CN107199021B - High-adsorbability composite hydrogel material and preparation method thereof - Google Patents
High-adsorbability composite hydrogel material and preparation method thereof Download PDFInfo
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- CN107199021B CN107199021B CN201710457476.1A CN201710457476A CN107199021B CN 107199021 B CN107199021 B CN 107199021B CN 201710457476 A CN201710457476 A CN 201710457476A CN 107199021 B CN107199021 B CN 107199021B
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- 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
Abstract
The invention discloses a high-adsorbability composite hydrogel material and a preparation method thereof, and belongs to the field of composite materials. The high-adsorbability composite hydrogel material is composed of cellulose nano microfiber and nano graphite-like carbon nitride. The preparation method of the high-adsorbability composite hydrogel material comprises the following steps: firstly, burning carbon nitride by dicyandiamide; secondly, dissolving the obtained carbon nitride powder in NaOH aqueous solution in proportion for ultrasonic treatment; thirdly, dialyzing the prepared carbon nitride solution; fourthly, dissolving cellulose in a prepared NaOH/urea/nitrogenated carbohydrate system by a rapid dissolution method; fifthly, obtaining the nano composite hydrogel by a tape casting film forming method; and sixthly, washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel. The method is simple, green and environment-friendly, and the obtained composite hydrogel material can be applied to the field of degrading organic pollutants with high adsorbability.
Description
Technical Field
The invention relates to a high-adsorbability composite hydrogel material and a preparation method thereof, belonging to the field of composite materials.
Background
In the past decade, people are increasingly paying more attention to environmental problems such as organic pollutants and toxic wastewater discharged by industry. The adsorption method is used for treating printing and dyeing sewage, and is characterized in that pollutants in a water body are enriched on the surface of an adsorption material by utilizing the adsorption affinity between dye molecules in the sewage and the adsorption material, so that the dye in the sewage is removed. The CN nano fiber has the advantages of high adsorption capacity, low price, no toxicity and no accumulation, and is used for treating pollutants as an adsorption material, but the CN nano fiber is not easy to recover and is currently commonly used as nitrogenated carbohydrate gel. However, the use of nitrogenated carbohydrate gels presents significant drawbacks and disadvantages: 1) preparation of hydrogel Using CO2As a trigger, is not environmentally friendly. 2) The prepared sample has a single structure and is thermodynamically unstable, and can become a sol in a heating state. 3) The shape of the prepared nitrogenated carbohydrate gel material cannot be controlled, and the strength is low.
The conventional carbon nitride nanofiber hydrogel for organic pollutants has the disadvantages of complex preparation process, single sample structure, low strength, thermodynamic instability and difficult shape control, and further utilization of the hydrogel is hindered.
The cellulose is a natural polymer with the largest storage capacity in the world, and has the advantages of low price, easy obtainment, good biocompatibility, high stability, excellent mechanical property and the like.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a composite hydrogel material with high-efficiency adsorption effect and a preparation method thereof. The high-adsorbability composite hydrogel material is composed of cellulose nano-microfiber and graphite-like carbon nitride.
The composite hydrogel material with high adsorbability utilizes the principle of interfacial action to disperse carbon nitride in a NaOH/urea water system, and the carbon nitride is uniformly distributed on regenerated cellulose by a dissolution-regeneration method, so that the composite hydrogel material keeps high adsorbability and has excellent mechanical property and thermal stability.
The composite hydrogel material with efficient adsorption effect and the preparation method thereof comprise the following steps:
1) dicyandiamide was fired in a muffle furnace at 450 ℃ ~ 650 ℃ for 2 ~ 6 hours.
2) The obtained carbon nitride powder was ground and dissolved in 3 mol/L ~ 10 mol/L NaOH aqueous solution for ultrasonic treatment.
3) The resulting carbon nitride solution was dialyzed for 12 ~ 48 hours.
4) The cellulose was immersed in a formulated NaOH/urea/nitrogenated carbohydrate system, wherein the water system consisted of 4 ~ 8wt% NaOH, 3 ~ 12 wt% urea and 10 ~ 70 wt% carbon nitride and water.
5) Cellulose was dissolved by a rapid dissolution method to give a solution with a cellulose content of 1 ~ 4 wt%.
6) And obtaining the primary nano composite hydrogel by a tape casting film forming method.
7) Washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel.
According to the technical scheme, the ultrasonic temperature in the second step is 30 ~ 80 ℃, and the ultrasonic time is 3 ~ 12 hours.
According to the technical scheme, the method is characterized in that in the sixth step, the casting film-forming method is immersed into ethanol, ethylene glycol or glycerol to obtain the nano-composite hydrogel, the temperature of the coagulant is 20 ~ 60 ℃, and the time is 5 ~ 10 min.
According to the technical scheme, the cellulose-based nano carbon nitride composite hydrogel is characterized in that the cellulose-based nano carbon nitride composite hydrogel is washed by deionized water, has high transparency and has adsorption performance on various dyes.
According to the technical scheme, the method is characterized in that after the composite hydrogel is washed for 30 ~ 50 times, the high adsorption performance is kept to be 95 ~ 99% of the original high adsorption performance.
Compared with the prior art, the technical scheme of the invention has obvious progress and can obtain the beneficial effects that: the invention well utilizes cellulose as a matrix material, and combines the nano-scale graphite-like carbon nitride with the cellulose, thereby greatly improving the high adsorption property of the composite material: a) the method from bottom to top is adopted, the experimental method is simple, and the prepared carbon nitride is distributed in the interior and on the surface of the cellulose framework and can be repeatedly used for many times; b) by utilizing the strong interface interaction between the carbon nitride and the cellulose matrix, the original mechanical property of the cellulose matrix material can be improved, and the purpose of stabilizing the carbon nitride is achieved; c) the composite gel material also has excellent thermal stability in view of strong hydrogen bonding between material components and excellent thermal stability of the original cellulose material.
Detailed description of the invention
The technical solution of the present invention will be further described with reference to specific examples.
Example 1
Firstly, placing dicyandiamide in a muffle furnace for firing, and heating for 2 hours at 450 ℃; secondly, grinding 1.25g of the obtained carbon nitride powder, dissolving in 50ml of 8mol/L NaOH aqueous solution, and carrying out ultrasonic treatment; thirdly, dialyzing the prepared carbon nitride solution for 48 hours, and cleaning; fourthly, soaking the cellulose into a prepared NaOH/urea/nitrogenated carbohydrate system, wherein the aqueous solvent consists of 7wt% of NaOH, 12 wt% of urea and 10wt% of nitrogenated carbohydrate solution; fifthly, dissolving cellulose by a rapid dissolution method, wherein the content of the cellulose is 5 wt%; sixthly, obtaining the nano composite hydrogel by a tape casting film forming method, wherein the temperature of the coagulant is 40 ℃, and the time is 8 min; and step seven, washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel.
The prepared composite hydrogel is constructed by cellulose nanometer microfiber, nanometer graphite-like carbon nitride and water, wherein the diameter of the cellulose nanometer microfiber is 40 nm, the obtained composite hydrogel has high-efficiency adsorbability of various dyes, under the environmental conditions of normal temperature and normal pressure, 1 mL of cellulose based nano carbon nitride composite hydrogel (8.9 mg/mL) is added into 1 mL of methylene blue solution (0.1 mg/mL), most methylene blue molecules are absorbed by the cellulose based nano carbon nitride composite hydrogel after 24 hours, 6.5 percent of methylene blue is detected in the original solution, after 50 times of washing, the original 95 percent of high adsorption performance is still remained, and has remarkable absorption and regeneration performances on azure B (absorption 87%), acridine yellow (absorption 84%), and safranin O (absorption 86%).
Example 2
Firstly, placing dicyandiamide in a muffle furnace for firing, and heating for 4 hours at 450 ℃; secondly, grinding 1.50g of the obtained carbon nitride powder, dissolving in 50ml of 8mol/L NaOH aqueous solution, and carrying out ultrasonic treatment; thirdly, dialyzing the prepared carbon nitride solution for 48 hours, and cleaning; fourthly, soaking the cellulose into a prepared NaOH/urea/nitrogenated carbohydrate system, wherein the aqueous solvent consists of 6wt% of NaOH, 10wt% of urea and 20wt% of nitrogenated carbohydrate solution; fifthly, dissolving cellulose by a rapid dissolution method, wherein the content of the cellulose is 5 wt%; sixthly, obtaining the nano composite hydrogel by a tape casting film forming method, wherein the temperature of the coagulant is 40 ℃, and the time is 8 min; and step seven, washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel.
The prepared composite hydrogel is constructed by cellulose nano microfiber, nano graphite-like carbon nitride and water, wherein the diameter of the cellulose nano microfiber is 40 nm, the obtained composite hydrogel has high-efficiency adsorbability of various dyes, 1 mL of cellulose-based nano carbon nitride composite hydrogel (8.9 mg/mL) is added into 1 mL of methylene blue solution (0.1 mg/mL) under the environmental conditions of normal temperature and normal pressure, most methylene blue molecules are absorbed by CN hydrogel after 24 hours, only 6.0% of methylene blue is detected in the original solution, after 50 times of washing, the original 96% of high adsorbability is still remained, and the composite hydrogel has remarkable adsorbability and regeneration performance on azure B (adsorbed 90%), acridine yellow (adsorbed 88%), and safranin O (adsorbed 91%).
Example 3
Firstly, placing dicyandiamide in a muffle furnace for firing, and heating for 4 hours at 550 ℃; secondly, grinding 1.8g of the obtained carbon nitride powder, dissolving in 50ml of 8mol/L NaOH aqueous solution, and carrying out ultrasonic treatment; thirdly, fully dialyzing the prepared carbon nitride solution and cleaning; fourthly, soaking the cellulose into a prepared NaOH/urea/nitrogenated carbohydrate system, wherein the aqueous solvent consists of 8wt% of NaOH, 11wt% of urea and 30wt% of nitrogenated carbohydrate solution; fifthly, dissolving the cellulose by a rapid dissolution method, wherein the cellulose content is 4 wt%; sixthly, obtaining the nano composite hydrogel by a tape casting film forming method, wherein the temperature of the coagulant is 40 ℃, and the time is 8 min; and step seven, washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel.
The prepared composite hydrogel is constructed by cellulose nano microfiber, nano graphite-like carbon nitride and water, wherein the diameter of the cellulose nano microfiber is 40 nm, the obtained composite hydrogel has high-efficiency adsorbability of various dyes, 1 mL of cellulose-based nano carbon nitride composite hydrogel (8.9 mg/mL) is added into 1 mL of methylene blue solution (0.1 mg/mL) under the environmental conditions of normal temperature and normal pressure, most methylene blue molecules are absorbed by CN hydrogel after 24 hours, only 4.5% of methylene blue is detected in the original solution, after 50 times of washing, the original 97% of high adsorbability is still remained, and the composite hydrogel has remarkable adsorbability and regeneration performance on azure B (92% of adsorbability), acridine yellow (90% of adsorbability) and safranin O (93% of adsorbability).
Example 4
Firstly, placing dicyandiamide in a muffle furnace for firing, and heating for 6 hours at 550 ℃; secondly, grinding 1.25g of the obtained carbon nitride powder, dissolving in 50ml of 8mol/L NaOH aqueous solution, and carrying out ultrasonic treatment; thirdly, dialyzing the prepared carbon nitride solution for 48 hours, and cleaning; fourthly, soaking the cellulose into a prepared NaOH/urea/nitrogenated carbohydrate system, wherein the aqueous solvent consists of 6wt% of NaOH, 12 wt% of urea and 40wt% of nitrogenated carbohydrate solution; fifthly, dissolving cellulose by a rapid dissolution method, wherein the content of the cellulose is 5 wt%; sixthly, obtaining the nano composite hydrogel by a tape casting film forming method, wherein the temperature of the coagulant is 40 ℃, and the time is 8 min; and step seven, washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel.
The prepared composite hydrogel is constructed by cellulose nano microfiber, nano graphite-like carbon nitride and water, wherein the diameter of the cellulose nano microfiber is 40 nm, the obtained composite hydrogel has high-efficiency adsorbability of various dyes, 1 mL of cellulose-based nano carbon nitride composite hydrogel (8.9 mg/mL) is added into 1 mL of methylene blue solution (0.1 mg/mL) under the environmental conditions of normal temperature and normal pressure, most methylene blue molecules are absorbed by CN hydrogel after 24 hours, only 3.5% of methylene blue is detected in the original solution, after 50 times of washing, the original 98% of high adsorbability is still remained, and the composite hydrogel has remarkable adsorbability and regeneration performance on azure B (95% of adsorbability), acridine yellow (93% of adsorbability) and safranin O (96% of adsorbability).
Example 5
Firstly, placing dicyandiamide in a muffle furnace for firing, and heating for 4 hours at 650 ℃; secondly, grinding 1.55g of the obtained carbon nitride powder, dissolving in 50ml of 8mol/L NaOH aqueous solution, and carrying out ultrasonic treatment; thirdly, dialyzing the prepared carbon nitride solution for 48 hours, and cleaning; fourthly, soaking the cellulose into a prepared NaOH/urea/nitrogenated carbohydrate system, wherein the aqueous solvent consists of 8wt% of NaOH, 9 wt% of urea and 50wt% of nitrogenated carbohydrate solution; fifthly, dissolving cellulose by a rapid dissolution method, wherein the content of the cellulose is 5 wt%; sixthly, obtaining the nano composite hydrogel by a tape casting film forming method, wherein the temperature of the coagulant is 40 ℃, and the time is 8 min; and step seven, washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel.
The prepared composite hydrogel is constructed by cellulose nano microfiber, nano graphite-like carbon nitride and water, wherein the diameter of the cellulose nano microfiber is 40 nm, the obtained composite hydrogel has high-efficiency adsorbability of various dyes, 1 mL of cellulose-based nano carbon nitride composite hydrogel (8.9 mg/mL) is added into 1 mL of methylene blue solution (0.1 mg/mL) under the environmental conditions of normal temperature and normal pressure, most methylene blue molecules are absorbed by CN hydrogel after 24 hours, only 4.0% of methylene blue is detected in the original solution, after 50 times of washing, the original 98% of high adsorbability is still remained, and the composite hydrogel has remarkable adsorbability and regeneration performance on azure B (96% of adsorbability), acridine yellow (94% of adsorbability) and safranin O (93% of adsorbability).
Example 6
Firstly, placing dicyandiamide in a muffle furnace for firing, and heating for 6 hours at 650 ℃; secondly, grinding 1.35g of the obtained carbon nitride powder, dissolving in 50ml of 8mol/L NaOH aqueous solution, and carrying out ultrasonic treatment; thirdly, dialyzing the prepared carbon nitride solution for 48 hours, and cleaning; fourthly, soaking the cellulose into a prepared NaOH/urea/nitrogenated carbohydrate system, wherein the aqueous solvent consists of 5wt% of NaOH, 10wt% of urea and 85 wt% of nitrogenated carbohydrate solution; fifthly, dissolving cellulose by a rapid dissolution method, wherein the content of the cellulose is 5 wt%; sixthly, obtaining the nano composite hydrogel by a tape casting film forming method, wherein the temperature of the coagulant is 40 ℃, and the time is 8 min; and step seven, washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel.
The prepared composite hydrogel is constructed by cellulose nano microfiber, nano graphite-like carbon nitride and water, wherein the diameter of the cellulose nano microfiber is 40 nm, the obtained composite hydrogel has high-efficiency adsorbability of various dyes, 1 mL of cellulose-based nano carbon nitride composite hydrogel (8.9 mg/mL) is added into 1 mL of methylene blue solution (0.1 mg/mL) under the environmental conditions of normal temperature and normal pressure, most methylene blue molecules are absorbed by CN hydrogel after 24 hours, only 4.5% of methylene blue is detected in the original solution, after 50 times of washing, the original 97% of high adsorbability is still obtained, and the composite hydrogel has remarkable adsorbability on azure B (99% of adsorbability), acridine yellow (98% of adsorbability) and safranin O (96% of adsorbability).
Claims (5)
1. A preparation method of a high-adsorbability composite hydrogel material is characterized in that the high-adsorbability composite hydrogel material is constructed by cellulose nanometer microfiber, nanoscale graphite-like carbon nitride and water, and is characterized in that: the method comprises the following steps:
firstly, placing dicyandiamide in a muffle furnace for firing, and heating at 450 ℃ and ~ 650 ℃ for 2 ~ 6 hours;
secondly, grinding the obtained carbon nitride powder and dissolving the carbon nitride powder in 3 mol/L ~ 10 mol/L NaOH aqueous solution for ultrasonic treatment;
thirdly, dialyzing the prepared carbon nitride solution for 12 ~ 48 hours;
fourthly, preparing a NaOH/urea/nitrogenated carbohydrate system by using a nitrogenated carbon dialysate, wherein the water system consists of 4 ~ 8wt% of NaOH, 3 ~ 12 wt% of urea, 10 ~ 70 wt% of nitrogenated carbon and water;
step five, soaking the cellulose into the water system and dissolving the cellulose by a rapid dissolution method, wherein the cellulose content in the solution obtained by dissolution is 1 ~ 4 wt%;
sixthly, obtaining preliminary nano composite hydrogel by a tape casting film forming method;
and seventhly, washing with deionized water to finally obtain the cellulose-based nano carbon nitride composite hydrogel.
2. The method for preparing the high-adsorptivity complex hydrogel material according to claim 1, wherein the ultrasound temperature in the second step is 30 ~ 80 ℃ and the ultrasound time is 3 ~ 12 hours.
3. The method for preparing the composite hydrogel material with high adsorbability according to claim 1, wherein the coagulant used in the casting film-forming method in the sixth step is ethanol, ethylene glycol or glycerol, the temperature of the coagulant is 20 ~ 60 ℃, and the time is 5 ~ 10 min.
4. The method for preparing a high adsorption composite hydrogel material according to claim 1, wherein the method comprises the following steps: and washing with deionized water to obtain the cellulose-based nano carbon nitride composite hydrogel with high transparency and adsorption performance on various dyes.
5. The method for preparing the high-adsorptivity complex hydrogel material according to claim 1, wherein the high-adsorptivity complex hydrogel is maintained at 95 ~ 99% of the original high-adsorptivity complex hydrogel after being washed 30 ~ 50 times.
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| CN108079966A (en) * | 2017-12-26 | 2018-05-29 | 肇庆市华师大光电产业研究院 | A kind of carbonitride/cellulose aerogels composite photo-catalyst and its preparation method and application |
| CN109592828B (en) * | 2019-01-24 | 2020-10-23 | 周诗健 | High-efficiency treatment method of high-concentration organic wastewater |
| CN110270317B (en) * | 2019-05-29 | 2021-11-09 | 绍兴文理学院元培学院 | Preparation method of cellulose-based hydrogel adsorbent for heavy metal wastewater treatment |
| CN110606991B (en) * | 2019-09-27 | 2021-06-01 | 枣庄学院 | High-thermal-stability amphiphilic g-C3N4 modified CNFs sponge and preparation method thereof |
| CN112646069B (en) * | 2020-12-15 | 2022-10-21 | 内蒙古民族大学 | Carbon nitride composite hydrogel and preparation method and application thereof |
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| WO2015110117A2 (en) * | 2014-01-23 | 2015-07-30 | Kevin Jablonka | Method for producing a polymeric carbon nitride catalyst |
| CN106513027A (en) * | 2016-09-30 | 2017-03-22 | 浙江理工大学 | Cellulose based three dimensional porous g-C3N4/C aerogel and preparation method thereof |
| CN106732793A (en) * | 2017-01-18 | 2017-05-31 | 浙江理工大学 | A kind of photocatalysis composite membrane material and preparation method thereof |
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| WO2015110117A2 (en) * | 2014-01-23 | 2015-07-30 | Kevin Jablonka | Method for producing a polymeric carbon nitride catalyst |
| CN106513027A (en) * | 2016-09-30 | 2017-03-22 | 浙江理工大学 | Cellulose based three dimensional porous g-C3N4/C aerogel and preparation method thereof |
| CN106732793A (en) * | 2017-01-18 | 2017-05-31 | 浙江理工大学 | A kind of photocatalysis composite membrane material and preparation method thereof |
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