Compositions or materials, methods for their production and uses thereof

Abstract

The present invention relates to a composition or material, in particular a catalytically active composition or material, comprising - permanently polarized hydroxyapatite and - vaterite and / or vaterite-like material. Further, the present invention relates to a method for producing said composition or material, a composition or material obtained or obtainable by said method and the use of said composition or material.

Description

Technical Field

[0001] This invention relates to a composition or material, a method for producing said composition or material, and its use. Background Technology

[0002] The synthetic mineral hydroxyapatite (HAp) is a crystalline form of calcium phosphate with the chemical formula Ca. 10 (PO4)6(OH)2, due to its similarity in composition and structure to bone and teeth, has significant biomedical value, prompting its application in repairing and reconstructing this hard tissue. HAp has a hexagonal structure, space group P63 / m, and cell size [missing information]. and It is stable at temperatures as high as 1273℃.

[0003] The electrical properties of HAp have been found to influence its biomedical applications. Therefore, early researchers were interested in the polarization of HAp, attempting to generate surface charges by applying DC potentials (i.e., 1.0–10.0 kV / cm) at elevated temperatures (i.e., from 200 °C to 800 °C) (Itoh, S.; Nakamura, S.;

[0004] Kobayashi, T.; Shinomiya, K.; Yamashita, K.; Itoh, S. Effect of ElectricalPolarization of Hydroxyapatite Ceramics on New Bone Formation. Calcif. Tissue Int. 2006, 78, 133-142).

[0005] This thermally stimulated polarization (TSP) process leads to defects within the grains and generates space charge polarization at the grain boundaries, both of which can cause the formation of electric dipoles (Nakamura, S.; Kobayashi, T.; Yamashita, K. Highly Oriented Calcification in Newly Formed Bones on Negatively Charged Hydroxyapatite Electrets. Key Eng. Mater. 2005, 284-286, 897-900).

[0006] However, the relaxation of this dipole over time suggests that the polarization is only partially maintained (semi-permanent), although this effect is not quantified.

[0007] Recently, permanently polarized hydroxyapatite was synthesized by applying a constant DC voltage of 500 V (i.e., a DC field of 3 kV / cm) to previously sintered crystalline HAp (cHAp) at 1000 °C for 1 h (Rivas, M.; del Valle, LJ; Armelin, E.; Bertran, O.; Turon, P.; Puiggalí, J.; Alemán, C. Hydroxyapatite with Permanent Electrical Polarization: Preparation, Characterization, and Response against Inorganic Adsorbates. Chem. Phys. Chem. 2018, 19, 1746-1755). This TSP process induces important chemical changes, such as OH... - The formation of defects (vacancies) and structural changes leading to increased crystallinity. Therefore, compared to cHAp (i.e., sintered HAp without TSP treatment), the electrochemical properties and conductivity of the resulting polarized minerals are significantly improved. For example, it has been found that under mild reaction conditions (i.e., from atmospheric pressure to 6 bar and 95 °C), permanently polarized hydroxyapatite can be used as a photoelectrochemical catalyst to obtain both glycine (Gly) and alanine (Ala; a racemic mixture of D / L) (Rivas, M.; del Valle, LJ; Turon, P.; Alemán, C.; Puiggalí, J. Sustainable Synthesis of Amino Acids by Catalytic Fixation of Molecular Dinitrogen and Carbon Dioxide. Green Chem. 2018, 20, 685-693).

[0008] Despite the progress made, there is still a greater need for compositions or materials containing permanently polarized hydroxyapatite, particularly as catalysts, preferably for the synthesis of high-value chemicals such as amino acids and other organic molecules.

[0009] Objectives and Solutions

[0010] In view of the above, the basic objective of the present invention is to provide compositions or materials that appropriately meet the above requirements, methods of their production, and uses.

[0011] This objective is achieved by the composition or material according to independent claims 1 and 11, the method for producing the composition or material according to claim 10, and the use of the composition or material according to claims 12-16. Preferred embodiments of the composition or material are defined in dependent claims 2-9. Further preferred embodiments of the invention are defined in this specification. The subject matter and wording of all claims are hereby expressly incorporated herein by reference.

[0012] According to a first aspect, the present invention relates to a composition or material, particularly a catalytically active composition or material (i.e., a catalyst), comprising...

[0013] - Permanently polarized hydroxyapatite and

[0014] - Permealumina and / or permealumina-like materials.

[0015] As used in this invention, the term "permanently polarized hydroxyapatite" refers to hydroxyapatite that has undergone complete structural redistribution, particularly near-perfect, with high crystallinity, i.e., especially with a small amount of amorphous calcium phosphate and the presence of vacancies detected by increased electrochemical activity and charge accumulation per unit mass and surface area, particularly synthetic hydroxyapatite. It possesses non-disappearing electrochemical activity and ion mobility. The corresponding characteristics of permanently polarized hydroxyapatite... 31 P-NMR spectra such as Figure 18 As shown. Preferably, the spectrum is performed using phosphoric acid (H3PO4) as a reference with solid hydroxyapatite and shows a unique peak at 2.6 ppm corresponding to the phosphate group of hydroxyapatite.

[0016] As used in this invention, the term "thermally polarized hydroxyapatite" preferably refers to permanently polarized hydroxyapatite obtained or obtainable by a method (thermal polarization method) including the following steps:

[0017] (a) Samples of sintered hydroxyapatite and / or amorphous calcium phosphate, particularly at temperatures between 700°C and 1200°C, and

[0018] (b) Apply a constant or variable DC voltage, particularly between 250V and 2500V, particularly between 900°C and 1200°C, particularly between 1000°C and 1200°C, to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (a), or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (a), for at least 1 minute.

[0019] An equivalent field is applied to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (a), or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (a), particularly between 1.49 kV / cm and 15 kV / cm, particularly between 900°C and 1200°C, particularly between 1000°C and 1200°C, for at least 1 min.

[0020] Apply electrostatic discharge, particularly between 2500V and 1500000V, particularly between 900℃ and 1200℃, particularly between 1000℃ and 1200℃, for >0 min to 24 h at a temperature between 2500V and 1500000V, particularly between 900℃ and 1200℃, particularly between 1000℃ and 1200℃.

[0021] An equivalent electric field is applied to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (a) or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (a), particularly between 148.9 kV / cm and 8928 kV / cm, particularly between 900°C and 1200°C, particularly between 1000°C and 1200°C, for a duration of >0 min to 24 h.

[0022] The hydroxyapatite sample in step (a) may be natural (i.e. naturally occurring) hydroxyapatite or synthetic hydroxyapatite.

[0023] Furthermore, the hydroxyapatite sample in step (a) is particularly a sample that can be crystalline hydroxyapatite.

[0024] Therefore, the permanently polarized hydroxyapatite of the composition or material according to the present invention is preferably obtained or can be obtained by the above method (thermal polarization method).

[0025] As used in this invention, the term "penetrating phosphate" refers to phosphate materials or phosphate minerals, particularly synthetic phosphate materials or synthetic phosphate minerals with the chemical formula CaHPO4·2H2O. In WAXS (wide-angle X-ray scattering) spectroscopy, the most representative peaks of pentophosphorus appear at 2θ = 29°, 31°, 35°, 42° and 51°, which are attributed to reflections at (141), (221), (121), (152) and (143) respectively (JCPDS card number 72-0713).

[0026] As used in this invention, the term "penetrating calcium phosphate-like material" refers to calcium phosphate material, which appears in Raman spectra at 878, 848, and 794 cm⁻¹. -1 Peaks exist at these locations, corresponding to HPO4. 2-The normal vibration mode, POH deformation mode and POH rotation mode.

[0027] As used in this invention, the term "room temperature" means a temperature of 15°C-35°C, particularly 18°C-30°C, preferably 20°C-30°C, more preferably 20°C-28°C, particularly 20°C-25°C.

[0028] This invention is based on the unexpected discovery that a new and versatile composition or material, particularly in the form of a catalyst, can be obtained, especially, by applying a thermally stimulated polarization (TSP) treatment to hydroxyapatite, wherein the hydroxyapatite is spaced apart from a positive electrode, and the positive and negative electrodes are used together for the TSP treatment. Unexpectedly, it has been found that this composition is particularly capable of producing or synthesizing high-value organic molecules, particularly amino acids and / or other organic molecules, such as carboxylic acids, aldehydes, ketones, alcohols, etc. Furthermore, it has been unexpectedly found that the selectivity of the reaction products, particularly with respect to their carbon number, can be advantageously tuned according to the presence of a permaphosphatite phase and / or a permaphosphatite-like material phase, preferably on the surface of a permanently polarized hydroxyapatite phase, particularly on the surface of a permanently polarized hydroxyapatite host phase.

[0029] In one embodiment of the invention, the composition or material is in the form of a catalyst, preferably a multiphase, particularly a biphase catalyst, wherein permanently polarized hydroxyapatite forms one phase of the catalyst, particularly the main phase, and permeapatite and / or permeapatite-like material forms another phase of the catalyst.

[0030] As used in this invention, the term "main phase" in a composition or material, particularly in the form of a catalyst, means, with respect to the total weight of the composition or material (particularly the catalyst), that the proportion of the main phase is greater than the proportion of the plurality or one remaining phase (also with respect to the total weight of the composition or material (particularly the catalyst)).

[0031] Preferably, permeapatite and / or permeapatite-like material are formed or present on the surface of the permanently polarized hydroxyapatite. In particular, the surface of the permanently polarized hydroxyapatite, more precisely, is at least partially, especially only partially or completely, layered or covered by permeapatite and / or permeapatite-like material.

[0032] In another embodiment, the composition or material has a wide-angle x-ray scattering (WAXS) pattern as shown in Figure 1(a). The x-ray scattering (WAXS) pattern shows peaks at 2θ = 29°, 31°, 35°, 42°, and 51°, particularly representative or unique peaks, attributed to (141), respectively. (121) and Reflection (JCPDS card number 72-0713). Preferably, the image is taken or obtained at room temperature, preferably at a temperature of 20°C-25°C and / or under atmospheric conditions, particularly under atmospheric humidity and / or atmospheric pressure.

[0033] In another embodiment, the composition or material has the Raman spectrum shown in Figure 1(b). The Raman spectrum is at 878 cm⁻¹. -1 848cm -1 and 794cm -1 Peaks are displayed at [location]. These peaks correspond to HPO4 and [other values]. 2- The normal vibrational modes, POH deformation modes, and POH rotation modes are recorded. Preferably, the spectra are obtained at room temperature, preferably at a temperature of 20°C-25°C, and / or under atmospheric conditions, particularly under atmospheric humidity and / or atmospheric pressure, and especially using a laser with a wavelength of 532 nm.

[0034] Furthermore, permanently polarized hydroxyapatite preferably has the following properties: Figure 16 shown 31 P-NMR spectra. The spectra show unique peaks corresponding to the phosphate groups of hydroxyapatite at 2.6 ppm or about 2.6 ppm, i.e., in the range of 2.5 ppm to 2.7 ppm. Preferably, the spectra are obtained using solid permanently polarized hydroxyapatite at a temperature of 20°C to 25°C and using phosphoric acid (H3PO4) as a reference. Further, the spectra are preferably obtained or can be obtained using a 400 MHz nuclear magnetic resonance (NMR) spectrometer. Typically, and particularly depending on the NMR spectrometer used, permanently polarized hydroxyapatite may have... 31 P-NMR spectrum, 31 The P-NMR spectrum has peaks corresponding to the phosphate groups of hydroxyapatite in the range of 2.3ppm-2.9ppm, particularly 2.4ppm-2.8ppm, preferably 2.5ppm-2.7ppm, and more preferably 2.5ppm-2.6ppm, especially distinctive peaks.

[0035] Furthermore, permanently polarized hydroxyapatite may have, in particular, a crystallinity of ≥65%, particularly 65%-99.9%, preferably 75%-99%, more preferably 80%-95%, as determined by wide-angle X-ray scattering (WAXS).

[0036] Furthermore, the crystallites of permanently polarized hydroxyapatite may have, in particular, a size of 20 nm to 500 nm, especially 50 nm to 200 nm, and preferably 70 nm to 100 nm, as determined particularly by wide-angle X-ray scattering (WAXS). Preferably, in this case, the term "size" refers to the average diameter of the crystallites of permanently polarized hydroxyapatite.

[0037] For further features and advantages of the permanently polarized hydroxyapatite used according to the present invention, reference is made to PCT application WO 2018 / 024727 A1, the contents of which are hereby expressly incorporated by reference.

[0038] In another embodiment of the invention, the proportion of permanently polarized hydroxyapatite is greater than the proportion of permeapatite and / or permeapatite-like material.

[0039] In another embodiment of the invention, the permanently polarized hydroxyapatite has a proportion of 50% to 99.9% by weight, particularly 65% ​​to 99.9% by weight, particularly 75% to 99% by weight, preferably 80% to 95% by weight, particularly 85% to 90% by weight, and particularly 85% to 88% by weight, based on the total weight of the composition or material.

[0040] In another embodiment of the invention, the percalcite and / or percalcite-like material has a crystallinity of 65%-99.9%, particularly 75%-99%, and preferably 80%-95%, as determined by wide-angle X-ray scattering (WAXS).

[0041] In another embodiment of the invention, the microcrystals of percalcite and / or percalcite-like materials have a size, particularly determined by wide-angle X-ray scattering (WAXS), ranging from 20 nm to 500 nm, especially 50 nm to 200 nm, and preferably 70 nm to 100 nm. Preferably, in this case, the term "size" refers to the average diameter of the microcrystals of percalcite and / or percalcite-like materials.

[0042] In another embodiment of the invention, the permealuminate and / or permealuminate-like material has a proportion of >0% to 50% by weight based on the total weight of the composition or material, particularly 0.1% to 35% by weight, particularly 1% to 25% by weight, preferably 5% to 20% by weight, particularly 10% to 15% by weight, particularly 12% to 15% by weight.

[0043] Further, the composition or material may particularly have a total catalytic activity ratio of permanently polarized hydroxyapatite to permeapatite and / or permeapatite-like material, with the sum of the yields of all products in the product mixture being 0.5:2, particularly 0.75:1.5, preferably 0.8:1.25. The total catalytic activity can preferably be determined by... 1 H-NMR (nuclear magnetic resonance) spectroscopy was used to determine this. For this purpose, 1 The peak area in the H-NMR spectrum is preferably normalized according to the number of protons in each product obtained.

[0044] Furthermore, the composition or material may have a proportion of amorphous calcium phosphate of >0% to 15% by weight, particularly >0% to 10% by weight, and preferably >0% to 5% by weight, based on the total weight of the composition or material.

[0045] Furthermore, the composition or material may not contain amorphous calcium phosphate.

[0046] Furthermore, the composition or material may have a proportion of tricalcium phosphate, particularly β-tricalcium phosphate, by weight >0% to 15% by weight, especially >0% to 10% by weight, and preferably >0% to 5% by weight, based on the total weight of the composition or material.

[0047] Furthermore, the composition or material may be free of tricalcium phosphate, especially β-tricalcium phosphate.

[0048] Furthermore, the composition or material may have 10 7 Ωcm 2 -10 5 Ωcm 2 Especially 10 7 Ωcm 2 -10 5 Ωcm 2 Preferably 10 5 Ωcm 2 The bulk resistance. In particular, the bulk resistance may increase by 4%-33%, especially 4%-63%, preferably 4% after 3 months. As used in this invention, the term "bulk resistance" refers to resistance to electron transfer and can be determined by electrochemical impedance spectroscopy.

[0049] Furthermore, the composition or material may have a surface capacitance reduction of less than 15%, particularly less than 8%, after 3 months. Preferably, the composition or material may have a surface capacitance reduction of 0% or >0% to 15%, more preferably 0% or >0% to 5%, after 3 months. As used in this invention, the term "surface capacitance" refers to the capacitance attributable to changes in the hydroxyapatite surface caused by the thermal polarization process, and can be determined by electrochemical impedance spectroscopy.

[0050] Furthermore, the composition or material may be in the form of particles. The particles may have a diameter of 20 nm to 500 nm, particularly 50 nm to 200 nm, preferably 70 nm to 100 nm, especially the diameter determined by wide-angle X-ray scattering (WAXS), preferably the average diameter.

[0051] Furthermore, the composition or material may be in powder form, particularly having particles as mentioned above.

[0052] Furthermore, the composition or material may be in the form of a molded body. The molded body may have a polygonal cross-section, such as a triangle, square or rectangle, pentagon, hexagon, heptagon, octagon or nonagon, or a cornerless cross-section, particularly a circular, oval or elliptical cross-section.

[0053] In particular, the shaped body can be in the form of a disk, a flat plate, a cone (cone), or a cylinder.

[0054] Furthermore, the molded body may have a thickness of >0cm-10cm, particularly >0cm-1cm, and preferably >0cm-0.2cm.

[0055] Furthermore, the composition or material may be in the form of a coating.

[0056] The composition or material may further comprise an active ingredient. The active ingredient may be, in particular, a biological or pharmaceutically active ingredient. The active ingredient may be, in particular, selected from antimicrobial (more particularly antibiotic) components, wound-healing components, disinfectant components, anti-inflammatory components, coagulation-promoting components, growth factors, cell differentiation factors, cell adhesion factors, cell recruitment factors, cell receptors, cell-binding factors, cytokines, peptides, structural proteins, extracellular proteins such as collagen, serum proteins such as albumin, polysaccharides such as hyaluronic acid, oligonucleotides, polynucleotides, DNA, RNA, their salts, stereoisomers, and more particularly, their diastereomers and mixtures thereof.

[0057] For example, the active ingredient may be selected from biguanides, polyhexamethylene biguanide (PHMB), triclosan, chlorhexidine, gentamicin, vitamins, copper, zinc, silver, gold and mixtures thereof.

[0058] The composition or material may further comprise a material selected from polymers, ceramics, silicates, organometallic compounds and mixtures thereof.

[0059] The polymer can be a biodegradable polymer, i.e., a polymer that degrades in vivo (i.e., in humans or animals), or a non-biodegradable polymer. Further, the polymer can be a biopolymer (i.e., a naturally occurring polymer) or a synthetic polymer (i.e., a technical or non-naturally occurring polymer). Further, the polymer can be a homopolymer or copolymer, i.e., a polymer containing at least two, and particularly only two or more, different monomer units.

[0060] The polymer may be particularly selected from polyolefins, polyesters, polyamides, polyimides, polyvinyl alcohol, polyurethanes, polycarbonates, alkyl terephthalates, aryl terephthalates, polyaryletherketones, polyhydroxyalkanoates, proteins such as extracellular proteins and / or globular proteins and / or enzymes and / or antibodies and / or coagulation factors, polysaccharides, and mixtures thereof.

[0061] In particular, the polymer can be selected from polyethylene, low-density polyethylene, high-density polyethylene, high molecular weight polyethylene, ultra-high molecular weight polyethylene, polypropylene, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyamide 6, polyamide 6-6, polyamide 6-12, polyamide 12, rayon, silk (especially spider silk), polytetrafluoroethylene, polyvinylidene chloride, polyvinylidene fluoride, polytetrafluoropropylene, polyhexafluoropropylene, polyvinyl alcohol, polyglycolic acid, polylactic acid, polydioxanone, polyhydroxybutyrate, poly3-hydroxybutyrate, poly4-hydroxybutyrate, and polytrimethylene carbonate. Poly(ε-caprolactone), collagen, gelatin, elastin, reticulin, fibronectin, laminin, fibrin, fibrinogen, albumin, starch, amylose, amylopectin, dextran, dextrin, cellulose, cellulose derivatives such as alkyl cellulose, methyl cellulose, hydroxyalkyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxyl cellulose, carboxymethyl cellulose, chitin, chitosan, hyaluronic acid, dextran sulfate, heparin, heparan sulfate, chondroitin sulfate, dermatan sulfate, DNA, RNA, their salts, their stereoisomers, their copolymers and mixtures thereof.

[0062] The composition or material may further comprise an inorganic catalyst, particularly an inorganic photocatalyst. More specifically, the composition or material may be at least partially, particularly only partially or completely coated with an inorganic catalyst, particularly a photocatalyst. The inorganic catalyst may be a catalyst such as TiO2, MgO2, MnO2, or a combination thereof.

[0063] Furthermore, the composition or material may be at least partially, particularly only partially or completely coated with aminotris(methylenephosphonic acid) and / or zirconium oxychloride (ZrOCl2) and / or zirconium oxide (ZrO2). More specifically, the composition or material may have a three-layer coating, particularly wherein the three-layer coating may consist of two layers of aminotris(methylenephosphonic acid) and one layer of zirconium oxychloride (ZrOCl2) or zirconium oxide (ZrO2), wherein the zirconium oxychloride layer is arranged or sandwiched between the two layers of aminotris(methylenephosphonic acid).

[0064] Furthermore, the composition or material may preferably be a medical, particularly pharmaceutical, composition or material.

[0065] Furthermore, the composition or material may preferably be a medical device, particularly an implant, such as a bone implant or prosthesis, especially a knee or hip prosthesis.

[0066] According to a second aspect, the present invention relates to a method for producing or synthesizing compositions or materials according to the first aspect of the invention.

[0067] The method includes the following steps:

[0068] (a) Provide samples of hydroxyapatite (especially natural or synthetic hydroxyapatite) and / or amorphous calcium phosphate.

[0069] (b) The hydroxyapatite and / or amorphous calcium phosphate sample provided in sintering step (a),

[0070] (c) Apply a constant or variable DC voltage between 250V and 2500V, particularly for at least 1 minute, to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), and / or at a temperature between 900°C and 1200°C, particularly between 1000°C and 1200°C.

[0071] Apply an equivalent electric field between 1.49 kV / cm and 15 kV / cm, particularly for at least 1 min, to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or at a temperature between 900°C and 1200°C, particularly between 1000°C and 1200°C.

[0072] Apply an electrostatic discharge between 2500V and 1500000V, particularly for a duration >0 min to 24 h, to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or at a temperature between 900°C and 1200°C, particularly 1000°C to 1200°C.

[0073] An equivalent electric field between 148.9 kV / cm and 8928 kV / cm is applied to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), particularly for a duration >0 min to 24 h and / or at a temperature between 900 °C and 1200 °C, particularly between 1000 °C and 1200 °C.

[0074] (d) Cool the sample obtained in step (c) while maintaining a DC voltage or equivalent electric field or

[0075] The sample obtained in cooling step (c) may or may not retain electrostatic discharge or equivalent electric field.

[0076] In step (c), the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is arranged between the positive and negative electrodes. This arrangement is used to apply a constant or variable DC voltage, equivalent electric field, or electrostatic discharge during step (c), such that the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is preferably spaced apart from one of the two electrodes, i.e., the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is preferably at a certain distance from one of the two electrodes, i.e., the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is preferably at a certain distance from the positive electrode.

[0077] Preferably, for step (c), the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is arranged between the positive and negative electrodes. This arrangement is used to apply a constant or variable DC voltage, equivalent electric field, or electrostatic discharge during step (c), such that the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is spaced apart from only one of the two electrodes, preferably only from the positive electrode. That is, the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is spaced apart from only one of the two electrodes, preferably only from the positive electrode. In other words, the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b) or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b) is preferably in contact with the other of the two electrodes, more preferably with the negative electrode.

[0078] Further, the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b) or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b) is placed with one of the two electrodes, preferably spaced from the positive electrode by a distance of >0 cm-10 cm, particularly >0 cm-5 cm, preferably >0 cm-0.1 cm.

[0079] Electrodes, particularly positive and / or negative electrodes, can have different shapes. Electrodes, particularly positive and / or negative electrodes, can have polygonal cross-sections, such as triangular, square or rectangular, pentagonal, hexagonal, heptagonal, octagonal or nonagonal cross-sections, or angularless cross-sections, particularly circular, oval or elliptical cross-sections. Furthermore, electrodes, particularly positive and / or negative electrodes, can be in the form of flat plates or disks, cones (cones) or cylinders.

[0080] Furthermore, the electrodes, particularly the positive and / or negative electrodes, may be made of steel, especially stainless steel.

[0081] Furthermore, the electrodes, i.e. the positive and negative electrodes, may have a mutual distance of 0.01 mm to 10 cm, particularly 0.01 mm to 5 cm, and preferably 0.01 mm to 1 mm.

[0082] Preferably, step (a) includes

[0083] - Hydrothermal treatment of suspensions containing calcium phosphate, especially aqueous alcohol suspensions.

[0084] As used in this invention, the term "aqueous alcohol suspension" means a suspension containing water and alcohol, particularly ethanol, as a solvent or a mixture of solvents.

[0085] Preferably, a calcium phosphate suspension is obtained by using an aqueous solution containing diammonium hydrogen phosphate ((NH4)2HPO4) and an alcohol-containing solution, particularly ethanol-containing solution, containing calcium nitride (Ca(NO3)2). More preferably, the pH of the calcium nitride is adjusted to 10-12, particularly 10-11.5, more preferably 10.5-11. More preferably, the aqueous solution containing diammonium hydrogen phosphate is added to the alcohol-containing solution, particularly ethanol-containing solution, containing calcium nitride. Further, preferably, the resulting mixture is stirred at room temperature, particularly for >0 h-24 h, to form the calcium phosphate suspension. The latter can also be referred to as the "aging" of the reaction mixture.

[0086] Furthermore, the hydrothermal treatment is preferably carried out in an autoclave, particularly at pressures of >0 bar to 200 bar, especially >0 bar to 50 bar, and preferably >0 bar to 20 bar.

[0087] Furthermore, the hydrothermal treatment is preferably carried out at a temperature of 50℃-240℃, particularly 100℃-240℃, more preferably 110℃-240℃, even more preferably 120℃-240℃, even more preferably 130℃-240℃, even more preferably 140℃-240℃, and especially preferably 150℃-240℃.

[0088] Furthermore, the hydrothermal treatment is preferably carried out for >0h-48h, particularly >0h-24h, and preferably 12h-24h.

[0089] More preferably, the hydrothermal treatment is carried out by autoclaving the above reaction mixture, especially after aging, at 150°C for 24 hours.

[0090] Step (a) may further include

[0091] - Cooling the hydrothermally treated suspension containing calcium phosphate to form a precipitate. In particular, the hydrothermally treated suspension containing calcium phosphate can be cooled to a temperature of 0°C-90°C, especially 10°C-75°C, preferably 25°C.

[0092] Step (a) may further include

[0093] - Separation of precipitates obtained by cooling a hydrothermally treated suspension containing calcium phosphate, particularly by centrifugation and / or filtration.

[0094] Step (a) may further include

[0095] Washing is the process of separating precipitates by cooling a hydrothermally treated suspension containing calcium phosphate, particularly using water and / or alcohol, especially ethanol.

[0096] Step (a) may further include

[0097] - Freeze-drying is the process of separating and optionally washing a precipitate obtained by cooling a hydrothermally treated suspension containing calcium phosphate to produce hydroxyapatite, particularly synthetic hydroxyapatite. Freeze-drying can be carried out for 1 to 4 days, particularly 2 to 3 days, preferably 3 days.

[0098] Furthermore, the hydroxyapatite sample in step (a) may specifically be a crystalline hydroxyapatite sample.

[0099] Furthermore, step (b) above can be performed at a temperature between 700°C and 1150°C, particularly between 800°C and 1100°C, and especially at 1000°C. Furthermore, the method according to the invention preferably includes another step (bc) between step (b) and step (c).

[0100] - Shaping, particularly pressing the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b) to form a shaped body.

[0101] Therefore, the shaped body can preferably be obtained by forming, in particular by pressing, a sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), from the sample.

[0102] In particular, step (bc) can be carried out at a pressure of 1 MPa-1000 MPa, especially 100 MPa-800 MPa, preferably 600 MPa-700 MPa. Further, step (bc) can be carried out for 1 min-90 min, especially 5 min-50 min, preferably 10 min-30 min.

[0103] The shaped body may be polygonal, such as triangular, square or rectangular, pentagonal, hexagonal, heptagonal, octagonal or nonagonal, or without corners, especially with a circular, oval or elliptical cross-section. Furthermore, the shaped body may have a thickness of 0.1cm-10cm, especially 0.1cm-5cm, preferably 0.5cm-2cm.

[0104] Preferably, the shaped body is in the form of a disk, a flat plate, a cone, or a cylinder.

[0105] Furthermore, a constant or variable DC voltage or equivalent electric field may be applied in step (c) above for 1 hour to 24 hours, particularly 0.1 hours to 10 hours, particularly 1 hour.

[0106] Furthermore, the DC voltage applied in step (c) above is preferably 500V, which is equivalent to a constant electric field of 3kV / cm.

[0107] Furthermore, the equivalent electric field applied in step (c) above is preferably 3 kV / cm.

[0108] Further, the temperature in step (c) is preferably at least 900°C, more preferably at least 1000°C, and particularly 1000°C. Preferably, the temperature in step (c) is 900°C-1200°C, and particularly 1000°C-1200°C.

[0109] Furthermore, step (d) above can be performed by cooling the sample obtained in step (c) to room temperature.

[0110] Furthermore, step (d) above can be performed for 1 min to 72 h, particularly 15 min to 5 h, preferably 15 min to 2 h.

[0111] Preferably, for step (c) above, the sample or its shaped sample obtained in step (b) is spaced >0 cm-10 cm, particularly 0.1 cm-7 cm, and preferably 1 cm-5 cm from one of the two electrodes (preferably the positive electrode). Preferably, the sample or its shaped sample obtained in step (b) is in physical contact with the other of the two electrodes, preferably the negative electrode.

[0112] According to a third aspect, the present invention relates to a composition or material, particularly preferably a composition or material (i.e., a catalyst) with catalytic activity according to the first aspect of the invention, obtained or obtainable by a method comprising the following steps:

[0113] (a) Provide samples of hydroxyapatite (especially natural or synthetic hydroxyapatite) and / or amorphous calcium phosphate.

[0114] (b) The hydroxyapatite and / or amorphous calcium phosphate sample provided in sintering step (a),

[0115] (c) Applying a constant or variable DC voltage between 250V and 2500V to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b) or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b) for at least 1 minute and / or at a temperature between 900°C and 1200°C, particularly between 1000°C and 1200°C.

[0116] Apply an equivalent electric field between 1.49 kV / cm and 15 kV / cm, particularly for at least 1 min, to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or at a temperature between 900°C and 1200°C, particularly between 1000°C and 1200°C.

[0117] Apply an electrostatic discharge between 2500V and 1500000V, particularly for a duration >0 min to 24 h, to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or to the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or at a temperature between 900°C and 1200°C, particularly 1000°C to 1200°C.

[0118] An equivalent electric field between 148.9 kV / cm and 8928 kV / cm is applied to the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), particularly for a duration >0 min to 24 h and / or at a temperature between 900 °C and 1200 °C, particularly between 1000 °C and 1200 °C.

[0119] (d) Cool the sample obtained in step (c) while maintaining a DC voltage or equivalent electric field or

[0120] The sample obtained in cooling step (c) may or may not retain electrostatic discharge or equivalent electric field.

[0121] In step (c), the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is arranged between the positive and negative electrodes. This arrangement is used to apply a constant or variable DC voltage, equivalent electric field, or electrostatic discharge during step (c), such that the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is preferably spaced apart from one of the two electrodes, i.e., the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is preferably at a certain distance from one of the two electrodes, i.e., the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), or the shaped body of the sintered sample of hydroxyapatite and / or amorphous calcium phosphate obtained in step (b), is preferably at a certain distance from the positive electrode.

[0122] Regarding further features and advantages, particularly with respect to compositions or materials and / or methods, reference is made entirely to the foregoing description, especially to embodiments disclosed in the first and / or second aspects of the invention. The features and advantages described in the foregoing description, particularly in accordance with the first and / or second aspects of the invention, are also applicable, with appropriate modifications, to compositions or materials according to the third aspect of the invention.

[0123] More preferably, the present invention relates to the use of compositions or materials for the production or synthesis, particularly the selective production or synthesis, of organic molecules, especially functionalized organic molecules, i.e., organic molecules containing or having functional groups particularly selected from the following: carboxyl, amino, aldehyde (formyl), ketone, hydroxyl, and combinations thereof. The organic molecules, particularly functionalized organic molecules, preferably contain or have 1-3 carbon atoms. Preferably, the organic molecules, particularly functionalized organic molecules, are selected from amino acids, carboxylic acids, aldehydes, ketones, alcohols, and mixtures thereof. In particular, one or more amino acids are glycine and / or alanine. Further, the carboxylic acids may be particularly selected from formic acid, acetic acid, malonic acid, and mixtures thereof. Further, the ketone is preferably acetone. Further, one or more alcohols are preferably methanol and / or ethanol.

[0124] In another embodiment of the invention, the invention relates to the use of a composition or material as a catalyst, particularly an electrocatalyst, preferably a photoelectrocatalyst.

[0125] Preferably, the use as a catalyst is in reactions for the production or synthesis, particularly the selective production or synthesis, of organic molecules, especially functionalized organic molecules, i.e., organic molecules containing or having functional groups particularly selected from: carboxyl, amino, aldehyde (formyl), ketone, hydroxyl, and combinations thereof. The organic molecules, especially functionalized organic molecules, preferably contain or have 1-3 carbon atoms.

[0126] In another embodiment of the invention, the use of the catalyst is in a reaction for the production or synthesis, particularly the selective production or synthesis of amino acids, especially natural amino acids, preferably glycine and / or alanine.

[0127] In another embodiment of the invention, the use of the catalyst is in a reaction for the production or synthesis, particularly the selective production or synthesis of carboxylic acids, especially formic acid, acetic acid, malonic acid or mixtures thereof.

[0128] In another embodiment of the invention, the use of the catalyst is in a reaction for the production or synthesis, particularly the selective production or synthesis of aldehydes or ketones, especially acetone.

[0129] In another embodiment of the invention, the use of the catalyst is in a reaction for the production or synthesis, particularly the selective production or synthesis of alcohols, especially methanol and / or ethanol.

[0130] Furthermore, the use as a catalyst is preferably in reactions for producing or synthesizing mixtures comprising carboxylic acids, aldehydes, ketones, alcohols and at least two of the aforementioned organic molecules, or mixtures consisting of carboxylic acids, aldehydes, ketones, alcohols and at least two of the aforementioned organic molecules.

[0131] Furthermore, the use as a catalyst is preferably in a reaction for producing or synthesizing a mixture comprising ethanol and at least one other organic molecule or thereof, wherein the at least one other organic molecule is particularly selected from formic acid, acetic acid, malonic acid, acetone, methanol and a mixture of at least two of the above organic molecules.

[0132] In particular, the use as a catalyst can be in reactions for producing or synthesizing a mixture of ethanol, formic acid, acetic acid, acetone and methanol or a mixture of ethanol, formic acid, acetic acid, acetone and methanol.

[0133] In particular, the use as a catalyst can be in reactions for producing or synthesizing a mixture of ethanol, acetic acid, malonic acid, acetone and methanol or a mixture of ethanol, acetic acid, malonic acid, acetone and methanol.

[0134] In particular, the use as a catalyst can be in reactions for producing or synthesizing a mixture of ethanol, acetic acid and acetone or a mixture of ethanol, acetic acid and acetone.

[0135] Furthermore, the present invention particularly relates to the use of compositions or materials in biomedical applications. Preferably, the biomedical applications are selected from cementum for teeth, bone, prostheses, medical devices, drug delivery, gene therapy, and tissue regeneration.

[0136] Furthermore, the present invention particularly relates to the use of compositions or materials as electrodes.

[0137] Furthermore, the present invention particularly relates to the use of compositions or materials for doping polymers.

[0138] Furthermore, the present invention particularly relates to the use of compositions or materials for supporting, preferably adsorbing, organic molecules. Preferably, the organic molecules are selected from organometallic compounds, carbohydrates, amino acids, lipids, ATP, polymers, and combinations thereof, especially mixtures thereof. Regarding the polymers, refer entirely to the preceding description.

[0139] Furthermore, the present invention particularly relates to the use of compositions or materials for supporting, preferably adsorbing, phosphorus-containing compounds such as pyrophosphates, triphosphates, triphosphonates, polyphosphates, or combinations thereof, especially mixtures thereof. The polyphosphates may be selected from any polyphosphate having 1-50,000 monomer units or any combination thereof.

[0140] Furthermore, the present invention particularly relates to the use of compositions or materials for supporting, preferably adsorbing, organometallic compounds, and more preferably metal phosphonates. The organometallic compound is preferably a compound containing a metal ion. Preferably, the metal ion is selected from transition metal ions, lanthanides, and combinations thereof. More preferably, the organometallic compound is a compound containing a metal ion, wherein the metal ion is selected from Sr... 2+ Mg 2+ Fe 2+ Fe 3+ Mn 2+ Zr 2+ Au + Ti 4+ and their combinations.

[0141] Furthermore, the present invention particularly relates to the use of compositions or materials for molecular recognition, especially racemic resolution.

[0142] Furthermore, the present invention particularly relates to the use of compositions or materials for treating bone degradation and / or malignant bone diseases such as osteoporosis.

[0143] Furthermore, the present invention particularly relates to compositions or materials, especially as drug delivery systems, for example for DNA and / or RNA.

[0144] Furthermore, the present invention particularly relates to compositions or materials for the prevention and / or treatment of diseases. Preferably, the diseases are selected from cancer, neuronal diseases, and diseases associated with tissue calcification. More preferably, the disease is selected from genetic disorders, including but not limited to achondroplasia, α-1 antitrypsin deficiency, antiphospholipid syndrome, autism, autosomal dominant polycystic kidney disease, breast cancer, charcot-marie-tooth disease, colon cancer, Cri-du-chat syndrome, Crohn's disease, cystic fibrosis, painful obesity, Down syndrome, retrograde ophthalmopathy, Duchenne muscular dystrophy, factor V Leiden thrombophilia, familial hypercholesterolemia, familial dediterranean fever, Fragile X syndrome, Gaucher disease, hemochromatosis, hemophilia, holoprosencephaly, Huntington's disease, Cranfield syndrome, Marfan syndrome, myotonic dystrophy, neurofibromatosis, Noonan syndrome, osteogenesis imperfecta, Parkinson's disease, phenylketonuria, and Poland syndrome. Anomaly, porphyria, progeria, prostate cancer, retinitis pigmentosa, severe combined immunodeficiency (SCID), sickle cell disease, skin cancer, spinal muscular atrophy, Tay-Sachs disease, thalassemia, rotten fish disease, Turner syndrome, velocardiofacial syndrome, WAGR syndrome, Wilson's disease, and diseases associated with small and large arteries, heart valves, brain (including cranial calcification), joints and tendons such as the knee joint and rotator cuff tendons, soft tissues such as the breast, muscles and fat, kidneys, bladder, and gallbladder.

[0145] Furthermore, the present invention particularly relates to the use of compositions or materials in solid-state batteries. Solid-state batteries, as used herein, are batteries having both solid electrodes and solid electrolytes.

[0146] Furthermore, the present invention particularly relates to the use of compositions or materials in energy harvesting chips, which are chips capable of generating their own energy. Energy harvesting is defined as the conversion of ambient energy into usable electrical energy. When compared to energy stored in ordinary storage elements such as batteries, the environment represents a relatively inexhaustible source of energy. Therefore, energy harvesting (i.e., extraction) methods must be characterized by their power density rather than their energy density.

[0147] Furthermore, the present invention particularly relates to the use of compositions or materials for the removal of harmful gases such as carbon dioxide, carbon monoxide, methane, or mixtures thereof from air or the atmosphere.

[0148] For further features and advantages of the uses described in the preceding paragraphs, please refer to the preceding description in its entirety.

[0149] Further features and advantages of the invention will become clear from the following drawings, description, and examples, in conjunction with the subject matter of the dependent claims. In one embodiment of the invention, individual features may be implemented individually or in combination thereof. Preferred embodiments are provided for illustration and better understanding of the invention and should not be construed as limiting the invention in any way. Attached Figure Description

[0150] The following is schematically shown in the accompanying drawings:

[0151] Figure 1. (a) Characteristic 2θ WAXS diffraction pattern of the heterogeneous HAp permealuminate catalyst (hereinafter referred to as C-2) in the range of 20°–60°; (b) PO4 of C-2. 3- Raman spectra of internal modes (ν1, ν2, ν3, and ν4). (c) WAXS diffraction patterns of characteristic 2θ in the 20°–60° range for single-phase hydroxyapatite (HAp) catalysts (hereinafter referred to as C-1) and C-2. (d) PO4 3- Raman spectra of internal modes (ν1, ν2, ν3, and ν4). Characteristic reflections and vibrational markers of HAp and percalcite in each subplot.

[0152] Figure 2 Superimposed Raman spectra of C-1 and C-2 catalysts obtained from a 7x4 array spaced 1 μm apart. The scale bar refers to the relative intensity of the peaks.

[0153] Figure 3 In-depth analysis of the regions of interest in C-1 and C-2 Raman spectra: (a) ν1 main mode; (b) lattice mode; and (c) 3500–3700 cm⁻¹ -1 O–H stretching vibration modes within the region (acquired using a 532 nm laser). Characteristic Raman vibrations of HAp and percalcite are marked in black and green, respectively.

[0154] Figure 4 XPS spectra of Ca 2p obtained from C-1 and C-2 catalysts.

[0155] Figure 5 The following areas 1 H-NMR spectra: (a) 0.5-4.0 ppm, (b) 5.5-8.5 ppm.

[0156] Figure 6 Comparison of catalytic performance of C-1 and C-2 catalysts: (a) product / ethanol ratio, (b) C-2 / C-1 ratio of all detected products.

[0157] Figure 7. (a) Unit cell of HAp crystal structure; (b) OH group along the c-axis of HAp crystal structure. - aisle.

[0158] Figure 8. (a) The unit cell of calcareous phosphate rock; (b) The unit cell of triclinic calcareous phosphate rock.

[0159] Figure 9. (a) and (b) Crystal structures of calcareous phosphate rock. Atoms involved in hydrogen bonding have been labeled.

[0160] Figure 10 (a) crystalline hydroxyapatite (hereinafter referred to as cHAp) was prepared by continuous hydrothermal treatment at different temperatures for 24 hours. h (a) and (b) thermally polarized crystals (T) h (hereinafter referred to as cHAp / tsp)(T) h Raman spectrum of ).

[0161] Figure 11 .cHAp(150℃) and cHAp / tsp(T h (a) 770-910cm (≥100℃) -1 and (b) 100-350cm -1 Raman spectra within the range.

[0162] Figure 12 (a) Raman spectra of cHAp (150 °C) and cHAp / tsp (150 °C) prepared using different HT times: 10 h and 24 h. (b) Raman spectra of cHAp / tsp (150 °C) prepared by applying different DC voltages to cHAp (150 °C). (c) Raman spectra of cHAp / tsp (150 °C) prepared by applying a voltage of 500 V and keeping the steel electrode in contact with or not in contact with the cHAp (150 °C) sample. cHAp (150 °C) was prepared by applying HT for 24 h in both (b) and (c).

[0163] Figure 13 (a) Raman spectra of different depths of cHAp / tsp (150 °C) obtained by applying HT for 24 h at 1000 °C and a polarization voltage of 500 V. (b) Raman spectra of 100–350 cm⁻¹ shown in (a). -1 Spectral magnification of the region.

[0164] Figure 14 Among them, T hcHAp(T) at 50, 100, 150, 200 and 240 °C h Low-magnification SEM micrographs of [images]. In all cases, HT was applied for 24 h. High-magnification micrographs of cHAp (150 °C) are also shown.

[0165] Figure 15 (a) corresponds to T in it. h cHAp(T) at 50, 100, 150, 200 and 240 °C h X-ray diffraction patterns of ) . In all cases, HT was applied for 24 h. In the diffraction pattern of cHAp (150 °C), reflections attributed to cHAp and percalcite are marked as filled rhombuses and hollow rhombuses, respectively, while those related to βTCP (β-tricalcium phosphate) are represented as filled circles in the diffraction pattern of cHAp (50 °C). (b) Where T h cHAp(T) at ≥100℃ h Distribution of cHAp and permafrost phases in ). This was obtained from the (211) reflection of cHAp and the (141) reflection of permafrost.

[0166] Figure 16 For samples obtained after reaction (95°C and 48 h) using a chamber pressure of 6 bar (i.e., 2 bar for each feed reaction gas) and a catalyst prepared by using cHAp (150°C): (a) a solution obtained after extracting amino acids from the catalyst by dissolving the sample in deuterated water containing 100 mM HCl and 50 mM NaCl. 1 (a) H NMR spectrum; and (b) solid-state catalyst for amino acid synthesis. 13 C NMR spectrum.

[0167] Figure 17 Yields of alanine and glycine in photoelectrochemical fixation of N2, CO2, and CH4 (in cm³) 2 (as a percentage of catalyst) as T h The function of . In all cases, the reaction (in triplicate) was carried out at 6 bar and 95°C for 48 h.

[0168] Figure 18 Permanently polarized hydroxyapatite 31 P-NMR spectrum.

[0169] Experimental Section

[0170] 1. Materials

[0171] Calcium nitrate (Ca(NO3)2), diammonium hydrogen phosphate [(NH4)2HPO4; purity >99.0%], 30% ammonium hydroxide solution [NH4OH; purity: 28-30% w / w], zirconium oxychloride (ZC; ZrOCl2·8H2O), and aminotris(methylenephosphonic acid) (ATMP) were purchased from Sigma Aldrich. Ethanol (purity >99.5%) was purchased from Scharlab. All experiments were performed using milli-Q water. N2, CH4, and CO2 gases with a purity >99.995% were purchased from Messer.

[0172] 2. Crystalline hydroxyapatite (cHA) p) Synthesis

[0173] 15 mL of 500 mM (NH4)2HPO4 in deionized water (pH adjusted to 10.5 ± 0.2 with ammonium hydroxide) was added dropwise (2 mL / min) to 25 mL of 500 mM Ca(NO3)2 in ethanol under gentle stirring (100 rpm). The mixture was stirred at room temperature for 1 h (100 rpm) to form a suspension. Unless otherwise specified, the suspension was subjected to hydrothermal (HT) treatment for 24 h using a Digestec DAB-2 autoclave at a temperature (T0). h The autoclave was kept within the range of 50℃-240℃. Before opening, the autoclave was allowed to cool. The white precipitate was separated by centrifugation and washed sequentially with water and a 60 / 40 v / v ethanol / water mixture at 8000 rpm for 5 minutes (twice). After freeze-drying for 3 days, the obtained powder was sintered at 1000℃ in air atmosphere for 2 hours, specifically using a Carbolite ELF11 / 6W / 301 furnace. The sample obtained using this procedure is then designated as cHAp(T). h ), where T h This refers to the temperature at which HT is applied to hydroxyapatite (HAp).

[0174] 3. Polarization process of thermal stimulation (TSP) )

[0175] According to the first method, 150 mg of sintered cHAp powder was uniaxially pressed at 620 MPa for 10 minutes (i.e., an applied weight of 5 tons) to obtain a disc with a diameter of 10 mm and a thickness of 1 mm. The disc was placed between two stainless steel (AISI 304) plates spaced 4 cm apart and heated in an air atmosphere at 1000 °C. Then, a DC voltage of 100 V, 500 V, or 1000 V was applied for 1 hour. Subsequently, the cHAp (T...) process was applied... h The obtained sample is represented as cHAp / tsp(T) h The applied voltage is clearly specified in each case.

[0176] According to the second method, catalytic activation was also successfully achieved by applying thermally stimulated polarization (TSP) treatment, which involved exposing the HAp disk to 500V and 1000°C for 1 hour. To obtain a single-phase HAp catalyst (hereinafter referred to as C-1), electrodes (two stainless steel AISI 304 plates) were placed in contact with the HAp disk. Conversely, a multiphase HAp-penetrating phosphate catalyst (hereinafter referred to as C-2) was obtained by spacing the positive electrode 4 cm away from the HAp disk and contacting the HAp disk with the negative electrode.

[0177] 4. Characterization

[0178] Structural characterization was performed using X-ray photoelectron spectroscopy (XPS), micro-Raman spectroscopy, and wide-angle X-ray scattering (WAXS). The crystallinity (χ²) was determined based on the WAXS spectra. c ) and crystallite size L hkl .

[0179] Furthermore, the structural fingerprints of the samples were investigated using an inVia Qontor confocal Raman microscope (Renishaw) equipped with a Renishaw Centrus 2957T2 detector. All measurements were performed using 532 and 785 nm lasers. To obtain representative results, all spectra presented in this study are averages of 42 points on a 105 × 90 μm grid. Depth profiles were also obtained using the same equipment.

[0180] Morphological characterization was performed using a Zeiss Neon 40 focused ion beam microscope equipped with a SEM GEMINI column and Shottky field emission. Samples were sputter-coated with a thin layer of carbon to prevent issues related to sample charge.

[0181] As previously mentioned, the Brucker D8 Advance model with Bragg Brentano 2θ construction and Cu K are used. α Crystallinity (χ²) was obtained by wide-angle X-ray scattering (WAXS) of radiation (λ = 0.1542 nm). c A one-dimensional Lynx Eye detector was used. Measurements were performed within a 2θ range of 20°–60°, with a step size of 0.02° and a scan rate of 2 s. χ was obtained using the following expression. c value:

[0182]

[0183] Where I 300 The intensity of the reflection at (300) and V 112 / 300The indentation intensity is defined as the difference between the (112) and (300) reflections. The crystallite size L is calculated using the Debye-Scherrer equation. hkl .

[0184]

[0185] Where λ is the wavelength of the monochromatic X-ray beam, B is the full width at half the maximum intensity peak, and θ is the wavelength of the monochromatic X-ray beam. hkl To satisfy the peak diffraction angle of the (hkl) plane Bragg's law.

[0186] 5. Carbon fixation

[0187] The reaction was carried out at 95°C for 72 h under UV irradiation (GPH265T5L4, 253.7 nm) in an inert reaction chamber with an atmosphere of 3 bar CO2 and 3 bar CH4. Before sealing, 0.5 mL of deionized liquid water was added to the reactor. 1 ¹H-NMR spectroscopy (Bruker Avance III-400) was used to analyze the reaction products from the catalyst surface. Commercial products at controlled concentrations were used as references to obtain reaction yields.

[0188] 6. Effect of TSP treatment on coexisting permeapatite phase

[0189] Figure 1a Comparison of the WAXS spectra recorded for C-1 and C-2 revealed the definite presence of highly crystalline HAp in both catalysts. Therefore, the peaks identified at 2θ = 31.8°, 32.2°, and 33.0° correspond to the (211), (112), and (300) reflections of HAp, respectively (JCPDS card number 9-0432). The most significant peaks of the coexisting percalcite appeared at 2θ = 29°, 31°, 35°, 42°, and 51°, attributed to (141), respectively. (121) and Reflection (JCPDS card number 72-0713). It can be seen that, although... Figure 1a In 2θ = 31.0° is the only distinguishable reflection from diatomite, but a comparison of the relative intensities obtained for C-1 and C-2 supports the presence of this coexisting apatite phase in the latter. One of the most relevant differences was observed at 2θ = 51.3°, which could be attributed to the (410) reflection of HAp or to the diatomite. Reflection. For C-1, the peak intensity at 2θ = 51.3° is less than 1 (I) compared to the peak intensity at 2θ = 52.1° (corresponding to (402)HAp reflection). 2θ＝51.0 / I 2θ＝52.1=0.96), indicating that the intensity of the former peak is slightly lower than that of the latter peak. For C-2, I 2θ＝51.0 / I 2θ＝52.1 Increase to I 51 / 52.1 =1.14, proving that the peak at 2θ = 51.3° is stronger than that at 2θ = 52.1°.

[0190] Peaks (112) and (300) are also used to determine crystallinity (χ²). c ;Eq S1), while (211) reflection is used to calculate the crystallite size (L 211 (Eq S2). The crystallinity is very high and similar for both catalysts, with χ² values ​​for C-1 and C-2. c The values ​​were 0.95±0.03 and 0.92±0.03, respectively. The crystallite sizes of the two catalysts were also similar, with the obtained values ​​(L for C-1 and C-2) being... 211 The wavelengths (75.2 ± 2.4 nm and 82.7 ± 3.72 nm, respectively) are consistent with those reported in the literature. Overall, these observations suggest that the differences applied during TSP treatment do not affect the major HAp phase.

[0191] Raman studies of C-1 and C-2 catalysts, such as Figure 1b As shown, the spectrum of the apatite phase is mainly dominated by its characteristic PO vibration. Vias corresponding to PO4 are visible in the catalyst's spectrum. 3- The four characteristic regions of the internal pattern HAp are: ν1 = 962 cm -1 ν2=400-900cm -1 ν3=570-625cm -1 And ν4 = 1020 - 1095 cm -1 The two samples were at 970 and 949 cm⁻¹. -1 The other two peaks at this location both exhibit slight ν1 mode splitting, which is attributed to three crystallographically nonequivalent PO4 groups found in the β-tricalcium phosphate (TCP) apatite phase. 3- Different PO stretching vibrations of the tetrahedron. Therefore, according to the literature, the presence of TCP is not related to TSP treatment, but rather to minor changes in the conditions applied during HT synthesis and subsequent sintering. Furthermore, previous studies have shown that TSP treatment increases crystallinity and reduces the TCP phase by applying a crystallographically specific orientation. Additionally, the fact that the two samples exhibit approximately the same relative TCP amount (i.e., for C-1 and C-2, 970 cm⁻¹) further supports this finding. -1 Raman displacement intensity at 962 cm -1 The ratio of the main peak intensity at I 970 / 962(0.12 and 0.10 respectively) demonstrate that the conditional differences applied during TSP processing are not a precursor to TCP generation. However, the effect of separating the positive electrode from the mineral disk during TSP processing is clearly shown in... Figure 1b More specifically, the presence of percalcite in sample C-2 was observed at 878, 848, and 794 cm⁻¹. -1 The peaks at these locations confirm that they correspond to HPO4. 2- The normal vibrational modes, POH deformation modes, and POH rotation modes were observed. Other differences found between the Raman spectra of the C-1 and C-2 catalysts are described below.

[0192] HPO4 2- The obvious presence of POH vibrations allows for tracking changes in the amount of permealuminate based on TSP conditions. In this sense, the synergistic activity between the HAp and permealuminate phases is strongly dependent on their exposed surfaces, and therefore, characterizing their surface distribution is of great interest. Figure 2 Twenty-eight Raman spectra of samples C-1 and C-2, recorded from a 7x4 array spaced 1 μm apart, were plotted. For clarity, all spectra are superimposed, and the scale bar indicates the relative intensity of the peaks. As expected, compared to sample C-2, the C-1 spectrum showed no trace of the aforementioned percalcite peaks. Surprisingly, C-2 showed a peak at 878 cm⁻¹. -1 The peak corresponds to HPO4 2– The normal vibrational modes exhibit a relative intensity variation as high as 90%, indicating a highly uneven distribution of the coexisting permaphos phase. From Figure 2 The results indicate that the geometry of the device used to apply the electric field plays a crucial role, defining the inhomogeneity of the two coexisting phases. To support this conclusion, the inventors conducted further experiments, repeating the TSP treatment with alternating positive electrodes. More specifically, the plates were removed, leaving only the copper cable as the positive electrode. Examination of the recorded Raman spectra confirmed the correlation between the permafrost phase and the geometry of the applied field. Not only the HPO4 peak... 2– The POH vibration peaks appear to be stronger (i.e., for C-2 catalysts prepared with and without plates at the cathode, respectively I...). 878 / 962 =0.22 and I 878 / 962 =0.73), and the sample is more uniform, 878cm -1 The peak at that location showed only a relative change of ~21%. Overall, the results indicate that the HAp / penetrating calcium phosphate ratio and catalyst inhomogeneity can be tuned by varying the distance between the plates and the electrical geometry during TSP treatment.

[0193] 7. Structural characterization of C-2 catalysts

[0194] Detailed structural characterization is crucial for understanding the synergistic effects occurring in catalysts containing percalciphosphorus. In this case study, the inventors focused on identifying how percalciphosphorus integrates into the HAp lattice with its boundary distortion, thereby creating new active edge sites and locally increasing conductivity. The most common polymorph of HAp is a hexagonal lattice (see Figure 7), with space group P63 / m. α=β=90°, γ=120°)PO4 3– The groups are arranged in an equivalent tetrahedron, while Ca 2+ The ions occupy two distinct crystallographic positions. In this crystalline phase, OH... - The groups are arranged column-wise along the c-axis, but their orientation is disordered due to electrostatic forces. After TSP treatment, OH - Groups tend to orient themselves along a specific direction of the electric field, thereby introducing crystallographic stress into the crystal lattice. This crystallographic stress in C-1 is as follows: Figure 3 As shown in figure a, the Raman spectrum in the dominant ν1 mode region is magnified. Meanwhile, the dominant ν1 vibrational mode of HAp in sample C-2 is at 962 cm⁻¹. -1 The value is consistent with the theoretical value, and the main peak of C-1 is located at 963 cm. -1 The location reflects PO4 3- The tetrahedral tensile strain. The fact that C-1 is the only sample exhibiting this change suggests that the permealuminate found in the C-2 catalyst compensates for the strain through OH-. - Localized tensile stress caused by chain rearrangement.

[0195] One of the most surprising aspects of the C-2 catalyst is the acquisition of the permeapatite phase, which seems to contradict the fact that TSP proceeds at high temperatures. At approximately 160 °C, permeapatite dehydrates to triclinic calcium phosphate (CaHPO4), and when the temperature is increased to 320, 700, and 1200 °C, it further deprotonates to different forms of calcium pyrophosphate (Ca2P2O7) in γ, β, and α forms, respectively. From 878, 848, and 794 cm⁻¹... -1 HPO4 at the location 2- Experimental evidence obtained from the POH vibration mode and at approximately 732 cm -1 The absence of POP vibrations at this location excludes the presence of Ca2P2O7. Analysis of lattice vibration modes clearly visualizes the difference between percalcite and triclinic phosphogypsum, as these structures crystallize in different space groups, as shown in Figure 8. Percalcite consists of a monoclinic structure and exhibits space group Ia symmetry. α=γ=90°, β=116.428°), while triclinic phosphate exhibits... triclinic unit cell with space group symmetry ( α=96.180°, β=103.82°, γ=88.34°). exist Figure 3The lattice patterns of the C-1 and C-2 catalysts were compared in b. C-1 presented the characteristic lattice patterns of HAp as follows: 140 and 155 cm -1 (attributed to the transitional vibrations of Ca1+Ca2 and Ca2 respectively); 193 and 205 cm -1 (the translational vibration of PO4 3- ); 235 and 288 cm -1 (the wagging vibration of PO4 3- ); 270 cm -1 (the transitional vibration of Ca1); and 332 cm -1 (the translational vibration of OH - ).

[0196] Compared with C-1, the spectra recorded for C-2 showed much stronger peaks at 111, 142, and 270 cm -1 , which were attributed to the contributions of the unique crystallographic sites of Ca in brushite. In addition, relative to C-1, the PO4 2+ translational mode at 205 cm -1 in C-2 was enhanced. Notably, although the peak at 142 cm 3- (attributed to the transitional vibrations of Ca1+Ca2 of HAp and Ca of brushite) was much stronger and showed a redshift of 2 cm -1 relative to C-1, the peak at 155 cm -1 remained unchanged because it was attributed to the HAp transitional vibration of Ca2, which is absent in the brushite phase. The redshift of the Ca -1 transitional vibration from 140 cm -1 in C-1 to 142 cm -1 in C-2 confirmed the presence of brushite rather than tricalcium phosphate in the latter. Therefore, due to group symmetry, the Raman shifts attributed to the Ca 2+ transitional vibration should be arranged as follows: tricalcium phosphate < HAp < brushite. Overall, 2+ the results shown in a-b not only confirmed the presence of brushite but also highlighted that the C-2 catalyst presented local Ca Figure 3 with higher mobility and smaller tensile stress, which may lead to a synergistic effect and result in improved catalytic performance. 2+

[0197] As shown in Fig. 9, the crystal structure of brushite can be understood as consisting of zigzag Ca 2+ parallel to the a-axis and growing along the c-axis and PO4 3- ​A layered system formed by alternating chains. These chains are bonded together along the b-axis by hydrogen bonds provided by H₂O molecules that form the intermediate layer. However, this water intermediate layer was not detected in the Raman spectrum of C₂. The characteristic stretching modes of water should have been detected in two pairs: 3539 and 3483 cm⁻¹. -1 ν2 of 3270 and 3163cm -1 . Figure 3 c shows 3574cm -1 The OH group corresponding to HAp at the location - The characteristic HAp peak of the scaling mode. Furthermore, in Figure 1b In general, it is located at 678cm. -1 Neither of the two water release patterns could be distinguished.

[0198] right Figure 3 Detailed analysis of the lattice mode in b reveals that C-2 at 323 cm⁻¹ -1 There is a strong new peak at this point, which is attributed to OH. - The translational vibrational mode of the functional group. This peak can be clearly deconvoluted to a position at 332 cm⁻¹. -1 (Matching the translational vibrations of HAp obtained in the C-1 spectrum) and 323 cm -1 The two distinct peaks at that point. The fact that this new peak exhibits a significant blue shift indicates the presence of different crystallographic OH groups with lower mobility and therefore bonded in some way. - Because they participate in hydrogen bonding interactions, the H2O molecules in pure permafrost are distorted relative to free molecules, creating two different crystallographic sites for water molecules (labeled H2O-O1 and H2O-O2 in Figure 9). The outer layers are bonded together by hydrogen bonds of O3…H2 (of H2O-O1) and OH1…H4 (of H2O-O2), exhibiting… and The short distances and almost linear angles of 167.3° and 175.7°, respectively. Considering the above theoretical aspects and consistent with the obtained experimental results, the hydroxyl groups occupying the crystallographic positions of the water molecule appear to be responsible for stabilizing the crystallographic clear phosphatite or clear phosphatite-like phase through hydrogen bonding interactions. The exchange of protons and hydroxyl groups at high temperatures, leading to changes in the HAp crystal structure, has been extensively studied. However, using OH... - Replacing H2O molecules may lead to other crystallographic distortions because the remaining water protons bonded to other oxygen-hydrogen bonds in the crystal lattice are suppressed. In the case of H2O-O2 water molecules, this is not crucial to the stability of permafrost because the bond between H5 and H2O-O1 water molecules is weak, and the distance between H5…H2O-O1 is… Therefore, alternating Ca 2+ and PO4 3-The ions form weaker interactions and therefore exhibit higher mobility. The sharp increase in the lattice mode intensity of these ions in the C-2 catalyst supports this hypothesis. Figure 3 b).

[0199] On the other hand, H2O-O1 water molecules also react with PO4 3- The O3 hydrogen bonds of the group are at a distance of In this situation, it is difficult to determine which hydrogen bond is formed by the OH group. - Substitution, because they are very similar in energy. However, assuming OH points pointing in both directions... - The combination of ions (O3…H2 and H3…O3) may be reasonable because the TSP treatment applies specific OH groups. - Orientation, while OH1…H4 and O3…H2 point backward.

[0200] Ca, which is highlighted for quantifying Raman spectra 2+ The increased ion lattice mobility was used to perform XPS measurements to capture the surface electronic binding states of Ca. Figure 4 XPS Ca2p of C-1 and C-2 catalysts were compared. Both spectra exhibited characteristic HAp Ca2p. 3 / 2 and Ca 2p 1 / 2 The peaks are located at 346.9 and 350.5 eV for C-1 and 346.4 and 350.0 eV for C-2. This observation is very consistent with recent XPS studies of HAp after TSP treatment. The binding energy of the Ca 2p peak is mainly related to Ca…PO4. 3- Bond correlation. Ca 2p 3 / 2 Standard values ​​are typically measured at ~347.2 eV, although displacements are observed at higher binding energies in some cases, such as when RCOO - When the group is adsorbed (i.e., Ca…COO), - Bond ratio Ca…PO4 3- (Stronger bonds). Conversely, for C-1 and C-2, the dissociation shifts to a smaller binding energy, which is consistent with the OH generated by TSP treatment. - Vacancies are a factor. Consistent with Raman spectroscopy, the shift in sample C-2 (-0.8 eV) is more pronounced than that in sample C-1 (-0.3 eV). This 0.5 eV difference is attributed to the presence of a permealuminate coexisting phase in the C-2 catalyst.

[0201] 8. The effect of the presence of calcium phosphate on catalyst selectivity

[0202] The detailed analysis completed in the previous section enabled the identification of structural differences between the C-1 and C-2 catalysts, highlighting some possible synergistic effects between the two phases detected in the latter. More specifically, the effect of coexisting percalophosphate on the catalytic properties of HAp can be explained as follows: 1) Ca 2+ The ions have small binding energies and are therefore usable as novel catalytic or adsorption sites; and 2) despite the presence of OH in both phases - But the arrangement of OH - The symmetry of the column may also be disrupted at the boundaries between phases, producing regions with lower electronic conductivity but higher accumulated charge. To determine the possible synergistic effect contributed by the percalciphos phase, carbon fixation reactions have been carried out for comparison using C-1 and C-2 catalysts. More specifically, the reaction was catalyzed at 95 °C under UV irradiation of the catalyst directly, using a mixture of CO2 and CH4 gases (3 bar each) and liquid water (1 mL) in an inert reaction chamber (120 mL).

[0203] Figure 5 The reaction yielded C-1 and C-2 catalysts dissolved in deuterated water containing 100 mM HCl and 50 mM NaCl after 72 h of reaction. 1 H-NMR spectroscopy allowed us to identify the reaction products formed on the catalyst surface. By examining the spectra in the low-frequency region, three reaction products from both catalysts were clearly identified. Figure 5 a) Ethanol (CH2 quartet and CH3 triplet at 3.50 and 1.06 ppm, respectively), acetone (CH3 singlet at 2.08 ppm), and acetic acid (CH3 singlet at 1.85 ppm). The OH peak of ethanol (the major product in both cases) (i.e., 13.13 ± 3.75 and 15.01 ± 4.62 μmol / g C-1 and C-2 catalyst, respectively) overlaps with a strong water peak at 4.65 ppm (not shown). In any case, Figure 5 The two spectra shown in a are relatively similar, indicating that the coexistence of percalcite does not have any significant effect on the yields of ethanol, acetone, and acetic acid.

[0204] In contrast, for the high-frequency region 1 Analysis of H-NMR spectra ( Figure 5 (b) Revealed very important and significant differences. More specifically, formic acid (a singlet at 8.28 ppm) and a peak at 5.81 ppm at which carbon compounds attributed to trace double bonds were detected only in the C-1 sample. This is a significant achievement because the formic acid yield of C-1 (8.06 ± 1.89 μmol) was very high, reaching 36% of the total yield (relative to 59% of ethanol). Table 1 summarizes the reaction yields using C-1 and C-2:

[0205]

[0206] Table 1. Yields of all reaction products catalyzed by C-1 and C-2 (in μmol of product per gram of catalyst).

[0207] To further understand the selectivity differences between C-1 and C-2 catalysts, the reaction yield relative to ethanol production was analyzed. Figure 6 a) and the C-2 / C-1 product ratio ( Figure 6 b). First, from C-2 总共 and C-1 总共 The ratio is defined as the total catalytic activity ratio (where C-2) 总共 and C-1 总共 The value (referring to all products obtained using C-2 and C-1 catalysts respectively) is 0.8. The fact that this value is close to 1 indicates that introducing a new phase to adjust the catalyst has no significant effect on the overall catalytic activity, but only on the selectivity. Therefore, the yields of acetone, acetic acid, and ethanol are higher with C-2 than with C-1, thus compensating for the amount of formic acid produced. Furthermore, the results demonstrate that the coexistence of HAp and percalcite phases promotes the incorporation of ·CH3, which is favorable for the conversion of formic acid to acetic acid. Consistently, the acetone yield is higher with C-2 than with C-1.

[0208] Overall, incorporating a small amount of permealuminate phase into HAp-based catalysts enhances the incorporation of ·CH3 species in CO2 and CH4 fixation reactions. This is attributed to: 1) charge accumulation favors the dissociation of CH4 into ·CH3; and 2) Ca 2+ They are more likely to adsorb substances because they have fewer bonds.

[0209] 9. Preparation of cHAp / tsp-based catalysts

[0210] A three-component catalyst was prepared by continuously dropping 100 μL of an aqueous solution of 50 mM ATMP, 10 mM ZC, and 50 mM ATMAP onto a cHAp / tsp disk (diameter: 10 mm; thickness: 1 mm). The sample was dried at room temperature for 8 h before each dropping step.

[0211] 10. Synthesis of amino acids

[0212] Amino acid synthesis was performed using a high-pressure stainless steel reactor. The reactor was characterized by an inert reaction chamber (120 mL) coated with a perfluoropolymer, into which both the catalyst and water were added. The reactor was equipped with inlet valves for N2, CH4, and CO2, and an outlet valve for recovering gaseous reaction products. A UV lamp (GPH265T5L / 4, 253.7 nm) was placed in the center of the reactor to directly irradiate the catalyst; the lamp was protected by a UV-protected transparent quartz tube. All surfaces were coated with a perfluoropolymer film to prevent any contact between the reaction medium and the reactor surface, thus eliminating the possibility of additional catalytic effects.

[0213] The reaction was carried out at 95°C for 48 hours. Approximately 150 mg of catalyst sample and 0.5 mL of deionized liquid water were first added to the reaction chamber. The chamber was then thoroughly purged with the first selected gas to eliminate initial air content. Each selected gas was introduced to increase the reaction chamber pressure (measured at room temperature) to the target pressure. In all cases, the chamber pressure was increased to up to 6 bar by sequentially introducing 2 bar of each feed reaction gas.

[0214] The reaction products were analyzed by NMR spectroscopy. All NMR spectra were acquired using a Bruker Avance III-400 spectrometer. 1 H and 13 C operated at frequencies of 400.1 MHz and 100.6 MHz, respectively. Tetramethylsilane was used. 1 H and 13 C) Used as an internal standard to calibrate chemical shifts. (For each...) 1 H and 13 C10 NMR records were obtained at scans 64 and 1000. To remove amino acids from the catalyst, the sample was dissolved in deuterated water containing 100 mM HCl and 50 mM NaCl, and then deuterated water was added at the end.

[0215] 11. cHAp: Used in hydrothermal (HT) ) Processing temperature

[0216] Precipitation of HAp and HT are crucial steps for adjusting stoichiometry and avoiding the formation of other phases, such as β-tricalcium phosphate (βTCP), which can be readily formed under certain conditions, and are often used in sintering at 1000-1200 °C to refine the crystal structure.

[0217] Figure 10 a comparison was made between the two methods performed after the precipitation step at T. h cHAp(T) was prepared by applying HT continuously for 24 hours at 50℃, 100℃, 150℃, 200℃ and 240℃. h The Raman spectrum recorded from the sample. PO4 is generally observed from Raman measurements of aqueous solutions. 3-The normal mode frequency of the tetrahedron is υ1 = 938 cm⁻¹. -1 υ2=420cm -1 υ3=1017cm -1 and υ4=567cm -1 In cHAp and βTCP, the crystallization field not only leads to PO4 3- The shift of normal modes, and the resulting splitting, although these effects depend on the crystallographic structure. Figure 10 The spectrum shown in a clearly indicates that PO4 3- The splitting of the normal mode decreases with increasing hydrothermal temperature. For example, in cHAp(T h The spectrum of the sample (≥100℃) is at 962 cm⁻¹ -1 Non-degenerate PO4 was detected at the location. 3- The υ1 mode produces a single strong peak, while several peaks are observed for cHAp (50℃). For cHAp (T h Similar characteristics were also observed for doubly degenerate υ2 and triplely degenerate υ3 and υ4 (≥100℃), spanning frequency ranges of 400-490, 570-625, and 1020-1095, respectively. In all cases, PO4 3- The frequency of the spectral bands is 20-25 cm higher than those corresponding to the free tetrahedral normal modes (i.e., in aqueous solution). -1 .

[0218] cHAp exhibits the space group P63 / m and the unit cell contains 6 equivalent PO4 groups. 3- Tetrahedral, while βTCP crystallizes in space group R3c, and its unit cell contains 42 PO4 atoms distributed across three non-equivalent types. 3- Tetrahedron. Therefore, it was observed at υ1 = 962 cm. -1 The single strong peak detected at [location] is two peaks and one shoulder peak for βTCP. This structural difference also affects υ2 and υ4, which span a frequency range greater than cHAp in βTCP. Furthermore, the frequency gap between υ2 and υ4 in βTCP is only 55 cm. -1 In cHAp, the frequency gap is 120cm. -1 .like Figure 10 As shown in figure a, the spectral fingerprint recorded for the cHAp (50 °C) sample is consistent with those expected for βTCP, indicating that this is the dominant phase when HT is performed at low temperatures.

[0219] For cHAp / tsp(T) h The Raman spectrum obtained is in Figure 10 As shown in b, it displays the relationship with cHAp(T) h PO4 3- The similar features described by the normal mode ( Figure 10 a). After TSP processing, for T h The sample prepared at 50℃, with PO4 3- The intensity and width of the relevant peaks correspond to the βTCP phase, while in T h cHAp can be clearly identified in samples hydrothermally treated at ≥100℃. However, in cHAp / tsp(T h Some samples can also be identified as T. h The unique characteristics of the function. For example, cHAp / tsp (150℃) at approximately 330cm -1 A weak peak was observed at [location], while no signal was detected for the remaining samples. Considering that the detection of these peaks depends on the crystallinity of the sample, the Raman results suggest that when [at T]... h The highest crystallinity was obtained when HT was performed at 150℃. Furthermore, the crystallinity of cHAp / tsp(T) was... h ≥100℃) at 878cm -1 A peak was detected at the location, such as Figure 11 This is clearly demonstrated. The signal is characteristic of percalcite minerals (i.e., CaHPO4·2H2O, understood as a precursor to apatite), and is attributed to HPO4. 2- The normal mode frequency. For T h The sample obtained at 150℃ showed a much stronger band, while the remaining portion exhibited a weak peak. Additionally, at 794 and 848 cm⁻¹... -1 Two typical bands of POH rotation and deformation modes appear at T. Although they are very weak in all cases, they are significant for T. h The sample obtained at 150℃ also showed the highest intensity of POH signal.

[0220] Figure 11 b compared the values ​​for cHAp (150℃) and cHAp / tsp (T) h ≥100℃) at 100-350cm -1 Weak intensity spectral bands were observed between these bands. These bands are attributed to Ca. 2+ (111, 139 and 154cm) -1 ), PO4 3- (287cm -1 ) and OH - (331 and 323cm) -1 Sublattice translation modes and PO4 3- Rotation mode of the group (205cm) -1 It can be seen that when the TSP method is applied to the cHAp (150℃) sample, both the intensity and narrowness of all these bands are at their maximum. Furthermore, with OH... –Intensity bands associated with the translation mode of sublattice production ( Figure 11 331 and 323cm in b -1 ) with POH rotation and deformation modes ( Figure 11 794 and 848cm in a -1 The linear increase in ) proves the structural correlation.

[0221] 12. Duration of HT and characteristics of TSP processing

[0222] The duration of HT is another factor affecting the HAp structure, and thus the performance of cHAp / tsp as a catalyst. Figure 12 a compared the results for T h Raman spectra of samples prepared at 150 °C with HT times of 10 or 24 h are shown. It can be seen that the spectra of cHAp samples obtained only after 10 h of HT show the peaks described for the βTCP phase in the previous section. Therefore, the conversion of the βTCP phase to cHAp can only be completed when the HT is sufficiently long, even at T... h This is also true when it is optimal. Interestingly, Figure 12 The results show that TSP treatment is beneficial for surface rearrangement in samples prepared using both 10 and 24 hours, as shown by 878 cm⁻¹. -1 The appearance of the permealuminate peak and 323cm -1 OH - The translation mode of the sublattice is evident. However, for the βTCP fingerprint identified in the cHAp (150℃) sample obtained using a 10-hour processing time, it differs from that of PO4. 3- The four normal mode frequencies are correlated and remain almost unchanged after the permanent polarization process. Therefore, the TSP process cannot be used to compensate for the undesirable structural effects caused by HT shortening.

[0223] By applying 100V, 500V, or 1000V (25, 125, and 250V·cm, respectively) to the cHAp (150℃) sample -1 The effect of the electric field strength used to induce permanent polarization of cHAp was examined using a DC voltage. Although the Raman spectra obtained for all the samples corresponded to cHAp ( Figure 12 b) However, some bands that are clearly related to the catalytic activity of cHAp / tsp are slightly affected by the DC voltage intensity. More specifically, for samples polarized at 500V, this is attributed to OH... - Translation mode of sublattice (323cm) -1 ), HPO4 2- Normal mode (878cm) -1 ) and POH rotation and deformation modes (794 and 848 cm) -1The peaks obtained at 100V and 1000V are stronger and clearer than those obtained at 100V and 1000V. Based on these results, changes in the voltage used for the TSP process are not expected to annihilate the activity of cHAp / tsp as a catalyst, but will cause minor changes in its effectiveness.

[0224] Finally, the effect of electrode geometry on TSP treatment was investigated. For this purpose, cHAp / tsp (150°C) samples were prepared using a DC voltage of 500V and two different electrode geometries: i) steel plates spaced 4cm apart, thus the cHAp (150°C) disk contacted only one electrode (i.e., the thickness of the sintered mineral disk was 1mm); and ii) steel plates spaced 1mm apart, thus each side of the cHAp (150°C) disk contacted an electrode. Figure 12 The recorded Raman spectra compared in c reveal that only when the TSP process hinders the steel-cHAp contact do the spectra appear at 794, 848, and 878 cm⁻¹. -1 A spectral band was observed at [location missing]. Furthermore, when the electrode spacing was 4 cm, [the band] was observed with OH [missing information]. - Translation mode of sublattice (323cm) -1 The related spectral band intensities are much higher.

[0225] In-depth profile Raman analysis was performed to monitor the extent of changes caused by TSP treatment. Figure 13 Raman spectra of cHAp / tsp (150 °C) prepared at 1000 °C with a polarization voltage of 500 V and subjected to HT for 24 h were compared at different depths (i.e., from the surface to a depth of 95 μm). Although the spectra showed the same fingerprint in all cases, the signal intensity decreased with increasing depth. This observation is relevant to HPO4. 2- (878cm -1 ) and POH rotation and deformation modes (794 and 848 cm) -1 The spectral bands of both are particularly prominent. These results indicate that the changes induced by TSP treatment are primarily located on the mineral surface. This is in Figure 13 This was confirmed in b, which showed that at 110 and 330 cm -1 The region detected essentially weak spectral bands. (Similar to PO4) 3- Rotation mode of the group (205cm) -1 ), and especially with Ca 2+ (111, 139 and 154cm) -1 ), PO4 3- (287cm -1 ) and OH - (323cm -1 The intensity of the spectral bands associated with the translation mode of the sublattice decreases with increasing depth.

[0226] 13. Morphological and structural characterization of cHAp samples

[0227] Figure 10 and 11 The Raman spectra shown in the image indicate that cHAp(T) h ) and cHAp / tsp(T h The chemical properties of ) and therefore the catalytic activity of the latter depend on T h To study T h The effects on the morphology and structure of cHAp were investigated using SEM and XRD.

[0228] Where T h = cHAp(T) at 50℃, 100℃, 150℃, 200℃ and 240℃ h Low-magnification SEM micrographs such as Figure 14 As shown. Except for having βTCP(T) h Except for the sample at 50℃, which exhibits the densest surface, the other samples show a morphology composed of alternating dense regions and numerous porous regions. For example... Figure 14 As shown, examination of high-magnification micrographs of cHAp (150℃) as a representative sample reveals that the porous region consists of columnar structures grown by the aggregation of mineral nanoparticles in a preferred direction. However, the morphology of the porous region is clearly different from that of T. h Irrelevant.

[0229] cHAp(T) was prepared using WAXD. h Structural characterization of samples Figure 15 a). Characteristic fingerprint of hexagonal crystal symmetry cHAp ( α = β = 90° and γ = 120°; JCPDS card number 9-0432) are generally associated with peaks at 32°–34°2θ, which correspond to (211), (112), and (300) reflections. These reflections are used in T h All samples prepared at ≥100℃ were clearly identified in the diffraction patterns and were also readily apparent in the diffraction pattern of the cHAp (50℃) sample. Other characteristic reflection peaks of cHAp appeared at 2θ = 32°, 34°, 40°, 47°, and 49°, corresponding to (211), (202), (130), (222), and (214) reflections. The (112) and (300) peaks were also used to determine crystallinity (χ²). c :Eqn 1), while (211) reflection is used to calculate the crystallite size (L 211 ;Eqn 2). For T h =100℃, 150℃, 200℃ and 240℃, cHAp(T h ) of χ cThe values ​​were 0.53, 0.82, 0.68, and 0.77, respectively. This is consistent with... Figure 10 The Raman spectra shown in a are completely consistent. Therefore, when in T h χ² of cHAp prepared at 150℃ c The largest is at T, followed by T. h The values ​​were obtained at 240 °C. Changes detected in cHAp (200 °C), and χ² values ​​relative to cHAp (150 °C) and cHAp (240 °C) are also shown. c The reduction (and this is experimentally reproducible) is attributed to the combined effects of the freeze-drying and sintering processes on the crystal, which appears to depend on the T used. h Value. This can explain not only when T h When the temperature increases from 150℃ to 200℃, χ c The decrease could explain the χ² of cHAp (240℃). c The fact that it is lower than cHAp (150℃). Furthermore, regarding T... h = cHAp(T) at 100℃, 150℃, 200℃ and 240℃ h ), calculated L 211 The values ​​correspond to 69.1, 82.7, 82.6 and 82.7 nm, respectively.

[0230] On the other hand, the most relevant reflection peak of percalcite (JCPDS card number 72-0713) was clearly observed in the X-ray diffraction pattern of cHAp (150℃). Percalcite has a monoclinic structure and a unit cell parameter of [missing information]. α=γ=90° and β=116.43° ( Figure 15 a). These reflections are weaker for cHAp (240℃) and much weaker for cHAp (100℃) and cHAp (200℃), corresponding to (141), (121), (152), and (143) for 2θ = 29°, 35°, 42°, and 51°, respectively. It is worth noting that although some of these reflections, such as (143), match other reflections found in the theoretical diffraction of pure cHAp, the variation in relative intensity indicates the coexistence of two phases, consistent with Raman spectroscopy. By comparing the (211) reflection of cHAp with the (141) reflection of percalcite, the X-ray diffraction patterns were used to roughly estimate the phases at T. h The amounts of cHAp and permealuminate phase in samples prepared at ≥100°C were determined. The results indicate that, although at T... h HT at ≥100℃ promotes the formation of the latter phase. Figure 15 b), but in all cases cHAp is clearly the dominant phase. However, the content of percalcite varies from T h =At 100℃ and 200℃, ~5% increases to T h= ~15% at 150℃ and 240℃.

[0231] Typically, in T h The anomalous behavior of the sample obtained at 200 °C is attributed to the dehydration process reported for percalciphosphatite at this temperature. Thus, the layered structure of percalciphosphatite CaHPO4·2H2O, where mineral layers are held together by hydrogen-bonded water molecules, transforms into the amorphous phase and triclinic calcium phosphatite CaHPO4. More specifically, although surface water evaporates at approximately 100 °C, two crystallographic water molecules of percalciphosphatite, associated with oxygen atoms in the phosphate groups via hydrogen bonds, remain stable at this temperature and leave the system at 200 °C. The structural transformation associated with percalciphosphatite dehydration at 200 °C explains the χ² c The decrease in [something], which in turn impairs catalytic activity.

[0232] Finally, examine the diffraction pattern obtained for cHAp (50℃). Figure 15 a) This allows for the identification of the reflection peaks generally reported for βTCP (JCPDS card number 09016), which are more dominant than those associated with cHAp. Therefore, orthorhombic βTCP appears as the dominant crystalline phase in the sample treated with HT at the lowest temperature.

[0233] 14.cHAp / tsp(T h )do Performance of catalysts for amino acid synthesis

[0234] In a recent study, the inventors catalyzed the fixation of nitrogen from N2 and carbon from CO2 and CH4 to obtain Glycine and Ala, two of the simplest amino acids. The catalyst was prepared by coating a cHAp / tsp (150°C) sample with two layers of ATMP separated by an intermediate ZC layer. For this purpose, the cHAp / tsp (150°C) plate was sequentially immersed in an aqueous solution of 5 mM ATMP, 5 mM ZC, and 1.25 mM ATMP for 5 h at room temperature. After each immersion, the sample was dried at 37°C for 3 h. The catalytic reaction was initiated in an inert reaction chamber from a simple gas mixture containing N2, CO2, CH4, and H2O under UV light irradiation and mild reaction conditions.

[0235] Figure 16 This demonstrates that changes in the application of ATMP and ZC coatings do not alter the performance of the catalyst. Figure 16 a shows the sample obtained by dissolving the catalyst prepared using cHAp (150 °C) and the reaction products after 48 h at 95 °C. 1¹H NMR spectra. The signal corresponding to the methylene group of ATMP shows a doublet at 3.53–3.56 ppm, while the signal corresponding to the methylene group of the generated Gly is a singlet at 3.37 ppm. The methine and methyl groups of Ala show a quartet at 3.84–3.87 ppm and a doublet at 1.60–1.62 ppm, respectively. Figure 16 b shows 13 The same compound was also detected in the C10 NMR spectrum, with only peaks belonging to the ATMP (53.82 and 52.92 ppm), Gly (172.26 and 41.35 ppm), and Ala (175.26, 50.56, and 16.18 ppm) units.

[0236] It should be noted that, for the use of T h cHAp(T) at ≥100℃ h The catalyst prepared by [the catalyst] also showed a positive reaction. The yield of the reaction was calculated using commercial Gly and Ala (purchased from Sigma-Aldrich) at controlled concentrations to calibrate the reaction. 1 1H NMR peaks. Changes in reaction yield are expressed relative to T. h % per cm 2 Catalysts, such as Figure 17 As shown, these values ​​are higher than those found in the inventors' previous study, which showed a value of 2.5 after 48 h (i.e., the Gly / Ala ratio decreased from 5.4 to 2.2 as the reaction time increased from 2 h to 96 h). This characteristic is attributed to the presence of the permeapatite phase, which was not observed in the catalysts prepared in the inventors' previous study. Therefore, the combination of permeapatite and cHAp obtained by the method described in this work clearly accelerates the conversion of Gly to Ala.

[0237] On the other hand, yield is related to cHAp / tsp(T) h ) in χ c This is related to both the content of transparent phosphate rock and the content of calcium phosphate. Therefore, for T h The catalysts prepared at 150 °C and 240 °C yielded the highest amino acid yields (2.8% and 2.7%, respectively) after 48 h, which not only demonstrates the highest χ² value... c (i.e., 0.82 and 0.77 respectively), and showed the highest content of permealuminate (i.e., 15% and 12% respectively). In contrast, for the χ c <0.7 cHAp / tsp(T h The overall yield of the catalyzed reaction was reduced by an order of magnitude, i.e., ~0.5-0.6%. This characteristic clearly reflects the very important role of spatial translation mode in promoting charge transport on the surface through oscillation and translational molecular motion after lattice excitation.

Claims

1. A composition comprising: a) permanently polarized hydroxyapatite and b) brushite and / or brushite-like material, characterized in that said permanently polarized hydroxyapatite being in a proportion of 50% by weight to 99.9% by weight and said brushite and / or said brushite-like material being in a proportion of 0.1% by weight to 35% by weight, each based on the total weight of the composition; the composition being obtained by applying a heat-stimulated polarization treatment to hydroxyapatite, wherein the hydroxyapatite is spaced apart from a positive electrode, the positive electrode being used together with a negative electrode for carrying out the heat-stimulated polarization treatment, the permanently polarized hydroxyapatite 31 The P-NMR spectrum has a peak in the range of 2.4 ppm - 2.8 ppm corresponding to the phosphate group of hydroxyapatite, said brushite having the chemical formula CaHPO4-2H2O, the peaks of the brushite appearing in wide-angle x-ray scattering spectra at 2Q = 29°, 31°, 35°, 42° and 51°, The brushite-like material has peaks in the Raman spectrum at 878 cm -1 , 848 cm -1 , and 794 cm -1 .

2. The composition of claim 1, wherein, said composition being in the form of a catalyst, wherein said permanently polarized hydroxyapatite forms a phase of said catalyst and said brushite and / or brushite-like material forms another phase of said catalyst.

3. The composition according to claim 2, wherein said catalyst is a heterogeneous catalyst.

4. The composition according to claim 2, wherein said permanently polarized hydroxyapatite forms a main phase of said catalyst.

5. The composition according to any one of claims 1-4, characterized in that, said permanently polarized hydroxyapatite being in a proportion of 75% by weight to 99% by weight based on the total weight of the composition.

6. The composition of claim 5, wherein, said permanently polarized hydroxyapatite being in a proportion of 80% by weight to 95% by weight based on the total weight of the composition.

7. The composition according to any one of claims 1-4, characterized in that, said brushite and / or said brushite-like material being in a proportion of 1% by weight to 25% by weight based on the total weight of the composition.

8. The composition of claim 7, wherein, said brushite and / or said brushite-like material being in a proportion of 5% by weight to 20% by weight based on the total weight of the composition.

9. The composition according to any one of claims 1-4, characterized in that, said brushite and / or said brushite-like material having a crystallinity of 65% to 99.9% as determined by wide-angle x-ray scattering.

10. The composition of claim 9, wherein, said brushite and / or said brushite-like material having a crystallinity of 75% to 99%.

11. The composition of claim 9, wherein, said brushite and / or said brushite-like material having a crystallinity of 80% to 95%.

12. The composition of any one of claims 1-4, wherein, said brushite and / or said brushite-like material having a crystallite size of 20 nm to 500 nm as determined by wide-angle X-ray.

13. The composition of claim 12, wherein said brushite and / or said brushite-like material having a crystallite size of 50 nm to 200 nm.

14. The composition of claim 12, wherein said brushite and / or said brushite-like material having a crystallite size of 70 nm to 100 nm.

15. Process for producing the composition according to any one of claims 1 to 14, characterized in that The method comprises the following steps: a) providing a sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate, b) sintering the sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate provided in step (a), c) applying a heat-stimulated polarization treatment to the sintered sample of step (b), wherein the hydroxyapatite is spaced apart from a positive electrode, the positive electrode being used together with a negative electrode for carrying out the heat-stimulated polarization treatment, c) applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) a constant or variable DC voltage between 250 V and 2500 V and a temperature between 900 °C and 1200 °C or applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) an equivalent electric field between 1.49 kV / cm and 15 kV / cm and a temperature between 900 °C and 1200 °C or applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) an electrostatic discharge between 2500 V and 1500000 V and a temperature between 900 °C and 1200 °C or applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) an equivalent electric field between 148.9 kV / cm and 8928 kV / cm and a temperature between 900 °C and 1200 °C and (d) cooling the sample obtained in step (c) while maintaining the DC voltage or the equivalent electric field or the electrostatic discharge, wherein for carrying out step (c), the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) is arranged between a positive electrode and a negative electrode for applying a constant or variable DC voltage, an equivalent electric field or an electrostatic discharge during step (c) such that the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) is spaced apart from the positive electrode.

16. The method according to claim 15, wherein in step (c) a constant or variable DC voltage between 250 V and 2500 V is applied for at least 1 min; an equivalent electric field between 1.49 kV / cm and 15 kV / cm is applied for at least 1 min; an electrostatic discharge between 2500 V and 1500000 V is applied for > 0 min to 24 h; an equivalent electric field between 148.9 kV / cm and 8928 kV / cm is applied for > 0 min to 24 h.

17. The method according to claim 15, wherein in step (c) a constant or variable DC voltage between 250 V and 2500 V is applied for at least 1 min and at a temperature of 1000 °C to 1200 °C; a constant or variable equivalent electric field between 1.49 kV / cm and 15 kV / cm is applied for at least 1 min and at a temperature of 1000 °C to 1200 °C; a static electric discharge between 2500 V and 1500000 V is applied for > 0 min to 24 h and at a temperature of 1000 °C to 1200 °C; a constant or variable equivalent electric field between 148.9 kV / cm and 8928 kV / cm is applied for > 0 min to 24 h and at a temperature of 1000 °C to 1200 °C.

18. The composition according to claim 1 obtained by a method comprising the steps of: a) providing a sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate, wherein the hydroxyapatite is natural or synthetic hydroxyapatite, b) sintering the sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate provided in step (a), c) applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) a constant or variable DC voltage between 250 V and 2500 V and a temperature between 900 °C and 1200 °C or applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) an equivalent electric field between 1.49 kV / cm and 15 kV / cm and a temperature between 900 °C and 1200 °C or applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) a static electric discharge between 2500 V and 1500000 V and a temperature between 900 °C and 1200 °C or applying to the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or to a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) an equivalent electric field between 148.9 kV / cm and 8928 kV / cm and a temperature between 900 °C and 1200 °C, and (d) cooling the sample obtained in step (c) while maintaining the DC voltage or the equivalent electric field or the static electric discharge, wherein For carrying out step (c), the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) is arranged between an anode and a cathode for applying a constant or variable DC voltage, an equivalent electric field or an electrostatic discharge during step (c) such that the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) or a shaped body derived from the sintered sample of hydroxyapatite or hydroxyapatite and amorphous calcium phosphate obtained in step (b) is spaced apart from the anode.

19. The composition according to claim 18, wherein in step (c) a constant or variable DC voltage between 250 V and 2500 V is applied for at least 1 min; applying an equivalent electric field between 1.49 kV / cm and 15 kV / cm for at least 1 min; applying an electrostatic discharge between 2500 V and 1500000 V for > 0 min to 24 h; applying an equivalent electric field between 148.9 kV / cm and 8928 kV / cm for > 0 min to 24 h.

20. The composition according to claim 19, wherein in step (c) a constant or variable DC voltage between 250 V and 2500 V is applied for at least 1 min and at a temperature between 1000 °C and 1200 °C; applying an equivalent electric field between 1.49 kV / cm and 15 kV / cm for at least 1 min and at a temperature between 1000 °C and 1200 °C; applying an electrostatic discharge between 2500 V and 1500000 V for > 0 min to 24 h and at a temperature between 1000 °C and 1200 °C; applying an equivalent electric field between 148.9 kV / cm and 8928 kV / cm for > 0 min to 24 h and at a temperature between 1000 °C and 1200 °C.

21. Use of the composition according to any one of claims 1 to 14 or according to any one of claims 18 to 20 as a catalyst in a reaction for the synthesis of an organic molecule.

22. The use according to claim 21, wherein the catalyst is an electrocatalyst or a photoelectrocatalyst.

23. Use according to claim 21 or 22, characterized in that the composition as a catalyst in a reaction for the synthesis of an amino acid.

24. The use according to claim 23, wherein the amino acid is a natural amino acid.

25. The use according to claim 24, wherein the natural amino acid is glycine and / or alanine.

26. Use according to claim 21 or 22, characterized in that the composition as a catalyst in a reaction for the synthesis of a carboxylic acid.

27. The use according to claim 26, wherein the carboxylic acid is formic acid, acetic acid, malonic acid or a mixture thereof.

28. Use according to claim 21 or 22, characterized in that the composition as a catalyst in a reaction for the synthesis of an aldehyde and / or a ketone.

29. The use according to claim 28, wherein the ketone is acetone.

30. Use according to claim 21 or 22, characterized in that the composition as a catalyst in a reaction for the synthesis of an alcohol. the composition as a catalyst in a reaction for the synthesis of an aldehyde and / or a ketone.

31. The use according to claim 30, wherein the alcohol is methanol and / or ethanol.

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