An Ambiphilic-Site Descriptor for Selecting Single-Atom Catalysts for the Electrochemical Regeneration of Sodium Borohydride

Abstract

The electrochemical regeneration of sodium borohydride (NaBH4) from spent metaborate is a central bottleneck for circular hydrogen storage. (1) Background: The eight-electron reduction of the aqueous borate species B(OH)4− to BH4− is thermodynamically out-competed by the hydrogen-evolution reaction (HER) by about 0.41 V at every pH, so selectivity can only be won kinetically. (2) Methods: We advance an ambiphilic-site hypothesis, screen 30 candidate metal centres using entirely experimental, tabulated descriptors (bulk HER exchange current density; gas-phase M-O bond energy) with no new electronic-structure computation, and then audit the transferability of both descriptor axes against published, corrected DFT datasets for nitrogen-coordinated single-atom sites. (3) Results: At the parent-metal level, the two axes are orthogonal (Spearman ρ = 0.02) and the score passes a family-level experimental validation over seven bulk-electrode metals (ρ = 0.69; exact permutation p = 0.050), separating the HER-dominated noble-metal family from the single-atom Mn benchmark. The site-level audit shows that the oxophilicity axis transfers to M-N4 sites almost quantitatively (ρ = −0.84 pyridine-4N, −0.95 pyrrole-4N, n = 23) while the bulk HER axis does not, and that site-level scaling between oxygen and hydrogen binding narrows the productive window to oxophilic centres that over-bind hydrogen. (4) Conclusions: The site-anchored screen redirects the search from the parent-metal leaders (La, Ce, Y, Ti, Sc) to refractory single-atom centres, with W, Nb and Mo as priority synthesis targets (Re excluded on scarcity; Zr, Hf, Ta as data-supported extensions; Ti as the sustainability-anchored borderline case) and the lanthanides retained only as explicitly extrapolative candidates. All data and analysis code are openly deposited.