Science Advances

Supplementary Materials

This PDF file includes:

  • Supplementary Text
  • Fig. S1. Morphologies of Pd/Al2O3 catalysts with various particle sizes.
  • Fig. S2. The corresponding Pd size distributions in the Pd/Al2O3 catalysts.
  • Fig. S3. The apparent activation energies for benzaldehyde and toluene formation.
  • Fig. S4. A representative TEM image of the 10Al2O3-Pd catalyst.
  • Fig. S5. A representative STEM image of the 8FeOx-Pd catalyst.
  • Fig. S6. The Pd particle size distributions of uncoated and oxide-coated samples.
  • Fig. S7. In situ XPS spectra of Pd/Al2O3, 10Al2O3-Pd, and 8FeOx-Pd samples in the Pd 3d region.
  • Fig. S8. Semiquantitative analysis of the DRIFT spectra.
  • Fig. S9. The ratios of exposed Pd HCSs to LCSs on oxide-coated and uncoated Pd/Al2O3 samples determined by semiquantitative analysis of the DRIFT CO chemisorption spectra.
  • Fig. S10. Catalytic performance of 4.2-nm Pd/Al2O3 catalysts with different cycles of alumina and FeOx overcoating in aerobic oxidation of benzyl alcohol at 120°C.
  • Fig. S11. Catalytic performance of 4.2-nm Pd/Al2O3 catalysts with different cycles of alumina overcoating in aerobic oxidation of benzyl alcohol at 120°C.
  • Fig. S12. Catalytic performance of 4.2-nm Pd/Al2O3 and 10Al2O3-Pd catalysts in aerobic oxidation of benzyl alcohol at different temperatures.
  • Fig. S13. Catalytic performance of 4.2-nm Pd/Al2O3 and 10Al2O3-Pd catalysts in aerobic oxidation of benzyl alcohol at 90°C.
  • Fig. S14. Catalytic performance of 4.2-nm Pd/Al2O3 and 10Al2O3-Pd catalysts in aerobic oxidation of benzyl alcohol at 140°C.
  • Fig. S15. Structural characterization of Al2O3- and FeOx-overcoated 5.1-nm Pd/Al2O3 samples and their catalytic performances.
  • Fig. S16. Morphology of the 2.9-nm Pd/C catalyst.
  • Fig. S17. Catalytic performance of the 2.9-nm Pd/C, 10Al2O3-Pd/C, and 8FeOx-Pd/C catalysts in aerobic oxidation of benzyl alcohol at 120°C.
  • Fig. S18. Recycling stability of the 10Al2O3-Pd catalyst.
  • Fig. S19. Optimized geometries and calculated binding energies of benzyl alcohol and its derived key intermediates on Pd surfaces.
  • Fig. S20. Optimized geometries and calculated binding energies of O2, O, H, OH, and H2O intermediates on Pd surfaces with respect to the corresponding species in the gas phase.
  • Fig. S21. The side views of optimized geometries of benzyl alcohol and its derived key intermediates on Pd surfaces.
  • Fig. S22. The transition states of elementary steps involved in benzyl alcohol oxidation on Pd(111).
  • Fig. S23. The transition states of elementary steps involved in benzyl alcohol oxidation on Pd(211).
  • Fig. S24. Energy profiles of the direct and oxidative dehydrogenation paths on Pd surfaces.
  • Fig. S25. Energy profiles of the hydrogenolysis path to toluene formation on Pd surfaces.
  • Fig. S26. Energy profiles of C–O scission of (C6H5)CH2OH*, (C6H5)CHOH*, and (C6H5)CH2O* on Pd surfaces.
  • Fig. S27. Models of freestanding Pd55, Pd147, and Pd309 clusters.
  • Fig. S28. The optimized most stable geometries of (C6H5)CH2OH*, (C6H5)CH2*, and OH* on freestanding Pd55, Pd147, and Pd309 clusters.
  • Fig. S29. Comparison of the side view of charge density difference upon adsorption of benzyl on Pd55, Pd147, Pd309, and Pd(211) surfaces.
  • Fig. S30. Comparison of the top view of charge density difference upon adsorption of benzyl on Pd55, Pd147, Pd309, and Pd(211) surfaces.
  • Fig. S31. Optimized transition state structures of the key steps involved in benzaldehyde and toluene formations on Pd55 cluster.
  • Fig. S32. Energy profiles of the oxidative dehydrogenation and hydrogenolysis paths on Pd55 cluster.
  • Table S1. Conditions for synthesis of Pd/Al2O3 samples with various Pd particle sizes using the WI method.
  • Table S2. Calculated activation barriers (Ea) and reaction energies (Er) of elementary steps in oxidation of benzyl alcohol on Pd(111) and Pd(211) surfaces.
  • Table S3. Pd dispersion determined by CO pulse chemisorption for various Pd catalysts.

Download PDF

Files in this Data Supplement: