Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) Centers

Yurina Shim, Ryan M. Young, Alexios P. Douvalis, Scott M. Dyar, Benjamin D. Yuhas, Thomas Bakas, Michael R. Wasielewski, Mercouri G. Kanatzidis*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

45 Scopus citations


Naturally abundant enzymes often feature active sites comprising transition metal cluster units that catalyze chemical processes and reduce small molecules as well as protons. We introduce a family of new chalcogenide aerogels (chalcogels), aiming to model the function of active sites and the structural features of a larger protective framework. New metal incorporated iron sulfur tin sulfide chalcogels referred to as ternary chalcogels and specifically the chalcogels M-ITS-cg3, fully integrate biological redox-active Fe4S4 clusters into a semiconducting porous framework by bridging them with Sn4S10 linking units. In the M-ITS-cg3 system we can tailor the electro- and photocatalytic properties of chalcogels through the control of spatial distance of redox-active Fe4S4 centers using additional linking metal ions, M2+ (Pt, Zn, Co, Ni, Sn). The presence of a third metal does not change the structural properties of the biomimetic chalcogels but modifies and even enhances their functional performance. M-ITS-cg3s exhibit electrocatalytic activity in proton reduction that arises from the Fe4S4 clusters but is tuned inductively by M2+. The metal ions alter the reduction potential of Fe4 S4 in a favorable manner for photochemical hydrogen production. The Pt incorporated ITS-cg3 shows the greatest improvement in the overall hydrogen yield compared to the binary ITS-cg3. The ability to manipulate the properties of biomimetic chalcogels through synthetic control of the composition, while retaining both structural and functional properties, illustrates the chalcogels' flexibility and potential in carrying out useful electrochemical and photochemical reactions.

Original languageEnglish (US)
Pages (from-to)13371-13380
Number of pages10
JournalJournal of the American Chemical Society
Issue number38
StatePublished - Sep 24 2014

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry


Dive into the research topics of 'Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) Centers'. Together they form a unique fingerprint.

Cite this