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A silver catalyst activated by stacking faults for the hydrogen evolution reaction


Finding highly active and low-cost catalysts is a crucial endeavour to harvest clean hydrogen via electrochemical water splitting. Currently, the best catalyst for the hydrogen evolution reaction is based on metallic platinum whose high price severely restricts large-scale application. Here we report a silver catalyst with superior activity and durability in an acid medium that outperforms commercial platinum on carbon, especially under high applied voltages. We adopt a physical technique—laser ablation in liquid—to generate a high density of stacking faults in silver nanoparticles. We find that the stacking faults can cause a low coordination number and high tensile strain, which jointly improve the adsorption energy and transform the non-active silver into a highly active catalyst. In light of the high activity, conductivity, durability and low price, the silver catalyst can serve as a promising alternative to commercial platinum on carbon for industrial application.

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Fig. 1: Preparation and characterization of L-Ag NPs.
Fig. 2: HER activity and durability in Ar-saturated 0.5 M H2SO4 aqueous electrolyte.
Fig. 3: Calculations on the CNs of L-Ag, S-Ag and T-Ag catalysts.
Fig. 4: Analysis of the tensile strain in L-Ag.
Fig. 5: Theoretical calculations for the effect of CN and tensile strain on the hydrogen adsorption Gibbs free energy.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.


  1. Su, J. W. et al. Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media. Nat. Commun. 8, 14969 (2017).

    Article  Google Scholar 

  2. Lu, X. F., Yu, L. & Lou, X. W. Highly crystalline Ni-doped FeP/carbon hollow nanorods as all-pH efficient and durable hydrogen evolving electrocatalysts. Sci. Adv. 5, 6009 (2019).

    Article  Google Scholar 

  3. Zheng, Y., Jiao, Y., Jaroniec, M. & Qiao, S. Z. Advancing the electrochemistry of the hydrogen evolution reaction through combining experiment and theory. Angew. Chem. Int. Ed. 54, 52–65 (2015).

    Article  CAS  Google Scholar 

  4. Jiao, Y., Zheng, Y., Jaroniec, M. & Qiao, S. Z. Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. Chem. Soc. Rev. 44, 2060–2086 (2015).

    Article  CAS  Google Scholar 

  5. Fan, X. B. et al. Controlled exfoliation of MoS2 crystals into trilayer nanosheets. J. Am. Chem. Soc. 138, 5143–5149 (2016).

    Article  CAS  Google Scholar 

  6. Xia, Y. N. In my element: silver. Chem. Eur. J. 24, 1–2 (2018).

    Article  Google Scholar 

  7. Zhou, Y. et al. Oxygen reduction at very low overpotential on nanoporous Ag catalysts. Adv. Energy Mater. 5, 1500149 (2015).

    Article  Google Scholar 

  8. Uchida, T., Mogami, H., Yamakata, A., Sasaki, Y. & Osawa, M. Hydrogen evolution reaction catalyzed by proton-coupled redox cycle of 4,4’-bipyridine monolayer adsorbed on silver electrodes. J. Am. Chem. Soc. 130, 10862–10863 (2008).

    Article  CAS  Google Scholar 

  9. Campbell, F. W., Belding, S. R., Baron, R., Xiao, L. & Compton, R. G. The hydrogen evolution reaction at silver nanoparticle array and a silver macroelectrode compared: changed electrode kinetics between the macro- and nanoscales. J. Phys. Chem. C. 113, 14852–14857 (2009).

    Article  CAS  Google Scholar 

  10. Safavi, A., kazemi, S. H. & Kazemi, H. Electrocatalytic behaviors of silver-palladium nanoalloys modified carbon ionic liquid electrode towards hydrogen evolution reaction. Fuel 118, 156–162 (2014).

    Article  CAS  Google Scholar 

  11. Khorshidi, A., Violet, J., Hashemi, J. & Peterson, A. A. How strain can break the scaling relations of catalysis. Nat. Catal. 1, 263–268 (2018).

    Article  Google Scholar 

  12. Calle-Vallejo, F. et al. Finding optimal surface sites on heterogeneous catalysts by counting nearest neighbors. Science 350, 185–189 (2015).

    Article  CAS  Google Scholar 

  13. Zambelli, T., Wintterlin, J., Trost, J. & Ertl, G. Identification of the “active sites” of a surface-catalyzed reaction. Science 273, 1688–1699 (1996).

    Article  CAS  Google Scholar 

  14. Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).

    Article  Google Scholar 

  15. Tedsree, K. et al. Hydrogen production from formic acid decomposition at room temperature using a Ag–Pd core–shell nanocatalyst. Nat. Nanotechnol. 6, 302–307 (2011).

    Article  CAS  Google Scholar 

  16. Escudero-Escribano, M. et al. Pt5Gd as a highly active and stable catalyst for oxygen electroreduction. J. Am. Chem. Soc. 134, 16476–16479 (2012).

    Article  CAS  Google Scholar 

  17. Wang, H. T. et al. Direct and continuous strain control of catalysts with tunable battery electrode materials. Science 354, 1031–1036 (2016).

    Article  CAS  Google Scholar 

  18. Wang, L. et al. Tunable intrinsic strain in two-dimensional transition metal electrocatalysts. Science 363, 870–874 (2019).

    Article  CAS  Google Scholar 

  19. Strasser, P. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2, 454–460 (2010).

    Article  CAS  Google Scholar 

  20. Escudero-Escribano, M. et al. Tuning the activity of Pt alloy electrocatalysts by means of the lanthanide contraction. Science 352, 73–76 (2016).

    Article  CAS  Google Scholar 

  21. Edalati, K. & Horita, Z. J. High-pressure torsion of pure metals: Influence of atomic bond parameters and stacking fault energy on grain size and correlation with hardness. Acta Mater. 59, 6831–6836 (2011).

    Article  CAS  Google Scholar 

  22. Qin, Y. C. et al. Microwave-assisted synthesis of multiply-twinned Au–Ag nanocrystals on reduced graphene oxide for high catalytic performance towards hydrogen evolution reaction. J. Mater. Chem. A 4, 3865 (2016).

    Article  CAS  Google Scholar 

  23. Xia, X. H., Shen, X., Zhao, X. J., Ye, W. C. & Wang, C. M. Operando synthesis of a dendritic and well-crystallized molybdenum oxide/silver catalyst for enhanced activity in the hydrogen evolution reaction. ChemCatChem 7, 2517–2525 (2015).

    Article  CAS  Google Scholar 

  24. Yin, J. et al. Ni–C–N nanosheets as catalyst for hydrogen evolution reaction. J. Am. Chem. Soc. 138, 14546–14549 (2016).

    Article  CAS  Google Scholar 

  25. Deng, J. et al. Multiscale structural and electronic control of molybdenum disulfide foam for highly efficient hydrogen production. Nat. Commun. 8, 14430 (2017).

    Article  CAS  Google Scholar 

  26. Kiritani, M. Story of stacking fault tetrahedra. Mater. Chem. Phys. 50, 133–138 (1997).

    Article  CAS  Google Scholar 

  27. Cao, L. L. et al. Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution. Nat. Catal. 2, 134–141 (2019).

    Article  CAS  Google Scholar 

  28. Jiao, J. Q. et al. Copper atom-pair catalyst anchored on alloy nanowires for selective and efficient electrochemical reduction of CO2. Nat. Chem. 11, 222–228 (2019).

    Article  CAS  Google Scholar 

  29. Sun, Y. F. et al. Pits confined in ultrathin cerium (iv) oxide for studying catalytic centers in carbon monoxide oxidation. Nat. Commun. 4, 2899 (2013).

    Article  Google Scholar 

  30. Behafarid, F. et al. Structural and electronic properties of micellar Au nanoparticles: size and ligand effects. ACS Nano 8, 6671–6681 (2014).

    Article  CAS  Google Scholar 

  31. Ling, T. et al. Activating cobalt (ii) oxide nanorods for efficient electrocatalysis by strain engineering. Nat. Commun. 8, 1509 (2017).

    Article  Google Scholar 

  32. Gan, L., Yu, R., Luo, J., Cheng, Z. Y. & Zhu, J. Lattice strain distributions in individual dealloyed Pt–Fe catalyst nanoparticles. J. Phys. Chem. Lett. 3, 934–938 (2012).

    Article  CAS  Google Scholar 

  33. Jiao, Y., Zheng, Y., Davey, K. & Qiao, S. Z. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nat. Energy 1, 16130 (2016).

    Article  CAS  Google Scholar 

  34. Wang, C. Q. et al. Creation of controllable high-density defects in silver nanowires for enhanced catalytic property. Nano Lett. 16, 5669–5674 (2016).

    Article  CAS  Google Scholar 

  35. Zheng, Y. et al. High electrocatalytic hydrogen evolution activity of an anomalous ruthenium catalyst. J. Am. Chem. Soc. 138, 16174–16181 (2016).

    Article  CAS  Google Scholar 

  36. Mahmood, J. et al. An efficient and pH-universal ruthenium-based catalyst for the hydrogen evolution reaction. Nat. Nanotechnol. 12, 441–446 (2017).

    Article  CAS  Google Scholar 

  37. Banerjee, A., Dick, G. R., Yoshino, T. & Kanan, M. W. Carbon dioxide utilization via carbonate-promoted C–H carboxylation. Nature 531, 215–219 (2014).

    Article  Google Scholar 

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This work was supported in part by the Natural Science Foundation of China (grant nos. 51871160, 51671141, 51471115). The authors thank the BL14W1 beam line of the Shanghai Synchrotron Radiation Facility for synchrotron beam time and Y. L. Liang from Shanghai Institute of Applied Physics (Chinese Academy of Sciences) for XAS measurements. The authors thank R. C. Luo from the State Key Laboratory of Metal Matrix Composites (Shanghai Jiao Tong University) for TEM measurements.

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Authors and Affiliations



X.-W.D. designed the project. Z.L. and Y.F. performed the experiment under the direction of X.-W.D. Z.L. and X.-WD. performed the experimental data analysis. J.-Y.F. and C.-K.D. performed the theoretical calculation. Z.L. and H.L. conducted the XAS test and analysed the data. Z.L. and X.-W.D. wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Hui Liu or Xi-Wen Du.

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Supplementary Information

Supplementary Figs. 1–54, Tables 1–3 and references.

Supplementary Dataset 1

Atomic coordinates of the optimized computational models.

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Li, Z., Fu, JY., Feng, Y. et al. A silver catalyst activated by stacking faults for the hydrogen evolution reaction. Nat Catal 2, 1107–1114 (2019).

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