CN114394615A - Slow-release hydrogen material and preparation method and application thereof - Google Patents
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Abstract
The invention relates to the technical field of hydrogen production, cosmetics and patches, in particular to a slow-release hydrogen material and a preparation method and application thereof. The slow-release hydrogen material is oxygen-deficient zinc oxide (ZnO)1‑xWherein 0 is<x<0.05, the slow-release hydrogen material is prepared by the reaction of soluble zinc salt, a reducing agent, water and a high-boiling-point polar solvent. The technical advantages of the invention are as follows: 1) the oxygen-deficient zinc oxide material prepared by the invention can slowly react with waterThe hydrogen is released, the hydrogen release rate is not obviously reduced after the hydrogen is released for 4 days, and the hydrogen release property is not obviously changed after the hydrogen is stored in the air for 1 month and the water reacts. 2) The slow-release hydrogen material prepared by the invention has important application prospect in the hydrogen health field such as hydrogen mask, hydrogen patch and the like.
Description
Technical Field
The invention relates to the technical field of hydrogen production, cosmetics and patches, in particular to a slow-release hydrogen material and a preparation method and application thereof.
Background
In 1975, Dole et al, written in Science, stated that they found that high-pressure hydrogen was effective in inhibiting tumor growth in mice with squamous cell carcinoma, and suggested the possibility of hydrogen therapy for the treatment of cancer. In 2007, professor of taitian adult men of the university of medical science in japan reports a selective antioxidant mechanism for hydrogen treatment of ischemia-reperfusion injury and inflammation, and rapid development of hydrogen biology and Medicine is promoted. Over the last decade, hydrogen has been found to have therapeutic effects on a variety of oxidative stress/inflammation-related diseases, including cancer, atherosclerosis, ischemia-reperfusion injury, stroke, diabetes, neurodegenerative diseases, arthritis, dermatitis, colitis, hepatitis, pancreatitis, and the like. Hydrogen therapy is receiving increasing attention for its high safety and broad spectrum effectiveness and is undergoing a significant evolution from research to clinical applications.
The research shows that: the hydrogen has certain anti-wrinkle cosmetic effect (Journal of Photochemistry and Photobiology B: Biology, 2012, 106, 24-33; Journal of dermatologic Treatment, 2014, 25, 182-); it also has certain therapeutic effect on skin diseases such as psoriasis and vitiligo (Molecular Medicine Reports, 2015, 12, 2757-. At present, related products of the hydrogen mask are proposed for facial beauty and care. For example, the hydrogen-rich masks disclosed in patents CN 111870546 a and CN 111067837 a, most of these hydrogen-rich masks are formed by directly adding hydrogen by a physical method, and the other hydrogen-rich masks are formed by using the reaction between active metals such as Mg and Al and organic acids, the hydrogen in the former is easily diffused, the reaction rate in the latter is generally too fast, and the active metals have adverse effects such as corrosion and allergy on human skin. And NaBH4As a hydrogen source, NaBH can be used for relatively smooth hydrolysis or alcoholysis hydrogen production4Chemical safety specification (MSDS) of (9) shows that the chemical strongly stimulates the mucosa, upper respiratory tract, eyes andskin, oral intake, erosive digestive tract, acute toxicity (LD 50) 18 mg/kg (abdominal cavity of rat).
Based on the effect of hydrogen on diseases such as arthritis, psoriasis and vitiligo and the high permeability of hydrogen molecules, the hydrogen patch is probably a good choice for hydrogen therapy aiming at the diseases, and related documents or patent reports of the hydrogen patch do not exist at present.
Zinc oxide (ZnO) is a common chemical additive, is widely applied to life, is an important and widely used physical sun-screening agent, and is nontoxic and harmless to human skin. Oxygen deficient zinc oxide (ZnO)1-x) Contains a small amount of oxygen vacancy, and most of the chemical properties of the zinc oxide are similar to those of zinc oxide and are relatively stable. Oxygen deficient zinc oxide (ZnO)1-x) The preparation method mainly comprises a mechanical ball milling method, a high-temperature hydrogen reduction method, a solution reduction method, a rapid crystallization method and the like (Ceramics International, 2018, 44, 7357-7377), wherein the operation is simpler by the solution method, but not all the prepared oxygen-deficient zinc oxide (ZnO)1-x) Can react with water to generate hydrogen stably and continuously.
Therefore, the invention provides a slow-release hydrogen material suitable for a hydrogen patch, which can stably and continuously generate hydrogen by reacting with water and is nontoxic and harmless to human skin.
Disclosure of Invention
In order to solve the problems in the prior art, an object of the present invention is to provide a slow-release hydrogen material, which is an oxygen-deficient zinc oxide material and can react with water to slowly release hydrogen, and the hydrogen release rate does not significantly decrease after 4 days, and the hydrogen release property does not significantly change after 1 month storage in air.
The invention also aims to provide a preparation method of the slow-release hydrogen material.
The invention further aims to provide application of the slow-release hydrogen material.
The technical scheme adopted for realizing the aim of the invention is as follows: a slow-release hydrogen material, which is oxygen-deficient zinc oxide (ZnO)1-xWherein X is 0<x<0.05, the slow-release hydrogen material is prepared by the reaction of soluble zinc salt, a reducing agent, water and a high-boiling-point polar solvent.
Preferably, the slow-release hydrogen material is prepared by the following preparation steps:
1) uniformly mixing soluble zinc salt, a reducing agent, water and a high-boiling-point polar solvent;
2) carrying out constant-temperature reflux reaction under the stirring condition, wherein the constant-temperature reaction condition is as follows: the constant temperature reaction temperature is 120-140 ℃, and the reflux reaction time is 1-3 h;
3) after the constant temperature reaction, naturally cooling, centrifugally separating, washing with water and ethanol, and airing to obtain the slow-release hydrogen material;
wherein, the mol ratio of the soluble zinc salt, the reducing agent, the water and the high-boiling polar solvent is 1: (5-20): (500-2000): (150-300).
Preferably, the soluble zinc salt is selected from one of zinc acetate or zinc acetylacetonate; the reducing agent is selected from one of sodium borohydride or potassium borohydride; the high boiling point polar solvent is selected from one of ethylene glycol or glycerol.
As a preferred embodiment of the invention, the slow-release hydrogen material is prepared by mixing zinc acetate, sodium borohydride, water and ethylene glycol, wherein the molar ratio of the zinc acetate, the sodium borohydride, the water and the ethylene glycol is 1: 8: 1000: 500.
as a preferred embodiment of the invention, the slow-release hydrogen material is prepared by mixing zinc acetate, sodium borohydride, water and ethylene glycol, wherein the molar ratio of the zinc acetate, the sodium borohydride, the water and the ethylene glycol is 1: 5: 1111: 523.
as a preferred embodiment of the invention, the slow-release hydrogen material is prepared by mixing zinc acetate, sodium borohydride, water and ethylene glycol, wherein the molar ratio of the zinc acetate, the sodium borohydride, the water and the ethylene glycol is 1: 20: 1111: 523.
as a preferred embodiment of the invention, the slow-release hydrogen material is prepared by mixing zinc acetate, sodium borohydride, water and ethylene glycol, wherein the molar ratio of the zinc acetate, the sodium borohydride, the water and the ethylene glycol is 1: 8: 500: 150.
as a preferred embodiment of the invention, the slow-release hydrogen material is prepared by mixing zinc acetate, sodium borohydride, water and ethylene glycol, wherein the molar ratio of the zinc acetate, the sodium borohydride, the water and the ethylene glycol is 1: 8: 2000: 300.
the technical scheme adopted for realizing the other purpose of the invention is as follows: a preparation method of a slow-release hydrogen material comprises the following preparation steps: mixing zinc acetate, sodium borohydride, water and ethylene glycol, then carrying out constant-temperature reflux reaction under the stirring condition, naturally cooling, then carrying out centrifugal separation, washing with water and ethanol, and airing to obtain the slow-release hydrogen material; wherein the constant temperature reflux reaction conditions are as follows: heating to 120-140 ℃, and refluxing for 1 h.
The technical scheme adopted for realizing the further purpose of the invention is as follows: application of a slow-release hydrogen material in a hydrogen patch or a hydrogen mask.
Compared with the prior art, the invention has the following advantages:
(1) the slow-release hydrogen material has stable chemical property, is nontoxic and harmless to human bodies, and can release hydrogen stably and durably in reaction with water.
(2) The solution method for preparing zinc oxide with oxygen defects avoids the use of strong alkali and a hydrothermal kettle, and has the advantages of simple operation, no need of high temperature and lower cost.
(3) The method adopts sodium borohydride or potassium borohydride as a reducing agent, and partially reduces zinc oxide generated by hydrolysis-pyrolysis of zinc acetate to obtain the zinc oxide with oxygen deficiency.
(4) According to the invention, ethylene glycol and water are used as solvents, the ethylene glycol and the water also participate in the preparation reaction, and the ethylene glycol also plays roles in increasing the boiling point of the solvent (zinc hydroxide can be decomposed into zinc oxide at 120-130 ℃) and limiting the particle size of the product (the surface forms coordinate bonds to limit the growth of precipitated particles).
(5) The oxygen-deficient zinc oxide material prepared by the invention can slowly release hydrogen by reacting with water, the hydrogen release rate is not obviously reduced after the material is continuously used for 4 days, and the hydrogen release property is not obviously changed after the material is stored in the air for 1 month.
(6) The slow-release hydrogen material prepared by the invention has important application prospect in the hydrogen health field such as hydrogen mask, hydrogen patch and the like.
Drawings
FIG. 1 shows a slow-release hydrogen material ZnO prepared in example 1 of the present invention1-xXRD of (a).
FIG. 2 shows a slow-release hydrogen material ZnO prepared in example 1 of the present invention1-xHydrogen evolution curve for reaction with water.
FIG. 3 shows the ZnO as the material for slow release of hydrogen produced in examples 2 and 3 of the present invention1-xHydrogen evolution curve for reaction with water.
FIG. 4 shows ZnO as the hydrogen-releasing material prepared in comparative examples 1, 2 and 31-xHydrogen evolution curve for reaction with water.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a slow-release hydrogen material which is oxygen-deficient zinc oxide (ZnO)1-x) Wherein 0 is<x<0.05, the slow-release hydrogen material is prepared by the reaction of soluble zinc salt, a reducing agent, water and a high-boiling-point polar solvent.
The working reaction principle is as follows:xH2O + ZnO1-x = ZnO + xH2wherein, 0<x<0.05。
The invention provides a slow-release hydrogen material ZnO1-xThe preparation method is a solution method, and the specific method is as follows: adding a certain amount of zinc acetate, sodium borohydride, water and glycolMixing in a molar ratio of 1: (5-20): (500-2000): (150-300), then heating and refluxing for 1-3 h at 120-140 ℃ under stirring, naturally cooling, then performing centrifugal separation, washing twice with water, washing twice with ethanol, and drying to obtain ZnO1-xAnd (3) powder.
The main reactions occurring in the preparation process are:
Zn(CH3COO)2+2H2O=Zn(OH)2+CH3COOH；
Zn(OH)2=ZnO+H2O （120~130℃）；
NaBH4 + 4CH3COOH = NaOOCCH3 + B(CH3COO)3 + 4H2；
NaBH4 + 4H2O = NaB(OH)4 + 4H2；
NaBH4 + 2HOCH2CH2OH = NaB(OCH2CH2O)2 + 4H2；
4ZnO + xNaBH4 = xNaB(OH)4 + 4ZnO1-x(ii) a (substantially NaBH)4The active hydrogen produced by hydrolysis acts as a reducing function).
The zinc acetate of the raw material can also be soluble zinc salt such as zinc acetylacetonate and the like, sodium borohydride can also be reducing agent such as potassium borohydride and the like which can be hydrolyzed to produce hydrogen, and glycol can also be high boiling polar solvent such as glycerol and the like.
Example 1
Mixing a certain amount of zinc acetate, sodium borohydride, water and glycol, wherein the zinc acetate is 10 mmol, and the molar ratio of the zinc acetate to the sodium borohydride is 1: 8: 1000: 500, then heating and refluxing for 1h at 130 ℃ under the condition of stirring, naturally cooling, then centrifugally separating, washing twice with water, washing twice with ethanol, and airing to obtain ZnO1-xAnd (3) powder. The ZnO1-xXRD of the powder is shown in fig. 1, and XRD shows that the powder has a ZnO structure.
500 mg of ZnO was weighed1-xThe powder was then mixed with 5 mL of deionized water, shaken, mixed and allowed to stand while recording time with a stopwatch, and the content of dissolved hydrogen in the recording liquid was measured with a DH200 water-solubility voltmeter. Due to dissolution in waterThe dissolved hydrogen will diffuse into the air continuously, and the curve of the measured dissolved hydrogen content changing with time reflects the ZnO indirectly1-xAnd water react to release hydrogen. From the results (fig. 2), it can be seen that the powder and water are able to produce hydrogen smoothly and continuously, without significant decay of the hydrogen production rate after 4 days (96 h).
Example 2
Mixing a certain amount of zinc acetate, sodium borohydride, water and glycol, wherein the zinc acetate is 10 mmol, and the molar ratio of the zinc acetate to the sodium borohydride is 1: 5: 1111: 523, heating and refluxing for 2h at 130 ℃ under stirring, naturally cooling, centrifuging, washing with water twice, washing with ethanol twice, and air drying to obtain ZnO1-xAnd (3) powder. Weighing 500 mg of the ZnO1-xThe powder was then mixed with 5 mL of deionized water, shaken, mixed and allowed to stand while recording time with a stopwatch, and the content of dissolved hydrogen in the recording liquid was measured with a DH200 water-solubility voltmeter. The measured hydrogen evolution curve is shown by the red line in FIG. 3, and the results show that the ZnO1-xThe powder can react with water to produce hydrogen steadily and continuously.
Example 3
Mixing a certain amount of zinc acetate, sodium borohydride, water and glycol, wherein the zinc acetate is 10 mmol, and the molar ratio of the zinc acetate to the sodium borohydride is 1: 20: 1111: 523, heating and refluxing for 3h at 130 ℃ under stirring, naturally cooling, centrifuging, washing with water twice, washing with ethanol twice, and air drying to obtain ZnO1-xAnd (3) powder. Weighing 500 mg of the ZnO1-xThe powder was then mixed with 5 mL of deionized water, shaken, mixed and allowed to stand while recording time with a stopwatch, and the content of dissolved hydrogen in the recording liquid was measured with a DH200 water-solubility voltmeter. The measured hydrogen evolution curve is shown by the black line in FIG. 3, and the results indicate that the ZnO1-xThe powder can react with water to produce hydrogen steadily and continuously, and the hydrogen production is obviously more than that of ZnO prepared in example 21-xThe hydrogen production of the powder and water reaction shows that increasing the input of sodium borohydride increases the oxygen vacancy concentration and thus increases the hydrogen production.
Example 4
Mixing a certain amount of zinc acetylacetonate, sodium borohydride, water and glycol, wherein the molar ratio of zinc acetate is 10 mmol: 8: 500:150, heating and refluxing for 1h at 120 ℃ under stirring, naturally cooling, centrifuging, washing with water twice, washing with ethanol twice, and air drying to obtain ZnO1-xAnd (3) powder. Weighing 500 mg of the ZnO1-xThe powder was then mixed with 5 mL of deionized water, shaken, mixed and allowed to stand while recording time with a stopwatch, and the content of dissolved hydrogen in the recording liquid was measured with a DH200 water-solubility voltmeter. The measured results show that the ZnO1-xThe powder can react with water to produce hydrogen steadily and continuously, and the hydrogen content in water of 20 h reaches 136 ppb.
Example 5
Mixing a certain amount of zinc acetate, potassium borohydride, water and glycol, wherein the zinc acetate is 10 mmol, and the molar ratio of the zinc acetate to the potassium borohydride is 1: 8: 2000: 300, then heating and refluxing for 1h at 140 ℃ under stirring, naturally cooling, then centrifugally separating, washing twice with water, washing twice with ethanol, and airing to obtain ZnO1-xAnd (3) powder. Weighing 500 mg of the ZnO1-xThe powder was then mixed with 5 mL of deionized water, shaken, mixed and allowed to stand while recording time with a stopwatch, and the content of dissolved hydrogen in the recording liquid was measured with a DH200 water-solubility voltmeter. The measured results show that the ZnO1-xThe powder can react with water to produce hydrogen steadily and continuously, and the hydrogen content in water of 20 h reaches 97 ppb.
Example 6
Mixing a certain amount of zinc acetate, sodium borohydride, water and glycerol, wherein the zinc acetate is 10 mmol, and the molar ratio of the zinc acetate to the sodium borohydride is 1: 8: 1000: 500, then heating and refluxing for 1h at 130 ℃ under stirring, naturally cooling, then centrifugally separating, washing twice with water, washing twice with ethanol, and airing to obtain ZnO1-xAnd (3) powder. Weighing 500 mg of the ZnO1-xThe powder was then mixed with 5 mL of deionized water, shaken, mixed and allowed to stand while recording time with a stopwatch, and the content of dissolved hydrogen in the recording liquid was measured with a DH200 water-solubility voltmeter. The measured results show that the ZnO1-xThe powder can react with water to produce hydrogen steadily and continuously, and the hydrogen content in water of 20 h reaches 157 ppb.
Comparative example 1
Mixing a certain amount of zinc acetate, sodium borohydride and water, wherein the zinc acetate is 10 mmol, and the molar ratio of the zinc acetate to the sodium borohydride is 1: 8: 1000, then atHeating and refluxing for 1h under stirring, naturally cooling, then performing centrifugal separation, washing twice with water, washing twice with ethanol, and air drying to obtain a powder product. Weighing 500 mg of the powder, adding 5 mL of deionized water, shaking, mixing, standing, recording time by using a stopwatch, and measuring and recording the content of dissolved hydrogen in the liquid by using a DH200 water solubility biotin meter. The measured results show that the powder can not react with water to smoothly and continuously produce hydrogen because the reaction temperature can not reach Zn (OH)2Thus Zn (OH)2Not completely decomposed (a small amount of hydrogen was previously generated probably due to the partial ZnO caused by the local over-temperature during the reaction1-xGeneration). (see fig. 4).
Comparative example 2
Mixing a certain amount of zinc acetate, water and ethylene glycol, wherein the zinc acetate accounts for 10 mmol, and the molar ratio of the zinc acetate to the water is 1: 1000: 500, heating and refluxing for 1h at 120 ℃ under stirring, naturally cooling, then centrifugally separating, washing twice with water, washing twice with ethanol, and airing to obtain a powder product. Weighing 500 mg of the powder, adding 5 mL of deionized water, shaking, mixing, standing, recording time by using a stopwatch, and measuring and recording the content of dissolved hydrogen in the liquid by using a DH200 water solubility biotin meter. The measured results show that the powder can not react with water to produce hydrogen smoothly and continuously, because the product obtained under the condition without the existence of strong reducing agent is ZnO (shown as figure 4) which is the product of zinc acetate hydrolysis and pyrolysis.
Comparative example 3
Putting a certain amount of ZnO into a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min in the hydrogen atmosphere of 1100 sccm, preserving the heat for 2h, and naturally cooling to obtain a powder product. Weighing 500 mg of the powder, adding 5 mL of deionized water, shaking, mixing, standing, recording time by using a stopwatch, and measuring and recording the content of dissolved hydrogen in the liquid by using a DH200 water solubility biotin meter. The measured results show that the powder cannot react with water to produce hydrogen smoothly and continuously, indicating that the hydrogen reduction under the conditions cannot generate enough oxygen vacancies in ZnO (as shown in FIG. 4).
Claims (10)
1. A slow-release hydrogen material, which is characterized in that: the slow-release hydrogen materialIs oxygen deficient zinc oxide ZnO1-xWherein 0 is<x<0.05, the slow-release hydrogen material is prepared by the reaction of soluble zinc salt, a reducing agent, water and a high-boiling-point polar solvent.
2. The slow-release hydrogen material of claim 1, wherein: the slow-release hydrogen material is prepared by the following preparation steps:
uniformly mixing soluble zinc salt, a reducing agent, water and a high-boiling-point polar solvent;
carrying out constant-temperature reflux reaction under the stirring condition, wherein the constant-temperature reaction condition is as follows: the constant temperature reaction temperature is 120-140 ℃, and the reflux reaction time is 1-3 h;
after the constant temperature reaction, naturally cooling, centrifugally separating, washing with water and ethanol, and airing to obtain the slow-release hydrogen material;
wherein, the mol ratio of the soluble zinc salt, the reducing agent, the water and the high-boiling polar solvent is 1: (5-20): (500-2000): (150-300).
3. The slow release hydrogen material of claim 2, wherein: the soluble zinc salt is selected from one of zinc acetate or zinc acetylacetonate; the reducing agent is selected from one of sodium borohydride or potassium borohydride; the high boiling point polar solvent is selected from one of ethylene glycol or glycerol.
4. The slow release hydrogen material of claim 3, wherein: the slow-release hydrogen material is prepared by reacting zinc acetate, sodium borohydride, water and glycol, wherein the molar ratio of the zinc acetate to the sodium borohydride to the water to the glycol is 1: 8: 1000: 500.
5. the slow release hydrogen material of claim 3, wherein: the slow-release hydrogen material is prepared by reacting zinc acetate, sodium borohydride, water and glycol, wherein the molar ratio of the zinc acetate to the sodium borohydride to the water to the glycol is 1: 5: 1111: 523.
6. the slow release hydrogen material of claim 3, wherein: the slow-release hydrogen material is prepared by reacting zinc acetate, sodium borohydride, water and glycol, wherein the molar ratio of the zinc acetate to the sodium borohydride to the water to the glycol is 1: 20: 1111: 523.
7. the slow release hydrogen material of claim 3, wherein: the slow-release hydrogen material is prepared by mixing zinc acetate, sodium borohydride, water and glycol according to a molar ratio of 1: 8: 500: 150.
8. the slow release hydrogen material of claim 3, wherein: the slow-release hydrogen material is prepared by reacting zinc acetate, sodium borohydride, water and glycol, wherein the molar ratio of the zinc acetate to the sodium borohydride to the water to the glycol is 1: 8: 2000: 300.
9. a method of preparing the hydrogen gas evolving material of claim 1, wherein: the preparation method comprises the following specific steps: mixing zinc acetate, sodium borohydride, water and ethylene glycol, then carrying out constant-temperature reflux reaction under the stirring condition, naturally cooling, then carrying out centrifugal separation, washing with water and ethanol, and airing to obtain the slow-release hydrogen material; wherein the constant temperature reflux reaction conditions are as follows: heating at 120-140 deg.c and refluxing for 1-3 hr.
10. Use of a material for the slow release of hydrogen gas according to claim 1, wherein: can be used in hydrogen patch or hydrogen mask.
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| CN115812702A (en) * | 2022-12-30 | 2023-03-21 | 深圳市芭田生态工程股份有限公司 | Controllable hydrogen release capsule and preparation method and application thereof |
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| CN1891632A (en) * | 2005-07-04 | 2007-01-10 | 同济大学 | Method for preparing nano zinc oxide powder |
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