CN110860688A - Core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body and preparation method thereof - Google Patents
Core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 41
- 239000011258 core-shell material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 19
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 19
- 239000000661 sodium alginate Substances 0.000 claims abstract description 19
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940072056 alginate Drugs 0.000 claims abstract description 16
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 16
- 229920000615 alginic acid Polymers 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003242 anti bacterial agent Substances 0.000 claims description 8
- 230000003115 biocidal effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- -1 iron ions Chemical class 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000012028 Fenton's reagent Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3206—Organic carriers, supports or substrates
- B01J20/3208—Polymeric carriers, supports or substrates
- B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B01J35/50—
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- B01J35/51—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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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
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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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The invention discloses a core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body and a preparation method thereof. The method comprises the following steps: and carrying out cross-linking reaction on the sodium alginate aqueous solution and the metal ion aqueous solution to obtain bimetal cross-linked alginate gel, and then carrying out high-temperature calcination under the conditions of protective atmosphere and metal substrate. The method for preparing the core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body by using the cheap and easily-obtained natural macromolecular sodium alginate as the raw material is simple, low in cost, green and environment-friendly, controllable in shape, high in yield, excellent in adsorption and catalytic performance and has outstanding application potential in the field of environmental pollution treatment.
Description
Technical Field
The invention belongs to the field of materials, and relates to a core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body and a preparation method thereof.
Background
In recent years, environmental pollution has become serious, and many persistent organic pollutants are difficult to be removed by conventional physical or biological means, so that advanced oxidation technology having the advantage of efficiently degrading pollutants has received much attention, of which fenton catalytic oxidation technology is a typical representative. The heterogeneous Fenton reaction overcomes the problems that the traditional homogeneous Fenton reaction is easy to generate iron mud and the like, but has the limitation of low electron transfer circulation rate. According to the invention, the graphene is used as an electron transport body, and the bimetallic covalent bonding graphene is used to obtain the bimetallic covalent bonding three-dimensional graphene macroscopic body with the core-shell structure, so that the catalytic degradation performance of pollutants is improved by utilizing the mutual cooperation of the bimetallic. The preparation process takes cheap and easily-obtained natural macromolecular sodium alginate as a raw material, and the method is simple, low in cost, green and environment-friendly, controllable in shape and high in yield, and has outstanding application potential in the field of environmental pollution treatment.
Disclosure of Invention
The invention aims to provide a bimetallic covalent bonding three-dimensional graphene macroscopic body with a core-shell structure and a preparation method thereof.
The invention provides a method for preparing a core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body, which comprises the following steps:
and carrying out cross-linking reaction on the sodium alginate aqueous solution and the metal ion aqueous solution to obtain bimetal cross-linked alginate gel, and then carrying out high-temperature calcination under the conditions of protective atmosphere and metal substrate.
In the aqueous solution of metal ions in the above method, the metal ions are selected from at least one of iron ions, cobalt ions and copper ions; the aqueous solution of metal ions is selected from FeSO4、Co(NO3)2、FeCl2And CuCl2At least one of (1);
the concentration of the sodium alginate aqueous solution is 5-200 mg/mL; specifically 20-50 mg/L; the concentration of the metal ion aqueous solution is 0.01-200 mg/mL; specifically 20-50 mg/L;
the molar ratio of the sodium alginate to the metal ions is 1: 1-100; specifically, 1: 2;
the molar ratio of the two metal ions can be 1: 1;
in the step of crosslinking reaction, the temperature is 20-500 ℃; in particular room temperature; for a period of at least 6 hours; in particular 12-48 h.
The protective atmosphere is selected from inert atmosphere or reducing atmosphere; the inert atmosphere is specifically nitrogen or argon atmosphere; the reducing atmosphere is specifically hydrogen;
the metal substrate is a transition metal substrate; specifically at least one selected from iron, cobalt, copper, silver, manganese and nickel.
In the calcining step, the temperature is 600-1000 ℃; in particular 800-900 ℃; the time is 6-24 h.
In addition, the core-shell structure bimetallic covalent bonding three-dimensional graphene macroscopic body prepared by the method and the application of the core-shell structure bimetallic covalent bonding three-dimensional graphene macroscopic body in adsorption and/or catalysis also belong to the protection scope of the invention.
Specifically, the core-shell structure bimetallic covalent bonding three-dimensional graphene macroscopic body consists of a shell and a core; the shell is single-layer sheet graphene, and the core is bimetal; and the shell and the core are covalently bonded.
In the adsorption, the adsorption pH value is 6; the dosage ratio of the core-shell structure bimetallic covalent bonding three-dimensional graphene macroscopic body to the to-be-adsorbed substance is 0.5-5 g/L; specifically 1 g/L; the adsorption temperature is normal temperature; in particular 25 ℃;
the substance to be adsorbed is water containing pollutants; the contaminant is specifically an antibiotic;
the method for preparing the core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body by using the cheap and easily-obtained natural macromolecular sodium alginate as the raw material is simple, low in cost, green and environment-friendly, controllable in shape, high in yield, excellent in adsorption and catalytic performance and has outstanding application potential in the field of environmental pollution treatment.
Drawings
Fig. 1 shows (a) a scanning electron micrograph of a single-metal iron-bonded three-dimensional graphene macroscopic body and (b) a core-shell structure double-metal covalent-bonded three-dimensional graphene macroscopic body.
Fig. 2 is a transmission electron microscope photograph of (a) an iron alginate gel (b) an Fe/Co bimetal cross-linked alginate gel (c) a core-shell structure Fe/Co bimetal covalent bonding three-dimensional graphene macroscopic body and (d) a single-metal iron bonding three-dimensional graphene macroscopic body.
FIG. 3 shows (a) ferric alginate gel, (b) Fe/Co bimetal cross-linked alginate gel, (c) transmission electron micrograph of single-metal iron bonded three-dimensional graphene macroscopic body, and (d) Fe/Co bimetal covalent bonded three-dimensional graphene macroscopic body with core-shell structure.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Examples 1,
The bimetallic covalent bonding three-dimensional graphene macroscopic body in the embodiment is prepared by the following specific steps:
preparing 100mL of 20mg/L sodium alginate solution and 100mL of FeSO4And Co (NO)3)2Mixing the solution of Fe2+And Co2+Are 20mg/L, and 100mL of 20mg/L FeSO is prepared for comparison with the single metal4And (3) solution. Dropwise adding a sodium alginate solution into a Fe/Co solution, standing at room temperature for 24h to obtain the bimetal crosslinked alginate gel ball, dropwise adding the sodium alginate solution into the Fe solution, and standing at room temperature for 24h to obtain the iron alginate gel ball. Adding two alginate gel balls into N2And (3) calcining for 6h at 800 ℃ under the protection and nickel substrate catalysis to obtain a Fe/Co bimetal covalent bonding three-dimensional graphene macroscopic body with a core-shell structure and a single-metal Fe bonding three-dimensional graphene macroscopic body.
As can be seen from the scanning electron micrographs of the two materials in fig. 2, the bi-metal bonded graphene has more abundant pores than the single metal.
As can be seen from the transmission electron microscope images before and after the two materials are calcined in fig. 3, the bimetallic crosslinked gel has a hierarchical ordered network structure, the single metal is an unordered structure, after the two materials are calcined, the bimetallic bonded graphene has a core-shell structure, the outer shell is single-layer sheet graphene, the inner bimetallic is a core, and the monometallic bonded graphene is a multilayer thick sheet structure.
Adsorbing 100mg/L of antibiotics in water by the material, wherein the adsorption pH value is 6; the dosage ratio of the core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body to water containing antibiotics is 1 g/L; the adsorption temperature is 25 ℃, the adsorption removal rate of the material to 100mg/L of antibiotics in water is 82.42%, and the Fenton catalytic degradation rate is 98.86% (the concentration of hydrogen peroxide is 0.5mmol/L, and the rest conditions are the same as the adsorption).
Examples 2,
Preparing 100mL of 20mg/L sodium alginate solution and 100mL of LFeCl2And CuCl2Mixing the solution of Fe2+And Cu2 +Are all 20 mg/L. And dropwise adding the sodium alginate solution into the Fe/Cu solution, and standing for 24h to obtain the bimetal cross-linked alginate gel ball. Adding alginate gel ball into N2And (3) calcining for 6h at 800 ℃ under the protection and nickel substrate catalysis to obtain the bimetallic covalent bonding three-dimensional graphene macroscopic body. Antibiotic adsorption removal and Fenton degradation tests were performed under the same conditions as in example 1, and it was found that the material had an antibiotic adsorption removal rate of 80.32% and a Fenton catalytic degradation rate of 95.13% for 100mg/L of water.
Example 3:
preparing 100mL of 20mg/L sodium alginate solution and 100mL of LFeCl2And CoCl2Mixing the solution of Fe2+And Co2 +Are all 20 mg/L. And dropwise adding the sodium alginate solution into the Fe/Co solution, and standing for 24 hours to obtain the bimetal cross-linked alginate gel ball. Adding alginate gel ball in H2And (3) calcining for 6h at 900 ℃ under the protection and the catalysis of a copper substrate to obtain the bimetallic covalent bonding three-dimensional graphene macroscopic body. Antibiotic adsorption removal and Fenton degradation tests were performed under the same conditions as in example 1, and it was found that the material had an antibiotic adsorption removal rate of 86.53% and a Fenton catalytic degradation rate of 99.25% for 100mg/L of water.
Examples 4,
Preparing 100mL of 50mg/L sodium alginate solution and 100mL of LFeCl2And CoCl2Mixing the solution of Fe2+And Co2 +Are all 50 mg/L. And dropwise adding the sodium alginate solution into the Fe/Co solution, and standing for 24 hours to obtain the bimetal cross-linked alginate gel ball. Adding alginate gel ball in H2And (3) calcining for 6h at 900 ℃ under the protection and the catalysis of a copper substrate to obtain the bimetallic covalent bonding three-dimensional graphene macroscopic body. Antibiotic adsorption removal and Fenton degradation tests were performed under the same conditions as in example 1, and it was found that the material had an antibiotic adsorption removal rate of 89.22% and a Fenton catalytic degradation rate of 99.98% for 100mg/L of water.
Claims (9)
1. A method for preparing a core-shell structure bimetallic covalent bonding three-dimensional graphene macroscopic body comprises the following steps:
and carrying out cross-linking reaction on the sodium alginate aqueous solution and the metal ion aqueous solution to obtain bimetal cross-linked alginate gel, and then carrying out high-temperature calcination under the conditions of protective atmosphere and metal substrate.
2. The method of claim 1, wherein: in the metal ion aqueous solution, the metal ions are selected from at least one of iron ions, cobalt ions and copper ions;
the concentration of the sodium alginate aqueous solution is 5-200 mg/mL; the concentration of the metal ion aqueous solution is 0.01-200 mg/mL;
the molar ratio of the sodium alginate to the metal ions is 1: 1-100; specifically, 1: 2.
3. the method according to claim 1 or 2, characterized in that: in the step of crosslinking reaction, the temperature is 20-500 ℃, and the time is at least 6 h; in particular 12-48 h.
4. A method according to any one of claims 1-3, characterized in that: the protective atmosphere is selected from inert atmosphere or reducing atmosphere; the inert atmosphere is specifically nitrogen or argon atmosphere; the reducing atmosphere is specifically hydrogen;
the metal substrate is a transition metal substrate; specifically at least one selected from iron, cobalt, copper, silver, manganese and nickel.
5. The method according to any one of claims 1-4, wherein: in the calcining step, the temperature is 600-1000 ℃; the time is 6-24 h.
6. The core-shell structure bimetallic covalently bonded three-dimensional graphene macroscopic body prepared by the method of any one of claims 1 to 5.
7. The core-shell structure bimetallic covalently bonded three-dimensional graphene macroscopic body of claim 6, characterized in that: the core-shell structure bimetal covalent bonding three-dimensional graphene macroscopic body consists of a shell and a core; the shell is single-layer sheet graphene, and the core is bimetal; and the shell and the core are covalently bonded.
8. Use of the core-shell structured bimetallic covalently bonded three-dimensional graphene macroscopic body of claim 6 or 7 in adsorption and/or catalysis.
9. Use according to claim 8, characterized in that: in the adsorption, the adsorption pH value is 6; the dosage ratio of the core-shell structure bimetallic covalent bonding three-dimensional graphene macroscopic body to the to-be-adsorbed substance is 0.5-5 g/L; specifically 1 g/L; the adsorption temperature is normal temperature; in particular 25 ℃;
the substance to be adsorbed is water containing pollutants; the contaminant is specifically an antibiotic;
the catalysis is carried out in the presence of a Fenton reagent; in the Fenton reagent, the concentration of hydrogen peroxide is 0.5 mmol/L; the pH of the catalyst is 6;
the dosage ratio of the core-shell structure bimetallic covalent bonding three-dimensional graphene macroscopic body to the object to be catalyzed is 0.5-5 g/L; specifically 1 g/L; the adsorption temperature is normal temperature; specifically 25 ℃.
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| CN114849647A (en) * | 2022-05-13 | 2022-08-05 | 海南师范大学 | Method for preparing spherical Cu/Fe biochar composite material by one-step method and application |
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