Wavelength downconverters

Abstract

Polyoxotitanate comprising a metal oxide core and a ligand shell, wherein the metal oxide core comprises titanium, oxygen, and a lanthanide, and the ligand shell comprises one or more light-harvesting

Description

FIELD OF INVENTION The invention relates to compounds that convert electromagnetic radiation to a longer wavelength, methods of their manufacture and their commercial implementation. BACKGROUND Many biological and synthetic processes utilise solar radiation as their energy source. Although most electromagnetic radiation received from the Sun falls within the wavelength range of 100 nm to 1 mm (i.e. ultraviolet to infrared), some processes use only a narrow bandwidth. Therefore, a significant amount of incident solar radiation is wasted. For such processes it is desirable to convert the non-utilised bandwidth to a wavelength range that can be utilized, thereby improving the process efficiency. For example, a photosynthesizing plant uses longer wavelengths, so downconverting the UV end of the spectrum would increase the energy available for photosynthesis. Photovoltaic cells also use a much narrower bandwidth of electromagnetic radiation than is incident from the Sun and could therefore be made more productive if the incident light were to be converted to the optimum wavelength for the semiconductor bandgap. Numerous improvements are desirable for existing spectral conversion materials. Synthesis routes are typically complex and costly, for example, manufacturing monodisperse quantum dots. SUMMARY The invention provides novel polyoxotitanates. These polyoxotitanates comprise a metal oxide core and a ligand shell. The metal oxide core comprises titanium, oxygen and europium. The ligand shell may also comprise one or more light-harvesting ligands (also known as antenna ligands) coordinated to europium. The one or more light-harvesting ligands is selected from substituted extended aromatic ligands and benzoate ligands. The one or more light-harvesting ligands may be one or both of a benzoate-based ligand and a phenanthroline-based ligand, according to the following structures: 5 In the phenanthroline structure, R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from H, C1-30 linear alkyl or alkoxy and C1-30 branched alkyl or alkoxy, with the proviso that at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is not H. In the benzoate structure, R", Rm, RIV, Rv and RVI are each independently selected from H, F, isopropyl, linear or branched C1-30 alkoxy, and linear or branched C5-30 alkyl. 10 In some embodiments, at least one of R1, R2, R3, R4, R5, R6, R7 and R8 may be selected from C12-18 linear alkyl, C12-18 branched alkyl, C12-18 linear alkoxy, C12-18 branched alkoxy. In some embodiments, at least one of R", RIH, RIV, Rv and RVI may be selected from C12-18 linear alkyl, C12-18 branched alkyl, C12-18 linear alkoxy, C12-18 branched alkoxy. These 15 longer alkyl and alkoxy chains help to solubilize the POTs in a polymer matrix. The one or more light harvesting ligands may comprise any functionalized carboxylate, nitrogen-based polyaromatic, or dye-like ligand molecule, in particular polyaromatic ligands such as phenanthroline. For example, the one or more light harvesting ligands may comprise a ligand selected from 4-methoxybenzoic acid, 4-isopropylbenzoic acid, benzoic acid, and 4,7-dimethoxy-1,10-phenanthroline. POTs having 4-methoxybenzoic acid ligands were found to exhibit improved solubility in a polymer matrix and to have a red-shifted absorption. POTs having 4-isopropylbenzoic acid ligands were found to exhibit improved solubility in a polymer matrix and a good PLQY. POTs having 4,7-dimethoxy-1,10-phenanthroline ligands were found to exhibit better solubility, further red-shifted absorption and improved PLQY, relative to related compounds which do not have electron-donating organic groups within their frameworks. The novel POTs may comprise one or more co-ligands in addition to the light-harvesting ligands. Herein these co-ligands are also referred to as “solubilizing ligands”, because they function to increase the solubility of the POTs in a polymer matrix. The solubilizing ligands are separate ligands and are preferably coordinated to Ti or O in the core, rather than to Eu. A suitable solubilizing ligand is methacrylate, which is especially useful when using a PMMA matrix. In some embodiments, the metal oxide core may be selected from EusTiwOx and Eu2Ti4Ox. In some embodiments, the novel polyoxotitanates may have one of the following formulae: Eu8Tii0(p3-O)i4(CH3COO)2(OMeba)34(H2O)4(THF)2(HOIVIeba)2, Eu8Tiio(p3-0)i4(CH3COO)2(iPrba)34(H20)4(THF)2(HiPrba)2, Eu8Tiio(p3-0)i4(CH3000)2(ba)34(H20)4(THF)2(Hba)2, Eu2Ti406(OMephen)2(ma)io. The invention also provides a method of making polyoxotitanates in a droplet flow reactor. The method comprises: providing precursors comprising a lanthanide compound, a titanium-oxygen compound and a ligand; combining the precursors and a solvent in one or more precursor flows; injecting the precursors, a carrier fluid and an antisolvent into a tubular reaction vessel and allowing the precursors to react to form a polyoxotitanate; and collecting the polyoxotitanate as it exits the reaction vessel. The method of the invention offers a significant decrease in synthesis time for polyoxotitanate compounds (POTs) compared to known methods such as autoclave and Schlenk-type reactors, from hours to minutes. In addition, no extreme temperature or pressure is required and a pure product, confirmed by X-ray crystallography, can be obtained using the method of the invention. The method may further comprise removing the carrier fluid. In an industrial setting, the carrier fluid may be recycled back to the start of the process. The tubular reaction vessel may be coiled for thermal and spatial efficiency. The reaction temperature, i.e. the temperature inside the reaction vessel, may be up to 100 °C, such as from 70 to 90 °C, such as about 80 °C. The reaction may be conducted at ambient pressure. The residence time inside the reaction vessel, for example tubing, may suitably be no greater than 20 minutes, such as from 1 to 20 minutes, such as from 5 to 15 minutes, such as about 10 minutes, to achieve an appropriate yield from the reaction. Progress of the reaction forming POTs within the reaction vessel can be tracked by in-line fluorescence measurement and white crystal formation is visible by eye. The flow rate of droplets in the tubular reaction vessel may suitably be from 0.040 to 0.250 ml / min, such as from 0.040 to 0.120 ml / min. The solvent, the antisolvent and the carrier fluid may each be selected based on the compound being manufactured. Suitable solvents for manufacturing POTs include tetrahydrofuran (THF), alcohols, methyl acetate and ethyl acetate. Suitable antisolvents include acetonitrile and hexane. Suitable carrier fluids include perfluorinated fluids such as Galden perfluorinated fluid, e.g. the HT series. Gases may also be used as carrier fluids. A stoichiometric ratio of 1:1:5 of Eu(CH3COO)3: Ti(O / Pr)4: CeHsCOOH may be used in the method of the invention (lanthanide compound : titanium-oxygen compound : ligand). Other stoichiometries may be used depending on the target product. A stoichiometric ratio of 1:3 of precursor solvent: antisolvent may be used in the method of the invention. The amount of carrier fluid used in the method depends on the total flow rate of precursor and antisolvent. The identity of the precursors is dependent on the POT being manufactured. The titanium-oxygen compound may suitably be Ti(O / Pr)4 or titanium bis(acetylacetonate)dichloride. The lanthanide compound may suitably be Eu(CH3COO)3or Eu[(CH3)2CH(CO)2]3. The ligand may be a single type of ligand or two or more different types of ligand. Any ligand that can coordinate to the core and form a POT may be used. Depending on the end use of the POTs, suitable ligands include those based on polyaromatic nitrogen frameworks (such as bipyridines and phenanthrolines), aliphatic and aromatic carboxylate ligands, alkoxides, acetonates, benzoates and methacrylate, amongst others. The invention also provides use of a droplet flow reactor to manufacture polyoxotitanates. Previous methods for manufacturing POTs take a long time - on the scale of hours - making it expensive and inconvenient to scale up manufacture. Droplet flow synthesis of POTs takes minutes and can be easily scaled up, for example by providing parallel synthesis lines. The invention also provides composite materials comprising polyoxotitanates dispersed in a polymer matrix. The polyoxotitanates are made according to the method of the invention or are the novel poly oxotitanates of the invention. The polymer matrix may be one or more of polyethylene, polypropylene, polymethylmethacrylate, polycarbonate, polyether ether ketone, ethylene-vinyl acetate, acrylate, and polyvinylacetate. The invention also provides polymer films comprising the composite material of the invention. The polymer film may be in the form of polytunnel sheeting. The polymer film may be in the form of a film for adhesion to greenhouse panels. The invention also provides methods of manufacturing the composite materials of the invention. One suitable method is photopolymerization. The photopolymerisation method for manufacturing a composite polymer film comprises: a. preparing a solution of monomers, polyoxotitanates and photoinitiator; b. injecting the solution into a mould; c. curing the solution in UV light; and d. removing the cured composite polymer film from the mould. Another suitable method is solution casting. The solution casting method for manufacturing a composite polymer film comprises: a. preparing a solution of a polymer, for example PMMA, polyoxotitanates and solvent; b. pouring the solution into a mould; c. curing the solution by solvent evaporation; d. removing the cured composite polymer film from the mould. The invention also provides use of europium-containing polyoxotitanates in agriculture to increase the amount of red light available to plants. For photosynthesis, plants do not use the whole solar spectrum. The emission spectrum of Eu is well-matched to the wavelength requirements for photosynthesis. Eu-doped POTs absorb the shorter wavelengths that are not useful to plants and fluoresce at useful wavelengths. This increases the amount of useable photon energy for photosynthesis compared to the solar spectrum. The invention also provides use of polyoxotitanates to increase the efficiency of a photovoltaic cell. The invention also provides the use of polyoxotitanates to decrease UV damage of an encapsulated material, such as an electronic component or a photovoltaic cell. BRIEF DESCRIPTION OF DRAWINGS Figure 1 shows a schematic of apparatus for droplet flow synthesis; Figures 2A-F show molecular diagrams of examples of novel POTs of the invention; Figure 3 shows a schematic of use of POTs in agriculture; Figure 4 is a graph of absorption spectra for POT-polymer composite materials; Figure 5 is a graph of emission spectra for POT-polymer composite materials; Figure 6 is a graph of absorption spectra for POTs. DETAILED DESCRIPTION Definitions “Spectral conversion” describes shifting electromagnetic radiation from one wavelength to another. “Downconversion” is used herein to describe spectral conversion from a first wavelength to a longer wavelength. “Downconverter” is used herein to describe a material that facilitates spectral conversion to a longer wavelength. A polyoxotitanate is a molecular structure comprising a metal oxide core and a ligand shell, the metal oxide core comprising titanium and a lanthanide. “Lambda max” and “Amax” refer to the wavelength at which a material exhibits its highest level of absorption of electromagnetic radiation. References to titanium oxide and to titania refer to any stoichiometry of titanium and oxygen. Abbreviations 4-terbutyl benzoic acid is referred to as “Htbba” and as “4-tBu benz” 4-methoxybenzoic acid is referred to as “HOMeba” and as “4-OMe benz” 4-isopropylbenzoic acid is referred to as “HiPrba” and as “4-iPr benz” Benzoic acid is referred to as “Hba” and as “benz” Methacrylate is referred to as “ma” 1,10-phenanthroline is referred to as “phen” 4,7-dimethoxy-1,10-phenanthroline is referred to as “OMe phen” and as “OMephen” Polymethylmethacrylate is abbreviated to “PMMA” Polyoxotitanate is abbreviated to “POT” Photoluminescence quantum yield is abbreviated to “PLQY” Novel polyoxotitanates Novel polyoxotitanates (POTs) have been developed, with particular benefits for agricultural applications. These POTs have a europium fluorophore, protected by a titania core structure, and an organic ligand exterior. Europium alone has a lambda max of around 200nm. This is too short a wavelength for efficient spectral conversion, because the greatest number of photons in solar radiation is found at around 400 nm. The novel POTs comprise a metal oxide core and a ligand shell. The metal oxide core comprises Ti, O and Eu and is essentially a titanium oxide cage with one or more of the titanium positions substituted with europium. The ratio of titanium to oxygen to europium in the core of the novel POTs is not important. Both large and small POT molecules have been found to be effective at downconverting solar radiation. The size and stoichiometry of the Ti-Eu-0 core cage is not especially important. The association of the Eu and the light-harvesting ligand(s) creates the photochemical properties of the POT. In particular, the quantum yield is not dependent on the relative amount of Eu in each POT molecule and instead is dependent on the alignment of energy levels between the Eu and the light-harvesting ligand(s), and the absorption coefficient of the light-harvesting ligand(s). The titanium oxide cage protects the coordination of Eu with its light-harvesting ligands so that the interaction can be retained, for example when the POTs are dispersed in a polymer matrix. Compared to an Eu-ligand complex, the novel POTs are believed to have increased quantum yield; reduced vibration losses and non-radiative losses; improved stability and resistance, for example resistance to UV degradation; and increased molecular rigidity. The ligand shell comprises at least one type of ligand, this essential ligand being a lightharvesting ligand (antenna ligand). The light-harvesting ligand is coordinated to Eu in the core of the molecule. This has the effect of increasing the lambda max for the POT, bringing it nearer to 400 nm, thereby increasing the efficiency of the spectral conversion achieved by the POT. The light-harvesting ligands change the absorption spectra of the POT compared to the metal oxide cage absent any light-harvesting ligands. With just the Ti-Eu-0 core, the absorption spectrum is not optimum because it is too far towards shorter wavelengths, at around 200 nm. Solar radiation has maximum photons at around 400 nm, therefore it is beneficial to have Amax as close as possible to 400nm so as to maximise the energy emitted at a longer wavelength. The light-harvesting ligands are preferably all or mostly associated with the Eu atoms in the core, for example bonded to Eu. This ensures efficient energy transfer from the ligand to the Eu fluorophore. Light-harvesting ligands associated instead with Ti or O in the core are less efficient at transferring solar energy to Eu, thereby decreasing the quantum yield. This is because an extra energy transfer step is required, that is omitted when the light-harvesting ligands coordinate directly to the Eu. For example, a phenanthroline ligand may absorb a photon and transfer the energy directly into the f electronic state of a Eu atom in the core cage, to which it is coordinated. The ligands preferably coordinate only to the outer sphere of the core, not within the core metal oxide cage. Suitable light-harvesting ligands include substituted and unsubstituted mono- and polycyclic aromatic ligands, for example ligands based on benzene, naphthalene, biphenyl, fluorene, anthracene, phenanthrene, phenalene, tetracene, chrysene, pentacene, benzo[c]fluorene, quinoline, quinazoline, quinoxaline, indole, indazole, carbazole, benzocarbazole, acridine, benz[a]acridine, benzimidazole, purine, cinnoline, phenanthridine, phenanthroline, and others. Preferred light-harvesting ligands are substituted and unsubstituted phenanthroline and substituted and unsubstituted benzoate ligands. These ligands in combination with the Eu-Ti-0 metal-oxo core cage have been found to exhibit excellent quantum yield. In order to make them useful for application in agriculture, the novel POTs also comprise means for solubilization in a polymer matrix. This may be either a moiety of the lightharvesting ligand, or a co-ligand such as methacrylate. Preferred moieties for solubilization include C12-18 branched and linear alkyl and alkoxy groups. The moiety or co-ligand for solubilisation may be selected based on compatibility with the polymer in which the POT is to be dispersed. For example, a methacrylate co-ligand is especially useful for solubilizing POTs in PMMA. Selected novel POTs according to the invention are illustrated in Figures 2A-F. Figure 2A shows a ball-and-stick representation of the structure of an EusTiw cage with benzoate (PhCO2) cage groups. C-atoms are depicted in wire-frame form, Eu (large grey balls), Ti (dark grey balls), O (small white balls). H-atoms and lattice solvent molecules have been omitted for clarity. Figure 2B shows a ball-and-stick representation of the structure of an EusTiw cage with 4-methoxy-benzoate (4-MeO-PhCO2) cage groups. C-atoms are depicted in wire-frame form, Eu (large grey balls), Ti (dark grey balls), O (small white balls). H-atoms and lattice solvent molecules have been omitted for clarity. Figure 2C shows a ball-and-stick representation of the structure of an EusTiw cage with 4-ethyoxy-benzoate (4-EtO-PhCO2) cage groups. C-atoms are depicted in wire-frame form, Eu (large grey balls), Ti (dark grey balls), O (small white balls). H-atoms have been omitted for clarity. Figure 2D shows a ball-and-stick representation of the structure of an EusTiw cage with 4-fluoro-benzoate (4-F-PhCO2) cage groups. C-atoms are depicted in wire-frame form, Eu (large grey balls), Ti (dark grey balls), O (small white balls), F (small grey balls). H-atoms have been omitted for clarity. Figure 2E shows a ball-and-stick representation of the structure of an Eu2Ti4 cage with methacrylate (CH2=C(Me)CO2) cage groups and 4,7-dimethoxy-phenanthroline lightharvesting ligands attached to Eu. C-atoms are depicted in wire-frame form, Eu (large grey balls), Ti (dark grey balls), O (small white balls), N (light grey balls on phenanthroline ligands). H-atoms and lattice solvent molecules have been omitted for clarity. Figure 2F shows a ball-and-stick representation of the structure of Eu2Ti4 cage with 4-methoxy-benzoate (4-MeO-Ph) cage groups and phenanthroline light-harvesting ligands attached to Eu. C-atoms are depicted in wire-frame form, Eu (large grey balls), Ti (dark grey balls), O (small white balls), N (light grey balls on phenanthroline ligands). H-atoms and lattice solvent molecules have been omitted for clarity. The benzoate; 4-methoxy-benzoate; 4-ethyoxy-benzoate; 4-fluoro-benzoate; 4,7-dimethoxy-phenanthroline; and phenanthroline ligands shown in Figures 2A-F, respectively, are coordinated to Eu in the core (the Eu in the EusTiw cages and the Eu2Ti4 cages) and capture incident light. The direct coordination of these ligands, known herein as “light-harvesting” ligands and as “antenna” ligands, allows for efficient energy transfer to Eu, reducing the possibility for losses such as vibrational losses. Also shown in Figure 2E, although not essential to the invention, are methacrylate solubilising co-ligands (methacrylate cage groups). These improve the solubility of the POT in a polymer matrix. The same function can be achieved by moieties that are part of the light-harvesting ligands, for example alkoxy or alkyl groups. Droplet flow synthesis The inventors have developed an improved synthesis route for POTs, using droplet microfluidics. Droplet microfluidic technology in general is known. However, this technology has not been implemented for POT manufacture. Suitable solvents include THF. The solvent is chosen so that the precursors can dissolve in the solvent and react with each other and so that the product has a low enough solubility to come out of solution when formed. Suitable antisolvents include acetonitrile and hexane. The antisolvent is added so that the product crystallises out of solution and a crystalline powder is obtained directly from the reactor. The carrier fluid can be liquid or gaseous. Suitable carrier fluids include perfluorinated compounds such as the Galden perfluorinated HT series and inert gases. The carrier fluid is an immiscible liquid or gas that causes the reagent phase to separate into a line of discrete, near-identical, low-volume droplets that passes through the channel at a regular speed. Due to their small (usually sub microlitre) volume, the droplets are exceptionally uniform with respect to chemical composition and temperature, and so provide an extremely controlled environment for chemical reactions. In the case of the perfluorinated liquid, the droplets are kept away from the channel walls by this liquid. This effectively lubricates the channel wall and prevents fouling due to precipitation of reactants or products on the channel wall. This ensures a constant, unchanging reaction environment. The carrier fluid must be inert and immiscible with all other components in the reaction mixture, so that the solvents and reactants can form droplets. The precursors used depend on the product being synthesised. For Eu-doped polyoxotitanates, suitable precursors include Eu(CH3COO)3; Eu[(CH3)2CH(CO)2]3; Ti(OiPr)4; titanium bis(acetylacetonate)dichloride; and ligand compounds. Depending on the POTs being manufactured, other lanthanides may be used, such as Samarium, Terbium, Erbium and Ytterbium. The droplets may be brought up to the reaction temperature by any suitable method, such as a brass heating rod or an oil bath. A droplet flow reactor for use in the method of the invention may comprise a mixing junction. Precursors dissolved in solvent may be flowed into the mixing junction with a carrier fluid. The carrier fluid creates droplets, each of which functions as a miniature chemical reactor in which the precursors react to form the desired POT. The droplets provide an efficient environment in which the reaction occurs: reaction times of 3 to 10 minutes are possible for POT synthesis, which offers a significant time saving compared to conventional methods, which are on the scale of hours for synthesis of the same products. The residence time in the reactor depends on both the flow rate and the tubing length and can be significantly longer if desired, up to a few hours. The progress of the reaction can be measured by in-line fluorescence, by virtue of the unique photoluminescence properties of the product. A flow rate of from 0.040 to 0.250 ml / min may suitably be used. In addition, the POT forms as a white crystalline product, which is visible in the droplets with the naked eye. The POT product may be collected and separated on exit from the reactor tubing, as a crystalline powder. Another major benefit of this synthesis route is that it can be conducted at ambient pressure, making it both environmentally and economically efficient compared to known POT synthesis routes. The carrier fluid may be a liquid or a gas. Gaseous carrier fluids are preferred because they are both cheaper and cleaner than liquid carrier fluids, but the method can be implemented with either. A suitable apparatus for use with the method is illustrated schematically in Figure 1. Droplet flow reactor 100 comprises injection inlets 102a, 102b and 102c. The number of injection inlets may be varied depending on precursors, solvents, antisolvents and carrier fluids used. In mixer 104 (mixing junction), droplets are formed, each droplet comprising all of the precursors and acting as a microreactor. The droplets travel through tubing 106, which may be coiled as shown at 108. The temperature in the coil 108 can be controlled by any suitable means, such as oil bath 110 ora central heating element within the coil 108 (not shown). A temperature of 80 °C is sufficient for POT synthesis in droplet flow reactor 100. Although coiling 108 is efficient for temperature control and space, it is not essential for the synthesis to complete and other configurations for droplet flow reactor 100 are possible. The POT product is collected at 112 on exit from tubing 106. The carrier fluid may be recycled back to the start of the process (not shown). POT-polymer composite materials POTs can be dispersed in a polymer matrix, to make them usable for a variety of applications. Previous means for photoluminescence have involved quantum dots or organic dyes. Compared to quantum dots, which need to have special manufacturing controls to make and maintain them in a monodisperse state, POTs are molecules, therefore are always monodisperse. Compared to organic dyes, which suffer from photobleaching, POTs are stable over time when subjected to light, because the fluorophore is inorganic, i.e. a lanthanide. Polymer matrices may quench the luminescent properties of a simple lanthanide-ligand complex by changing the coordination environment of the lanthanide and its ligands. The use of POTs overcomes this drawback, because the coordination of the lanthanide and its ligands is protected by the rigid Ti-O-La core framework, thereby maintaining the photophysical characteristics of the lanthanide in the core. Furthermore, the substitution of the ligands, for example benzoate ligands, does not alter the structure of the metal oxide core. This means that absorption spectrum effects can be tied to the ligands used for a single type of metal oxide core cage. The PLQY of POTs outside of a polymer matrix is usually greater than that achieved within a polymer matrix. However, whilst POTs alone are interesting in a laboratory setting, solubilizing POTs into a polymer matrix renders them useful in a variety of real-world applications whilst still achieving a good PLQY. POTs may be dispersed into a variety of polymers. Any polymer that may be made into a substantially transparent film, coating or sheet may be implemented. Suitable polymers include polyethylene (PE), polypropylene (PP), polymethyl methacrylate (PMMA), polycarbonate (PC), ethylene-vinyl acetate (EVA), acrylates such as acrylate paint, and polyvinyl chloride (PVC). For example, polytunnels used in agriculture are typically made from PE. The plants grown within may benefit from increased amounts of light in the wavelength range that is suitable for photosynthesis, if a POT-PE composite film was used instead of conventional PE. PC is used today for glass alternatives and may be used for greenhouse panels. Similar to a polytunnel, plants inside a greenhouse utilizing POT-PC composite panels may benefit from increased amounts of the best wavelengths of light for photosynthesis. POT-polymer film composites and paint-type coatings may be made to retrofit existing greenhouses, without needing to replace the panels, for the same benefit. POT-polymer composites may be manufactured by any suitable polymer processing route. For example, solution casting, photopolymerization, extrusion, and others. The POT-polymer composites of the invention are preferably substantially transparent in the visible spectrum. The thickness of the POT-polymer composites may be selected based on the end use application. For example, polytunnel sheeting may have a thickness of approximately 150-200 pm; siding materials may have a thickness of approximately 1-10 mm; painttype coatings may have a thickness of approximately 1-500 pm, such as 1-300 pm, for example 30-300 pm or 1-10 pm. Applications of the invention The composites and the novel POTs of the invention are particularly suitable for agricultural application. Plants that are grown in polytunnels or in greenhouses may benefit from increased amounts of light in the wavelength range that is useful for photosynthesis, when POTs are implemented in greenhouse panels or in polytunnel films. Greenhouse panels may be rigid plastic, with POTs dispersed in the rigid plastic, or alternatively glass or any other rigid transparent material, with a POT-polymer composite film disposed thereon. A schematic of how the invention may be implemented in agriculture is shown in Figure 3. A downconverter panel 300 is placed between the Sun 302 and a plant 312. The panel 300 comprises POTs 306 dispersed in a film or panel 308. Solar radiation passes through the panel 300 to the plant 312. Incident solar radiation has a wavelength spectrum 304. Some of the incident light passes through panel 300 unchanged. Some of the light is absorbed by the POTs and emitted at longer wavelength 310. The proportion of useful wavelength radiation 310 is increased for the plant by the POTs 306 in the panel 300. The energy available for photosynthesis is thus increased compared to a panel without POTs. The inventive compounds may be used in a coating or paint. A coating or paint according to the invention comprises the POTs described above and / or POTs made according to the method described above. A coating or paint according to the invention is preferably transparent or translucent. The coating or paint may be used, for example, to retrofit a greenhouse with spectral downconversion capability, by applying the coating or paint to an existing greenhouse panel. This may be more practical than replacing existing panels and provides a quick and convenient method by which to increase agricultural efficiency. The paint or coating may be applied in applications other than agriculture, for example, but not limited to, UV protection for buildings and vehicles; art installations; safety signage; and other applications. A non-limiting method of manufacturing a coating or paint in accordance with the invention is as follows: A solution of the desired polyoxotitanate (POT) in acrylic paint in ethanol is prepared by diluting the paint in the ethanol and then adding and combining the POT into the diluted paint. A suitable ratio is about 1 to 15 mg of POT per gram of acrylate in the paint, for example 37.5 mg of POT per 5 g of paint, to give a final concentration of 15 mg of POT per g of acrylate. The ratio of paint to ethanol is not particularly limited. A suitable ratio is 2 ml of ethanol in 1 g of paint. The mixture of paint, ethanol solvent and POT is stirred for approximately 10 hours, depending on the amounts and ratios of reagents, in a sealed vessel to prevent solvent evaporation. The solution is then coated onto a substrate, for example by pouring, spraying, dip coating, spin coating or another method. The substrate may be any suitable substrate, for example a glass plate. The coated substrate is covered to avoid dust settling in the solution, and is left to evaporate and dry, for example for at least 24 hours. The residual material forms a transparent film. The film thickness may typically be 0.03 to 0.3 mm thick, depending on the amounts and concentrations used in the preparation of the solution. The inventive compounds may be used as a fluorescent chemical in any suitable application. Currently-known fluorescent compounds may be substituted in part or in full by the inventive compounds. The inventive materials may be implemented in a healthcare capacity. It is known that evening exposure to blue light disrupts the circadian rhythm. The inventive materials may be used to convert ambient light to a longer wavelength, thereby increasing the availability of red light and decreasing the amount of blue light. The inventive materials may be implemented in this setting as, for example, coatings for spectacles lenses; lampshades, lightbulbs, LEDs, GaN-based lights and other types of light; computer and other device screen filters; window coatings; and other such devices. Some high-value objects and devices deteriorate over time when exposed to UV radiation. Such objects and devices may be encapsulated in an encapsulant, such as a polymeric encapsulant. The inventive materials may be incorporated into an encapsulant to reduce or prevent UV damage to an encapsulated item. For example, a circuit board may be encapsulated in a polymer incorporating the inventive materials. The inventive materials may be used to prevent or retard UV damage to a polymer into which they are incorporated. For example, a polytunnel film, typically used for agriculture, experiences high solar UV exposure, which deteriorates the polymer over time. Incorporating the inventive materials into the polymer film may retard this degradation, by converting the harmful UV radiation to longer wavelengths. Other polymeric materials exposed to the elements may similarly benefit from incorporation of the inventive materials. The inventive materials may be used in display technologies. Quantum dots and other materials currently in use for display technologies are rather costly and could be replaced in part or in full by the inventive compounds. The inventive material may be used in 3D printing filaments. Typically, a plastic such as PIA PTE, ABS, etc. contains a dye or pigment to give colour to the polymer and thereby to the printed product. The dye or pigment may be replaced or supplemented by POTs, resulting in a filament that glows under UV. Such a filament may be prepared in a manner similar to that described above with respect to POT-containing films: compounding and extruding polymer and POTs into a masterbatch, adjusting the concentration as required; extruding to a filament ready for 3D printing. Other uses of the inventive materials are contemplated, such as solar photovoltaic encapsulation; sensors, such as light detectors; fluorophores for bioassays; UV protection; lighting; encapsulants; screens and displays, for example televisions and device screens; toys; hazard signs; paints, for example for the creative and construction industries; printing inks; suncream; tattoo inks; glow sticks; security paint; anti-counterfeit measures; and luminescent material for clothing. The application examples presented here are merely illustrative of the myriad benefits of the invention and are not limiting on the scope of the claims. EXAMPLES Example 1: production of a downconverter polymer product using solution casting: A solution of the desired polyoxotitanate (POT) in polymethylmethacrylate (PMMA) in dichloromethane and toluene is prepared by first dissolving the POT in dichloromethane, then adding toluene and PMMA. The molecular weight of PMMA may be approximately 350,000, but this is not critical for the process. Typical ratios are 1-10 mg of POT per g of PMMA (e.g., 25 mg of POT per 5 g of PMMA for a final concentration of 5 mg of POT per g of PMMA). Per g of PMMA, typically 4 ml of dichloromethane and 4 ml of toluene are used, but the ratios and amounts can be varied if needed. The POT / PMMA / solvent mixtures are stirred until a clear solution is obtained, approximately two hours, depending on amounts and ratios of reagents. The solution is poured into an open-top mould consisting of a glass plate (the bottom of the mould) and a “border” on 4 sides made from polytetrafluoroethylene of defined thickness (typically 2 mm, but other sizes can be used as desired). The mould is covered to avoid dust falling into the solution and left to evaporate for at least 24 hours. The residual material forms a transparent film; typical thickness is 0.1 - 0.5 mm, depending on the amounts and concentrations used in the preparation of the solution. Example 2: production of a downconverter polymer product using photopolymerization: A solution of polyoxotitanate in a mixture of acrylate monomers is prepared. The mixture of acrylate monomers is not crucial. A suitable mixture is 60 wt% isobornyl methacrylate, 30 wt% isodecyl acrylate and 10 wt% 1,6-hexanediol dimethacrylate. A solution of photoinitiator in the same acrylate formulation is added to the poly oxotitanate solution. The type of photoinitiator and its concentration in the acrylate solution is not crucial. A suitable example is 1 wt% 2-hydroxy-2-methyl-1-phenylpropanone, commercially available as SpeedCure 73 from Sartomer. A suitable ratio of the polyoxotitanate solution to the photoinitiator solution is 90:10 by volume. This ratio is not critical for the production method. The final concentration of polyoxotitanate in acrylate may be in the range of 1-10 wt%, e.g. 5 mg of POT in 1 g of acrylate. The solution is degassed to remove oxygen from the mix, for example by repeated application of vacuum and re-filling the vessel with an inert gas such as argon or nitrogen. The degassed solution is then injected into injection moulds consisting of two glass plates separated by a polytetrafluoroethylene spacer of suitable size and thickness (typically 0.05 - 1 mm). The bottom glass plate is typically made of borosilicate glass that has either been pre-treated to release the resulting film (by application of a perfluorosilane coating, e.g. trichloro (1H, 1H, 2H, 2H-perfluorooctyl)silane)) or to bond with the resulting film (by application of a polymerizable silane coating, e.g., 3-(trimethoxysilyl)propyl methacrylate. The top glass plate is typically made from fused silica (“quartz”) glass, into which two holes had been drilled to allow for injection of the monomer mix. This top plate will also typically have been treated with a suitable perfluorosilane coating to facilitate the release of the resulting film. The filled moulds are then placed under a suitable UV light source (compatible with the photoinitiator used) and cured, typically from 10-120 minutes. Example 3: absorbance and emission of a downconverter polymer product The emission spectrum of the downconverters of the invention are controlled solely by the lanthanide in the core of the POTs. The matrix material, its thickness, the concentration of the POTs and the exact formula of the POTs are all irrelevant for the emission spectrum. The emission spectra of an example POT in PMMA matrix are shown in Figure 5. The absorbance spectrum of the downconverters of the invention is influenced by both the lanthanide in the core and the light-absorbing ligands in the shell of the POTs. The lambda max of a europium-titanium-oxygen complex without any ligands is approximately 200 nm. The type of ligands in the shell and the manner in which they are coordinated to the metal oxide core affect the absorption spectrum of the overall compound. Figure 6 shows the spectra of a known POT having 4-fBu benzoate ligands and new POT having 4-OMe ligands. The lambda max of the new compound is shifted closer to 400 nm, which is desirable in order to capture more photons from incident solar radiation to be emitted at longer, red wavelengths. Example 4: general method for synthesising POTs using droplet flow synthesis • Weigh La(OAC)3 (e.g. Eu(OAC)3) and ligands into a vial, add solvent (e.g. tetrahydrofuran) and Ti(OiPr)4 and sonicate for 30 mins to achieve complete dissolution. These precursors may be all combined, or alternatively two precursor flows may be used; • Load precursors into syringe(s); • Add antisolvent (e.g. acetonitrile or hexane) into another syringe; • Place carrier fluid (e.g. a perfluorinated fluid) into a separate syringe; • Place the syringes on different pumps and connect via tubes (e.g. perfluoroalkoxy tubing) to the mixer (e.g. a 9 meters long PFA tube, immersed in a temperature-controlled oil bath); • Set the desired temperature and flow rate; • Start the experiment and collect the product as it flows out of the system; • Remove the carrier fluid and prepare the sample for characterisation. Droplet flow synthesis such as this method is suitable for the novel POTs of the invention as well as POTs in general, including those already known in the literature. A schematic of the apparatus is shown in Figure 1. The following POTs were made using this general method, with residence time and temperature in the reactor as indicated. The first two compounds are known in the literature, but have significantly longer synthesis times when using conventional methods such as autoclave and Schlenk-type reactors. X-ray diffraction confirmed that these compounds made via droplet flow synthesis were the same as made when via conventional synthesis routes. Conventional method* 12 hours 10 hours Temperature Room temperature O o o 00 o o o co O o o co o o o CO Q o o co O 0 0 co O 0 0 co O 0 0 co Residence time 3 minutes 10 minutes 10 minutes 10 minutes 10 minutes 10 minutes 10 minutes 10 minutes 10 minutes Ligand 4-terbutylbenzoic acid 4-terbutylbenzoic acid 4-isopropylbenzoic acid 4-fluorobenzoic acid benzoic acid 4-methoxybenzoic acid 4-methoxybenzoic acid 4-ethoxybenzoic acid 4-iso-propoxy-benzoic acid Polyoxotitanate o f CM CO o CM o Km o o LD I (D CD o co o d o ^"cO D LU EusTiw EUsTiloC2540g4N2Hl72F34 EusTiw Ce4 H56 EuOso Ti4 H503 Eui6 Ti2o C562O252N5 EusTiw EusTiw * data from Inorg. Chem. 2017, 56, 20, 12186-12192, September 28, 2017; DOI: 5 10.1021 / acs.inorgchem.7b01522 Example 5: synthesis of POTs with 4-tert-butylbenzoic acid ligands Eu(Ac)3.xH2O (0.0192 g. 0.05 mmol) and 4-tert-butylbenzoic acid (0.044 g, 0.25 mmol) were added to 0.75 ml of tetrahydrofuran in a glass vial, Ti(O / Pr)4 (18.0 pl, 0.06 mmol) was added. The mixture was ultrasonicated for 30 minutes for complete dissolution. The 5 clear precursor solution, hexane and carrier fluid (perfluorinated fluid) was loaded into separate 10 ml Luer Lock Syringe. Syringe pumps were used to inject the solutions into 9 m long PFA tube (kinesis 1.5 mm internal diameter) immersed in an oil bath at 80 °C. The flowrate of the precursor was maintained at 0.030 ml / mins, hexane 0.120 ml / min, and 0.120 ml / min carrier fluid. The solutions met in a mixing junction (manifold Assy 7 10 port), the residence time in the reactor was 10 minutes. The white powder product was collected in a centrifuge tube and centrifuged at 7000 rpm for 2 min, then washed thrice with hexane and dried en vacuo. Single crystals suitable for X-ray diffraction analysis were obtained by recrystallizing the powder with THF and hexane via slow evaporation at room temperature to give colourless block crystals. 15

Claims

1. Polyoxotitanate comprising a metal oxide core and a ligand shell,wherein the metal oxide core comprises titanium, oxygen and a lanthanide;wherein the ligand shell comprises one or more light-harvesting ligands coordinated to the lanthanide;wherein the one or more light-harvesting ligands comprises one or more of a substituted extended aromatic ligand and a benzoate ligand.

2. Polyoxotitanate according to claim 1, wherein the lanthanide is europium and wherein the one or more light-harvesting ligands comprises at least one selected from a benzoate ligand and a substituted phenanthroline ligand according to the following structures:wherein R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from H, C1-30 linear alkoxy, C1-30 branched alkoxy, C1-30 linear alkyl, C1-30 branched alkyl, and C1-30 fatty acids, with the proviso that at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is not Hwherein R", R1", RIV, Rv and RVI are each independently selected from H, F, isopropyl, linear or branched C1-30 alkoxy, linear or branched C1-4 alkyl and linear or branched C5-30 alkyl.

3. Polyoxotitanate according to claim 2, wherein R1 and R8 are H and wherein R2, R3, R4, R5, R6 and R7 are each independently selected from C12-18 linear alkyl, C12-18 branched alkyl, C12-18 linear alkoxy, C12-18 branched alkoxy; andwherein R" and RVI are H and wherein R1", RIV and Rv are each independently selected from C12-18 linear alkyl, C12-18 branched alkyl, C12-18 linear alkoxy, C12-18 branched alkoxy.

4. Polyoxotitanate according to claim 1, wherein the one or more light-harvesting ligands comprises a ligand selected from 4-methoxybenzoic acid, 4-isopropylbenzoic acid, benzoic acid, and 4,7-dimethoxy-1,10-phenanthroline.

5. Polyoxotitanate according to any preceding claim, wherein the ligand shell comprises one or more solubilizing ligands that are separate from the one or more lightharvesting ligands, optionally wherein the one or more solubilizing ligands comprises methacrylate, a fatty acid, or a carboxylic acid.

6. Polyoxotitanate according to any preceding claim, wherein the metal in the metal oxide core is selected from EusTiw and Eu2Ti4.

7. Polyoxotitanates according to claim 1 and having the formula Eu8Tii0(p3-O)i4(CH3COO)2(OMeba)34(H2O)4(THF)2(HOMeba)2, or Eu8Tiio(M3-0)i4(CH3COO)2(iPrba)34(H20)4(THF)2(HiPrba)2, Eu8Tiw(|J3-O)i4(CH3COO)2(ba)34(H2O)4(THF)2(Hba)2, or Eu2Ti406(OMephen)2(ma)io.

8. Method of making polyoxotitanates in a droplet flow reactor, the method comprising:a. providing precursors comprising a lanthanide compound, a titaniumoxygen compound and a ligand;b. combining the precursors and a solvent in one or more precursor flows;c. injecting the precursors, a carrier fluid and an antisolvent into a reaction vessel and allowing the precursors to react to form a polyoxotitanate;d. collecting the polyoxotitanate as it exits the reaction vessel.

9. Method according to claim 8, wherein the reaction vessel is a tube.

10. Method according to claim 8 or claim 9, wherein the temperature of the reactionvessel is up to 300 °C, such as from 10 °C to 90 °C.

11. Method according to any of claims 8 to 10, further comprising: e. removing the carrier fluid.

12. Method according to any of claims 8 to 11, wherein the lanthanide compound is Eu(CH3COO)3.

13. Method according to any of claims 8 to 12, wherein the precursors comprise Ti(O / Pr)4.

14. Method according to any of claims 8 to 13, wherein the solvent is selected from tetrahydrofuran (THF), an alcohol and acetate.

15. Method according to any of claims 8 to 14, wherein the antisolvent is acetonitrile or hexane.

16. Use of a droplet flow reactor to manufacture polyoxotitanates.

17. Composite material comprising polyoxotitanates dispersed in a polymer matrix, wherein the polyoxotitanates are as defined in any of claims 1 to 7 or made according to the method defined in any of claims 8 to 15.

18. Composite material according to claim 17, wherein the polymer matrix is one or more of polyethylene, polypropylene, polymethylmethacrylate, polycarbonate, polyether ether ketone, polyvinylacetate, ethylene-vinyl acetate, and acrylate.

19. Polytunnel sheeting comprising the composite material of claim 17 or claim 18.

20. Coating or paint comprising the composite material of claim 17 or claim 18.

21. Method for manufacturing a composite film by photopolymerization, comprising:a. preparing a solution of monomers, polyoxotitanates and photoinitiator;b. injecting the solution into a mould;c. curing the solution in UV light; andd. removing the cured composite polymer film from the mould.

22. Method for manufacturing a composite film by solution casting, comprising:a. preparing a solution of polymer, polyoxotitanates and solvent;b. pouring the solution into a mould;c. curing the solution by solvent evaporation;d. removing the cured composite polymer film from the mould.

523. Use of europium-containing polyoxotitanates in agriculture to increase the amount of red light available to plants.

24. Use of polyoxotitanates to increase the efficiency of a photovoltaic cell. 1025. Use of polyoxotitanates to decrease UV damage of an encapsulated material.

26. Use according to any of claims 23 to 25, wherein the polyoxotitanates are as defined in any of claims 1 to 7 or are made according to the method of any of claims 8 15 to 15.AMENDMENTS TO THE CLAIMS HAVE BEEN FILED AS FOLLOWS:CLAIMS1. Polyoxotitanate comprising a metal oxide core and a ligand shell,wherein the metal oxide core comprises titanium, oxygen and a lanthanide;wherein the ligand shell comprises one or more light-harvesting ligands coordinated to the lanthanide;wherein the lanthanide is europium and wherein the one or more lightharvesting ligands comprises at least one substituted phenanthroline ligand according to the following structure:21 03 25wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently selected from H, Ci-30 linear alkoxy, C1-30 branched alkoxy, C1-30 linear alkyl, C1-30 branched alkyl, and C1-30 fatty acids, with the proviso that at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is not H, and wherein the light-harvesting ligands are all associated with the Eu atoms in the core.

2. Polyoxotitanate according to claim 1, wherein the one or more light-harvestingligands comprises at least one benzoate ligand according to the following structure:21 03 25wherein R", R1", RIV, Rv and RVI are each independently selected from H, F, isopropyl, linear or branched C1-30 alkoxy, linear or branched C1-4 alkyl and linear or branched C5-30 alkyl.

3. Polyoxotitanate according to any of claims 1 or 2, wherein R1 and R8 are H andwherein R2, R3, R4, R5, R6 and R7 are each independently selected from C12-18 linear alkyl, C12-18 branched alkyl, C12-18 linear alkoxy, C12-18 branched alkoxy.

4. Polyoxotitanate according to any of claims 2 or 3, wherein R" and RVI are H andwherein RIH, RIV and Rv are each independently selected from C12-18 linear alkyl, C12-18 branched alkyl, C12-18 linear alkoxy, C12-18 branched alkoxy.

5. Polyoxotitanate according to claim 1, wherein the one or more light-harvestingligands comprises a ligand selected from 4-methoxybenzoic acid, 4-isopropylbenzoic acid, benzoic acid, and 4,7-dimethoxy-1,10-phenanthroline.

6. Polyoxotitanate according to any preceding claim, wherein the ligand shellcomprises one or more co-ligands that are separate from the one or more light-harvesting ligands, optionally wherein the one or more co-ligands comprises methacrylate, a fatty acid, or a carboxylic acid.

7. Polyoxotitanate according to any preceding claim, wherein the metal in themetal oxide core is selected from EusTiw and Eu2Ti4.

8. Polyoxotitanates according to claim 1 and having the formulaEu2Ti4O6(OMephen)2(ma)w.21 03 259. Method of making polyoxotitanates according to any of claims 1 to 8 in a dropletflow reactor, the method comprising:a. providing precursors comprising a lanthanide compound, a titanium-oxygen compound and a ligand;b. combining the precursors and a solvent in one or more precursor flows;c. injecting the precursors, a carrier fluid and an antisolvent into a reaction vessel and allowing the precursors to react to form a polyoxotitanate;d. collecting the polyoxotitanate as it exits the reaction vessel.

10. Method according to claim 9, wherein the reaction vessel is a tube.

11. Method according to claim 9 or claim 10, wherein the temperature of thereaction vessel is up to 300 °C, such as from 10 °C to 90 °C.

12. Method according to any of claims 9 to 11, further comprising:e. removing the carrier fluid.

13. Method according to any of claims 9 to 12, wherein the lanthanide compound isEu(CH3COO)3.

14. Method according to any of claims 9 to 13, wherein the precursors compriseTi(O / Pr)4.

15. Method according to any of claims 9 to 14, wherein the solvent is selected fromtetra hydrofuran (THF), an alcohol and acetate.

16. Method according to any of claims 9 to 15, wherein the antisolvent isacetonitrile or hexane.

17. Use of a droplet flow reactor to manufacture polyoxotitanates according to anyof claims 1 to 8.

18. Composite material comprising polyoxotitanates dispersed in a polymer matrix,wherein the polyoxotitanates are as defined in any of claims 1 to 8.21 03 2519. Composite material according to claim 18, wherein the polymer matrix is one ormore of polyethylene, polypropylene, polymethylmethacrylate, polycarbonate, polyether ether ketone, polyvinylacetate, ethylene-vinyl acetate, and acrylate.

20. Polytunnel sheeting comprising the composite material of claim 18 or claim 19.

21. Coating or paint comprising the composite material of claim 18 or claim 19.

22. Method for manufacturing a composite film by photopolymerization, comprising:a. preparing a solution of monomers, polyoxotitanates and photoinitiator;b. injecting the solution into a mould;c. curing the solution in UV light; andd. removing the cured composite polymer film from the mould, wherein the polyoxotitanates are defined in any of claims 1 to 8.

23. Method for manufacturing a composite film by solution casting, comprising:a. preparing a solution of polymer, polyoxotitanates and solvent;b. pouring the solution into a mould;c. curing the solution by solvent evaporation;d. removing the cured composite polymer film from the mould, wherein the polyoxotitanates are defined in any of claims 1 to 8.

24. Use of polyoxotitanates according to any of claims 1 to 8 in agriculture toincrease the amount of red light available to plants.

25. Use of polyoxotitanates according to any of claims 1 to 8 to decrease UVdamage of an encapsulated material.

26. Use according to any of claims 24 to 25, wherein the polyoxotitanates are asdefined in any of claims 1 to 8.Application No: GB2304166.8Claims searched: 1-7 and in part 17-20Examiner: Dr Danielle MerrikinDate of search: 18 May 2023Patents Act 1977: Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance X 1-7, 17, 18, and 20 Inorganic chemistry, vol. 59, no. 15, 2020, Shu Xian-Ping et al., "Eu-phen Bonded Titanium Oxo-Clusters, Precursors for a Facile Preparation of High Luminescent Materials and Films.", p. 10422-10429 see whole document X 1-6, 17, 18, and 20 CN113061368 A See Summary of Invention X 1-6, 17, 18, and 20 Chemical communications (Cambridge, England), vol. 59, no. 3, 2023, Liu Wei-Dong et al., "Circularly polarized luminescence and performance modulation of chiral europium-titanium (Eu2Ti4)-oxo clusters.", p. 346-349. See whole document X 1-7, 17, 18, and 20 Inorganic chemistry, vol. 56, no. 20, 2017, Lu Dong-Fei et al., "High-Nuclearity Lanthanide-Titanium Oxo Clusters as Luminescent Molecular Thermometers with High Quantum Yields.", p. 12186-12192. See whole document v A 1-6, 17, 18, &20 Inorganic chemistry, vol. 59, no. 17, 2020, Zheng Hao et al., "Lanthanide-Titanium Oxo Clusters as the Luminescence Sensor for Nitrobenzene Detection.", p. 12404-12409. See whole document X 1-5, 17, 18, and 20 Chemistry (Weinheim an der Bergstrasse, Germany), vol. 27, no. 2, 2020, Deng Yong-Kai et al., "Preparation of a Lanthanide-Titanium Oxo Cluster-Polymer Composite by Cu-Catalyzed Click Chemistry.", p. 614-617. See abstractCategories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if P Document published on or after the declared priority date but combined with one or more other documents of same category. before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:Search of GB, EP, WO &US patent documents classified in the following areas of the UKCX :Worldwide search of patent documents classified in the following areas of the IPC__________________B01J; C09K__________________________________________________________The following online and other databases have been used in the preparation of this search report______ WPI, EPODOC, Patent Fulltext, INSPEC, BIOSIS, MEDLINE, XPESP, SPRINGERInternational Classification:Subclass Subgroup Valid From C09K 0011 / 77 01 / 01 / 2006 B01J 0008 / 00 01 / 01 / 2006 B01J 0019 / 00 01 / 01 / 2006 COIF 0017 / 30 01 / 01 / 2020 C01G 0023 / 00 01 / 01 / 2006 C08F 0002 / 04 01 / 01 / 2006 C08F 0002 / 48 01 / 01 / 2006 C09D 0001 / 00 01 / 01 / 2006Application No: GB2304166.8Claims searched: 8-15, and in part 17-20Examiner: Dr Danielle MerrikinDate of search: 20 July 2023Patents Act 1977Further Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance A 8-15 J. AM. CHEM. SOC., M. Faustini et al., vol 135, 2013, "Microfluidic Approach toward Continuous and Ultrafast Synthesis of MetalOrganic Framework Crystals and Hetero Structures in Confined Microdroplets", p. 14619-14626 see whole document A 8-15 CHEMICAL ENGINEERING SCIENCE, vol. 112, 2014, Zhao Chun-Xia et al., "Titania microparticles using a facile microfluidic masstransfer control method", p. 10-14. see whole document, in particular Figure 2 and Experimental A 8-15 CHEMICAL ENGINEERING SCIENCE, vol. 191, 2018, Stolzenburg Pierre et al., "Microfluidic synthesis of metal oxide nanoparticles via the nonaqueous method", p. 500-510. see whole document, in particular Materials and Methods A 8-15 MICROFLUIDICS AND NANOFLUIDICS, vol. 14, 2013, Zhao Chun-Xia et al., "One-step fabrication of titania hollow spheres by controlled interfacial reaction in a droplet-based microfluidic system", p. 703-709 see whole document, in particular Materials and Methods A 8-15 CHEM. MATER., vol 21, 2009, Eun Tai Hee et al., "Single-Step Fabrication of Monodisperse TiO2 Hollow Spheres with Embedded Nanoparticles in Microfluidic Devices", p. 201-203 see whole document A 8-15 CHEM. COMM UN., 2009, Gong Xiuqing et al., "Design and fabrication of monodisperse hollow titania microspheres from a microfluidic droplet-template", p. 4690-4692 see whole document X 17, 18, and 20 INORGANIC CHEMISTRY, vol. 59, no. 15, 2020, Shu Xian-Ping et al., "Eu-phen Bonded Titanium Oxo-Clusters, Precursors for a Facile Preparation of High Luminescent Materials and Films", p. 10422-10429 see whole document X 17, 18, and 20 CN113061368 A see Summary of InventionX 19 AU 4400700 A (BAYER AG;) see whole document X 19 EP 1621071 Al (DON &LOW LTD) see whole document X 19 JP 2000355632 A (KASEI CO C I) see whole documentCategories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if P Document published on or after the declared priority date but combined with one or more other documents of same category. before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:International Classification:Subclass Subgroup Valid From C09K 0011 / 77 01 / 01 / 2006 BOU 0008 / 00 01 / 01 / 2006 B01J 0019 / 00 01 / 01 / 2006 COIF 0017 / 30 01 / 01 / 2020 C01G 0023 / 00 01 / 01 / 2006 C08F 0002 / 04 01 / 01 / 2006 C08F 0002 / 48 01 / 01 / 2006 C09D 0001 / 00 01 / 01 / 2006Application No: GB2304166.8Claims searched: 16Examiner: Dr Danielle MerrikinDate of search: 20 July 2023Patents Act 1977Further Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance v A 16 CHEMICAL ENGINEERING SCIENCE, vol. 112, 2014, Zhao Chun-Xia et al., "Titania microparticles using a facile microfluidic masstransfer control method", p. 10-14. see whole document, in particular Figure 2 and Experimental X 16 CHEMICAL ENGINEERING SCIENCE, vol. 191, 2018, Stolzenburg Pierre et al., "Microfluidic synthesis of metal oxide nanoparticles via the nonaqueous method", p. 500-510. see whole document, in particular Materials and Methods X 16 MICROFLUIDICS AND NANOFLUIDICS, vol. 14, 2013, Zhao Chun-Xia et al., "One-step fabrication of titania hollow spheres by controlled interfacial reaction in a droplet-based microfluidic system", p. 703-709 see whole document, in particular Materials and Methods X 16 CHEM. MATER., vol 21, 2009, Eun Tai Hee et al., "Single-Step Fabrication of Monodisperse TiO2 Hollow Spheres with Embedded Nanoparticles in Microfluidic Devices", p. 201-203 see whole document X 16 CHEM. COMMUN., 2009, Gong Xiuqing et al., "Design and fabrication of monodisperse hollow titania microspheres from a microfluidic droplet-template", p. 4690-4692 see whole documentCategories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if p Document published on or after the declared priority date but combined with one or more other documents of same category. before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:The following online and other databases have been used in the preparation of this search reportSEARCH-PATENT, SEARCH-NPLInternational Classification:Subclass Subgroup Valid From C09K 0011 / 77 01 / 01 / 2006 BOU 0008 / 00 01 / 01 / 2006 B01J 0019 / 00 01 / 01 / 2006 COIF 0017 / 30 01 / 01 / 2020 C01G 0023 / 00 01 / 01 / 2006 C08F 0002 / 04 01 / 01 / 2006 C08F 0002 / 48 01 / 01 / 2006 C09D 0001 / 00 01 / 01 / 2006Application No: GB2304166.8Examiner: Dr Danielle MerrikinClaims searched: 21Date of search: 20 July 2023Patents Act 1977Further Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance v A 21 US 2010 / 0010138 Al (KIKUCHI et a| ) see whole document, in particular paragraphs [0059], [0065], [0068], and [0101]-[0104] X 21 JP 7232877 B (MOLECULAR IMPRINTS INC) see whole document, in particular Summary and paragraph [0044] v A 21 US 7101942 B2 (MOSZNER et al.) see whole document X 21 JP 5056827 B2 (KONICA MINOLTA HOLDINGS INC) see whole document, in particular paragraphs [0034], [0046], and [0133]-[0134] X 21 US 2014 / 0096893 Al (VEERASAMY) see whole document, in particular paragraphs [0064]-[0067]Categories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if P Document published on or after the declared priority date but combined with one or more other documents of same category. before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:International Classification:SubclassSubgroupValid FromSubclass Subgroup Valid From C09K 0011 / 77 01 / 01 / 2006 BOU 0008 / 00 01 / 01 / 2006 B01J 0019 / 00 01 / 01 / 2006 COIF 0017 / 30 01 / 01 / 2020 C01G 0023 / 00 01 / 01 / 2006 C08F 0002 / 04 01 / 01 / 2006 C08F 0002 / 48 01 / 01 / 2006 C09D 0001 / 00 01 / 01 / 2006Application No: GB2304166.8Examiner: Dr Danielle MerrikinClaims searched: 22Date of search: 20 July 2023Patents Act 1977Further Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance v A 22 CN 114249906 A (UNIV BEIJING CHEMICAL) see whole document, in particular Summary of Invention X 22 CN 111786024 A (UNIV XIAMEN) see whole document, in particular Summary of Invention v A 22 CN 105440298 A (UNIV ZHEJIANG TECHNOLOGY) see whole document, in particular "(3) Invention Content" X 22 Polymer Bulletin, vol. 77, no. 10, 2019, Salomatina E V et al., "Biocompatible compositions based on chitosan and copolymer (lactidetitanium oxide) for engineering of tissue substitutes for wound healing", p. 5083-5101. see whole document, in particular Materials and Methods v A 22 RSC Adv., vol. 6, 2016, Yaokang Lv et al., "Novel Eu-containing titania composites derived from a new Eu(III)-doped polyoxotitanate cage", p. 57-60. See whole document, in particular the experimental in Supplementary Information X 22 Thermochimica ACTA, vol. 705, 2021, Apryatina Kristina Victorovna et al., "Specific features of thermal properties of polymer composites containing conductive nanoparticles in non-conductive polymer matrices". see whole document, in particular ExperimentalCategories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if P Document published on or after the declared priority date but combined with one or more other documents of same category. before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:Search of GB, EP, WO &US patent documents classified in the following areas of the UKCX :Worldwide search of patent documents classified in the following areas of the IPCThe following online and other databases have been used in the preparation of this search report SEARCH-PATENT, SEARCH-NPLInternational Classification:Subclass Subgroup Valid From C09K 0011 / 77 01 / 01 / 2006 B01J 0008 / 00 01 / 01 / 2006 B01J 0019 / 00 01 / 01 / 2006 COIF 0017 / 30 01 / 01 / 2020 C01G 0023 / 00 01 / 01 / 2006 C08F 0002 / 04 01 / 01 / 2006 C08F 0002 / 48 01 / 01 / 2006 C09D 0001 / 00 01 / 01 / 2006

Images