1. Department of Biological Chemistry,
2. Department of Molecular Microbiology, John Innes Centre, Norwich NR4 7UH, UK
3. Department of Biotechnology and Biosciences, University of Milano-Bicocca, Piazza della Scienza 2, 20126-Milan, Italy
4. Department of Physics, Washington State University, 2710 University Drive, Richland, and WR Wiley Environmental Science Laboratory and Chemical Sciences Division, Pacific Northwest National Laboratory, PO Box 999, MS K8-88, Richland, Washington 99352, USA

Correspondence to: Christopher J. Pickett¹ Correspondence and requests for materials should be addressed to C.J.P. (Email: chris.pickett@bbsrc.ac.uk).
Crystal structure data for B have been deposited at the Cambridge Crystallographic Data Centre, and allocated the deposition number CCDC 256735.

Abstract

The metal-sulphur active sites of hydrogenases catalyse hydrogen evolution or uptake at rapid rates. Understanding the structure and function of these active sites—through mechanistic studies of hydrogenases^{1, 2, 3, 4}, synthetic assemblies^{5, 6, 7, 8, 9, 10, 11, 12} and in silico models^{13, 14, 15}—will help guide the design of new materials for hydrogen production or uptake¹⁶. Here we report the assembly of the iron-sulphur framework of the active site of iron-only hydrogenase (the H-cluster), and show that it functions as an electrocatalyst for proton reduction. Through linking of a di-iron subsite to a {4Fe4S} cluster, we achieve the first synthesis of a metallosulphur cluster core involved in small-molecule catalysis. In addition to advancing our understanding of the natural biological system, the availability of an active, free-standing analogue of the H-cluster may enable us to develop useful electrocatalytic materials for application in, for example, reversible hydrogen fuel cells. (Platinum is currently the preferred electrocatalyst for such applications, but is expensive, limited in availability and, in the long term, unsustainable¹⁷.)

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