Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts

Abstract

Hydrogen spillover is a well-known phenomenon in heterogeneous catalysis; it involves H2 cleavage on an active metal followed by the migration of dissociated H species over an ‘inert’ support1,2,3,4,5. Although catalytic hydrogenation using the spilled H species, namely, spillover hydrogenation, has long been proposed, very limited knowledge has been obtained about what kind of support structure is required to achieve spillover hydrogenation1,5. By dispersing Pd atoms onto Cu nanomaterials with different exposed facets, Cu(111) and Cu(100), we demonstrate in this work that while the hydrogen spillover from Pd to Cu is facet independent, the spillover hydrogenation only occurs on Pd1/Cu(100), where the hydrogen atoms spilled from Pd are readily utilized for the semi-hydrogenation of alkynes. This work thus helps to create an effective method for fabricating cost-effective nanocatalysts with an extremely low Pd loading, at the level of 50 ppm, toward the semi-hydrogenation of a broad range of alkynes with extremely high activity and selectivity.

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Fig. 1: Structure characterizations and catalytic performance of Pd1/Cu with different facets.
Fig. 2: Facet-dependent hydrogenation revealed by DFT calculations.
Fig. 3: Evidence of spillover hydrogenation over Pd1/Cu(111).

Data Availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. The DFT structures can be found in the supplementary Computational Data 1. Source data are provided with this paper.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2017YFA0207302, 2017YFA0207303), the National Natural Science Foundation of China (21890752, 21731005, 21573178, 91845102, 21721001) and the fundamental research funds for central universities (20720180026). N.Z. acknowledges support from the Tencent Foundation through the XPLORER PRIZE. We also thank the beamline BL14W1 (Shanghai Synchrotron Radiation Facility) and SP8 12B2 beamline (National Synchrotron Radiation Research Center) for providing beam time.

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Authors

Contributions

L.J. and K.L. contributed equally to this work. N.Z. and G.F. conceived of and designed the experiment. L.J. performed the DFT calculations and predictions, and K.L. performed the synthesis and catalytic experiments. L.Z. assisted in the data collection and analysis. S.F.H. and H.M.C. performed the EXAFS experiments, and Q.Z. and L.G. performed the TEM characterizations. N.Z., G.F., L.J. and K.L. cowrote the manuscript. All the authors contributed to the overall scientific interpretation.

Corresponding authors

Correspondence to Gang Fu or Nanfeng Zheng.

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The authors declare no competing interests.

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Peer review information Nature Nanotechnology thanks Jinlong Gong, Ai-Qin Wang and Feng-Shou Xiao for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 The electronic structure of Pd1/Cu.

In situ FTIR spectra of CO adsorption on (a) Pd1/Cu(111), (b) Pd1/Cu(100). For Pd1/Cu, the band at ~2030 cm−1 is ascribed to CO linearly adsorbed on Pdδ-, confirming that the electronic transfer from Cu to Pd in Pd1/Cu and the Pd atoms in Pd1/Cu are atomically dispersed. (c) X-ray absorption near-edge structure (XANES) of different Pd1/Cu catalysts and Pd foil. In comparison with Pd foil, the white line of Pd1/Cu shows a slight shift to lower energy for the adsorption edge (E0), suggesting that Pd in Pd1/Cu carries negative charge. The Bader charge analysis of (d) Pd1/Cu(111) and (e) Pd1/Cu(100) reveals that isolated Pd atoms carry substantially negative charges, confirming the experiment observations. Source data

Extended Data Fig. 2 Structure stability of Pd1/Cu (Pd, 0.2 wt%).

Representative transmission electron microscope (TEM) characterizations of (a) Pd1/Cu(111), and (b) Pd1/Cu(100) after semihydrogenation of phenylacetylene. In situ FTIR spectra of CO adsorption on (c) Pd1/Cu(111), and (d) Pd1/Cu(100) after semihydrogenation of phenylacetylene. Source data

Extended Data Fig. 3 Hydrogen spillover on Pd1/Cu(111) and Pd1/Cu(100).

(a) Calculated barriers for hydrogen spillover over Pd1/Cu(111) and Pd1/Cu(100). (b) Color change of physical mixture of WO3 and Pd1/Cu before and after treated with H2 at 303 K.

Extended Data Fig. 4 Optimized structures of the transition states (TSs) for the stepwise-hydrogenation of PhC ≡ CH to PhCH2CH3 over different active sites.

(a) Pd1/Cu(111) and (b) Pd1/Cu(100).

Extended Data Fig. 5 The long-distance spillover hydrogenation over Pd1/Cu(111)/Cu(100).

(a) Schematic diagram of the hydrogen spillover over the different size of Cu nanocubes when mixing with Pd1/Cu(111) (b) The reactivtiy of physically mixtures by adding the same number but different size of Cu nanocubes (75-500 nm) into Pd1/Cu(111). (c) The reactivtiy of physically mixtures by adding different amount of 500 nm Cu nanocubes into Pd1/Cu(111). Reaction conditions: 10 mL ethanol; 1 μmol Pd; 10 mmol PA; T = 303 K; pressure = 0.1 MPa. Source data

Extended Data Fig. 6 Scale-up synthesis of the Pd1/Cu(100) catalyst.

(a) The photograph of the reaction system that was enlarged by 15 times. (b) TEM image of the as-prepared Cu nanocubes. (c) in situ FTIR spectra of CO adsorption on the Pd1/Cu(100) catalyst that was scale-up synthesized. (d) Catalytic performance of the scale-up Pd1/Cu(100) catalyst. Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–34, Tables 1–9 and refs. 46–52.

Computational Data 1

The coordinates of the structure models for the DFT calculations in the work.

Source data

Source Data Fig. 1

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Extended Data Fig. 1

Statistical source data.

Source Data Extended Data Fig. 2

Statistical source data.

Source Data Extended Data Fig. 5

Statistical source data.

Source Data Extended Data Fig. 6

Statistical source data.

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Jiang, L., Liu, K., Hung, S. et al. Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts. Nat. Nanotechnol. 15, 848–853 (2020). https://doi.org/10.1038/s41565-020-0746-x

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