Size-dependent electronic interface effect of Pd nanocube-based heterojunctions on universally boosting phenol hydrogenation reactions

doi:10.1016/S1872-2067(23)64442-0

Abstract

Abstract:

As mainstream catalysts for phenol hydrogenation with good reusability and high selectivity under mild conditions, Pt- and Pd-based heterogeneous catalysts suffer from unsatisfied catalyst costs. The structures of metals (i.e., particle sizes, alloy structures, and porosity) and the acidity of the support were optimized to boost the intrinsic activity of noble metal nanocatalysts with a maximum promoting factor of 3.3. There is considerable scope for exploring more powerful methods for boosting the mass activity of metal catalysts. Herein, we demonstrate a novel size-dependent electronic interface effect in the heterojunctions of Pd nanocubes and sulfur-doped carbon (SC) supports to enhance phenol hydrogenation activity. Theoretical calculations and experimental results indicate that the size-dependent electron deficiency of Pd nanocubes on the designed SCs as electron acceptors results in an unexpected and universal promotion of phenol hydrogenation activity, outperforming free-standing Pd nanocubes by a factor of 9-19.

Key words: Electronic interface effect, Phenol hydrogenation, Pd nanocube, Schottky heterojunction, Heterogeneous catalysis

Si-Yuan Xia, Qi-Yuan Li, Shi-Nan Zhang, Dong Xu, Xiu Lin, Lu-Han Sun, Jingsan Xu, Jie-Sheng Chen, Guo-Dong Li, Xin-Hao Li. Size-dependent electronic interface effect of Pd nanocube-based heterojunctions on universally boosting phenol hydrogenation reactions[J]. Chinese Journal of Catalysis, 2023, 49: 180-187.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64442-0

https://www.cjcatal.com/EN/Y2023/V49/I6/180

Figures/Tables 4

Fig. 1. Synthesis and characterization of Pd/SC heterojunctions. (a) Synthetic process of typical Pd/SC catalysts via aging the mixture of Pd nanocubes and SC support at 150 °C. The SC support was prepared through the thermal condensation of carbon black and dibenzyl disulfide at 900 °C in a N2 atmosphere. (b-d) High-resolution TEM images of Pd-5, Pd-11, and Pd-15 nanocubes, respectively. (e) S 2p XPS spectra of the SC support. (f) High-resolution TEM image of a typical Pd-5/SC sample. (g) Electron density difference stereogram of the Pd/SC model. Red/blue areas indicate a negative/positive charge. (h) Pd 3d XPS spectra of the free-standing Pd-5 and Pd-5/SC samples.

Fig. 2. Phenol hydrogenation activity of the Pd-5/SC catalyst and controls. (a) Yields of cyclohexanone (green) and cyclohexanol (dark green) over the Pd-5/SC catalyst (Pd content: 3 wt%) at different reaction times. Reaction conditions: 20 mg Pd-5/SC catalyst (Pd 1.13 mol%), 0.5 mmol phenol, 5 mL water, 60 °C, 10 bar H2. (b) Conversions of phenol over the Pd-5, Pd-5/SC, and SC catalysts. Reaction conditions: 0.6 mg Pd-5 catalyst (Pd 1.13 mol%; reaction time: 4 h), 20 mg Pd-x/SC catalyst (Pd 1.13 mol%; reaction time: 4 h), or 19.4 mg SC support (reaction time: 4 h); 0.5 mmol phenol; 5 mL water; 60 °C; 10 bar H2. (c) TOF values of the Pd-5 (grey circles) and Pd-5/SC (blue spheres) catalysts at different H2 pressures. (d) Corresponding Arrhenius plots of the Pd-5 (grey circles) and Pd-5/SC (blue spheres) catalysts. (e) Conversions (Con.: blue spheres) of phenol and selectivity (Sel.: green spheres) to cyclohexanone for four runs over the Pd-5/SC catalyst. (f) Size distribution and high-resolution TEM image (inset) of the used Pd-5/SC catalyst after four runs.

Fig. 3. Origin of electronic interface-promoted phenol hydrogenation activity on Pd-x/SC catalysts. (a) TOF values of the free-standing Pd-x and Pd-x/SC catalysts. Reaction conditions: 0.6 mg Pd-x catalyst (Pd 1.13 mol%; reaction time: 40 h) or 20 mg Pd-x/SC catalyst (Pd 1.13 mol%; reaction time: 4 h), 0.5 mmol phenol, 5 mL water, 60 °C, 10 bar H2. (b) Electron distribution at the electronic interface of the Pd/SC Schottky contact model and (c) calculated numbers of electrons transferred from the Pd-x models to the same SC support model using the finite element simulation method. (d) Measured work functions (Φ) of the free-standing Pd-x and Pd-x/SC samples via ultraviolet photoelectron spectroscopy (UPS). (e) Pd 3d XPS spectra of the Pd-x/SC catalysts.

Fig. 4. Electronic interface effect on phenol hydrogenation reactions over the Pd-5/SC heterojunction. (a) The calculated adsorption energies Eads?H2 of H2 molecules on the surface of the neutral Pd model (gray) for free-standing Pd nanocubes and the electron-deficient Pd (blue, Pd-e-) model for Pd/SC heterojunctions. (b) Calculated adsorption energies Eads-phenol of pre-adsorbed phenol molecules on the surface of the neutral Pd (gray) and electron-deficient Pd (blue, Pd-e-) models and (c) the corresponding electron density difference stereograms. Red/blue areas indicate a negative/positive charge. (d) Gibbs free energy diagrams of phenol hydrogenation on the neutral Pd (gray, top) and electron-deficient Pd (blue, Pd-e-) models. (e) Promoted TOF values from the free-standing Pd-5 to Pd-5/SC catalysts for the hydrogenation of phenol and substituted phenols according to Table S9. Reaction conditions: 0.6 mg Pd-5 catalyst (Pd 1.13 mol%; reaction time: 40 h) or 20 mg Pd-5/SC catalyst (Pd 1.13 mol%; reaction time: 4 h), 0.5 mmol substrates, 5 mL water, 60 °C, 10 bar H2.

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