Aqueous Photocurrent Measurements Correlated to Ultrafast Electron Transfer Dynamics at Ruthenium Tris Diimine Sensitized NiO Photocathodes

Queyriaux, Nicolas; Wahyuono, Ruri Agung; Fize, Jennifer; Gablin, Corinne; Wächtler, Maria; Martínez, E.; Léonard, Didier; Dietzek, Benjamin; Artero, Vincent; Chavarot‐Kerlidou, Murielle

doi:10.1021/acs.jpcc.6b12536

Cited by 37 publications

(59 citation statements)

References 102 publications

(244 reference statements)

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“…Overall, the introduction of four methylphosphonate anchoring groups in the coordination sphere of [Ru(bpy) 2 (N ^ N)](PF 6 ) 2 photosensitizers does not significantly modify their properties, consistent with the electronic decoupling provided by the methylene spacer , …”

Section: Resultsmentioning

confidence: 61%

“…The reaction in refluxing ethanol between two equivalents of 4,4′‐(CH 2 PO 3 Et 2 ) 2 ‐bpy and four different organometallic precursors varying by the nature of either the arene (benzene or p ‐cymene) or the anionic ligand (OTf or Cl) was monitored by UV/Vis absorption spectroscopy (Figure ). The wavelength of 459 nm was selected to detect the formation of RuP 4 OEt ‐bpy (MLCT transition) and to determine its conversion yield. As expected, the triflate [(η 6 ‐arene)Ru(bpy)(OTf)](OTf) complexes are more reactive than their chloride counterparts with 30–35 % conversion for the former vs. < 10 % for the latter.…”

Section: Resultsmentioning

confidence: 99%

“…[Ru(4,4′‐(CH 2 PO 3 Et 2 ) 2 ‐bpy) 2 (bpy)](PF 6 ) 2 (RuP 4 OEt ‐bpy): Yield: 58 % (method A: benzene); 58 % (method B: benzene); 60 % (method B: p ‐cymene).…”

Section: Methodsmentioning

confidence: 99%

“…An improved stability of the grafting was observed for phosphonic acids covalently anchored onto oxide films compared to carboxylic acids, especially at low pH (≤ 5), making them anchoring groups of choice for DS‐PEC applications , . In a previous study, we established that the number of phosphonate anchoring groups present on the Ru photosensitizer significantly improves the grafting efficiency on nickel oxide films, the surface concentration with four phosphonate anchoring groups being roughly twice higher than the one determined with only two anchoring groups. In addition, insertion of a methylene spacer between the bipyridine (bpy) ligand and the phosphonate group electronically insulates the anchors from the complex, which could help stabilizing the excess electron density on the third diimine ligand present in the Ru coordination sphere, thus away from the surface , .…”

Section: Introductionmentioning

confidence: 91%

“…In a previous study, we established that the number of phosphonate anchoring groups present on the Ru photosensitizer significantly improves the grafting efficiency on nickel oxide films, the surface concentration with four phosphonate anchoring groups being roughly twice higher than the one determined with only two anchoring groups. In addition, insertion of a methylene spacer between the bipyridine (bpy) ligand and the phosphonate group electronically insulates the anchors from the complex, which could help stabilizing the excess electron density on the third diimine ligand present in the Ru coordination sphere, thus away from the surface , . This warrants a better hole injection efficiency in the context of photocathode applications.…”

Section: Introductionmentioning

confidence: 92%

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Synthesis of Ruthenium Tris‐Diimine Photosensitizers Substituted by Four Methylphosphonate Anchoring Groups for Dye‐Sensitized Photoelectrochemical Cell Applications

et al. 2019

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The design and synthesis of ruthenium tris‐diimine photosensitizers appropriately functionalized to be (i) anchored onto transparent conductive oxides (TCO) and (ii) covalently coupled with a water‐splitting catalyst represents an important target for solar fuel production in dye‐sensitized photoelectrochemical cells (DS‐PECs). In this study, two different synthetic routes to prepare heteroleptic [Ru(4,4′‐(CH2PO3Et2)2‐bpy)2(N^N)](PF6)2 complexes are evaluated, the scope and limitations of the organometallic pathway involving half‐sandwich η6‐arene ruthenium complexes as synthetic intermediates being especially studied. The spectroscopic and electrochemical characterization of a series of novel structures varying by the nature of the third diimine N^N ligand is reported.

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Section: Resultsmentioning

confidence: 61%

Section: Resultsmentioning

confidence: 99%

“…[Ru(4,4′‐(CH 2 PO 3 Et 2 ) 2 ‐bpy) 2 (bpy)](PF 6 ) 2 (RuP 4 OEt ‐bpy): Yield: 58 % (method A: benzene); 58 % (method B: benzene); 60 % (method B: p ‐cymene).…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 92%

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Synthesis of Ruthenium Tris‐Diimine Photosensitizers Substituted by Four Methylphosphonate Anchoring Groups for Dye‐Sensitized Photoelectrochemical Cell Applications

et al. 2019

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Photoelectrochemical Hydrogen Production by a Cobalt Tetrapyridyl Catalyst Using Push–Pull Dye‐Sensitized NiO Photocathodes

Bourguignon,

Moinel,

Huet

et al. 2023

Adv Energy and Sustain Res

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Herein, the synthesis and optoelectronic properties of a novel push–pull organic dye, pRK1, specifically designed for use in dye‐sensitized photocathodes for hydrogen generation, are reported. The chemical structure of this dye, which incorporates a benzothiadiazole moiety, is inspired by RK1, a dye previously reported as a photosensitizer in n‐type dye‐sensitized solar cells (DSSCs) with power conversion efficiencies above 10% and high stability. The photoelectrochemical activity for hydrogen evolution of pRK1 after grafting onto NiO photocathodes in combination with a cobalt tetrapyridyl catalyst [Co(bapbpy)(OH2)2](BF4)2 in aqueous solution is evaluated and compared with two reference dyes from the literature, RuP2‐bpy and P1. It is shown that among the three photocathodes studied in this work, NiO|pRK1 is the most efficient, producing up to 1.9 μmol cm−2 of hydrogen with a faradaic efficiency of 66%, under visible light irradiation in aqueous electrolyte at pH 4.5. pRK1 shows a turnover number (TONdye) of up to 145 during the 6 h chronoamperometric test, almost twice that of P1. This study demonstrates that the chemical structure of high performance dyes commonly used in DSSCs can be successfully modified to meet the requirements for light‐driven water splitting in dye‐sensitized photoelectrochemical cells.

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Structure of Diethyl‐Phosphonic Acid Anchoring Group Affects the Charge‐Separated State on an Iridium(III) Complex Functionalized NiO Surface

et al. 2020

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Cyclometalated Iridium(III) complexes, i. e. [Ir(C N)2(dppz)][PF6], bearing either two or four ‐CH2PO(OH)2 anchoring groups (IrP2dppz or IrP4dppz) are explored as photosensitizers for p‐type dye sensitized solar cell (DSSC). The synthetic route is described and the iridium(III) complexes are characterized with respect to their electrochemical and photophysical properties. The modified anchoring ligand geometry exploited in this work not only alters the electronic nature of the complex (that is by destabilizing the LUMO energetically) but more importantly improves the grafting ability of the complex towards the NiO surface. The photoinduced long‐lived charge separated state (CSS) at the NiO|IrPxdppz interface is of a different nature comparing the two complexes. For IrP2dppz and IrP4dppz the electron density of the CSS dominantly resides on the dppz and the C N ligand, respectively. The stability of the CSS can be correlated to the solar cell performance in NiO‐based p‐DSSCs, which yield conversion efficiencies which are among the highest in the class of iridium(III) complexes developed for p‐DSSCs.

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Aqueous Photocurrent Measurements Correlated to Ultrafast Electron Transfer Dynamics at Ruthenium Tris Diimine Sensitized NiO Photocathodes

Cited by 37 publications

References 102 publications

Synthesis of Ruthenium Tris‐Diimine Photosensitizers Substituted by Four Methylphosphonate Anchoring Groups for Dye‐Sensitized Photoelectrochemical Cell Applications

Synthesis of Ruthenium Tris‐Diimine Photosensitizers Substituted by Four Methylphosphonate Anchoring Groups for Dye‐Sensitized Photoelectrochemical Cell Applications

Photoelectrochemical Hydrogen Production by a Cobalt Tetrapyridyl Catalyst Using Push–Pull Dye‐Sensitized NiO Photocathodes

Structure of Diethyl‐Phosphonic Acid Anchoring Group Affects the Charge‐Separated State on an Iridium(III) Complex Functionalized NiO Surface

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