CN110237811B - Nano iron-molybdenum-graphene composite material and preparation method and application thereof - Google Patents

Nano iron-molybdenum-graphene composite material and preparation method and application thereof Download PDF

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CN110237811B
CN110237811B CN201910453657.6A CN201910453657A CN110237811B CN 110237811 B CN110237811 B CN 110237811B CN 201910453657 A CN201910453657 A CN 201910453657A CN 110237811 B CN110237811 B CN 110237811B
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molybdenum
graphene
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iron
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杨改霞
王先行
谢武
何佳正
苏冬
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Institute Of Resources Comprehensive Utilization Guangdong Academy Of Sciences
Institute of Resource Utilization and Rare Earth Development of Guangdong Academy of Sciences
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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
    • B01J20/0218—Compounds of Cr, Mo, W
    • 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
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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

Abstract

The invention relates to a nano iron-molybdenum-graphene composite material and a preparation method and application thereof. The preparation method comprises the following steps: and ultrasonically dispersing graphene oxide in water, adding ferric salt and molybdenum salt, and then adding a reducing agent for reaction to obtain the nano iron-molybdenum-graphene composite material. According to the invention, a one-pot method is selected for preparation, iron salt, molybdenum salt and graphene oxide are respectively reduced into nano iron, nano molybdenum and graphene through a reducing agent, and simultaneously, the loading of the nano iron and the nano molybdenum on the graphene is realized, the loaded iron and molybdenum can be chelated with organic matters and heavy metal ions in wastewater to improve the adsorption capacity of the graphene, and the iron can improve the loading ratio of the molybdenum, so that the obtained composite material has the characteristic of large adsorption capacity, and has a good adsorption effect on heavy metal ions or organic matter adsorbents in a solution system. The preparation method has the advantages of easily available raw materials, simple process, high reaction efficiency, simple and convenient product separation treatment and low use cost, and is beneficial to industrial application.

Description

Nano iron-molybdenum-graphene composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a nano iron-molybdenum-graphene composite material and a preparation method and application thereof.
Background
The waste water in the industries of metal processing, hard and brittle material processing, printing and dyeing, mineral processing, chemical engineering and the like contains a large amount of organic pollutants and heavy metal ions, and the common waste water comprises methylene blue, methylene orange, ethylamine, aniline, monoethylamine, dimethylamine, diethylamine, trimethylamine, monopropylamine, dipropylamine, isopropylamine, ethylenediamine, monoethanolamine, diethanolamine and triethanolamine, so that the water body is easily eutrophicated, and a large amount of oxygen is consumed in the decomposition process to influence the growth of aquatic organisms. Heavy metal wastewater and organic wastewater are retained, accumulated and migrated after entering the environment or ecosystem, and seriously threaten the ecological environment and human health.
The heavy metal wastewater and organic wastewater treatment method comprises chemical precipitation, membrane separation, ion exchange and adsorption, photocatalytic degradation, Fenton oxidation and the like, and is considered as an economic and effective method in wastewater treatment. However, the conventional adsorbent has disadvantages of low adsorption capacity, difficulty in separation, and the like. The carbon nano-material adsorption material has the characteristics of high specific surface area, easiness in preparation, stable physical and chemical structures and the like, and has become a research hotspot in recent years. Graphene is a novel carbon nanomaterial, is widely applied to the fields of electronics, biosensors, drug delivery, environmental water purification and the like, and shows great application potential in the field of environmental water purification.
CN 108854162A discloses that graphene oxide is firmly attached to the surface of a sponge by dopamine, then hydrazine hydrate is used for reducing the graphene oxide into graphene, and the graphene composite material is soaked in a gamma-methacryloxypropyl trimethoxy silane solution to prepare the graphene composite material, and the graphene composite material is strong in adsorption capacity and good in oil-water separation effect. CN 108905973A discloses three-dimensional graphene/Fe3O4The magnetic nano-adsorption material is prepared by carrying out ultrasonic crushing on graphene oxide and adding Fe3+And L-Cys are obtained by one-pot coprecipitation under alkaline conditions and are used for adsorbing printing and dyeing wastewater. CN109012598A discloses a ciprofloxacin purifying agent based on manganese dioxide/graphene oxide nano composite material. The invention discloses a preparation method of L-arginine modified graphene oxide sponge. CN108620028A discloses a graphene material compounded with calcium carbonate, which is obtained by activating graphene with stearic acid, dispersing light calcium carbonate into an amide solution, and blending with activated graphene, and has good adsorption performance.
The method for modifying the graphene material to improve the adsorption effect of the graphene material becomes a research hotspot in the field of adsorption materials, and the development of the modified graphene material with high adsorption capacity for organic matters and heavy metal ions has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provides a preparation method of a nano iron-molybdenum-graphene composite material. The graphene is used as a carrier to load nano iron and nano molybdenum, so that the composite adsorption material with a stable structure is obtained, the composite adsorption material has the characteristic of large adsorption capacity, has an adsorption effect on heavy metal ions or organic matter adsorbents in a solution system, and particularly has a good adsorption effect on organic matters such as methylene blue, methylene orange, monoethanolamine, diethanolamine, triethanolamine and the like, and metal ions such as manganese ions, copper ions, lead ions, zinc ions, chromium ions, cadmium ions, mercury ions, arsenic ions, cobalt ions, nickel ions and the like in the solution system; the preparation method provided by the invention has the advantages of easily available raw materials, simple preparation process, high reaction efficiency, simple and convenient product separation treatment and low use cost, and is beneficial to industrial application.
Another object of the present invention is to provide a nano iron-molybdenum-graphene composite material.
The invention also aims to provide application of the nano iron-molybdenum-graphene composite material as an adsorption material in adsorbing organic matters or heavy metal ions in an aqueous solution system.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nano iron molybdenum-graphene composite material comprises the following steps: ultrasonically dispersing graphene oxide in water, adding ferric salt and molybdenum salt, and then adding a reducing agent for reaction to obtain the nano iron-molybdenum-graphene composite material; the mass ratio of the iron element to the graphene oxide in the ferric salt is 0.1-5: 1; the mass ratio of molybdenum element to graphene oxide in the molybdenum salt is 0.1-5: 1.
According to the invention, the adsorption performance of graphene is improved by loading nano metal, and researches show that the adsorption performance of graphene is basically not improved when only nano iron is loaded; when the nano molybdenum is loaded, the loading of the nano molybdenum cannot be realized independently. When nano iron and nano molybdenum are loaded at the same time, the adsorption performance is greatly improved.
Specifically, the nano iron-molybdenum-graphene composite material is prepared by a one-pot method, iron salt, molybdenum salt and graphene oxide are reduced into nano iron, nano molybdenum and graphene respectively through a reducing agent, the nano iron and the nano molybdenum are loaded on the graphene, the iron and the molybdenum loaded on the graphene can be chelated with organic matters and heavy metal ions in wastewater to improve the adsorption capacity of the graphene, the iron can improve the load ratio of the molybdenum, and the obtained nano iron-molybdenum-graphene composite material has the characteristic of large adsorption capacity, has an adsorption effect on heavy metal ions or organic matter adsorbents in a solution system, and particularly has an adsorption effect on methylene blue, methylene orange, monoethanolamine, diethanolamine, triethanolamine and other organic matters, manganese ions, copper ions, lead ions, zinc ions, chromium ions, cadmium ions, mercury ions and the like in the solution system, The metal ions such as arsenic ions, cobalt ions, nickel ions and the like have good adsorption effect.
The preparation method provided by the invention has the advantages of easily available raw materials, simple preparation process, high reaction efficiency, simple and convenient product separation treatment and low use cost, and is beneficial to industrial application.
The graphene oxide in the invention can be obtained by purchasing or preparing according to the conventional method in the prior art.
The invention also provides a preparation method of the graphene oxide.
Preferably, the graphene oxide is prepared by the following method: graphite powder, sodium nitrate and concentrated sulfuric acid are mixed and stirred in ice bath, potassium permanganate is added, stirring is carried out, then heating, reflux and stirring are carried out, H is added after cooling2O2And (4) reacting and filtering to obtain the graphene oxide.
Preferably, the iron salt is one or more of ferric sulfate, ferrous sulfate, ferric chloride, ferrous nitrate, ferric phosphate, ferrous pyrophosphate, sodium ferrate, potassium ferrate, ferric bromide, ferrous bromide, ferric fluoride, ferrous fluoride or ferric thiocyanide and hydrates thereof.
Preferably, the molybdenum salt is one or more of sodium molybdate, potassium molybdate, ammonium molybdate, lithium molybdate, bismuth molybdate, phosphomolybdic acid, ammonium phosphomolybdate or ammonium tetramolybdate and hydrates thereof.
Preferably, the reducing agent is one or more of potassium borohydride, sodium borohydride, hydrazine hydrate or sodium hypophosphite.
Preferably, the reaction temperature is 5-40 ℃ and the reaction time is 0.5-4 h.
Preferably, the mass ratio of the iron element in the ferric salt to the graphene oxide is 1-3: 1; the mass ratio of molybdenum element to graphene oxide in the molybdenum salt is 1-3: 1.
The nano iron-molybdenum-graphene composite material is prepared by the preparation method.
The application of the nano iron-molybdenum-graphene composite material as an adsorption material in adsorbing organic matters or heavy metal ions in an aqueous solution system is also within the protection scope of the invention.
Preferably, the organic matter is one or more of methylene blue, methylene orange, methyl red, fast green, rhodamine B, ethylamine, aniline, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, isopropylamine, ethylenediamine, 1, 2-propanediamine, butylamine, octylamine, 1, 4-butanediamine, 1, 10-decanediamine, monoethanolamine, diethanolamine, triethanolamine, diphenylamine, propanolamine, reactive black 5, azure, phenol, bisphenol A, salicylic acid or p-toluenesulfonic acid.
Preferably, the heavy metal ions are one or more of manganese ions, copper ions, lead ions, zinc ions, chromium ions, cadmium ions, mercury ions, arsenic ions, cobalt ions or nickel ions.
Compared with the prior art, the invention has the following beneficial effects:
the invention selects a one-pot method to prepare the nano iron-molybdenum-graphene composite material, reduces iron salt, molybdenum salt and graphene oxide into nano iron, nano molybdenum and graphene respectively through a reducing agent, simultaneously realizes the loading of the nano iron and the nano molybdenum on the graphene, iron and molybdenum loaded on the graphene can be chelated with organic matters and heavy metal ions in wastewater to improve the adsorption capacity of the graphene, iron can improve the loading ratio of the molybdenum, and the obtained nano iron-molybdenum-graphene composite material has the characteristic of large adsorption capacity, has adsorption effect on heavy metal ions or organic matter adsorbents in a solution system, and particularly has adsorption effect on organic matters such as methylene blue, methylene orange, monoethanolamine, diethanolamine and triethanolamine and manganese ions, copper ions, lead ions, zinc ions, chromium ions, cadmium ions, mercury ions and arsenic ions in the solution system, The cobalt ion, nickel ion and other metal ions have good adsorption effect.
The preparation method provided by the invention has the advantages of easily available raw materials, simple preparation process, high reaction efficiency, simple and convenient product separation treatment and low use cost, and is beneficial to industrial application.
Drawings
Fig. 1 is an infrared spectrum of the nano iron molybdenum-graphene composite material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
The graphene oxide in each example was obtained by the following method: weighing 1.0g of graphite powder in 60mL of concentrated sulfuric acid, adding 0.75g of sodium nitrate, slowly adding 4g of potassium permanganate in an ice bath, carrying out ice bath for 1h, placing the mixture into normal temperature to react for 1h after the ice bath is finished, then slowly adding 100mL of water, heating to 98 ℃, refluxing for 1h, and heating to finish. Cooled to 55 ℃ and 6mL of H are added dropwise2O2And after reacting for half an hour, filtering, washing with distilled water for three times, then adding hydrochloric acid for washing, and washing with water until the filtrate is neutral to obtain a solid, namely graphene oxide.
Example 1
This example provides a nano iron-molybdenum-graphene composite material, in which Fe: Mo: C is 3:1:1 (mass ratio), and a preparation method thereof is as follows.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, and adding 14g of FeSO4·6H2O and 2.5g Na2MoO4·2H2And (4) continuing ultrasound for half an hour after O, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the composite material of Fe, Mo and C, wherein the ratio of Fe to Mo to C is 3:1: 1.
Fig. 1 shows an infrared spectrum of the nano iron-molybdenum-graphene composite material. As can be seen from the figure, the prepared graphene has the carbonyl group basically reduced and certain C-O exists.
Example 2
This example provides a nano iron-molybdenum-graphene composite material, in which Fe: Mo: C is 2:1:1 (mass ratio), and a preparation method thereof is as follows.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, and adding 4.65g of FeSO4·6H2O and 2.5g Na2MoO4·2H2And (4) continuing ultrasonic treatment for half an hour after O, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the composite material of Fe, Mo and C, wherein the ratio of Fe to Mo to C is 2:1: 1.
Example 3
This example provides a nano iron-molybdenum-graphene composite material, in which Fe: Mo: C is 2:2:1 (mass ratio), and a preparation method thereof is as follows.
Putting the obtained solid into a reaction bottle, adding 200mL of water, and adding 4.65g of FeSO by ultrasonic treatment for half an hour4·6H2O and 5g Na2MoO4·2H2And (4) continuing ultrasonic treatment for half an hour after O, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the composite material of Fe, Mo and C, wherein the ratio of Fe to Mo to C is 2:2: 1.
Example 4
This example provides a nano iron-molybdenum-graphene composite material, in which Fe: Mo: C is 1:3:1 (mass ratio), and a preparation method thereof is as follows.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, and adding 2.33g of FeSO4·6H2O and 7.5g Na2MoO4·2H2And (4) continuing ultrasound for half an hour after O, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the composite material of Fe, Mo and C, wherein the ratio of Fe to Mo to C is 1:3: 1.
Example 5
This example provides a nano iron-molybdenum-graphene composite material, in which Fe: Mo: C is 1:2:1 (mass ratio), and a preparation method thereof is as follows.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, and adding 2.33g of FeSO4·6H2O and 5g Na2MoO4·2H2And (4) continuing ultrasonic treatment for half an hour after O, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the composite material of Fe, Mo and C, wherein the ratio of Fe to Mo to C is 1:2: 1.
Example 6
This example provides a nano iron-molybdenum-graphene composite material, in which Fe: Mo: C is 0.5:5:1 (mass ratio), and a preparation method thereof is as follows.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, and adding 0.90g of FeCl2·4H2O and 11.88g (NH)4)2Mo4O13·2H2And (4) continuing ultrasonic treatment for half an hour after O, dropwise adding 100mL of hydrazine hydrate, reacting at 5 ℃ for 4 hours, and filtering to obtain the composite material of Fe, Mo and C, wherein the ratio of Fe to Mo to C is 0.5:5: 1.
Example 7
This example provides a nano iron-molybdenum-graphene composite material, in which Fe: Mo: C is 5:0.5:1 (mass ratio), and a preparation method thereof is as follows.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, and adding 36.08g of Fe (NO) by ultrasonic treatment for half an hour3)3·9H2O and 0.79gH3PO4·12MoO3·H2Continuing to perform ultrasonic treatment for half an hour after O, dropwise adding 8g of potassium borohydride, reacting at 40 ℃ for 0.5h, and filtering to obtain the composite material of Fe, Mo and C, wherein the ratio of Fe to Mo to C is 5:0.5: 1.
Comparative example 1
The comparative example provides graphene prepared by the following method.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the graphene material.
Comparative example 2
The comparative example provides graphene prepared by the following method.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, and adding 7.5g of Na2MoO4·2H2Continuing to perform ultrasonic treatment for half an hour after O, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the adsorbing material, wherein the adsorbing material is determined to be graphene, and molybdenum is not completely loaded in the process.
Comparative example 3
The comparative example provides a nano iron-graphene composite material, in which Fe: C is 1:1 (mass ratio), and the preparation method is as follows.
Putting graphene oxide (1g) into a reaction bottle, adding 200mL of water, performing ultrasonic treatment for half an hour, and adding 2.33g of FeSO4·6H2And continuing ultrasound for half an hour after O, dropwise adding 6g of potassium borohydride, reacting for 1 hour, and filtering to obtain the composite material with Fe: C being 1: 1.
Performance testing
Taking the nano iron molybdenum-graphene composite materials provided in the embodiments 1 and 4 as examples, and taking the graphene provided in the comparative examples 1-2 and the nano iron-graphene composite material provided in the comparative example 3 as comparison, the adsorption performance of the nano iron molybdenum-graphene composite materials was tested.
(1) Preparing a methylene blue solution with the concentration of 150mg/L, taking 50mL of the solution, adding 0.01g of the adsorbing material prepared in the example 1, controlling the adsorption temperature to be 35 ℃ and the adsorption time to be 1h, and measuring the adsorption capacity of the material to be 90.32 mg/g.
(2) Preparing a methylene blue solution with the concentration of 150mg/L, taking 50mL of the solution, adding 0.01g of the adsorbing material prepared in the example 4, controlling the adsorption temperature to be 35 ℃ and the adsorption time to be 1h, and measuring the adsorption capacity of the material to be 116.54 mg/g.
(3) Preparing a methylene blue solution with the concentration of 150mg/L, taking 50mL of the solution, adding 0.01g of the graphene prepared in the comparative example 1, controlling the adsorption temperature to be 35 ℃ and the adsorption time to be 1h, and measuring the adsorption capacity of the material to be 32.79 mg/g.
(4) Preparing a methylene blue solution with the concentration of 150mg/L, taking 50mL of the solution, adding 0.01g of the graphene prepared in the comparative example 2, controlling the adsorption temperature to be 35 ℃ and the adsorption time to be 1h, and measuring the adsorption capacity of the material to be 36.15 mg/g.
(5) Preparing a methylene blue solution with the concentration of 150mg/L, taking 50mL of the solution, adding 0.01g of the nano iron-graphene composite material prepared in the comparative example 2, controlling the adsorption temperature to be 35 ℃ and the adsorption time to be 1h, and measuring the adsorption capacity of the material to be 30.56 mg/g.
In conclusion, the nano iron-molybdenum-graphene composite material provided by the invention greatly improves the adsorption capacity of the composite material by loading nano iron and nano molybdenum, and has more excellent adsorption performance compared with pure graphene and graphene only loaded with iron; in addition, the loading of iron will affect the loading ratio of molybdenum, which in turn affects the adsorption performance.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a nano iron molybdenum-graphene composite material for adsorbing organic matters or heavy metal ions in an aqueous solution system is characterized by comprising the following steps: ultrasonically dispersing graphene oxide in water, adding ferric salt and molybdenum salt, and then adding a reducing agent for reaction to obtain the nano iron-molybdenum-graphene composite material; the mass ratio of the iron element to the graphene oxide in the ferric salt is 0.1-5: 1; the mass ratio of molybdenum element to graphene oxide in the molybdenum salt is 0.1-5: 1;
the nano iron-molybdenum-graphene composite material takes graphene as a carrier and loads nano iron and nano molybdenum.
2. The preparation method according to claim 1, wherein the graphene oxide is prepared by the following method: mixing graphite powder, sodium nitrate and concentrated sulfuric acid, stirring in ice bath, adding potassium permanganate, stirring, and adding potassium permanganateHeating, reflux stirring, cooling, and adding H2O2And (4) reacting and filtering to obtain the graphene oxide.
3. The method according to claim 1, wherein the iron salt is one or more of ferric sulfate, ferrous sulfate, ferric chloride, ferrous nitrate, ferric phosphate, ferrous pyrophosphate, sodium ferrate, potassium ferrate, ferric bromide, ferrous bromide, ferric fluoride, ferrous fluoride, or ferric thiocyanide, and hydrates thereof.
4. The method of claim 1, wherein the molybdenum salt is one or more of sodium molybdate, potassium molybdate, ammonium molybdate, lithium molybdate, bismuth molybdate, phosphomolybdic acid, ammonium phosphomolybdate, or ammonium tetramolybdate, and hydrates thereof.
5. The preparation method according to claim 1, wherein the reducing agent is one or more of potassium borohydride, sodium borohydride or hydrazine hydrate.
6. The preparation method according to claim 1, wherein the reaction temperature is 5-40 ℃ and the reaction time is 0.5-4 h.
7. The preparation method according to claim 1, wherein the mass ratio of the iron element in the iron salt to the graphene oxide is 1-3: 1; the mass ratio of molybdenum element to graphene oxide in the molybdenum salt is 1-3: 1.
8. A nano iron molybdenum-graphene composite material for adsorbing organic matters or heavy metal ions in an aqueous solution system is characterized by being prepared by the preparation method of any one of claims 1-7.
9. The use of the nano iron molybdenum-graphene composite material for adsorbing organic matters or heavy metal ions in an aqueous solution system according to claim 8 as an adsorbing material for adsorbing organic matters or heavy metal ions in an aqueous solution system.
10. The use according to claim 9, wherein the organic substance is one or more of methylene blue, methylene orange, methyl red, fast green, rhodamine B, ethylamine, aniline, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, monopropylamine, dipropylamine, tripropylamine, isopropylamine, ethylenediamine, 1, 2-propylenediamine, butylamine, octylamine, 1, 4-butylenediamine, 1, 10-decyldiamine, monoethanolamine, diethanolamine, triethanolamine, diphenylamine, propanolamine, reactive black 5, azure, phenol, bisphenol a, salicylic acid or p-toluenesulfonic acid; the heavy metal ions are one or more of manganese ions, copper ions, lead ions, zinc ions, chromium ions, cadmium ions, mercury ions, arsenic ions, cobalt ions or nickel ions.
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CN113198498A (en) * 2021-04-27 2021-08-03 南京工业大学 FePO4-MoOXPreparation method of-graphene aerogel catalyst material
CN113603190B (en) * 2021-08-05 2023-04-28 中国科学院合肥物质科学研究院 Graphene loaded nano zero-valent copper/iron bimetallic composite material based on nano primary cell effect and preparation method and application thereof
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