Probst, B; Rodenberg, A; Guttentag, M; Hamm, P; Alberto, R (2010). A highly stable rhenium-cobalt system for photocatalytic H(2) production: unraveling the performance-limiting steps. Inorganic Chemistry, 49(14):6453-6460.
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Increased long-term performance was found for photocatalytic H(2) production in a homogeneous combination of [Re(NCS)(CO)(3)bipy] (1; bipy = 2,2'-bipyridine), [Co(dmgH)(2)] (dmgH(2) = dimethylglyoxime), triethanolamine (TEOA), and [HTEOA][BF(4)] in N,N-dimethylformamide, achieving TON(Re) up to 6000 (H/Re). The system proceeded by reductive quenching of *1 by TEOA, followed by fast (k(1) = 1.3 x 10(8) M(-1) s(-1)) electron transfer to [Co(II)(dmgH)(2)] and subsequent protonation (K(2)) and elimination (k(3), second-order process in cobalt) of H(2). Observed quantum yields were up to approximately 90% (H produced per absorbed photon). The type of acid had a substantial effect on the long-term stability. A decomposition pathway involving cobalt is limiting the long-term performance. Time-resolved infrared (IR) spectroscopy confirmed that photooxidized TEOA generates a second reducing equivalent, which can be transferred to 1 (70%, k(2e)(-) = 3.3 x 10(8) M(-1) s(-1)) if no [Co(II)(dmgH)(2)] is present.
|Item Type:||Journal Article, refereed, original work|
|Communities & Collections:||07 Faculty of Science > Institute of Inorganic Chemistry|
07 Faculty of Science > Institute of Physical Chemistry
|Deposited On:||23 Feb 2011 18:05|
|Last Modified:||27 Nov 2013 21:37|
|Publisher:||American Chemical Society|
|Funders:||Swiss National Science Foundation|
|Other Identification Number:||ISI:000279621200030|
|Citations:||Web of Science®. Times Cited: 57|
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