CN111530464A - Preparation method of three-dimensional graphene zero-valent iron-carrying composite material - Google Patents
Preparation method of three-dimensional graphene zero-valent iron-carrying composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 31
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000007710 freezing Methods 0.000 claims abstract description 5
- 230000008014 freezing Effects 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 4
- 235000020188 drinking water Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 206010018901 Haemoglobinaemia Diseases 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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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
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
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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
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
The invention relates to a preparation method of a three-dimensional graphene zero-valent iron-loaded composite material, which comprises the steps of firstly dissolving ferric salt in graphite oxide dispersion liquid, and fully stirring to obtain a solution A; and dissolving an organic ligand in an organic solvent to obtain a solution B, quickly adding the solution A into the solution B, uniformly mixing, carrying out centrifugal separation, cleaning the obtained filter residue, freezing and drying, then placing in a tubular furnace, heating to 600-1000 ℃ under the protection of inert gas, calcining, and finally naturally cooling to obtain the catalyst. According to the invention, the nano zero-valent iron is prepared by an organic-inorganic complexing method, so that the high dispersion of the nano zero-valent iron can be realized, and the adopted three-dimensional graphene carrier has strong conductivity and a porous structure, so that the effective transfer of electrons can be promoted, and the rapid diffusion of nitrate can be promoted. The method is simple and convenient to operate, and the prepared composite material has high treatment efficiency on nitrate and high selectivity of nitrogen.
Description
Technical Field
The invention relates to a preparation method of a three-dimensional graphene zero-valent iron-carrying composite material, and belongs to the technical field of material preparation.
Background
Water resources are the root for human survival and are the key of production and life. However, the excessive use of nitrogen fertilizer, the substandard discharge of urban domestic sewage and nitrogen-containing industrial wastewater and unreasonable sewage irrigation cause that drinking water sources of many countries in the world are polluted by nitrate with different degrees. Nitrate can cause water eutrophication to be more and more severe, and simultaneously, excessive nitrate in drinking water is easily converted into nitrite in human bodies, so that Fe in hemoglobin in the human bodies can be caused2+Oxidation to Fe3+It is also known that hyperhemoglobinemia is caused by hypoxia, which is a cause of carcinogenesis and mutation in human body, and seriously harms human health. Drinking water NO regulated by world health organization in Drinking Water quality Standard3-N concentration not exceeding 10 mg/L. Therefore, effective control and treatment of nitrate in water are urgent.
At present, the traditional method for removing nitrate at home and abroad mainly comprises a physical method, a biological method and a reduction method. The physical method only concentrates or transfers the nitrate pollution and needs secondary treatment; the biological treatment technology needs to add organic matters into the water body, so that secondary pollution is easily caused and the treatment period is long; the active metal reduction method can also achieve chemical reduction of nitrate by using metal powder, but the product is usually ammonia nitrogen instead of nitrogen. The catalytic reduction method uses hydrogen as a reducing agent and noble metal and transition metal as catalysts to realize nitrate radical reduction, but the catalytic reaction efficiency and selectivity are difficult to control, by-product ammonia nitrogen is often generated, and certain safety problems exist in the transportation and use of pressurized hydrogen. Therefore, the research and development of the high-efficiency and environment-friendly nitrate radical removal technology has bright application prospect. The electrochemical reduction technology mainly realizes the cathodic reduction of nitrate and the anodic oxidation of byproducts thereof through an electron transfer process, and finally converts and removes the nitrate through a continuous reduction-oxidation circulation process. Noble metal catalysts have been extensively studied for electrochemical reduction of nitrates, but have limited reserves and high costs. Therefore, the invention of the non-noble metal catalyst is the key for promoting the development and the practical application of the electrochemical reduction technology.
In recent years, zero-valent iron has been widely used for removing pollutants in water due to its low price and strong reducing power. The application number 201310312657.7 discloses a method for removing nitrate in water by using a zero-valent iron/oxidant/zeolite synergistic system, wherein the nitrate is reduced into ammonia nitrogen by using the zero-valent iron, and the ammonia nitrogen in the water is removed by using the zeolite to efficiently and selectively adsorb the ammonia nitrogen, however, in the method, the zero-valent iron is easily consumed as a reducing agent, the ammonia nitrogen of a conversion product is still polluted nitrogen, and the nitrate is not removed fundamentally. The Chinese patent with application number 201810348539.4 discloses a method for combining nano zero-valent iron with an electrochemical reduction technology, which takes resin as a carrier and nano zero-valent iron as a catalyst to convert nitrate into nitrogen under the coordination of two stages of yin and yang; the application number 201610358771.7 discloses a high-dispersion nano zero-valent iron/carbon composite material, which is used as a working electrode, adopts a three-electrode electrochemical method, and removes nitrate in water through electrocatalytic reduction, so that the nitrate treatment efficiency is high, and the selectivity of nitrogen is improved. However, the following disadvantages still exist in the two prior arts: the zero-valent iron carrier loaded has poor conductivity and is not beneficial to the rapid transfer of electrons in the electrochemical reduction process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of a three-dimensional graphene zero-valent iron-carrying composite material, which is simple and convenient to operate, and the prepared three-dimensional graphene zero-valent iron-carrying composite material has high dispersibility, high conductivity and a three-dimensional porous structure, and is beneficial to the diffusion of nitrate and the transmission of electrons.
Technical scheme
A preparation method of a three-dimensional graphene zero-valent iron-carrying composite material comprises the following steps:
(1) dissolving ferric salt in graphite oxide dispersion liquid, and fully stirring to obtain a solution A;
(2) dissolving an organic ligand in an organic solvent to obtain a solution B, quickly adding the solution A into the solution B, uniformly mixing, carrying out centrifugal separation, cleaning the obtained filter residue, freezing and drying, then placing in a tubular furnace, heating to 600-fold-by-one temperature for calcining under the protection of inert gas, and finally naturally cooling to obtain the three-dimensional graphene zero-valent iron-loaded composite material.
In the step (1), the concentration of the graphite oxide dispersion liquid is 0.5-10mg/L, and a three-dimensional structure beyond the range is not easy to form.
Further, in the step (1), the iron salt is selected from any one of ferric chloride, ferric nitrate, ferric sulfate, ferrous chloride, ferrous nitrate or ferrous sulfate.
Further, in the step (1), the mass ratio of the iron salt to the graphite oxide is (2-10) to 1; above this range, zero-valent iron is not easily dispersed, and below this range, the zero-valent iron in the product is too small, and the activity cannot be effectively exerted.
Further, in the step (2), the organic ligand is selected from any one of ethylenediamine tetraacetic acid, terephthalic acid, triethylamine or trimesic acid.
Further, in the step (2), the molar ratio of the organic ligand to the ferric salt is (0.5-1):1, and below the ratio, the organic ligand is too little, the coordination reaction is incomplete, so that the calcined carbon carrier is too little, and the embedded structure cannot be formed; if the ratio is higher than the above ratio, the organic ligand is too much, so that the calcined carbon carrier is too much, the content of the nano zero-valent iron-nickel compound is too low, and the active site is reduced.
Further, in the step (2), the inert gas is pure N2Or argon.
Further, in the step (2), the heating rate is 1-5 ℃/min.
Further, in the step (2), the flow rate of the inert gas is 50 to 150 mL/min.
Compared with the prior art, the method has the advantages that (1) the nano zero-valent iron is prepared by an organic-inorganic complex method, so that the high dispersion of the nano zero-valent iron can be realized; (2) the nanometer zero-valent iron can be anchored by forming defects on the surface of the carrier in situ by an in-situ carbothermic method, and the agglomeration of the nanometer zero-valent iron is prevented by the steric hindrance of the carrier; (3) the three-dimensional graphene carrier has strong conductivity and a porous structure, and can promote effective transfer of electrons and rapid diffusion of nitrate.
Drawings
Fig. 1 is a TEM image of the three-dimensional graphene zero-valent iron-loaded composite material prepared in example 1.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
Example 1
Dissolving ferric chloride in graphite oxide dispersion liquid with the concentration of 1.0mg/L, stirring for 2 hours to obtain a solution A, dissolving ethylenediaminetetraacetic acid (the molar ratio of the ethylenediaminetetraacetic acid to ferric salt is 0.5:1) in 20mLN, N-dimethylformamide to obtain a solution B, quickly adding the solution A into the solution B, stirring for 5 minutes, centrifuging, washing filter residues with N, N-dimethylformamide, freezing and drying, then placing in a tubular furnace, controlling the heating rate to be 2 ℃/min and the gas flow rate to be 50mL/min under the protection of pure nitrogen, heating to 700 ℃, preserving heat for 3 hours, and naturally cooling to obtain the three-dimensional graphene zero-valent iron-loaded composite material.
A TEM image of the three-dimensional graphene zero-valent iron-loaded composite material prepared in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the three-dimensional graphene zero-valent iron-loaded composite material has a three-dimensional structure and nano zero-valent iron is uniformly dispersed.
Example 2
Dissolving ferric nitrate in graphite oxide dispersion liquid with the concentration of 4.0mg/L, stirring for 2 hours to obtain solution A, dissolving trimesic acid (the molar ratio of ferric chloride to ferric salt is 0.7:1) in 20mLN, N-dimethylformamide solution to obtain solution B, quickly adding solution A into solution B, stirring for 5 minutes, centrifuging, washing filter residue with N, N-dimethylformamide, freezing, drying, placing in a tubular furnace, controlling the heating rate to be 5 ℃/min and the gas flow rate to be 50mL/min under the protection of pure nitrogen, heating to 800 ℃, preserving heat for 2 hours, and naturally cooling to obtain the three-dimensional graphene zero-valent iron-loaded composite material.
Example 3
Dissolving ferric sulfate in graphite oxide dispersion liquid with the concentration of 2.0mg/L, wherein the mass ratio of ferric sulfate to graphite oxide is 6:1, stirring for 2 hours to obtain a solution A, dissolving terephthalic acid (the molar ratio of terephthalic acid to ferric salt is 1:1) in 20mLN, N-dimethylformamide solution to obtain a solution B, quickly adding the solution A into the solution B, stirring for 5 minutes, performing centrifugal separation, washing filter residue with N, N-dimethylformamide, performing freeze drying, placing in a tubular furnace, controlling the temperature rise rate to be 1 ℃/min and the gas flow rate to be 50mL/min under the protection of pure nitrogen, raising the temperature to 600 ℃, preserving heat for 1 hour, and naturally cooling to obtain the three-dimensional graphene zero-valent iron-loaded composite material.
Application test:
the three-dimensional graphene zero-valent iron-carrying composite material prepared in the embodiment 1-3 is used as a working electrode to reduce nitrate in water, and the specific process is as follows: preparing a working electrode from 5mg of the three-dimensional graphene zero-valent iron-carrying composite material, wherein the composite material comprises the following components in parts by weight: PVDF (polyvinylidene fluoride) is mixed into slurry according to the weight ratio of 9:1, the slurry is coated on a nickel screen with the thickness of 1 x 1cm, the slurry is dried for 2h at the temperature of 60 ℃, dried for 12h in vacuum at the temperature of 120 ℃, a platinum sheet is taken as a counter electrode, a saturated calomel electrode is taken as a reference electrode, nitrate is subjected to electrocatalytic reduction under a three-electrode system, the concentration of the nitrate is 100mg/L, 0.02M sodium sulfate is taken as a supporting electrolyte, the constant voltage is-1.3V, and after 24h of reaction, NO in a reaction solution is tested3 -、NO2 -And NH4 +And then the removal rate and nitrogen selectivity were calculated according to the following formulas:
removal rate ([ NO ]3 -]0-[NO3 -]f)/[NO3 -]0
Selectivity to nitrogen ([ NO ]3 -]0-[NO3 -]f-[NO2 -]f-[NH4 +]f)/([NO3 -]0-[NO3 -]f)
The results are shown in Table 1:
TABLE 1
| Examples | Removal Rate (%) | Selectivity to nitrogen (%) |
| 1 | 0.930 | 0.81 |
| 2 | 0.851 | 0.75 |
| 3 | 0.783 | 0.69 |
As can be seen from Table 1, the three-dimensional graphene zero-valent iron-carrying composite material prepared in the embodiments 1 to 3 of the invention is used as a working electrode for reducing nitrate in water, and has high treatment efficiency on the nitrate and high selectivity of nitrogen.
Claims (8)
1. A preparation method of a three-dimensional graphene zero-valent iron-carrying composite material is characterized by comprising the following steps:
(1) dissolving ferric salt in graphite oxide dispersion liquid, and fully stirring to obtain a solution A;
(2) dissolving an organic ligand in an organic solvent to obtain a solution B, quickly adding the solution A into the solution B, uniformly mixing, carrying out centrifugal separation, cleaning the obtained filter residue, freezing and drying, then placing in a tubular furnace, heating to 600-1000 ℃ under the protection of inert gas for calcining, and finally naturally cooling to obtain the three-dimensional graphene zero-valent iron-loaded composite material;
in the step (1), the concentration of the graphite oxide dispersion liquid is 0.5-10 mg/L.
2. The preparation method of the three-dimensional graphene zero-valent iron-carrying composite material according to claim 1, wherein in the step (1), the iron salt is selected from any one of ferric chloride, ferric nitrate, ferric sulfate, ferrous chloride, ferrous nitrate or ferrous sulfate.
3. The preparation method of the three-dimensional graphene zero-valent iron-carrying composite material according to claim 1, wherein in the step (1), the mass ratio of the iron salt to the graphite oxide is (2-10): 1.
4. The method for preparing the three-dimensional graphene zero-valent iron-loaded composite material according to claim 1, wherein in the step (2), the organic ligand is selected from any one of ethylenediamine tetraacetic acid, terephthalic acid, triethylamine or trimesic acid.
5. The preparation method of the three-dimensional graphene zero-valent iron-carrying composite material according to claim 1, wherein in the step (2), the molar ratio of the organic ligand to the iron salt is (0.5-1): 1.
6. The preparation method of the three-dimensional graphene zero-valent iron-carrying composite material according to claim 1, wherein in the step (2), the inert gas is pure N2Or argon.
7. The preparation method of the three-dimensional graphene zero-valent iron-carrying composite material according to claim 1, wherein in the step (2), the temperature rise rate is 1-5 ℃/min.
8. The method for preparing the three-dimensional graphene zero-valent iron-carrying composite material according to any one of claims 1 to 7, wherein in the step (2), the flow rate of the inert gas is 50 to 150 mL/min.
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| CN113441142A (en) * | 2021-06-29 | 2021-09-28 | 同济大学 | Preparation method and application of oxygen vacancy-rich graphene-loaded porous nano ferroelectric oxide catalyst |
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