Charge-transfer dynamics at the dye–semiconductor interface of photocathodes for solar energy applications

Black, Fiona A.; Wood, Christopher J.; Ngwerume, Simbarashe; Summers, Gareth H.; Clark, Ian P.; Towrie, Michael; Camp, J. E.; Gibson, Elizabeth A.

doi:10.1039/c6fd00228e

Cited by 10 publications

(12 citation statements)

References 25 publications

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“…7,12,[17][18][19] The suboptimal photocathode performance could originate from many factors, including the NiO electrode, which exhibits slow hole mobility and large losses in efficiency due to charge recombination between holes in the NiO and reduced dye or catalyst molecules. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] These issues make developing an efficient photocathode quite difficult. Thus, is it crucial that fundamental studies are performed to gain understanding of the processes occurring in photocathodes if performance is to be rationally improved.…”

Section: Introductionmentioning

confidence: 99%

Using Surface Amide Couplings to Assemble Photocathodes for Solar Fuel Production Applications

Materna

Lalaoui

Laureanti

et al. 2019

ACS Appl. Mater. Interfaces

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A facile surface-amide coupling method was examined to attach dye and catalyst molecules to silatrane-decorated NiO electrodes. Using this method, electrodes with a push-pull dye were assembled, and characterized by photoelectrochemistry and transient absorption spectroscopy. The dye-sensitized electrodes exhibited hole injection into NiO and good photoelectrochemical stability in water, highlighting the stability of the silatrane anchoring group and the amide linkage. The amide coupling protocol was further applied to electrodes that contain additional proton reduction nickel catalysts for use in photocathode architectures. Evidence for catalyst reduction was observed during photoelectrochemical measurements and via fs-transient absorption spectroscopy demonstrating the possibility for application in photocathodes.

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Section: Introductionmentioning

confidence: 99%

Using Surface Amide Couplings to Assemble Photocathodes for Solar Fuel Production Applications

Materna

Lalaoui

Laureanti

et al. 2019

ACS Appl. Mater. Interfaces

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“…This in turn demonstrates the feasibility of all-polymer photocathodes for application in solar energy conversion.Artificial photosynthesis is a promising pathway for solar-fuel production 1-5 . One way of realizing an artificial photosynthetic system is to graft redox-active photosensitizers and catalysts to semiconductor electrodes to give dye-sensitized photoelectrochemical cells [3][4][5][6] . Ru II poly-pyridyl complexes are widely used as chromophores for dye-sensitized electrodes.…”

mentioning

confidence: 99%

“…Ru II poly-pyridyl complexes are widely used as chromophores for dye-sensitized electrodes. They exhibit high absorptivity in the visible region and redox properties that are easily tuned by ligand modification [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] . In the case of Ru II polypyridyl complex-sensitized photocathodes for hydrogen generation, the semiconductor electrodes play the role of electron donor while the chromophores act as light harvesting and charge-separating units [7][8][9][10][11][12] .…”

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confidence: 99%

Photocathodes beyond NiO: charge transfer dynamics in a π-conjugated polymer functionalized with Ru photosensitizers

Wahyuono

Seidler

Bold

et al. 2021

Sci Rep

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A conductive polymer (poly(p-phenylenevinylene), PPV) was covalently modified with RuII complexes to develop an all-polymer photocathode as a conceptual alternative to dye-sensitized NiO, which is the current state-of-the-art photocathode in solar fuels research. Photocathodes require efficient light-induced charge-transfer processes and we investigated these processes within our photocathodes using spectroscopic and spectro-electrochemical techniques. Ultrafast hole-injection dynamics in the polymer were investigated by transient absorption spectroscopy and charge transfer at the electrode–electrolyte interface was examined with chopped-light chronoamperometry. Light-induced hole injection from the photosensitizers into the PPV backbone was observed within 10 ps and the resulting charge-separated state (CSS) recombined within ~ 5 ns. This is comparable to CSS lifetimes of conventional NiO-photocathodes. Chopped-light chronoamperometry indicates enhanced charge-transfer at the electrode–electrolyte interface upon sensitization of the PPV with the RuII complexes and p-type behavior of the photocathode. The results presented here show that the polymer backbone behaves like classical molecularly sensitized NiO photocathodes and operates as a hole accepting semiconductor. This in turn demonstrates the feasibility of all-polymer photocathodes for application in solar energy conversion.

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“…which is aw eaker Lewis acid than Ti IV in TiO 2 .F or fast hole injection into the NiO valence band, the HOMO of the dye must mix with the valence band, which implies that the anchoring group orbitalsm ust give as ignificantc ontribution to the HOMO.T his is the opposites ituation for TiO 2 sensitizers, which must be composed of electron-deficient anchoring groupso n which the LUMO should be delocalized. [16] We have investigated the replacement of carboxylic acid by catechol, [17] carbodithioic acid, [17] phosphonic acid, [17] acetyla cetone( acac), [18] alkoxysilane [19] and other teams have investigated pyridine, [20][21][22] di(carboxylic acid)pyrrole, [23,24] hydroxamic acid, [25] and di(carboxylic acid)triazole [26] as alternative anchoring groups for NiO photocathodes.O wing to the scarcity of systematic studies on NiO anchoring groups, we have been interested to investigate the properties of as eries of dyes that differ only by the nature of the anchoring group ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

“…This is the opposite situation for TiO 2 sensitizers, which must be composed of electron‐deficient anchoring groups on which the LUMO should be delocalized . We have investigated the replacement of carboxylic acid by catechol, carbodithioic acid, phosphonic acid, acetyl acetone (acac), alkoxysilane and other teams have investigated pyridine, di(carboxylic acid)pyrrole, hydroxamic acid, and di(carboxylic acid)triazole as alternative anchoring groups for NiO photocathodes. Owing to the scarcity of systematic studies on NiO anchoring groups, we have been interested to investigate the properties of a series of dyes that differ only by the nature of the anchoring group (Figure ).…”

Section: Introductionmentioning

confidence: 99%

A Comparative Investigation of the Role of the Anchoring Group on Perylene Monoimide Dyes in NiO‐Based Dye‐Sensitized Solar Cells

et al. 2020

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The anchoring group of a sensitizer may strongly affect the overall properties and stability of the resulting dye‐sensitized solar cells (DSSCs) and dye‐sensitized photoelectrosynthetic solar cells (DSPECs). The properties of seven perylene monoimide (PMI) dyes have been comprehensively studied for their immobilization on nanocrystalline NiO film. The PMI dyes differ only by the nature of the anchoring group, which are: carboxylic acid (PMI‐CO2H), phosphonic acid (PMI‐PO3H2), acetyl acetone (PMI‐acac), pyridine (PMI‐Py), aniline (PMI‐NH2), hydroxyquinoline (PMI‐HQ), and dipicolinic acid (PMI‐DPA). The dyes are investigated by cyclic voltammetry and spectroelectrochemistry and modeled by TD‐DFT quantum chemical calculations. The mode of binding of these anchoring groups is investigated by infrared spectroscopy and the stability of the binding to NiO surface is studied by desorption experiments in acidic and basic media. The phosphonic acid group is found to offer the strongest binding to the NiO surface in terms of stability and dye loading. Finally, a photophysical study by ultrafast transient absorption spectroscopy shows that all dyes inject a hole in NiO with rate constants on a subpicosecond timescale and display similar charge recombination kinetics. The photovoltaic properties of the dyes show that PMI‐HQ and PMI‐acac give the highest photovoltaic performances, owing to a lower degree of aggregation on the surface.

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Charge-transfer dynamics at the dye–semiconductor interface of photocathodes for solar energy applications

Cited by 10 publications

References 25 publications

Using Surface Amide Couplings to Assemble Photocathodes for Solar Fuel Production Applications

Using Surface Amide Couplings to Assemble Photocathodes for Solar Fuel Production Applications

Photocathodes beyond NiO: charge transfer dynamics in a π-conjugated polymer functionalized with Ru photosensitizers

A Comparative Investigation of the Role of the Anchoring Group on Perylene Monoimide Dyes in NiO‐Based Dye‐Sensitized Solar Cells

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