CN115301194B - Nanocomposite and preparation method and application thereof - Google Patents
Nanocomposite and preparation method and application thereof Download PDFInfo
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- CN115301194B CN115301194B CN202210868128.4A CN202210868128A CN115301194B CN 115301194 B CN115301194 B CN 115301194B CN 202210868128 A CN202210868128 A CN 202210868128A CN 115301194 B CN115301194 B CN 115301194B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 32
- 150000002696 manganese Chemical class 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 40
- 229910021641 deionized water Inorganic materials 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 30
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 24
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 21
- 150000004763 sulfides Chemical class 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 7
- 238000011069 regeneration method Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005067 remediation Methods 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 230000000052 comparative effect Effects 0.000 description 56
- 239000002086 nanomaterial Substances 0.000 description 33
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 239000001257 hydrogen Substances 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- 238000012360 testing method Methods 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000011734 sodium Substances 0.000 description 21
- 239000011572 manganese Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000005273 aeration Methods 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001927 high performance liquid chromatography-inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000003895 groundwater pollution Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
-
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0285—Sulfides of compounds other than those provided for in B01J20/045
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the field of environmental remediation, in particular to a nanocomposite and a preparation method and application thereof. The invention provides a preparation method of a nanocomposite, which comprises the following steps: mixing the mixed solution of ferrous salt and divalent manganese salt with the solution of metal sulfide salt, stirring, separating solid from liquid, washing and drying to obtain the nanocomposite; the molar ratio of the ferrous salt to the divalent manganese salt in the mixed solution of the ferrous salt and the divalent manganese salt is (9-11): 1. the nanocomposite obtained by the preparation method of the nanocomposite provided by the invention can effectively remove Cr (VI), and the regeneration rate of the treated Cr (VI) is lower.
Description
Technical Field
The invention relates to the field of environmental remediation, in particular to a nanocomposite and a preparation method and application thereof.
Background
With the rapid promotion of economic growth, industrialization and city, a large number of heavy metals are widely used in industrial exploitation and production processes, so that a large amount of heavy metals are discharged into soil and groundwater. Therefore, how to repair soil groundwater pollution, especially Cr (VI) pollution, faster, more efficiently and more safely is an urgent problem to be solved.
Chromium ions usually exist in two valence states of Cr (III) and Cr (VI), and Cr (VI) seriously jeopardizes human body and ecological safety due to high solubility, mobility and toxicity. In the prior art, feS is generally adopted to remove Cr (VI) in water, however, in the actual pollutant field and industrial wastewater treatment process, feS often loses reducing capability due to the problems of easy oxidation to form an iron (hydrogen) oxide passivation layer and the like, thereby influencing the pollutant removal efficiency; meanwhile, under the general environmental condition, a large amount of negative charges exist on the surface of FeS, so that strong electrostatic repulsive force exists between the FeS and the Cr (VI) oxygen-containing anionic pollutants, and strong adsorption is difficult to realize, so that the removal efficiency of the FeS on the Cr (VI) oxygen-containing anionic pollutants is reduced. In addition, feS can reduce and fix Cr (VI) into Cr xFe1-x(OH)3 to obviously reduce the environmental toxicity of the Cr (VI), but a large amount of oxidants (oxygen, manganese oxide, active oxygen free radicals and the like) are often present in natural water and polluted sites, so that Cr xFe1-x(OH)3 is oxidized into Cr (VI) again to realize regeneration.
To sum up, the prior art cannot effectively remove Cr (VI) by FeS, and has problems that treated Cr (VI) is easily regenerated.
Disclosure of Invention
Therefore, the invention aims to solve the technical problems that the prior art cannot effectively remove Cr (VI) by FeS and the treated Cr (VI) is easy to regenerate, thereby providing a nanocomposite and a preparation method and application thereof.
The invention provides a preparation method of a nanocomposite, which comprises the following steps:
Mixing the mixed solution of ferrous salt and divalent manganese salt with the solution of metal sulfide salt, stirring, separating solid from liquid, washing and drying to obtain the nanocomposite; the molar ratio of the ferrous salt to the divalent manganese salt in the mixed solution of the ferrous salt and the divalent manganese salt is (9-11): 1.
Preferably, the mixing step is to add a mixed solution of ferrous salt and divalent manganese salt to a metal sulfide salt solution for mixing.
Preferably, the concentration of the ferrous salt in the mixed solution of the ferrous salt and the divalent manganese salt is 4.16-4.84 mmol/L, and the concentration of the divalent manganese salt is 0.16-0.84 mmol/L;
The concentration of the metal sulfide salt solution is 4.8-5.2 mmol/L, and the volume ratio of the mixed solution of ferrous salt and divalent manganese salt to the metal sulfide salt solution is (0.8-1.1): (0.8-1.1).
Preferably, the molar ratio of the ferrous salt to the divalent manganese salt in the mixed solution of the ferrous salt and the divalent manganese salt is 10:1.
Preferably, the metal sulfide salt solution is Na 2 S solution, the ferrous salt is FeSO 4, and the divalent manganese salt is MnSO 4.
Optionally, the metal sulfide salt solution is Na 2S·9H2 O solution, the ferrous salt is FeSO 4·7H2 O, and the divalent manganese salt is MnSO 4·H2 O.
Preferably, the stirring temperature is 23-26 ℃, the stirring speed is 80-120 rpm, and the stirring time is 5-7 h;
the solid-liquid separation is carried out in a centrifugal mode;
the washing step adopts deoxidized deionized water for washing, and the washing times are 4-6 times;
the drying step is freeze drying, the drying temperature is-40 to-30 ℃, and the drying time is 12 to 24 hours.
Preferably, the preparation method of the mixed solution of ferrous salt and divalent manganese salt comprises the following steps: mixing ferrous salt, divalent manganese salt and deoxidized deionized water in an anaerobic environment to obtain the composite material;
the preparation method of the vulcanized metal salt solution comprises the following steps: mixing the vulcanized metal salt with deoxidized deionized water in an anaerobic environment.
Optionally, the anaerobic environment is formed in an anaerobic tank, and further, the anaerobic tank contains protective gases of nitrogen and hydrogen, wherein the volume ratio of the nitrogen to the hydrogen is (90-95%): (5-10%).
Preferably, the preparation method of the deoxidized deionized water comprises the steps of introducing nitrogen into deionized water for deoxidization treatment to obtain deoxidized deionized water, wherein the purity of the nitrogen is more than or equal to 99.999 percent, and the introducing time of the nitrogen is more than or equal to 2 hours.
The invention also provides a nanocomposite material prepared by the preparation method.
Preferably, the nanocomposite comprises ferrous sulfide and manganese sulfide in a molar ratio of (9-11): 1.
Preferably, the molar ratio of ferrous sulfide to manganese sulfide in the nanocomposite is 10:1.
Preferably, the average particle size of the nanocomposite is 3 to 35nm.
The invention also provides an application of the nanocomposite in removing heavy metals in polluted water or polluted sites.
Preferably, the heavy metal is Cr (VI).
The technical scheme of the invention has the following advantages:
1. The invention provides a preparation method of a nanocomposite, which comprises the following steps: mixing the mixed solution of ferrous salt and divalent manganese salt with the solution of metal sulfide salt, stirring, separating solid from liquid, washing and drying to obtain the nanocomposite; the molar ratio of the ferrous salt to the divalent manganese salt in the mixed solution of the ferrous salt and the divalent manganese salt is (9-11): 1.
According to the invention, the mixed solution of ferrous salt and divalent manganese salt in a specific molar ratio is mixed and reacted with the metal sulfide salt solution to obtain the nanocomposite of ferrous sulfide and manganese sulfide, wherein the composition of n-type semiconductor ferrous sulfide and p-type semiconductor manganese sulfide effectively adjusts the atomic coordination and electronic structure of ferrous sulfide, improves the chemical complexation of ferrous sulfide to Cr (VI), enhances the adsorption of Cr (VI), and improves the removal efficiency of ferrous sulfide to Cr (VI); meanwhile, cr xFe1-x(OH)3 generated by ferrous sulfide and Cr (VI) has increased stability in an oxidizing environment due to the existence of manganese sulfide, so that the regeneration rate of Cr (VI) is reduced. The nanocomposite obtained by the preparation method of the nanocomposite provided by the invention can effectively remove Cr (VI), and the regeneration rate of the treated Cr (VI) is lower.
2. According to the nanocomposite provided by the invention, the nanocomposite with higher Cr (VI) removal rate and lower Cr (VI) regeneration rate can be obtained by adjusting the molar ratio of iron to manganese in the nanocomposite, so that the environmental risk caused by oxyanion (Cr (VI)) is greatly reduced. Nanocomposite materials have the greatest advantage in Cr (VI) contaminant removal applications when the molar ratio of iron to manganese in the nanocomposite is 10:1.
3. Compared with the nano composite material prepared by loading or packaging ferrous sulfide in a porous material (carbon material, zeolite, molecular sieve, metal organic framework and covalent organic framework), the nano composite material provided by the invention has lower economic cost and operability, better compatibility in the environment and accords with the concept of green sustainable development.
4. The preparation method of the nanocomposite provided by the invention has the advantages of low operation cost, short operation time, high repeatability, no secondary pollution and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray powder diffraction pattern of the nanocomposite of example 1, comparative examples 1-3, and the nanomaterials of comparative examples 4 and 5 of the present invention;
FIGS. 2 to 13 are transmission electron microscope images and corresponding high resolution transmission electron microscope images of the nanocomposite material of example 1, comparative examples 1 to 3, and the nanomaterial of comparative examples 4 and 5 in this order;
FIGS. 14 to 19 are graphs showing the changes in mole percentages of adsorbed Cr (VI), liquid-phase Cr (VI), solid-phase Cr (III) and liquid-phase Cr (III) with respect to initial liquid-phase Cr (VI) during the test of the nanocomposite materials of example 1, comparative examples 1 to 3 and the nanomaterials of comparative examples 4 and 5 according to the present invention, with respect to time and the test environment, in order;
FIG. 20 is a zeta potential plot under anaerobic conditions for the nanocomposites of example 1, comparative examples 1-3 and the nanocomposites of comparative examples 4 and 5 of the present invention;
FIG. 21 is a graph showing the release amount of Fe 2+ with time under anaerobic conditions for the nanocomposites of example 1, comparative examples 1-3 and the nanocomposites of comparative examples 4 and 5;
FIG. 22 is a graph showing the release amount of Mn 2+ with time under anaerobic conditions for the nanocomposites of example 1, comparative examples 1-3 and the nanocomposites of comparative examples 4 and 5.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a nanocomposite, which comprises the following steps:
1) Introducing nitrogen with the purity of 99.999% into 1L of deionized water for deoxidization treatment, wherein the aeration time is 2 hours, so as to obtain deoxidized deionized water;
2) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of Na 2S·9H2 O, 0.120g of which was mixed with 0.1L of the deoxidized deionized water prepared in step 1), and magnetically stirred at 25℃for 0.5h at a rotational speed of 100rpm to obtain Na 2 S solution;
3) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of FeSO 4·7H2 O of 0.1264g and MnSO 4·H2 O of 0.0077g were mixed with the deoxidized and deionized water prepared in step 1) of 0.1L, and magnetically stirred at 100rpm for 0.5h at 25℃to obtain a mixed solution of FeSO 4-MnSO4;
4) Adding the FeSO 4-MnSO4 mixed solution obtained in the step 3) into the Na 2 S solution obtained in the step 2) at 25 ℃, carrying out magnetic stirring at a rotating speed of 100rpm, continuing to magnetically stir at the rotating speed of 100rpm for 6 hours at 25 ℃ after adding, carrying out solid-liquid separation by a high-speed centrifuge, repeatedly flushing the obtained product with the deoxidized deionized water prepared in the step 1) for 5 times, and drying the washed product in a freeze dryer at-40 ℃ for 12 hours to obtain the nanocomposite.
The nanocomposite comprises ferrous sulfide and manganese sulfide, wherein the average particle size of the nanocomposite is 12.8+/-2.3 nm, and the molar ratio of the ferrous sulfide to the manganese sulfide in the nanocomposite is 10:1.
The nanocomposite was stored in an anaerobic tank for subsequent testing.
Comparative example 1
The comparative example provides a method for preparing a nanocomposite material, comprising the steps of:
1) Introducing nitrogen with the purity of 99.999% into 1L of deionized water to deoxidize the deionized water, wherein the aeration time is 2 hours, so as to obtain deoxidized deionized water;
2) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of Na 2S·9H2 O, 0.120g of which was mixed with 0.1L of the deoxidized deionized water prepared in step 1), and magnetically stirred at 25℃for 0.5h at a rotational speed of 100rpm to obtain Na 2 S solution;
3) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of FeSO 4·7H2 O of 0.1345g and MnSO 4·H2 O of 0.0027g are mixed with the deoxidized and deionized water prepared in the step 1) of 0.1L, and the mixture is magnetically stirred at the temperature of 25 ℃ for 0.5h at the rotating speed of 100rpm to obtain a FeSO 4-MnSO4 mixed solution;
4) Adding the FeSO 4-MnSO4 mixed solution obtained in the step 3) into the Na 2 S solution obtained in the step 2) at 25 ℃, carrying out magnetic stirring at a rotating speed of 100rpm, continuing to magnetically stir at the rotating speed of 100rpm for 6 hours at 25 ℃ after adding, carrying out solid-liquid separation by a high-speed centrifuge, repeatedly flushing the obtained product with the deoxidized deionized water prepared in the step 1) for 5 times, and drying the washed product in a freeze dryer at-40 ℃ for 12 hours to obtain the nanocomposite.
The nanocomposite comprises ferrous sulfide and manganese sulfide, wherein the average particle size of the nanocomposite is 10.2+/-3.9 nm, and the molar ratio of the ferrous sulfide to the manganese sulfide in the nanocomposite is 30:1.
The nanocomposite was stored in an anaerobic tank for subsequent testing.
Comparative example 2
The comparative example provides a method for preparing a nanocomposite material, comprising the steps of:
1) Introducing nitrogen with the purity of 99.999% into 1L of deionized water for deoxidization treatment, wherein the aeration time is 2 hours, so as to obtain deoxidized deionized water;
2) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of Na 2S·9H2 O, 0.120g of which was mixed with 0.1L of the deoxidized deionized water prepared in step 1), and magnetically stirred at 25℃for 0.5h at a rotational speed of 100rpm to obtain Na 2 S solution;
3) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of FeSO 4·7H2 O of 0.1324g and MnSO 4·H2 O of 0.0040g were mixed with the deoxidized and deionized water prepared in step 1) of 0.1L, and magnetically stirred at 25℃for 0.5h at a rotational speed of 100rpm to obtain a mixed solution of FeSO 4-MnSO4;
4) Adding the FeSO 4-MnSO4 mixed solution obtained in the step 3) into the Na 2 S solution obtained in the step 2) at 25 ℃, carrying out magnetic stirring at a rotating speed of 100rpm, continuing to magnetically stir at the rotating speed of 100rpm for 6 hours at 25 ℃ after adding, carrying out solid-liquid separation by a high-speed centrifuge, repeatedly flushing the obtained product with the deoxidized deionized water prepared in the step 1) for 5 times, and drying the washed product in a freeze dryer at-40 ℃ for 12 hours to obtain the nanocomposite.
The nanocomposite comprises ferrous sulfide and manganese sulfide, wherein the average particle size of the nanocomposite is 12.7+/-4.1 nm, and the molar ratio of the ferrous sulfide to the manganese sulfide in the nanocomposite is 20:1.
The nanocomposite was stored in an anaerobic tank for subsequent testing.
Comparative example 3
The comparative example provides a method for preparing a nanocomposite material, comprising the steps of:
1) Introducing nitrogen with the purity of 99.999% into deionized water for deoxidization treatment, wherein the aeration time is 2 hours, and obtaining deoxidized deionized water;
2) Mixing 0.120g of Na 2S·9H2 O with 0.1L of the deoxidized deionized water prepared in the step 1) in an anaerobic box, and magnetically stirring at a speed of 100rpm for 0.5h at 25 ℃ to obtain Na 2 S solution;
3) 0.1158g of FeSO 4·7H2 O and 0.0141g of MnSO 4·H2 O are mixed with the deoxidization and deionization prepared in the step 1) in 0.1L in an anaerobic box, and magnetically stirred at a speed of 100rpm for 0.5h at 25 ℃ to obtain a FeSO 4-MnSO4 mixed solution;
4) Adding the FeSO 4-MnSO4 mixed solution obtained in the step 3) into the Na 2 S solution obtained in the step 2) at 25 ℃, carrying out magnetic stirring at a rotating speed of 100rpm, continuing to magnetically stir at the rotating speed of 100rpm for 6 hours at 25 ℃ after adding, carrying out solid-liquid separation by a high-speed centrifuge, repeatedly flushing the obtained product with the deoxidized deionized water prepared in the step 1) for 5 times, and drying the washed product in a freeze dryer at-40 ℃ for 12 hours to obtain the nanocomposite.
The nanocomposite comprises ferrous sulfide and manganese sulfide, wherein the average particle size of the nanocomposite is 28.7+/-4.7 nm, and the molar ratio of the ferrous sulfide to the manganese sulfide in the nanocomposite is 5:1.
The nanocomposite was stored in an anaerobic tank for subsequent testing.
Comparative example 4
The comparative example provides a preparation method of ferrous sulfide nano material, which comprises the following steps:
1) Introducing nitrogen with the purity of 99.999% into 1L of deionized water for deoxidization treatment, wherein the aeration time is 2 hours, so as to obtain deoxidized deionized water;
2) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of Na 2S·9H2 O, 0.120g of which was mixed with 0.1L of the deoxidized deionized water prepared in step 1), and magnetically stirred at 25 ℃ for 0.5h at a rotational speed of 100rpm to obtain Na 2 S solution;
3) In an anaerobic tank (the atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) and 0.139g FeSO 4·7H2 O was mixed with 0.1L of the deoxidized and deionized water prepared in step 1), and magnetically stirred at 25 ℃ for 0.5h at a rotational speed of 100rpm to obtain FeSO 4 solution;
4) Adding the FeSO 4 solution obtained in the step 3) into the Na 2 S solution obtained in the step 2) at 25 ℃, carrying out magnetic stirring at a rotating speed of 100rpm, continuing to magnetically stir at the rotating speed of 100rpm for 6 hours at the temperature of 25 ℃ after adding, carrying out solid-liquid separation by a high-speed centrifuge, repeatedly flushing the obtained product with the deoxidized deionized water prepared in the step 1) for 5 times, and drying the washed product in a freeze dryer at the temperature of minus 40 ℃ for 12 hours to obtain the ferrous sulfide nano material.
The average grain diameter of the ferrous sulfide nano material is 3.2+/-0.5 nm.
The nanocomposite was stored in an anaerobic tank for subsequent testing.
Comparative example 5
The comparative example provides a preparation method of manganese sulfide nanomaterial, comprising the following steps:
1) Introducing nitrogen with the purity of 99.999% into 1L of deionized water for deoxidization treatment, wherein the aeration time is 2 hours, so as to obtain deoxidized deionized water;
2) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of Na 2S·9H2 O, 0.120g of which was mixed with 0.1L of the deoxidized deionized water prepared in step 1), and magnetically stirred at 25℃for 0.5h at a rotational speed of 100rpm to obtain Na 2 S solution;
3) In the anaerobic tank (atmosphere in the anaerobic tank is nitrogen and hydrogen, the volume ratio of nitrogen and hydrogen is 95%: 5%) of MnSO 4·H2 O of 0.0845g was mixed with the deoxidized and deionized water prepared in step 1) of 0.1L, and magnetically stirred at 100rpm for 0.5h at 25℃to obtain a MnSO 4 solution;
4) Adding the MnSO 4 solution obtained in the step 3) into the Na 2 S solution obtained in the step 2) at 25 ℃, carrying out magnetic stirring at a rotating speed of 100rpm, continuing to magnetically stir at the rotating speed of 100rpm for 6 hours at the temperature of 25 ℃ after adding, carrying out solid-liquid separation by a high-speed centrifuge, repeatedly flushing the obtained product with the deoxidized deionized water prepared in the step 1) for 5 times, and drying the washed product in a freeze dryer at the temperature of minus 40 ℃ for 12 hours to obtain the manganese sulfide nanomaterial.
The average grain diameter of the manganese sulfide nano material is 7.9+/-1.3 nm.
The manganese sulfide nanomaterial is placed in an anaerobic tank for storage for subsequent testing.
Test example 1
The nanocomposite materials and the nanomaterial in examples and comparative examples were subjected to phase and morphology analysis using X-ray powder diffraction and high resolution transmission electron microscopy.
FIG. 1 is an X-ray powder diffraction pattern of the nanocomposite of example 1, comparative examples 1-3, and the nanomaterial of comparative examples 4 and 5 of the present invention, from which it is known that pure phase tetragonal pyrite (FeS) and blue Bei Gedan (MnS) can be successfully produced by mixing a solution of FeSO 4 and/or MnSO 4 with a Na 2 S solution. By adjusting the molar ratio of Fe to Mn, a series of nanocomposite materials with different Fe and Mn molar ratios can be obtained, and with the increase of Mn 2+ content, the (001) peak of FeS can be found to shift to the right, which indicates that the incorporation of Mn 2+ can possibly induce residual stress of the nanomaterial.
Fig. 2 to 13 are transmission electron microscope images of the nanocomposite materials of example 1, comparative examples 1 to 3 and the nanomaterial materials of comparative examples 4 and 5 and their corresponding high resolution transmission electron microscope images in this order. It can be seen from fig. 10 to 13 that the ferrous sulfide nanomaterial in comparative example 4 and the manganese sulfide nanomaterial in comparative example 5 are uniform, dispersed oval-shaped nanoparticles, and the particle size of the ferrous sulfide nanomaterial is generally smaller than that of the manganese sulfide nanomaterial. As can be seen from fig. 2 to 9, the nanoparticles of the ferrous sulfide-manganese sulfide nanocomposite materials of example 1 and comparative examples 1 to 3 tend to exist in the form of clusters, and the larger the cluster particle diameter formed as the Mn content increases. Depending on the nature of FeS that the solubility product constant is slightly higher than that of MnS, mnS nanoparticles may preferentially form in the presence of Fe 2+、Mn2+, but the cases of inventive example 1 and comparative examples 1-3 are not consistent with this assumption, and MnS does not preferentially form but preferentially form FeS nanoparticles in the presence of higher Fe content. In addition, since the synthesis conditions are strongly alkaline, the surface of the preferentially generated FeS nanoparticle has a large amount of negative charges, so that Mn 2+ may exist on the FeS surface in an adsorbed state, and then co-precipitate with the rest of S 2- to form MnS nanoparticle, which further appears that when Mn 2+ exists, the nanoparticle forms clusters.
Test example 2
The nanocomposite materials of example 1, comparative examples 1-3 and the nanomaterials of comparative examples 4 and 5 were tested for their performance in anaerobic conditions (testing was performed in an anaerobic tank in which the atmosphere was nitrogen and hydrogen, the volume ratio of nitrogen to hydrogen was 95%: 5%) and aerobic conditions (testing was performed in air) to remove Cr (VI) from a body of water.
The specific test steps are as follows:
In an anaerobic tank, 6 parts of a test solution having a Cr (VI) concentration of 5mg/L was prepared, each 1L, 200mg of the nanocomposite obtained by the preparation methods of example 1 and comparative examples 1 to 3 and the nanomaterial obtained by the preparation methods of comparative examples 4 and 5 were put into the test solution, respectively, and the test was performed by sampling at intervals (sampling volume: 3 ml), each sampling was equally divided into 3 parts, one part was used for detecting the contents of Cr (VI) and Cr (III) in the liquid phase, one part was used for detecting the adsorbed Cr (VI), and the other part was used for detecting the solid phase Cr (III). After 180 minutes of testing under anaerobic conditions, the test solution was placed in an air environment, samples were taken separately at intervals (sampling volume was 3 ml) and each sample was equally divided into 3 parts, one for detecting the contents of Cr (VI) and Cr (III) in the liquid phase, one for detecting the adsorbed Cr (VI) and the other for detecting the solid phase Cr (III).
Detecting the contents of Cr (VI) and Cr (III) in the solution phase by adopting a high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) method; extracting adsorbed Cr (VI) on the nanomaterial by adding 0.15M phosphate buffer (phosphate is disodium hydrogen phosphate and sodium dihydrogen phosphate, wherein the molar ratio of disodium hydrogen phosphate to sodium dihydrogen phosphate is 1:1) (ph=10.0) (measuring the content of the adsorbed Cr (VI) by inductively coupled plasma mass spectrometry (ICP-MS); and adding 2.0mL of aqua regia solution to digest the precipitate after reaction for 24 hours, so as to dissolve the adsorbed Cr (VI) of each nano composite material or nano material and the total Cr of the solid Cr (III) (the total Cr content of the adsorbed Cr (VI) and the solid Cr (III) is measured by utilizing inductively coupled plasma mass spectrometry (ICP-MS)), and calculating the content of the solid Cr (III) by a difference method.
FIGS. 14 to 19 are graphs showing the mole percentages of adsorbed Cr (VI), liquid-phase Cr (VI), solid-phase Cr (III) and liquid-phase Cr (III) with respect to the initial liquid-phase Cr (VI) during the test of the nanocomposite materials of example 1, comparative examples 1 to 3 and the nanomaterials of comparative examples 4 and 5, respectively, as a function of time and the test environment.
From fig. 14 to 19, it can be seen that the nanomaterial in comparative example 5has an optimal Cr (VI) removal effect under anaerobic and ph=7.0 conditions, i.e., the liquid phase Cr (VI) is completely removed in the aqueous phase and can be reduced to the solid phase Cr (III) to the greatest extent. For the nanocomposite materials of example 1 and comparative examples 1-3, the three nanocomposite materials of comparative examples 1-3 can slightly improve the adsorption capacity of original FeS to Cr (VI), the content of solid Cr (III) produced by reduction is substantially equal, the Mn 2+ doping process can improve the removal efficiency of original FeS nanomaterial to Cr (VI), and by comparison, it can be found that the nanocomposite material of example 1 (Fe/mn=10/1) has the best performance. Although Cr xFe1-x(OH)3 obtained by FeS reduction has high stability, the conditions under which Cr is present are often complex and high amounts of oxygen or strong oxidants are present, so that the Cr xFe1-x(OH)3 product obtained by reduction may be oxidized again to Cr (VI).
Under the aerobic condition, the nano material in comparative example 5 can be oxidized on the surface under the action of air to generate manganese oxide and manganese oxyhydroxide with strong oxidability, so that obvious Cr (VI) regeneration phenomenon can be observed. While no significant Cr (VI) regeneration was observed for the nanocomposites of examples 1, comparative examples 1-3 over the same period of time, it is notable that the nanocomposite of example 1, which performed most excellent under anaerobic conditions, still did not oxidize Cr (III) to Cr (VI) under aerobic conditions, indicating not only a higher removal efficiency, but also a higher stability of the resulting product.
Test example 3
The nanocomposites of example 1, comparative examples 1-3 and the nanomaterials of comparative examples 4 and 5 were tested for zeta potential under anaerobic conditions using Litesizer 500 (Anton paar) equipment. FIG. 20 is a zeta potential plot of the nanocomposites of example 1, comparative examples 1-3 and the nanomaterials of comparative examples 4 and 5 under anaerobic conditions.
As can be seen from FIG. 20, the nanocomposite materials of comparative examples 1,3, the isoelectric points of the nanomaterial of comparative examples 4 and 5 are each 3.0 to 4.0, and the isoelectric points of example 1 and comparative example 2 are lower than 2.0. In addition, the surface potential of the Mn 2+ doped nanocomposite was more negative in the pH range of 2.0-10.0, except for the nanocomposite of comparative example 1. Thus, the nanocomposite material of example 1 does not have improved adsorption capacity for Cr (VI) by simple physical adsorption (electrostatic effect) but has improved chemisorption for Cr (VI) by adjusting the electronic structure of the material by doping process, which may be derived from p-n junction between FeS (n-type semiconductor) and MnS (p-type semiconductor).
Test example 4
The nanocomposite materials of example 1, comparative examples 1-3 and the nanomaterial of comparative examples 4 and 5 were tested for release of Fe 2+ and Mn 2+ under anaerobic conditions in test example 2, respectively, using an enzyme-labeled instrument and an inductively coupled plasma mass spectrometer device.
The specific test steps are as follows:
determination of Fe 2+: the sample after shaking 0.1mL was filtered through a 0.22 μm filter head and placed in a 2mL centrifuge tube, 0.1mL of 6M hydrochloric acid solution, 0.4mL of ammonium acetate solution, 0.2mL of deionized water and 0.2mL of phenanthroline chromogenic agent were added, and the measurement was performed with an enzyme-labeled instrument at a wavelength of 510nm in 10min. Determination of Mn 2+: the oscillated samples were filtered through a 0.22 μm filter and measured directly by inductively coupled plasma mass spectrometry (ICP-MS).
Fig. 21 and 22 are the release amounts of Fe 2+ and Mn 2+ under anaerobic conditions in test example 2 for the nanocomposite of example 1, comparative examples 1-3, and the nanomaterial of comparative examples 4 and 5, respectively.
Solubility is one of the important indicators that need to be considered in nanomaterial properties. As can be seen from fig. 21 and 22, the nanocomposite materials of example 1, comparative examples 1 to 3 and the nanocomposite material of comparative example 4 each had a small amount of elution (maximum elution amount of 0.20 mg/L) under anaerobic and ph=7.0 conditions, and the present Fe 2+ elution amount was calculated to reduce only 0.08mg/L of Cr (VI) based on the stoichiometric ratio between the chemical reactions of Fe 2+ and Cr (VI), and it was found to be 3% of the nanocomposite material removal rate of example 1. In addition, the dissolution condition of Mn 2+ in the nano material is examined at the same time, according to the stoichiometric ratio calculation method, mn 2+ can be found to account for only 1% in the Cr (VI) removal process of the composite material in the embodiment 1, so that the nano composite materials with different Fe and Mn molar ratios and the removal of Cr (VI) by FeS and MnS are all heterogeneous reactions, and the subsequent sealing and storage of Cr (III) are facilitated.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (7)
1. The application of the nanocomposite material in removing hexavalent Cr in polluted water or polluted places is characterized in that the preparation method of the nanocomposite material comprises the following steps:
mixing the mixed solution of ferrous salt and divalent manganese salt with the solution of metal sulfide salt, stirring, separating solid from liquid, washing and drying to obtain the nanocomposite; the molar ratio of the ferrous salt to the divalent manganese salt in the mixed solution of the ferrous salt and the divalent manganese salt is (9-11): 1, a step of;
the nanocomposite comprises ferrous sulfide and manganese sulfide, wherein the molar ratio of the ferrous sulfide to the manganese sulfide is (9-11): 1, a step of;
the preparation method of the mixed solution of ferrous salt and divalent manganese salt comprises the following steps: mixing ferrous salt, divalent manganese salt and deoxidized deionized water in an anaerobic environment to obtain the composite material;
the preparation method of the vulcanized metal salt solution comprises the following steps: mixing the vulcanized metal salt with deoxidized deionized water in an anaerobic environment.
2. The use according to claim 1, wherein the mixing step is to add a mixed solution of ferrous salt and divalent manganese salt to a solution of metal sulfide salt for mixing.
3. The use according to claim 1, wherein the concentration of the ferrous salt in the mixed solution of the ferrous salt and the divalent manganese salt is 4.16-4.84 mmol/L, and the concentration of the divalent manganese salt is 0.16-0.84 mmol/L;
The concentration of the metal sulfide salt solution is 4.8-5.2 mmol/L, and the volume ratio of the mixed solution of ferrous salt and divalent manganese salt to the metal sulfide salt solution is (0.8-1.1): (0.8 to 1.1).
4. The use according to claim 1, wherein the molar ratio of ferrous salt to manganous salt in the mixed solution of ferrous salt and manganous salt is 10:1.
5. The use according to claim 4, wherein the solution of the metal sulfide salt is Na 2 S solution, the ferrous salt is FeSO 4 and the divalent manganese salt is MnSO 4.
6. The use according to claim 1, wherein the stirring temperature is 23-26 ℃, the stirring speed is 80-120 rpm, and the stirring time is 5-7 hours;
the solid-liquid separation is carried out in a centrifugal mode;
The washing step is carried out by deoxidized deionized water, and the washing times are 4-6 times;
the drying step is freeze drying, the drying temperature is-40 to-30 ℃, and the drying time is 12-24 hours.
7. The use according to claim 1, wherein the nanocomposite has an average particle size of 3-35 nm.
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