Improved efficiency of PbS quantum dot sensitized NiO photocathodes with naphthalene diimide electron acceptor bound to the surface of the nanocrystals

Hybrid materials combining a wide bandgap metal oxide semiconductor, metal chalcogenide nanocrystals and molecular systems represent very attractive materials for fabricating devices with new function or improved photoelectrochemical performance. This study deals with sensitization of NiO, which is a p-type semiconductor, by quantum dots (QDs) of PbS with an average diameter of 3 nm. The PbS QDs were attached to the monocrystalline film of NiO by mercaptopropionic acid linker and were subsequently capped with methyl-pyridine naphthalene diimide (NDI) units to prepare quantum dot sensitized solar cells (p-QDSSCs) on NiO electrodes. Time-resolved photoluminescence measurements of the PbS emission were used to determine the rate constants for charge transfer from the PbS exciton to the NiO, cobalt based redox mediator and NDI. Notably, it was shown that NDI quenches the PbS exciton by electron transfer with a quite fast rate constant (6.9 × 107 s−1). The PbS QDs sensitized NiO films were finally used to fabricate solar cells with tris(4,4′-ditert-butyl-2,2′-bipyridine) cobalt(III/II) as redox mediator. It was observed that the presence of NDI on PbS improved the photovoltaic performance by 50% relative to that of cells without NDI, leading to a device with the following characteristics: Jsc = 5.75 mA/cm2, Voc = 226 mV, ff = 34% and PCE = 0.44%. This study demonstrates that photogalvanic processes can be a productive pathway to better performing sensitized p-type semiconductor for p-QDSSC. In other words, photoinduced electron transfer from the QDs towards the electrolyte rather than initial photoinduced charge injection into the p-type semiconductor can be a favorable operative mechanism in QD sensitized NiO films and might be exploited further for the construction of better performing solar cells or photocatalytic devices

Inverse Opal CuCrO2 Photocathodes for H2 Production Using Organic Dyes and a Molecular Ni Catalyst.

Dye-sensitized photoelectrochemical (DSPEC) cells are an emerging approach to producing solar fuels. The recent development of delafossite CuCrO2 as a p-type semiconductor has enabled H2 generation through the coassembly of catalyst and dye components. Here, we present a CuCrO2 electrode based on a high-surface-area inverse opal (IO) architecture with benchmark performance in DSPEC H2 generation. Coimmobilization of a phosphonated diketopyrrolopyrrole (DPP-P) or perylene monoimide (PMI-P) dye with a phosphonated molecular Ni catalyst (NiP) demonstrates the ability of IO-CuCrO2 to photogenerate H2. A positive photocurrent onset potential of approximately +0.8 V vs RHE was achieved with these photocathodes. The DPP-P-based photoelectrodes delivered photocurrents of -18 μA cm-2 and generated 160 ± 24 nmol of H2 cm-2, whereas the PMI-P-based photocathodes displayed higher photocurrents of -25 μA cm-2 and produced 215 ± 10 nmol of H2 cm-2 at 0.0 V vs RHE over the course of 2 h under visible light illumination (100 mW cm-2, AM 1.5G, λ > 420 nm, 25 °C). The high performance of the PMI-constructed system is attributed to the well-suited molecular structure and photophysical properties for p-type sensitization. These precious-metal-free photocathodes highlight the benefits of using bespoke IO-CuCrO2 electrodes as well as the important role of the molecular dye structure in DSPEC fuel synthesis

Improved efficiency of PbS quantum dot sensitized NiO photocathodes with naphthalene diimide electron acceptor bound to the surface of the nanocrystals

Funding: European Research Council (grant number 321305) and the EPSRC (grant number EP/L017008/1). IDWS is a Royal Society Wolfson Research Merit award holder.Hybrid materials combining a wide bandgap metal oxide semiconductor, metal chalcogenide nanocrystals and molecular systems represent very attractive materials for fabricating devices with new function or improved photoelectrochemical performances. This study deals with sensitization of NiO, which is a p-type semiconductor, by quantum dots (QDs) of PbS with an average diameter of 3 nm. The PbS QDs were attached to the monocrystalline film of NiO by mercaptopropionic acid linker and were subsequently capped with methyl-pyridine naphthalene diimide (NDI) units to prepare quantum dot sensitized solar cells (p-QDSSCs) on NiO electrodes. Time-resolved photoluminescence measurements of the PbS emission were used to determine the rate constants for charge transfer from the PbS exciton to the NiO, cobalt based redox mediator and NDI. Notably, it was shown that NDI quenches the PbS exciton by electron transfer with a quite fast rate constant (6.9 x 107 s-1). The PbS QDs sensitized NiO films were finally used to fabricate solar cells with tris(4,4’-ditert-butyl-2,2’-bipyridine) cobalt(III/II) as redox mediator. It was observed that the presence of NDI on PbS improved the photovoltaic performance by 50% relative to that of cells without NDI, leading to a device with the following characteristics: Jsc = 5.75 mA/cm2, Voc = 226 mV, ff = 34% and PCE = 0.44%. This study demonstrates that photogalvanic processes can be a productive pathway to better performing sensitized p-type semiconductor for p-QDSSC. In other words, photoinduced electron transfer from the QDs towards the electrolyte rather than initial photoinduced charge injection into the p-type semiconductor can be a favorable operative mechanism in QD sensitized NiO films and might be exploited further for the construction of better performing solar cells or photocatalytic devices.PostprintPostprintPeer reviewe

Inverse Opal CuCrO2 Photocathodes for H2 Production Using Organic Dyes and a Molecular Ni Catalyst.

Dye-sensitized photoelectrochemical (DSPEC) cells are an emerging approach to producing solar fuels. The recent development of delafossite CuCrO2 as a p-type semiconductor has enabled H2 generation through the coassembly of catalyst and dye components. Here, we present a CuCrO2 electrode based on a high-surface-area inverse opal (IO) architecture with benchmark performance in DSPEC H2 generation. Coimmobilization of a phosphonated diketopyrrolopyrrole (DPP-P) or perylene monoimide (PMI-P) dye with a phosphonated molecular Ni catalyst (NiP) demonstrates the ability of IO-CuCrO2 to photogenerate H2. A positive photocurrent onset potential of approximately +0.8 V vs RHE was achieved with these photocathodes. The DPP-P-based photoelectrodes delivered photocurrents of -18 μA cm-2 and generated 160 ± 24 nmol of H2 cm-2, whereas the PMI-P-based photocathodes displayed higher photocurrents of -25 μA cm-2 and produced 215 ± 10 nmol of H2 cm-2 at 0.0 V vs RHE over the course of 2 h under visible light illumination (100 mW cm-2, AM 1.5G, λ > 420 nm, 25 °C). The high performance of the PMI-constructed system is attributed to the well-suited molecular structure and photophysical properties for p-type sensitization. These precious-metal-free photocathodes highlight the benefits of using bespoke IO-CuCrO2 electrodes as well as the important role of the molecular dye structure in DSPEC fuel synthesis

Solar electricity and fuel production with perylene monoimide dye-sensitised TiO2 in water.

Dye-sensitisation of TiO2 and other metal oxides is an established strategy to couple solar light harvesting with efficient charge separation for the production of electricity in dye-sensitised solar cells (DSCs) or fuels in dye-sensitised semiconductor photocatalysis (DSP). Perylene monoimide (PMI) dyes have emerged as promising organic dyes, but they have not previously been used in a functional assembly with TiO2 in aqueous solution. Here, five novel PMI dyes bearing carboxylic acid, phosphonic acid, acetylacetone, hydroxyquinoline or dipicolinic acid anchoring groups for attachment onto TiO2 are reported. We identified functional DSC and DSP systems with PMI-sensitised TiO2 in aqueous solution, which permitted a side-by-side comparison with respect to performance between the two systems. Structure-activity relationships allowed us to suggest anchor-condition-system associations to suit specific anchoring groups at various pH values, and with different electron mediators (redox couple or sacrificial electron donor) and catalysts in DSC and DSP schemes. A DSC sensitised with the hydroxyquinoline-modified PMI dye reached the highest short-circuit current density (J SC ≈ 1.4 mA cm-2) in aqueous electrolyte solution during irradiation with simulated solar light. This dye also achieved a turnover number (TONPMI) of approximately 4900 for sacrificial proton reduction after 24 h irradiation in a DSP scheme with Pt as a H2-evolving co-catalyst at pH 4.5. This performance was only surpassed by the carboxylic acid-bearing dye, which reached a new benchmark turnover number (TONPMI ≈ 1.1 × 104 after 72 h) for an organic dye in nanoparticulate DSP for solar fuel production. At higher pH (8.5), our results showed that the phosphonic acid group allows for higher performance due to a stronger anchoring ability. This study provides a platform for aqueous PMI dye-sensitised TiO2 chemistry and gives valuable insights into the performance of different anchoring groups in DSC and DSP systems.Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and National Foundation for Research, Technology and Development), the OMV Group, Agence National de la Recherche (ANR) through the program POSITIF (ANR-12-PRGE-0016-01), and Région des Pays de la Loire for the project LUMOMA

Cu2O@CuO core-shell nanoparticles as photocathode for p-type dye sensitized solar cell

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CuO nanomaterials for p-type dye-sensitized solar cells

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Copper borate as a photocathode in p-type dye-sensitized solar cells

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Experimental and theoretical evidences of p-type conductivity in nickel carbodiimide nanoparticles with a delafossite structure type

International audienceNickel carbodiimide (NiCN) was synthesized using a two-step precipitation-decomposition route leading to a brown powder with gypsum-flower-like morphology and a large specific surface area (75 m/g). This layered material crystallizes in the 2H structure type of delafossite (space group P6/mmc), which is built upon infinite /[NiN] layers connected by linear carbodiimide ([N═C═N]) bridges. An X-ray diffraction Rietveld refinement and thermal analyses pointed out some nickel deficiencies in the material, and band structure calculations carried out on the defect compound predicted p-type conductivity in relation to a slight amount of N. This p-type conductivity was demonstrated by electrochemical impedance spectroscopy measurements, and a flat band potential of 0.90 V vs SCE at pH 9.4 was measured. This value, which is more positive than those of CuGaO and CuCrO delafossite oxides and NiO, prompted us to test NiCN nanoparticles as a photocathode in p-type dye-sensitized solar cells

Towards efficient solid-state p-type dye-sensitized solar cells: the dye matters

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