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    • 专利摘要:
    Nickel oxide catalytic film, procedure for obtaining it and its uses. The present invention relates to an improved nickel oxide catalytic film provided with an inorganic part including non-stoichiometric nickel oxides dispersed in an organic matrix, the catalytic film being supported on a substrate. The invention also relates to a process for obtaining the catalytic film as well as its uses as an electrode in electrocatalysis of water or in photocatalysis. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2800224A1
    申请号:ES201930558
    申请日:2019-06-19
    公开日:2020-12-28
    发明作者:Lopez Rafael Abargues；Jaume Noguera；Pastor Juan P Martinez；Julia Sixto Gimenez；Tecedor Miguel Garcia；Pedro J Rodriguez-Canto
    申请人:Universitat Jaume I de Castello；Universitat de Valencia；
    IPC主号:
    专利说明:

    [0002] NICKEL OXIDE CATALYTIC SHEET, PROCEDURE FOR OBTAINING ITS AND ITS USES
    [0004] The present invention is framed in the field of catalysts. In particular, the invention relates to an improved catalytic film based on nickel oxide.
    [0006] The catalytic film of the invention is provided with an inorganic part that includes non-stoichiometric nickel oxides dispersed in an organic part that supports non-stoichiometric nickel oxides, the catalytic film being supported on a substrate.
    [0008] Background of the invention
    [0010] At present, the need to generate clean energy from renewable energies is increasing. The development of clean energies is essential to combat climate change and limit its most devastating effects. One of the sources is the H 2 generation from water hydrolysis. The use of H 2 as a fuel for the generation of electricity in a fuel cell is one of the most promising solutions as it is a completely clean energy since its combustion generates H 2 O as a reaction product.
    [0012] The hydrolysis of water is an endothermic process that requires very high temperatures, around 220 ° C, for the reaction to occur spontaneously. An alternative is the hydrolysis of water at room temperature by electrochemical methods. In this process the following reactions occur:
    [0014] H 2 OOHH 2 (g) O 2 (g) Hydrolysis
    [0015] 2H + (aq) + 2e- ^ H2 (g) Reduction at the cathode (Reduction of water) 2H2O (l) ^ O2 (g) + 4H + (aq) + 4e- Oxidation at the anode (Oxidation of water)
    [0017] The hydrolysis of water by electrochemical means (electrolysis) is carried out by direct electrical current applied between two electrodes, anode and cathode. Thus, at the cathode there is the reduction of water to generate H 2 and at the anode the oxidation of water to produce O 2 is carried out . However, electrolysis of water requires a large amount of extra energy in the form of overpotential, with respect to the theoretically necessary to carry it out, which is 1.23 V, because, as in any chemical reaction, it is necessary to exceed the activation energy of the reaction so that this happens. Catalysts are used to reduce the overpower because they significantly reduce the activation energy.
    [0019] Among the existing materials for use as selective electrodes for the oxidation of water, the oxides of iridium (IrO 2 ) and ruthenium (RuO 2 ) are the electrocatalysts known to date with the best results. These electrocatalysts can also be used for water reduction. However, the significant cost of Ru and Ir, due to their scarcity, is one of the main factors limiting their implementation on an industrial scale.
    [0021] Therefore, because both Ir and Ru are rare and expensive metals, there is a need to develop new metal-based catalysts that are more abundant in the earth's crust and therefore cheaper. The viability of obtaining clean energy in this way depends on, apart from using low-cost materials, that the catalysts can be manufactured with these materials by means of low-cost techniques and that the generation of H 2 is carried out with improved yields.
    [0023] Although the use of photoelectrochemistry in hydrogen production processes has enormous potential, until now it has not been possible to develop an application capable of competing economically with conventional processes, such as methane reforming that allows the production of hydrogen. at a lower cost, although with a significant carbon footprint that must be eliminated.
    [0025] On the other hand, catalysts based on solid state metal oxides such as CoPi, Co-Bi, CoOx, MnOx and NiOx are known. However, most of these oxides are deposited by chemical, electrochemical, physical methods such as sputtering, and photochemical deposition methods.
    [0027] Patent CN103974769 describes the obtaining of metal oxides for catalytic purposes. However, they employ a technique called photochemical metal-organic deposition (PMOD) that requires the use of ultraviolet (UV) radiation. In particular, a precursor is deposited which is then irradiated with UV light until all the organic material is decomposed and metals are formed in a metallic state that are then oxidized using high temperatures. This technique requires several stages, in addition to irradiating with UV light and using high temperatures for the formation of metal oxides and eliminating any organic residue initially present.
    [0029] On the other hand, patent JP2015049973 describes the synthesis of Ni (0) nickel 0 nanoparticles in a metallic state from Ni (+2). After the reaction, the Ni (0) nanoparticles are deposited on an electrode.
    [0031] At a technological level, in order to promote alternative technologies based on the use of renewable energies such as photoelectrocatalysis, it is necessary to reduce both the costs of the materials used and the costs of the manufacturing processes of the devices for generating H 2 . In turn, a continuous improvement of the H 2 generation yields is necessary.
    [0033] Recently, the obtaining of electrodes for the generation of O 2 has been investigated since it is precisely these electrodes that limit the increase in the performance of the water hydrolysis reaction. This is due to the fact that the oxidation reaction of water is more difficult because there are a greater number of species (4 electrons and 4H +) as opposed to the reduction reaction of water (2 electrons and 2H +). This means that, at the anode, the existing overpotentials are very low, while at the cathode high overpotentials are registered due to a higher activation energy of the reaction. Therefore, there is a great kinetic limitation of the electrochemical reaction for the generation of oxygen that also limits the efficiency of the hydrolysis of water by electrocatalysis.
    [0035] There is, therefore, a need to provide an improved catalyst based on metal oxides abundant in the earth's crust, which can be manufactured by low cost techniques and is useful for the oxidation of water to O 2 with good yields.
    [0037] Regarding the photocatalytic properties, there are numerous research works in which mainly broadband semiconductors are used, mainly titanium oxide and zinc oxide.
    [0038] Therefore, there is also a need to develop new improved catalysts for the decomposition of pollutants mainly present in water but also in air, with industrially applicable manufacturing processes.
    [0040] Description of the invention
    [0042] With the catalytic film of the invention, it is possible to solve at least one of the aforementioned drawbacks, presenting other advantages that will be described.
    [0044] In a first aspect, the invention provides a catalytic nickel oxide film, characterized by the fact that it comprises non-stoichiometric and crystalline nickel oxide in the oxidation state Ni 2+ and Ni3 + dispersed in an organic matrix, the catalytic film supported on a substrate.
    [0046] The catalytic film comprises non-stoichiometric nickel oxide that includes mixtures of Ni (II) and Ni (III).
    [0048] Advantageously, the existence of Ni (II) and Ni (III) in the catalytic film surprisingly improves the catalytic properties of an electrode containing it compared to an electrode with Ni (0).
    [0050] The catalytic film of the invention comprises an organic part as a support matrix for the non-stoichiometric nickel oxides that represents at least 10% by weight of the total weight of the catalytic film. The organic part can represent values of the order of 15-30%.
    [0052] The present inventors have found that the presence of an amount of organic matter provides a porosity to the catalytic film that unexpectedly improves its catalytic properties.
    [0054] The organic matrix can be formed by at least one organic compound selected from an alkoxide, acetate, amine and / or a derivative of any one thereof.
    [0056] Thus, the catalytic film of the invention is a viable alternative for the oxidation of water to O 2 with good yields, low cost of the material to obtain the catalyst and ease of manufacture using low cost techniques as will be described hereinafter.
    [0058] It is also a further object of the present invention to provide a catalytic film of improved catalytic properties with reduced thickness.
    [0060] The catalytic film of the invention may have a thickness of less than 10pm, preferably a thickness of between 20-600nm, still more preferably a thickness of between 50-300nm.
    [0062] The catalytic film of the invention can be obtained with good catalytic properties with the presence of an organic part and reduced thickness. In the present invention, the thickness values given above refer to the thickness of the layer of the catalytic film supported on the substrate, not including the thickness of the substrate.
    [0064] The catalytic film can be made up of one or more layers, the various layers forming the catalytic film supported on the substrate. These layers can be the same or different. The same or different in the present invention is understood to be the same or different composition, the composition being understood as the variation in the concentration of nickel oxide Ni + 2 and / or of nickel oxide Ni + 3 and / or of the organic material, and even the variation in the percentage of organic material present in the organic part of the catalytic film.
    [0066] The catalytic film can further include metal nanoparticles and / or metal oxide nanoparticles. These metal nanoparticles and / or metal oxide nanoparticles are dispersed in the organic part that acts as a support matrix for said nanoparticles.
    [0068] Nanoparticles are formed from salts and / or oxides of metals other than nickel, such as salts and / or oxides of Ag, Au, Ru, Ir, Pd, Pt, Re, Co, Fe, Os, Rh, Mo, V, salts and / or oxides in solution that are added during the process of obtaining the catalytic film for the formation of nanocomposites dispersed in the organic matrix together with the oxides of Ni (II) and Ni (III). These nanocomposites can include mixed oxides.
    [0070] Advantageously, the presence of said metal and / or oxide nanoparticles metallic provides a catalytic film with greater application versatility. Thus, the catalytic film according to the first aspect of the invention also provides a multifunctional catalytic film that allows optimizing its catalytic properties through the incorporation of cocatalysts.
    [0072] The structure and morphology of the catalytic film of the invention makes it possible to use a substrate of insulating material, electrically conductive material or electrically semiconductor material, and even an organic material. Likewise, the substrate can be made of a flexible, rigid or semi-rigid material. The substrate can also be transparent or opaque.
    [0074] Among the materials of the substrate, the following can be cited as a non-limiting example of the invention: transparent as ITO and FTO on glass; rigid or semi-rigid such as thin sheets of nickel, aluminum, steel or other metallic supports as well as foam of metals such as nickel, and other types of rigid substrates such as flexible vitreous carbon such as ITO, FTO, and metals such as Au, Pt deposited on polyethylene terephthalate (PET ), polyethylene naphthalene (PEN), polypropylene (PP), polyethylene (PE), polyimide (Kapton Tape); organic like cellulose.
    [0076] In one embodiment, the catalytic film of the invention supported on a substrate is an electrode.
    [0078] In a second aspect, the invention provides a process for obtaining the catalytic film according to the first aspect of the invention.
    [0080] The procedure for obtaining the catalytic film defined in the first aspect of the invention is carried out wet on a substrate as follows:
    [0082] i) preparing a nickel oxide precursor solution;
    [0084] ii) depositing the prepared solution on the substrate;
    [0086] iii) curing the solution deposited on the substrate to obtain the nickel oxide catalytic film;
    [0088] and is characterized by the fact that it comprises:
    [0089] in stage i)
    [0091] a) - select an organic counter ion nickel salt;
    [0093] b) - dissolving the salt in a nonaqueous solvent of glycol ethers, glycol ethers acetates and derivatives thereof in the presence of an aminoalcohol chelating agent to obtain a solution of the nickel salt;
    [0095] c) - heating the solution to a temperature comprised between 20-200 ° C and keeping the solution thermostatted under stirring for a certain time to obtain an aged solution;
    [0097] in stage ii)
    [0099] d) - depositing the aged solution by means of a conventional wet deposition technique on the substrate to give a wet film; and
    [0101] in stage iii)
    [0103] e) - curing the aged solution deposited on the substrate at a temperature between room temperature and 200 ° C,
    [0105] so that the catalytic film is formed on the substrate, the film comprising non-stoichiometric and crystalline nickel oxide in the oxidation state Ni 2+ and Ni3 + dispersed in the organic matrix.
    [0107] The procedure defined here allows Ni (II) to be deposited directly on the electrode without prior reaction, which implies greater simplicity and ease of using any type of deposition method. The purpose of the process is not to generate Ni (0) but rather non-stoichiometric nickel oxide that comprises mixtures of Ni (II) and Ni (III), these oxidation states being responsible for the improvements in the catalytic properties of the film with respect to State-of-the-art films or films with nickel in the Ni (0) oxidation state.
    [0109] Advantageously, the catalytic film of the invention can be obtained by the wet route. using numerous techniques of deposition on substrates [step ii) -d]. Among the conventional techniques within the reach of a person skilled in the art can be mentioned spincoating, spraycoating, dipcoating or Dr. Blade. Likewise, it is compatible with "roll-to-roll" techniques and printing techniques such as inkjet printing, screencaoting and flexography.
    [0111] In step i) -a) the organic counter ion is selected from one of the following: acetate, formate, oxalate, carbonate, octanoate hydroxyacetate, terephthalate, acetylacetonate, hexafluoroacetylacetonate ethylhexanoate, methoxyethoxide, sulfamate.
    [0113] In step i) -b), preferably the nickel salt in solution is present at a concentration equal to or greater than 0.05M. Preferably greater than 0.1M.
    [0115] The non-aqueous solvent for glycol ethers, glycol ethers acetates and derivatives thereof has the function of dissolving and stabilizing nickel salts.
    [0117] Preferably the non-aqueous solvent is selected from 2-Methoxyethanol, 2-Ethoxyethanol, 2-Butoxyethanol, 2- (2-Ethoxy-ethoxy) ethanol, 2-Propoxyethanol, 2-Isopropoxyethanol, 2-Bezyloxyethanol, 2- (2-Methoxyethoxy) ethanol, 2- (2-Butoxyethoxy) ethanol and derivatives or mixtures thereof.
    [0119] The aminoalcohol chelating agent has the function of increasing the solubility and stability of the nickel salt in the solvent. Especially at high concentrations of nickel, its absence in the solution causes the hydrolysis of the nickel salts and their precipitation in the form of a gel.
    [0121] Preferably, the amino alcohol chelating agent is selected from monoethanolamine (MEA), di-ethanolamine (DEA), tri-ethanolamine (TEA), and derivatives or mixtures thereof.
    [0123] In step i) -c), preferably the solution is heated to a temperature comprised between 50-100 ° C, more preferably between 40-80 ° C.
    [0125] In this stage i) -c), the solution is allowed to age until it has a viscosity between 1.5 and 1000 mPas, preferably between 1.5 and 100 mPa s measured by rotational viscometry at room temperature with a solution volume of 15 mL.
    [0127] In step iii) -e), a curing of the aged solution deposited on the substrate is carried out, preferably at a temperature between room temperature and 100 ° C. During this heating the solvent is removed. In the invention by room temperature is meant a temperature of 22-24 ° C at atmospheric pressure.
    [0129] Preferably, the temperature of the first cure is selected as a function of the volatility value of the organic compound present in the matrix so that said curing temperature does not completely eliminate the organic material so that the catalytic film comprises an organic part that is, in part, responsible for improving the catalytic properties of the catalytic film of the invention. As a general rule, curing is carried out at a higher temperature when the organic compounds have lower volatility, and vice versa.
    [0131] In an embodiment of the invention the method according to the second aspect of the invention further comprises:
    [0133] in step i) -b)
    [0135] - adding a previously prepared solution of one or more metal salts and / or metal oxides to the nickel solution; and,
    [0137] in step iii) -e)
    [0139] - carry out a second cure of the aged solution deposited on the substrate, where the second cure is carried out at a temperature higher than the temperature of the first cure,
    [0141] where the rest of the stages are carried out as defined above in the procedure for obtaining the catalytic film, so that the catalytic film is formed on the substrate, the film comprising non-stoichiometric and crystalline nickel oxide in the Ni 2+ and Ni3 + oxidation state, and nanoparticles of metals and / or metal oxides dispersed in the organic matrix.
    [0142] In this embodiment, the metal salts and / or metal oxides are of metals other than nickel, which can be selected from one or more salts and / or one or more oxides of Fe, Au, Ag, Ru, Ir, Pt, Pd, Re , Os, Rh, Mo, V and mixtures thereof, preferably Fe, Au, Ag, Pt, Pd, Ru and Ir.
    [0144] In this embodiment it is necessary to carry out a second curing in order to form the metallic nanoparticles and / or the metallic oxides in the organic matrix. In one embodiment, the second cure is carried out at a temperature greater than 100 ° C, preferably greater than 200 ° C. Alternatively, curing with an ultraviolet lamp can be carried out. With these treatments, metal nanoparticles and metal oxides are generated that provide new properties to the material.
    [0146] In a third aspect, the present invention relates to the use of the nickel oxide catalytic film according to the first aspect of the invention as an electrode in electrocatalysis of water.
    [0148] Advantageously, the electrode has an overpotential of approximately 0.29V.
    [0150] In a different embodiment, the present invention also relates to the use of the nickel oxide catalytic film according to the first aspect of the invention as an electrode in photocatalysis.
    [0152] Advantageously, with the catalytic film of the invention reactive oxygen species (ROS) such as hydroxyl radicals (OH) or superoxides (O 2 ") can be generated that possess REDOX properties for the decomposition of pollutants in water and the atmosphere.
    [0154] The authors of the present invention have been able to verify that the organic part remains after the curing process, mainly due to the fact that lower temperatures are used, this organic part participating in the formation of pores that allow water to penetrate and thus increase contact with the catalyst and, consequently, improve the catalytic properties of the catalytic film defined in the invention.
    [0156] On the contrary, in the state of the art, a cure is usually carried out at elevated temperatures in order to eliminate the organic components so that the catalyst include only inorganic part. Although with very thick films, of the order of microns, when it is very hot it can generate pores, with thin films of the order of a few microns or nanometers, when generating the gap there is not enough space and it compacts very quickly. Furthermore, in the state of the art, high temperatures are preferred in order to obtain better compaction, considering that with said compaction the catalytic properties are improved and the stability of the catalyst is increased.
    [0158] Unexpectedly, the authors of the invention have found that at a lower temperature a film with organic material in the middle of the pores is obtained; These pores allow water to flow between them. Therefore, contrary to what could be expected, at lower temperatures, the catalytic film has better catalytic properties while maintaining adequate stability.
    [0160] Brief description of the figures
    [0162] For a better understanding of what has been explained, some drawings are attached in which, schematically and only as a non-limiting example, a practical case of embodiment is represented.
    [0164] Figure 1 shows a graph of UV-Visible absorbance of a catalytic film obtained according to Example 1 of a 0.9M Ni (AcO) 2 solution in methoxyethanol for different aging times in step i) -c) and constant temperature of 50 ° C.
    [0166] Figure 2 shows a graph of the UV-Visible transmission spectrum of a catalytic film obtained according to Example 2 for different curing temperatures in step iii) -e).
    [0168] Figure 3 shows a graph of the X-ray diffraction spectrum of a catalytic film obtained according to Example 2 for different curing temperatures in step iii) -e).
    [0170] Figure 4 shows images obtained with a transmission electron microscope (TEM) of a catalytic film obtained according to Example 2 and cured, in step iii) -e), at a temperature of 100 ° C compared to a cure at a temperature of 500 ° C.
    [0172] Figure 5 shows a graph of the hydrolysis of water using the catalytic film obtained according to Example 2 of the invention with a curing temperature of 100 ° C.
    [0174] Figure 6 shows a bar diagram of the overpotential (V) of the state of the art oxides in 1M NaOH at 10 mA cm-2 described by McCrory et al in "Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction" in J. Am. Chem. Soc. 2013, 135, 16977-16987.
    [0176] Detailed description of the invention
    [0178] In the following, preferred embodiments for carrying out the present invention are described.
    [0180] Example 1
    [0182] Initially, the NiOx precursor solution was prepared. A 0.9 M solution of Nickel Acetate tetrahydrate (2.2 g) in methoxyethanol (V = 10 mL) was prepared to which 0.04 mL of MEA was added. The mixture was stirred dissolving a part of the Ni (AcO) 2 . The mixture was then heated in a thermostat bath at 30-70 ° C for 5-60 min. It was found that after 5 min all the Ni (AcO) 2 had dissolved. The aging step was followed by UV-VIS spectroscopy (see Figure 1).
    [0184] Figure 1 shows a narrow band of absorbance in the UV at 397 nm, and another broad band in the visible one at 670 nm with a shoulder at 754 nm. After 10 minutes of aging, the bands became more intense and shifted slightly towards the IR 400, 679 and 755 nm, respectively. As the reaction time increased, the bands remained in wavelength, but slightly increased in intensity up to 60 min, time in which the reaction was considered finished since no change in intensity was observed until 180 min. After 180 min, it was observed that the solution stopped being transparent crystalline due to the formation of a translucent turquoise gel. This change was attributed to the hydrolysis and polycondensation of the nickel complexes giving rise to the formation of Ni (Ni (OH) 2 , NiOOH) acetate oxyhydroxides with sizes above 100 nm and no gelation of the solution. desirable.
    [0186] Example 2
    [0187] From the data extracted from the absorbance spectra of Example 1, a 0.45 M Ni (AcO) 2 solution aged 60 min at 70 ° C was used as the NiOx precursor solution. A thin NiOx film was deposited on a glass substrate by spincoating at a speed of 2,000 rpm for 20 s. Figure 2 shows the transmittance curves for different curing temperatures carried out during a period of time of 20 min at that temperature.
    [0189] The formation of the NiOx layers was followed by UV-Vis spectroscopy (see Figure 2). The presence of non-stoichiometric NiOx was confirmed by absorption in the visible between 900 and 350 nm. The decrease in transmittance from 350 nm was due to the fact that the glass is not transparent in the UV. It should be noted that stoichiometric NiO (Ni (II)) is a broadband semiconductor that does not absorb light in the visible spectrum, so the absorption of radiation was due to the fact that the Ni part was present in the form of Ni (III ) that does absorb into the visible. As the curing temperature was increased from 50 ° C to 500 ° C (see Figure 2), the absorption in the visible increased due to the formation of more Ni (III), as the temperature increased the evaporation of the solvent took place as well as the decomposition of acetates and methoxyethoxides and MEA, generating NiOx with a greater relative amount of Ni (III). An inflection point was observed at curing temperatures above 200 ° C, where the transmittance at 550 nm went from 91% at 50 ° C to 80% at 200 ° C. From 200 ° C the change was less significant.
    [0191] essays
    [0193] In order to determine the crystallinity of the non-stoichiometric nickel oxide formed in the catalytic film, an X-ray diffraction test was carried out for different curing temperatures (see Figure 3).
    [0195] It was observed that at different curing temperatures from 50 ° C to 500 ° C, NiOx did not show diffraction peaks, even at temperatures up to 500 ° C. All the peaks observed belonged to silicon, which is the substrate used to take the measurements. The absence of characteristic peaks of NiO, NiOOH or Ni (OH) 2 confirmed that the NiOx films were formed by nanometric crystalline domains, that is to say, nanocrystals of very small size.
    [0197] To determine the presence of organic part after the curing stage, images with a transmission electron microscope (TEM) (see Figure 4). Figure 4 shows the differences obtained between a film cured, for example, at 100 ° C with respect to another film cured at 500 ° C, from a solution with the same composition. With the 500 ° C film, a very compact material was obtained, about 25 nanometers thick. Surprisingly, the film with a 100 ° C cure was obtained with a thickness of 100 nanometers with separation between the grains. Contrary to what might be expected, at lower temperatures, the material showed better catalytic properties and adequate stability.
    [0199] A test of the catalytic properties of the catalytic film obtained was continued. The most representative measure of the catalytic activity was taken as the overpotential necessary to reach current densities of 10 mA / cm2. The overpotential is defined as the excess energy that has to be applied for the reaction to occur, that is, the activation energy. In general, all chemical reactions have an activation energy. Catalysts reduce this activation energy. In electrochemical terms, the activation energy can in some way be equated with the overpotential. Therefore, the overpotential necessary to perform the electrolysis of water was checked using an electrode formed by a Nickel sheet with the catalytic film. The overpotentials obtained were of the order of 0.29 V (290 mV) (see Figure 5), which showed to improve the overpotentials measured with reference materials such as Ir and Ru oxides (see Figure 6), where specifically the IrOx (oxide of non-stoichiometric iridium) shows an overpotential of 0.33 V. Finally, the small peak around 100mV (Figure 5) evidenced the formation of Ni (III) oxide and, therefore, the passage of a part of Ni (II) from Ni (II) to Ni (III) state.
    权利要求:
    Claims (25)
    [1]
    1. Catalytic nickel oxide film, characterized in that it comprises non-stoichiometric and crystalline nickel oxide in the oxidation state Ni 2+ and Ni3 + dispersed in an organic matrix, the catalytic film being supported on a substrate.
    [2]
    2. Catalytic film according to claim 1, wherein the organic matrix represents at least 10% by weight of the total weight of the catalytic film.
    [3]
    3. Catalytic film according to any one of claims 1-2, wherein the organic matrix is formed by at least one organic compound selected from an alkoxide, acetate, amine and / or a derivative of any one thereof.
    [4]
    4. Catalytic film according to any one of the preceding claims, wherein the catalytic film has a thickness of less than 10pm.
    [5]
    5. Catalytic film according to any one of the preceding claims, wherein the catalytic film has a thickness between 20-600nm.
    [6]
    6. Catalytic film according to any one of the preceding claims, wherein the catalytic film has a thickness between 50-300nm.
    [7]
    Catalytic film according to any one of the preceding claims, wherein the catalytic film is made up of one or more layers, the various layers forming the catalytic film supported on the substrate.
    [8]
    8. Catalytic film according to any one of the preceding claims, wherein the organic matrix further comprises metal nanoparticles and / or metal oxide nanoparticles dispersed therein.
    [9]
    9. Catalytic film according to any one of the preceding claims, wherein the substrate is selected from an insulating material, an electrically conductive material and an electrically semiconductor material.
    [10]
    10. Catalytic film according to any one of the preceding claims, wherein the substrate is selected from a flexible, rigid and semi-rigid material.
    [11]
    11. Catalytic film according to any one of the preceding claims, wherein the catalytic film supported on a substrate is an electrode.
    [12]
    12. Process for obtaining a catalytic film defined according to any one of claims 1-11, where the process is carried out wet on a substrate as follows:
    i) preparing a nickel oxide precursor solution;
    ii) depositing the prepared solution on the substrate;
    iii) curing the solution deposited on the substrate to obtain the nickel oxide catalytic film;
    characterized by the fact that it comprises:
    in stage i)
    a) - select an organic counter ion nickel salt;
    b) - dissolving the salt in a non-aqueous solvent of glycol ethers, acetates of glycol ethers and the derivatives thereof in the presence of an aminoalcohol chelating agent to obtain a solution of the nickel salt;
    c) - heating the solution to a temperature comprised between 20-200 ° C and keeping the solution thermostatted under stirring for a certain time to obtain an aged solution;
    in stage ii)
    d) - depositing the aged solution by means of a conventional wet deposition technique on the substrate to give a wet film; and
    in stage iii)
    e) - curing the aged solution deposited on the substrate at a temperature between room temperature and 200 ° C,
    so that the catalytic film is formed on the substrate, the film comprising non-stoichiometric and crystalline nickel oxide in the oxidation state Ni 2+ and Ni3 + dispersed in the organic matrix.
    [13]
    13. Process according to claim 12, wherein, in step i) -c), the solution is heated to a temperature comprised between 50-100 ° C, preferably between 40-80 ° C.
    [14]
    14. Process according to any one of claims 12-13, wherein, in step iii) -e), a curing of the aged solution deposited on the substrate is carried out at a temperature between room temperature and 100 ° C.
    [15]
    15. Process according to any one of claims 12-14, wherein, in step i) -c), the aged solution has a viscosity between 1.5 and 1000 mPas.
    [16]
    16. Process according to any one of claims 12-15, where the organic counterion is selected from one of the following: acetate, formate, oxalate, carbonate, octanoate, hydroxyacetate, terephthalate, acetylacetonate, hexafluoroacetylacetonate, ethylhexanoate, methoxyethoxide, sulfamate.
    [17]
    17. Process according to any one of claims 12-16, wherein, in step i) -b), the concentration of the nickel salt in the solution is equal to or greater than 0.05M.
    [18]
    18. Process according to any one of claims 12-17, wherein, in step i) -b), the non-aqueous solvent of glycol ether is selected from 2-Methoxyethanol, 2-Ethoxyethanol, 2-Butoxyethanol, 2- (2 -Ethoxy-ethoxy) ethanol, 2-Propoxyethanol, 2-Isopropoxyethanol, 2-Bezyloxyethanol, 2- (2-Methoxyethoxy) ethanol, 2- (2-Butoxyethoxy) ethanol and derivatives or mixtures thereof.
    [19]
    19. Process according to any one of claims 12-18, wherein, in the step i) -b), the ethanolamine chelating agent is selected from mono-ethanolamine, di-ethanolamine, tri-ethanolamine and derivatives or mixtures thereof.
    [20]
    20. Process according to any one of claims 12-19, further comprising:
    in step i) -b)
    - adding a previously prepared solution of one or more metal salts and / or metal oxides to the nickel solution; and,
    in step iii) -e)
    - carry out a second cure of the aged solution deposited on the substrate, where the second cure is carried out at a temperature higher than the temperature of the first cure,
    where the rest of the steps are carried out as defined in any one of claims 12-19, so that the catalytic film is formed on the substrate, the film comprising non-stoichiometric and crystalline nickel oxide in the oxidation state Ni 2+ and Ni3 +, and nanoparticles of metals and / or metal oxides dispersed in the organic matrix.
    [21]
    21. Process according to claim 20, where metal salts and / or metal oxides are other than nickel and are selected from a salt and / or oxide of Au, Ag, Ru, Ir, Pt, Pd, Re, Os, Rh, Mo , V, Co, Fe, and mixtures thereof.
    [22]
    22. Process according to any one of claims 20-21, wherein the second curing is carried out at a temperature higher than 100 ° C, preferably higher than 200 ° C, or alternatively with ultraviolet radiation.
    [23]
    23. Use of a nickel oxide catalytic film as defined in any one of claims 1-11 as an electrode in electrocatalysis of water.
    [24]
    24. Use according to claim 23, wherein the electrode has a overpotential of approximately 0.29V.
    [25]
    25. Use of a nickel oxide catalytic film as defined in any one of claims 1-11 as an electrode in photocatalysis.
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    CA3143401A1|2020-12-24|
    AU2020298111A1|2022-01-27|
    CN114007740A|2022-02-01|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN103974769B|2011-09-01|2018-11-09|西蒙·特鲁德尔|Electrocatalysis material and its manufacturing method|
    JP2015049973A|2013-08-30|2015-03-16|新日鉄住金化学株式会社|Conductive paste and method for manufacturing composite nickel fine particle used therefor|
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