• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Battery compound. The present invention relates to a compound for carrying out the division of water by means of an electrolysis process. More specifically, the compound is useful for producing hydrogen and for producing oxygen. The invention also relates to an electrode, a cell, and methods for preparing the electrode. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2796448A1
    申请号:ES202030912
    申请日:2020-09-08
    公开日:2020-11-26
    发明作者:Lopez Maria Del Carmen Gimenez；Diez Eugenia Pilar Quiros；Soler Melanie Guillen
    申请人:Universidade de Santiago de Compostela；
    IPC主号:
    专利说明:

    [0002] Battery compound
    [0004] Technical sector
    [0006] The present invention relates to a compound for carrying out the division of water by an electrolysis process. More specifically, the compound is useful for producing hydrogen and for producing oxygen. The invention also relates to an electrode, to the methods of preparing the electrode, to a cell, to the method of preparing the compound and its uses.
    [0008] Background
    [0010] The development of highly active, versatile and durable electrocatalytic materials for the production of clean and sustainable energy is at the forefront of the technological challenges facing humanity.
    [0011] Electrochemical technologies rely heavily on rare and endangered chemical elements, such as platinum, iridium or ruthenium, the shortage of which is creating a bottleneck for future technological progress. Therefore, the use of more abundant and greener sources is highly desirable.
    [0012] Also, these items often work well for only one type of reaction. For example, platinum is the best known catalyst for water reduction, while iridium and ruthenium are used for water oxidation.
    [0014] Since the surface requirements of the catalyst during the reduction and oxidation of water are totally different, the development of bifunctional catalysts for the division of water that in turn must be compatible with operation in acidic conditions and avoid corrosion is, therefore therefore extremely difficult.
    [0016] Polyoxometalate clusters have been applied as electrocatalysts for both the reduction and oxidation of water, although they are mainly restricted to their use at neutral and basic pH, especially in the oxidation reaction of water.
    [0018] Thus, it is still necessary to design new bifunctional electrocatalysts that can be used at acidic pH, thus allowing their use at an industrial level, preferably with the use of proton exchange membranes that present a high current density together with the possibility of producing hydrogen. high purity gas.
    [0020] Brief description of the invention
    [0022] The present inventors have designed a new polyoxomethalate (POM) -based compound capable of kinetically rapid water oxidation or reduction under strong acidic conditions, for example at pH less than 1, when found on an electrode. In addition, it allows electrolysis in acidic conditions, being much more stable than other electrodes.
    [0024] Thus, in a first aspect, the invention is directed to a compound (I) comprising
    [0026] a) a polyoxometalate,
    [0027] b) at least one ligand comprising a head that is capable of attracting protons and a tail that in an acidic medium has at least one positive charge,
    [0029] c) a counter ion of positive charge,
    [0031] d) at least one water molecule.
    [0033] In a second aspect, the invention is directed to an electrode comprising a compound (I) as described above.
    [0035] In a third aspect, the invention is directed to the preparation of electrodes comprising a compound (I) as described above.
    [0037] In a fourth aspect, the invention is directed to a cell comprising an electrode as described in the second aspect of the invention.
    [0039] In a fifth aspect the invention is directed to a method for the preparation of the compound of the first aspect of the invention.
    [0041] Another aspect of the invention is directed to use.
    [0043] Description of the figures
    [0045] Figure 1 shows SEM images at 20 kV of the compound prepared in Example 1.
    [0047] Figure 2 shows the a) Raman and b) FT-IR spectrum of compound (1) prepared in example 1.
    [0049] Figure 3 shows the comparison of the measurements of the cyclic voltammograms at 50 mV / s under a nitrogen atmosphere using sulfuric acid in the electrolyte, of: a) 1 / CB prepared in example 2.2 and CB; and b) 1 / CNT prepared in Example 2.2 and CNT.
    [0051] Figure 4 shows the comparison of the behavior of the oxygen evolution reaction (OER) of 1 / CNT prepared in example 2.2, CNT and Ir / C.
    [0053] Figure 5 shows a 1 @ CNT HR-TEM image prepared in Example 3.1.
    [0055] Figure 6 shows the comparison of the behavior of the hydrogen evolution reaction (HER) of 1 / CNT prepared in Example 2.2., 1 @ CNT prepared in Example 3.2, and CNT. The black arrow shows the change in electrochemical behavior.
    [0057] Figure 7 shows the comparison of chronoamperiometry measurements of 1 @ CNT // 1 / CNT and Pt / C // Ir / C in a two-electrode configuration under acidic conditions (pH <0.5).
    [0059] Detailed description of the invention
    [0061] In a first aspect, the invention is directed to a compound (I) comprising
    [0063] a) a polyoxometalate,
    [0065] b) at least one ligand comprising a head that is capable of attracting protons and a tail that in an acidic medium has at least one positive charge,
    [0066] c) a counter ion of positive charge,
    [0068] d) at least one water molecule.
    [0070] In a particular embodiment, the metal of the polyoxymethalate in compound (I) is selected from vanadium, tungsten, molybdenum, niobium, tantalum, zirconium and titanium.
    [0072] In a particular embodiment, the positively charged counter ion in compound (I) is selected from sodium, potassium and lithium.
    [0074] In a particular embodiment, the head of the ligand in compound (I) is a hydrocarbon chain of 1 to 12 carbon atoms, straight or branched, cyclic or acyclic, having more than 2 hydroxyl groups.
    [0075] In a particular embodiment, the head of the ligand in compound (I) is a group of formula (AlqOH) 3Alq, where each Alq can be the same or different and is independently selected from a hydrocarbon chain of between 1 to 12 carbon atoms, linear or branched, cyclic or acyclic.
    [0077] In a particular embodiment, each Alk in compound (I) can be the same or different and is independently selected from a straight or branched chain, acyclic hydrocarbon with between 1 to 4 carbon atoms.
    [0079] In a particular embodiment, the tail in compound (I) is selected from an amino and phosphonium group.
    [0080] In a particular embodiment, the ligand in compound (I) has the formula tris (hydroxyalkyl (C1-C4) amino (C1-C4) alkyl).
    [0082] In a particular embodiment, compound (I) is Zn (H2O) m [(AlqOH) 3AlqNH2] l [MXOY],
    [0084] where Z is an alkali metal selected from sodium, potassium and lithium,
    [0086] each Alk may be the same or different and is independently selected from a hydrocarbon chain of between 1 to 12 carbon atoms, straight or branched, cyclic or acyclic, preferably it is a C1-C4 alkyl,
    [0088] M is a transition metal selected from vanadium, tungsten, molybdenum, niobium, tantalum, zirconium and titanium,
    [0090] n has a value between 2 and 10,
    [0092] m has a value between 0 and 16,
    [0094] l has a value of 1, 2, 3 or 4,
    [0096] x has a value between 6 and 36,
    [0098] and has a value between 16 and 112.
    [0100] In a particular embodiment, the compound of formula (I) is Na4 (H2O) 12 [(CH2OH) 3CNH3] 2 [V10O28] .4H2O.
    [0101] In a second aspect, the invention is directed to an electrode comprising compound (I) as described above.
    [0102] In a particular embodiment, the electrode also comprises a carbon source. In a more particular embodiment, the carbon source is selected from a carbon nanotube, carbon black and a carbon nanofiber, preferably it is a multi-wall nanotube.
    [0104] The interaction of compound (I) with the carbon source influences the usefulness of the electrode of the invention. Thus, when compound (I) is simply physically mixed with the carbon source in the electrode of the invention, then the electrode is useful for oxygen production, as demonstrated in example 2. When the carbon source is A multi-walled nanotube gives the best results in oxygen production as evidenced by the higher current density compared to the current density when the carbon source is carbon black.
    [0106] The hypothesis that can explain this reaction is that the cation is stabilized by the ligand and in this conformation the cation activates the oxygen atom in the water and finally oxidation of the same occurs.
    [0107] Thus, in a particular embodiment, the invention relates to an electrode comprising a physical mixture of the compound of formula (I) and a carbon source. Preferably the carbon source is a carbon nanotube, more preferably a multiwall nanotube. In another embodiment the invention relates to the use of this electrode for the production of oxygen or for the oxidation of water.
    [0109] However, when the compound (I) is assembled (assembly) or coating the surface of the carbon source, the electrode is useful for hydrogen production, as demonstrated in Example 3.
    [0111] The hypothesis that can explain that due to this interaction of compound (I) with the carbon source generates hydrogen, is that the ligand acts as a sponge supporting the polyoxometalate in the attraction of hydrogen atoms and finally the reduction of water takes place.
    [0113] In a particular embodiment, the invention relates to an electrode comprising compound (I) covering the surface of a carbon source. In another embodiment the invention relates to the use of this electrode for the production of hydrogen or for the reduction of water.
    [0115] In another embodiment, the invention relates to a method for preparing an electrode for oxygen production, comprising:
    [0117] a) grinding a carbon source, preferably a carbon nanotube,
    [0119] b) mixing the result of step a) with the compound (I) of the invention until a homogeneous mixture is obtained, and then suspending it in an oil, and
    [0121] c) spreading the suspension resulting from step b) on a support.
    [0123] The grinding of step a) can be carried out in a mortar or similar equipment, and has the purpose of obtaining smaller particles from the carbon source. The person skilled in the art will be able to select different oils of the art to prepare the suspension, such as a mineral oil.
    [0125] In another embodiment, the invention relates to a method for preparing an electrode for hydrogen production, comprising:
    [0127] a) dissolve the compound (I) of the invention in water,
    [0129] b) add the solution from a) under sonication on a carbon source, previously ground, c) filter,
    [0131] d) resuspend the solid obtained in c), and
    [0133] e) dispersing the mixture obtained in d) on a support.
    [0135] In stage b) of this process, the solution can be added dropwise or by means of an addition equipment in which the amount added can be controlled over time to ensure the assembly of compound (I) on the carbon surface. The resuspension of the solid described in step d) can be carried out with materials generally used for this purpose and known to those skilled in the art, such as polymers, copolymers, oils, in some cases also using an alcoholic, glycolic solvent or mixtures of both of them.
    [0137] In a particular embodiment, the carbon source used in the methods of the invention is selected from carbon nanotubes, black carbon or carbon nanofibers.
    [0139] In a fourth aspect, the invention is directed to a cell comprising an electrode as described in the third aspect of the invention.
    [0141] In a particular embodiment, the electrolyte of the cell of the invention has an acid pH, preferably between 0.05 and 5.
    [0143] As demonstrated in example 4, a battery prepared with electrodes made up of a compound of formula (I), in which the electrolyte has a very acidic pH, for example below pH = 1, is much more stable than a battery formed by electrocatalysts that are referenced in the state of the art as Pt / C and Ir / C. This constitutes a significant advantage of the electrodes of the invention since they allow working for longer times at a strong acid pH.
    [0145] In a fifth aspect, the invention is directed to the preparation of a compound (I), which comprises:
    [0147] a) dissolving a salt of a metal oxide in an aqueous solution, and
    [0148] b) adding a ligand comprising a head that is capable of attracting protons and a tail that has at least one positive charge in an acid medium.
    [0150] Step b) of this process may require heating the mixture to between 25 ° C and 100 ° C with stirring. The process may require a final filtering to remove by-products that precipitate in the reaction medium in order to obtain the final compound by evaporation of the water from the solution. This evaporation process can be carried out under atmospheric conditions or under reduced pressure.
    [0152] The following examples serve to illustrate the invention and should not be construed as a limitation thereof.
    [0154] Materials and methods
    [0156] Sodium metavanadate (96%) and HCl (37%) were purchased from Alfa Aesar. Ultra pure (> 99%) Tris (hydroxymethyl) aminomethane (TRIS) was obtained from Molekula.
    [0157] All of these reagents and solvents were used as received. Carbon Nanotubes (CNTs), Multiwall Nanotubes, were purchased from Pyrograf Products Inc., USA XC-72 Carbon Black (CB) was purchased from FuelCellStore, Mineral Oil (Nujol) was purchased from Sigma Aldrich. Ir supported on carbon (Ir / C) (20% Ir) was obtained from Premeter co. Platinum supported on carbon (Pt / C) (20% Pt) and HISPEC 3000 were purchased from Alfa Aesar.
    [0158] Infrared spectra were measured using a Bruker Alpha FTIR spectrometer with a platinum ATR module. Grinding was carried out using a Retsch MM400 high energy ball mill instrument.
    [0160] Voltammetric measurements.
    [0161] Electrochemical experiments were performed in a typical three-electrode configuration with an AUTOLAB 302N electrochemical potentiostat using a glassy carbon electrode (GCE), a hydrogen electrode (RHE), and Pt wire as the working, reference, and counter electrode, respectively. . Cyclic voltammetry was performed in 1M H2SO4 saturated with nitrogen with a sweep speed of 50 mV / s between -0.5 V and 1.8 V.
    [0163] Electrocatalytic measurements.
    [0164] The electrocatalytic activities of the prepared catalyst electrodes were examined by polarization curves using linear scanning voltammetry (LSV) at a scanning rate of 5 mV / s conducted in a 1M H2SO4 solution. For the oxygen evolution reaction, the electrolyte was previously saturated with oxygen and the material was compared with commercial iridium on carbon (Ir / C), while for the hydrogen evolution reaction the electrolyte was saturated with hydrogen before the measurements, and the material was compared to commercial platinum on carbon (Pt / C) under the same conditions.
    [0165] Oxygen production was detected with an Ocean Optics NeoFOX oxygen detection system equipped with a FOXY probe, previously calibrated, inserted into the electrolyte.
    [0167] The Faradaic Efficiency (FE) was calculated using the following equation:
    [0169] FE = experimental moles of O 2 released ( measured with NeoFOX) / theoretical moles of O 2
    [0171] Where the theoretical moles of O2 were calculated using the following equation:
    [0173] Theoretical moles of O2 released = Q / nF
    [0175] where Q is the charge produced (coulombs), n is the number of electrons during the oxygen evolution reaction (4 electrons) and F is the Faradaica constant. The experimental moles of oxygen evolved during the oxygen evolution reaction were measured by NeoFox.
    [0177] Example 1. Preparation of Na4 (H2O) i2 [(CH2OH) 3CNH3] 2 [VioO28] .4H2O (1)
    [0179] In a 100 mL round bottom flask, 2.51 g of NaVO3 (20.6 mmol, 5 eq) were dissolved in 21 mL of water with stirring and hot at 85 ° C. After dissolving NaVO3, 6.18 were added dropwise ml (12.36 mmol, 3 eq) of an aqueous solution of HCl (2 M) until reaching a pH of 4. The initial yellow solution turned dark red upon addition of the acid. Then 0.5 g of TRIS was added [(CH2OH) 3CNH2] (4.12 mmol, 1 eq) to the solution and the reaction temperature was kept at 85 ° C for 6 hours with stirring. After that, the reaction was allowed to gradually cool to room temperature. The solution was filtered to remove the precipitate formed. The orange-red filtrate was allowed to evaporate slowly and after one day orange crystals of compound 1 were obtained which were collected by filtration (10% yield of Na4 (H2O) 12 [(CH2OH) 3CNH3] 2 [V10O28] .4H2O ( 1 )) (figure 1).
    [0181] The compound obtained was characterized by Raman (figure 2 a) and by FT-IT (figure 2b).
    [0183] Example 2. Preparation of an electrode for oxygen production (OER)
    [0184] 2.1. Preparation of "short CNT". CNTs were shortened by mechanical ball milling. In a typical experiment, 50 mg of CNT was placed in a stainless steel container (5 mL) with a stainless steel ball (10 mm in diameter) and ground in air for 90 min at 10 Hz.
    [0185] 2.2. Preparation of the OER electrode. The carbon paste modified electrode (CPME) was prepared as follows. In a typical experiment, 22.5 mg of the carbon material to be used (CB or short CNT) and 2 mg of compound 1 obtained in example 1 were mixed in a mortar to obtain a homogeneous mixture, to which 50 pL of nujol to form a suspension. Then, it was spread on a Vitreous Carbon Electrode (GCE) with an area of 1 cm2. The electrode was allowed to dry before electrochemical measurements.
    [0187] The cyclic voltammogram (CV) of the CMPE obtained in acidic media showed that the changes observed in the current with variations in the applied potential can only be assigned to 1 , since both the electrode additives used (that is, mineral oil, CNT and CB), as the TRIS ligand does not show any redox process under the same conditions.
    [0189] Cyclic voltammogram under acidic conditions (pH <0.5) revealed current density values ten times higher for 1 / CNT compared to 1 / CB for the same amount of 1 (Figures 3a and 3b). While the CNT shows only a double layer capacitance in the potential region of -0.5 to 1.4V, 1 / CNT exhibits reversible redox processes of one electron at assigned -0.24, 1.05 and 1.2 V to the V4 / V5 pair of different vanadiums in the cluster. Furthermore, 1 / CNT exhibited an unexpected higher OER activity compared to 1 / CB and the rest of the recently reported polyoxometalate-based electrocatalyst electrode materials, of which only very few are active at acidic pH (Table 1), which is quite remarkable. Surprisingly, the values obtained for the potential at which the reaction takes place ( onset potential) and the over potential at 10 (mA / cm2) ( over potential) are relatively small (1.45 and 1.58 V) as required for a Highly active OER electrocatalyst electrode material. And these values are very close to the values obtained for the standard iridium electrocatalyst (Ir / C) (1.42 V and 1.48 V) used under the same conditions (Figure 4).
    [0191] Table 1. Comparative summary of the performance of different electrocatalyst materials for POM-based OERs.
    [0193]
    [0194]
    [0197] [1] Y. Ding, H. Li, and Y. Hou, Mater. Lett., 2018 , 221, 264-266.
    [0198] [2] Y. Wang, Y. Wang, L. Zhang, C.-S. Liu, and H. Pang, Chem. Asian J, 2019 , 14, 2790-2795.
    [0199] [3] M. Martín-Sabi, J. Soriano-López, RS Winter, JJ. Chen, L. Vila-Nadal, DL. Long, JR Galán-Mascarós, and L. Cronin, Nat. Catal., 2018 , 1, 208-213.
    [0200] [4] GY Lee, I. Kim, J. Lim, MY Yang, DS Choi, Y. Gu, Y. Oh, SH Kang, YS Nam, and SO Kim, J. Mater. Chem. A. , 2017 , 5 , 1941-1947.
    [0202] In addition, an oxygen sensor was immersed in the electrolyte to confirm oxygen production when performing a linear scanning voltammogram from 1.0V to 1.9V. And indeed there was an increase in density to 1.44V after approximately 45 seconds, which correlates with an increase in oxygen production as the sensor showed. According to the calculations carried out, 5.09 micromoles of oxygen were generated, representing an EF for oxygen evolution of 94.1%.
    [0204] Example 3. Preparation of an electrode for hydrogen production (HER)
    [0205] 3.1. Preparation of 1 @ CNT.
    [0207] 100 mg of 1 was dissolved in 1.5 ml of ionized water and added to a suspension of short CNTs (5 mg in 1.5 ml of acetone) dropwise under sonication. The mixture was stirred at room temperature for 3 days and then filtered through a polytetrafluoroethylene (PTFE) membrane filter, washed repeatedly and with plenty of water to collect a yellowish black solid (20 mg). By high resolution transmission electron microscopy (HR-TEM) it is observed that an amorphous material is assembled on the surface of the CNT both externally and internally (Figure 5). By means of energy dispersive X-ray spectroscopy using STEM-EDS that allows an elemental mapping of the sample, it is shown that the amorphous material is composed of vanadium, nitrogen and sodium, and therefore, on the surface of the CNT the vanadate is deposited , sodium ion and TRIS ion.
    [0209] 3.2. Preparation of the HER electrode.
    [0211] 10 mg of the material (1 @ CNT) was carefully dispersed in 2 mL of isopropanol with 40 pL of Nafion solution (1%) and sonicated for 15 minutes. Then, 200 pL of the suspension was dropped onto the glassy carbon electrode to form a film, the final charge being 1 mg of the material on the GCE (surface area = 1 cm2). The film thickness was optimized by adjusting the volume and / or concentration of the graphene suspension. The electrode was allowed to dry before electrochemical measurements.
    [0213] The same procedure was carried out with CB instead of carbon nanotubes (CNT).
    [0214] The change in structure between compound 1 and CNT obtained in Example 3.1. compared to that obtained in Example 2.1. led to a change in electrochemical behavior. And so the electrode prepared in 3.2. It no longer showed activity in the production of oxygen and showed activity in the production of hydrogen (Figure 6).
    [0216] Table 2. Comparative summary of the performance of different electrocatalyst materials for HER based on POM.
    [0218]
    [0221] Compared to other electrodes for hydrogen production, the electrode prepared in this example exhibited excellent performance (Table 2).
    [0223] [1] J. Miao, Z. Lang, X. Zhang, W. Kong, O. Peng, Y. Yang, S. Wang, J. Cheng, T. He, A. Amini, Q. Wu, Z. Zheng , Z. Tang, and C. Cheng, Adv. Funct. Mater., 2019 , 29, 1805893.
    [0224] [2] DM Fernandes, MP Araújo, A. Haider, A. Mougharbel, AJS Fernandes, U. Kortz, and C. Freire, ChemElectroChem., 2018 , 5, 273-283.
    [0225] [3] JS. Qin, DY. Du, W. Guan, XJ Bo, Ya-F. Li, Li-P. Guo, ZM. Su, YY. Wang, YQ. Lan, and HC. Zhou, J. Am. Chem. Soc., 2015 , 137, 7169-7177.
    [0226] [4] KK Dey, S. Jha, A. Kumar, G. Gupta, AK Srivastava, and PP Ingole, Electrochem. Acta., 2019 , 312, 89-99.
    [0228] Example 4. Stack at strong acid pH
    [0230] To evaluate the behavior of electrocatalysts against water splitting, a typical water splitting cell (two electrode system) was constructed using 1 / CNT on the positive electrode and 1 @ CNT on the negative electrode. The chronoamperometry test was carried out in a H2SO41 M solution applying a potential of 3.1 V for 120 s. This behavior was compared with the behavior shown by the reference standards for the division of the Pt / C // Ir / C water carried out under the same conditions applying a voltage of 1.8 V.
    [0232] As shown in Figure 7, the configuration (1 @ CNT // 1 / CNT) under conditions of strong pH (pH <0.5) exhibited much greater stability than that observed for the stack formed with the standard reference electrodes. (Pt / C and Ir / C) under the same conditions. After 120 seconds, the drop in current density observed at 1.8 V for our electrolyzer (15%) is more than five times less than that observed for Pt / C // Ir / C (80%) at the same potential . However, for our battery a higher potential (1.8 V versus> 3 V) is required to initially produce the same current.
    1
    权利要求:
    Claims (20)
    [1]
    1. - Compound (I) comprising
    a) a polyoxometalate,
    b) at least one ligand comprising a head that is capable of attracting protons and a tail that in an acidic medium has at least one positive charge,
    c) a counter ion of positive charge,
    d) at least one water molecule.
    [2]
    2. Compound (I) according to claim 2, wherein the metal of the polyoxymethalate is selected from vanadium, tungsten, molybdenum, niobium, tantalum, zirconium and titanium.
    [3]
    3. Compound (I) according to the preceding claims, wherein the positively charged counter ion is selected from sodium, potassium and lithium.
    [4]
    4. Compound (I) according to any one of the preceding claims, wherein the head of the ligand is a hydrocarbon chain with 1 to 12 carbon atoms, linear or branched, cyclic or acyclic, having more than 2 hydroxyl groups.
    [5]
    5. Compound (I) according to claim 4, where the head of the ligand is a group of formula (AlqOH) 3Alq, where each Alq can be the same or different and is independently selected from a hydrocarbon chain of between 1 to 12 carbon atoms , linear or branched, cyclic or acyclic.
    [6]
    6. Compound (I) according to claim 4, wherein each Alk can be the same or different and is independently selected from a straight or branched chain, acyclic hydrocarbon of between 1 to 4 carbon atoms.
    [7]
    7. Compound (I) according to any of the preceding claims, wherein the tail is selected from an amino and phosphonium group.
    [8]
    8. Compound (I) according to any of the preceding claims, wherein the ligand has the formula tris (hydroxyalkyl (C1-C4) aminoalkyl (C1-C4).
    [9]
    9. Compound (I) according to claim 1, of formula Zn (H2O) m [(AlqOH) 3AlqNH2] l [MXOY]
    where Z is an alkali metal selected from sodium, potassium and lithium,
    each Alq can be the same or different and is independently selected from a hydrocarbon chain of between 1 to 12 carbon atoms, linear or branched, cyclic or acyclic,
    M is a transition metal selected from vanadium, tungsten, molybdenum, niobium, tantalum, zirconium and titanium,
    n has a value between 2 and 10
    m has a value between 0 and 16,
    l has a value of 1, 2, 3 or 4,
    x has a value between 6 and 36,
    and has a value between 16 and 112.
    [10]
    10. The compound of formula (I) according to claim 1 is Na4 (H2O) 12 [(CH2OH) 3CNH3] 2 [V1oO28] .4H2O
    [11]
    11. Electrode comprising the compound defined in any of claims 1-10.
    [12]
    12. Electrode comprising a physical mixture of compound (I) defined in any of claims 1-10 and a carbon source.
    [13]
    13. Electrode comprising compound (I) assembled on the surface of a carbon surface.
    [14]
    14. A method of preparing an electrode according to claim 12, comprising:
    a) grind a carbon source,
    b) mixing the result of step a) with the compound according to any of claims 1-10 until obtaining a homogeneous mixture, and then suspending it in an oil, and
    c) spreading the suspension resulting from step b) on a support.
    [15]
    15. A method of preparing an electrode according to claim 13, comprising:
    a) dissolving the compound according to any of claims 1-10 in water,
    b) add the solution from a) under sonication on a carbon source, previously ground,
    c) filter, and
    d) resuspend the solid obtained in c), and
    e) dispersing the mixture obtained in d) on a support.
    [16]
    16. Use of the electrode according to claim 12, for the production of oxygen or for the oxidation of water.
    [17]
    17. Use of the electrode according to claim 13, for the production of hydrogen or for the reduction of water.
    [18]
    18. A cell comprising an electrode according to any of claims 11-13.
    [19]
    19. Cell according to claim 18, in which the electrolyte has an acidic pH.
    [20]
    20. A method for preparing a compound (I) according to any of claims 1-10, comprising:
    a) dissolving a salt of a metal oxide in an aqueous solution, and
    b) adding a ligand comprising a head that is capable of attracting protons and a tail that has at least one positive charge in an acid medium.
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