CN113145061A - Magnetic composite metal oxide adsorbent with double-shell core-shell structure and preparation method thereof - Google Patents
Magnetic composite metal oxide adsorbent with double-shell core-shell structure and preparation method thereof Download PDFInfo
- Publication number
- CN113145061A CN113145061A CN202110289092.XA CN202110289092A CN113145061A CN 113145061 A CN113145061 A CN 113145061A CN 202110289092 A CN202110289092 A CN 202110289092A CN 113145061 A CN113145061 A CN 113145061A
- Authority
- CN
- China
- Prior art keywords
- double
- shell
- shell structure
- shell core
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011258 core-shell material Substances 0.000 title claims abstract description 98
- 239000003463 adsorbent Substances 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 52
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 46
- 230000003068 static effect Effects 0.000 claims abstract description 17
- 239000002135 nanosheet Substances 0.000 claims abstract description 13
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 68
- 239000000243 solution Substances 0.000 claims description 61
- 239000012266 salt solution Substances 0.000 claims description 60
- 239000002002 slurry Substances 0.000 claims description 58
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 239000003513 alkali Substances 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 23
- 238000010907 mechanical stirring Methods 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 18
- 230000000087 stabilizing effect Effects 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000008399 tap water Substances 0.000 claims description 11
- 235000020679 tap water Nutrition 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000004005 microsphere Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 33
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 abstract description 19
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 13
- 239000002585 base Substances 0.000 description 7
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 7
- 239000000975 dye Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 229910001566 austenite Inorganic materials 0.000 description 5
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 229920001690 polydopamine Polymers 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- -1 Cr (VI) Chemical class 0.000 description 3
- 229910020091 MgCa Inorganic materials 0.000 description 3
- 101100003996 Mus musculus Atrn gene Proteins 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- 239000002156 adsorbate Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/28009—Magnetic properties
-
- 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
- B01J20/28014—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 form
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28059—Surface area, e.g. B.E.T specific surface area being less than 100 m2/g
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A magnetic composite metal oxide adsorbent with a double-shell core-shell structure and a preparation method thereof belong to the technical field of novel composite material adsorption. The adsorbent has the expression M2+ xM3+ y‑LDO/LDO/γ‑Fe2O3. The adsorbent is prepared by firstly preparing a double-shell core-shell structure by a step-by-step coprecipitation methodThe precursor is characterized in that LDH nanosheets grow on the surface of 270-350 nm spherical ferroferric oxide layer by layer in an ab-plane vertical orientation mode, and then are calcined for 4-8 hours at 450-550 ℃ in static air or nitrogen atmosphere to obtain the double-shell-layer core-shell-structure magnetic composite metal oxide adsorbent. The double-shell core-shell structure has the advantages that the double-shell core-shell structure has large specific surface area and abundant mesoporous structure, is used for adsorption test of organic dye or heavy metal ions and the like in aqueous solution, shows extremely excellent adsorption performance and cyclic utilization rate, is simple and convenient in preparation method, and is convenient for external magnetic field separation.
Description
Technical Field
The invention belongs to the technical field of novel composite material adsorption, and particularly provides a magnetic composite metal oxide adsorbent with a double-shell core-shell structure and a preparation method thereof.
Background
Advanced novel composite materials are expected to solve the increasingly serious problem of environmental pollution. A large amount of dyes and heavy metal ions are flowing into the ecological environment with industrial wastewater. Among them, congo red, methyl orange and methylene blue are anionic organic dyes that are toxic themselves and difficult to degrade, and cr (vi), cd (ii) and cu (ii) are heavy metal ions that are highly toxic or potentially toxic, thereby seriously threatening human health and ecological balance. The removal methods commonly used at present are photocatalysis, electrocatalysis, reduction, coagulation and adsorption, etc., of which adsorption method is considered as the most attractive method due to its simple operation, high efficiency, economy and environmental friendliness (adv. mater,2016,28, 10443-. The key point is to develop and create a novel adsorbent with low cost, high specific surface area, high adsorption capacity and high cycle efficiency.
Layered double metal hydroxide (LDH) is a typical two-dimensional anion material, has a layered structure, adjustable layered lattice metal cations, exchangeable interlayer anions and relatively high specific surface area, and is widely applied to adsorption of organic dyes and heavy metal ions in wastewater. In particular, layered bimetals can be obtained by calcining LDHs at appropriate temperaturesAn oxide (LDO). However, simple LDH or LDO prepared by the conventional method is not only reduced in specific surface area and effective adsorption sites due to easy stacking, but also difficult to separate and recycle. To solve these problems, nanoscale Fe3O4Or gamma-Fe2O3Spheres were first used as a matrix due to their large specific surface area, high stability and superparamagnetism. Two-dimensional LDH or LDO nanosheet and magnetic Fe3O4Or gamma-Fe2O3Organic compounding of the spheres is expected to result in a magnetic adsorbent material of novel structure, thereby exhibiting significantly improved adsorption performance based on increased specific surface area and effective adsorption sites. Li et al (J.Mater.chem.A.,2016,4,1737-1746) reported the formation of Fe3O4Magnetic polydopamine bifunctional material (65.38 m) assembled by Polydopamine (PDA) and MgAl-LDH2g-1) Wherein the LDH nanosheets are randomly attached to Fe by hydrothermal treatment3O4The equilibrium adsorption amounts of the @ PDA spherical copolymer (diameter about 200nm) on Cu (II), methyl orange and Congo red were 75.01, 624.89 and 584.56mg g, respectively-1After 5 times of magnetic separation cycle, the adsorption efficiency of Cu (II) is reduced by 20%. However, LDH nanosheets of about 38-54 nm are randomly attached to Fe3O4The morphology of the surface of the @ PDA spherical copolymer leads to stacking of the LDH nano-sheets, thereby greatly limiting the improvement of the adsorption performance of the LDH nano-sheets. Zhang et al (chem. Commun., 2011, 47, 12804-3O4@ MgAl-LDH @ Au, magnetic carrier Fe of honeycomb structure3O4@ MgAl-LDH exhibits a uniform vertical oriented growth of LDH at about 150nm of Fe at about 450nm3O4Topographical features of the surface of spherical particles. The catalyst exhibits significantly improved 1-phenylethanol oxidation performance based on increased specific surface area and more accessible active Au sites. However, relative to 450nm Fe3O4The core, 150nm thick LDH shell layer, only accounts for 25%. Meanwhile, considering that the hydroxyl on the surface of the laminate is subjected to dehydration condensation after the LDH is properly calcined, interlayer anions and water molecules can overflow the laminate in the form of small molecular gas, and the LDO with the mesoporous structure and the large specific surface area is formed. Therefore, the temperature of the molten metal is controlled,provides a novel magnetic composite metal oxide adsorbent with a double LDO shell core-shell structure, which is used for adsorbing toxic organic dye and heavy metal in water and related fields. So far, no report is available about the magnetic composite metal oxide adsorbent with a double-shell core-shell structure.
Disclosure of Invention
The invention aims to provide a magnetic composite metal oxide adsorbent with a double-shell core-shell structure and a preparation method thereof, and solves the problems that an LDO composite metal oxide adsorbent prepared by a traditional method is single in appearance, small in specific surface area, low in adsorption capacity and cycle efficiency and the like.
The magnetic composite metal oxide adsorbent with the double-shell core-shell structure is spherical ferroferric oxide (Fe) with the two-layer hexagonal LDH nanosheets grown in 270-350 nm in ab-plane vertical orientation relay mode and prepared through a fractional coprecipitation method3O4) Magnetic bimetallic hydroxide precursor M with double-shell core-shell structure on surface2+ xM3+ y-LDH/LDH/Fe3O4Then calcining the mixture for 4 to 8 hours in static air or flowing nitrogen at the temperature of 450 to 550 ℃ to obtain the magnetic composite metal oxide adsorbent M with the double-shell core-shell structure2+ xM3+ y-LDO/LDO/γ-Fe2O3Wherein M is2+Represents Mg2+、Ca2+、Co2+、Ni2+And Zn2+Either or both, M3+Represents Fe3+And Al3+Either or both, x and y each represent M2+And M3+The number of moles of (a) and the value of x/y is 1.5 to 3. The adsorbent is characterized in that the vertical orientation anchor chain of the double-layer LDO nanosheet is spherical gamma-Fe with the particle size of 270-350 nm2O3The magnetic composite metal oxide with the double-shell core-shell structure formed on the surface provides a large specific surface area (95-212 m) based on the double-shell core-shell structure2 g-1) And abundant mesoporous structure, thereby showing extremely excellent adsorption capacity and cycle efficiency in the adsorption test of aqueous solution containing organic dyes such as Congo red, methyl orange, methylene blue and the like or heavy metal ions such as Cr (VI), Cd (II), Cu (II) and the like, and being simple, convenient and greenThe preparation method and the convenient separation of the external magnetic field lead the magnetic field to have wide application prospect.
The invention prepares the magnetic composite metal oxide adsorbent with a double-shell core-shell structure by a step-by-step coprecipitation method and moderate calcination. Firstly, two layers of LDH nano sheets are prepared by a step-by-step coprecipitation method, and the two layers of LDH nano sheets grow on spherical Fe in a relay manner with the ab-plane vertical orientation3O4And calcining the precursor of the magnetic bimetallic hydroxide with the double-shell core-shell structure on the surface under a moderate condition to obtain the magnetic composite metal oxide adsorbent with the double-shell core-shell structure. The double-shell core-shell structure adsorbent has a large specific surface area and a rich mesoporous structure, and is applied to adsorbing organic dyes such as Congo red, methyl orange, methylene blue and the like or heavy metal ions such as Cr (VI), Cd (II), Cu (II) and the like in an aqueous solution, so that excellent adsorption capacity and cycle efficiency are obtained. The process comprises the following steps:
(1) preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe3O4Subbicrosphere particles and 150mL deionized water or CO2Mixing the mixture with deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; adding mixed alkali solution (NaOH and Na) under mechanical stirring2CO3，[OH-]/[CO3 2-]＝3.2，[CO3 2-]/[M3+]When the divalent metal salt is Ca (NO)3)3·4H2When O is present, Na is not added2CO3) Adjusting the above Fe3O4Stabilizing the pH value of the suspension liquid at 9.9-11.6, beginning to drop mixed salt solution after stabilizing for 10 minutes, and simultaneously dropping mixed alkali solution to keep the pH value of the solution stable at 9.9-11.6, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a water bath at the temperature of 30-80 ℃, crystallizing for 2-5 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to cool the temperature of the slurry in the flask to room temperature; and then, regulating the pH value of the obtained slurry by using the mixed alkali solution, stabilizing the pH value of the obtained slurry to 9.9-11.6 for 10 minutes, and then, dropwise adding the mixed alkali solution and the mixed salt simultaneouslyKeeping the pH of the solution at 9.9-11.6, after 30mL of mixed salt solution is dripped, transferring the obtained slurry into a water bath at 30-80 ℃ for crystallization for 2-5 hours, finally separating the obtained precipitate through an external magnetic field, washing the precipitate with deionized water for three times, and freeze-drying to obtain the double-shell core-shell structure magnetic layered double-metal hydroxide precursor M2+ xM3+ y-LDH/LDH/Fe3O4；
(2) Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor M of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained2+ xM3+ y-LDH/LDH/Fe3O4Calcining in static air or flowing nitrogen to obtain the magnetic composite metal oxide adsorbent M with the double-shell core-shell structure2+ xM3+ y-LDO/LDO/γ-Fe2O3。
Fe used in step (1)3O4The size range of the sub-microsphere particles is 270-350 nm.
The divalent metal salt in the mixed salt solution used in the step (1) is Mg (NO)3)2·6H2O、Ca(NO3)2·4H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O and Zn (NO)3)2·6H2One or two of O, and Fe (NO) as trivalent metal salt3)3·9H2O and Al (NO)3)3·9H2And any one or two of O, the molar ratio of the divalent metal salt to the trivalent metal salt is 1.5-3, and the total mole number of the metal salts is 9-12 mmol.
In the step (2), the calcining temperature ranges from 450 ℃ to 550 ℃, the calcining time ranges from 4 hours to 8 hours, and the temperature rise rate ranges from 1 ℃/min to 5 ℃/min.
The invention has the advantages that:
(1) provides a magnetic composite metal oxide adsorbent with a double-shell core-shell structure and a preparation method thereof. In particular to firstly preparing the magnetic layered double-metal hydrogen with the double-shell core-shell structure by a step-by-step coprecipitation methodAn oxide precursor, wherein the precursor is characterized in that LDH nanosheets grow in an ab-plane vertical orientation relay manner in a spherical Fe range from 270nm to 350nm3O4And calcining the surface of the magnetic composite metal oxide adsorbent in static air or flowing nitrogen at the temperature of 450-550 ℃ for 4-8 hours to obtain the magnetic composite metal oxide adsorbent with the double-shell core-shell structure. The adsorbent with the double-shell core-shell structure has a large specific surface area (95-212 m)2 g-1) And a rich mesoporous structure.
(2) The prepared novel magnetic composite metal oxide adsorbent with the double-shell core-shell structure shows extremely excellent adsorption capacity and cycle efficiency in an adsorption test of aqueous solutions containing organic dyes such as Congo red, methyl orange, methylene blue and the like or heavy metal ions such as Cr (VI), Cd (II), Cu (II) and the like, and has wide application prospect due to the simple and green preparation method and convenient external magnetic field separation.
Drawings
FIG. 1 is an X-ray crystal diffraction pattern of the precursor in example 1.
FIG. 2 is an X-ray crystal diffraction pattern of the sample of example 1.
FIG. 3 is a transmission electron micrograph of the sample of example 1.
FIG. 4 is the adsorption isotherm for Congo red adsorption for the sample of example 6.
FIG. 5 is a magnetization curve of the sample in example 7.
Detailed Description
The invention will be further described with reference to specific examples, but the invention is not limited thereto.
Example 1
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Mixing the sub-microsphere particles with 150mL of deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; a mixed base solution (19.2mmol of NaOH and 6mmol of Na) was added with mechanical stirring2CO3Dissolved in 90mL of deionized water) to adjust the above-mentioned Fe3O4The pH of the suspension was allowed to stabilize at 10. + -. 0.1, and after 10 minutes of stabilization, it beganThe mixed salt solution (6mmol of Mg (NO) is added dropwise3)2·6H2O and 3mmol of Al (NO)3)3·9H2Dissolving O in 30mL of deionized water), and simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable within 10 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a water bath at 30 ℃ and crystallizing for 5 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry by using the mixed alkali solution, stabilizing the pH value of the obtained slurry to 10 +/-0.1, after stabilizing for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution, keeping the pH value to 10 +/-0.1, after 30mL of the mixed salt solution is dropwise added, transferring the obtained slurry to a 30 ℃ water bath for crystallization for 5 hours, finally separating the obtained precipitate through an external magnetic field, washing the precipitate with deionized water for three times, and freeze-drying to obtain a double-shell core-shell structure magnetic layered double-metal hydroxide precursor MgAl-LDH/LDH/Fe3O4；
The precursor MgAl-LDH/LDH/Fe3O4Shows typical hexagonal MgAl-LDH phases (Standard card No. 14-0191) at 11.5 ° (003), 22.9 ° (006), 39.1 ° (015), 46.3 ° (018) and 60.5 ° (110) and shows corresponding Fe at 18.2 ° (111),29.9 ° (220),35.5 ° (311),42.9 ° (400),53.2 ° (442),56.7 ° (511) and 62.2 ° (400) in the X-ray diffractogram of (see FIG. 1)3O4Diffraction peaks of phase (Standard card number 86-1354) indicating MgAl-LDH and Fe3O4Effective recombination of the two phases.
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgAl-LDH/LDH/Fe of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained3O4Heating to 450 ℃ at the speed of 2 ℃/min in static air and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgAl-LDO/LDO/gamma-Fe2O3。
The adsorbent MgAl-LDO/LDO/gamma-Fe2O3The X-ray crystal diffractogram of (see FIG. 2) shows MgAl-LD in the precursorH is cancelled and a layered double metal composite oxide phase (LDO) of MgO phase and amorphous alumina phase appears, and Fe in the precursor3O4The diffraction peaks of each crystal face are slightly shifted to high angles, which indicates that gamma-Fe is formed2O3The phase shows that the magnetic composite metal oxide adsorbent with the double-shell core-shell structure consists of LDO and gamma-Fe2O3Two phases are formed. The transmission electron microscope (see figure 3) clearly shows that the spherical gamma-Fe of the two-layer LDO nanosheet vertical orientation relay anchor chain is about 270nm2O3The surface forms a double-shell core-shell structure.
At low temperature N2The adsorbent has a specific surface area of 212m as analyzed by adsorption and desorption tests2 g-1。
The adsorbent has an adsorption capacity of 123.4mg g Cr (VI) in an aqueous solution with a pH of 2.5 at 25 ℃ according to ultraviolet-visible spectrophotometry analysis-1。
The adsorbent MgAl-LDO/LDO/gamma-Fe2O3The adsorption capacity of the catalyst on Cr (VI) after 4 cycles is 104.8mg g-1The cycle efficiency E is greater than 84%.
The calculation formula of the circulation efficiency E is as follows:
in the formula: q. q.snIs the adsorption capacity of the adsorbent to the adsorbate after n times of desorption/adsorption, q0Is the initial adsorption capacity of the adsorbent to the adsorbate.
Example 2
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgAl-LDH/LDH/Fe of the double-shell core-shell structure magnetic layered double hydroxide in example 13O4Heating to 550 ℃ at the speed of 2 ℃/min in static air and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgAl-LDO/LDO/gamma-Fe2O3-550。
Analyzing by ultraviolet and visible spectrophotometryThe adsorbent has an adsorption capacity of 1637mg g of methyl orange in an aqueous solution with pH of 7.1 at 25 DEG C-1。
Example 3
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgAl-LDH/LDH/Fe of the double-shell core-shell structure magnetic layered double hydroxide in example 13O4Heating to 450 ℃ at the speed of 2 ℃/min in static air and keeping for 8 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgAl-LDO/LDO/gamma-Fe2O3-8h。
The adsorbent MgAl-LDO/LDO/gamma-Fe is analyzed by an inductive coupling plasma method2O3-8h an adsorption capacity for Cu (II) ions of 84.1mg g in an aqueous solution at 25 ℃ and pH 5.1-1。
Example 4
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgAl-LDH/LDH/Fe of the double-shell core-shell structure magnetic layered double hydroxide in example 13O4Heating to 450 ℃ at the speed of 1 ℃/min in static air and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgAl-LDO/LDO/gamma-Fe2O3-r1。
The adsorbent MgAl-LDO/LDO/gamma-Fe is analyzed by ultraviolet-visible spectrophotometry2O3R1 adsorption Capacity for methylene blue 77.8mg g in pH 6.4 aqueous solution at 25 deg.C-1。
Example 5
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgAl-LDH/LDH/Fe of the double-shell core-shell structure magnetic layered double hydroxide in example 13O4Heating to 450 ℃ at the speed of 5 ℃/min in static air and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgAl-LDO/LDO/gamma-Fe2O3-r5。
Example 6
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Mixing the sub-microsphere particles with 150mL of deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; a mixed base solution (19.2mmol of NaOH and 6mmol of Na) was added with mechanical stirring2CO3Dissolved in 90mL of deionized water) to adjust the above-mentioned Fe3O4The suspension was allowed to stabilize at pH 10. + -. 0.1 and after 10 minutes, addition of mixed salt solution (6mmol of Mg (NO) was started3)2·6H2O, 0.3mmol of Fe (NO)3)3·9H2O and 2.7mmol of Al (NO)3)3·9H2Dissolving O in 30mL of deionized water), and simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable within 10 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a water bath at 30 ℃ and crystallizing for 5 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry by using the mixed alkali solution, stabilizing the pH value of the obtained slurry to 10 +/-0.1, after stabilizing for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution, keeping the pH value to 10 +/-0.1, after 30mL of the mixed salt solution is completely dropwise added, transferring the obtained slurry to a 30 ℃ water bath for crystallization for 5 hours, finally separating the obtained precipitate through an external magnetic field, washing the precipitate with deionized water for three times, and freeze-drying to obtain a double-shell core-shell structure magnetic layered double-metal hydroxide precursor MgFe0.1Al-LDH/LDH/Fe3O4；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgFe of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained0.1Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in static air and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgFe0.1Al-LDO/LDO/γ-Fe2O3。
The adsorbent MgFe is analyzed by ultraviolet-visible spectrophotometry0.1Al-LDO/LDO/γ-Fe2O3The adsorption capacity of Congo red in an aqueous solution with pH of 8.8 at 30 ℃ is 3672mg g-1(FIG. 4).
Example 7
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Mixing the sub-microsphere particles with 150mL of deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; a mixed base solution (19.2mmol of NaOH and 6mmol of Na) was added with mechanical stirring2CO3Dissolved in 90mL of deionized water) to adjust the above-mentioned Fe3O4The suspension was allowed to stabilize at pH 10. + -. 0.1 and after 10 minutes, addition of mixed salt solution (6mmol of Mg (NO) was started3)2·6H2O, 1.5mmol of Fe (NO)3)3·9H2O and 1.5mmol of Al (NO)3)3·9H2Dissolving O in 30mL of deionized water), and simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable within 10 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a water bath at 30 ℃ and crystallizing for 5 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry by using the mixed alkali solution, stabilizing the pH value of the obtained slurry to 10 +/-0.1, after stabilizing for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution, keeping the pH value to 10 +/-0.1, after 30mL of the mixed salt solution is completely dropwise added, transferring the obtained slurry to a 30 ℃ water bath for crystallization for 5 hours, finally separating the obtained precipitate through an external magnetic field, washing the precipitate with deionized water for three times, and freeze-drying to obtain a double-shell core-shell structure magnetic layered double-metal hydroxide precursor MgFe0.5Al-LDH/LDH/Fe3O4；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The obtained magnetic layered bimetal hydroxide with the double-shell core-shell structurePrecursor of compound MgFe0.5Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in static air and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgFe0.5Al-LDO/LDO/γ-Fe2O3。
The adsorbent MgFe is determined by a specific magnetic saturation intensity method0.5Al-LDO/LDO/γ-Fe2O3Has a saturation magnetization of 22.7emu g-1(FIG. 5).
The adsorbent MgFe is analyzed by an inductive coupling plasma method0.5Al-LDO/LDO/γ-Fe2O3The adsorption capacity for Cd (II) ions in an aqueous solution having a pH of 5.7 at 25 ℃ was 78.3mg g-1。
Example 8
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Mixing the sub-microsphere particles with 150mL of deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; a mixed base solution (19.2mmol of NaOH and 6mmol of Na) was added with mechanical stirring2CO3Dissolved in 90mL of deionized water) to adjust the above-mentioned Fe3O4The suspension was allowed to stabilize at pH 10. + -. 0.1 and after 10 minutes, addition of mixed salt solution (9mmol of Mg (NO)3)2·6H2O and 3mmol of Al (NO)3)3·9H2Dissolving O in 30mL of deionized water), and simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable within 10 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a water bath at 30 ℃ and crystallizing for 5 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry by using the mixed alkali solution, stabilizing the pH value of the obtained slurry to be 10 +/-0.1, after the slurry is stabilized for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution, keeping the pH value to be 10 +/-0.1, after 30mL of the mixed salt solution is completely dropwise added, transferring the obtained slurry to a 30 ℃ water bath for crystallization for 5 hours, and finally, obtaining a precipitateSeparating by an external magnetic field, washing with deionized water for three times, and freeze-drying to obtain the precursor Mg of the magnetic layered double hydroxide with the double-shell core-shell structure3Al-LDH/LDH/Fe3O4；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor Mg of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained3Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in static air and keeping for 4 hours to obtain the magnetic composite metal oxide adsorbent Mg with the double-shell core-shell structure3Al-LDO/LDO/γ-Fe2O3。
Example 9
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Subbicrosphere particles and 150mL of CO2Mixing deionized water and carrying out ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; adding alkali solution (19.2mmol of NaOH dissolved in 90mL of solution for removing CO) under mechanical stirring2In deionized water) adjusting the above Fe3O4The suspension was allowed to stabilize at pH 11.5. + -. 0.1 for 10 minutes, after which time addition of mixed salt solution (5.4mmol of Mg (NO)3)2·6H2O, 0.6mmol of Ca (NO)3)3·4H2O and 3mmol of Al (NO)3)3·9H2Dissolving O in 30mL to remove CO2In deionized water), simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable at 11.5 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a water bath at 80 ℃ and crystallizing for 2 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry by using the alkali solution, stabilizing the pH value of the obtained slurry to 11.5 +/-0.1, after stabilizing for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution while keeping the pH value to 11.5 +/-0.1, after 30mL of the mixed salt solution is completely dropwise added, transferring the obtained slurry to a water bath at 80 ℃ for crystallization for 2 hours, and finally, crystallizing the obtained slurry in the water bath at 80 ℃ to obtain the productSeparating the obtained precipitate with an external magnetic field, washing with deionized water for three times, and freeze-drying to obtain double-shell core-shell structure magnetic layered double hydroxide precursor MgCa0.1Al-LDH/LDH/Fe3O4；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgCa of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained0.1Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in flowing nitrogen and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgCa0.1Al-LDO/LDO/γ-Fe2O3。
Example 10
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Subbicrosphere particles and 150mL of CO2Mixing deionized water and carrying out ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; adding alkali solution (19.2mmol of NaOH dissolved in 90mL of solution for removing CO) under mechanical stirring2In deionized water) adjusting the above Fe3O4The suspension was allowed to stabilize at pH 11.5. + -. 0.1 for 10 minutes, after which time addition of mixed salt solution (4.2mmol of Mg (NO)3)2·6H2O, 1.8mmol of Ca (NO)3)3·4H2O and 3mmol of Al (NO)3)3·9H2Dissolving O in 30mL to remove CO2In deionized water), simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable at 11.5 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a water bath at 80 ℃ and crystallizing for 2 hours under continuous mechanical stirring, and after the reaction is finished, washing the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting pH value of the obtained slurry with the above alkali solution to be stable at 11.5 + -0.1 for 10 min, simultaneously dripping the above mixed alkali solution and mixed salt solution while maintaining pH at 11.5 + -0.1, transferring the obtained slurry to 80 deg.C water bath after 30mL mixed salt solution is drippedCrystallizing for 2 hours, separating the obtained precipitate by an external magnetic field, washing with deionized water for three times, and freeze-drying to obtain the precursor MgCa of the magnetic layered double hydroxide with the double-shell core-shell structure0.3Al-LDH/LDH/Fe3O4；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor MgCa of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained0.3Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in flowing nitrogen and keeping for 4 hours to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent MgCa0.3Al-LDO/LDO/γ-Fe2O3。
Example 11
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 350nm3O4Mixing the sub-microsphere particles with 150mL of deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; a mixed base solution (19.2mmol of NaOH and 6mmol of Na) was added with mechanical stirring2CO3Dissolved in 90mL of deionized water) to adjust the above-mentioned Fe3O4The suspension was allowed to stabilize at pH 10. + -. 0.1 and after 10 minutes, addition of mixed salt solution (6mmol of Ni (NO) was started3)2·6H2O and 3mmol of Al (NO)3)3·9H2Dissolving O in 30mL of deionized water), and simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable within 10 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a 65 ℃ water bath, crystallizing for 4 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry by using the mixed alkali solution, stabilizing the pH value of the obtained slurry to be 10 +/-0.1, after the slurry is stabilized for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution, keeping the pH value to be 10 +/-0.1, after 30mL of the mixed salt solution is completely dropwise added, transferring the obtained slurry to a water bath at 65 ℃ for crystallization for 4 hours, and finally, precipitating the obtained slurrySeparating the precipitate with an external magnetic field, washing with deionized water for three times, and freeze-drying to obtain the precursor Ni of the magnetic layered double hydroxide with the double-shell core-shell structure2Al-LDH/LDH/Fe3O4-350nm；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor Ni of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained2Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in static air at the speed of-350 nm and keeping for 4 hours to obtain the magnetic composite metal oxide adsorbent Ni with the double-shell core-shell structure2Al-LDO/LDO/γ-Fe2O3-350nm。
Example 12
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Mixing the sub-microsphere particles with 150mL of deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; a mixed base solution (19.2mmol of NaOH and 6mmol of Na) was added with mechanical stirring2CO3Dissolved in 90mL of deionized water) to adjust the above-mentioned Fe3O4The suspension was allowed to stabilize at pH 10. + -. 0.1 and after 10 minutes, addition of mixed salt solution (9mmol of Co (NO) was started3)2·6H2O and 3mmol of Al (NO)3)3·9H2Dissolving O in 30mL of deionized water), and simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable within 10 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, transferring the obtained slurry into a 65 ℃ water bath, crystallizing for 4 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; then utilizing the mixed alkali solution to adjust the pH value of the obtained slurry and stabilize the slurry at 10 +/-0.1, after stabilizing for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution and keeping the pH value at 10 +/-0.1, after 30mL of the mixed salt solution is completely dropwise added, transferring the obtained slurry to a water bath at 65 ℃ for crystallization for 4 hours, and finally separating the obtained precipitate through an external magnetic field,washing with deionized water for three times, and freeze-drying to obtain the precursor Co of the magnetic layered double hydroxide with the double-shell core-shell structure3Al-LDH/LDH/Fe3O4；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor Co of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained3Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in static air and keeping for 4 hours to obtain the magnetic composite metal oxide adsorbent Co with the double-shell core-shell structure3Al-LDO/LDO/γ-Fe2O3。
Example 13
Preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe of about 270nm3O4Mixing the sub-microsphere particles with 150mL of deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; a mixed base solution (19.2mmol of NaOH and 6mmol of Na) was added with mechanical stirring2CO3Dissolved in 90mL of deionized water) to adjust the above-mentioned Fe3O4The suspension was allowed to stabilize at pH 10. + -. 0.1 and after 10 minutes, addition of mixed salt solution (9mmol of Zn (NO) was started3)2·6H2O and 3mmol of Al (NO)3)3·9H2Dissolving O in 30mL of deionized water), and simultaneously dropwise adding a mixed alkali solution to keep the pH of the solution stable within 10 +/-0.1, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after the dropwise addition of 30mL of mixed salt solution is finished, dropwise adding the mixed alkali solution and 30mL of mixed salt solution at the same time, keeping the pH of the solution stable at 10 +/-0.1 all the time, and controlling the dropping speed to be-0.5 mL/min; after the mixed salt solution is dripped, transferring the obtained slurry into a water bath at 65 ℃ and crystallizing for 4 hours under continuous mechanical stirring, and after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry to be 10 +/-0.1 by using the mixed alkali solution, after the slurry is stabilized for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution while keeping the pH value to be 10 +/-0.1, and after 30mL of the mixed salt solution is dropwise addedAfter the crystallization is finished, the obtained slurry is transferred to a 65 ℃ water bath for crystallization for 4 hours, then the mixed alkali solution and 30mL of mixed salt solution are simultaneously dripped, the pH value is kept to be 10 +/-0.1, after the dripping of the mixed salt solution is finished, the obtained slurry is transferred to the 65 ℃ water bath for crystallization for 4 hours, finally the obtained precipitate is separated by an external magnetic field, washed three times by deionized water, and freeze-dried to obtain the precursor Zn of the magnetic layered double hydroxide with the double-shell core-shell structure3Al-LDH/LDH/Fe3O4；
Preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
The precursor Zn of the magnetic layered double hydroxide with the double-shell core-shell structure is obtained3Al-LDH/LDH/Fe3O4Heating to 450 ℃ at the speed of 2 ℃/min in static air and keeping for 4 hours to obtain the magnetic composite metal oxide adsorbent Zn with the double-shell core-shell structure3Al-LDO/LDO/γ-Fe2O3。
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (5)
1. A magnetic composite metal oxide adsorbent with a double-shell core-shell structure is characterized in that a double-shell core-shell structure magnetic layered double-metal hydroxide (LDH) precursor is prepared by a step-by-step coprecipitation method, and the precursor is characterized in that two layers of LDH nanosheets of a hexagonal crystal system grow on a 270-350 nm spherical ferroferric oxide surface in an ab-surface vertical orientation relay manner, and then are calcined in static air or flowing nitrogen at 450-550 ℃ to obtain the magnetic composite metal oxide adsorbent with the double-shell core-shell structure; the adsorbent with the double-shell core-shell structure has a large specific surface area of 95-212 m2g-1And a rich mesoporous structure.
2. The preparation method of the double-shell core-shell structure magnetic composite metal oxide adsorbent according to claim 1, characterized by comprising the following steps:
(1) preparation of double-shell core-shell structure magnetic layered double-metal hydroxide precursor
0.232g of Fe3O4Subbicrosphere particles and 150mL deionized water or CO2Mixing the mixture with deionized water and performing ultrasonic dispersion for 20 minutes to obtain uniform Fe3O4A suspension; adding mixed alkali solution (NaOH and Na) under mechanical stirring2CO3，[OH-]/[CO3 2-]＝3.2，[CO3 2-]/[M3+]When the divalent metal salt is Ca (NO)3)3·4H2When O is present, Na is not added2CO3) Adjusting the above Fe3O4Stabilizing the pH value of the suspension liquid at 9.9-11.6, beginning to drop mixed salt solution after stabilizing for 10 minutes, and simultaneously dropping mixed alkali solution to keep the pH value of the solution stable at 9.9-11.6, wherein the dropping speed of the mixed salt solution is-0.5 mL/min; after 30mL of mixed salt solution is dripped, transferring the obtained slurry into a water bath at the temperature of 30-80 ℃ and crystallizing for 2-5 hours under continuous mechanical stirring; after the reaction is finished, washing the outer wall of the flask by using tap water to reduce the temperature of the slurry in the flask to room temperature; adjusting the pH value of the obtained slurry by using the mixed alkali solution, stabilizing the pH value of the obtained slurry at 9.9-11.6, after stabilizing for 10 minutes, simultaneously dropwise adding the mixed alkali solution and the mixed salt solution, keeping the pH value at 9.9-11.6, after 30mL of the mixed salt solution is dropwise added, transferring the obtained slurry to a water bath at 30-80 ℃ for crystallization for 2-5 hours, finally separating the obtained precipitate by an external magnetic field, washing the precipitate with deionized water for three times, and freeze-drying to obtain a double-shell core-shell structure magnetic layered double hydroxide precursor;
(2) preparation of magnetic composite metal oxide adsorbent with double-shell core-shell structure
And calcining the obtained double-shell core-shell structure magnetic layered double-metal hydroxide precursor in static air or flowing nitrogen to obtain the double-shell core-shell structure magnetic composite metal oxide adsorbent.
3. A process according to claim 2, characterized in that Fe is used in step (1)3O4The size range of the sub-microsphere particles is 270-350 nm.
4. The method according to claim 2, wherein the divalent metal salt in the mixed salt solution used in step (1) is Mg (NO)3)2·6H2O、Ca(NO3)3·4H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O and Zn (NO)3)2·6H2One or two of O, and Fe (NO) as trivalent metal salt3)3·9H2O and Al (NO)3)3·9H2And any one or two of O, the molar ratio of the divalent metal salt to the trivalent metal salt is 1.5-3, and the total mole number of the metal salts is 9-12 mmol.
5. The method according to claim 2, wherein the calcination temperature in the step (2) is in the range of 450 to 550 ℃, the calcination time is in the range of 4 to 8 hours, and the temperature rise rate is in the range of 1 to 5 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110289092.XA CN113145061B (en) | 2021-03-18 | 2021-03-18 | Double-shell core-shell structure magnetic composite metal oxide adsorbent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110289092.XA CN113145061B (en) | 2021-03-18 | 2021-03-18 | Double-shell core-shell structure magnetic composite metal oxide adsorbent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113145061A true CN113145061A (en) | 2021-07-23 |
| CN113145061B CN113145061B (en) | 2024-08-06 |
Family
ID=76887731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110289092.XA Active CN113145061B (en) | 2021-03-18 | 2021-03-18 | Double-shell core-shell structure magnetic composite metal oxide adsorbent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113145061B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413864A (en) * | 2021-07-30 | 2021-09-21 | 宁夏医科大学 | Layered double-metal hydroxide complex for adsorbing heavy metal ions and preparation method and application thereof |
| CN113694876A (en) * | 2021-09-06 | 2021-11-26 | 信阳学院 | Preparation and application of nano magnetic layered double hydroxide adsorbent |
| CN113952935A (en) * | 2021-11-19 | 2022-01-21 | 中国农业科学院蔬菜花卉研究所 | Magnetic MOFs composite material and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101647780A (en) * | 2009-09-23 | 2010-02-17 | 北京化工大学 | Core-shell type magnetic nano-composite particle based on Fe3O4 and houghite and preparation method thereof |
| CN106390909A (en) * | 2016-11-03 | 2017-02-15 | 孙顺秋 | Ferroferric-oxide magnetic heavy-metal-ion adsorbent being of double-shell hollow structure and preparation method thereof |
| CN106495192A (en) * | 2016-11-14 | 2017-03-15 | 南华大学 | A kind of method of the hydrotalcite for preparing even particle size distribution |
| CN110085453A (en) * | 2019-04-10 | 2019-08-02 | 南京航空航天大学 | The preparation method and application of the hud typed Ni-Co LDH@Ni-Mn LDH of carbon nanotube foam support |
| KR20210001642A (en) * | 2019-06-28 | 2021-01-06 | 고려대학교 산학협력단 | Method of Preparing Layered Double Hydroxide Based Adsorbent and Method of Removing Heavy Metals in Water Using the Same Prepared thereby |
-
2021
- 2021-03-18 CN CN202110289092.XA patent/CN113145061B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101647780A (en) * | 2009-09-23 | 2010-02-17 | 北京化工大学 | Core-shell type magnetic nano-composite particle based on Fe3O4 and houghite and preparation method thereof |
| CN106390909A (en) * | 2016-11-03 | 2017-02-15 | 孙顺秋 | Ferroferric-oxide magnetic heavy-metal-ion adsorbent being of double-shell hollow structure and preparation method thereof |
| CN106495192A (en) * | 2016-11-14 | 2017-03-15 | 南华大学 | A kind of method of the hydrotalcite for preparing even particle size distribution |
| CN110085453A (en) * | 2019-04-10 | 2019-08-02 | 南京航空航天大学 | The preparation method and application of the hud typed Ni-Co LDH@Ni-Mn LDH of carbon nanotube foam support |
| KR20210001642A (en) * | 2019-06-28 | 2021-01-06 | 고려대학교 산학협력단 | Method of Preparing Layered Double Hydroxide Based Adsorbent and Method of Removing Heavy Metals in Water Using the Same Prepared thereby |
Non-Patent Citations (1)
| Title |
|---|
| SHENG TANG ET AL.: "Magnetic core–shell iron(II, III) oxide@layered double oxide microspheres for removal of 2, 5-dihydroxybenzoic acid from aqueous solutions", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 437, 23 September 2014 (2014-09-23), pages 316 - 323 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413864A (en) * | 2021-07-30 | 2021-09-21 | 宁夏医科大学 | Layered double-metal hydroxide complex for adsorbing heavy metal ions and preparation method and application thereof |
| CN113694876A (en) * | 2021-09-06 | 2021-11-26 | 信阳学院 | Preparation and application of nano magnetic layered double hydroxide adsorbent |
| CN113694876B (en) * | 2021-09-06 | 2023-08-22 | 信阳学院 | Preparation and application of nano magnetic layered double hydroxide adsorbent |
| CN113952935A (en) * | 2021-11-19 | 2022-01-21 | 中国农业科学院蔬菜花卉研究所 | Magnetic MOFs composite material and preparation method and application thereof |
| CN113952935B (en) * | 2021-11-19 | 2023-08-01 | 中国农业科学院蔬菜花卉研究所 | Magnetic MOFs composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113145061B (en) | 2024-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113145061A (en) | Magnetic composite metal oxide adsorbent with double-shell core-shell structure and preparation method thereof | |
| CN107376825B (en) | Hexagonal boron nitride material and preparation method and application thereof | |
| Ren et al. | From three‐dimensional flower‐like α‐Ni (OH) 2 nanostructures to hierarchical porous NiO nanoflowers: microwave‐assisted fabrication and supercapacitor properties | |
| Sun et al. | Magnetically separable porous graphitic carbon with large surface area as excellent adsorbents for metal ions and dye | |
| Wu et al. | Efficient removal of methyl orange by a flower-like TiO 2/MIL-101 (Cr) composite nanomaterial | |
| CN110270333B (en) | Bimetallic organic framework nanoflower and derivative thereof, and preparation method and application thereof | |
| Pal et al. | Hierarchically order porous lotus shaped nano-structured MnO 2 through MnCO 3: chelate mediated growth and shape dependent improved catalytic activity | |
| Manikandan et al. | Aloe vera plant extracted green synthesis, structural and opto-magnetic characterizations of spinel Co x Zn1-x Al2O4 nano-catalysts | |
| CN107486141B (en) | Preparation method of magnesium oxide chemically modified diatomite with high adsorption capacity | |
| CN113145062B (en) | Preparation method of magnetic adsorption material based on Prussian blue and hydrotalcite | |
| Guo et al. | Fabrication of Co@ SiO 2@ C/Ni submicrorattles as highly efficient catalysts for 4-nitrophenol reduction | |
| Cai et al. | Template-free synthesis of hierarchical γ-Al 2 O 3 nanostructures and their adsorption affinity toward phenol and CO 2 | |
| CN101274847A (en) | Spinel type ferrite magnetic hollow microsphere and preparation thereof | |
| Zhou et al. | Synthesis and properties of octahedral Co 3 O 4 single-crystalline nanoparticles enclosed by (111) facets | |
| CN108821311B (en) | Preparation method of prussian white mesomorphic material with fine and adjustable ferromanganese component | |
| Wu et al. | A green-chemical synthetic route to fabricate a lamellar-structured Co/Co (OH) 2 nanocomposite exhibiting a high removal ability for organic dye | |
| CN113044877A (en) | Zn-based ternary hydrotalcite, preparation method and application thereof, Zn-based ternary composite metal oxide, and preparation method and application thereof | |
| JP2011213572A (en) | Iron oxide porous body, air purifying material obtained by using the same and method for producing iron oxide porous body | |
| Kang et al. | Functionalized MIL-53 and its derivatives modified Bi2WO6 as effective piezocatalysts and membranes for adsorption and decomposition of organic pollutants | |
| Shi et al. | Core–shell structured Fe 3 O 4@ SiO 2@ CdS nanoparticles with enhanced visible-light photocatalytic activities | |
| CN104923154A (en) | Hexagonal sheet magnetic metal/metal oxide/carbon nanocomposite adsorbing material and preparation method therefor | |
| CN110813303A (en) | Preparation of flower-like iron-doped cerium dioxide with porous structure and desulfurization application of flower-like iron-doped cerium dioxide | |
| CN114260027B (en) | Method for preparing metal oxide@metal organic framework core-shell material | |
| Li et al. | Modular preparation of functional bimetallic spinels from metal–organic frameworks: a deep exploration from macro and micro perspectives | |
| JP2023106421A (en) | Layered double hydroxide crystal and anion adsorbent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |