In the present work we report an inexpensive and robust photoelectrochemical reduction system for the homogenous catalytic reduction of protons to hydrogen which consists of an illuminated and biased p-type Silicon (Si) photocathode, an [FeFe] electrocatalyst, and a proton source (HClO4). [Fe2(�-bdt)(CO)6] (bdt = benzene-1,2-dithiolate) ([FeFe] complex) has reversible reductive electrochemistry and maintains its structural integrity to a large extent even in reduced and protonated state. Dithiolate bridged [FeFe] complexes (molecular catalyst for proton reduction) has been photoelectrochemically reduced by p-type Si photocathode at potential around 500 mV less negative potential compared to glassy carbon electrode. In presence of HClO4, hydrogen generation has been achieved at a photovoltage of 600 mV with a 105 � 5 % faradaic efficiency. Importance of catalytic current density for homogeneous catalysis matching with photocurrent density for semiconductor/liquid junction has been elucidated.

Photoelectrochemical hydrogen generation by an [FeFe] hydrogenase active site mimic at a p-type silicon/molecular electrocatalyst junction

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.