CN109133195B - Biomass porous carbon material doped with bimetallic oxide, preparation method thereof and application of biomass porous carbon material in dye adsorption - Google Patents
Biomass porous carbon material doped with bimetallic oxide, preparation method thereof and application of biomass porous carbon material in dye adsorption Download PDFInfo
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- CN109133195B CN109133195B CN201811100914.XA CN201811100914A CN109133195B CN 109133195 B CN109133195 B CN 109133195B CN 201811100914 A CN201811100914 A CN 201811100914A CN 109133195 B CN109133195 B CN 109133195B
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- 239000002028 Biomass Substances 0.000 title claims abstract description 48
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 18
- 241000196252 Ulva Species 0.000 claims abstract description 38
- MCPLVIGCWWTHFH-UHFFFAOYSA-L Methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- -1 cobalt-molybdenum Chemical compound 0.000 claims abstract description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N Cobalt(II) nitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- QGAVSDVURUSLQK-UHFFFAOYSA-N Ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 7
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 7
- 239000000975 dye Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000004140 cleaning Methods 0.000 claims description 17
- SUKJFIGYRHOWBL-UHFFFAOYSA-N Sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 16
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 13
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 229960000583 Acetic Acid Drugs 0.000 claims description 10
- 229940042115 Methylene blue Drugs 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 10
- HSXUHWZMNJHFRV-QIKYXUGXSA-L orange G Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1\N=N\C1=CC=CC=C1 HSXUHWZMNJHFRV-QIKYXUGXSA-L 0.000 claims description 10
- 229940081623 Rose Bengal Drugs 0.000 claims description 9
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000010865 sewage Substances 0.000 abstract description 7
- 238000005470 impregnation Methods 0.000 abstract description 4
- 241000195493 Cryptophyta Species 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 abstract description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 15
- 229910002451 CoOx Inorganic materials 0.000 description 10
- CXKWCBBOMKCUKX-UHFFFAOYSA-M Methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 8
- 241000196253 Ulva prolifera Species 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052803 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- LBFUKZWYPLNNJC-UHFFFAOYSA-N Cobalt(II,III) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000010192 crystallographic characterization Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- QUEGLSKBMHQYJU-UHFFFAOYSA-N cobalt;oxomolybdenum Chemical compound [Mo].[Co]=O QUEGLSKBMHQYJU-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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 provides a bimetallic oxide doped biomass porous carbon material which is prepared by taking algae enteromorpha flooded in summer in the east coast of China as a carbon source through decoloring treatment, cobalt nitrate and ammonium molybdate mixed solution impregnation and calcination carbonization in an inert gas atmosphere. The prepared cobalt-molybdenum bimetallic oxide doped biomass porous carbon material has a net structure, a rich pore structure and a large specific surface area, and the doped cobalt-molybdenum metal oxide nano particles are uniformly dispersed in the material. The biomass porous material can quickly remove methyl blue in a water body (within 3 minutes), has high adsorption capacity, obvious adsorption effect on organic dye, and has high application value in the aspect of sewage treatment.
Description
Technical Field
The invention belongs to the technical field of biomass porous carbon materials, and particularly relates to a novel double-metal oxide doped biomass porous carbon material, a preparation method thereof and application thereof in dye adsorption.
Background
With the rapid development of economy, the environmental pollution problem is also becoming more serious. According to statistics, the annual sewage discharge amount in China is up to 400 hundred million tons, wherein except 70 percent of industrial wastewater and 10 percent of domestic sewage which are treated and discharged, the rest polluted wastewater is directly discharged without being treated, so that the environmental water quality is seriously deteriorated. Wherein the discharge amount of the dye wastewater accounts for about 20 percent of the total amount of the industrial wastewater. In recent years, various adsorbing materials have been developed for adsorbing organic dyes in aqueous solutions, including activated carbon, zeolite, alumina, silica gel, and the like. The porous carbon material has the advantages of unique super-large specific surface area, strong adsorption capacity, high mechanical strength, good chemical stability, easy regeneration and the like, and is widely applied.
Biomass porous carbon is an artificial material that is enriched in carbon by pyrolysis or incomplete combustion of biomass material. The biomass carbon is a clean renewable energy source which can be utilized in a large scale, and the preparation method utilizes the existing and renewable substances in the nature, such as wood chips, straws, livestock manure and the like, so that the biomass carbon has great ecological benefit. In recent years, due to global climate change, water eutrophication and other reasons, marine large-scale marine algae (enteromorpha) has developed green tide. A large amount of enteromorpha is floated and gathered to the bank side, blocks a navigation channel, simultaneously destroys a marine ecosystem, and seriously threatens the development of coastal fishery and tourism industry.
The biomass carbon generates pore structures with different shapes and sizes in the preparation process, and in the sewage treatment process, macropores can be used for storing and adsorbing solution, mesopores are used for transmitting solution medium, and micropores are used for adsorbing. At present, research shows that the biomass carbon material has the most remarkable effect on removing organic pollutants in national water standard of domestic drinking water. Therefore, how to further develop and utilize high-performance biomass carbon materials has become the focus of current research interest.
Disclosure of Invention
The invention aims to provide a novel double-metal oxide doped biomass porous carbon material which has a rich pore structure and a higher specific surface area, can realize high-efficiency, high-capacity and high-selectivity adsorption of organic dye in a water body, and has a higher application value in industrial sewage treatment.
The invention also aims to provide a preparation method of the novel double-metal oxide doped biomass porous carbon material and application of the novel double-metal oxide doped biomass porous carbon material in the aspect of adsorbing dyes in water.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a biomass porous carbon material doped with a bimetallic oxide comprises the steps of dipping Enteromorpha subjected to decoloration treatment in a mixed solution of cobalt nitrate and ammonium molybdate, and then calcining and carbonizing in an inert gas atmosphere to obtain the biomass porous carbon material doped with the bimetallic oxide.
The preparation method of the double-metal oxide doped biomass porous carbon material specifically comprises the following steps:
1) soaking clean and dry Enteromorpha in a decolorizing agent, decolorizing at 65-85 deg.C until the Enteromorpha turns into milky gel, cleaning, and drying to obtain Enteromorpha precursor (APEP);
wherein the decolorizing agent is mixed aqueous solution containing sodium hypochlorite and glacial acetic acid, and the concentration of sodium hypochlorite in the decolorizing agent is 0.10-0.15 mol L-1The molar ratio of sodium hypochlorite to glacial acetic acid is 1: 1;
2) putting the enteromorpha precursor into a solution with the concentration of 0.05-0.2 mol L-1And 0.01-0.05 mol L of cobalt nitrate-1The mixed solution of ammonium molybdate is dipped for 12 to 24 hours, and after the dipping is finished, the dipped enteromorpha (Co-Mo-doped) is obtained by cleaning and drying2+/Mo2+@APEP）；
3) Calcining and carbonizing the cobalt-molybdenum doped impregnated Enteromorpha prolifera at the temperature of 550-650 ℃ for 2-6 h in the inert gas atmosphere to obtain the bimetallic oxide doped biomass porous carbon material (CoO)x/MoOy@ MSBC). The porous carbon material has a biomass porous carbon skeleton with a net structure, and cobalt and molybdenum metal oxide nanoparticles are distributed on the surface of the porous carbon material.
Specifically, in order to obtain a good decolorizing treatment effect, in the step 1), clean and dry enteromorpha is soaked in a decolorizing agent, uniformly stirred and placed in a forced air drying oven for decolorizing at a constant temperature of 75 ℃ for 1 h; repeating the above operations until the Enteromorpha prolifera turns into milk white gel. More preferably, in the step 1), the concentration of sodium hypochlorite in the decoloring agent is 0.13 mol L-1It is preferable.
Further, in order to obtain a better impregnation effect, in the step 2), the enteromorpha precursor is placed at a concentration of 0.05 mol L-1And 0.0 of cobalt nitrate1 mol L-1The mixed solution of ammonium molybdate is preferably immersed for 12 hours.
Further preferably, in the step 3), the cobalt-molybdenum-doped impregnated enteromorpha is calcined and carbonized for 2 hours at 600 ℃ in an inert gas atmosphere.
The invention provides a biomass porous carbon material doped with a bimetallic oxide prepared by the preparation method.
The invention also provides application of the bimetallic oxide doped biomass porous carbon material in dye adsorption. Further, the dye may be methylene blue, methyl blue, rose bengal, orange G, or the like.
In order to effectively utilize renewable resources, the invention takes ocean algae enteromorpha which is inundated in summer in the east coast of China as a carbon source, and prepares a novel biomass porous carbon material (CoO) with a net structure by acidification, decoloration, metal salt solution impregnation, calcination and carbonizationx/MoOy@ MSBC), the novel biomass porous carbon material can realize high-efficiency, high-capacity and high-selectivity adsorption of organic dyes (such as methylene blue, methyl blue, rose red, orange G and the like) in water; the preparation process route is as follows:
。
compared with the prior art, the invention has the following beneficial effects:
1) the invention firstly takes enteromorpha as a raw material, and prepares the novel molybdenum-cobalt bimetallic oxide doped biomass porous carbon material with a net structure by simple decoloration treatment, metal salt solution impregnation and calcination carbonization. The method has the advantages of cheap and easily-obtained raw materials, simple and convenient operation in the preparation process, easy realization of tonnage-level industrial production, and rich pore structure and higher specific surface area of the prepared biomass porous carbon material;
2) the adsorption performance test shows that: the biomass porous carbon material doped with the bimetallic oxide can quickly and efficiently remove organic dyes in water, such as methylene blue, methyl blue, rose bengal, orange G and the like, has obvious effects of high selectivity and high adsorption capacity on the organic dyes, and has high application value in industrial sewage treatment.
Drawings
FIG. 1 shows CoO prepared in example 1x/MoOyScanning electron micrographs of @ MSBC;
FIG. 2 shows CoO prepared in example 1x/MoOyThe nitrogen adsorption/desorption isotherm plot (left) and pore size distribution curve (right) of @ MSBC;
FIG. 3 shows CoO prepared in example 1x/MoOyX-ray diffraction pattern of @ MSBC;
FIG. 4 shows CoO prepared in example 1x/MoOyX-ray photoelectron spectroscopy (A) and C of @ MSBC composite material1s（B）、Co2p(C) And Mo3d(D) High resolution energy spectrum of;
FIG. 5 shows CoO prepared in example 1x/MoOyThe adsorption behavior of the @ MSBC composite material to the dye in different pH environments;
FIG. 6 shows CoO prepared in example 1x/MoOyPlot of adsorption capacity of @ MSBC for MB (left) and RB (right) versus time;
FIG. 7 shows CoO prepared in example 1x/MoOyThe @ MSBC vs MB adsorption capacity as a function of concentration plot.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the following examples, the main experimental reagents and instruments used are listed below:
sodium hypochlorite, glacial acetic acid, cobalt nitrate (Co (NO)3)2) Ammonium molybdate ((NH)4)6Mo7O24) Methylene blue (MeB), Methyl Blue (MB), Rose Bengal (RB), yellow Orange G (OG), DHG-9030A type blast drying oven, BSA22AS type single-disk electronic balance, vacuum tube furnace, freeze dryer, U-2910 ultraviolet-visible spectrophotometer, Zeiss Ultra Plus field emission scanning Electron microscope, ESCALB 250 photoelectron Spectroscopy, DX 2700X-ray diffractometer (Cu Ka ray, scanning speed 2)oMin), micromeritics tristar3000 adsorbers.
Example 1
A preparation method of a bimetallic oxide doped biomass porous carbon material specifically comprises the following steps:
1) collecting enteromorpha prolifera on coastal areas, cleaning and drying for later use;
2) 1.5 mL of glacial acetic acid is taken, 2 g of sodium hypochlorite is weighed, and 195 mL of distilled water is added to prepare a decolorizing agent. Then, soaking the enteromorpha in a decolorizing agent, fully stirring, and then placing in a 75 ℃ forced air drying oven for constant temperature decolorization for 1 hour; and repeating the operation until the enteromorpha is completely changed into milky white gel (generally two to three times). Cleaning with distilled water for 3-4 times, removing most of starch and pectin to obtain decolorized enteromorpha, and performing vacuum drying to obtain an enteromorpha precursor (APEP) for later use;
3) placing the enteromorpha precursor in a concentration of 0.05 mol L-1And 0.01 mol L of cobalt nitrate-1Soaking the obtained mixed solution for 12h, cleaning with distilled water to remove unadsorbed metal ions after soaking, and freeze drying to obtain cobalt-molybdenum-doped soaked enteromorpha prolifera (Co-Mo)2+/Mo2+@APEP）；
4) Calcining and carbonizing the cobalt-molybdenum doped impregnated enteromorpha at 600 ℃ for 2h in an inert gas atmosphere to obtain the double-metal oxide doped biomass porous carbon material (CoO)x/MoOy@MSBC）。
Characterization experiment
The prepared bimetallic oxide doped biomass porous carbon material CoOx/MoOyThe structure and performance of @ MSBC are characterized as follows.
1) Characterization by a scanning electron microscope: the scanning electron micrograph is shown in FIG. 1, and the prepared CoOx/MoOyThe @ MSBC composite material is of a net structure, and an internal pore channel is complex and intricate, so that the specific surface area of the material can be greatly improved. Uniformly distributing metal oxygen with uniform particle size on the surface of the materialThe particle size of the compound nanoparticles is about 30 nm.
2) Nitrogen adsorption/desorption isotherm: the nitrogen adsorption/desorption isotherm (left) of figure 2 shows a clear type IV curve accompanied by a significant type H2 hysteresis loop, the specific surface area and pore volume of the material, calculated from the BET and BJH formulae, being 544.6 m respectively, based on the adsorption branch of the curve2 g-1And 0.78 cm3 g-1. According to the pore size distribution curve, the composite material has wider pore size distribution and comprises micropores, mesopores and macropores. The results show that: CoOx/MoOyThe @ MSBC has higher specific surface area and pore volume, and is favorable for providing large loading capacity for guest molecules.
3) X-ray diffraction pattern: FIG. 3 is CoOx/MoOyX-ray diffraction pattern of @ MSBC. As shown in fig. 3, the broad peak with 2 θ angle in the range of 20 to 30 ° belongs to the amorphous carbon skeleton of porous carbon; diffraction peaks at 29.36 degrees and 78.63 degrees are caused by cobalt oxide nano particles doped in the material; the diffraction peak at 45.82 ° was attributed to the molybdenum oxide nanoparticles. The result shows that cobalt and molybdenum oxide nano particles are successfully introduced into the porous carbon structure.
4) X-ray photoelectron spectroscopy: as can be seen from FIG. 4 (A), CoOx/MoOy@ MSBC composite material containing C1s、O1s、Mo3dAnd Co2pPeaks of four components. High resolution C1sPeaks at 284.4 eV and 284.8 eV in the spectrum are typical for C = C/C-C bonds; the introduction of the metal oxides of cobalt and molybdenum has characteristic peaks at 780.1 eV, 802.3 eV, 233.5 eV and 236.8 eV respectively. The results further illustrate that cobalt and molybdenum oxide nanoparticles are successfully grown in the porous carbon skeleton.
5）CoOx/MoOyAdsorption Performance of @ MSBC for dyes:
(1) selective adsorption capacity: CoO was measured at different pH's (4, 5, 6, 7, 8, 9, 10) using the four typical dyes methylene blue (MeB), Methyl Blue (MB), Orange G (OG) and Rose Bengal (RB) in wastewater as modelsx/MoOy@ MSBC adsorption efficiency.As shown in FIG. 5, CoO was generated under alkaline conditions (pH 10)x/MoOy@ MSBC selectively adsorbs MB, and the removal rate can reach 100 percent; under acidic conditions (pH 4), CoOx/MoOy@ MSBC has higher selectivity to RB; and the removal rate of MeB and OG is less fluctuated along with the change of pH.
(2) Adsorption equilibrium time: determination of CoO separatelyx/MoOyThe adsorption capacities of @ MSBC for MB and RB were plotted against time, and the results are shown in FIG. 6. As can be seen from fig. 6: CoOx/MoOyThe adsorption of @ MSBC on the two dyes can reach equilibrium within 3 min.
(3) Adsorption capacity: FIG. 7 is CoOx/MoOyThe adsorption capacity of @ MSBC to MB is plotted as a function of concentration. As can be seen from fig. 7: as the concentration of MB increases, the adsorption capacity of the material increases. To be provided withLangmuirThe isotherm model is subjected to fitting analysis, and a fitting curve shows good linearity (R)2>0.99），CoOx/MoOy@ MSBC adsorbing MB with monomolecular layer, and the adsorption capacity can reach 1250 mg g at pH 10-1。
Example 2
A preparation method of a bimetallic oxide doped biomass porous carbon material specifically comprises the following steps:
1) soaking clean and dry enteromorpha in a decolorizing agent, decolorizing at 85 ℃ until the enteromorpha becomes milky gel, cleaning with distilled water after decolorizing treatment, and vacuum drying to obtain an enteromorpha precursor (APEP);
wherein the decolorizing agent is mixed aqueous solution containing sodium hypochlorite and glacial acetic acid, and the concentration of sodium hypochlorite in the decolorizing agent is 0.10 mol L-1The molar ratio of sodium hypochlorite to glacial acetic acid is 1: 1;
2) placing the enteromorpha precursor in a concentration of 0.2 mol L-1And 0.05 mol L of cobalt nitrate-1Soaking the obtained mixed solution for 12h, cleaning with distilled water to remove unadsorbed metal ions after soaking, and freeze drying to obtain cobalt-molybdenum-doped soaked enteromorpha prolifera (Co-Mo)2+/Mo2+@APEP）；
3) Calcining and carbonizing the cobalt-molybdenum doped impregnated enteromorpha at 650 ℃ for 2h in an inert gas atmosphere to obtain the double-metal oxide doped biomass porous carbon material (CoO)x/MoOy@MSBC）。
Example 3
A preparation method of a bimetallic oxide doped biomass porous carbon material specifically comprises the following steps:
1) soaking clean and dry enteromorpha in a decolorizing agent, decolorizing at 65 ℃ until the enteromorpha becomes milky gel, cleaning with distilled water after decolorizing treatment, and vacuum drying to obtain an enteromorpha precursor (APEP);
wherein the decolorizing agent is mixed aqueous solution containing sodium hypochlorite and glacial acetic acid, and the concentration of sodium hypochlorite in the decolorizing agent is 0.15 mol L-1The molar ratio of sodium hypochlorite to glacial acetic acid is 1: 1;
2) placing the enteromorpha precursor in a concentration of 0.1 mol L-1And 0.02 mol L of cobalt nitrate-1Soaking the obtained mixed solution for 12h, cleaning with distilled water to remove unadsorbed metal ions after soaking, and freeze drying to obtain cobalt-molybdenum-doped soaked enteromorpha prolifera (Co-Mo)2+/Mo2+@APEP）；
3) Calcining and carbonizing the cobalt-molybdenum doped impregnated enteromorpha at 550 ℃ for 4h in an inert gas atmosphere to obtain the double-metal oxide doped biomass porous carbon material (CoO)x/MoOy@MSBC）。
In conclusion, the invention adopts enteromorpha prolifera abused in summer in the eastern sea area of China as a raw material to prepare the biomass porous carbon material with the reticular structure, and the cobalt oxide/molybdenum oxide nano particles grow in situ. The method is simple and easy to implement, has low cost and is easy to realize tonnage-level industrial production. The prepared biomass porous carbon material has rich pore channel structures and higher specific surface area, and the doped metal oxide nano particles are uniformly dispersed in the material. The biomass porous material can quickly remove methyl blue in a water body (within 3 minutes), has high adsorption capacity, obvious adsorption effect on organic dye, and has high application value in the aspect of sewage treatment.
Finally, it should be noted that: the above embodiments are merely illustrative and not restrictive of the technical solutions of the present invention, and any equivalent substitutions and modifications or partial substitutions made without departing from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.
Claims (6)
1. A preparation method of a double-metal oxide doped biomass porous carbon material adsorbing dyes of methylene blue, methyl blue, rose bengal or orange G is characterized by comprising the following steps:
1) soaking clean and dry enteromorpha in a decolorizing agent, decolorizing at 65-85 ℃ until the enteromorpha becomes milky gel, and cleaning and drying after decolorizing treatment to obtain an enteromorpha precursor;
wherein the decolorizing agent is mixed aqueous solution containing sodium hypochlorite and glacial acetic acid, and the concentration of sodium hypochlorite in the decolorizing agent is 0.10-0.15 mol L-1The molar ratio of sodium hypochlorite to glacial acetic acid is 1: 1;
2) putting the enteromorpha precursor into a solution with the concentration of 0.05-0.2 mol L-1And 0.01-0.05 mol L of cobalt nitrate-1Soaking the obtained mixture in the ammonium molybdate mixed solution for 12-24 h, and cleaning and drying the obtained product after the soaking is finished to obtain cobalt-molybdenum doped soaked enteromorpha;
3) calcining and carbonizing the cobalt-molybdenum doped impregnated enteromorpha at 550-650 ℃ in an inert gas atmosphere for 2-6 h to obtain the bimetallic oxide doped biomass porous carbon material.
2. The method for preparing the bimetallic oxide doped biomass porous carbon material as claimed in claim 1, wherein in the step 1), the concentration of sodium hypochlorite in the decoloring agent is 0.13 mol L-1。
3. The preparation method of the double-metal oxide doped biomass porous carbon material as claimed in claim 1, wherein in the step 2), the enteromorpha precursor is placed in a concentration of 0.05 mol L-1And 0.01 mol L of cobalt nitrate-1The mixed solution of ammonium molybdate is soaked for 12 hours.
4. The preparation method of the bimetallic oxide doped biomass porous carbon material as claimed in claim 1, wherein in the step 3), the cobalt molybdenum doped impregnated enteromorpha is calcined and carbonized at 600 ℃ for 2h under an inert gas atmosphere.
5. The double metal oxide doped biomass porous carbon material prepared by the preparation method of any one of claims 1 to 4.
6. The use of a bimetallic oxide doped biomass porous carbon material as claimed in claim 5, characterized in that the dye is methylene blue, methyl blue, rose bengal or orange G.
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