1. Nanomaterials for Energy Center for Nanoscience University of Missouri-St Louis, St. Louis, MO63121 Center for Nanoscience University of Missouri-St Louis, St. Louis, MO63121 Missouri Energy Summit, Columbia, MO, 23 April 2009 Jingyue (Jimmy) Liu and Eric Majzoub Patrick Kinlen Crosslink, St. Louis, MO 63026 Patrick Kinlen Crosslink, St. Louis, MO 63026

2. Outline 1)Introduction to energy usage 2)The role of nanocatalysts 3)Nanomaterials for hydrogen storage 4)Nanostructured polymer solar cells 5)Supecapacitors and batteries 6)Summary 1)Introduction to energy usage 2)The role of nanocatalysts 3)Nanomaterials for hydrogen storage 4)Nanostructured polymer solar cells 5)Supecapacitors and batteries 6)Summary

3. Clothing Shelter Water The Necessities of Human Survival Food What More Do We Want?

4. Improving Quality of Life Transportation Health Communication Environment

5. Food Water Shelter Clothing Health Environment Transportation Communication Energy Natural Gas Nuclear Coal Petroleum Biomass Hydro Geothermal Wind Solar

6. EIA

7. US Energy Consumption by Source (1980-2030) QBtu EIA We will still depend on dwindling fossil fuels unless major events occur

8. The role of nanocatalysis in energy Energy efficiency for existing chemical processes Coal to liquid (CTL) fuel and gas to liquid (GTL) fuel processes for mid-term Hydrogen production Low temperature hydrogen or alcohol fuel cells

9. CTL technology could be a competitive and an assured source of transportation fuels. Coal gasification offers less costly capture and compression of CO 2, and with sequestration Fischer-Tropsch fuels can have a lower carbon footprint than traditional petroleum-based fuels. Coal-to-liquids (CTL) technology by Fischer-Tropsch processes (2n+1)H 2 + nCO C n H (2n+2) + nH 2 O C n H (2n+2) + ½ nO 2 (n+1)H 2 + nCO CH x + H 2 O (1+0.5x)H 2 + CO F-T process Syngas process Catalysts consist of Co, Ni, Ru or combinations

10. Hildebrandt et al., Science 323 (2009) 1680 3C + 4H 2 O 2CO + 4H 2 + CO 2 2(-CH 2 -) + 2H 2 O + CO 3C + 6H 2 O 3CO 2 + 6H 2 2(-CH 2 -) + 4H 2 O + CO 2 New reaction processes can reduce energy and CO 2 emissions

11. Storage type Energy density by mass (MJ/Kg) Energy density by volume (MJ/L) Hydrogen (700bar)1435.6 Hydrogen liquid14310.1 Hydrogen gas1430.01079 Methane (1.03bar55.60.0378 Natural gas53.610 LPG propane49.625.3 LPG butane49.127.7 Gasoline46.434.2 Biodiesel42.233 Butanol36.629.2 Ethanol3024 Methanol19.715.6 Glucose15.5523.9 Zinc5.338 Energy density of various energy carriers

12. Stored H 2 PEM Fuel cell H2OH2O H2H2 Electricity CAT H 2 Production from H 2 O CAT Technical challenge: High efficiency, long life time, low cost and safety Technical challenge: High efficiency, long life time, low cost and safety Hydrogen Energy Carrier H2H2 Metal Hydrides CNT Metal-organic Frameworks

14. CH 3 OH + H 2 O CO 2 + 3H 2 CH 3 OH -- CO + 2H 2 CO + H 2 O -- CO 2 + H 2 Cu/ZnO/Al 2 O 3 Hydrogen Production by Steam Reforming of Methanol Catalyst issue: Deactivation caused by Cu sintering Safety issue

15. Hydrogen Production by Steam Reforming of Methanol Catalyst issue: Pd/ZnO generates high amount of CO Iwasas group obtained better CO selectivity and catalyst stability by reducing Pd/ZnO at moderate to high temperatures Explanation: formation of PdZn alloy nanoparticles (similar band structure to Cu) Detailed nanostructural mechanisms are lacking

16. Our recent research is to develop practical nanostructured model catalyst to understand the synthesis-structure- performance relationships of the Pd/ZnO nanocatalyst Preparation and characterization of Pd/ZnO precursor materials In situ heat treatment at various temperatures and characterization In situ catalytic reactions and characterization

17. 1 m ZnO Nanoblets/Nanoribbons

18. In situ Heat Treatment 400°C 55 min Layers of Pd and Zn atoms Formation of PdZn L10 alloy [100] zone axis Zn Pd

19. Anode: H 2 (g) 2H + (aq) + 2e - Cat Catalysts: Pt, PtRu, PtMo, … Major issues: CO, CO 2 Cathode: O 2 (g) + 4H + (aq) +4e - 2H 2 O(l) Cat Catalysts: Pt, PtNi, PtCr, PtCo, … Major issues: activity, stability

20. Influence of the surface morphology and electronic surface properties on the kinetics of ORR. RRDE measurements for ORR in HClO4 (0.1 M) at 333 K with 1600 revolutions per minute on Pt3Ni(hkl) surfaces as compared to the corresponding Pt(hkl) surfaces Marković/Ross 2007

21. 1 nm 4-nm Pt-Ni alloy nanoparticle showing the preferentially exposed (111) surfaces, which provide much better catalytic performance in hydrogen based fuel cells. 2 nm Design and Fabricate Desired Nanoparticle Fuel Cell Catalysts

22. Hydrogen Storage Another key challenge to the hydrogen economy

23. Majzoub Research Group Theory and Experiment For Energy Utilization Theory and Experiment For Energy Utilization Kinetics H 2 storage targets Thermodynamics And Phase Stability Thermodynamics And Phase Stability

24. Modern Hydrogen Storage Materials NaAlH 4 band structure Complex Ionic Hydrides Wide gap insulators (vs. metal interstitial) Large wt.% of hydrogen LiBH 4 18% LaNi 5 H 6 1.2% Complex Ionic Hydrides Wide gap insulators (vs. metal interstitial) Large wt.% of hydrogen LiBH 4 18% LaNi 5 H 6 1.2% Desirable hydrogen enthalpy: 20-40 kJ/mol H 2 Nanoscale materials for thermodynamic tuning Control particle size and S/V ratio MgH 2 : ΔH = 75kJ/mol H 2 Develop new materials with size control of nanoparticle metals! Desirable hydrogen enthalpy: 20-40 kJ/mol H 2 Nanoscale materials for thermodynamic tuning Control particle size and S/V ratio MgH 2 : ΔH = 75kJ/mol H 2 Develop new materials with size control of nanoparticle metals! (de Jong, JACS, 127, 16675, 2005)

25. The Sun Provides Us Energy Harvest 1 hour of sunlight is enough for 1 years energy use for the whole world

26. Solar Panels: Directly Convert Sun Energy to Electricity or Heat What is the problem?

27. Advanced Technology of New Nanostructured Polymer Solar Cells Flexible, high efficiency and low cost 3 rd G4 th G

28. Printable & Flexible Plastic Solar Cells Photoactive polymer blend P3HT:PCBM Conducting polymer Al e + P3HB: poly(3-hexylthiophene) PCBM: [6,6]-phenyl-C61 butyric acid methyl ester Electron donor and transporter of holes Electron acceptor and transporter 100 nm Printable Electronics

30. Super Capacitors and Batteries New nanostructures can make significant improvement

31. Coin Cell Supercapacitor: Role of PANI Conductivity on Device Performance Enhancement in conductivity of PANI Film contributes to Boost Coin Cell Energy and Power Densities

32. Coin Cell Supercapacitor: Role of PANI Conductivity on Device Performance Polyaniline (PANI) Film Electrical Conductivit y (S/cm) 2 Specific Capacitance (F/g) 3 Energy Density (WH/Kg) 4 PAC 1003 film 0.21.20.38 Novel Secondary Doped PAC 1003 Film 2506.131.92 100012.483.39 400017.215.38

33. Summary Nanostructured materials play a major role in solving the energy challenges in the 21 st century The Center for Nanoscience at UM-St. Louis, working together with local research institutions and companies, is poised to develop alternative energy sources Nanostructured materials play a major role in solving the energy challenges in the 21 st century The Center for Nanoscience at UM-St. Louis, working together with local research institutions and companies, is poised to develop alternative energy sources