CN112924514A - Nickel-iron-aluminum LDHs modified biomass charcoal material and application thereof in heavy metal ion detection - Google Patents
Nickel-iron-aluminum LDHs modified biomass charcoal material and application thereof in heavy metal ion detection Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 131
- 239000003610 charcoal Substances 0.000 title claims abstract description 106
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000001514 detection method Methods 0.000 title claims abstract description 90
- -1 Nickel-iron-aluminum Chemical compound 0.000 title claims description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims description 56
- 150000003839 salts Chemical class 0.000 claims description 44
- 150000002815 nickel Chemical class 0.000 claims description 39
- 239000011259 mixed solution Substances 0.000 claims description 27
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000012716 precipitator Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 17
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 17
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- 239000007853 buffer solution Substances 0.000 claims description 11
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- 239000002904 solvent Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 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 8
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 8
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- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 8
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- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 235000020232 peanut Nutrition 0.000 claims description 8
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- 230000007935 neutral effect Effects 0.000 claims description 7
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical group CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 4
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 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
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 150000001661 cadmium Chemical class 0.000 claims description 4
- 235000009120 camo Nutrition 0.000 claims description 4
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- 239000011487 hemp Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
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- 150000002696 manganese Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002730 mercury Chemical class 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 2
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- 125000000524 functional group Chemical group 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 29
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 229920001661 Chitosan Polymers 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to an LDHs modified biomass charcoal material and application thereof in heavy metal ion detection. The LDHs modified biomass charcoal material has rich functional groups, good layer structure and high specific surface area. The detection method is beneficial to trapping heavy metal ions in the water body, is simple and feasible, and is a good method for detecting the heavy metal ions.
Description
Technical Field
The invention relates to the field of modified materials, in particular to a biomass charcoal material modified by LDHs, and specifically relates to a preparation method of a material for modifying biomass charcoal by a nickel-iron-aluminum LDHs 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, and the balance and development of the whole ecological system are seriously influenced by the presence of heavy metal pollutants in water bodies. The growth of organisms needs trace heavy metal elements, but when heavy metals are accumulated in a large amount and discharged into a water environment, the heavy metals exist in the water environment for a long time, and pollution to the water system is caused to different degrees. When the concentration of heavy metals exceeds the bearing capacity of water organisms, the heavy metals can affect the balance of a water ecological system, thereby causing great harm. After aquatic animals ingest water plants, heavy metals enter the animals through the food chain, and the heavy metals in the animals are not easy to degrade and absorb, and finally exist in the animals for a long time and enter human bodies through the food chain, so that the health and life safety of human beings are endangered. Because the content is minimum, heavy metal pollutants are often difficult to be perceived by people, and can be detected by special detection means, so that the method has high concealment and great harm.
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 (LDHs) are novel inorganic materials with abundant layer structures, and have the characteristics of acidity-basicity, thermal stability, interlaminar anion exchangeability, structural memory effect and the like, and 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.
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. At present, the material for detecting heavy metals in water is mainly a graphene composite material, but the preparation process of the graphene composite material is long in time consumption and high in cost, and the graphene composite material cannot be used for industrial production in a large scale.
Due to the reasons, the LDHs modified biomass charcoal material and the application thereof in heavy metal ion detection are provided, the method combines the layered double hydroxide with the biomass charcoal, and when the biomass charcoal is used as a support frame of a nano material, the aggregation of the nano material can be reduced, so that the LDHs modified biomass charcoal material is an environment-friendly energy-saving material.
Disclosure of Invention
In order to overcome the problems, the inventor of the present invention has conducted intensive research to design a LDHs-modified biomass charcoal material and an application thereof in heavy metal ion detection, and the biomass is prepared into biomass charcoal through a pyrolysis method, then the obtained biomass charcoal is mixed with an iron-aluminum-nickel nitrate aqueous solution, a proper amount of urea is added into the mixture for stirring, the uniformly stirred mixed solution is subjected to hydrothermal treatment, and finally, the pure LDHs-modified biomass charcoal material is obtained through post-treatment. The LDHs 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.
Specifically, one of the purposes of the invention is to provide an LDHs modified biomass charcoal material, which is obtained from metal salt, biomass charcoal and a precipitator.
The LDHs modified biomass charcoal material is an iron-aluminum-nickel multi-metal hydroxide Ni/Fe/Al-LDHs modified biomass charcoal material;
the metal salt comprises one or more of copper salt, lead salt, zinc salt, ferric salt, nickel salt, manganese salt, cadmium salt, cobalt salt, aluminum salt and mercury salt, and preferably, the metal salt is a composition of aluminum salt, ferric salt and nickel salt;
the biomass carbon source is selected from residual solid fertilizers of crops, preferably, the biomass carbon source is selected from one or more of peanut shells, hemp stems, straws and rice hulls, and more preferably, the biomass carbon source is the peanut shells;
the precipitator is one or more selected from urea, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and preferably, the precipitator is urea.
The ferric salt is selected from one or more of ferric nitrate, ferric chloride, ferric sulfate and ferric carbonate, preferably, the ferric salt is ferric nitrate, and more preferably, the ferric salt is ferric nitrate nonahydrate;
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;
the nickel salt is selected from one or more of nickel nitrate, nickel chloride, nickel sulfate and nickel carbonate, preferably, the nickel salt is nickel nitrate, and more preferably, the nickel salt is nickel nitrate hexahydrate.
The molar ratio of the nickel salt, the ferric salt and the aluminum salt is 1: (0.5-4): (0.5 to 4), preferably 1: (0.5-2): (0.5 to 2), more preferably 1: (1-1.5): (1-1.5);
the mass ratio of the biomass charcoal to the nickel salt is 1 (0.5-10), preferably 1 (2-8), more preferably 1: (5-7);
the molar ratio of the nickel salt to the precipitant is 1: (0.1 to 15), preferably 1 (0.2 to 7), more preferably 1 (0.5 to 2).
The invention also aims to provide a preparation method of the LDHs modified biomass charcoal material as claimed in any one of claims 1 to 4, wherein the preparation method comprises the following steps:
step 1: preparing biomass charcoal from biomass;
step 2: putting the biomass charcoal obtained in the step 1, metal salt and a precipitator into a solvent for mixing to obtain a mixed solution;
and step 3: carrying out hydrothermal reaction on the mixed solution;
and 4, step 4: and (5) post-treatment.
In the step 1, the biomass charcoal is obtained by performing pyrolysis treatment on a biomass carbon source;
the pyrolysis temperature is 300-700 ℃, and preferably 350-550 ℃; more preferably 450 ℃;
the pyrolysis time is 0.5-3 h, preferably 1-2 h, and more preferably 1 h.
In the step 2, putting the weighed cobalt salt, nickel salt, biomass charcoal and precipitator into a solvent for mixing to prepare a mixed solution;
preferably, the solvent is water;
the mixing mode is mechanical mixing, preferably stirring;
the stirring time is 5-60 min, preferably 30 min.
The post-processing comprises the following sub-steps:
step 4-1: filtering to obtain a precipitate;
step 4-2; washing;
step 4-3: drying;
in step 4-2, washing the filtered precipitate with deionized water, preferably washing the precipitate with water until the pH of the washing solution is neutral;
after the pH value of the washing liquid is neutral, washing the precipitate by using absolute ethyl alcohol, preferably washing for 2-3 times;
in the step 4-3, 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.
The invention also aims to provide an application of the LDHs modified biomass charcoal material of one of claims 1 to 4 or the LDHs modified biomass charcoal material prepared by the method of claims 5 to 8 in heavy metal ion detection, wherein the application comprises detection of single heavy metal ion and detection of a mixed solution of multiple heavy metal ions;
the heavy metal ions comprise Cd (II), Pb (II), Cu (II) and Hg (II).
The fourth objective of the present invention is to provide a method for detecting heavy metal ions by using an LDHs-modified biomass charcoal material, wherein the LDHs-modified biomass charcoal material is preferably the LDHs-modified biomass charcoal material according to any one of claims 1 to 4 or the LDHs-modified biomass charcoal material prepared by the method according to any one of claims 5 to 8, and the detection method comprises the following steps:
step a, preparing a buffer solution;
b, preparing a modified electrode;
and c, detecting the solution to be detected of the heavy metal ions.
The invention has the advantages that:
(1) the Ni/Fe/Al-LDHs modified biomass charcoal material provided by the invention 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 Ni/Fe/Al-LDHs modified biomass charcoal material provided by the invention 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 Ni/Fe/Al-LDHs modified biomass charcoal material provided by the invention has a good crystal form, high crystallinity and stable performance.
(4) The preparation method of the Ni/Fe/Al-LDHs modified biomass charcoal material provided by the invention has the advantages of simple steps and low preparation cost, and develops a new method and a new idea for detecting and removing heavy metal ions.
(5) According to the application of the Ni/Fe/Al-LDHs modified biomass charcoal material in heavy metal ion detection, single heavy metal ions can be detected, mixed solutions of various heavy metal ions can be detected at the same time, and the Ni/Fe/Al-LDHs modified biomass charcoal material is wide in application and strong in universality.
(6) According to the method for detecting the heavy metal ions by using the Ni/Fe/Al-LDHs modified biomass charcoal material, provided by the invention, the detection sensitivity is high, the detection limit is low, and the detection time is short.
Drawings
FIG. 1 shows the XRD spectrum of a sample prepared in example 1;
FIG. 2 shows SEM scanning electron micrographs of samples prepared in example 1;
FIG. 3 is a graph showing the relationship between the intensity of detected Zn (II) ion current and the deposition potential of the sample prepared in example 2;
FIG. 4 is a graph showing the relationship between the intensity of the detected Zn (II) ion current and the deposition time of the sample prepared in example 2;
FIG. 5 is a graph showing the data of the detection experiment for detecting Zn (II) ions at different concentrations in the sample prepared in example 2;
FIG. 6 is a schematic diagram showing the relationship between the Cd (II) ion current intensity and the deposition potential in the detection of the sample prepared in example 3;
FIG. 7 is a schematic diagram showing the relationship between the Cd (II) ion current intensity and the deposition time in the detection of the sample prepared in example 3;
FIG. 8 is a graph showing the data of the detection experiment for detecting Cd (II) ions with different concentrations by using the sample prepared in example 3;
FIG. 9 is a graph showing the relationship between the intensity of the detected Pb (II) ion current and the deposition potential of the sample prepared in example 4;
FIG. 10 is a graph showing the relationship between the intensity of the detected Pb (II) ion current and the deposition time for the sample prepared in example 4;
FIG. 11 is a graph showing data of an experiment for detecting Pb (II) ions at different concentrations in a sample prepared in example 4;
FIG. 12 is a graph showing the relationship between the detected Cu (II) ion current intensity and the deposition potential of the sample prepared in example 5;
FIG. 13 is a graph showing the relationship between the intensity of the Cu (II) ion current detected and the deposition time for the sample prepared in example 5;
FIG. 14 is a graph showing data of an experiment for detecting Cu (II) ions at different concentrations in samples prepared in example 6;
FIG. 15 is a data chart of the detection experiment for detecting Cd (II), Pd (II), Cu (II) and Zn (II) ions with different concentrations in the sample prepared in example 6.
Detailed Description
The invention is explained in more detail below with reference to the figures and examples. The features and advantages of the present invention will become more apparent from the description.
The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. While the various aspects of the embodiments are presented in drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
According to the LDHs modified biomass charcoal material provided by the invention, the LDHs modified biomass charcoal material is obtained from metal salt, biomass charcoal and a precipitator.
The LDHs modified biomass charcoal material is nickel iron aluminum metal hydroxide Ni/Fe/Al-LDHs;
the metal salt comprises one or more of copper salt, lead salt, zinc salt, ferric salt, nickel salt, manganese salt, cadmium salt, cobalt salt, aluminum salt and mercury salt, and preferably, the metal salt is a composition of aluminum salt, ferric salt and nickel salt;
the biomass carbon source is selected from residual solid fertilizers of crops, preferably, the biomass carbon source is selected from one or more of peanut shells, hemp stems, straws and rice hulls, and more preferably, the biomass carbon source is the peanut shells;
the precipitator is one or more selected from urea, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and preferably, the precipitator is urea.
The inventor researches and discovers that the LDHs nano material can enable the surface of the biomass charcoal to obtain a form with a good interlayer structure and rich functional groups, so that the prepared biomass charcoal 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 ferric salt is selected from one or more of ferric nitrate, ferric chloride, ferric sulfate and ferric carbonate, preferably, the ferric salt is ferric nitrate, and more preferably, the ferric salt is ferric nitrate nonahydrate;
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;
the nickel salt is selected from one or more of nickel nitrate, nickel chloride, nickel sulfate and nickel carbonate, preferably, the nickel salt is nickel nitrate, and more preferably, the nickel salt is nickel nitrate hexahydrate.
According to a preferred embodiment of the invention, the molar ratio of the nickel salt, iron salt and aluminum salt is 1: (0.5-4): (0.5 to 4), preferably 1: (0.5-2): (0.5 to 2), more preferably 1: (1-1.5): (1 to 1.5), for example, 1: 1: 1.
the mass ratio of the biomass charcoal to the nickel salt is 1 (0.5-10), preferably 1 (2-8), more preferably 1: (5-7), for example 1: 6.
In the invention, the molar ratio of the nickel salt to the precipitant is 1: (0.1-15), preferably the molar ratio of the nickel salt to the precipitant is 1 (0.2-7), more preferably the molar ratio of the nickel to the precipitant is 1 (0.5-2), for example, the molar ratio of the precipitant to the nickel salt is 1:1 or 1: 2.
According to the invention, the LDH modified biomass charcoal material with better peak type and good crystal structure can be obtained through the molar ratio of the cobalt salt to the ferric salt, the mass ratio of the biomass charcoal to the ferric salt and the molar ratio of the ferric salt to the precipitator; when the ratio is not within the range, the peak pattern is disordered and the peak is not sharp, indicating that the crystal structure is not good.
According to the invention, the LDH modified biomass charcoal material has obvious diffraction peaks at 11.5 degrees, 23.3 degrees, 34.6 degrees, 39.0 degrees, 46.4 degrees, 60.3 degrees and 61.3 degrees.
The LDHs forms a flower-shaped structure on the surface of the biomass charcoal, and has a good layer structure, so that the prepared LDHs modified biomass charcoal material has a large specific surface area, and is more favorable for trapping heavy metal ions.
According to the preparation method of the LDHs modified biomass charcoal material provided by the invention, the preparation method comprises the following steps:
step 1: preparing biomass charcoal from biomass;
step 2: mixing the biomass charcoal obtained in the step 1 with metal salt and a precipitator to obtain a mixed solution;
and step 3: carrying out hydrothermal reaction on the mixed solution;
and 4, step 4: and (5) post-treatment.
Step 1, preparing biomass charcoal from biomass
In the invention, the biomass carbon source is selected from residual solid fertilizers of crops, preferably, the biomass carbon source is selected from one or more of peanut shells, hemp stems, straws and rice hulls, and more preferably, the biomass carbon source is the peanut shells.
Biomass refers to all organic substances formed by directly or indirectly utilizing photosynthesis of green plants, including plants, animals, and microorganisms except fossil fuels, and excretions and metabolites thereof.
In the step 1, the biomass charcoal is obtained by performing 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.
The pyrolysis treatment is a chemical decomposition process of heating organic matters in an oxygen-free or oxygen-deficient state to enable the organic matters to become gaseous, liquid or solid combustible substances. Pyrolysis treatment is a traditional industrial operation and is widely applied to the processing and treatment processes of fuels such as wood, coal, heavy oil and the like.
According to a preferred embodiment of the invention, the pyrolysis temperature is 300-700 ℃, preferably 350-550 ℃; more preferably 450 deg.c.
The pyrolysis time is 0.5-3 h, preferably 1-2 h, and more preferably 1 h.
Step 2, mixing the biomass charcoal obtained in the step 1 with metal salt and a precipitator to obtain a mixed solution
According to the invention, in step 2, the metal salt comprises one or more of copper salt, lead salt, zinc salt, iron salt, nickel salt, manganese salt, cadmium salt, cobalt salt, aluminum salt and mercury salt, and preferably, the metal salt is a combination of aluminum salt, iron salt and nickel salt.
The ferric salt is selected from one or more of ferric nitrate, ferric chloride, ferric sulfate and ferric carbonate, preferably, the ferric salt is ferric nitrate, and more preferably, the ferric salt is ferric nitrate nonahydrate;
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;
the nickel salt is selected from one or more of nickel nitrate, nickel chloride, nickel sulfate and nickel carbonate, preferably, the nickel salt is nickel nitrate, and more preferably, the nickel salt is nickel nitrate hexahydrate.
The precipitator is one or more selected from urea, sodium hydroxide solution, potassium hydroxide solution and ammonia water, and preferably, the precipitator is urea.
The molar ratio of the nickel salt, the ferric salt and the aluminum salt is 1: (0.5-4): (0.5 to 4), preferably 1: (0.5-2): (0.5 to 2), more preferably 1: (1-1.5): (1-1.5);
the mass ratio of the biomass charcoal to the nickel salt is 1 (0.5-10), preferably 1 (2-8), more preferably 1: (5-7).
The molar ratio of the nickel salt to the precipitant is 1: (0.1-15), preferably 1 (0.2-7), more preferably 1 (0.5-2), for example, the molar ratio of the precipitant to the nickel salt is 1:1 or 2: 1.
In the step 2, putting the weighed cobalt salt, nickel salt, biomass charcoal and precipitator into a solvent for mixing to prepare a mixed solution;
preferably, the solvent is water;
the mixing mode is mechanical mixing, preferably stirring;
the stirring time is 5-60 min, preferably 30 min.
The cobalt salt, the nickel salt, the biomass charcoal and the precipitator are fully mixed in the solvent through stirring, and the prepared mixed solution is more uniform and is convenient for subsequent hydrothermal reaction.
And step 3: carrying out hydrothermal reaction on the mixed solution
And (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2), preferably, carrying out the hydrothermal reaction in a stainless steel high-pressure lining kettle.
The hydrothermal reaction is a method for synthesizing or treating a material by using water as a solvent and creating a relatively high-temperature and high-pressure reaction environment in a closed reaction kettle in a heating mode to dissolve and recrystallize a difficultly soluble or insoluble substance.
The inventor researches and discovers that in the hydrothermal reaction, an 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.
According to a preferred embodiment of the present invention, in step 3, the reaction temperature of the hydrothermal reaction cannot be lower than 90 ℃, the reaction environment is alkaline due to the stable decomposition of urea 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, which is not favorable for the reaction.
In the step 3, the hydrothermal reaction temperature is 90-150 ℃, preferably 100-130 ℃, and more preferably 120 ℃.
The hydrothermal reaction time is 4-18 h, preferably 6-14 h, and more preferably 10 h.
Through the step 3, the metal salt and the biomass charcoal are combined, parameters are allowed to be changed in a wide range through hydrothermal synthesis, and two or more compounds are reacted to obtain a hydrothermal product.
Step 4, post-treatment
According to a preferred embodiment of the present invention, the hydrothermal product obtained in step 3 is subjected to a post-treatment comprising the following sub-steps:
step 4-1: filtering to obtain a precipitate;
step 4-2; washing;
step 4-3: and (5) drying.
In step 4-1, the product obtained in step 3 is 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.
In step 4-2, the filtered precipitate is washed with deionized water, preferably until the pH of the washing solution is neutral.
According to a preferred embodiment of the present application, after the pH of the washing solution is neutral, the precipitate is washed with absolute ethanol, preferably 2 to 3 times, and more preferably 3 times.
According to the application, in step 4-3, the precipitate obtained after washing is dried to obtain the LDHs modified biomass charcoal material, and preferably, the drying is carried out in a drying oven.
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.
The invention provides an application of the LDHs modified biomass charcoal material of one of claims 1 to 4 or the LDHs modified biomass charcoal material prepared by the method of one of claims 5 to 8 in heavy metal ion detection;
the application comprises the steps of detecting single heavy metal ions and detecting mixed solution of multiple heavy metal ions at the same time;
the heavy metal ions include but are not limited to Cd (II), Pb (II), Cu (II), Hg (II).
According to the invention, the LDHs modified biomass charcoal material is preferably the LDHs modified biomass charcoal material described in any one of claims 1 to 4 or the LDHs modified biomass charcoal material prepared by the method described in any one of claims 5 to 8.
The detection method comprises the following steps:
step a, preparing a buffer solution;
b, preparing a modified electrode;
and c, detecting heavy metal ions.
Step a, preparing a buffer solution
In the invention, the buffer solution system is HAc-NaAc, and the selected electrolyte solution is 0.1 mol.L- 1KCl。
In a preferred embodiment, the acetic acid and sodium acetate solution are at the same concentration;
in a more preferred embodiment, the concentration of acetic acid and sodium acetate is 0.05 to 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.
In the invention, acetic acid with the same concentration and volume is selected to be mixed with sodium acetate solution to prepare buffer solution with pH of 5.
Step b, preparing a modified electrode
The following substeps are also included in step b:
step b-1, dissolving the LDHs modified biomass charcoal material prepared by the invention in a proper amount of water to obtain an aqueous solution of the LDHs modified biomass charcoal material;
the mass concentration of the aqueous solution is 2-8 g.L-1Preferably 5 g.L-1。
Step b-2, preparing a binder;
when the modified electrode is prepared, in order to prevent the LDHs modified biomass charcoal material from falling off on the electrode during detection and influencing the detection effect and the detection progress, a binder is preferably added during preparation of the modified electrode to prevent the modified material from falling off.
According to a preferred embodiment of the present application, the binder is selected from naphthol and chitosan, preferably the binder is chitosan, more preferably a chitosan solution.
The inventor researches and discovers that when naphthol is selected as the binder, the binding effect is poor, and the naphthol is easy to fall off in the washing process. When chitosan is selected as the adhesive, the adhesive effect is better and the shedding rate is low.
According to the invention, the chitosan solution is a chitosan acetic acid solution prepared by dissolving chitosan in an acetic acid solution, and the final concentration of chitosan in the chitosan acetic acid solution is 0.5%.
Step b-3, mixing the aqueous solution of the LDHs modified biomass charcoal material and the chitosan acetic acid solution according to the volume ratio of 20: 1 to prepare a mixed solution.
The research of the invention finds that the mixed solution is mixed under the ultrasound to obtain the mixed solution with more uniform dispersion degree, and preferably, the mixed solution is mixed for 1min under the ultrasound.
The water temperature can be increased due to the overlong ultrasonic time, so that the Brownian motion is intensified, the collision chance among particles is increased, and the probability of flocculation is increased; the ultrasonic time is too short, the mixing effect of the mixed liquid is poor, and the accuracy of the detection result can be influenced in the subsequent ion detection.
And b-4, uniformly dropwise adding the mixed solution prepared in the step b-3 onto the glassy carbon electrode, and airing to obtain the glassy carbon electrode modified by the modified material, wherein preferably, airing is naturally airing.
Step c, detecting the solution to be detected of heavy metal ions
In the present application, the detection of the heavy metal ion solution to be detected is preferably performed in an electrochemical workstation.
In the step c, firstly, adding the water body sample into the electrolyte solution and the buffer solution prepared in the step a to prepare heavy metal ion solutions to be detected with different concentrations for later use.
The water body sample refers to a solution containing heavy metal ions;
the electrolyte solution is selected from NaCl, KCl, (NH)4)2SO4、Fe(NO3)3And BaSO4One or more of the above; preferably, the electrolyte solution is selected from one or more of NaCl and KCl, and more 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 0.09E to E0.11mol·L-1For example 0.1 mol. L-1。
According to a preferred embodiment of the present invention, the volume ratio of the electrolyte solution to the buffer solution is 1 (1 to 3), preferably 1 (1.5 to 2.5), and more preferably 1: 2.
After the solution to be detected of the heavy metal ions is prepared, a reference electrode, a glassy carbon electrode and a platinum sheet electrode are sequentially inserted into the solution to be detected of the heavy metal ions, then an electrochemical workstation is started, and electrochemical workstation software is operated on a computer for detection;
and c, preparing the glassy carbon electrode as the modified electrode prepared in the step b.
According to a preferred embodiment of the present invention, when the heavy metal ions in the solution to be detected of heavy metal ions are single ions, the detection method comprises the following steps:
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.
The inventor researches and discovers that the response degree 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, and the selection and the judgment are carried out according to the actual situation.
According to another preferred embodiment of the present invention, when the heavy metal ions in the solution to be detected of heavy metal ions are mixed ions, the detection method is the same as that of a single ion, except that a plurality of heavy metal ions are added simultaneously, and when there are multiple metal ions in the solution, the concentrations of the plurality of heavy metal ions can be detected simultaneously and analyzed quantitatively.
According to the invention, when the deposition potential of the LDHs biomass charcoal material is-1.5V and the deposition time is 240s, the lowest detection concentration of Zn (II) is 0.1 mu mol.L-1(ii) a When the deposition potential is-1.4V and the deposition time is 240s, the minimum concentration of the detected Cd (II) is 0.1 mu mol.L-1(ii) a The minimum concentration of Pb (II) detected at a deposition potential of-1.3V for a deposition time of 180s was 0.1. mu. mol. L-1(ii) a The lowest concentration of Cu (II) detected is 0.1 mu mol.L at a deposition potential of-1.4V and a deposition time of 180s-1(ii) a When the deposition potential is-1.4V and the deposition time is 240s, the minimum detection concentration of the four mixed ions is 0.5 mu mol.L-1。
According to the invention, in the preparation process of the LDHs modified biomass charcoal material, on one hand, carbonate ions are inserted into the laminate as laminate anions, 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 research of the inventor finds that the LDHs modified biomass charcoal 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 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.
Examples
Example 1Preparation of LDHs modified biomass charcoal material
(1) Putting a proper amount of biomass into a porcelain boat, and putting the porcelain boat into a tubular furnace to pyrolyze for 1h at 450 ℃ in the environment of nitrogen protection to obtain required biomass charcoal;
(2) weighing 0.291g of nickel nitrate hexahydrate, 0.404g of ferric nitrate nonahydrate, 0.375g of aluminum nitrate nonahydrate, 0.05g of biomass charcoal obtained in the step (1) and 0.582g of urea, adding the mixture into a beaker filled with 30mL of deionized water, mixing, and stirring for 0.5h to obtain a mixed solution;
(3) pouring the mixed solution obtained in the step (2) into a stainless steel high-pressure lining kettle, and carrying out continuous hydrothermal reaction for 12 hours at 120 ℃ in a hydrothermal oven;
(4) filtering the hydrothermal reaction solution obtained in the step (3);
(5) washing the precipitate obtained by filtering with deionized water until the pH value of the filtrate is neutral, and then washing the precipitate with a proper amount of absolute ethyl alcohol for 3 times;
(6) and (3) placing the precipitate washed by the absolute ethyl alcohol in a drying box at 70 ℃ for drying for 12h to obtain the Ni/Fe/Al-LDHs modified biomass charcoal material.
Example 2Detection of Zn (II) in water body
(1) 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;
(2) preparing a modified electrode: dissolving 5mg of the LDHs modified biomass charcoal material of the embodiment 1 in 1mL of water to obtain a water 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) to obtain the glassy carbon electrode modified by the modified material;
(3) preparing Zn (II) heavy metal ion solutions to be tested with different concentrations: taking 1 mu mol.L-1 Zn (II) preparation as an example, 0.5mL of 200 mu mol.L-1 Zn (II) solution is added into a 100mL three-necked bottle containing 20mL of 0.1 mol.L-1 electrolyte KCl solution and 40mL of buffer solution, and 39.5mL of distilled water is added to reach 100mL, so as to obtain 1 mu mol.L-1 Zn (II) solution; then, 0.1. mu. mol. L was prepared in this order-1，0.4μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，1.5μmol·L-1，2.0μmol·L-1，3.0μmol·L-1A heavy metal ion solution of Zn (II);
(4) and (3) detecting the solution containing the Zn (II) heavy metal ions by using an electrochemical workstation at room temperature, respectively detecting the Zn (II) heavy metal ion solution with each concentration during detection, and recording, analyzing and detecting results.
Example 3Detection of Cd (II) in water body
The procedure was the same as in example 2, except that the heavy metal ions were different, and Zn (II) was changed to Cd (II).
Example 4Detection of Pb (II) in water body
The procedure was the same as in example 2, except that the heavy metal ion was different, and Zn (II) was changed to Pb (II).
Example 5Detection of Cu (II) in water body
The procedure was the same as in example 2, except that the heavy metal ions were different, and Zn (II) was changed to Cu (II).
Example 6Detecting four mixed ions of Cd (II), Pd (II), Cu (II) and Zn (II) in water body
The steps are the same as those of the embodiment 2, and the difference is that the prepared solution to be detected is a solution containing four mixed ions of Cd (II), Pd (II), Cu (II) and Zn (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-1Electrolyte KCl solution and 40mL bufferAdding 38mL of distilled water into a 100mL three-necked bottle of the solution, and fixing the volume to 100mL to obtain a total of 100mL of the solution of mixed ions (wherein the concentrations of Cd (II), Pd (II), Cu (II) and Zn (II) are all 1 mu M); then 0.1. mu. mol/L-1, 0.4. mu. mol/L-1, 0.8. mu. mol/L-1, 1.0. mu. mol/L are prepared respectively-1，1.5μmol·L-1，2.0μmol·L-1，3.0μmol·L-1The four mixed ions of (1) to be tested.
Examples of the experiments
Experimental example 1XRD analysis of prepared material samples
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 11.5 °, 23.3 °, 34.6 °, 39.0 °, 46.4 °, 60.3 °, and 61.3 °. Corresponding to the (003), (006), (012), (015), (018), (110), (113) planes. The LDHs modified biomass charcoal material prepared by the invention has good crystal form and higher crystallinity.
Experimental example 2SEM analysis of prepared Material samples
SEM analysis was performed on the sample prepared in example 1, and the results are shown in FIG. 2.
As can be seen from FIG. 2, the prepared Ni/Fe/Al-LDHs form a needle-like structure on the surface of the biomass charcoal, and have a good layer structure, so that the specific surface area is larger, and the adsorption of heavy metal ions is facilitated.
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 to adsorb heavy metal ions.
Experimental example 3Detection results of Cd (II), Pb (II), Cu (II) and Zn (II) in water body
The results of the lowest concentration in examples 2 to 6 are shown in Table 1.
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-1Determining the optimal deposition potential to be-1.5V according to the detection experiment data graph of the Zn (II) deposition potential; FIG. 4 shows the fixed deposition potential at-1.5V versus 1. mu. mol. L-1Determining the relatively optimal deposition time to be 240s according to the detection experiment data graph of the Zn (II) deposition time; FIG. 5 is a graph of experimental data obtained by setting the deposition potential of the operating system to-1.5V and the deposition time to 240s, and then detecting different concentrations of Zn (II) (i.e., the current intensity represents the magnitude of the response of the film material to metal ions, i.e., the sensitivity is high and low, and the current intensity represents the higher response to metal ions, the higher the current intensity is), wherein the detected concentration is 0.1. mu. mol. L-1，0.4μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，1.5μmol·L-1，2.0μmol·L-1，3.0μmol·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 is used for detecting the solution to be detected of heavy metal in the embodiment 3, the detection results are shown in a figure 6, a figure 7 and a figure 8, the figure 6 is a data diagram of a detection experiment on Cd (II) deposition potential, and the optimal deposition potential is determined to be-1.4V; FIG. 7 is a data diagram of a detection experiment for Cd (II) deposition time, determining the relatively optimal deposition time to be 240 s; FIG. 8 is a data diagram of the detection experiment for different concentrations of Cd (II), the detected concentration is 0.1 μmol. L-1，0.4μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，1.5μmol·L-1，2.0μmol·L-1，3.0μmol·L-1As can be seen from the figure, the detection method of the present invention can detectHas a minimum concentration of 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 a graph showing data of an experimental test for detecting a deposition potential of Pb (II), from which it can be determined that an optimum deposition potential is-1.3V; FIG. 10 is a graph showing experimental data for the detection of Pb (II) deposition time, from which it can be determined that the relatively optimum detection time is 180 s; FIG. 11 is a graph showing the data of the test for different concentrations of Pb (II) at 0.1. mu. mol. L-1，0.4μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，1.5μmol·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 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 a graph of experimental data for the detection of Cu (II) deposition potential from which it can be determined that the optimum deposition potential is-1.4V; FIG. 13 is a graph of experimental data for detection of Cu (II) deposition time from which a relatively optimal detection time of 180s can be determined; FIG. 14 is a graph showing experimental data for detecting Cu (II) at different concentrations of 0.1. mu. mol. L-1，0.4μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，1.5μmol·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 the four mixed heavy metals in the embodiment 6, the detection result is shown in figure 15, and under the condition of integrating the deposition potentials and the deposition times of the four ions, the deposition potential is selected to be-1.5V, the deposition time is 240s and the concentration is 0.1 mu mol.L through a test experiment-1，0.4μmol·L-1，0.8μmol·L-1，1.0μmol·L-1，1.5μmol·L-1，2.0μmol·L-1，3.0μmol·L-1Is the solute in the solutionThe concentration is expressed by the parts per million of the total solution mass and can be mutually replaced with ppm), and because certain interference exists among ions and the response degree of the prepared modified material (LDHs modified biomass charcoal material) to different ions is different, part of ions can not be trapped under lower concentration, and further good stripping peaks can not be generated.
In conclusion, the LDHs 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 favorably, 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 present invention has been described above in connection with preferred embodiments, but these embodiments are merely exemplary and merely illustrative. On the basis of the above, the invention can be subjected to various substitutions and modifications, and the substitutions and the modifications are all within the protection scope of the invention.
Claims (10)
1. An LDHs modified biomass charcoal material is characterized in that the modified biomass charcoal material is obtained from metal salt, biomass charcoal and a precipitator.
2. The modified biomass charcoal material according to claim 1,
the metal salt comprises one or more of copper salt, lead salt, zinc salt, ferric salt, nickel salt, manganese salt, cadmium salt, cobalt salt, aluminum salt and mercury salt, and preferably, the metal salt is a composition of aluminum salt, ferric salt and nickel salt;
the biomass carbon source is selected from residual solid fertilizers of crops, preferably, the biomass carbon source is selected from one or more of peanut shells, hemp stems, straws and rice hulls, and more preferably, the biomass carbon source is the peanut shells;
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. The modified biomass charcoal material according to claim 1 or 2,
the ferric salt is selected from one or more of ferric nitrate, ferric chloride, ferric sulfate and ferric carbonate, preferably, the ferric salt is ferric nitrate, and more preferably, the ferric salt is ferric nitrate nonahydrate;
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;
the nickel salt is selected from one or more of nickel nitrate, nickel chloride, nickel sulfate and nickel carbonate, preferably, the nickel salt is nickel nitrate, and more preferably, the nickel salt is nickel nitrate hexahydrate.
4. The modified biomass charcoal material according to one of claims 1 to 3,
the molar ratio of the nickel salt, the ferric salt and the aluminum salt is 1: (0.5-4): (0.5 to 4), preferably 1: (0.5-2): (0.5 to 2), more preferably 1: (1-1.5): (1-1.5);
the mass ratio of the biomass charcoal to the nickel salt is 1 (0.5-10), preferably 1 (2-8), more preferably 1: (5-7);
the molar ratio of the nickel salt to the precipitant is 1: (0.1 to 15), preferably 1 (0.2 to 7), more preferably 1 (0.5 to 2).
5. A preparation method of LDHs modified biomass charcoal material as claimed in any one of claims 1 to 4, which is characterized in that,
the preparation method comprises the following steps:
step 1: preparing biomass charcoal from biomass;
step 2: putting the biomass charcoal obtained in the step 1, metal salt and a precipitator into a solvent for mixing to obtain a mixed solution;
and step 3: carrying out hydrothermal reaction on the mixed solution;
and 4, step 4: and (5) post-treatment.
6. The production method according to claim 5,
in the step 1, the biomass charcoal is obtained by performing pyrolysis treatment on a biomass carbon source;
the pyrolysis temperature is 300-700 ℃, and preferably 350-550 ℃; more preferably 450 ℃;
the pyrolysis time is 0.5-3 h, preferably 1-2 h, and more preferably 1 h.
7. The production method according to claim 5,
in the step 2, putting the weighed cobalt salt, nickel salt, biomass charcoal and precipitator into a solvent for mixing to prepare a mixed solution;
preferably, the solvent is water;
the mixing mode is mechanical mixing, preferably stirring;
the stirring time is 5-60 min, preferably 30 min.
8. The production method according to claim 6,
the post-processing comprises the following sub-steps:
step 4-1: filtering to obtain a precipitate;
step 4-2; washing;
step 4-3: drying;
in step 4-2, washing the filtered precipitate with deionized water, preferably washing the precipitate with water until the pH of the washing solution is neutral;
after the pH value of the washing liquid is neutral, washing the precipitate by using absolute ethyl alcohol, preferably washing for 2-3 times;
in the step 4-3, 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.
9. An application of the LDHs modified biomass charcoal material as described in any one of claims 1 to 4 or the LDHs modified biomass charcoal material prepared by the method as described in any one of claims 5 to 8 in heavy metal ion detection,
the application comprises the steps of detecting single heavy metal ions and detecting mixed solution of multiple heavy metal ions at the same time;
the heavy metal ions comprise Cd (II), Pb (II), Cu (II) and Hg (II).
10. A method for detecting heavy metal ions by using LDHs modified biomass charcoal material, wherein the LDHs modified biomass charcoal material preferably adopts the LDHs modified biomass charcoal material of one of claims 1 to 4 or the LDHs modified biomass charcoal material prepared by the method of one of claims 5 to 8,
the detection method comprises the following steps:
step a, preparing a buffer solution;
b, preparing a modified electrode;
and c, detecting the solution to be detected of the heavy metal ions.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114487052A (en) * | 2022-01-07 | 2022-05-13 | 武汉轻工大学 | Preparation method and application of high-salt food heavy metal detection electrode |
| CN115041173A (en) * | 2022-07-09 | 2022-09-13 | 山东省科学院能源研究所 | Ferronickel bimetallic flower-like cluster catalyst and preparation and application methods thereof |
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- 2021-01-15 CN CN202110057913.7A patent/CN112924514A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114487052A (en) * | 2022-01-07 | 2022-05-13 | 武汉轻工大学 | Preparation method and application of high-salt food heavy metal detection electrode |
| CN114487052B (en) * | 2022-01-07 | 2023-05-12 | 武汉轻工大学 | Preparation method and application of high-salt food heavy metal detection electrode |
| CN115041173A (en) * | 2022-07-09 | 2022-09-13 | 山东省科学院能源研究所 | Ferronickel bimetallic flower-like cluster catalyst and preparation and application methods thereof |
| CN115041173B (en) * | 2022-07-09 | 2024-02-02 | 山东省科学院能源研究所 | Ferronickel bimetallic flower-like cluster catalyst and preparation and application methods thereof |
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Application publication date: 20210608 |