Oxygen tolerance of an in silico-designed bioinspired hydrogen-evolving catalyst in water

Certain bacterial enzymes, the diiron hydrogenases, have turnover numbers for hydrogen production fromwater as large as 10⁴/s. Their much smaller common active site, composed of earth-abundant materials, has a structure that is an attractive starting point for the design of a practical catalyst for electrocatalytic or solar photocatalytic hydrogen production fromwater. In earlierwork, our group has reported the computational design of [FeFe]_P/FeS₂, a hydrogenaseinspired catalyst/electrode complex, which is efficient and stable throughout the production cycle. However, the diiron hydrogenases are highly sensitive to ambient oxygen by a mechanism not yet understood in detail. An issue critical for practical use of [FeFe] _P/FeS₂ is whether this catalyst/electrode complex is tolerant to the ambient oxygen. We report demonstration by ab initio simulations that the complex is indeed tolerant to dissolved oxygen over timescales long enough for practical application, reducing it efficiently. This promising hydrogen-producing catalyst, composed of earth-abundant materials and with a diffusion-limited rate in acidified water, is efficient as well as oxygen tolerant.