Spin-Polarized Nonferromagnetic Surfaces for Electrocatalysis: Chemo-Spintronics.

Catalysts achieve changes in the rate through modification of the free energy of adsorbed intermediates and transition states (TrS). Binding energies of intermediates and TrS are strongly correlated, and modifications in catalyst composition are often ineffective in breaking these correlations, leading to minimal change in rate. Such scaling relationships are reported throughout catalysis. The surface spin state of a magnetic metal can change adsorption energies, offering a way to overcome scaling relationships. However, experimentally, this approach appears reliant on the use of ferromagnetic materials, limiting applicability. Here, we show that tunable changes in electrocatalytic activity for the hydrogen evolution reaction (HER) can be achieved at (originally) nonmagnetic metals (Au and Pt) through the use of a multilayer electrode structure that contains a ferromagnetic alloy (CoB) beneath a thin (5-20 nm) film of Pt or Au. Analysis of the dependence of the catalytic current on the thickness of the Au or Pt capping layer and on the direction of the stray magnetic field allows us to rule out the presence of magnetohydrodynamic effects. Instead, we conclude that transfer of ferromagnetism from the ferromagnet to the Au or Pt takes place through proximity-induced magnetism (PIM) via exchange interactions and/or a spin polarized current. Density Functional Theory simulations trace changes in the breaking of the scaling relationship for the Tafel HER mechanism. Overall, our experiments show that thin-film electrodes, based on routine structures from the spintronics community, are a potentially versatile platform for achieving spin-polarized catalysis at originally nonmagnetic metals.