High-Throughput Screening of Earth-Abundant Water Reduction Catalysts toward Photocatalytic Hydrogen Evolution

Noble-metal photosensitizers and water reduction co-catalysts (WRCs) still present the highest activity in homogeneous photocatalytic hydrogen production. The search for earth-abundant alternatives is usually limited by the time required to screen new catalyst combinations; however, here, we utilize newly designed and developed high-throughput photoreactors for the parallel synthesis of novel WRCs and colorimetric screening of hydrogen evolution. This unique approach allowed rapid optimization of photocatalytic water reduction using the organic photosensitizer Eosin Y and the archetypal cobaloxime WRC [Co­(GL1)2pyCl], where GL1 is dimethylglyoxime and py is pyridine. Subsequent combinatorial synthesis generated 646 unique cobalt complexes of the type [Co­(LL)2pyCl], where LL is a bidentate ligand, that identified promising new WRC candidates for hydrogen production. Density functional theory (DFT) calculations performed on such cobaloxime derivative complexes demonstrated that reactivity depends on hydride affinity. Alkyl-substituted glyoximes were necessary for hydrogen production and showed increased activity when paired with ligands containing strong hydrogen-bond donors.