija Tripković, ICTM-Department of Electrochemistry, University of Belgrade

Number of Researchers:

16

Aim and Scope:

Research in the project is based on a new approach in designing materials for energy conversion (fuel and solar cells) and energy storage (supercapacitors and Li-ion batteries) systems.
The project consists of three subprojects:

1. EFFECT OF SURFACE MORPHOLOGY ON CATALYTIC ACTIVITY
2. SYNTHESIS AND CHARACTERIZATION OF NANOCATALYSTS
3. SYNTHESIS AND CHARACTERIZATION OF MATERIALS FOR ENERGY STORAGE

The first and second subproject are related to designing materials for conversion of chemical into electrical energy in the fuel cells based on the correlation between the macroscopic activity and nano-structure of materials. Catalytic activity and stability of these materials will be studied in H2(CO)/O2 fuel cell reactions as well as in the oxidation of CH3OH and HCOOH. Model systems (Pt single crystals and single crystal binary alloys) will be studied aiming to determination, characterization and stabilization of active sites at the electrode for the reaction of interest. Theoretical DFT calculations will be used to explain the link between activity and surface morphology. The correlation between the crystal structure of nanoparticles and monocrystals should enable designing effective and stable nanocatalysts based on the results obtained on model systems. Non-platinum catalysts, composed of transition metal oxides and their alloys, will be synthesized.

The third subproject includes research of multi-component fine grained electrode materials for supercapacitors based on oxides of noble and transition metals and/or carbon materials as well as their synthesis by sol-gel procedures, their chemical structural and electrochemical characterization. These composites of mixed oxides of noble and transition metals and/or C materials may also find application in electrochemical synthesis, degradation of environmental pollutants and corrosion protection. Research will proceed in two directions:

a) Study of composite materials based on metal oxide and/or carbon materials for energy storage
b) Photoelectrocatalytic activity of titanium and copper oxides

Electrochemical, spectroscopic and microscopic methods will be used for characterization of the materials.

Major Results:

On the basis of the proposed research the following results are expected:

• Detection and characterization of morphological elements at the surface of the model systems (nano-sized islands, steps, terraces, clusters…);
• It will be determined which of the morphological elements are the active sites for the reactions examined;
• In order to obtain efficient catalysts, methods for synthesis and stabilization of the active sites will be established;
• It will be reviled how alloying metals affect changes of Pt electronic structure in the alloy compared to pure metal and degree of the metal segregation in alloys;
• The effect of these changes on the activity and stability of catalysts in the reaction will be shown;
• The best alloying metal for the reaction of interest will be defined;
• Nanocatalysts matching the characteristics of Pt-skin structure should be synthesized;
• Nonplatinum catalysts will be synthesized;
• Synthesis procedures for different types of high-capacitance composite materials (carbon and / or oxide materials impregnated by various metal oxides) will be developed, optimized and used as catalyst supports as well;
• Physical, chemical and structural characterization of the composites obtained will be performed, characteristics and capacity determined and procedures for their production optimized;
• A laboratory prototype of supercapacitors will be constructed and its voltage-current characteristics will be tested in the hybrid system with fuel cell;
• Synthesis process for metal oxides that are important for Li-ion batteries will be developed and fundamental electrochemical characterization of а hybrid cell composed of Li-ion battery and supercapacitor performed;
• In order to obtain highly active materials for photovoltaic cells and oxidation of organic molecules, it will be determined how conditions of sol-gel and electrochemical synthesis of Ti and Cu oxides affect their photocatalytic properties.

Selected publications:

1. B. Genorio, R. Subbaraman, D. Strmcnik, D. Tripković, V. R. Stamenković, N. M. Marković, “Tailoring the selectivity and stabilisty of chemically modified platinum nanocatalysts to design highly durable anodes for PEM fuel cells” Angewandte Chemie, 50 (24) (2011) 5468-5472.
2. R. Subbaraman, D. Tripković, D. Strmcnik, K.-C. Chang, M. Uchimura, A. P. Paulikas, V. Stamenković, N. M. Marković, “Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces”, Science, 334 (6060), 1256-1260.
3. T.R. Vidaković-Koch, V.V. Panić, M. Andrić, M.T. Petkovska, K. Sundmacher, “Nonlinear Frequency Response Analysis of the Ferrocyanide Oxidation Kinetics. Part I. A Theoretical Analysis”, J.Phys.Chem. C, 115 (35) (2011) 17341-17351.
4. V.V. Panić, T.R. Vidaković-Koch, M. Andrić, M.T. Petkovska, K. Sundmacher, “Nonlinear Frequency Response Analysis of the Ferrocyanide Oxidation Kinetics. Part II. Measurement Routine and Experimental Validation J.Phys.Chem. C, 115 (35) (2011) 17352-17358.
5. V. Tripković, M. E. Bjorketun, E. Skulason, J. Rossmeisl, “Standard hydrogen electrode and potential of zero charge in density functional calculations”, Phys. Rev. B, 84 (2011) 115452-115452-11.
6. J. D. Lović, K. Đ. Popović, A. V. Tripković, “Impact of modification of carbon supported Pt based catalysts by irreversibly adsorbed Sn, Ru and Rh on ethanol oxidation”, J. Serb. Chem. Soc., 76 (11)(2011) 1523-1536.
7. S.I. Stevanović, V.V. Panić, A.B. Dekanski, A.V. Tripković, V.M. Jovanović, “Relationships between structure and activity of carbon as a multifunctional support for electrocatalysts”, Phys. Chem. Chem. Phys., 14 (26) (2012) 9475-9485.
8. S. Stevanović, D. Tripković, J. Rogan, K.Đ. Popović, J.D. Lović, A. Tripković, V.M. Jovanović, “Microwave assisted polyol synthesis of carbon supported platinum based bimetallic catalysts for ethanol oxidation”, J. Solid State Electrochem., 16 (2012) 3147.
9. B.B. Petković, S.I. Stevanović, M.V. Budimir, S.P. Sovilj, V.M. Jovanović, “Electrochemical Examination of Copper(II) Complexes with Octaazamacrocyclic Ligand and Heterocyclic Dithiocarbamate”, Electroanalysis, 24(7) (2012) 1605-1612
10. J.D. Lović, M.D. Obradović, D.V. Tripković, K.Đ. Popović, V.M. Jovanović, S.Lj. Gojković, A V. Tripković, “High activity and stability of Pt2Bi catalyst in formic acid oxidation”, Electrocatalysis (2012) DOI 10.1007/s12678-012-0099-9.

Contacts:

Dr Amalija Tripković, ICTM-Department of Electrochemistry, 11000 Beograd, Njegoševa 12
E-mail: amalija@tmf.bg.ac.rs