1. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 1 Institute of Catalysis and Surface Chemistry Polish Academy of Sciences 6 months research activities new catalyst formulations based on Cu-Mn mixed oxides synthesis physico-chemical characterization preliminary catalytic testing WP2.2 Advanced Catalyst Development

2. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 2 Synthetic approach for preparation of mixed oxide precursors: citrate method (sol-gel) hydrotalcite method WP2.2 Advanced Catalyst Development

3. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 3 WP2.2 Advanced Catalyst Development Cu(II), Mn(II), Al(III) nitrates 2.5 M Citric acid Viscous solution Citrate Gel Xerogel Mixed oxide Calcination 550 o C Drying 250 o C Stirring 65 o C Citrate methodHydrotalcite method Cu(II), Mn(II), Al(III) nitrates 1 M Na 2 CO 3 /NaOH Precipitation pH=9, 55 o C Hydrotalcite Mixed oxide Calcination 450 o C Drying 50 o C

4. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 4 Brucite Mg(OH) 2 Hydrotalcite [(Mg 0.75 Al 0.25 )(OH) 2 ](CO 3 ) 0.125 ·0.5H 2 O [(Mg 0.75 Al 0.25 )(OH) 2 ] 0.25+ (CO 3 ) 2- 0.125 (H 2 O) 0.5 Synthetic hydrotalcite [M 2+ (1-x) M 3+ x (OH) 2 ] x+ A n- x/n  yH 2 O

5. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 5 Synthetic hydrotalcite [M 2+ (1-x) M 3+ x (OH) 2 ] x+ A n- x/n Synthetic hydrotalcite M 2+ = Mg, Ni, Zn, Fe, Co, Cu, Mn… M 3+ = Al, Mn, Fe, Cr …. A n - = CO 3 2 –, NO 3 -, Cr 2 O 7 2-, PMo 12 O 40 3- … 0.20<x<0.33 [M 2+ (1-x) M 3+ x ](OH) 2 A n- [M 2+ (1-x) M 3+ x ](OH) 2 A n- H2OH2OH2OH2O H2OH2O H2OH2O H2OH2O H2OH2O H2OH2O H2OH2O H2OH2O Natural Hydrotalcite M 2+ = Mg 2+ M 3+ = Al 3+ A n- = CO 3 2-, NO 3 - x = 0.25 WP2.2 Advanced Catalyst Development

6. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 6 WP2.2 Advanced Catalyst Development XRD of Cu-Mn-Al hydrotalcite-like precursors

7. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 7 WP2.2 Advanced Catalyst Development Thermal decomposition of CuMnAl/1:1:1/ hydrotalcite-like precursor monitored in a high temperature XRD chamber

8. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 8 Sample Oxidic phases after calcination at 373 K473 K573 K673 K773 K873 K973 K1073 K1173 K CuAlCO 3 (2:1) HT --- CuO Cu 2 Al 4 O 7 CuO Cu 2 Al 4 O 7 CuO Cu 2 Al 4 O 7 CuMnAlCO 3 (12:5:1) HT R R--- CuMn 2 O 4 CuO CuMn 2 O 4 CuO CuMn 2 O 4 CuO CuMn 2 O 4 CuO CuMn 2 O 4 CuO CuMnAlCO 3 (4:4:1) HT R R--- CuMn 2 O 4 CuO traces Mn 2 O 3 traces CuMn 2 O 4 CuO Mn 2 O 3 Mn 2 AlO 4 CuMn 2 O 4 CuO Mn 2 AlO 4 CuMn 2 O 4 CuO CuMnO 2 MnAl 2 O 4 CuMnAlCO 3 (2:1:1) HT--- CuMn 2 O 4 CuO traces CuMn 2 O 4 MnAl 2 O 4 CuO CuMn 2 O 4 MnAl 2 O 4 CuO CuMn 2 O 4 CuO MnAl 2 O 4 CuMnAlCO 3 (1:1:1) HT R R--- CuMn 2 O 4 (weak) Mn 1+x Al 2-x O 4 CuMn 2 O 4 Mn 2 AlO 4 MnAl 2 O 4 CuMn 2 O 4 CuO Mn 2 AlO 4 CuMn 2 O 4 CuO Mn 2 AlO 4 CuMnAlCO 3 (1:2:1) HT R R--- CuMn 2 O 4 Mn 2 O 3 CuMn 2 O 4 Mn 2 O 3 Mn 2 AlO 4 CuMn 2 O 4 Mn 2 O 3 traces Mn 2 AlO 4 CuMn 2 O 4 MnAlCO 3 (2:1) HT R --- Mn 3 O 4 Mn 2 AlO 4 Mn 2 O 3 Mn 2 AlO 4 WP2.2 Advanced Catalyst Development

9. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 9 XRD of mixed oxides derived from hydrotalcite-like precursors WP2.2 Advanced Catalyst Development

10. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 10 Bulk vs. surface chemical composition SampleCu:Mn:Al atomic ratios -bulk values (ICP OES) Cu:Mn:Al atomic ratios -surface values (XPS) BET [m 2 /g] CuMnAl (12:5:1)13:5.1:14.7:2.1:14.7:2.1:155 CuMnAl (4:4:1)4.1:4.2:14.1:4.2:10.9:1.6:10.9:1.6:161 CuMnAl (1:1:1)1.1:1.2:11.1:1.2:11.2:1.8:11.2:1.8:196 CuMnAl (2:1:1)2.1:1.1:12.1:1.1:11.2:0.6:11.2:0.6:162 CuMnAl (1:2:1)1.1:2.2:11.1:2.2:10.9:1:10.9:1:1132 MnAl (2:1)2.3:12.3:10.4:10.4:1237 CuAl (2:1)2.2:12.2:10.2:10.2:130 WP2.2 Advanced Catalyst Development

11. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 11 CuMnAl (1:1:1) HAADF STEM shows that CuMnAl (1:1:1) is a mixture of semi-amorphous oxide phases of different composition. HRTEM proves that one of them is nanocrystalline spinel CuMn 2 O 4. HAADF STEM Transmission Electron Microscopy STEM of CuMnAl 6:2:1 5 nm HRTEM WP2.2 Advanced Catalyst Development

12. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 12 WP2.2 Advanced Catalyst Development CuAl (2:1)CuMnAl (2:1:1)CuMnAl (4:4:1) precursor calcined Scanning Electron Microscopy

13. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 13 Cu 2p 3/2,1/2 Mn 2p 3/2,1/2 XPS Sample% Cu + % Cu 2+ % Mn 2+ % Mn 4+ CuMn 135 0 C5.15.142.6531.568.5 CuMn 240 0 C61.235.527.572.5 Contribution of various Cu and Mn oxidation states at the surface of a CuMnAl/2:1:1/Ht catalyst after exposure to air at different temperatures reduction oxidation WP2.2 Advanced Catalyst Development

14. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 14 WP2.2 Advanced Catalyst Development H 2 TPR of Cu-Mn-Al mixed oxides derived from hydrotalcite precursors

15. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 15 WP2.2 Advanced Catalyst Development XRD patterns of Cu-Mn-Al mixed oxides derived from citrate precursors.

16. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 16 WP2.2 Advanced Catalyst Development MnAl/2:1/Ht MnAl/2:1/Cit Influence of the nature of precursor 237 m 2 /g77 m 2 /g

17. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 17 WP2.2 Advanced Catalyst Development CH 4 combustion fixed-bed flow glass reactor, p=1 bar, temperature = 175-525 o C, catalyst - 0.5 ml, [CH 4 ] = 1g/m 3, GHSV = 10 000 h -1. Sample T 50 [ o C] BET [m 2 /g] CuMnAl/4:4:1/Ht38961 CuMnAl/1:2:1/Ht411132 MnAl/2:1/Ht412237 CuAl/2:1/Ht 470 30 MnAl/2:1/Cit47877 MnAl/1:2/Cit439324 Cu/Mn/1:2/Cit45818 ECOCAT washcoat255n.d.

18. INGAS 6-months Meeting, Prague, Czech Republic, 25-26 May 2009 INGAS INtegrated GAS Powertrain 18 WP2.2 Advanced Catalyst Development Future action Further exploration along the compositions based on mixed Cu and Mn oxides, aiming at maximization of the specific surface area and simultaneous formation of the copper-rich spinel phase. Investigation of compositions enriched with promoters (e.g. Ce, Zr). Synthesis of perovskite and hexaaluminate precursors containing Co and La.