CN114210367B - Halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and preparation method and application thereof - Google Patents
Halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114210367B CN114210367B CN202111334062.2A CN202111334062A CN114210367B CN 114210367 B CN114210367 B CN 114210367B CN 202111334062 A CN202111334062 A CN 202111334062A CN 114210367 B CN114210367 B CN 114210367B
- Authority
- CN
- China
- Prior art keywords
- solution
- polyvinyl alcohol
- sponge
- modified polyvinyl
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention belongs to the technical field of reduction of 4-NP organic dye in industrial wastewater, and particularly relates to a halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and a preparation method and application thereof. The halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material prepared by mechanical foaming has a hydrophilic and porous structure, and is easy to adsorb water pollutants. In addition, because HNTs and PVA have strong anchoring capability to Ag ions, the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material has high catalytic performance on reduction of 4-NP.
Description
Technical Field
The invention belongs to the technical field of reduction of 4-NP in industrial wastewater, and particularly relates to a halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and a preparation method and application thereof.
Background
With the development of the chemical industry, large-scale industrialization has led to an increase in water pollution. In particular, 4-nitrophenol (4-NP) derivatives in wastewater are very dangerous to humans and aquatic organisms. Therefore, it is necessary to find an environmentally friendly, durable, efficient catalyst to degrade toxic 4-NPs.
The conversion of 4-nitrophenol to para-aminophenol (4-AP) by means of the reducing agent sodium borohydride using silver nanoparticles (AgNPs) has been a very valuable process. On the one hand, the conversion product para-aminophenol is a major intermediate in the manufacture of pharmaceuticals, lubricants and dyes; on the other hand, agNPs have larger specific surface due to quantum size effect, and have higher reduction performance on 4-NP. However, one of the biggest challenges faced by AgNPs is the agglomeration problem. In addition, agNPs are difficult to recycle and are prone to leakage into the environment causing pollution. For this reason, silver nanoparticles are often supported in various carriers to prevent agglomeration thereof and to limit leakage thereof. However, the conventional method is complex, the recovery performance of the AgNPs needs to be further improved, and the loading capacity of the carrier material to the AgNPs is limited, so how to quickly and stably prepare the high-efficiency recyclable AgNPs catalyst is still a great challenge.
In recent years, halloysite Nanotubes (HNTs) have been widely used as catalyst support materials because of their unique hollow tubular structure, large specific surface area, negatively charged outer walls, and al—oh group-rich inner surfaces, which facilitate anchoring of metal ions. Typically, HNTs may be added as powders or to polymer composites. However, there is a problem in that HNTs are used directly, and they are easily immersed in water to form stable colloidal suspensions, making separation difficult. Therefore, there is a need to find other convenient methods to further enhance the catalytic performance of 4-NPs.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a Halloysite Nanotube (HNTs) modified polyvinyl alcohol (PVA) sponge silver-carrying material, and a preparation method and application thereof.
The technical scheme provided by the invention is as follows:
the preparation method of the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material comprises the following steps:
s1, weighing 0.06-0.42 part of HNTs and 54 parts of water, mixing the materials into a container, and then performing ultrasonic dispersion for 1-1.5 hours;
s2, adding 3-9 parts of PVA into a container, heating to 85-95 ℃, and mechanically stirring until the PVA is completely dissolved;
s3, cooling the HNTs and PVA mixed solution after dissolution to room temperature, stirring, adding 5-10 parts of formaldehyde and 2.5-5 parts of 30wt% alkylphenol ethoxylate (10) ether (OP-10) solution, and stirring for 30-35 min;
s4, adding 15-30 parts of 50wt% H 2 SO 4 Stirring the solution for 5-10 min to obtain a foam solution;
s5, weighing 0.05 to 1 part of AgNO 3 Dissolving in 5-10 parts of water, magnetically stirring until the water is completely dissolved, adding the solution into the foam solution obtained in the step S4, and stirring for 2-5 min;
s6, pouring the mixture obtained in the step S5 into an empty container, and putting the empty container into a baking oven at the temperature of 45-60 ℃ for curing for 2-4 hours to obtain a semi-finished sponge product;
s7, washing the prepared sponge semi-finished product to be neutral by using clear water or dilute ammonia water, removing unreacted sulfuric acid, and drying in an oven;
s8, soaking the dried sponge semi-finished product in sodium borohydride solution, then washing the sponge with clear water to remove unreacted sodium borohydride, and drying in an oven to obtain the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material.
According to the technical scheme, the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material prepared by mechanical foaming has a hydrophilic and porous structure, and is easy to adsorb water pollutants. The adsorption capacity can reach 4.21ml/g. In addition, because HNTs and PVA have strong anchoring capability to Ag ions, the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material has high catalytic performance on reduction of 4-NP.
Specifically, in the step S8, the sponge semi-finished product is soaked in the sodium borohydride solution for 10-30 min, and the concentration of the sodium borohydride solution is 0.1-1.0 mol/L.
Specifically, in step S2, the molecular weight of PVA is PVA-1788 or PVA-1799.
The invention also provides the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material prepared by the preparation method.
The invention also provides application of the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material as a degradation material of 4-NP in industrial wastewater.
The catalytic efficiency of the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material provided by the invention is still maintained above 98% after 5 times of circulation.
The halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material provided by the invention is low in development cost, high in efficiency and recyclable, provides a simple and feasible strategy for degrading 4-NP, and has a good application prospect in wastewater treatment.
Drawings
FIG. 1 is a graph showing the effect of halloysite nanotube modified polyvinyl alcohol sponge silver-loaded material prepared in example 3 of the invention on sodium borohydride catalysis of 4-NP reduction.
FIG. 2 is a chart showing the cyclic test of sodium borohydride catalysis of 4-NP reduction of halloysite nanotube modified polyvinyl alcohol sponge silver-loaded materials prepared in example 3 of the present invention.
Detailed Description
The principles and features of the present invention are described below with examples only to illustrate the present invention and not to limit the scope of the present invention.
Example 1
S1, weighing 0.18 part of HNTs (Sesamin Chuangda Biotechnology Co., ltd.,99 percent; the same for each of the other examples), 54 parts of water, and the mixture was added to the flask and sonicated for 1 hour.
S2, adding 6 parts of PVA-1788 into the flask, heating to 90 ℃, and mechanically stirring until the PVA is completely dissolved.
S3, cooling the HNTs/PVA mixed solution after dissolution to room temperature, starting stirring for 3min, adding 10 parts of formaldehyde and 5 parts of 30wt% OP-10 solution, and stirring for 30min.
S4, adding 30 parts of 50wt% H 2 SO 4 The solution was stirred for 5min to give a foam solution.
S5, weighing 0.472 part of AgNO 3 Dissolved in10 parts of water, stirring magnetically until the water is completely dissolved, adding the mixture into the foam solution obtained in the step S4, and stirring the mixture for 3 minutes.
S6, pouring the mixture obtained in the step S5 into an empty container, and putting the empty container into a 45 ℃ oven for curing for 2 hours to obtain a semi-finished sponge product.
S7, washing the prepared semi-finished sponge product with clear water or dilute ammonia water to be neutral, removing unreacted sulfuric acid, and drying in an oven.
S8, soaking the dried sponge in sodium borohydride solution, then washing the sponge with clear water to remove unreacted sodium borohydride, and drying in an oven to obtain the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material.
Example 2
S1, weighing 0.24 part of HNTs and 54 parts of water, and adding into a flask for ultrasonic dispersion for 1h.
S2, adding 6 parts of PVA into the flask, heating to 90 ℃, and mechanically stirring until the PVA is completely dissolved.
S3, cooling the HNTs/PVA mixed solution after dissolution to room temperature, starting stirring for 3min, adding 10 parts of formaldehyde and 5 parts of 30wt% OP-10 solution, and stirring for 30min.
S4, adding 30 parts of 50wt% H 2 SO 4 The solution was stirred for 5min to give a foam solution.
S5, weighing 0.472 part of AgNO 3 Dissolving in 10 parts of water, magnetically stirring until the solution is completely dissolved, adding the solution into the foam solution obtained in the step S4, and stirring for 3min.
S6, pouring the mixture obtained in the step S5 into an empty container, and putting the empty container into a 45 ℃ oven for curing for 2 hours to obtain a semi-finished sponge product.
S7, washing the prepared semi-finished sponge product with clear water or dilute ammonia water to be neutral, removing unreacted sulfuric acid, and drying in an oven.
S8, soaking the dried sponge in sodium borohydride solution, then washing the sponge with clear water to remove unreacted sodium borohydride, and drying in an oven to obtain the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material.
Example 3
S1, weighing 0.30 part of HNTs and 54 parts of water, and adding into a flask for ultrasonic dispersion for 1h.
S2, adding 6 parts of PVA-1788 into the flask, heating to 90 ℃, and mechanically stirring until the PVA is completely dissolved.
S3, cooling the HNTs/PVA mixed solution after dissolution to room temperature, starting stirring for 3min, adding 10 parts of formaldehyde and 5 parts of 30wt% OP-10 solution, and stirring for 30min.
S4, adding 30 parts of 50wt% H 2 SO 4 The solution was stirred for 5min to give a foam solution.
S5, weighing 0.472 part of AgNO 3 Dissolving in 10 parts of water, magnetically stirring until the solution is completely dissolved, adding the solution into the foam solution obtained in the step S4, and stirring for 3min.
S6, pouring the mixture obtained in the step S5 into an empty container, and putting the empty container into a 45 ℃ oven for curing for 2 hours to obtain a semi-finished sponge product.
S7, washing the prepared semi-finished sponge product with clear water or dilute ammonia water to be neutral, removing unreacted sulfuric acid, and drying in an oven.
S8, soaking the dried sponge in sodium borohydride solution, then washing the sponge with clear water to remove unreacted sodium borohydride, and drying in an oven to obtain the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material.
Example 4
S1, weighing 0.36 part of HNTs and 54 parts of water, and adding into a flask for ultrasonic dispersion for 1h.
S2, adding 6 parts of PVA into the flask, heating to 90 ℃, and mechanically stirring until the PVA is completely dissolved.
S3, cooling the HNTs/PVA mixed solution after dissolution to room temperature, starting stirring for 3min, adding 10 parts of formaldehyde and 5 parts of 30wt% OP-10 solution, and stirring for 30min.
S4, adding 30 parts of 50wt% H 2 SO 4 The solution was stirred for 5min to give a foam solution.
S5, weighing 0.472 part of AgNO 3 Dissolving in 10 parts of water, magnetically stirring until the solution is completely dissolved, adding the solution into the foam solution obtained in the step S4, and stirring for 3min.
S6, pouring the mixture obtained in the step S5 into an empty container, and putting the empty container into a 45 ℃ oven for curing for 2 hours to obtain a semi-finished sponge product.
S7, washing the prepared semi-finished sponge product with clear water or dilute ammonia water to be neutral, removing unreacted sulfuric acid, and drying in an oven.
S8, soaking the dried sponge in sodium borohydride solution, then washing the sponge with clear water to remove unreacted sodium borohydride, and drying in an oven to obtain the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material.
Example 5
S1, weighing 0.42 part of HNTs and 54 parts of water, and adding into a flask for ultrasonic dispersion for 1h.
S2, adding 6 parts of PVA into the flask, heating to 90 ℃, and mechanically stirring until the PVA is completely dissolved.
S3, cooling the HNTs/PVA mixed solution after dissolution to room temperature, starting stirring for 3min, adding 10 parts of formaldehyde and 5 parts of 30wt% OP-10 solution, and stirring for 30min.
S4, adding 30 parts of 50wt% H 2 SO 4 The solution was stirred for 5min to give a foam solution.
S5, weighing 0.472 part of AgNO 3 Dissolving in 10 parts of water, magnetically stirring until the solution is completely dissolved, adding the solution into the foam solution obtained in the step S4, and stirring for 3min.
S6, pouring the mixture obtained in the step S5 into an empty container, and putting the empty container into a 45 ℃ oven for curing for 2 hours to obtain a semi-finished sponge product.
S7, washing the prepared semi-finished sponge product with clear water or dilute ammonia water to be neutral, removing unreacted sulfuric acid, and drying in an oven.
S8, soaking the dried sponge in sodium borohydride solution, then washing the sponge with clear water to remove unreacted sodium borohydride, and drying in an oven to obtain the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material.
Effect example
The halloysite nanotube modified polyvinyl alcohol sponge silver-loaded material prepared in example 3 is used for catalytic reduction of 4-NP.
Immersing the prepared polyvinyl alcohol sponge loaded with nano silver particles into 4-NP (0.2 mmol,30 mL) and NaBH 4 （80 mmol，30 mL）In the mixed aqueous solution of (2), the reaction temperature is room temperature, the concentration of 4-NP is monitored through an ultraviolet-visible spectrum with the scanning range of 250-550 nm, and the spectrum is collected every 2min until the peak of 4-nitrophenol ions at 400nm is completely disappeared, so that the catalytic reaction reduction is basically completed, and the catalytic effect of the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material on sodium borohydride is shown in figure 1. The effect of the cycling test of the cleaning sponge after the catalysis is completed is shown in figure 2. The results show that: the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material prepared by the invention has excellent catalytic activity and recoverability in sodium borohydride degradation 4-NP experiment.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (3)
1. The application of halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material is characterized in that: as a degradation material of 4-nitrophenol in industrial wastewater, the preparation method of the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material comprises the following steps:
s1, weighing 0.06-0.42 part of HNTs and 54 parts of water, mixing the materials into a container, and then performing ultrasonic dispersion for 1-1.5 hours;
s2, adding 3-9 parts of PVA into a container, heating to 85-95 ℃, and mechanically stirring until the PVA is completely dissolved;
s3, cooling the HNTs and PVA mixed solution after dissolution to room temperature, stirring, adding 5-10 parts of formaldehyde and 2.5-5 parts of 30wt% OP-10 solution, and stirring for 30-35 min;
s4, adding 15-30 parts of 50wt% H 2 SO 4 Stirring the solution for 5-10 min to obtain a foam solution;
s5, weighing 0.05 to 1 part of AgNO 3 Dissolving in 5-10 parts of water, magnetically stirring until the water is completely dissolved, adding the solution into the foam solution obtained in the step S4, and stirring for 2-5 min;
s6, pouring the mixture obtained in the step S5 into an empty container, and putting the empty container into a baking oven at the temperature of 45-60 ℃ for curing for 2-4 hours to obtain a semi-finished sponge product;
s7, washing the prepared sponge semi-finished product to be neutral by using clear water or dilute ammonia water, removing unreacted sulfuric acid, and drying in an oven;
s8, soaking the dried sponge semi-finished product in sodium borohydride solution, then washing the sponge with clear water to remove unreacted sodium borohydride, and drying in an oven to obtain the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material.
2. The application of the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material according to claim 1, which is characterized in that: in the step S8, the sponge semi-finished product is soaked in the sodium borohydride solution for 10-30 min, and the concentration of the sodium borohydride solution is 0.1-1.0 mol/L.
3. The application of the halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material according to claim 1, which is characterized in that: in step S2, the PVA is of the type PVA-1788 or PVA-1799.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111334062.2A CN114210367B (en) | 2021-11-11 | 2021-11-11 | Halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111334062.2A CN114210367B (en) | 2021-11-11 | 2021-11-11 | Halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114210367A CN114210367A (en) | 2022-03-22 |
| CN114210367B true CN114210367B (en) | 2023-09-19 |
Family
ID=80696936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111334062.2A Active CN114210367B (en) | 2021-11-11 | 2021-11-11 | Halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114210367B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115722268B (en) * | 2022-11-18 | 2024-04-05 | 武汉工程大学 | Sponge-loaded nano copper-silver alloy composite material and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3190843A (en) * | 1960-03-17 | 1965-06-22 | Kalle Ag | Process of making a modified polyvinyl alcohol foam |
| CN103638944A (en) * | 2013-11-22 | 2014-03-19 | 江苏大学 | Preparation method of magnetic composite catalyst Ag/HNTs/Fe3O4 |
| CN105175591A (en) * | 2015-10-23 | 2015-12-23 | 武汉工程大学 | Preparation method of organic montmorillonite-modified polyvinyl formal sponge |
| CN105413496A (en) * | 2015-12-29 | 2016-03-23 | 华南理工大学 | Silver-loaded halloysite nanotube-polyvinyl alcohol separation membrane and preparation and application thereof |
| JP2016044309A (en) * | 2014-08-20 | 2016-04-04 | ダイワボウホールディングス株式会社 | Cellulose sponge and production method therefor |
| CN108404992A (en) * | 2018-03-12 | 2018-08-17 | 武汉工程大学 | A kind of preparation method of PVA sponges loading nano silvery material and application |
| CN113457738A (en) * | 2021-07-23 | 2021-10-01 | 武汉工程大学 | PVA silver-carrying sponge and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814958B (en) * | 2016-09-12 | 2020-10-27 | 山西加乐医疗科技有限责任公司 | Preparation method of cellulose sponge and mixed solution thereof |
-
2021
- 2021-11-11 CN CN202111334062.2A patent/CN114210367B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3190843A (en) * | 1960-03-17 | 1965-06-22 | Kalle Ag | Process of making a modified polyvinyl alcohol foam |
| CN103638944A (en) * | 2013-11-22 | 2014-03-19 | 江苏大学 | Preparation method of magnetic composite catalyst Ag/HNTs/Fe3O4 |
| JP2016044309A (en) * | 2014-08-20 | 2016-04-04 | ダイワボウホールディングス株式会社 | Cellulose sponge and production method therefor |
| CN105175591A (en) * | 2015-10-23 | 2015-12-23 | 武汉工程大学 | Preparation method of organic montmorillonite-modified polyvinyl formal sponge |
| CN105413496A (en) * | 2015-12-29 | 2016-03-23 | 华南理工大学 | Silver-loaded halloysite nanotube-polyvinyl alcohol separation membrane and preparation and application thereof |
| CN108404992A (en) * | 2018-03-12 | 2018-08-17 | 武汉工程大学 | A kind of preparation method of PVA sponges loading nano silvery material and application |
| CN113457738A (en) * | 2021-07-23 | 2021-10-01 | 武汉工程大学 | PVA silver-carrying sponge and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Polyethylene glycol/halloysite@Ag nanocomposite PCM for thermal energy storage:Simultaneously high latent heat and enhanced thermal conductivity;Shaokun Song等;《Solar Energy Materials and Solar Cells》;20190122;第193卷;第237-245页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114210367A (en) | 2022-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110813251B (en) | Modified nano material and application thereof in antimony-containing wastewater treatment | |
| CN103638979B (en) | A kind of magnetic class zeolite imidazole ester metal-organic framework materials, preparation and for liquid phase condensations catalytic reaction | |
| CN109529931B (en) | Graphene oxide covalent immobilized metal phthalocyanine catalyst and preparation method and application thereof | |
| CN104310565B (en) | A kind of based on iron-based organic-method of the embryonic stem-like cells process organic waste water of framework material | |
| CN107008507B (en) | Mesoporous Fe-based MOF @ AgI efficient composite visible light photocatalytic material and preparation method and application thereof | |
| CN107008326A (en) | A kind of carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material | |
| El Messaoudi et al. | A comparative review of the adsorption and photocatalytic degradation of tetracycline in aquatic environment by g-C3N4-based materials | |
| CN107519934A (en) | A kind of ferrous metals organic framework material type Fenton catalyst preparation method of ferrocene modification | |
| CN114210367B (en) | Halloysite nanotube modified polyvinyl alcohol sponge silver-carrying material, and preparation method and application thereof | |
| CN108855083A (en) | A method of sulfa drugs in water removal is removed with modified zeolite activation Peracetic acid | |
| CN108043458A (en) | A kind of preparation method and applications of the heterogeneous fenton catalyst of immobilization | |
| CN110882725A (en) | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof | |
| CN106807414A (en) | A kind of silver orthophosphate/bromination silver/carbon nanotube composite photo-catalyst and preparation and application | |
| WO2012109846A1 (en) | Methods for preparation and use of catalyst for hydrazine degradation | |
| CN112718009A (en) | PDI/MOF heterojunction photocatalyst and preparation method and use method thereof | |
| CN111569882A (en) | Cobaltosic oxide supported copper nano catalyst and preparation method thereof | |
| CN112246283A (en) | Bismuth tungstate @ MIL-100(Fe) composite material and preparation method and application thereof | |
| CN102174730A (en) | Method for preparing composite nanoscale fiber felt containing nanoscale iron-palladium bimetallic particles | |
| CN101708464B (en) | Cation resin matrix CdS-loaded composite material and preparation method thereof | |
| CN108314214B (en) | Process for degrading printing and dyeing wastewater through heterogeneous ozone catalysis | |
| Liu et al. | Rational design of a MOF@ Au@ COF catalyst with electron synergy for the reduction of 4-nitrophenol | |
| CN105289748A (en) | Preparation method for auxiliarily compounding magnetic confined noble metal catalysts through soft template | |
| CN102433734A (en) | Method for preparing composite nanofiber felt containing iron-nickel bimetal nanoparticles | |
| CN108636439A (en) | A kind of nitrogen-doped carbon quantum dot-three-dimensional grapheme aerogels and its preparation and application | |
| CN106881154A (en) | A kind of polyaniline bismuth molybdate heterojunction photocatalyst and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |