CN115582137A - Nano material for photocatalysis and photodynamic therapy and preparation method and application thereof - Google Patents
Nano material for photocatalysis and photodynamic therapy and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nano material for photocatalysis and photodynamic therapy and a preparation method and application thereof, wherein the nano material comprises graphene and a metal nitrogen dopant loaded by graphene oxide; wherein the metal nitrogen dopant is prepared from a metal precursor and a nitrogen precursor; the metal precursor is one or two of ferric salt, cobalt salt and nickel salt. By introducing the metal elements into the nano material, the metal elements can be uniformly dispersed on the nitrogen-doped graphene oxide, and the nano material has the advantages of high catalytic activity and high quantum yield. According to the invention, after the metal nitrogen dopant is loaded on the graphene oxide, two times of annealing treatment are required, and the effect of controlling the concentration of the metal element is achieved by controlling the temperature, so that the metal atoms are uniformly dispersed on the graphene oxide.
Description
Technical Field
The invention relates to the technical field of metal catalysts, in particular to a nano material for photocatalysis and photodynamic therapy and a preparation method and application thereof.
Background
With the maximum utilization of metal atoms, monatomic catalysts (SACs) and diatomic catalysts (DACs) exhibit high activity and selectivity. By introducing atomically dispersed metal atoms, the electronic and excited structures can be tailored to achieve the appropriate exciton and charge transfer to the desired application.
The use of monatomic catalysts in photochemical reactions is rarely reported. Common catalysts have low quantum yields, which makes them inefficient for photochemical reactions.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a nano material for photocatalysis and photodynamic therapy, wherein the catalyst is a monoatomic catalyst and a diatomic catalyst and has the advantage of high quantum yield; the second purpose of the invention is to provide a preparation method of nano material for photocatalysis and photodynamic therapy, which controls the concentration of metal atoms through a two-step annealing process, and finally realizes the high quantum yield of the photocatalyst with high photocatalytic activity; it is a further object of the present invention to provide the use of nanomaterials for photocatalytic and photodynamic therapy, which catalysts are useful as high quantum yield materials for photocatalytic reactions and also as photodynamic therapy (PDT) agents to prevent the growth of tumor cells.
One of the purposes of the invention is realized by adopting the following technical scheme:
a nanomaterial for use in photocatalytic and photodynamic therapy, the nanomaterial comprising graphene and a metal nitrogen dopant supported by graphene oxide; wherein the metal nitrogen dopant is prepared from a metal precursor and a nitrogen precursor; the metal precursor is one or two of ferric salt, cobalt salt and nickel salt. If only one metal element is selected as the metal precursor, the metal precursor is a monatomic nanomaterial, specifically FeN 4 、CoN 4 And NiN 4 One of (1); if two metal elements are selected as the metal precondition, the metal element is a diatomic nano material, preferably FeNiN 4 Diatomic nanomaterials.
Further, the graphene oxide is prepared by using expanded graphite through high-temperature stripping and oxidation.
Further, the nitrogen precursor is acrylamide.
Further, the metal loading of the nano material is 0.3 to 5wt%.
The second purpose of the invention is realized by adopting the following technical scheme:
the preparation method of the nano material for photocatalysis and photodynamic therapy comprises the following steps:
21 ) preparing a metal precursor into a solution to obtain a solution containing metal ions;
22 Adding graphene oxide into water to prepare a graphene oxide dispersion liquid;
23 Adding the solution containing the metal ions and the nitrogen precursor into the dispersion liquid, uniformly stirring, and freeze-drying to obtain a freeze-dried mixture;
24 A first annealing treatment of the freeze-dried mixture;
25 ) carrying out secondary annealing treatment on the freeze-dried mixture to obtain the nano material for photocatalysis and photodynamic therapy.
Further, the mass ratio of the metal precursor, the nitrogen precursor and the graphene oxide is 1: (4-10): (300-400).
Further, in step 23), the mixed solution is washed with a sulfuric acid solution and an ethanol solution before freeze-drying. The acid washing can remove unreacted metal ions, thereby playing a role in controlling the ion concentration.
Further, in step 24), the conditions of the first annealing treatment are as follows: annealing at 250-350 deg.c in inert gas atmosphere for 2-4 hr.
Further, in the step 25), the conditions of the second annealing treatment are as follows: annealing at 450-550 ℃ for 2-4 h in the atmosphere of inert gas.
The third purpose of the invention is realized by adopting the following technical scheme:
the application of the nano material for photocatalysis and photodynamic therapy is that the nano material is used for a catalyst of photocatalysis reaction and/or is used for preparing a photodynamic therapeutic agent.
Compared with the prior art, the invention has the beneficial effects that:
(1) The nano material comprises graphene and a metal nitrogen dopant loaded by graphene oxide; wherein the metal nitrogen dopant is prepared from a metal precursor and a nitrogen precursor; the metal precursor is one or two of iron salt, cobalt salt and nickel salt. If the metal precursor is selected from only one metal element, the metal precursor is a single-atom nano material, specifically FeN 4 、CoN 4 And NiN 4 One of (a) and (b); if the metal precondition selects two metal elements, the diatomic nano material is obtained; according to the nano material disclosed by the invention, the metal elements are introduced, and can be uniformly dispersed on the nitrogen-doped graphene oxide, so that the activity of the nano material can be effectively improved, and the quantum yield of the nano material is improved.
(2) According to the preparation method of the nano material, after the metal nitrogen dopant is loaded on the graphene oxide, freeze drying is carried out, then annealing treatment is carried out twice, the effect of controlling the concentration of the metal element is achieved by controlling the temperature, the aggregation of metal atoms is reduced to the maximum extent, and the metal atoms are uniformly dispersed on the graphene oxide, so that the high quantum yield of the nano material is improved, and the photocatalytic activity is improved.
(3) The nano material of the invention, no matter as a monoatomic catalyst or a diatomic catalyst, belongs to a material with high quantum yield, has remarkable photocatalytic activity, can be used as a catalyst of a photocatalytic reaction, and can be tested to obtain the nano material, the catalyst can effectively increase the generation of singlet oxygen (1O 2) and inhibit the formation of tumor cells, so the nano material can also be used as a photodynamic therapy (PDT) agent to prevent the growth of the tumor cells, and side effects of skin infection, pruritus, prickling, burning pain and the like of common PDT can not be generated, and the nano material is economical and practical.
Drawings
FIG. 1 is a schematic illustration of an annealing step of a catalyst;
FIG. 2 shows FeN4 of example 1 - SEM images of monatomic catalyst samples;
FIG. 3 is an SEM image of a sample of the FeNiN 4-diatomic catalyst of example 2
FIG. 4 shows FeN4 of example 1 - TEM images of monatomic catalyst samples;
FIG. 5 is an EDS elemental map of a sample of the FeNiN 4-diatomic catalyst of example 2;
FIG. 6 is a Raman spectrum of a sample of the FeN 4-monatomic catalyst of example 1;
FIG. 7 is a UV-Vis spectrum of the catalysts of comparative example 1 and examples 1 to 4;
FIG. 8 is a Tauc diagram for the FeN 4-monatomic catalyst of example 1;
FIG. 9 is the Tauc diagram for the FeNiN 4-diatomic catalyst of example 2;
FIG. 10 is a Tauc plot for the catalyst of comparative example 1;
FIG. 11 is a schematic view of the charge adsorption of oxygen on the catalyst of example 1.
FIG. 12 is a schematic view of the charge adsorption of oxygen on the catalyst of example 1.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
Example 1
A nanomaterial for photocatalysis and photodynamic therapy, the nanomaterial is prepared from a metal nitrogen dopant loaded by graphene oxide; wherein the metal nitrogen dopant is FeN 4 Therefore, the catalyst of this example is FeN 4 A monatomic catalyst. The thickness of the graphene oxide is less than 1nm, and the particle size is 100nm.
Specifically, the preparation method of the graphene oxide comprises the following steps:
11 1g of microwave expanded graphite is put into a 500mL round-bottom flask, and is dispersed into 30mL of sulfuric acid solution with the mass concentration of 98 percent, and is stirred in ice-water bath for 2 hours to obtain suspension;
12 5g of potassium permanganate is added into the suspension under the condition of stirring in an ice-water bath, and the mixture is stirred for 4 hours until the color of the suspension becomes light brown;
13 Adding 50mL of deionized water into the suspension obtained in the step 12) for dilution to change the color into brown, continuously adding 200mL of deionized water for dilution, and stirring at room temperature for 2 hours to obtain a mixed solution;
14 Adding sufficient hydrogen peroxide into the mixed solution to reduce the residual potassium permanganate until the color of the solution is changed into bright green, continuing stirring for 2h, standing for 24h to obtain graphene oxide, centrifuging, washing for at least 9 times at the rotating speed of 15000rpm for 30min by using deionized water, and adding the centrifuged Graphene Oxide (GO) solution into water to disperse to form a graphene oxide solution with the concentration of 8 mg/mL. Wherein the addition amount of the hydrogen peroxide accounts for 30% of the mass of the graphene oxide;
FeN 4 -a process for the preparation of a monatomic catalyst, comprising the following steps:
21 FeCl) a metal precursor 3 ·6H 2 Adding deionized water to dissolve O to prepare FeCl of 0.05mol/L 3 A solution;
22 12.5mL of graphene oxide solution with the concentration of 8mg/mL is mixed into 120mL of deionized water to obtain diluted graphene oxide suspension;
23 250 μ L FeCl with a concentration of 0.05mol/L 3 The solution, 1.2mL of 25% by mass acrylamide and the suspension of step 22) were mixed and stirred for 23H to obtain a mixture, H was used 2 SO 4 (0.05M) and ethanol (96%) three times and the mixture was freeze-dried for 4d to give a brown lyophilized mixture;
24 A first annealing of the freeze-dried mixture at 300 ℃ for 3h under Ar (202s.c.c.m) in a quartz tube furnace as shown in fig. 1;
25 Adjusting the tube furnace to raise the temperature to 500 ℃ within 20min, and then carrying out second annealing treatment for 3h under Ar (202s.c.c.m) and 500 ℃ to ensure the stability of metal atoms to obtain FeN 4 A monatomic catalyst.
Example 2
A nanomaterial for photocatalytic and photodynamic therapy, the nanomaterial being a metal loaded by graphene oxidePreparing a nitrogen dopant; wherein the metal nitrogen dopant is prepared from a metal precursor and a nitrogen precursor, and is specifically FeNiN 4 Therefore, the catalyst of this example is FeNiN 4 A diatomic catalyst. The thickness of the graphene oxide is less than 1nm, and the particle size is 100nm.
Specifically, the preparation method of the graphene oxide comprises the following steps:
11 1g of microwave expanded graphite is put into a 500mL round-bottom flask, and is dispersed into 30mL of sulfuric acid solution with the mass concentration of 98 percent, and is stirred in ice-water bath for 2 hours to obtain suspension;
12 5g of potassium permanganate is added into the suspension under the condition of stirring in an ice-water bath, and the suspension is stirred for 4 hours until the color of the suspension becomes light brown;
13 Adding 50mL of deionized water into the suspension obtained in the step 12) for dilution to change the color into brown, continuously adding 200mL of deionized water for dilution, and stirring at room temperature for 2 hours to obtain a mixed solution;
14 Adding sufficient hydrogen peroxide into the mixed solution to reduce the residual potassium permanganate until the color of the solution is changed into bright green, continuing stirring for 2h, standing for 24h to obtain graphene oxide, centrifuging, washing for at least 9 times at the rotating speed of 15000rpm for 30min by using deionized water, and adding the centrifuged Graphene Oxide (GO) solution into water to disperse to form a graphene oxide solution with the concentration of 8 mg/mL. Wherein the addition amount of the hydrogen peroxide accounts for 30% of the mass of the graphene oxide;
FeN 4 -a process for the preparation of a monatomic catalyst, comprising the following steps:
21 FeCl) a metal precursor 3 ·6H 2 O and NiCl 2 ·6H 2 O is respectively added into deionized water to be dissolved to prepare FeCl with 0.05mol/L 3 Solution and 0.05mol/L NiCl 2 ；
22 12.5mL of graphene oxide solution with the concentration of 8mg/mL is mixed into 120mL of deionized water to obtain diluted graphene oxide suspension;
23 250 μ L of FeCl with a concentration of 0.05mol/L 3 Solution, 250. Mu.L of NiCl with a concentration of 0.05mol/L 2 The solution, 1.2mL of 25% by mass acrylamide and the suspension of step 22) were mixed and stirred for 23H to obtain a mixture, H was used 2 SO 4 (0.05M) and ethanol (96%) three times and the mixture was freeze-dried for 4d to give a brown lyophilized mixture;
24 A first annealing of the freeze-dried mixture at 300 ℃ for 3h under Ar (202s.c.c.m) in a quartz tube furnace as shown in fig. 1;
25 Adjusting the tube furnace to raise the temperature to 500 ℃ within 20min, and then carrying out second annealing treatment for 3h under Ar (202s.c.c.m) and 500 ℃ to ensure the stability of metal atoms to obtain the FeNiN 4-diatomic catalyst.
Example 3
A nanomaterial for photocatalysis and photodynamic therapy, the nanomaterial is prepared from a metal nitrogen dopant loaded by graphene oxide; wherein the metal nitrogen dopant is CoN 4 Therefore, the catalyst of this example is CoN 4 A monatomic catalyst. The thickness of the graphene oxide is less than 1nm, and the particle size is 100nm.
Specifically, the preparation method of the graphene oxide comprises the following steps:
11 1g of microwave expanded graphite is put into a 500mL round-bottom flask, and is dispersed into 30mL of sulfuric acid solution with the mass concentration of 98 percent, and is stirred in ice-water bath for 2 hours to obtain suspension;
12 5g of potassium permanganate is added into the suspension under the condition of stirring in an ice-water bath, and the mixture is stirred for 4 hours until the color of the suspension becomes light brown;
13 Adding 50mL of deionized water into the suspension obtained in the step 12) for dilution to change the color into brown, continuously adding 200mL of deionized water for dilution, and stirring at room temperature for 2 hours to obtain a mixed solution;
14 Adding sufficient hydrogen peroxide into the mixed solution to reduce the residual potassium permanganate until the color of the solution is changed into bright green, continuing stirring for 2h, standing for 24h to obtain graphene oxide, centrifuging, washing for at least 9 times at the rotating speed of 15000rpm for 30min by using deionized water, and adding the centrifuged Graphene Oxide (GO) solution into water to disperse to form a graphene oxide solution with the concentration of 8 mg/mL. Wherein the addition amount of the hydrogen peroxide accounts for 30% of the mass of the graphene oxide;
CoN 4 -a process for the preparation of a monatomic catalyst, comprising the following steps:
21 ) metal precursor CoCl 2 ·6H 2 Adding deionized water to dissolve O to prepare 0.05mol/L CoCl 2 A solution;
22 12.5mL of graphene oxide solution with the concentration of 8mg/mL is mixed into 120mL of deionized water to obtain diluted graphene oxide suspension;
23 250 μ L of CoCl with a concentration of 0.05mol/L 2 The solution, 1.2mL of 25% acrylamide by mass, and the suspension of step 22) were mixed and stirred for 23H to obtain a mixture, using H 2 SO 4 (0.05M) and ethanol (96%) three times, and the mixture was freeze-dried for 4d to give a brown lyophilized mixture;
24 As shown in fig. 1), the lyophilized mixture was first annealed at 250 ℃ for 4h under Ar (202s.c.c.m) in a quartz tube furnace;
25 Adjusting the tube furnace to raise the temperature to 450 ℃ within 20min, and then carrying out a second annealing treatment for 4h under Ar (202s.c.c.m) and 450 ℃ to ensure the stability of metal atoms to obtain CoN 4 A monatomic catalyst.
Example 4
A nanomaterial for photocatalysis and photodynamic therapy, the nanomaterial is prepared from a metal nitrogen dopant loaded by graphene oxide; wherein the metal nitrogen dopant is NiN 4 Therefore, the catalyst of this example is NiN 4 A monatomic catalyst. The thickness of the graphene oxide is less than 1nm, and the particle size is 100nm.
Specifically, the preparation method of the graphene oxide comprises the following steps:
11 1g of microwave expanded graphite is put into a 500mL round-bottom flask, and is dispersed into 30mL of sulfuric acid solution with the mass concentration of 98 percent, and is stirred in ice-water bath for 2 hours to obtain suspension;
12 5g of potassium permanganate is added into the suspension under the condition of stirring in an ice-water bath, and the suspension is stirred for 4 hours until the color of the suspension becomes light brown;
13 Adding 50mL of deionized water into the suspension obtained in the step 12) for dilution to change the color into brown, continuously adding 200mL of deionized water for dilution, and stirring at room temperature for 2 hours to obtain a mixed solution;
14 Adding sufficient hydrogen peroxide into the mixed solution to reduce the residual potassium permanganate until the color of the solution is changed into bright green, continuing stirring for 2h, standing for 24h to obtain graphene oxide, centrifuging, washing for at least 9 times at the rotating speed of 15000rpm for 30min by using deionized water, and adding the centrifuged Graphene Oxide (GO) solution into water to disperse to form a graphene oxide solution with the concentration of 8 mg/mL. Wherein the addition amount of the hydrogen peroxide accounts for 30% of the mass of the graphene oxide;
NiN 4 -a process for the preparation of a monatomic catalyst, comprising the following steps:
21 A metal precursor NiCl) 2 ·6H 2 Adding deionized water to dissolve O to prepare 0.05mol/L NiCl 2 A solution;
22 12.5mL of graphene oxide solution with the concentration of 8mg/mL is mixed into 120mL of deionized water to obtain diluted graphene oxide suspension;
23 250 μ L NiCl with a concentration of 0.05 mol/L) 2 The solution, 1.2mL of 25% by mass acrylamide and the suspension of step 22) were mixed and stirred for 23H to obtain a mixture, H was used 2 SO 4 (0.05M) and ethanol (96%) three times and the mixture was freeze-dried for 4d to give a brown lyophilized mixture;
24 A first annealing of the freeze-dried mixture at 350 ℃ for 2h under Ar (202s.c.c.m) in a quartz tube furnace as shown in fig. 1;
25 Adjusting the tube furnace to raise the temperature to 550 ℃ within 20min, and then carrying out secondary annealing treatment for 2h under Ar (202s.c.c.m) and 550 ℃ to ensure the metal atoms to be stable to obtain NiN 4 -a monoatomic catalyst.
Comparative example 1
Comparative example 1 is different from example 1 in that the catalyst of comparative example 1 is prepared without adding a metal precursor, and the catalyst is prepared by loading nitrogen dopant on graphene oxide, and the amount of the added nitrogen precursor is the same as that of example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that: comparative example 2 has only a first annealing step at 300 deg.C
Comparative example 3
Comparative example 3 differs from example 1 in that: the catalyst of comparative example 3 was prepared in a first annealing step at a temperature of 500 ℃.
Performance test
1. Loading of metals in catalysts
The loading of the metal in the catalyst was measured by x-ray photoelectron spectroscopy (XPS) method, as shown in table 1.
TABLE 1 Supports for metals in the catalysts of the respective groups
As can be seen from table 1, the metal loading in the catalysts of examples 1 to 3 is smaller than that in the catalysts of comparative examples 1 to 3, which shows that the catalysts prepared by the two-step annealing process can reduce the aggregation of metal elements, improve the dispersion degree of metals, and thus improve the activity of the catalysts. Comparative example 2 and comparative example 3 only adopt one-time annealing method, the metal loading is improved, but the agglomeration effect of the metal in the graphene oxide occurs, thereby influencing the activity of the catalyst.
2. Catalyst characterization test
As shown in FIGS. 2 to 4, feN of example 1 4 Monatomic catalyst and FeNiN of example 2 4 The diatomic catalyst had good homogeneity, the Fe atoms were homogeneously dispersed, and no significant aggregation was seen.
As shown in fig. 5, TEM imaging and EDX elemental mapping of the FeNiN 4-diatomic catalyst at elements C, N, O, ni and Fe confirmed the presence of elements Fe, ni, N and C in the synthesized FeNiN 4-diatomic catalyst and the uniform dispersion of the above elements.
As shown in FIG. 6, feN of example 1 4 Increase of the intensity ratio of the D/G band (ID/IG) in the Raman spectrum of the monatomic catalyst from 0.714 of Graphene Oxide (GO) to FeN 4 0.867 for the monatomic catalyst sample, indicating an increase in its density, the presence of defect vacancies, which increase the mass transfer on the catalyst surface and increase its activity.
As shown in fig. 7, the UV-Vis spectra of the catalysts of examples 1 to 4 and the catalyst of comparative example 1 were in the ultraviolet range (pi-pi transition), while the light trapping ability in the visible light range was relatively low and the absorbance was weak. To find the optical band gap (Eg) of the samples, we obtained Tauc plots from the UV-Vis spectra of each sample. As shown in fig. 8 to 10, the Eg values for the N-doped (comparative example 1), feN 4-monatomic catalyst (example 1) and FeN 4-diatomic catalyst (example 2) samples were 1.90, 2.35 and 2.27eV, respectively. Examples 1 to 2 the introduction of metal atoms increased the band gap energy compared to comparative example 1. The expansion of the band gap is due to the presence of metal atoms and the lower level of delocalization resulting in a reduction of the flatness of the framework. In addition, the catalysts of examples 1 to 2 have increased charge transfer due to an increase in band gap, thereby improving photocatalytic activity.
In the simulation calculations, the monatomic catalyst of example 1 and the diatomic catalyst of example 2 were modeled and optimized. Oxygen was placed on the surface of the monatomic catalyst of example 1, and the adsorption energy was calculated and compared. As shown in FIG. 11, the FeN 4-monatomic catalyst was able to adsorb oxygen, indicating the O-O bond length, the monatomic catalyst, and the O 2 The distance between them and the charge transfer. On the FeN 4-monatomic catalyst, the adsorption energy of oxygen is 0.96eV, and the sensitization of oxygen is promoted. As shown in fig. 12, the adsorption energy of oxygen on the N-doped sample (comparative example 1) was only 0.1eV, which is not suitable for PDT.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A nanomaterial for use in photocatalytic and photodynamic therapy, characterized in that the nanomaterial comprises graphene and a metal nitrogen dopant supported by graphene oxide; wherein the metal nitrogen dopant is prepared from a metal precursor and a nitrogen precursor; the metal precursor is one or two of ferric salt, cobalt salt and nickel salt.
2. The nanomaterial for photocatalytic and photodynamic therapy according to claim 1, wherein the graphene oxide is prepared by high temperature exfoliation and oxidation using expanded graphite.
3. Nanomaterial for photocatalytic and photodynamic therapy according to claim 1, characterized in that the nitrogen precursor is acrylamide.
4. The nanomaterial for photocatalytic and photodynamic therapy according to claim 1, wherein the metal loading of the nanomaterial is 0.3 to 5wt%.
5. The method for preparing nano-materials for photocatalytic and photodynamic therapy according to any one of claims 1 to 4, characterized by comprising the steps of:
21 ) preparing a metal precursor into a solution to obtain a solution containing metal ions;
22 Adding graphene oxide into water to prepare a graphene oxide dispersion liquid;
23 Adding the solution containing the metal ions and the nitrogen precursor into the dispersion liquid, uniformly stirring, and freeze-drying to obtain a freeze-dried mixture;
24 Subjecting the lyophilized mixture to a first annealing treatment;
25 ) carrying out secondary annealing treatment on the freeze-dried mixture to obtain the nano material for photocatalysis and photodynamic therapy.
6. The method of preparing nanomaterial for photocatalytic and photodynamic therapy according to claim 5, wherein the mass ratio of the metal precursor, nitrogen precursor and graphene oxide is 1: (4-10): (300-400).
7. The method of preparing nano-materials for photocatalytic and photodynamic therapy according to claim 5, wherein, in the step 23), the mixed solution is washed with a sulfuric acid solution and an ethanol solution before freeze-drying.
8. The method for preparing nano-materials for photocatalytic and photodynamic therapy according to claim 5, wherein the conditions of the first annealing treatment in the step 24) are as follows: annealing for 2-4 h at 250-350 ℃ under the atmosphere of inert gas.
9. The method for preparing nano-materials for photocatalytic and photodynamic therapy according to claim 5, wherein the conditions of the second annealing treatment in the step 25) are: annealing at 450-550 ℃ for 2-4 h in the atmosphere of inert gas.
10. Use of nanomaterial for photocatalytic and photodynamic therapy according to any one of claims 1 to 4, characterized in that it is used as a catalyst for photocatalytic reactions and/or in the preparation of photodynamic therapeutic agents.
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