TWI877458B - Multifunctional composite material - Google Patents

Abstract

The present disclosure provides a multifunctional composite material, including: a plurality of porous silicate particles and a modified layer formed on the surface of the porous silicate particles and the inner wall surface of the open pores of the porous silicate particles, wherein the porous silicate particles includes a glass phase matrix and an active metal dispersed in the glass phase matrix, and the modified layer contains at least one functional metal ion selected from the group consisting of group IA, group IIA and transition metal elements. The multifunctional composite material of the present disclosure has the characteristics of a high pore volume structure and a high proportion of functional metal ions, so that it can provide excellent performance in applications of humidity control, antibacterial, and deodorization, and has a bright prospect in the fields.

Description

Multifunctional composite materials

The present disclosure relates to a porous composite material, and more particularly to a porous composite material having the functions of moisture regulation, deodorization and antibacterial.

With the improvement of living standards, the requirements for environmental quality are also increasing day by day, and air quality and environmental cleanliness are particularly concerned by all walks of life. Although there are various adsorption materials on the market, they still cannot meet the actual application needs. Therefore, in order to improve the performance of materials, it is necessary to continuously optimize the structure of materials, develop the physical and chemical properties of materials and their raw material sources, so as to meet the diverse application needs and create the greatest benefits.

At present, porous composite materials with silicate as the main structure and metal salt are mainly produced by adding metal salts in the front-end silicon source synthesis process. However, in addition to the disadvantages of complicated preparation procedures and difficulty in large-scale production, the addition of metal salts is also limited by the compatibility of the synthesis reaction, so that the metal content of the porous composite material is low, and therefore it is impossible to have good performance. It is difficult to meet the high-difficulty application requirements, especially applications in humidification, antibacterial, deodorization, etc.

In view of this, it is necessary to propose a porous composite material that can carry a high metal content to meet the current diverse application requirements.

A multifunctional composite material includes: a plurality of porous silicate particles, the surface of which has a plurality of open pores with an average pore size of 3 to 50 nanometers, and the porous silicate particles contain a glass phase matrix and an active metal dispersed in the glass phase matrix having at least one element selected from sodium, potassium, calcium and magnesium; and a modified layer formed on the surface of the porous silicate particles and the inner wall surface of the open pores, which accounts for more than 3 weight % of the total weight of the multifunctional composite material, and the modified layer contains functional metal ions selected from at least one of group IA, group IIA and transition metal elements.

According to the disclosure, based on the structure of high pore volume, the functional metal ion content carried by the multifunctional composite material is higher than other commercially available products, so it can provide better adsorption performance in applications such as humidification, antibacterial, deodorization, etc. On the other hand, the multifunctional composite material disclosed in the disclosure can be prepared by using waste liquid crystal panel glass as raw material through nanoporous treatment, which can not only effectively reduce material costs, but also create the benefits of waste recycling, and has real value for industrial application.

The following describes the implementation of the present disclosure through specific specific embodiments. Those skilled in the art can easily understand the advantages and effects of the present disclosure from the content disclosed in this specification. The present disclosure can also be implemented or applied through other different implementations. Various details in this specification can also be modified and changed based on different viewpoints and applications without departing from the spirit of the disclosure. In addition, all ranges and values herein are inclusive and combinable. Any value or point that falls within the range described in this article, such as any integer, can be used as a minimum or maximum value to derive a lower range, etc.

According to the present disclosure, a multifunctional composite material is provided, which includes: a plurality of porous silicate particles, whose surface has a plurality of open pores with an average pore size of 3 to 50 nanometers; and a modified layer formed on the surface of the porous silicate particles and the inner wall of the open pores, which accounts for more than 3 weight % of the total weight of the multifunctional composite material; wherein the porous silicate particles include a glass phase matrix and an active metal dispersed in the glass phase matrix; and the modified layer includes functional metal ions.

In the text, the "glass phase" refers to a non-crystalline semi-solid state, which is the main body of the porous silicate particles disclosed in the present invention; and the composition structure in the glass phase matrix is complex, so the composition is expressed in the form of oxides of various metals rather than in the form of salts.

In the present disclosure, the porous silicate particles are prepared using sodium calcium glass or liquid crystal panel glass as raw materials, and the preparation process includes the following steps: first, the liquid crystal panel glass or general sodium calcium glass is crushed into silicate powder, and the powder particle size range is from a few microns to a few millimeters, and there is no special limitation; then, the silicate powder is treated with an active metal precursor at a temperature of 800 to 1500°C for nanoporation; and the reaction mixture is cooled to room temperature to form a plurality of porous silicate particles with a glass phase matrix and a plurality of open pores on the surface.

The silicate powder is derived from sodium calcium glass or liquid crystal panel glass material, and its composition includes an oxide of at least one element selected from Group IA, Group IIA, Group IIIA, and Group IVA. In a specific embodiment, the silicate powder is composed of silicon oxide, aluminum oxide, boron oxide, barium oxide, and cesium oxide, and the weight ratio of silicon oxide to aluminum oxide is 2 to 5, and the content of boron oxide exceeds 5% by weight. In another specific embodiment, the silicate powder further includes sodium oxide, magnesium oxide, and calcium oxide, so the prepared porous silicate particles can have considerable strength and high chemical resistance.

Through the above-mentioned nanoporous treatment, the average pore diameter of the open pores of the porous silicate particles disclosed herein is between 3 and 50 nanometers. In other embodiments, the average pore diameter of the open pores may be 5, 7, 10, 15, 20, 25, 30, 35, 40 or 45 nanometers, but is not limited thereto.

In another embodiment, at least 60% of the pore volume of the porous silicate particles has a pore diameter in the range of 3 to 50 nm. In other words, at least 60% of the pore volume of the porous silicate particles is contributed by pores with a diameter of 3 to 50 nm.

In one embodiment, the porous silicate particles disclosed herein have a sufficient surface area when the average pore size of the open pores is in the range of 3 to 50 nm, so that the pore volume of the porous silicate particles reaches the range of 0.02 to 0.8 cm ³ /g, which is sufficient to support a high proportion of functional metals.

In other embodiments, the pore volume may be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7 or 0.75 cm ³ /g, but is not limited thereto.

In one embodiment, the specific gravity of the porous silicate particles is 0.5 to 0.8 g/cm ³ . In other embodiments, the specific gravity of the porous silicate particles may be 0.55, 0.6, 0.65, 0.7 or 0.75 g/cm ³ , but is not limited thereto.

Herein, the "active metal" refers to a metal used to partially or completely replace the Group IIIA elements dispersed in the glass phase matrix of the silicate particles, for example, at least one element selected from Group IA or Group IIA to provide active sites that can be combined with functional metal ions.

In one embodiment, the active metal comprises at least one element selected from sodium, potassium, calcium and magnesium.

On the other hand, through the nanoporous treatment, the active metal replaces the boron oxide dispersed in the glass phase matrix of the silicate particles, so that the boron oxide content in the prepared porous silicate particles is less than 5 wt%.

Regarding the preparation method of porous silicate particles, their structure and the composition ratio of active metals, reference may be made to U.S. Patent No. 20160375433A1 and U.S. Patent No. 20160375422A1, all disclosures of which are also cited in this disclosure.

Next, the porous silicate particles are subjected to surface activation treatment to form a modified layer on the surface of the porous silicate particles and the inner wall surface of the open pores to activate the surface of the porous silicate particles and the inner wall surface of the open pores.

Specifically, the "surface activation treatment" mentioned above can be performed by impregnating the porous silicate particles with the functional metal precursor to form an ionic modified layer on the surface and the inner wall of the open pores, but the preparation method is not limited thereto.

In the text, the "functional metal" is selected from at least one of Group IA, Group IIA and transition metal elements, and its source can also be obtained from wastewater or contaminated soil, but is not limited thereto. In the present disclosure, the functional metal ions include potassium, calcium, magnesium, zinc, copper, nickel, cobalt, chromium, iron or a combination thereof, but is not limited thereto.

In the present disclosure, due to the grafting of the functional metal ions, a large amount of asymmetric charges are formed on the surface of the multifunctional composite material and the inner wall of the open pores, thereby giving the porous silicate particles new functions different from the inherent properties.

Specifically, in humidification applications, calcium, magnesium or potassium ions can absorb and desorb water vapor to provide humidity regulation functions; in odor purification applications, copper or nickel ions can chemically adsorb odor molecules containing sulfur or ammonia to achieve the deodorization function; in antibacterial applications, copper ions can effectively destroy the protein enzyme function in bacteria and have the effect of inactivating bacteria, providing antibacterial and bactericidal functions.

In one embodiment, the modified layer accounts for more than 3% by weight of the multifunctional composite material; in another embodiment, the modified layer accounts for 3 to 40% by weight, for example, 3 to 20% by weight of the multifunctional composite material. If the modified layer ratio is too low, the effect of humidification, deodorization, antibacterial or sterilization is poor; if the modified layer ratio is too high, it may cause pore blockage and high preparation cost, which is not economical.

In other embodiments, the modified layer may account for 5, 7, 10, 15, 20, 25, 30 or 35 weight %, but is not limited thereto.

Through the above-mentioned nanoporous technology and surface activation treatment, not only the limitations of the existing synthesis method are overcome, but the obtained multifunctional composite material has the characteristics of a high pore volume structure and a high content of functional metal ions. Therefore, when used in humidification applications, it can provide a humidification capacity of 15 to 55%, greatly improving its humidification function; when used in antibacterial products, the antibacterial rate or bactericidal rate can be greater than 99%, which can show an excellent antibacterial effect; when used in deodorization applications, its odor removal rate is greater than 98%, and it has good adsorption capacity for various odor molecules, showing that the multifunctional composite material disclosed in the present invention has considerable application value in air quality and environmental purification.

The present disclosure is further described in detail below through specific embodiments, but the scope of the present disclosure is not limited by the embodiments.

Preparation example 1 ：Preparation of multifunctional composite materials containing calcium modified layer

Preparation of porous silicate particles : Waste liquid crystal panel glass is crushed to prepare silicate powder, 100 g of silicate powder is mixed with 200 g of sodium carbonate, and then nanoporous treatment is performed at 1300 ^° C to obtain porous silicate particles.

Surface activation treatment : 10 g of porous silicate particles were added to 100 mL of 20.0 wt% _CaCl2 solution for immersion and thorough mixing. After stirring to allow calcium ions to fully bond with the porous silicate particles, the grafting reaction was allowed to proceed for 4 hours. The mixture was then washed with deionized water, filtered and dried to obtain a multifunctional composite material containing a calcium-modified layer.

Finally, the multifunctional composite material prepared as described above was subjected to subsequent testing and analysis: (1) Appearance morphology observation and surface element analysis: After the porous silicate particles were cut open, the morphology of the material was observed using a scanning electron microscope (SEM, JEOL JSM-6500F) (as shown in FIG. 1 ); at the same time, the surface element composition was analyzed using energy dispersive X-ray spectroscopy (EDS, Oxford INCA) as shown in Table 1. It can be seen that the calcium content of the multifunctional composite material of this embodiment is 13.14 wt %. Table 1 element Content (wt%) O 46.95 Na 2.27 Al 10.84 Si 21.67 Cl 5.14 Ca 13.14 (2) Pore size measurement: A small amount of porous silicate particles was placed in a sample tube and the pore size distribution and pore volume of the material were measured using a surface area analyzer (ASAP 2420). The pore size distribution measurement results are recorded in Figure 2, and the pore volume measurement result is 0.62 cm ³ /g.

Preparation example 2 ：Preparation of multifunctional composite materials containing calcium modified layer

The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 4.0 wt% _CaCl2 solution for immersion and thorough mixing. After stirring to allow calcium ions to fully bond with the porous silicate particles, the grafting reaction is carried out for 4 hours. The particles are then washed with deionized water, filtered and dried to obtain a multifunctional composite material containing a calcium-modified layer. Surface element analysis shows that the calcium content is 4.6 wt%.

Preparation example 3 ：Preparation of multifunctional composites containing magnesium modified layers

The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 8.3 wt% Mg(NO ₃ ) ₂ solution for immersion and thorough mixing. After stirring to allow magnesium ions to fully bond with the porous silicate particles, the grafting reaction is carried out for 4 hours. The particles are then washed with deionized water, filtered and dried to obtain a multifunctional composite material containing a magnesium modified layer. Surface element analysis shows that the magnesium content is 3.0 wt%.

Preparation example 4 ：Preparation of multifunctional composite materials containing potassium modified layer

The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 7.5 wt% _K2CO3 solution _for immersion and thorough mixing. After stirring to allow potassium ions to fully bond with the porous silicate particles, the grafting reaction is carried out for 4 hours. The particles are then washed with deionized water, filtered and dried to obtain a multifunctional composite material containing a potassium-modified layer. Surface element analysis shows that the potassium content is 17.0 wt%.

Preparation example 5 ：Preparation of multifunctional composites containing nickel modified layers

The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 39 wt% _NiSO4 solution for immersion and thorough mixing. After stirring to allow nickel ions to fully bond with the porous silicate particles, the grafting reaction is carried out for 3 days. The particles are then washed with deionized water, filtered and dried to obtain a multifunctional composite material containing a nickel modified layer. Surface element analysis shows that the nickel content is 16.0 wt%.

Preparation example 6 to 8 ：Preparation of multifunctional composites containing copper modified layers

The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 20 wt% _CuSO4 solution for immersion and thorough mixing. After stirring to allow copper ions to fully bond with the porous silicate particles, the grafting reaction is carried out for 4 hours, 3 days, and 7 days, respectively. The particles are then washed with deionized water, filtered, and dried to obtain multifunctional composite materials containing copper modified layers of Preparation Examples 6 to 8. Surface element analysis shows that the copper content is 6.0, 10.0, and 16.4 wt%, respectively.

Comparative Example 1 : The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are washed with 0.1 N sulfuric acid and deionized water to remove surface calcium, copper and nickel, and then filtered and dried. After surface element analysis, it is found that the calcium, copper and nickel contents are all 0 wt%.

Comparative Example 2 : The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 2.0 wt% _CaCl2 solution, immersed and fully mixed, stirred to allow calcium ions to fully bond with the porous silicate particles, and then grafted for 4 hours. Subsequently, the mixture is washed with deionized water, filtered and dried to obtain a multifunctional composite material containing a calcium-modified layer. Surface element analysis shows that the calcium content is 2.1 wt%.

Comparative Example 3 : The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 1.0 wt% Cu(NO ₃ ) ₂ solution to form a mixture. The mixture is placed in a reciprocating shaker and then vibrated at 120 ppm for 5 minutes to allow the mixture to be fully mixed. The mixture is then placed in an 800 W microwave for 5 minutes to allow the copper ions to fully bond with the porous silicate particles. After cooling to room temperature, the mixture is washed with deionized water, filtered and dried to obtain a composite material containing a copper-modified layer. Surface element analysis shows that the copper content is 1.6 wt%.

Comparative Example 4 : The method for preparing porous silicate particles is the same as that of Preparation Example 1. 10 g of porous silicate particles are added to 100 mL of 0.05 wt% _CuSO4 solution for immersion and thorough mixing. The mixture is stirred to allow copper ions to fully bond with the porous silicate particles, and then the grafting reaction is carried out for 10 minutes. The mixture is then washed with deionized water, filtered and dried to obtain a multifunctional composite material containing a copper modified layer with a copper content of 0.2 wt%.

Test example 1 ：The humidifying ability of multifunctional composite materials

Take about 10 g of sample and dry it thoroughly, then weigh it to get the dry weight W ₀ of the sample. Place the dried sample in a relative humidity environment of 90% for 24 hours, then weigh it to get the moisture absorption weight W ₁ of the sample. Then place the sample in a relative humidity environment of 50% for 24 hours, then weigh it to get the moisture release weight W ₂ of the sample. Calculate the difference dW between W1 and W2, and calculate the relative percentage of dW to W ₀ to get the humidifying capacity (%). The humidifying capacity of the samples of Preparation Examples 1 to 4 and Comparative Examples 1 to 2 was tested using the above method, and the results are shown in Figure 3.

According to the results in Figure 3, it is shown that because the modified layer contains calcium ions, magnesium ions or potassium ions, and the concentration of the functional metal ions reaches 3% by weight or more, the humidification capacity of the multifunctional composite material can reach more than 24%. When the concentration of the functional metal ions is less than 3% by weight, the humidification capacity is low. Therefore, the above experiments show that the multifunctional composite material can effectively improve the humidification capacity of the material because it has a modified layer with high concentrations of calcium ions, magnesium ions or potassium ions.

Test example 2 ：Deodorizing ability of multifunctional composite materials

Take about 10 g of sample and dry it thoroughly, then put it into a sealed bag of polyvinyl fluoride (PVF), introduce 4 L of odor containing 160 ppm of methyl mercaptan and react. At 0 minutes of reaction, the concentration of methyl mercaptan in the odor is analyzed to be S ₀ . At 120 minutes of reaction, the concentration of methyl mercaptan in the odor is analyzed to be S ₁ . Calculate the difference dS between S ₀ and S ₁ , and calculate the relative percentage of dS to S ₀ to obtain the odor removal rate (%). The deodorization ability of the samples of Preparation Examples 5 to 6, Comparative Examples 1 and Comparative Examples 3 was tested by the above method, and the results are shown in Figure 4.

According to the results in Figure 4, it is shown that because the modified layer contains copper ions or nickel ions, and the functional metal ion concentration reaches 3% by weight or more, the odor removal rate of the multifunctional composite material can reach more than 98%. When the functional metal ion concentration is less than 3% by weight, the odor removal rate is low. Therefore, the above experiments show that the multifunctional composite material can improve the deodorization ability of the material because it has a modified layer with high concentration of copper ions or nickel ions.

Test example 3 ：Antibacterial ability of multifunctional composite materials

1 mL of bacterial solution containing Staphylococcus aureus and Escherichia coli was dripped into 1 g of dried sample, and the contact reaction lasted for 24 hours. The bacterial concentration of the bacterial solution that was not in contact with the sample after 24 hours was analyzed as A, the bacterial concentration of the bacterial solution that was in contact with the sample after 0 hours was B, and the bacterial concentration of the bacterial solution that was in contact with the sample after 24 hours was C. The difference value d ₁ between A and C was calculated, and the relative percentage of d ₁ to A was calculated to obtain the inhibition rate (%); the difference value d ₂ between B and C was calculated, and the relative percentage of d ₂ to B was calculated to obtain the sterilization rate (%). The antibacterial ability of the samples of Preparation Examples 7 to 8 and Comparative Examples 3 to 4 was tested using the above method, and the results are shown in Figures 5A and 5B.

According to the results of Figures 5A and 5B, it is shown that because the modified layer contains copper ions and the functional metal ion concentration reaches 3% by weight or more, the antibacterial rate of the multifunctional composite material against both bacteria can reach 99.99%, and the sterilization rate can also reach 99.8% or more. When the functional metal ion concentration is less than 3% by weight, the antibacterial rate and sterilization rate are low. Therefore, the above experiments show that the multifunctional composite material can improve the antibacterial ability of the material because it has a modified layer with a high concentration of copper ions.

In summary, the multifunctional composite material disclosed herein has the characteristics of a high pore volume structure and a high proportion of functional metal ions, and therefore can provide excellent adsorption performance in applications such as humidification, antibacterial, and deodorization. On the other hand, the multifunctional composite material disclosed herein can be prepared by using waste liquid crystal panel glass as a raw material through nanoporous treatment, which can not only effectively reduce material costs, but also create the benefits of waste recycling, and is indeed valuable for industrial applications.

The above embodiments are merely illustrative and not intended to limit the present disclosure. Anyone skilled in the art may modify and alter the above embodiments without violating the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure is defined by the scope of the patent application attached to the present disclosure. As long as the effect and implementation purpose of the present disclosure are not affected, the technical content of the present disclosure shall be included.

without

The implementation method of the present disclosure is described by means of exemplary reference figures: FIG. 1 is a surface image of the multifunctional composite material of the present disclosure observed by a scanning electron microscope; FIG. 2 is a pore size distribution diagram of the multifunctional composite material of the present disclosure, wherein V of the vertical coordinate represents the pore volume, D represents the pore diameter, and dV/dlog(D) represents the pore volume of all pores per unit pore diameter; FIG. 3 is a comparison diagram of the moisturizing ability test of the present disclosure embodiment and the comparative example; FIG. 4 is a comparison diagram of the deodorizing ability test of the present disclosure embodiment and the comparative example; FIG. 5A is a comparison diagram of the antibacterial ability test of the present disclosure embodiment and the comparative example; and Figure 5B is a comparison chart of the sterilization ability test of the disclosed embodiment and the comparative example.

without

Claims (10)

A multifunctional composite material comprises: a plurality of porous silicate particles, the surface of which has a plurality of open pores with an average pore size of 3 to 50 nanometers, and the porous silicate particles contain a glass phase matrix and an active metal of at least one element selected from sodium, potassium, calcium and magnesium dispersed in the glass phase matrix; and a modified layer formed on the surface of the porous silicate particles and the inner wall of the open pores, accounting for more than 3 weight % of the total weight of the multifunctional composite material, and the modified layer contains at least one functional metal ion selected from Group IA, Group IIA and transition metal elements, wherein the pore volume of the porous silicate particles is 0.02 to 0.8 ^cm3 /g. The multifunctional composite material as described in claim 1, wherein the porous silicate particles are made from sodium calcium glass or liquid crystal panel glass. The multifunctional composite material as described in claim 1, wherein the porous silicate particles contain silicon oxide, aluminum oxide, barium oxide, cesium oxide and boron oxide, and the weight ratio of silicon oxide to aluminum oxide is 2 to 5. The multifunctional composite material as described in claim 1, wherein at least 60% of the pore volume of the porous silicate particles has a pore size of 3 to 50 nanometers. The multifunctional composite material as claimed in claim 1, wherein the specific gravity of the porous silicate particles is 0.5 to 0.8 g/cm ³ . The multifunctional composite material as described in claim 1, wherein the modified layer accounts for 3 to 40 weight % of the total weight of the multifunctional composite material. The multifunctional composite material as described in claim 1, wherein the functional metal ions include potassium, calcium, magnesium, zinc, copper, nickel, cobalt, chromium, iron or a combination thereof. The multifunctional composite material as described in claim 1 has a humidifying capacity of 15 to 55%. The multifunctional composite material as described in claim 1 has an odor removal rate greater than 98%. The multifunctional composite material described in claim 1 has an antibacterial or sterilizing rate greater than 99%.