Supporting Online Information High Activity Redox Catalysts Synthesised by Chemical Vapour Impregnation Michael M. Forde, 1 Lokesh Kesavan, 1 Mohd Izham bin Saiman, 1 Qian He, 2 Nikolaos Dimitratos, 1 Jose Antonio Lopez-Sanchez, 1 Robert L. Jenkins, 1 Stuart H. Taylor, 1 Christopher J. Kiely, 2 and Graham J. Hutchings 1 1 Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building Park Place, Cardiff, CF10 3AT, United Kingdom. Tel.: +442920874059; Fax: +442090874030 2 Department of Materials Science and Engineering, Lehigh University, 5 East Packer Avenue, Bethlehem, PA 18015-3195, USA.
Directory of contents Table S1. Liquid phase oxidation of benzyl alcohol using Pd, Pt and Pd-Pt catalysts supported on TiO 2 prepared by the chemical vapour impregnation method. Table S2. Liquid phase oxidation of benzyl alcohol using Pd, Pt and Pd-Pt catalysts supported on TiO 2 and C prepared by the sol-immobilisation (SI) and impregnation (IW) methods. Table S3. Comparison of catalysts used in hydrogenation of levulinic acid to γ-valerolactone from recent literature Figure S1. Additional STEM-HAADF micrographs showing typical metal cluster morphologies for CVI prepared samples of (a) Pd/TiO 2 (b) Pt/TiO 2 and (c) Pd-Pt/TiO 2. Figure S2. STEM-HAADF and STEM-BF images of a 2.5wt%Pd/TiO 2 CVI catalyst that had been exposed to air for long periods. Figure S3. GC spectrum from the GC-MS analysis of the reaction mixture from the hydrogenation of levulinic acid using 1.25wt%Pd-1.25wt%Pt/TiO 2 catalyst. Figure S4. MS analysis of the reaction products (separated by GC) from the hydrogenation of levulinic acid using a 1.25wt/%Pd- 1.25wt%Pt/TiO 2 catalyst prepared by CVI.
Table S1. Liquid phase oxidation of benzyl alcohol using Pd, Pt and Pd-Pt catalysts supported on TiO 2 prepared by the chemical vapour impregnation method. a Selectivity (%) Catalyst Conv. Toluene Benzaldehyde Benzoic Benzyl TOF /h -1 b (%) acid benzoate 2.5% Pd/TiO 2 91.1 24.6 60.6 9.6 5.2 12000 2.5% Pd-2.5% Pt/TiO 2 40.2 1.4 79.4 6.5 12.7 6000 2%Pd-0.5%Pt/TiO 2 65.7 1.9 81.3 6 10.8 9000 1.25%Pd-1.25%Pt/TiO 2 24.8 2.0 81.0 5.3 11.7 6000 2.5% Pt/TiO 2 4.3 0.0 97.2 0.9 1.9 2300 a Reaction conditions: 40ml benzyl alcohol, 0.05g of catalyst, T = 120 ºC, po 2 = 150 psi, reaction time = 6h. b Calculation of TOF (h -1 ) was performed after 0.5 h of reaction. TOF numbers were calculated on the basis of total metal loading as measured by ICP except for the 2.5wt%Pd-2.5wt%Pt/TiO 2 catalyst where nominal metal loading was used.
Table S2. Liquid phase oxidation of benzyl alcohol using Pd, Pt and Pd-Pt catalysts supported on TiO 2 and C prepared by the sol-immobilisation (SI) and impregnation (IW) methods. a Catalyst Selectivity (%) TOF/ Toluene Benzaldehyde Benzoic acid Benzyl benzoate h -1 b 5% (2.5Pd+2.5Pt)/TiO 2 IW 1.1 91.3 4.3 3.3 1220 5% (2.5Au+2.5Pd)/TiO 2 IW 13.6 74.2 9.4 2.8 6420 5% (2.5Au+2.5Pd)/C IW 16.6 79.7 1.8 1.9 7830 1wt%Pt/C SI 0.0 90.7 0.7 8.6 2910 1wt%Pd/C SI 6.8 74.7 10.4 8.1 12200 1wt% (0.5Pd+0.5Pt)/C SI 0.7 84.7 5.7 8.9 9580 1wt% (0.5Au+0.5Pd)/C SI 3.4 67.0 23.1 6.5 63800 a Reaction conditions as given in Reference 1. b Calculation of TOF (h -1 ) was performed after 0.5 h of reaction.
Table S3. Comparison of catalysts used in the hydrogenation of levulinic acid to γ-valerolactone from recent literature. Catalyst Conditions Solvent 5% Ru/C 50-100mg 5% Ru/C Cu/ZrO 2 and Cu/Al 2 O 3 500mg 1%Pt/TiO 2 LA= levulinic acid GVL= γ-valerolactone 130 C 5% LA 12 bar H 2 150 C, 50% LA 35 bar H 2 200 C 5%LA 34.5bar H 2 200 C 11% LA 40 bar H 2 Conversion % Selectivity to GVL % Ref. water 99.5 86.6 2 water 100 96 3 water 100 100 4 water 95 100 5
a b c Figure S1. Additional STEM-HAADF micrographs showing typical metal cluster morphologies for CVI prepared samples of (a) Pd/TiO2 (b) Pt/TiO2 and (c) Pd-Pt/TiO2.
d e Figure S2. (a, b) STEM-HAADF and (c) STEM-BF images of a 2.5wt%Pd/TiO 2 CVI catalyst that had been exposed to air for long periods ( > 6months). The Pd nanoparticle interiors are metallic in nature, but the fuzzy outer surface appearance in (a) and (b) could indicate that a thin PdO x layer is coating the particle. Similar surface structures were also noted for the 6 month aged 1.25wt%Pd-1.25wt%Pt/TiO 2 CVI catalyst (d) and (e), but not for the 6 month aged 2.5wt%Pt/TiO 2 CVI catalyst.
Figure S3. GC spectrum from the GC-MS analysis of the reaction mixture from the hydrogenation of levulinic acid using 1.25wt%Pd-1.25wt%Pt/TiO 2 catalyst. A longer reaction time of 8h at 150 C was used to demonstrate the formation of other products for purposes of the analysis. 3.5 min-mthf; 7.2 min- pentan-1-ol; 14.5 min-pentanoic acid (valeric acid); 16.5 minγ-valerolactone; 17.3 min-1,4-pentanediol, 19.3 min- hydroxyvaleric acid. Pseudo-levulinic acid was not observed by GC or GC-MS techniques in any reaction.
Figure S4. MS analysis of the reaction products (separated by GC) from the hydrogenation of levulinic acid using a 1.25wt/%Pd - 1.25wt%Pt/TiO 2 catalyst prepared by CVI. A longer reaction time of 8h at 150 C was used to demonstrate the formation of other products for purposes of the analysis.
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