Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts


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.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.


  1. 1.

    Prins, R. Hydrogen spillover. Facts and fiction. Chem. Rev. 112, 2714–2738 (2012).

    CAS  Article  Google Scholar 

  2. 2.

    Zaera, F. Chemistry: the long and winding road to catalysis. Nature 541, 37–38 (2017).

    CAS  Article  Google Scholar 

  3. 3.

    Im, J. et al. Maximizing the catalytic function of hydrogen spillover in platinum-encapsulated aluminosilicates with controlled nanostructures. Nat. Commun. 5, 3370 (2014).

    Article  Google Scholar 

  4. 4.

    Karim, W. et al. Catalyst support effects on hydrogen spillover. Nature 541, 68–71 (2017).

    CAS  Article  Google Scholar 

  5. 5.

    Kyriakou, G. et al. Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations. Science 335, 1209–1212 (2012).

    CAS  Article  Google Scholar 

  6. 6.

    Lucci, F. R. et al. Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit. Nat. Commun. 6, 8550 (2015).

    Article  Google Scholar 

  7. 7.

    Yang, X. F. et al. Single-atom catalysts: a new frontier in heterogeneous catalysis. Acc. Chem. Res. 46, 1740–1748 (2013).

    CAS  Article  Google Scholar 

  8. 8.

    Liu, J. L. et al. Tackling CO poisoning with single-atom alloy catalysts. J. Am. Chem. Soc. 138, 6396–6399 (2016).

    CAS  Article  Google Scholar 

  9. 9.

    Pei, G. X. et al. Performance of Cu-alloyed Pd single-atom catalyst for semihydrogenation of acetylene under simulated front-end conditions. ACS Catal. 7, 1491–1500 (2017).

    CAS  Article  Google Scholar 

  10. 10.

    Pei, G. X. et al. Promotional effect of Pd single atoms on Au nanoparticles supported on silica for the selective hydrogenation of acetylene in excess ethylene. New J. Chem. 38, 2043–2051 (2014).

    CAS  Article  Google Scholar 

  11. 11.

    Pei, G. X. et al. Ag alloyed Pd single-atom catalysts for efficient selective hydrogenation of acetylene to ethylene in excess ethylene. ACS Catal. 5, 3717–3725 (2015).

    CAS  Article  Google Scholar 

  12. 12.

    Jorgensen, M. & Gronbeck, H. Selective acetylene hydrogenation over single-atom alloy nanoparticles by kinetic Monte Carlo. J. Am. Chem. Soc. 141, 8541–8549 (2019).

    Article  Google Scholar 

  13. 13.

    Kruppe, C. M., Krooswyk, J. D. & Trenary, M. Selective hydrogenation of acetylene to ethylene in the presence of a carbonaceous surface layer on a Pd/Cu(111) single-atom alloy. ACS Catal. 7, 8042–8049 (2017).

    CAS  Article  Google Scholar 

  14. 14.

    Yang, K. R. & Yang, B. Identification of the active and selective sites over a single Pt atom-alloyed Cu catalyst for the hydrogenation of 1,3-butadiene: a combined DFT and microkinetic modeling study. J. Phys. Chem. C 122, 10883–10891 (2018).

    CAS  Article  Google Scholar 

  15. 15.

    Huang, Y., Handoko, A. D., Hirunsit, P. & Yeo, B. S. Electrochemical reduction of CO2 using copper single-crystal surfaces: effects of CO* coverage on the selective formation of ethylene. ACS Catal. 7, 1749–1756 (2017).

    CAS  Article  Google Scholar 

  16. 16.

    Wang, W. et al. Synthesis of CuO and Cu2O crystalline nanowires using Cu(OH)2 nanowire templates. J. Mater. Res. 18, 2756–2759 (2011).

    Article  Google Scholar 

  17. 17.

    Abeywickrama, T., Sreeramulu, N. N., Xu, L. & Rathnayake, H. A versatile method to prepare size- and shape-controlled copper nanocubes using an aqueous phase green synthesis. RSC Adv. 6, 91949–91955 (2016).

    CAS  Article  Google Scholar 

  18. 18.

    Boucher, M. B. et al. Single atom alloy surface analogs in Pd0.18Cu15 nanoparticles for selective hydrogenation reactions. Phys. Chem. Chem. Phys. 15, 12187–12196 (2013).

    CAS  Article  Google Scholar 

  19. 19.

    Liu, K. et al. Cu2O-supported atomically dispersed Pd catalysts for semihydrogenation of terminal alkynes: critical role of oxide supports. CCS Chem. 1, 207–214 (2019).

    CAS  Article  Google Scholar 

  20. 20.

    Spanjers, C. S. et al. In situ spectroscopic characterization of Ni1-xZnx/ZnO catalysts and their selectivity for acetylene semihydrogenation in excess ethylene. ACS Catal. 5, 3304–3315 (2015).

    CAS  Article  Google Scholar 

  21. 21.

    Chung, J. et al. Selective semihydrogenation of alkynes on shape-controlled palladium nanocrystals. Chem. Asian J. 8, 919–925 (2013).

    CAS  Article  Google Scholar 

  22. 22.

    Fu, Q. & Luo, Y. Catalytic activity of single transition-metal atom doped in Cu(111) surface for heterogeneous hydrogenation. J. Phys. Chem. C 117, 14618–14624 (2013).

    CAS  Article  Google Scholar 

  23. 23.

    Wang, C. et al. Product selectivity controlled by nanoporous environments in zeolite crystals enveloping rhodium nanoparticle catalysts for CO2 hydrogenation. J. Am. Chem. Soc. 141, 8482–8488 (2019).

    CAS  Article  Google Scholar 

  24. 24.

    Lee, Y.-A. et al. Highly sensitive gasochromic H2 sensing by nano-columnar WO3-Pd films with surface moisture. Sens. Actuators B 238, 111–119 (2017).

    CAS  Article  Google Scholar 

  25. 25.

    Papoian, G., Norskov, J. K. & Hoffmann, R. A comparative theoretical study of the hydrogen, methyl, and ethyl chemisorption on the Pt(111) surface. J. Am. Chem. Soc. 122, 4129–4144 (2000).

    CAS  Article  Google Scholar 

  26. 26.

    Albright, T. A., Burdett, J. K. & Whangbo, M. H. Orbital Interactions in Chemistry 2nd edn (John Wiley & Sons, 2013).

  27. 27.

    Feng, Q. C. et al. Isolated single-atom Pd sites in intermetallic nanostructures: high catalytic selectivity for semihydrogenation of alkynes. J. Am. Chem. Soc. 139, 7294–7301 (2017).

    CAS  Article  Google Scholar 

  28. 28.

    Studt, F. et al. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene. Science 320, 1320–1322 (2008).

    CAS  Article  Google Scholar 

  29. 29.

    Marcinkowski, M. D. et al. Controlling a spillover pathway with the molecular cork effect. Nat. Mater. 12, 523–528 (2013).

    CAS  Article  Google Scholar 

  30. 30.

    Wei, J. et al. In situ Raman monitoring and manipulating of interfacial hydrogen spillover by precise fabrication of Au/TiO2/Pt sandwich structures. Angew. Chem. Int. Ed. https://doi.org/10.1002/anie.202000426 (2020).

  31. 31.

    Zhao, G. et al. Metal/oxide interfacial effects on the selective oxidation of primary alcohols. Nat. Commun. 8, 14039 (2017).

    Article  Google Scholar 

  32. 32.

    Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    CAS  Article  Google Scholar 

  33. 33.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    CAS  Article  Google Scholar 

  34. 34.

    Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).

    CAS  Article  Google Scholar 

  35. 35.

    Kresse, G. & Hafner, J. Ab-initio molecular-dynamics for open-shell transition-metals. Phys. Rev. B 47, 558–561 (1993).

    CAS  Article  Google Scholar 

  36. 36.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    CAS  Article  Google Scholar 

  37. 37.

    Rosenbaum, E. J. Physical Chemistry (Appleton-Century-Crofts, 1970).

  38. 38.

    McQuarrie, D. A. Statistical Mechanics (Harper and Row, 1976).

  39. 39.

    Ter Haar, D. & Wergeland, H. Elements of Thermodynamics (Addison-Wesley, 1966).

  40. 40.

    Kittel, C. & Kroemer, H. Thermal Physics 2nd edn (W. H. Freeman & Company, 1980).

  41. 41.

    Gaussian 09 v. Revision D01 (Gaussian, 2009).

  42. 42.

    Liang, Y. et al. Mechanism, regioselectivity, and the kinetics of phosphine-catalyzed [3 + 2] cycloaddition reactions of allenoates and electron-deficient alkenes. Chem. Eur. J. 14, 4361–4373 (2008).

    CAS  Article  Google Scholar 

  43. 43.

    Hermans, J. & Wang, L. Inclusion of loss of translational and rotational freedom in theoretical estimates of free energies of binding application to a complex of benzene and mutant T4 lysozyme. J. Am. Chem. Soc. 119, 2707–2714 (1997).

    CAS  Article  Google Scholar 

  44. 44.

    Goldsmith, C. F. Estimating the thermochemistry of adsorbates based upon gas-phase properties. Top. Catal. 55, 366–375 (2012).

    CAS  Article  Google Scholar 

  45. 45.

    Gokhale, A. A. et al. Molecular-level descriptions of surface chemistry in kinetic models using density functional theory. Chem. Eng. Sci. 59, 4679–4691 (2004).

    CAS  Article  Google Scholar 

Download references


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.

Author information




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.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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

Download citation

Further reading


Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research