Fig. 3 TEM morphology and size distribution of HB-Pd/C, AB-Pd/C, CB-Pd/C, and commercial Pd/C. TEM morphology of (A) as-synthesized HB-Pd/C, (B) as-synthesized AB-Pd/C, (C) as-synthesized CB-Pd/C, (D) commercial Pd/C, (E) HB-Pd/C after 24-hour reaction, (F) AB-Pd/C after 24-hour reaction, (G) CB-Pd/C after 24-hour reaction, and (H) commercial Pd/C after 24-hour reaction. Scale bars, 40 nm. Inset histograms represent the size distribution of the corresponding samples.
- Table 1 The TON of heterogeneous catalyst HB-Pd/C and homogeneous catalyst Pd(TFA)2 under different reaction conditions.
Under a low turnover condition, the substrate/catalyst ratio is 100:3; under a high turnover condition, the substrate/catalyst ratio is 1000:3; and under an ultrahigh turnover condition, the substrate/catalyst ratio is 10,000:3.
Entry Catalyst Low turnover High turnover Ultrahigh turnover 1 HB-Pd/C 31 314 >3000 (linear) 2 Pd(TFA)2 20 28 — - Table 2 The yield of various heterogeneous catalysts mediated for 3-methylcyclohexenone dehydrogenative oxidation.
The reactions were carried out in 10 ml of dimethyl sulfoxide (DMSO) solutions containing 1 mmol of 3-methylcyclohexenone, 0.03 mmol of Pd-equivalent catalysts, and 1.2 mmol of TFA under 1 atm of oxygen at 100°C for 24 hours.
Entry Catalyst First-cycle yield (%) Second-cycle yield (%) 1 HB-Pd/C 93 83 2 AB-Pd/C 74 24 3 CB-Pd/C 57 48 4 Commercial Pd/C 67 <1 - Table 3 Zeta potential measurements on Pd nanoparticles before and after dispersing into a TFA/DMSO reaction solution.
Entry Catalyst Zeta potential (mV)
(as prepared)Zeta potential (mV)
(after dispersing into
reaction solution)1 HB-Pd −23.2 −2.79 2 CB-Pd −21.6 −3.76 3 AB-Pd −18.4 2.41
Supplementary Materials
Supplementary material for this article is available at http://advances.sciencemag.org/cgi/content/full/3/1/e1600615/DC1
fig. S1. FTIR spectrum of HB-Pd/C and HB.
fig. S2. TEM image of large particle formation after homogeneous Pd(TFA)2-catalyzed reaction.
fig. S3. Hot filtration test of HB-Pd/C–catalyzed aerobic oxidation reaction.
fig. S4. XPS spectra of CB-Pd/C before and after reaction in Pd 3d region.
fig. S5. TEM morphology and size distribution of BB-Pd/C and catalytic behavior.
Additional Files
Supplementary Materials
This PDF file includes:
- fig. S1. FTIR spectrum of HB-Pd/C and HB.
- fig. S2. TEM image of large particle formation after homogeneous Pd(TFA)2-catalyzed
reaction.
- fig. S3. Hot filtration test of HB-Pd/C–catalyzed aerobic oxidation reaction.
- fig. S4. XPS spectra of CB-Pd/C before and after reaction in Pd 3d region.
- fig. S5. TEM morphology and size distribution of BB-Pd/C and catalytic behavior.
Files in this Data Supplement:
- fig. S1. FTIR spectrum of HB-Pd/C and HB.
