Abstract
It is successfully shown that photocatalytic proton reduction to dihydrogen in the presence of a sacrificial electron donor, such as trimethylamine (TEA) and ascorbate, can be driven by compact sensitizer–catalyst dyads, that is, dithiolate-bridged [FeFe] hydrogenase models tethered to organic sensitizers, such as fluorenes and silafluorenes (1 a–4 a). The sensitizer–catalyst dyads 1 a–4 a show remarkable and promising catalytic activities as well as enhanced stabilities during photocatalysis performed under UV-light irradiation. The photocatalysis was carried out both in non-aqueous and aqueous media. The latter experiments were performed by solubilizing the photocatalysts within micelles formed by either sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB). In this study a turnover number of 539 (7 h) is achieved under optimized conditions, which corresponds to an exceptionally high turnover frequency of 77 h−1. Theoretical investigations as well as emission decay experiments were performed to understand the observed phenomena together with the mechanisms of photocatalytic H2 generation.
| Original language | English |
|---|---|
| Pages (from-to) | 334-345 |
| Number of pages | 12 |
| Journal | Chemistry - A European Journal |
| Volume | 23 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - Jan 5 2017 |
Fingerprint
All Science Journal Classification (ASJC) codes
- Catalysis
- Organic Chemistry
Cite this
Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers. / Goy, Roman; Bertini, Luca; Rudolph, Tobias; Lin, Shu; Schulz, Martin; Zampella, Giuseppe; Dietzek, Benjamin; Schacher, Felix H.; De Gioia, Luca; Sakai, Ken; Weigand, Wolfgang.
In: Chemistry - A European Journal, Vol. 23, No. 2, 05.01.2017, p. 334-345.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Photocatalytic Hydrogen Evolution Driven by [FeFe] Hydrogenase Models Tethered to Fluorene and Silafluorene Sensitizers
AU - Goy, Roman
AU - Bertini, Luca
AU - Rudolph, Tobias
AU - Lin, Shu
AU - Schulz, Martin
AU - Zampella, Giuseppe
AU - Dietzek, Benjamin
AU - Schacher, Felix H.
AU - De Gioia, Luca
AU - Sakai, Ken
AU - Weigand, Wolfgang
PY - 2017/1/5
Y1 - 2017/1/5
N2 - It is successfully shown that photocatalytic proton reduction to dihydrogen in the presence of a sacrificial electron donor, such as trimethylamine (TEA) and ascorbate, can be driven by compact sensitizer–catalyst dyads, that is, dithiolate-bridged [FeFe] hydrogenase models tethered to organic sensitizers, such as fluorenes and silafluorenes (1 a–4 a). The sensitizer–catalyst dyads 1 a–4 a show remarkable and promising catalytic activities as well as enhanced stabilities during photocatalysis performed under UV-light irradiation. The photocatalysis was carried out both in non-aqueous and aqueous media. The latter experiments were performed by solubilizing the photocatalysts within micelles formed by either sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB). In this study a turnover number of 539 (7 h) is achieved under optimized conditions, which corresponds to an exceptionally high turnover frequency of 77 h−1. Theoretical investigations as well as emission decay experiments were performed to understand the observed phenomena together with the mechanisms of photocatalytic H2 generation.
AB - It is successfully shown that photocatalytic proton reduction to dihydrogen in the presence of a sacrificial electron donor, such as trimethylamine (TEA) and ascorbate, can be driven by compact sensitizer–catalyst dyads, that is, dithiolate-bridged [FeFe] hydrogenase models tethered to organic sensitizers, such as fluorenes and silafluorenes (1 a–4 a). The sensitizer–catalyst dyads 1 a–4 a show remarkable and promising catalytic activities as well as enhanced stabilities during photocatalysis performed under UV-light irradiation. The photocatalysis was carried out both in non-aqueous and aqueous media. The latter experiments were performed by solubilizing the photocatalysts within micelles formed by either sodium dodecyl sulfate (SDS) or cetyltrimethylammonium bromide (CTAB). In this study a turnover number of 539 (7 h) is achieved under optimized conditions, which corresponds to an exceptionally high turnover frequency of 77 h−1. Theoretical investigations as well as emission decay experiments were performed to understand the observed phenomena together with the mechanisms of photocatalytic H2 generation.
UR - http://www.scopus.com/inward/record.url?scp=85006284707&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85006284707&partnerID=8YFLogxK
U2 - 10.1002/chem.201603140
DO - 10.1002/chem.201603140
M3 - Article
C2 - 27910141
AN - SCOPUS:85006284707
VL - 23
SP - 334
EP - 345
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 2
ER -