Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/0046—Ruthenium compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/36—Compounds of titanium
  • C09C1/3607—Titanium dioxide
  • C09C1/3669—Treatment with low-molecular organic compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
  • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
  • H01G9/20—Light-sensitive devices
  • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/30—Coordination compounds
  • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
  • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
  • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/542—Dye sensitized solar cells

Definitions

• the present invention pertains to the field of photovoltaic technology and in particular to dye sensitized solar cells.
• the dye sensitized solar cell is arguably the best positioned to penetrate the market in the immediate future.
• the stability of the DSSC nonetheless remains a significant impediment to commercialization due to the hermetic sealing of the electrolyte, and the degradation and desorption of the dye.
• 1"4 While recent advances in solid-state hole-transport materials (e.g., perovskites, polymers) could help to resolve problems associated with the liquid electrolyte, 5 ' 6 charge-transport limitations have thus far confined performance to efficiencies of less than -8.5%, which is at least 4% less than that achieved with liquid electrolytes.
• Another key degradation pathway within conventional DSSCs is the desorption of the dye from the Ti0 2 .
• the electrolyte in state-of-the-art devices is typically dissolved in an organic medium, and requires the rigorous exclusion of water to avoid hydrolysis of the anchoring groups of the dye that are bound to Ti0 2 in order to operate efficiently over prolonged periods of time (e.g., ca. 10 yrs).
• the exclusion of adventitious water due to environmental factors over the required cell lifetime cannot be guaranteed, however, therefore providing the imperative to design dyes that are inherently tolerant of water.
• phosphonates exhibit a binding constant that is a 10-fold greater than that of the carboxylate linker due to the tri-dentate chelating mode of the phosphonate.
• the sp 3 hybridization of the phosphorus center compromises the injection of electrons from the excited state of the dye into titania.
• An object of the present invention is to provide a system for sensitization of metal oxides.
• a system for sensitization of metal oxides comprising a ruthenium(il) complex comprising at least two ligands bound to a ruthenium(Ii) center, wherein the at least two ligands comprises at least one first ligand being functionalized to provide high binding stability to the metal oxide, and at least one second ligand functionalized to provide efficient electron injection to the metal oxide.
• Figure 1 illustrates a schematic showing how the phosphonates and carboxylate anchoring groups can be used in conjunction with each to achieve injection.
• Figures 2 and 3 depict the synthetic scheme for the synthesis of the complexes of the present invention.
• Figure 4 illustrates X-ray structures of complexes 1 and 2 and a molecular model of complex 3.
• Figure 5a depicts the UV-vis spectrum of complexes 1-3 absorbed to mesoporous Ti0 2 substrates (10 ⁇ thick), and the inset depicts the optical spectra of complexes 1-3 recorded in MeOH.
• Figure 5b depicts the FTIR data of complexes 1-3 absorbed to Ti0 2 .
• the vibrational spectrum of the fully deprotonated form of complex 3 pressed in a KBr pellet is provided for comparison.
• Figure 6 depicts the temporal stability of complex 3 absorbed to a mesoporous Ti0 2 substrate in water. Data for N 3 and the black dye are also shown to highlight the enhanced stability engendered by the phosphonate groups. Inset: Zoomed in region of temporal stability.
• Figure 7 depicts incident-photon-to-current efficiency (IPCE) data for complex 3 absorbed to a mesoporous Ti0 2 substrate.
• Cell conditions AM 1 .5 with a 0.88 cm 2 active area.
• the present invention provides a sensitizer system formed of a ruthenium(II) complex comprising at least two ligands attached to the ruthenium(II) center, one of which is functionalized to provide high binding stability to the metal oxide, while the other is functionalized to provide efficient electron injection.
• a sensitizer system formed of a ruthenium(II) complex comprising at least two ligands attached to the ruthenium(II) center, one of which is functionalized to provide high binding stability to the metal oxide, while the other is functionalized to provide efficient electron injection.
• Each of these functions is provided by respective linking groups, each of which binds to the surface of the metal oxide through a suitable anchor moiety.
• anchor is used to describe the functional group that binds to the surface of the metal oxide.
• the anchor may be attached directly to the ligand or indirectly through a bridging moiety.
• linker or “linking group” is used to describe the portion of the sensitizer system that comprises an anchor portion as defined above and an optional bridging moiety between the anchor and the ligand bound to the ruthenium(II) center.
• Suitable anchoring groups for binding to metal oxides include phosphonic acids and derivatives thereof (such as phosphonate esters and salts), carboxylic acids and derivatives thereof (such as esters, acid chlorides, carboxylate salts or amides), silanes, ethers, acetylacetonate and salicylates.
• the sensitizer system utilizes phosphonate anchors to bind to the surface while maintaining efficient electron injection into the metal oxide substrate using a carboxylate linker, as shown in Figure 1.
• This molecular design keeps the carboxylate linker on the electron deficient ligand that will be the site responsible for injecting electrons into the metal oxide, while positioning the phosphonate on the adjacent chelating ligand.
• the resultant dye is then poised to retain a strong dye-surface interaction while also enabling facile charge transfer into the metal oxide.
• the binding stability linker comprises a phosphonic acid or its derivatives.
• the electron injection linker and the high binding stability linker are located on separate ligands in the dye complex. In one embodiment, the electron injection linker and the high binding stability linker are located on the same ligand in the dye complex.
• ruthenium(II) complex having the structure:
• Ri is an anchoring moiety that provides the efficient electron injection, for example, carboxylic acid and its derivatives, such as esters, acid chlorides, carboxylate salts or amides; and R 2 is an anchoring moiety that provides high binding stability, for example, phosphonic acid and its derivatives, such as phosphonate esters and salts.
• Ri is COOH and R is ⁇ 33 ⁇ 4.
• a sensitizer system that combines the efficient electron injection afforded by carboxylate linkers, with the binding stability of phosphonate groups.
• the sensitizer system of the present invention is also suitable for use with metal oxides other than Ti0 2 , for example, ZnO, Fe 2 0 3 , W0 3 , Sn0 2 and Zr0 2 .
• metal oxides other than Ti0 2 , for example, ZnO, Fe 2 0 3 , W0 3 , Sn0 2 and Zr0 2 .
• Such alternative metal oxides are considered to be within the scope of the present invention.
• Yi,Y 2 (C,N) or (N,N) or (N,C);
• ⁇ , ⁇ , ⁇ (C,N,N) or (C,C,N) or ( ⁇ , ⁇ , ⁇ ); or
• X,,X 2 ,X 3 (N,N,N) or (N,C,N) or ( ,C, ) or (N,N,C) or (C,N,C) or (C,N,N);
• the anchoring group A may be defined as follows:
• Figure 4 depicts structures of complexes 1 and 2 determined by single crystal X- ray diffraction techniques, and a molecular model of complex 3 showing that the phosphonate and/or carboxylate anchoring groups are appropriately positioned for collective binding. Hydrogens, counter ions and ester linkages omitted for clarity.
• the narrow MLCT band in the visible region for each complex is a manifestation of the C 2v symmetry and the nearly degenerate ⁇ * orbitals of both ligands.
• the electrochemical behaviour was investigated by square-wave cyclic voltammetry where the working electrode was the dye covered titania fluorine doped tin oxide (FTO) glass.
• the title complexes 1-3 were observed to show a ruthenium (II/III) oxidation potential at -1.2 V.
• Electron injection efficiency was demonstrated by construction of dye-sensitized solar cells that were characterized under AM 1 .5 conditions. Complex 3 exhibited the highest ⁇ at 0.316%. The incident photon to current efficiency (IPCE) was also investigated which demonstrated the ability of the complexes to produce photo injected electrons. As expected complex 2 exhibited poor energy conversion efficiency with no carboxylate linker to provide the critical electron injection pathway from the terpy fragment. The ⁇ of complex 1 was intermediate due to the steric hindrance the methyl groups P T/CA2013/050624

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• 2013
  • 2013-08-14 WO PCT/CA2013/050624 patent/WO2014026285A1/fr not_active Ceased

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