CN111250043A - LDH (layered double hydroxide) modified biomass charcoal material and application thereof in heavy metal ion detection - Google Patents
LDH (layered double hydroxide) modified biomass charcoal material and application thereof in heavy metal ion detection Download PDFInfo
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- biomass charcoal
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- 239000002028 Biomass Substances 0.000 title claims abstract description 96
- 238000001514 detection method Methods 0.000 title claims abstract description 94
- 239000000463 material Substances 0.000 title claims abstract description 89
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 77
- 239000003610 charcoal Substances 0.000 title claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 45
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 37
- 159000000003 magnesium salts Chemical class 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- 239000012716 precipitator Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000000197 pyrolysis Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 244000025254 Cannabis sativa Species 0.000 claims description 8
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 8
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 235000009120 camo Nutrition 0.000 claims description 8
- 235000005607 chanvre indien Nutrition 0.000 claims description 8
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 claims description 8
- 239000011487 hemp Substances 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 7
- -1 and preferably Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- 229940118662 aluminum carbonate Drugs 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 239000002910 solid waste Substances 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 125000000524 functional group Chemical group 0.000 abstract description 10
- 239000011229 interlayer Substances 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 26
- 239000011777 magnesium Substances 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 12
- 239000002086 nanomaterial Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 229910021397 glassy carbon Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical group CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- UIQORMPFIFWPOG-UHFFFAOYSA-N aluminum;magnesium;pentanitrate Chemical compound [Mg+2].[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O UIQORMPFIFWPOG-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229940124447 delivery agent Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 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
- 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
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/4166—Systems measuring a particular property of an electrolyte
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
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- Immunology (AREA)
- General Physics & Mathematics (AREA)
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- Molecular Biology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method of an LDH (layered double hydroxide) modified biomass carbon material and application of the material in detection of heavy metal ions in a water body. The preparation method provided by the invention is simple and feasible, the prepared modified material has rich oxygen-containing functional groups and good interlayer structure, the trapping capacity of the biomass charcoal on heavy metal ions is further improved by adding the layered hydroxide, and the detection sensitivity is improved.
Description
Technical Field
The invention relates to the technical field of nano materials and modified materials, in particular to a preparation method of a material for modifying biomass carbon by using a Mg/Al double-metal hydroxide nano material and application of the material in detection of heavy metal ions in a water body.
Background
Heavy metal pollution has become a global environmental problem, especially heavy metal pollution to water, because of its characteristics of concealment, irreversibility and long-term nature. In China, heavy metal pollution becomes one of the main factors of water body environmental pollution in China. Therefore, various water body sensing materials are developed to rapidly and accurately detect the types of heavy metal ions at room temperature, and are of great importance to the environmental protection of human life, production and the like.
The biomass charcoal has good adsorption effect in the aspect of environmental purification, the surface of the biomass charcoal is rich in a large number of functional groups such as hydroxyl, carboxyl and the like, but the binding capacity of the biomass charcoal and heavy metal ions is limited, and the detection effect obtained by detecting the heavy metal ions by an electrochemical method is not ideal. The biological carbon is modified by the nano material, so that the biological carbon can be improved, and the detection effect on heavy metal ions can be improved, for example, the metal nano material is selected.
Layered double hydroxides (LDH, the same below) are novel inorganic materials with abundant layer structures, and the acid-base property, the thermal stability, the interlaminar anion exchangeability, the structure memory effect and other characteristics of the layered double hydroxides are widely used as catalysts, anion exchange materials, flame retardants, adsorbents, drug delivery agents and the like. The adsorption capacity of the biomass carbon modified by the layered hydroxide nano material to heavy metals can be better improved, however, the application of the modified material as a material for detecting the heavy metals in a water body is rarely reported.
At present, the material for detecting heavy metals in water is mainly a graphene composite material, the time and cost of the preparation process are higher than those of an LDH modified biomass carbon material, and the biomass carbon is an environment-friendly energy-saving material.
Disclosure of Invention
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that: preparing biomass into biomass charcoal by a pyrolysis method, mixing the obtained biomass charcoal with a magnesium aluminum nitrate aqueous solution, adding a proper amount of urea into the mixture, stirring, carrying out hydrothermal treatment on the uniformly stirred mixed solution, and finally carrying out aftertreatment to obtain the pure LDH modified biomass charcoal material. The prepared LDH modified biomass charcoal material contains rich functional groups and a good layer structure, has a large specific surface area, is beneficial to trapping heavy metal ions in a water body, and improves the detection sensitivity, thereby completing the invention.
The first aspect of the invention provides an LDH modified biomass charcoal material which is prepared from magnesium salt, aluminum salt, biomass charcoal and a precipitator.
The magnesium salt is selected from one or two of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium carbonate;
the aluminum salt is selected from one or two of aluminum nitrate, aluminum chloride, aluminum sulfate and aluminum carbonate.
A second aspect of the invention provides a method for preparing an LDH-modified biomass charcoal material according to the first aspect of the invention, the method comprising the steps of:
step 2, uniformly mixing the magnesium salt, the aluminum salt, the biomass charcoal and the precipitator to obtain a mixed solution;
step 3, carrying out hydrothermal reaction on the mixed solution;
and 4, performing post-treatment to obtain the LDH modified biomass charcoal material.
A third aspect of the invention provides a use of the material according to the first aspect of the invention or the material prepared by the preparation method according to the second aspect for detecting heavy metal ions in a water body, preferably, the heavy metal ions comprise Cd (ii), Pb (ii), Cu (ii), Hg (ii).
A fourth aspect of the present invention provides a method for detecting heavy metal ions, the method comprising the steps of:
(1) preparing a buffer solution;
(2) preparing a modified electrode;
(3) and (5) detecting heavy metal ions.
According to the preparation of the Mg/Al-LDH @ BC modified material (the Mg/Al-LDH @ BC modified material is an LDH modified biomass charcoal material) and the application thereof in the detection of heavy metals in water, the invention has the following beneficial effects:
(1) the Mg/Al-LDH @ BC modified material prepared by the method contains rich functional groups and a good layer structure, has a larger specific surface area, effectively increases an electron transmission channel, and improves the sensitivity;
(2) the Mg/Al-LDH @ BC modified material has a good heavy metal detection effect, can improve the detection sensitivity and reduce the detection limit, can detect various metal ions, and has high detection efficiency;
(3) the Mg/Al-LDH @ BC modified material has a good crystal form, high crystallinity and stable performance;
(4) the Mg/Al-LDH @ BC modified material disclosed by the invention is simple in preparation method and low in preparation cost, and develops a new method and a new idea for detecting and removing heavy metal ions.
Drawings
FIG. 1 shows the XRD spectrum of a sample prepared in example 1;
FIG. 2 shows SEM scan photographs of samples prepared in example 1;
FIG. 3 shows the detection of Cd by the sample prepared in example 12+The relationship between the ionic current intensity and the deposition potential is shown schematically;
FIG. 4 shows the detection of Cd by the sample prepared in example 12+The ion current intensity and the deposition time are schematically shown;
FIG. 5 shows that the samples prepared in example 1 are used for detecting Cd in different concentrations2+A data graph of an ion detection experiment;
FIG. 6 shows Pd detection of sample prepared in example 12+The relationship between the ionic current intensity and the deposition potential is shown schematically;
FIG. 7 shows Pd detection of sample prepared in example 12+The ion current intensity and the deposition time are schematically shown;
FIG. 8 shows the detection of Pd at different concentrations for the samples obtained in example 12+A data graph of an ion detection experiment;
FIG. 9 shows the Cu detection of the sample prepared in example 12+The relationship between the ionic current intensity and the deposition potential is shown schematically;
FIG. 10 shows the Cu detection of a sample prepared in example 12+The ion current intensity and the deposition time are schematically shown;
FIG. 11 shows that samples obtained in example 1 were tested for Cu at different concentrations2+A data graph of an ion detection experiment;
FIG. 12 shows Hg detection of samples prepared in example 12+The relationship between the ionic current intensity and the deposition potential is shown schematically;
FIG. 13 shows Hg detection of samples prepared in example 12+The ion current intensity and the deposition time are schematically shown;
FIG. 14 shows the measurement of different Hg concentrations for samples prepared in example 12+A data graph of an ion detection experiment;
FIG. 15 shows that the sample prepared in example 1 detects four mixed ions (Cd) with different concentrations2+、Pd2+、Cu2+And Hg2+) The data of the test experiment of (1).
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The first aspect of the invention provides an LDH modified biomass charcoal material, wherein the LDH is Mg/Al-LDH, and the LDH modified biomass charcoal material is prepared from magnesium salt, aluminum salt, biomass charcoal and a precipitator.
The inventor finds that the addition of the Mg/Al-LDH nano material can enable the surface of the biomass carbon to obtain a form with a good interlayer structure and rich functional groups, so that the prepared biomass carbon modified material can better trap heavy metal ions in a water body, and when the prepared material is applied to detection of the heavy metal ions in the water body, the detection sensitivity is improved, meanwhile, the detection lower limit is lower, and the detection efficiency is improved.
The magnesium salt is selected from one or more of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium carbonate, preferably, the magnesium salt is magnesium nitrate, and more preferably, the magnesium salt is magnesium nitrate hexahydrate.
The aluminum salt is selected from one or more of aluminum nitrate, aluminum chloride, aluminum sulfate and aluminum carbonate, preferably, the aluminum salt is aluminum nitrate, and more preferably, the aluminum salt is aluminum nitrate nonahydrate.
In the invention, the molar ratio of the magnesium salt to the aluminum salt is (0.5-8): 1, preferably, the molar ratio of the magnesium salt to the aluminum salt is (1-4): 1, more preferably, the molar ratio of the magnesium salt to the aluminum salt is (2-3:): 1, e.g. 2: 1.
The biomass carbon source is selected from residual solid fertilizers of crops, preferably, the biomass carbon source is selected from one or more of hemp stems, straws and rice husks, and more preferably, the biomass carbon source is the hemp stems;
in the invention, the mass ratio of the biomass charcoal to the aluminum salt is 1 (0.5-10), preferably 1 (2-8), more preferably 1: (5-7), for example 1: 6.3.
The precipitator is one or more selected from urea, sodium hydroxide solution, potassium hydroxide solution and ammonia water, preferably, the precipitator is urea;
in the invention, the molar ratio of the aluminum salt to the precipitant is (0.1-15): preferably, the molar ratio of the aluminum salt to the precipitant is (0.2-7): 1, more preferably, the molar ratio of the aluminum salt to the precipitant is (0.5-2): 1, for example, the molar ratio of the precipitant to the aluminum salt is 1:1 or 2: 1.
The LDH forms an acicular structure on the surface of the biomass charcoal, and has a good layer structure, so that the prepared LDH modified biomass charcoal material has a large specific surface area, and is more favorable for trapping heavy metal ions.
The LDH modified biomass charcoal material has obvious diffraction peaks at 11.568 degrees, 23.256 degrees, 35.195 degrees, 39.369 degrees, 46.760 degrees and 60.755 degrees.
A second aspect of the invention provides a method for preparing an LDH-modified biomass charcoal material according to the first aspect of the invention, the method comprising the steps of:
in the invention, LDH is layered double hydroxide which is widely applied to the aspects of pollutant adsorption and separation and the like. The inventor finds that LDH modified biomass charcoal material can be used for simultaneously integrating excellent structures of LDH modified biomass charcoal material and LDH modified biomass charcoal material, so that the biomass charcoal material surface can obtain a form with a good interlayer structure and rich functional groups, heavy metal ions in a water body can be better trapped, and when the LDH modified biomass charcoal material is applied to detection of the heavy metal ions, the lower limit of detection is reduced, and meanwhile, the detection efficiency is higher. In the invention, the LDH is Mg/Al-LDH.
In the invention, the carbon source of the biomass carbon is selected from one or more of hemp stalk, straw and rice hull; preferably, the carbon source of the biomass charcoal is hemp stalk.
The biomass charcoal is obtained by carrying out pyrolysis treatment on a biomass carbon source; preferably, the pyrolysis treatment is carried out in a tube furnace; more preferably, the pyrolysis treatment is carried out in an inert atmosphere, for example under a nitrogen blanket.
In the invention, the pyrolysis temperature is 400-800 ℃, and preferably 550-650 ℃; more preferably 600 deg.c.
The pyrolysis time is 0.5-3 h, preferably 1-2 h, and more preferably 1 h.
Step 2, uniformly mixing the magnesium salt, the aluminum salt, the biomass charcoal and the precipitator to obtain a mixed solution;
the magnesium salt is selected from one or more of magnesium nitrate, magnesium chloride, magnesium sulfate and magnesium carbonate, preferably, the magnesium salt is magnesium nitrate, and more preferably, the magnesium salt is magnesium nitrate hexahydrate.
In the invention, the aluminum salt is selected from one or more of aluminum nitrate, aluminum chloride, aluminum sulfate and aluminum carbonate, preferably, the aluminum salt is aluminum nitrate, and more preferably, the aluminum salt is aluminum nitrate nonahydrate.
In the invention, the molar ratio of the magnesium salt to the aluminum salt is (0.5-8): 1, preferably, the molar ratio of the magnesium salt to the aluminum salt is (1-4): 1, more preferably, the molar ratio of the magnesium salt to the aluminum salt is (2-3:): 1, e.g. 2: 1.
The biomass carbon source is selected from one or more of hemp stems, straws and rice hulls, and preferably, the biomass carbon is hemp stem carbon;
in the invention, the addition amount of the biomass charcoal is 1 (0.5-10), preferably 1 (2-8), more preferably 1: (5-7), for example, 1: 6.3.
The precipitator is one or more selected from urea, sodium hydroxide solution, potassium hydroxide solution and ammonia water, preferably, the precipitator is urea;
the molar ratio of the aluminum salt to the precipitant is (0.1-15): preferably, the molar ratio of the aluminum salt to the precipitant is (0.2-7): 1, more preferably, the molar ratio of the aluminum salt to the precipitant is (0.5-2): 1, for example, the molar ratio of the precipitant to the aluminum salt is 1:1 or 2: 1.
Adding weighed magnesium salt, aluminum salt, biomass charcoal and precipitant into a beaker filled with a solvent, and mixing, wherein the solvent is water.
The mixing means is mechanical mixing, preferably stirring.
The stirring time is 5-60 min, preferably 30min, and a mixed solution is obtained.
And 3, carrying out hydrothermal reaction on the mixed solution.
And (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2), wherein the hydrothermal reaction is carried out in a stainless steel high-pressure lining kettle.
The inventor finds that in the hydrothermal reaction, the alkaline solution is used as a precipitator, so that a more stable and good alkaline environment can be created for the mixed solution prepared in the step 2, and the reaction is more favorably carried out.
In the invention, the reaction temperature of the hydrothermal reaction cannot be lower than 90 ℃, the reaction environment is alkaline because urea starts to be stably decomposed at 90 ℃ to generate ammonia gas, and if the reaction temperature of the hydrothermal reaction is lower than 90 ℃, the reaction environment is not alkaline, thus being not beneficial to the reaction.
In the invention, the hydrothermal reaction temperature is 90-150 ℃, preferably 100-120 ℃, and more preferably 110 ℃.
The hydrothermal reaction time is 2-12 h, preferably 4-10 h, more preferably 5-8 h, for example 6 h.
And 4, performing post-treatment to obtain the LDH modified biomass charcoal material.
The post-treatment comprises filtering, washing and drying the product after the hydrothermal reaction in the step 3. The product obtained in step 3 is first filtered to obtain a precipitate, and in the present invention, the filtration method is not particularly limited as long as the precipitate can be obtained by filtration.
Washing the precipitate obtained by filtering with deionized water, preferably washing the precipitate with water until the pH of a washing liquid is neutral, more preferably washing the precipitate washed to neutral with water with absolute ethyl alcohol for 2-3 times, preferably washing with absolute ethyl alcohol for 3 times.
And drying the precipitate obtained after washing, preferably, drying in a drying oven to obtain the LDH modified biomass charcoal material.
The drying temperature is 50-90 ℃, preferably 60-80 ℃, and more preferably 70 ℃.
The drying time is 10-24 h, preferably 11-18 h, and more preferably 12 h.
A third aspect of the invention provides a use of the material according to the first aspect of the invention or the LDH-modified biomass charcoal material prepared by the preparation method according to the second aspect of the invention, for the detection of heavy metals in water.
The LDH modified biomass charcoal material can detect single heavy metal ions and can also detect mixed solution of multiple heavy metal ions. The heavy metal ions include but are not limited to Cd (II), Pb (II), Cu (II), Hg (II).
A fourth aspect of the present invention provides a method for detecting heavy metal ions, the method comprising the steps of:
(1) and (4) preparing a buffer solution.
In the invention, the buffer solution system is HAc-NaAc, and the concentration of the acetic acid is the same as that of the sodium acetate solution.
In the invention, the concentration of acetic acid and sodium acetate is 0.05-0.2 mol.L-1Preferably 0.07 to 0.15 mol.L-1More preferably 0.09 to 0.12 mol.L-1For example 0.1 mol. L-1Acetic acid and sodium acetate solution.
The same volume of acetic acid was mixed with the sodium acetate solution to prepare a buffer solution with a pH of 5.
In the present invention, the electrolyte solution is selected to be 0.1 mol. L-1KCl。
(2) And preparing a modified electrode.
Dissolving the LDH modified biomass carbon material prepared by the invention in a proper amount of water to obtain an aqueous solution of the LDH modified biomass carbon material; the mass concentration of the aqueous solution is 5 g.L-1。
When the modified electrode is prepared, in order to prevent the LDH modified biomass charcoal material from falling off on the electrode during detection, so that the detection effect and the detection progress are influenced, the adhesive chitosan is added during preparation of the modified electrode, so that the modified material is prevented from falling off.
The chitosan was dissolved in acetic acid solution to make 0.5% chitosan acetic acid solution.
Mixing the aqueous solution of the LDH modified biomass charcoal material and a chitosan acetic acid solution according to the volume ratio of 20: 1 to prepare a mixed solution.
To obtain a mixed solution with uniform dispersion degree, the mixing is preferably performed under ultrasound for 1 min.
And uniformly dropwise adding the mixed solution onto the glassy carbon electrode, and airing to obtain the modified material modified glassy carbon electrode, wherein preferably, airing is naturally airing.
(3) And (5) detecting heavy metal ions.
And the detection of the solution to be detected of the heavy metal ions is carried out in an electrochemical workstation.
Adding a water body sample (the water body sample refers to a solution containing heavy metal ions) into an electrolyte solution and NaAc and HAc buffer solutions to prepare heavy metal ion solutions to be detected with different concentrations, and directly detecting by using an electrochemical workstation.
The electrolyte solution is selected from NaCl, LiCl, KCl, (NH)4)2SO4、Fe(NO3)3And BaSO4One or more of them. Preferably, the electrolyte solution is selected from the group consisting of NaCl, KCl and (NH)4)2SO4More preferably KCl.
The concentration of the electrolyte solution is 0.05-0.5 mol.L-1Preferably 0.07 to 0.2 mol.L-1More preferably 0.09 to 0.11 mol.L-1For example 0.1 mol. L-1。
In the detection method, the volume ratio of the electrolyte solution to the buffer solution is 1 (1-3), preferably 1 (1.5-2.5), and more preferably 1: 2.
When an electrochemical workstation is used for detecting a solution to be detected of heavy metal ions, a reference electrode, a glassy carbon electrode and a platinum sheet electrode are sequentially inserted into the prepared solution to be detected of heavy metal ions, then the electrochemical workstation is started, and electrochemical workstation software is started on a computer for detection.
And the glassy carbon electrode is the LDH modified biomass charcoal material modified glassy carbon electrode in the step (1).
In the present invention, for single ion detection:
in the detection process, the deposition potential is detected according to the deposition time of 300s (relatively long time can enable adsorption to reach relative saturation), the deposition potential is detected by taking the deposition time as reference, an approximate parabola can be formed by taking a determined deposition potential range, and the corresponding deposition potential with the highest stripping peak (namely the highest current intensity) is the optimal deposition potential.
Then, a relatively optimal deposition time is searched for at the optimal deposition potential. Since theoretically the peak value of the peeling peak increases with time, i.e. the longer the detection time, the larger the peeling peak value will be. However, as time increases, the amount of heavy metal ions in the solution to be measured will be less and less, so that less and less ions can be trapped, and in a relative time, the change of the peak value of the stripping peak is small, so that a relatively optimal deposition time can be considered to be obtained.
In the present invention, the peeling peak represents a chemical change process of electron transfer on the electrode surface, which is represented by the magnitude of current intensity. The higher the current intensity is, the higher the response degree of the material prepared by the invention to heavy metal ions is, and the stronger the trapping capacity is.
After the deposition potential and the relative optimal deposition time are determined, the detected change concentration of the heavy metal ions is detected under the deposition potential and the deposition time.
Note: the degree of response of each metal ion to different modified materials is different, so that in the detection process, the ions are different, and the corresponding deposition potential and time are also different.
In the invention, single ions are detected first, and then mixed ions are detected.
In the invention, the minimum concentration of the Mg/Al-LDH @ BC modified material for detecting Cd (II) is 0.1 mu mol.L when the deposition potential is-1.8V and the deposition time is 360s-1(ii) a The minimum concentration of Pb (II) detected at a deposition potential of-1.9V for a deposition time of 360s was 0.1. mu. mol. L-1(ii) a The lowest detection concentration of Cu (II) is 0.2 mu mol.L when the deposition potential is-1.4V and the deposition time is 360s-1(ii) a The minimum Hg (II) concentration was 0.1. mu. mol. L at a deposition potential of-1.1V for a deposition time of 360s-1(ii) a When the deposition potential is-1.8V and the deposition time is 360s, the minimum detection concentration of the four mixed ions is 0.2 mu mol.L-1。
The inventor believes that in the preparation process of the Mg/Al-LDH @ BC modified material, on one hand, carbonate ions are inserted into the laminate as the anions of the laminate, and the insertion of the carbonate ions is equivalent to the propping of a metal cation layer, so that the interlayer spacing is changed; on the other hand, due to the addition of the LDHs, a good interlayer structure and rich functional groups are formed on the surface of the biomass charcoal, so that the biomass charcoal is more beneficial to trapping heavy metal ions, and the detection sensitivity is improved.
The inventor finds that the Mg/Al-LDH @ BC modified material has a good interlayer structure and rich functional groups, so that the specific surface area of the material is larger, more active sites can be provided for trapping heavy metal ions, the heavy metal ions can be trapped, and an electron transmission channel is increased; therefore, the modified material modified by the biomass carbon by utilizing the nano material has good heavy metal detection effect, can improve the detection sensitivity and reduce the detection limit, and has short detection time.
According to the preparation of the Mg/Al-LDH @ BC modified material and the application of the modified material in the detection of heavy metals in water, the Mg/Al-LDH @ BC modified material has the following beneficial effects:
(1) the Mg/Al-LDH @ BC modified material prepared by the method contains rich functional groups and a good layer structure, has a larger specific surface area, and is more beneficial to trapping heavy metal ions in a water body, so that the heavy metal ions are trapped, an electron transmission channel is increased, and the sensitivity is improved;
(2) the Mg/Al-LDH @ BC modified material has a good heavy metal detection effect, can improve the detection sensitivity and reduce the detection limit, and has short detection time; the kit can detect single heavy metal ions and can also detect mixed solution of multiple heavy metal ions, wherein the heavy metal ions include but are not limited to Cd (II), Pb (II), Cu (II) and Hg (II);
(3) the fine and high XRD diffraction peak of the Mg/Al-LDH @ BC modified material shows that the crystallinity of the material is good, and the modified material can still form a good crystal form and keep higher crystallinity, so that the performance of the material is more stable;
(4) firstly, obtaining biomass charcoal through a pyrolysis method, then mixing the biomass charcoal with a magnesium aluminum nitrate aqueous solution, and obtaining an Mg/Al-LDH @ BC modified material by a urea hydrothermal method; the preparation method is simple, and compared with the graphene composite material, the graphene composite material is low in cost and easy to prepare.
Examples
Example 1 preparation of LDH-modified biomass charcoal material
And putting a proper amount of biomass into a porcelain boat, and putting the porcelain boat into a tubular furnace to pyrolyze for 1h at 600 ℃ in the environment of nitrogen protection to obtain the required biomass charcoal.
2.564g of magnesium nitrate hexahydrate, 1.88g of aluminum nitrate nonahydrate, 0.3g of biomass charcoal obtained by pyrolysis and 0.711g of urea are weighed and added into a beaker filled with 30mL of deionized water for mixing, and then the mixture is stirred for 30min to obtain a mixed solution;
pouring the obtained mixed solution into a stainless steel high-pressure lining kettle, and keeping the temperature of a hydrothermal oven at 110 ℃ for 6 hours;
filtering, washing the precipitate with deionized water until the pH of the filtrate is neutral, and washing the precipitate with appropriate amount of anhydrous ethanol for 3 times; and (3) drying the washed precipitate for 12h at 70 ℃ in a drying oven to obtain the Mg/Al-LDH @ BC modified material.
Example 2 detection of Cd (II) in Water
Firstly, preparing a buffer solution: the adopted system is HAc-NaAc, and the prepared acetic acid and sodium acetate solution are both 0.1 mol.L-1Preparing buffer solution with pH of 5 by taking the same volume;
preparing a modified electrode: dissolving 5Mg of the Mg/Al-LDH @ BC modified material obtained in the embodiment 1 in 1mL of water to obtain an aqueous solution for preparing the material; mixing the water solution of the material with 50 mu L of 0.5% chitosan acetic acid solution, and performing ultrasonic treatment for 1 min; dripping 5 mu L of the mixed solution after ultrasonic treatment on a glassy carbon electrode; naturally airing (naturally volatilizing water at room temperature); obtaining the glassy carbon electrode modified by the modified material;
preparing Cd with different concentrations2+Heavy metal ion solution to be tested: at 1. mu. mol. L-1Cd2+Preparation is an example, 0.5mL of 200. mu. mol. L-1Cd (2)2+The solution was added to a solution containing 20mL of 0.1 mol. L-1Adding electrolyte KCl solution and 40mL buffer solution into 100mL three-necked flask, adding 39.5mL distilled water, and diluting to 100mL to obtain 1 μmol/L-1Cd2+A solution; then, 0.1. mu. mol. L was prepared in this order-1，0.2μmol·L-1，0.4μmol·L-1，0.6μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，2.0μmol·L-1，3.0μmol·L-1Heavy metal ion solution of Cd (II);
pairing Cd at room temperature using an electrochemical workstation2+Detecting heavy metal ion solution, and detecting Cd of each concentration2+And respectively detecting the heavy metal ion solutions, and recording, analyzing and detecting results.
Example 3 detection of Pb (II) in Water
The same detection method as in example 2, except that Pd was prepared2+And (5) heavy metal ion solution to be detected.
Example 4 detection of Cu (II) in Water
The same test method as in example 2 was used, except that Cu was prepared2+And (5) heavy metal ion solution to be detected.
Example 5 detection of Hg (II) in a Water body
This example was the same as that used in example 2, except that Hg was formulated2+And (5) heavy metal ion solution to be detected.
Example 6 detection of four Mixed ions of Cd (II), Pd (II), Cu (II) and Hg (II) in Water
The method of this embodiment is the same as that of embodiment 2, except that the prepared solution to be tested is a solution containing four mixed ions of Cd (II), Pd (II), Cu (II) and Hg (II);
at a concentration of 1. mu. mol. L-1The solution of mixed ions of (a) is prepared as an example: the concentration of four prepared heavy metals is 200 mu mol.L-10.5mL of each heavy metal ion solution was taken in a 250mL volumetric flask, and added to a solution containing 20mL of 0.1 mol. L-1In a 100mL three-necked flask of an electrolyte KCl solution and 40mL of a buffer solution, andadding 38mL of distilled water to 100mL of a total volume of 100mL of mixed ion solution (wherein Cd is2+、Pb2+、Cu2+、Hg2+Concentrations were all 1 μ M); then respectively preparing 0.1 mu mol/L-1，0.2μmol·L-1，0.4μmol·L-1，0.6μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，2.0μmol·L-1，3.0μmol·L-1The four mixed ions of (1) to be tested.
Examples of the experiments
Experimental example 1 XRD analysis of samples of the materials prepared
X-ray analysis was performed on a sample of the material prepared in example 1, and the results are shown in FIG. 1.
As can be seen from fig. 1, 2 θ has stronger diffraction peaks at 11.568 °, 23.256 °, 35.195 °, 39.369 °, 46.760 ° and 60.755 °. Corresponding to (003), (006), (009), (015), (018), (110) planes. The LDH modified biomass carbon material prepared by the invention has good crystal form and higher crystallinity.
Experimental example 2 SEM analysis of samples of the prepared materials
SEM analysis was performed on the sample prepared in example 1, and the results are shown in FIG. 2.
As can be seen from figure 2, the prepared Mg/Al-LDH forms a needle-shaped structure on the surface of the biomass charcoal, has a good layer structure, has a larger specific surface area, and is more beneficial to the trapping of heavy metal ions.
The inventor believes that the addition of the nano material and the needle-shaped structure formed on the surface of the biomass charcoal enable the specific surface area to be larger, and can provide more active sites for trapping heavy metal ions.
Experimental example 3 results of detecting Cd (II), Pb (II), Cu (II) and Hg (II) in water
The results of the lowest concentration in examples 2 to 6 are shown in Table 1. In the present invention, Cd (II) and Cd2+Has the same meaning as Pb (II)2+Same meaning, Cu (II) and Cu2+Hg (II) has the same meaning as Hg2+The meaning is the same.
TABLE 1 detection results for respective heavy metal ions
The detection method of the invention is used for detecting the solution to be detected of heavy metal in the embodiment 2, the detection results are shown in figure 3, figure 4 and figure 5, and figure 3 shows that the concentration is 3 mu mol.L-1Cd (2)2+Determining the optimal deposition potential to be-1.8V according to a detection experiment data graph of the deposition potential; FIG. 4 shows the fixed deposition potential at-1.8V versus a concentration of 3. mu. mol. L-1Cd (2)2+Detecting an experimental data graph of the deposition time, and determining that the relatively optimal deposition time is 360 s; FIG. 5 shows the deposition potential of-1.8V and deposition time of 360s for Cd2+The detected concentration is 0.1 mu mol.L (namely the current intensity and the deposition potential are in corresponding relation under different concentrations, the current intensity represents the magnitude of the response degree of the membrane substance to the metal ions, namely the sensitivity is high and low, the larger the current intensity is, the higher the response degree to the metal ions is), and the detected concentration is 0.1 mu mol.L-1，0.2μmol·L-1，0.4μmol·L-1，0.6μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，2.0μmol·L-1，3.0μmol·L-1(μmol·L-1The concentration is expressed by the parts per million of the solute in the solution and can also be expressed by the parts per million), and the lowest concentration detectable by the detection method of the invention is 0.1 mu mol.L-1. In fig. 5, the ordinate in the small graph is the current intensity (μ a). As can be seen from fig. 5, the linearity of the current intensity and the concentration is high, reaching above 0.99.
The detection method of the invention is used for detecting the solution to be detected of heavy metal in the embodiment 3, the detection results are shown in figure 6, figure 7 and figure 8, and figure 6 shows the detection result for Pb2+Determining the optimal deposition potential to be-1.9V according to a detection experiment data graph of the deposition potential; FIG. 7 shows the relation to Pb2+Detecting an experimental data graph of the deposition time, and determining that the relatively optimal deposition time is 360 s; FIG. 8 shows the relation to Pb2+Detection of different concentrationsThe detected concentration is 0.1 mu mol.L by measuring an experimental data chart-1，0.2μmol·L-1，0.4μmol·L-1，0.6μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，2.0μmol·L-1，3.0μmol·L-1As can be seen from the figure, the lowest concentration detectable by the detection method of the present invention is 0.1. mu. mol. L-1。
The detection method of the invention is used for detecting the solution to be detected of heavy metal in the embodiment 4, and the detection result is shown in figure 9, figure 10 and figure 11. FIG. 9 is for Cu2+A data graph of an experimental detection of the deposition potential, from which an optimal deposition potential of-1.4V can be determined; FIG. 10 is for Cu2+A detection experiment data graph of the deposition time, wherein the relatively optimal detection time can be determined to be 360 s; FIG. 11 is for Cu2+The detected concentration is 0.1 mu mol.L in the data chart of the detection experiment of different concentrations-1，0.2μmol·L-1，0.4μmol·L-1，0.6μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，2.0μmol·L-1，3.0μmol·L-1As can be seen from the figure, the lowest concentration detectable by the detection method of the present invention is 0.2. mu. mol. L-1。
The detection method provided by the invention is used for detecting the solution to be detected of heavy metal in the embodiment 5, and the detection result is shown in fig. 12, fig. 13 and fig. 14. FIG. 12 is for Hg2+A data graph of an experimental detection of the deposition potential, from which the optimal deposition potential can be determined to be-1.1V; FIG. 13 is for Hg2+A detection experiment data graph of the deposition time, wherein the relatively optimal detection time can be determined to be 360 s; FIG. 14 is for Hg2+The detected concentration is 0.1 mu mol.L in the data chart of the detection experiment of different concentrations-1，0.2μmol·L-1，0.4μmol·L-1，0.6μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，2.0μmol·L-1，3.0μmol·L-1As can be seen from the figure, the lowest concentration detectable by the detection method of the present invention is 0.1. mu. mol. L-1。
The detection method of the invention is used for the embodiment6, detecting the solution to be detected of the four mixed heavy metals, wherein the detection result is shown in figure 15, and under the condition of synthesizing the deposition potentials and the deposition times of the four ions, the deposition potential is selected to be-1.8V, the deposition time is 360s, and the concentration is 0.4 mu mol.L through a test experiment-1，0.6μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，2.0μmol·L-1，3.0μmol·L-1(μmol·L-1The concentration is expressed by the parts per million of the solute in the solution, and the parts per million can be replaced with ppm), because certain interference exists among ions and the response degree of the prepared modified material (LDH modified biomass charcoal material) to different ions is different, part of ions can not be trapped under lower concentration, and a good stripping peak can not be generated.
In conclusion, the LDH modified biomass charcoal material has a good interlayer structure and rich functional groups, so that the specific surface area is larger, more active sites can be provided to trap heavy metal ions, the heavy metal ions can be trapped, and an electron transmission channel is increased; therefore, the modified material modified by the biomass carbon by utilizing the nano material has good heavy metal detection effect, can improve the detection sensitivity and reduce the detection limit, and has short detection time.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. An LDH modified biomass charcoal material is characterized in that the modified material is prepared from magnesium salt, aluminum salt, biomass charcoal and a precipitator.
2. An LDH modified biomass charcoal material as claimed in claim 1, wherein the magnesium salt is selected from one or more of magnesium nitrate, magnesium chloride, magnesium sulfate, magnesium carbonate, preferably the magnesium salt is magnesium nitrate;
the aluminum salt is selected from one or more of aluminum nitrate, aluminum chloride, aluminum sulfate and aluminum carbonate, and preferably, the aluminum salt is aluminum nitrate;
the biomass charcoal is obtained by pyrolyzing biomass carbon source;
the precipitator is one or more selected from urea, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and preferably, the precipitator is urea.
3. An LDH-modified biomass charcoal material as claimed in claim 1 or 2, wherein the biomass charcoal source is selected from residual solid waste of crops, preferably the biomass charcoal carbon source is selected from one or more of hemp stalk, straw, rice hull, more preferably the biomass charcoal source is hemp stalk.
4. Material according to one of claims 1 to 3,
the molar ratio of the magnesium salt to the aluminum salt is (0.5-8): 1, preferably, the molar ratio of the magnesium salt to the aluminum salt is (1-4): 1, more preferably, the molar ratio of the magnesium salt to the aluminum salt is (2-3:): 1;
the mass ratio of the biomass charcoal to the aluminum salt is 1 (0.5-10), preferably 1 (2-8), more preferably 1: (5-7);
the molar ratio of the aluminum salt to the precipitant is (0.1-15): 1 is preferably (0.2-7): 1, and more preferably (0.5-2): 1.
5. A method for preparing an LDH modified biomass charcoal material as claimed in any one of claims 1 to 4, comprising the steps of:
step 1, preparing biomass charcoal;
step 2, uniformly mixing the magnesium salt, the aluminum salt, the biomass charcoal and the precipitator to obtain a mixed solution;
step 3, carrying out hydrothermal reaction on the mixed solution;
and 4, performing post-treatment to obtain the LDH modified biomass charcoal material.
6. The production method according to claim 5, wherein, in step 1,
the biomass charcoal is obtained by carrying out pyrolysis treatment on a biomass carbon source, preferably, the pyrolysis treatment is carried out in an inert atmosphere, and more preferably, the pyrolysis treatment is carried out in a nitrogen protection atmosphere;
the pyrolysis temperature is 400-800 ℃, and preferably 550-650 ℃;
the pyrolysis time is 0.5-3 h, preferably 1-2 h.
7. The production method according to claim 5, wherein, in the step 2 and the step 3,
adding weighed magnesium salt, aluminum salt, biomass charcoal and precipitator into a beaker filled with a solvent for mixing, wherein the mixing mode is mechanical mixing;
carrying out hydrothermal reaction on the mixed solution obtained in the step 2, wherein the hydrothermal reaction temperature is 90-150 ℃, and preferably 100-120 ℃;
the hydrothermal reaction time is 2-12 h, preferably 4-10 h, and more preferably 5-8 h.
8. The production method according to claim 5, wherein, in step 4,
the post-treatment comprises filtering, washing and drying the product after the hydrothermal reaction in the step 3;
washing the filtered precipitate with deionized water, preferably washing the precipitate with water until the pH of a washing solution is neutral, and more preferably washing the precipitate washed with water to neutral with absolute ethyl alcohol for 2-3 times;
the drying temperature is 50-90 ℃, and preferably 60-80 ℃;
the drying time is 10-24 h, preferably 11-18 h.
9. Use of an LDH-modified biomass charcoal material according to any one of claims 1 to 4 or an LDH-modified biomass charcoal material produced by the production method according to any one of claims 5 to 8,
the method is used for detecting heavy metal ions in the water body, and preferably, the heavy metal ions comprise Cd (II), Pb (II), Cu (II) and Hg (II).
10. An LDH-modified biomass charcoal material according to any one of claims 1 to 4 or an LDH-modified biomass charcoal material prepared by a preparation method according to any one of claims 5 to 8, for detecting heavy metal ions, wherein the detection method comprises the steps of:
(1) preparing a buffer solution;
(2) preparing a modified electrode;
(3) and (5) detecting heavy metal ions.
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| CN113311043A (en) * | 2021-06-07 | 2021-08-27 | 江西农业大学 | Detect Pb2+And Hg2+Electrochemical sensor and preparation method and application thereof |
| CN114054030A (en) * | 2021-11-01 | 2022-02-18 | 南昌航空大学 | Preparation method of two-dimensional nickel-aluminum LDH composite material and application of two-dimensional nickel-aluminum LDH composite material in photocatalytic degradation of antibiotics |
| CN114082403A (en) * | 2021-11-25 | 2022-02-25 | 华中科技大学 | Sulfur-based intercalated hydrotalcite-modified biochar-based adsorption material, and preparation and application thereof |
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