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

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

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
Pages (from-to)13371-13380
Number of pages10
JournalJournal of the American Chemical Society
Volume136
Issue number38
DOIs
Publication statusPublished - Sep 24 2014

Fingerprint

Biomimetics
Aerogels
Hydrogen
Metals
Oxidation-Reduction
Protons
Catalytic Domain
Chemical Phenomena
Ions
Metal ions
Sulfur
Iron
Photochemical reactions
Hydrogen production
Tin
Transition metals
Structural properties
Enzymes
Molecules
Chemical analysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry
  • Medicine(all)

Cite this

Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) Centers. / Shim, Yurina; Young, Ryan M.; Douvalis, Alexios P.; Dyar, Scott M.; Yuhas, Benjamin D.; Bakas, Thomas; Wasielewski, Michael R; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 136, No. 38, 24.09.2014, p. 13371-13380.

Research output: Contribution to journalArticle

Shim, Yurina ; Young, Ryan M. ; Douvalis, Alexios P. ; Dyar, Scott M. ; Yuhas, Benjamin D. ; Bakas, Thomas ; Wasielewski, Michael R ; Kanatzidis, Mercouri G. / Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) Centers. In: Journal of the American Chemical Society. 2014 ; Vol. 136, No. 38. pp. 13371-13380.
@article{156d9ff0a54b4c798b0aeb6a448dc87b,
title = "Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) Centers",
abstract = "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.",
author = "Yurina Shim and Young, {Ryan M.} and Douvalis, {Alexios P.} and Dyar, {Scott M.} and Yuhas, {Benjamin D.} and Thomas Bakas and Wasielewski, {Michael R} and Kanatzidis, {Mercouri G}",
year = "2014",
month = "9",
day = "24",
doi = "10.1021/ja507297p",
language = "English",
volume = "136",
pages = "13371--13380",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "38",

}

TY - JOUR

T1 - Enhanced photochemical hydrogen evolution from Fe4S4-based biomimetic chalcogels containing M2+ (M = Pt, Zn, Co, Ni, Sn) Centers

AU - Shim, Yurina

AU - Young, Ryan M.

AU - Douvalis, Alexios P.

AU - Dyar, Scott M.

AU - Yuhas, Benjamin D.

AU - Bakas, Thomas

AU - Wasielewski, Michael R

AU - Kanatzidis, Mercouri G

PY - 2014/9/24

Y1 - 2014/9/24

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84923576236&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84923576236&partnerID=8YFLogxK

U2 - 10.1021/ja507297p

DO - 10.1021/ja507297p

M3 - Article

VL - 136

SP - 13371

EP - 13380

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 38

ER -