Photochemical hydrogen production from water using the new photocatalyst [{(bpy)2Ru(dpp)}2RhBr2](PF6)5

Arachchige, Shamindri M.; Brown, Jared R.; Brewer, Karen J.

doi:10.1016/j.jphotochem.2007.11.026

Cited by 72 publications

(81 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The first PEC, [{(bpy) 2 Ru-(dpb)} 2 IrCl 2 ](PF 6 ) 5 (dpb = 2,3-bis(2-pyridyl)benzoquinoxaline), [40] and later [(phen) 2 Ru(BL)Ru(phen) 2 ](PF 6 ) 4 (BL = 9,11,20,22-tetraazatetrapyrido[3,2-a:2'3'-c:3'',2''-1:2''',3'''-n]pentacene (tatpp) or 9,11,20,22-tetraazatetrapyrido[3,2-a:2'3'-c:3'',2''-1:2''',3'''-n]pentacene-10,21-quinone (tatpq)), [41] collect multiple reducing equivalents on the bridging ligand (p*) orbitals, but are not shown to deliver these electrons to substrates. [(bpy) 2 5+ showing enhanced photocatalytic activity with 38 TONs in 4 h. [31,32,34] To date only preliminary studies with 4 h experiments have appeared, with 0.27 mL of H 2 produced. Photoinitiated electron collection affords a Rh I species that provides reducing equivalents to H 2 O to make H 2 fuel (Figure 1).…”

Section: +mentioning

confidence: 99%

High Turnover in a Photocatalytic System for Water Reduction to Produce Hydrogen Using a Ru, Rh, Ru Photoinitiated Electron Collector

et al. 2011

Self Cite

View full text Add to dashboard Cite

Covalent coupling of Ru(II) light absorbers to a Rh(III) electron collecting site through polyazine bridging ligands affords photocatalytic production of H(2) in the presence of visible light and a sacrificial electron donor. A robust photocatalytic system displaying a high turnover of the photocatalyst has been developed using the photoinitiated electron collector [{(bpy)(2)Ru(dpp)}(2)RhBr(2)](5+) (bpy=2,2'-bipyridine; dpp=2,3-bis(2-pyridyl)pyrazine) and N,N-dimethylaniline in DMF/H(2)O. Studies have shown that increased [DMA], the headspace volume, and the use of DMF solvent improves the systems performance and stability providing mechanistic insight into the deactivation routes of the photocatalytic system. Photolysis of the system at 460 nm generates 20 mL of H(2) in 19.5 h with a maximum Φ=0.023 based on H(2) produced and an overall Φ=0.014 and 280 turnovers of the photocatalyst. The photocatalytic system also displays long-term photostability with 30 mL of H(2) generated and 420 turnovers in 50 h under the same conditions. Prolonged photolysis provides 820 mol H(2) per mole of catalyst.

show abstract

Section: +mentioning

confidence: 99%

High Turnover in a Photocatalytic System for Water Reduction to Produce Hydrogen Using a Ru, Rh, Ru Photoinitiated Electron Collector

et al. 2011

Self Cite

View full text Add to dashboard Cite

show abstract

“…Analogous trimetallic complexes with chloro-ligands at the Rh center were also explored. [16] In the course of two-electron reduction, the Rh center is thought to release its two halide ligands to produce a four-coordinate Rh(i) intermediate which reduces aqueous protons to H 2 under suitable conditions. Specifically, when using CH 3 CN with 1.5 M N,N-dimethylaniline and water acidified with triflic acid to pH 2 and irradiating at 470 nm with an LED, 38 catalytic turnovers were observed in 4 h for the system shown in Fig.…”

Section: A Few Specific Case Studies Of Photoinduced Charge Accumulationmentioning

confidence: 99%

Photoinduced Charge Accumulation in Molecular Systems

Bonn

Wenger²

2015

Chimia

View full text Add to dashboard Cite

Fuel-forming reactions such as CO 2 reduction or water splitting require multiple redox equivalents. When aiming at light-driven production of energy-rich chemicals, nowadays often referred to as solar fuels, it therefore becomes important to master the photoinduced accumulation of electrons or holes on individual molecular components. Featured in this short review are some of the key molecular systems explored in this emerging field of research. This includes for example a trinuclear Ru(ii)-Rh(iii)-Ru(iii) complex or an Ir(iii)-sensitized polyoxotungstate hybrid, but also several systems in which electron or hole collection occurs at organic moieties such as perylenebis(dicarboximide), quinone-containing or oligotriarylamine-based units. In many cases the photodriven accumulation of charge requires the use of sacrificial electron donors, but there exist also a handful of studies in which redox equivalents can be accumulated without the use of such additives.

show abstract

“…These states are known to undergo excitedstate electron transfer reactions in an inter-and intramolecular fashion. [21,54,55] The complexes [{(phen) 2 Ru(dpp)} 2 Ru(dpq)](PF 6 ) 6 and [{(phen) 2 Ru(dpp)} 2 Ru(dpq)PtCl 2 ](PF 6 ) 6 both display visible light emissions centered at 752 nm from their lowest lying Ru(dp)!dpp(p*) 3 MLCT excited state. The photophysical data at room temperature and 77 K for these complexes is shown in Table 3.…”

Section: Emission Spectroscopy and Photophysicsmentioning

confidence: 99%

“…The early PECs, [{(bpy) 2 Ru(dpb)} 2 IrCl 2 ](PF 6 ) 5 (dpb = 2,3-bis(2-pyridyl)benzoquinoxaline), [32,33] and [(phen) 2 Ru(BL)Ru(phen) 2 ](PF 6 ) 4 (BL = 9,11,20,22-tetraazatetrapyrido[3,2-a:2'3'-c:3'',2''-1:2''',3'''-n]pentacene (tatpp) or 9,11,20,22-tetraazatetrapyrido[3,2-a:2'3'-c:3'',2''-1:2''',3'''-n]pentacene-10,21-quinone (tatpq)), [34,35] 3 + collect multiple reducing equivalents on Rh and photocatalyze hydrogen production from water in the presence of N,N-dimethylaniline (DMA), F = 0.01. [20][21][22][23][24]38] The [{(bpy) 2 Ru-(dpp)} 2 RhBr 2 ]…”

Section: Introductionmentioning

confidence: 99%

A Structurally Diverse Ru^II,Pt^II Tetrametallic Motif for Photoinitiated Electron Collection and Photocatalytic Hydrogen Production

Knoll¹,

Arachchige²,

Brewer³

2010

ChemSusChem

Self Cite

View full text Add to dashboard Cite

Coupling a reactive metal to light absorbers affords molecular devices for photoinitiated electron collection and photocatalytic conversion of substrates to fuels. A new Ru(II),Pt(II) tetrametallic supramolecule, [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](PF(6))(6), and the trimetallic precursors, [{(phen)(2)Ru(dpp)}(2)RuCl(2)](PF(6))(4) and [{(phen)(2)Ru(dpp)}(2)Ru(dpq)](PF(6))(6), have been synthesized, and their redox, spectroscopic, spectroelectrochemical, photophysical and photocatalytic properties studied. They efficiently absorb UV and visible light. The electrochemistry of [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](PF(6))(6) suggests a lowest-lying terminal Ru→dpq charge-separated state that quenches the emission of the parent complex with non-unity population of the emissive (3)MLCT excited state. Photolysis of [{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)](6+) at 470 nm with DMA gives multielectron reduction, storing electrons in a new manner on the central (dpp)(2)Ru(II)(dpq) moiety. Addition of H(2)O to the photolysis system produces 21 μmol of H(2) in 5 h, with 115 turnovers of the tetrametallic photocatalyst.

show abstract

Photochemical hydrogen production from water using the new photocatalyst [{(bpy)2Ru(dpp)}2RhBr2](PF6)5

Cited by 72 publications

References 27 publications

High Turnover in a Photocatalytic System for Water Reduction to Produce Hydrogen Using a Ru, Rh, Ru Photoinitiated Electron Collector

High Turnover in a Photocatalytic System for Water Reduction to Produce Hydrogen Using a Ru, Rh, Ru Photoinitiated Electron Collector

Photoinduced Charge Accumulation in Molecular Systems

A Structurally Diverse Ru^II,Pt^II Tetrametallic Motif for Photoinitiated Electron Collection and Photocatalytic Hydrogen Production

Contact Info

Product

Resources

About

Photochemical hydrogen production from water using the new photocatalyst [{(bpy)2Ru(dpp)}2RhBr2](PF6)5

Cited by 72 publications

References 27 publications

High Turnover in a Photocatalytic System for Water Reduction to Produce Hydrogen Using a Ru, Rh, Ru Photoinitiated Electron Collector

High Turnover in a Photocatalytic System for Water Reduction to Produce Hydrogen Using a Ru, Rh, Ru Photoinitiated Electron Collector

Photoinduced Charge Accumulation in Molecular Systems

A Structurally Diverse RuII,PtII Tetrametallic Motif for Photoinitiated Electron Collection and Photocatalytic Hydrogen Production

Contact Info

Product

Resources

About

A Structurally Diverse Ru^II,Pt^II Tetrametallic Motif for Photoinitiated Electron Collection and Photocatalytic Hydrogen Production