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Copyright © 2020 Jun Liu et al.Designing highly active and robust platinum-free electrocatalysts for hydrogen evolution reaction is vital for large-scale and efficient production of hydrogen through electrochemical water splitting. Here, we report nonprecious intermetallic Cu5Zr clusters that are in situ anchored on hierarchical nanoporous copper (NP Cu/Cu5Zr) for efficient hydrogen evolution in alkaline medium. By virtue of hydroxygenated zirconium atoms activating their nearby Cu-Cu bridge sites with appropriate hydrogen-binding ene