Morphology-controllable mesoporous copper-based nanomaterial and preparation method thereof

Abstract

The present application belongs to the field of nanomaterials. The mesoporous copper-based nanomaterial provided by the present application has a particle size of 50-400 nm, a pore size of 2-20 nm, and a divergent center channel structure. The present application provides a preparation method of the mesoporous copper-based nanomaterial. Hexadecyl trimethyl ammonium bromide or hexadecyl trimethyl ammonium chloride, hexamethylene tetramine or urea, citric acid, sodium citrate or malic acid, copper chloride or copper nitrate, and sodium salicylate or sodium benzoate are sequentially added to water, and stirred to obtain a clear solution. Then, cyclohexane or 1,3,5-trimethylbenzene is added, and the mixture is stirred vigorously to obtain an emulsion. The mixture is heated for hydrolysis. After the reaction is completed, the mixture is centrifuged and dried. The mesoporous copper-based nanomaterial provided by the present application has high photo-thermal conversion efficiency, excellent catalytic performance, and can load small molecules, enzymes, nanoparticles and other substances of different sizes as required. In addition, other substances can be further coated or doped according to requirements, so as to form a nanocomposite material with more functions.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterials, specifically relating to a mesoporous copper-based nanomaterial and its preparation method. Background Technology

[0002] Copper, as a core component of many enzymes (such as cytochrome C oxidase, metallothionein, and superoxide dismutase), plays an indispensable role in a wide variety of life activities. Its unique variable valence properties endow copper-based materials with excellent redox properties. Copper can not only assemble with ligand molecules such as amino acids and catechols into nanoparticles, but it can also be effectively loaded or doped into carriers such as silica and dopamine nanoparticles, thus finding wide application in many fields such as disease diagnosis and treatment, gas sensing, environmental remediation, and energy.

[0003] Mesoporous materials, with their unique mesoporous structure, exhibit significant advantages such as ultra-high specific surface area, large pore volume, and low density. In particular, the centrally radiating pore structure has attracted much attention due to its adjustable pore size and high accessibility of internal components. Furthermore, mesoporous materials can be integrated with other functional units through encapsulation, loading, and other methods to achieve multifunctional integration.

[0004] Chinese invention patent application No. 202510043158.5 discloses a method for preparing mesoporous copper oxide and its application. The preparation method includes the following steps: S1: using calcium carbonate paper as a substrate and copper nitrate as a solvent to prepare hydroxylated copper nitrate microplates; S2: synthesizing ordered copper hydroxide nanowire assemblies through an alkaline reaction; S3: annealing in a muffle furnace to obtain mesoporous copper oxide microplates. Chinese invention patent application No. 202411187731.1 discloses a nanomotor that induces the death of proliferative scar copper and its preparation method. First, spherical mesoporous organosilicon nanoparticles are synthesized using hexadecyltrimethylammonium bromide and diethane; then, these are added to a mixture of deionized water, ethanol, hexadecyltrimethylammonium bromide, and tetraethyl orthosilicate to react and obtain Janus silica nanoparticles. A Cu(NO3)2 precursor is added to the Janus silica nanoparticle solution, and hexamethylenetetramine is added... Tetraamine-catalyzed hydrolysis of Cu(NO3)2 yields copper-loaded Janus silica nanoparticles and Cu and Mn-containing Janus silica nanoparticles M-Cu@J. Nanomotors are then prepared to obtain amino-functionalized M-Cu@J nanomotors, DSF-loaded M-CuD@J nanomotors, and HM-CuD@J nanomotors. This invention solves the problems of existing nanomotors lacking the ability to actively transport within the microenvironment of hypertrophic scars and failing to effectively induce copper death in hypertrophic scar cells (HSF).

[0005] The unique feature of mesoporous copper-based nanomaterials lies in their combination of the excellent catalytic, conductive, and antibacterial properties of metallic copper with the high specific surface area, well-ordered channels, and confinement effect brought about by the mesoporous structure. This makes them stand out from traditional copper materials, demonstrating irreplaceable application value in multiple cutting-edge fields. To adapt to different application scenarios, the preparation methods of mesoporous copper-based materials are constantly being optimized, resulting in the preparation of mesoporous copper-based materials with even better performance. Summary of the Invention

[0006] The purpose of this invention is to provide a mesoporous copper-based nanomaterial with excellent catalytic performance, high photothermal conversion efficiency, and strong loading capacity, as well as its preparation method.

[0007] This invention ingeniously introduces mesoporous structures into copper-based nanomaterials, achieving an organic combination of the high specific surface area and strong loading capacity of mesoporous materials with the optical, thermal, and catalytic properties of copper-based materials. The mesoporous copper-based nanomaterials provided by this invention are spherical nanoparticles with centrally radiating mesoporous channels, ranging in size from 50 to 400 nm and having a pore size of 2 to 20 nm. The mesoporous copper-based nanomaterials provided by this invention are composed of either mesoporous copper hydroxide nanomaterials or mesoporous copper oxide nanomaterials, and can be encapsulated and doped with other substances to form multifunctional nanocomposite materials.

[0008] The method for preparing mesoporous copper-based nanomaterials according to the present invention involves a reaction carried out in a water-cyclohexane or 1,3,5-trimethylbenzene emulsion system, using hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride as a surfactant, hexamethylenetetramine or urea as a base source, citric acid, sodium citrate or malic acid as a bridging agent, copper chloride or copper nitrate as a copper metal source, and sodium salicylate or sodium benzoate as a viscosity modifier, and conducting a hydrolysis reaction under heating conditions. The specific preparation steps of the mesoporous copper hydroxide nanomaterials are as follows: (1) Add hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride, hexamethylenetetramine or urea, sodium citrate, copper chloride or copper nitrate, sodium salicylate or sodium benzoate to water in sequence and stir to obtain a clear solution; (2) Add cyclohexane or 1,3,5-trimethylbenzene and stir vigorously to obtain an emulsion; (3) Adjust the reaction temperature to 40-80 ℃ and react for 4-24 h; (4) After the reaction is complete, centrifuge the reaction solution, wash the precipitate and dry it.

[0009] An emulsion system refers to a multiphase dispersion system in which one or more liquids are dispersed in the form of tiny droplets in another liquid that is immiscible (or incompletely miscible). In this invention, the emulsion system can be selected from, but is not limited to, aqueous solutions of water-cyclohexane or 1,3,5-trimethylbenzene. Preferably, the added cyclohexane or 1,3,5-trimethylbenzene, by volume, is water:cyclohexane or 1,3,5-trimethylbenzene = 1:(0.01-3). More preferably, the ratio of water:cyclohexane or 1,3,5-trimethylbenzene is 1:(0.05-0.5).

[0010] Surfactant, also known as interfacial surfactant, is a substance that, when added in small amounts, can significantly change the interfacial state of a solution system. In this invention, the surfactant can be selected from, but is not limited to, hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride. Preferably, in the clarified solution described in step (1), the concentration of hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride is 0.02-3 wt%. More preferably, the concentration of the surfactant is 0.05-2 wt%.

[0011] An alkali source refers to the origin of an alkali. An alkali is a compound that, upon ionization, produces only hydroxide ions as anions. It typically neutralizes acids in water and is an inorganic compound. This invention uses hexamethylenetetramine or urea as the alkali source. Preferably, the concentration of hexamethylenetetramine or urea is 0.003-0.9 wt%. More preferably, the concentration of hexamethylenetetramine or urea is 0.005-0.3 wt%.

[0012] A bridging agent is a substance in a chemical or material system that can connect two or more molecules, atoms, groups, or material surfaces. Also known as a crosslinking agent, it is used to connect reaction precursors and construct a three-dimensional network structure. In this invention, the bridging agent can be selected from citric acid, sodium citrate, or malic acid. Preferably, the concentration of citric acid, sodium citrate, or malic acid is 0.02-0.2 wt%. More preferably, the concentration of the bridging agent is 0.02-0.15 wt%.

[0013] A copper metal source refers to a substance that provides copper ions. In this invention, copper chloride or copper nitrate is used as the copper metal source. Preferably, the concentration of copper chloride or copper nitrate is 0.05-6 wt%. More preferably, the concentration of copper chloride or copper nitrate is 0.1-1 wt%.

[0014] Viscosity modifiers are agents primarily used to increase the viscosity of a system and slow down reaction kinetics. This invention uses sodium salicylate or sodium benzoate as the viscosity modifier. Preferably, the concentration of sodium salicylate or sodium benzoate is 0.005-0.4 wt%. More preferably, the concentration of sodium salicylate or sodium benzoate is 0.05-0.2 wt%.

[0015] Preferably, the stirring rate in step (2) is 300-2000 rpm. More preferably, the stirring rate is 500-1000 rpm.

[0016] Step (3) is a hydrolysis reaction involving heating. Preferably, the reaction temperature is adjusted to 40-80 ℃, more preferably 60-70 ℃. The reaction time is 4-24 h, preferably 6-18 h. Even better, the reaction time is 8-12 h.

[0017] The preparation method of the mesoporous copper hydroxide nanomaterials of this invention involves a reaction carried out under calcination conditions. The specific steps are as follows: the mesoporous copper hydroxide nanomaterials are placed in a tube furnace or muffle furnace, and the calcination temperature is adjusted to 150-220 °C for 1-8 h. Preferably, the calcination temperature is 160-200 °C. More preferably, the calcination temperature is 180-190 °C. The calcination time is preferably 2-6 h. More preferably, the calcination time is preferably 3-5 h.

[0018] Preferably, the heating rate of the tube furnace or muffle furnace is 0.1 ℃ / min to 4 ℃ / min. More preferably, the heating rate is 0.5 ℃ / min to 1 ℃ / min.

[0019] The research of this invention shows that although many mesoporous materials are obtained by reacting surfactants, bridging agents, viscosity modifiers, and alkali sources in an emulsion, the components and their amounts used are precisely matched for copper-based materials. For example, if sodium citrate is used as the bridging agent, reducing the sodium citrate content in the system from 0.15% to 0.005% results in an irregular structure of copper hydroxide with no pore distribution, and the system yield will be significantly reduced. In other words, mesoporous copper-based nanomaterials that meet the requirements of this invention cannot be obtained.

[0020] The mesoporous copper-based nanomaterials obtained by the preparation method of this invention combine the mesopores with the inherent activity of the copper matrix, enabling their application in numerous scenarios. The mesoporous structure provides a large specific surface area, allowing more copper atoms to be exposed and improving catalytic performance. The well-ordered channels not only facilitate the rapid entry and exit of reactants and products but also confine reaction intermediates within the channels, forcing the reaction to proceed along the intended pathway and enhancing selectivity.

[0021] Mesoporous copper-based materials can serve as nanozymes, utilizing the acidic nature of the tumor microenvironment through chemokinetic therapy to convert endogenous hydrogen peroxide into highly toxic hydroxyl radicals to kill cancer cells. More importantly, their mesoporous structure can act as a nanoreactor, simultaneously loading chemotherapeutic drugs or calcium peroxide to achieve synergistic chemotherapy-chemokinetic therapy, or enhancing therapeutic effects by releasing calcium ions to induce calcium overload. Mesoporous copper-based materials are a rising star in the field of electrocatalysis, their advantage lying in utilizing the mesoporous structure to stabilize highly reactive copper ions in specific valence states, thereby achieving precise control over reaction pathways.

[0022] The mesoporous copper-based nanomaterials provided by this invention, when encapsulated or doped with other substances, form mesoporous multifunctional nanocomposite materials.

[0023] The preparation method of the mesoporous multifunctional nanocomposite material of the present invention is based on the preparation method of mesoporous copper hydroxide nanomaterial, by further adding nanomaterials or metal salts to the clear solution in step (1).

[0024] Preferably, the nanomaterial is selected from, but not limited to, one or more of silica, Prussian blue, iron oxide, iron oxide, and noble metal nanoparticles. The concentration of the nanomaterial can be 0.01-5 wt%. Preferably, the concentration of the nanomaterial in the clear solution is 0.05-3 wt%, more preferably 0.1-1 wt%.

[0025] Preferably, the metal salt is selected from, but not limited to, one or more of the following: scandium chloride, yttrium chloride, lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, ferric chloride, cobalt chloride, nickel chloride, zinc chloride, aluminum chloride, chromium chloride, manganese chloride, scandium nitrate, yttrium nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, promethium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, terbium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, lutetium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, aluminum nitrate, chromium nitrate, and manganese nitrate. The concentration of the metal salt can be 0.0001-4 wt%. Preferably, the concentration of metal salt in the clarified solution is 0.008-0.2 wt%, more preferably 0.1-0.15 wt%.

[0026] The mesoporous copper-based nanomaterials provided by this invention exhibit high photothermal conversion efficiency, excellent catalytic performance, and the ability to load small molecules, enzymes, and nanoparticles of various sizes. Furthermore, the mesoporous copper-based nanomaterials of this invention can be further encapsulated and doped with other substances as needed to form nanocomposite materials with even more functions. Attached Figure Description

[0027] To more clearly illustrate the technical solutions of this application, the drawings used in the embodiments will be briefly introduced below. Obviously, each drawing described below is for a part of the embodiments of this application. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0028] Figure 1 Scanning electron microscope image of the mesoporous copper hydroxide nanomaterial prepared in this invention. The copper hydroxide material consists of spherical nanoparticles with numerous open mesoporous channels distributed on its surface.

[0029] Figure 2 Transmission electron microscopy (TEM) image of the mesoporous copper hydroxide nanomaterials prepared in this invention. The mesoporous channels are uniformly distributed within the particles, and the channel sizes are uniform.

[0030] Figure 3 Scanning electron microscope (SEM) image of the mesoporous copper oxide nanomaterials prepared in this invention. Mesoporous copper hydroxide nanoparticles are obtained by calcination. The crystallization process causes the material to shrink, and the image shows that the mesoporous pore walls become thinner, the pore size increases, the particle adhesion decreases, and the monodispersity is enhanced.

[0031] Figure 4 Transmission electron microscopy (TEM) image of the mesoporous copper oxide nanomaterials prepared in this invention. After calcination, the pore structure of the mesoporous copper oxide nanoparticles remains intact, and the interconnected pore structures are clear and complete.

[0032] Figure 5 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with a hexadecyltrimethylammonium bromide concentration of 0.03%. Compared with Example 1, even with a reduced hexadecyltrimethylammonium bromide concentration, the pores of the mesoporous copper hydroxide nanoparticles remained, but the degree of particle adhesion increased.

[0033] Figure 6 Scanning electron microscopy (SEM) image of mesoporous copper hydroxide prepared with hexadecyltrimethylammonium chloride at a concentration of 1.5%. Choosing hexadecyltrimethylammonium chloride as a pore-forming agent still allows for the synthesis of mesoporous copper hydroxide nanoparticles.

[0034] Figure 7 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared by replacing urea with hexamethylenetetramine at a concentration of 0.005%. Compared with Example 1, the synthesis of mesoporous copper hydroxide nanoparticles can still be achieved by replacing urea with hexamethylenetetramine.

[0035] Figure 8 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with a urea concentration of 0.2%. Compared with Example 1, the size of the mesoporous copper hydroxide nanoparticles decreased after increasing the urea content.

[0036] Figure 9 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with a sodium citrate concentration of 0.1%. Compared to Example 1, the size of the mesoporous copper hydroxide nanoparticles decreased after reducing the amount of citric acid added.

[0037] Figure 10 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with a malic acid concentration of 0.005%. Compared with Example 1, replacing citric acid with malic acid resulted in the continued presence of pores in the copper hydroxide nanoparticles, but with increased particle adhesion.

[0038] Figure 11 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with a copper chloride concentration of 0.6%. Compared with Example 1, reducing the amount of copper chloride added significantly increased the pore size of the copper hydroxide nanoparticles.

[0039] Figure 12 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with a copper nitrate concentration of 3%. Compared to Example 1, copper chloride was replaced with copper nitrate, and the amount of copper salt added was increased, resulting in thicker pore walls and smaller pore sizes in the copper hydroxide nanoparticles.

[0040] Figure 13 Scanning electron microscopy (SEM) image of mesoporous copper hydroxide prepared with a sodium salicylate concentration of 0.01%. Compared with Example 1, reducing the amount of sodium salicylate in the system resulted in smaller pore sizes and less distinct pore structures.

[0041] Figure 14 The image shows a scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with sodium benzoate at a concentration of 0.2%. Compared with Example 1, replacing sodium salicylate with sodium benzoate still allows for the synthesis of mesoporous copper hydroxide nanoparticles.

[0042] Figure 15 Scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared with a water to cyclohexane volume ratio of 1:0.05. Compared with Example 1, replacing 1,3,5-trimethylbenzene with cyclohexane still allows for the synthesis of mesoporous copper hydroxide nanoparticles.

[0043] Figure 16 Scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared by mixing water and 1,3,5-trimethylbenzene in a volume ratio of 1:0.5. Compared with Example 1, increasing the amount of 1,3,5-trimethylbenzene significantly increased the pore size of the mesoporous copper hydroxide nanoparticles.

[0044] Figure 17 Scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared at a reaction temperature of 40 °C. Compared with Example 1, lowering the reaction temperature still allows for the synthesis of mesoporous copper hydroxide nanoparticles, with an increased particle size.

[0045] Figure 18 Scanning electron microscope (SEM) image of mesoporous copper hydroxide prepared at a reaction temperature of 80 °C. Compared with Example 1, increasing the reaction temperature still enables the synthesis of mesoporous copper hydroxide nanoparticles, but the particle size is reduced and the degree of adhesion is increased.

[0046] Figure 19 Scanning electron microscope (SEM) image of mesoporous copper oxide prepared at a calcination temperature of 200 °C. Compared with Example 2, increasing the calcination temperature makes the pores of the mesoporous copper oxide nanoparticles less obvious, and a clear grain distribution can be seen.

[0047] Figure 20 Transmission electron microscopy (TEM) image of the mesoporous copper oxide nanomaterials prepared in this invention. After calcination of the mesoporous copper hydroxide material in Example 3, the pore structure of the mesoporous copper oxide nanoparticles remained intact.

[0048] Figure 21 Transmission electron microscopy (TEM) image of a composite material containing mesoporous copper hydroxide encapsulated with Prussian blue nanoparticles. The mesoporous copper hydroxide material is uniformly coated on the outside of the Prussian blue nanoparticles.

[0049] Figure 22 Transmission electron microscopy (TEM) image of zinc-doped mesoporous copper hydroxide composite material. Zinc and copper elements are uniformly distributed within the nanoparticles without phase separation, and the particles retain a clear pore structure.

[0050] Figure 23 Scanning electron microscopy (SEM) image of mesoporous copper hydroxide prepared with 0.005% sodium citrate. The resulting copper hydroxide has an irregular structure with no pore distribution, and the yield of the system is significantly reduced. Detailed Implementation

[0051] This invention provides a mesoporous copper-based nanomaterial. The material comprises copper hydroxide and copper oxide, and is shaped as nanoparticles with a centrally radiating pore structure. The material size is 50-400 nm, and the pore size is adjustable from 2-20 nm. The pore structure is centrally radiating. The copper-based nanomaterial can also be encapsulated or doped with other substances to form multifunctional nanocomposite materials. This invention ingeniously introduces a mesoporous structure into copper-based nanomaterials, achieving an organic combination of the high specific surface area and strong loading capacity of mesoporous materials with the photoelectric, thermal, and catalytic properties of copper-based materials. The mesoporous copper-based nanomaterial provided by this invention has high photothermal conversion efficiency; excellent catalytic performance; and can load small molecules, enzymes, and nanoparticles of different sizes. The mesoporous copper-based nanomaterial of this invention can be further encapsulated or doped with other substances as needed to form nanocomposite materials with even more functions.

[0052] This invention provides a specific method for preparing the mesoporous copper hydroxide nanomaterial.

[0053] (1) Add hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride, hexamethylenetetramine or urea, citric acid, sodium citrate or malic acid, copper chloride or copper nitrate, sodium salicylate or sodium benzoate to water in sequence and stir to obtain a clear solution; (2) Add cyclohexane or 1,3,5-trimethylbenzene and stir vigorously to obtain an emulsion; (3) Adjust the reaction temperature to 40-80 ℃ and react for 4-24 h; (4) After the reaction is complete, centrifuge the reaction solution, wash the precipitate and dry it.

[0054] In the clarified solution of step (1), the ratio of hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride to aqueous solution is 0.02-3 wt%; the ratio of hexamethylenetetramine or urea to aqueous solution is 0.003-0.9 wt%; the ratio of sodium citrate, sodium citrate or malic acid to aqueous solution is 0.02-0.2 wt%; the ratio of copper chloride or copper nitrate to aqueous solution is 0.05-6 wt%; and the ratio of sodium salicylate or sodium benzoate to aqueous solution is 0.005-0.4 wt%. In step (2), the volume ratio of cyclohexane or 1,3,5-trimethylbenzene to aqueous solution is 0.01-3 vol%.

[0055] This invention provides a specific method for preparing the mesoporous copper hydroxide nanomaterials. The mesoporous copper hydroxide nanomaterials are placed in a tube furnace or muffle furnace, and the calcination temperature is adjusted to 150-220 °C for 1-8 h. The heating rate of the tube furnace or muffle furnace is 0.1-4 °C / min.

[0056] This invention further provides a specific preparation method for the aforementioned mesoporous multifunctional nanocomposite material. Based on the preparation method of mesoporous copper hydroxide nanomaterials, nanomaterials or metal salts are further added to the clarified solution in step (1). The types of nanomaterials include: silicon dioxide, Prussian blue, iron tetroxide, iron oxide, and noble metal nanoparticles; the concentration of the nanomaterials is 0.01-5 wt%. The metal salts include: scandium chloride, yttrium chloride, lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, ferric chloride, cobalt chloride, nickel chloride, zinc chloride, aluminum chloride, chromium chloride, manganese chloride, scandium nitrate, yttrium nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, promethium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, terbium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, lutetium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, aluminum nitrate, chromium nitrate, and manganese nitrate; the concentration of the metal salts is 0.0001-4 wt%.

[0057] The technical solution will be clearly and completely described below through embodiments of this application. Obviously, the described embodiments are only some preferred embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of this application.

[0058] Unless otherwise specified, all percentages in this invention are mass percentages.

[0059] Example 1 Hexadecyltrimethylammonium bromide (0.05%), copper chloride (1%), sodium citrate (0.15%), sodium salicylate (0.1%), and urea (0.3%) were dissolved sequentially in water. Then, 1,3,5-trimethylbenzene (0.4 vol%) was added and the mixture was stirred vigorously. The reaction solution was incubated in a 60 °C oil bath for 7 h, followed by centrifugation, washing, and drying of the product. The scanning electron microscope image of the product is shown below. Figure 1 As shown, the transmission electron microscope image is as follows: Figure 2 As shown.

[0060] Example 2 The product described in Example 1 was transferred to a crucible and placed in a tube furnace. The temperature was increased from 25°C to 190°C at a rate of 1°C / min and held for 5 hours. The scanning electron microscope image of the product after natural cooling is shown below. Figure 3 As shown, the transmission electron microscope image is as follows: Figure 4 As shown.

[0061] Example 3 Hexadecyltrimethylammonium chloride (0.05%), copper nitrate (3%), sodium citrate (0.15%), sodium salicylate (0.1%), and hexamethylenetetramine (0.3%) were dissolved sequentially in water. Then, 1,3,5-trimethylbenzene (0.4 vol%) was added and the mixture was stirred vigorously. The reaction solution was incubated in a 60 °C oil bath for 7 h, followed by centrifugation, washing, and drying of the product. The scanning electron microscope image of the product is shown below. Figure 12 As shown.

[0062] Example 4 The product described in Example 3 was transferred to a crucible and placed in a tube furnace. The temperature was increased from 25°C to 190°C at a rate of 1°C / min and held for 5 hours. The scanning electron microscope image of the product after natural cooling is shown below. Figure 20 As shown. After calcination of the mesoporous copper hydroxide material in Example 3, the pore structure of the mesoporous copper oxide nanoparticles remained intact. The scanning electron microscope image of the product is shown below. Figure 20 As shown.

[0063] Example 5 Prussian blue nanoparticles (0.05%), hexadecyltrimethylammonium bromide (0.05%), copper chloride (1%), sodium citrate (0.15%), sodium salicylate (0.1%), and urea (0.3%) were dissolved sequentially in water. Then, 1,3,5-trimethylbenzene (0.4 vol%) was added and the mixture was stirred vigorously. The reaction solution was incubated in a 60 °C oil bath for 7 h, followed by centrifugation, washing, and drying of the product. The transmission electron microscopy (TEM) image of the product is shown below. Figure 21 As shown.

[0064] Example 6 Zinc nitrate (0.08%), hexadecyltrimethylammonium bromide (0.05%), copper chloride (1%), sodium citrate (0.15%), sodium salicylate (0.1%), and urea (0.3%) were dissolved sequentially in water. Then, 1,3,5-trimethylbenzene (0.4 vol%) was added and the mixture was stirred vigorously. The reaction solution was incubated in a 60 °C oil bath for 7 h, followed by centrifugation, washing, and drying of the product. The transmission electron microscopy (TEM) image of the product is shown below. Figure 22 As shown.

[0065] Example 7 Both Examples 1 and 3 used mesoporous copper hydroxide nanoparticles, but the material in Example 1 had a larger pore size. Using 3,3,5,5-tetramethylbenzidine (TMB) as a substrate, the catalytic activity of the two nanoparticles in producing •OH from the decomposition of H₂O₂ was tested in PBS at pH 7.4. •OH oxidizes colorless TMB to oxTMB, which has a characteristic absorption peak at 652 nm. The formation rate of •OH can be indirectly obtained by measuring the absorbance at 652 nm over time under different H₂O₂ concentrations (0.31-10 mM). Under the same H₂O₂ concentration, the system in Example 1 showed a significantly greater increase in absorbance at 652 nm than that in Example 3, corresponding to superior catalytic performance.

[0066] In the description of this invention, the terms "comprising," "including," or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising a reference structure" does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element. It should be noted that, herein, relational terms such as "first," "second," etc., are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations.

[0067] The embodiments described above are merely specific implementations of this application, but the scope of protection of this application is not limited thereto. Any variations or substitutions that can be conceived by those skilled in the art within the scope of the technology disclosed in this application without creative effort should be included within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of protection of the claims in this application.

Claims

1. A method for preparing mesoporous copper-based nanomaterials, characterized in that, The steps are as follows: (1) Add hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride, hexamethylenetetramine or urea, citric acid, sodium citrate or malic acid, copper chloride or copper nitrate, sodium salicylate or sodium benzoate to water in sequence and stir to obtain a clear solution; (2) Add cyclohexane or 1,3,5-trimethylbenzene and stir vigorously to obtain an emulsion; (3) Adjust the reaction temperature to 40-80 ℃ and react for 4-24 h; (4) After the reaction is complete, centrifuge the reaction solution, wash the precipitate and dry it.

2. The preparation method according to claim 1, characterized in that, In the clarified solution described in step (1), the concentration of hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride is 0.02-3 wt%; the concentration of hexamethylenetetramine or urea is 0.003-0.9 wt%; the concentration of citric acid, sodium citrate or malic acid is 0.02-0.2 wt%; the concentration of copper chloride or copper nitrate is 0.05-6 wt%; and the concentration of sodium salicylate or sodium benzoate is 0.005-0.4 wt%. In step (2), the cyclohexane or 1,3,5-trimethylbenzene added is in a volume ratio of water:cyclohexane or 1,3,5-trimethylbenzene = 1:(0.01-3); the stirring speed is 300-2000 rpm.

3. The preparation method according to claim 1, characterized in that, The reaction is carried out in a water-cyclohexane or 1,3,5-trimethylbenzene emulsion system, using hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride as surfactants, hexamethylenetetramine or urea as base sources, citric acid, sodium citrate or malic acid as bridging agents, copper chloride or copper nitrate as copper metal sources, and sodium salicylate or sodium benzoate as viscosity modifiers, and the hydrolysis reaction is carried out under heating conditions; In the clarified solution described in step (1), the concentration of hexadecyltrimethylammonium bromide or hexadecyltrimethylammonium chloride is 0.05-2 wt%; the concentration of hexamethylenetetramine or urea is 0.005-0.3 wt%; the concentration of citric acid, sodium citrate or malic acid is 0.02-0.15 wt%; the concentration of copper chloride or copper nitrate is 0.1-1 wt%; and the concentration of sodium salicylate or sodium benzoate is 0.05-0.2 wt%. In step (2), the cyclohexane or 1,3,5-trimethylbenzene added is in a volume ratio of water:cyclohexane or 1,3,5-trimethylbenzene = 1:(0.05-0.5); the stirring speed is 500-1000 rpm.

4. The preparation method according to claim 1, characterized in that, The preparation method further includes a calcination step: calcining the mesoporous copper-based nanomaterials obtained in step (4) at a temperature of 150-220 °C for 1-8 h.

5. The preparation method according to claim 4, characterized in that, Calcination is carried out in a tube furnace or muffle furnace, with a heating rate of 0.1-4 ℃ / min.

6. A mesoporous copper-based nanomaterial, characterized in that, The shape is spherical nanoparticles with centrally radiating mesoporous channels, with a size of 50-400 nm and a pore size of 2-20 nm. The specific components are mesoporous copper hydroxide nanomaterials or mesoporous copper oxide nanomaterials.

7. A nanocomposite material, characterized in that, Other substances are encapsulated and doped inside the mesoporous copper-based nanomaterial as described in claim 6.

8. The method for preparing the nanocomposite material according to claim 7, characterized in that, In step (1) of the preparation method according to claim 1, nanomaterials or metal salts are added to water and stirred to obtain a clear solution.

9. The preparation method according to claim 8, characterized in that, The nanomaterials are selected from one or more of the following: silica, Prussian blue, iron oxide, iron oxide, and noble metal nanoparticles; the concentration of the nanomaterials is 0.01-5%. The metal salt is selected from one or more of the following: scandium chloride, yttrium chloride, lanthanum chloride, cerium chloride, praseodymium chloride, neodymium chloride, promethium chloride, samarium chloride, europium chloride, gadolinium chloride, terbium chloride, dysprosium chloride, holmium chloride, erbium chloride, thulium chloride, ytterbium chloride, lutetium chloride, ferric chloride, cobalt chloride, nickel chloride, zinc chloride, aluminum chloride, chromium chloride, manganese chloride, scandium nitrate, yttrium nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, promethium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, terbium nitrate, dysprosium nitrate, holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, lutetium nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, aluminum nitrate, chromium nitrate, and manganese nitrate; the concentration of the metal salt is 0.0001-4 wt%.

10. The preparation method according to claim 8, characterized in that, The concentration of nanomaterials is 0.05-3 wt%, and the concentration of metal salts is 0.008-0.2 wt%.

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