CN113292086A - 一种CoAl2O4纳米粉体、制备方法及应用 - Google Patents
一种CoAl2O4纳米粉体、制备方法及应用 Download PDFInfo
- Publication number
- CN113292086A CN113292086A CN202110760603.1A CN202110760603A CN113292086A CN 113292086 A CN113292086 A CN 113292086A CN 202110760603 A CN202110760603 A CN 202110760603A CN 113292086 A CN113292086 A CN 113292086A
- Authority
- CN
- China
- Prior art keywords
- coal
- nano powder
- powder
- preparation
- nano
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 title description 23
- 239000011858 nanopowder Substances 0.000 claims abstract description 55
- 229910019114 CoAl2O4 Inorganic materials 0.000 claims abstract description 39
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 29
- 229910002515 CoAl Inorganic materials 0.000 claims abstract description 26
- 239000003245 coal Substances 0.000 claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 21
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 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 claims abstract description 12
- 229940012189 methyl orange Drugs 0.000 claims abstract description 12
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 22
- 239000007790 solid phase Substances 0.000 claims description 19
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000000919 ceramic Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002071 nanotube Substances 0.000 abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 3
- 239000012703 sol-gel precursor Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000001055 blue pigment Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- -1 transition metal cobalt salt Chemical class 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 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 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
-
- 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
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Geology (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种CoAl2O4纳米粉体的制备方法，以埃洛石为铝源，Co(NO3)2·6H2O和/或CoCl2·6H2O为钴源，通过在埃洛石纳米管上负载钴源并控温煅烧制备得到CoAl2O4纳米粉体，制备方法简单、原料种类少、适合大规模生产。通过上述制备方法制得的CoAl2O4纳米粉体具有标志性的蓝色，纯度高，且保留了埃洛石的纳米管状结构，可用于吸附或催化降解废水中的染料分子，所述的染料为亚甲基蓝、罗丹明B或甲基橙中的至少一种，且CoAl2O4纳米粉体的纳米管状结构使其与染料废水的接触面积大，对甲基橙的催化降解率可达100％。此外，本发明制备得到的CoAl2O4纳米粉体可用作陶瓷颜料。
Description
技术领域
本发明属于无机粉体材料技术领域，尤其涉及一种CoAl2O4纳米粉体、制备方法及应用。
背景技术
铝酸钴(CoAl2O4)是一种着色力强、抗老化能力好的无机着色剂，一般称之为钴蓝，常用作耐高温陶瓷釉料。它具有典型的钴铝尖晶石结构，应用广泛。近年来，有研究表明CoAl2O4可以用于光催化降解染料、CO2催化转化等(Mo,L.Y.；Zheng,X.M.；et al.A novelcatalyst Pt/CoAl2O4/Al2O3 for combination CO2 reforming and partial oxidationof CH4.Catal Lett 2002,80(3-4),165-169.)。
目前，CoAl2O4常见的制备方法主要是固相煅烧法以及液相法中的沉淀法、水热法、溶胶凝胶法等，固相煅烧法是将钴铝金属盐或金属氧化物按照一定比例混合，经高温煅烧得到蓝色粉体，固相法的不足之处主要在于反应过程需要较高的煅烧温度，一般大于1000℃，甚至还需要矿化剂，而且固相法制备得到的CoAl2O4一般颗粒尺寸较大，难以得到CoAl2O4纳米粉体。相较而言，液相法可以通过控制反应条件、改变原料比例等方法得到具有良好形貌结构的CoAl2O4，但液相法制备过程易产生废水、相对不环保。因此，开发低成本、制备工艺简单的CoAl2O4纳米粉体制备方法具有重要意义。
公开号为CN101575465B的中国专利文献中公开了一种纳米钴蓝颜料CoAl2O4的制备方法，该发明将乙酸钴粉末与硫酸铝粉末分别溶于蒸馏水后混合得均匀澄清混合溶液，使用氮气喷枪将其分散在液氮中预冻，随后将其置于冻干机中进行真空干燥得到冻干粉末；在空气气氛中对冻干粉末进行煅烧得到鲜亮的蓝色粉体，即纳米钴蓝粉体；所述的煅烧温度为800-1000℃。但该发明对仪器设备要求较高，生产成本较高。
公开号为CN106830917A的中国专利文献中公开了一种钴铝尖晶石型蓝色纳米陶瓷颜料的合成及在制备太阳能吸光涂层中的应用，该发明将是将过渡金属钴盐、金属铝盐溶解于蒸馏水中得起始溶液；将螯合剂、酯化剂的混合水溶液滴加到起始溶液中，搅拌加热得到溶胶-凝胶前驱体；调节溶胶-凝胶前驱体至pH＝6～7，继续搅拌加热使其水解形成溶胶溶液；将溶胶溶液蒸发溶剂得到干凝胶，然后用无水乙醇引燃干凝胶使其充分自蔓延燃烧得燃烧产物，最后将燃烧产物于400～800℃下热处理，得到CoAl2O4尖晶石型蓝色纳米陶瓷颜料。该钴蓝颜料CoAl2O4的合成方法相对繁琐。
发明内容
本发明提供了一种CoAl2O4纳米粉体的制备方法，工艺简单、原料种类少、所需设备种类少、适合大规模生产，制备得到的CoAl2O4纳米粉体具有纳米管状结构，纯度高，对染料废水的催化降解性能好。
具体采用的技术方案如下：
一种CoAl2O4纳米粉体的制备方法，包括以下步骤：
(1)将埃洛石分散在无水乙醇中，再加入钴源超声搅拌混匀后得到悬浊液；
(2)将2-甲基咪唑溶于无水乙醇中，得到溶液，将溶液加入到步骤(1)的悬浊液中，超声搅拌，静置陈化，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，清洗、真空干燥、研磨后进行煅烧，得到CoAl2O4纳米粉体；
所述的钴源为Co(NO3)2·6H2O和/或CoCl2·6H2O。
埃洛石具有天然的纳米管状结构，其可作为铝源高温下分解产生Al2O3相，因此通过在埃洛石纳米管上负载钴源并控温煅烧即可制备得到CoAl2O4纳米粉体。
步骤(1)中，所述的埃洛石、无水乙醇和钴源的加入量比为：1g：30-50mL：1-2g。
步骤(2)中，所述的2-甲基咪唑与无水乙醇的加入量比为：1-1.5g：10-15mL；所述的溶液与步骤(1)的悬浊液的体积比为1：0.5-2。
考虑到原料利用率，优选的，步骤(1)中，所述的埃洛石、无水乙醇和钴源的加入量为：1g：35-40mL：1～2g；步骤(2)中，所述的2-甲基咪唑与无水乙醇的加入量比为：1～1.5g：10-12mL，所述的溶液与步骤(1)的悬浊液的体积比为1：0.5-1。
所述的超声搅拌时间为20-35min。
步骤(2)中，所述的静置陈化时间为16-26h。
步骤(3)中，所述的清洗条件为：用无水乙醇和去离子水淋洗固相2-5次。
步骤(3)中，所述的真空干燥的条件为：50-70℃，12-20h。
步骤(3)中，所述的煅烧条件为：温度：750-1200℃，升温速率为1-5℃/min，保温时间为1-3h。
为了提高反应效率以及使煅烧更充分，优选的，所述的煅烧条件为：温度：900-1000℃，升温速率为1-5℃/min，保温时间为1-3h。
本发明还提供了所述的CoAl2O4纳米粉体的制备方法制备得到的CoAl2O4纳米粉体。该CoAl2O4纳米粉体具有标志性的蓝色，纯度高，且保留了埃洛石的纳米管状结构。
本发明还提供了所述的CoAl2O4纳米粉体在处理染料废水中的应用，所述的染料为亚甲基蓝、罗丹明B或甲基橙中的至少一种。
所述的应用方式为：将CoAl2O4纳米粉体分散到染料废水中，再加入氧化剂后催化降解染料，其中，所述的氧化剂为过硫酸氢钾、双氧水或过硫酸钠中的至少一种；所述的染料浓度为10-100mg/L；所述的CoAl2O4纳米粉体、氧化剂和染料废水的配比为0.2-2g：0.2-3g：1L。
本发明还提供了所述的CoAl2O4纳米粉体作为颜料的应用。所述的CoAl2O4纳米粉体可以分散到釉料、坯料中用于建筑卫生陶瓷、日用陶瓷的装饰，或将其分散到涂料、乳胶漆中用以染色。
本发明与现有技术相比，有益效果主要体现在：
(1)本发明公开的CoAl2O4纳米粉体的制备工艺简单、原料种类少、所需设备种类少、适合工业化生产。
(2)本发明公开的CoAl2O4纳米粉体微观形貌特殊，保留了埃洛石的纳米管状结构，呈蓝色，纯度高，可以用于吸附或催化降解废水中的染料。且由于该CoAl2O4纳米粉体具有纳米管状结构，在应用处理染料废水时，与染料废水的接触面积较大，催化效果好，催化降解率可达100％。
附图说明
图1为实施例2中制备得到的CoAl2O4纳米粉体的XRD图。
图2为实施例2中制备得到的CoAl2O4纳米粉体的SEM图。
图3为实施例2中制备得到的CoAl2O4纳米粉体与原料埃洛石的粒度分布对比图。
具体实施方式
实施例1
(1)将1.5g埃洛石分散在60mL无水乙醇中，超声搅拌30min，再加入2.328g的Co(NO3)2·6H2O，超声搅拌30min混匀后得到悬浊液；
(2)称取6.56g的2-甲基咪唑溶于60mL无水乙醇中，得到溶液，将60mL溶液缓慢加入到步骤(1)制得的60mL悬浊液中，超声搅拌30min后，继续静置陈化24h，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，用无水乙醇和去离子水淋洗固相4次，60℃真空干燥16h后，研磨得到紫色粉末，取紫色粉末0.3g置于管式炉中900℃进行煅烧，升温速率为2℃/min，保温时间为2h，得到蓝色的CoAl2O4纳米粉体。
实施例2
(1)将1.5g埃洛石分散在60mL无水乙醇中，超声搅拌30min，再加入2.328g的Co(NO3)2·6H2O，超声搅拌30min混匀后得到悬浊液；
(2)称取6.56g的2-甲基咪唑溶于60mL无水乙醇中，得到溶液；将60mL溶液缓慢加入到步骤(1)制得的60mL悬浊液中，超声搅拌30min后，继续静置陈化24h，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，用无水乙醇和去离子水淋洗固相4次，60℃真空干燥15h后，研磨得到紫色粉末，取紫色粉末0.3g置于管式炉中800℃进行煅烧，升温速率为2℃/min，保温时间为2h，得到蓝色的CoAl2O4纳米粉体；
该CoAl2O4纳米粉体的XRD图如图1所示，该样品的晶相成分主要是CoAl2O4，无明显其他杂质晶相。
该CoAl2O4纳米粉体的SEM图如图2所示，该样品的形貌可以看到明显的纳米管状结构，说明CoAl2O4纳米粉体保留了埃洛石的纳米管状结构，是一种纳米尺度材料。
该CoAl2O4纳米粉体的粒度分布图如图3所示，其粒度分布曲线与埃洛石原料接近，粒径范围比埃洛石略大，埃洛石原料本身为天然纳米管状结构，即该CoAl2O4纳米粉体的粒径尺度也属于纳米级。
实施例3
(1)将1.4g埃洛石分散在60mL无水乙醇中，超声搅拌30min，再加入2.328g的Co(NO3)2·6H2O，超声搅拌30min混匀后得到悬浊液；
(2)称取6.816g的2-甲基咪唑溶于60mL无水乙醇中，得到溶液；将60mL溶液缓慢加入到步骤(1)得到的60mL悬浊液中，超声搅拌30min后，继续静置陈化22h，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，用无水乙醇和去离子水淋洗固相4次，60℃真空干燥18h后，研磨得到紫色粉末，取紫色粉末0.3g置于管式炉中900℃进行煅烧，升温速率为2℃/min，保温时间为2h，得到蓝色的CoAl2O4纳米粉体。
实施例4
(1)将1g埃洛石分散在35mL无水乙醇中，超声搅拌35min，再加入1.25g的CoCl2·6H2O，超声搅拌30min混匀后得到悬浊液；
(2)称取4.544g的2-甲基咪唑溶于40mL无水乙醇中，得到溶液；将40mL溶液缓慢加入到步骤(1)得到的35mL悬浊液中，超声搅拌25min后，继续静置陈化20h，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，用无水乙醇和去离子水淋洗固相4次，60℃真空干燥20h后，研磨得到紫色粉末，取紫色粉末0.3g置于管式炉中1000℃进行煅烧，升温速率为2℃/min，保温时间为2h，得到蓝色的CoAl2O4纳米粉体。
实施例5
(1)将1.5g埃洛石分散在60mL无水乙醇中，超声搅拌30min，再加入0.952g的CoCl2·6H2O和1.164g的Co(NO3)2·6H2O，超声搅拌30min混匀后得到悬浊液；
(2)称取6.816g的2-甲基咪唑溶于60mL无水乙醇中，得到溶液；将60mL溶液缓慢加入到步骤(1)得到的60mL悬浊液中，超声搅拌30min后，继续静置陈化22h，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，用无水乙醇和去离子水淋洗固相4次，60℃真空干燥20h后，研磨得到紫色粉末，取紫色粉末0.3g置于管式炉中950℃进行煅烧，升温速率为2℃/min，保温时间为3h，得到蓝色的CoAl2O4纳米粉体。
对比例1
(1)将1.5g埃洛石分散在60mL无水乙醇中，超声搅拌30min，再加入2.328g的Co(NO3)2·6H2O，超声搅拌30min混匀后得到悬浊液；
(2)称取6.56g的2-甲基咪唑溶于60mL无水乙醇中，得到溶液；将60mL溶液缓慢加入到步骤(1)得到的60mL悬浊液中，超声搅拌30min后，继续静置陈化24h，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，用无水乙醇和去离子水淋洗固相4次，60℃真空干燥15h后，研磨得到紫色粉末，取紫色粉末0.3g置于管式炉中400℃进行煅烧，升温速率为2℃/min，保温时间为2h，得到棕色粉体。
对比例2
(1)将1.5g埃洛石分散在60mL无水乙醇中，超声搅拌30min，再加入2.328g的Co(NO3)2·6H2O，超声并搅拌30min混匀后得到悬浊液；
(2)称取6.56g的2-甲基咪唑溶于60mL无水乙醇中，得到溶液；将60mL溶液缓慢加入到步骤(1)得到的60mL悬浊液中，超声搅拌30min后，继续静置陈化24h，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，用无水乙醇和去离子水淋洗固相4次，60℃真空干燥15h后，研磨得到紫色粉末，取紫色粉末0.3g置于管式炉中700℃进行煅烧，升温速率为2℃/min，保温时间为2h，得到灰色粉体。
应用例
对实施例1-3制得的样品进行染料吸附降解测试，具体步骤如下：
首先在烧杯中加入50mL初始浓度50mg/L的甲基橙(MO)溶液模拟染料废水，分别称取0.05g实施例1-3中制备的CoAl2O4纳米粉体及埃洛石分别加入到甲基橙溶液中，超声搅拌使样品在甲基橙溶液中分散均匀，然后加入过硫酸氢钾(PMS)0.015g，反应10min后，通过紫外可见分光光度计测试混合溶液中剩余MO浓度，计算MO的降解率(％)。设置对照组在相同条件下不加入过硫酸氢钾，以测试样品对甲基橙分子(50mg/L MO)的吸附率。结果如表1所示：
表1样品对甲基橙染料分子(50mg/L MO)的吸附率和降解率
通过表1中实施例1的降解率和吸附率数据可见，实施例1的样品同时具有吸附性能和催化降解性能。
通过表1中实施例1～3的降解率数据可见，实施例1～3的样品同时具有良好的催化降解性能。
通过表1中实施例1与埃洛石原料的吸附率对比可见，实施例1的样品同时具有良好的吸附性能。
样品分析
对实施例1-3和对比例制得的样品进行色度测试，测试数据如表2所示。表中，L取值范围是[0,100]，表示从纯黑到纯白；a取值范围是[127,–128]表示从红色到绿色的范围；b取值范围是[127,–128]，表示从黄色到蓝色的范围。
表2实施例和对比例样品的色度值表
通过表2中实施例1和实施例2与对比例1和2的色度值对比可见，随着煅烧温度的升高，CoAl2O4物相逐渐形成，制得的样品颜色也在逐渐变成CoAl2O4标志性的蓝色。
通过表2中实施例1～3与埃洛石原料的色度值对比可见，埃洛石不具备CoAl2O4标志性的蓝色。
Claims (10)
1.一种CoAl2O4纳米粉体的制备方法，其特征在于，包括以下步骤：
(1)将埃洛石分散在无水乙醇中，再加入钴源超声搅拌混匀后得到悬浊液；
(2)将2-甲基咪唑溶于无水乙醇中，得到溶液，将溶液加入到步骤(1)的悬浊液中，超声搅拌，静置陈化，得到分层的混合液；
(3)将分层的混合液抽滤得到固相，清洗、真空干燥、研磨后进行煅烧，得到CoAl2O4纳米粉体；
所述的钴源为Co(NO3)2·6H2O和/或CoCl2·6H2O。
2.根据权利要求1所述的CoAl2O4纳米粉体的制备方法，其特征在于，步骤(1)中，所述的埃洛石、无水乙醇和钴源的加入量比为：1g：30-50mL：1-2g。
3.根据权利要求1所述的CoAl2O4纳米粉体的制备方法，其特征在于，步骤(2)中，所述的2-甲基咪唑与无水乙醇的加入量比为：1-1.5g：10-15mL；所述的溶液与步骤(1)的悬浊液的体积比为1：0.5-2。
4.根据权利要求1所述的CoAl2O4纳米粉体的制备方法，其特征在于，步骤(1)中，所述的埃洛石、无水乙醇和钴源的加入量为：1g：35-40mL：1～2g；步骤(2)中，所述的2-甲基咪唑与无水乙醇的加入量比为：1～1.5g：10-12mL，所述的溶液与步骤(1)的悬浊液的体积比为1：0.5-1。
5.根据权利要求1所述的CoAl2O4纳米粉体的制备方法，其特征在于，步骤(2)中，所述的静置陈化时间为16-26h。
6.根据权利要求1所述的CoAl2O4纳米粉体的制备方法，其特征在于，步骤(3)中，所述的煅烧条件为：温度：750-1200℃，升温速率为1-5℃/min，保温时间为1-3h。
7.根据权利要求1-6任一项所述的CoAl2O4纳米粉体的制备方法制备得到CoAl2O4纳米粉体。
8.根据权利要求7所述的CoAl2O4纳米粉体在处理染料废水中的应用，所述的染料为亚甲基蓝、罗丹明B或甲基橙中的至少一种。
9.根据权利要求8所述的CoAl2O4纳米粉体在处理染料废水中的应用，所述的应用方式为：将CoAl2O4纳米粉体分散到染料废水中，再加入氧化剂后催化降解染料，其中，所述的氧化剂为过硫酸氢钾、双氧水或过硫酸钠中的至少一种；所述的染料浓度为10-100mg/L；所述的CoAl2O4纳米粉体、氧化剂和染料废水的配比为0.2-2g：0.2-3g：1L。
10.根据权利要求7所述的CoAl2O4纳米粉体作为颜料的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760603.1A CN113292086B (zh) | 2021-07-06 | 2021-07-06 | 一种CoAl2O4纳米粉体、制备方法及应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110760603.1A CN113292086B (zh) | 2021-07-06 | 2021-07-06 | 一种CoAl2O4纳米粉体、制备方法及应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113292086A true CN113292086A (zh) | 2021-08-24 |
| CN113292086B CN113292086B (zh) | 2022-04-29 |
Family
ID=77330522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110760603.1A Active CN113292086B (zh) | 2021-07-06 | 2021-07-06 | 一种CoAl2O4纳米粉体、制备方法及应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113292086B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254116A (zh) * | 2022-08-12 | 2022-11-01 | 浙江工业大学 | 改性钴基金属氧化物/埃洛石复合材料及其应用 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830917A (zh) * | 2017-02-22 | 2017-06-13 | 中国科学院兰州化学物理研究所 | 钴铝尖晶石型蓝色纳米陶瓷颜料的合成及在制备太阳能吸光涂层中的应用 |
| CN106925274A (zh) * | 2017-04-25 | 2017-07-07 | 河北工业大学 | 一种负载型金属钴催化剂的制备方法 |
| CN108640172A (zh) * | 2018-05-15 | 2018-10-12 | 武汉工程大学 | 一种含有铝酸钴的水体有机物降解的水处理剂及水处理方法 |
| CN109181369A (zh) * | 2018-10-15 | 2019-01-11 | 中国科学院兰州化学物理研究所 | 微波水热辅助制备高色度钴蓝/黏土矿物杂化颜料的方法 |
| CN109264787A (zh) * | 2018-09-20 | 2019-01-25 | 济南大学 | 一种ZnFe2O4立方块体结构的制备方法及所得产品 |
| CN111218131A (zh) * | 2019-12-12 | 2020-06-02 | 西北永新涂料有限公司 | 一种固相法制备钴蓝/黏土矿物杂化颜料的制备方法 |
-
2021
- 2021-07-06 CN CN202110760603.1A patent/CN113292086B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830917A (zh) * | 2017-02-22 | 2017-06-13 | 中国科学院兰州化学物理研究所 | 钴铝尖晶石型蓝色纳米陶瓷颜料的合成及在制备太阳能吸光涂层中的应用 |
| CN106925274A (zh) * | 2017-04-25 | 2017-07-07 | 河北工业大学 | 一种负载型金属钴催化剂的制备方法 |
| CN108640172A (zh) * | 2018-05-15 | 2018-10-12 | 武汉工程大学 | 一种含有铝酸钴的水体有机物降解的水处理剂及水处理方法 |
| CN109264787A (zh) * | 2018-09-20 | 2019-01-25 | 济南大学 | 一种ZnFe2O4立方块体结构的制备方法及所得产品 |
| CN109181369A (zh) * | 2018-10-15 | 2019-01-11 | 中国科学院兰州化学物理研究所 | 微波水热辅助制备高色度钴蓝/黏土矿物杂化颜料的方法 |
| CN111218131A (zh) * | 2019-12-12 | 2020-06-02 | 西北永新涂料有限公司 | 一种固相法制备钴蓝/黏土矿物杂化颜料的制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 刘会娟等: "尖晶石型纳米CoAl_2O_4粉体的制备及其光催化还原CO_2制甲酸", 《化工新型材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254116A (zh) * | 2022-08-12 | 2022-11-01 | 浙江工业大学 | 改性钴基金属氧化物/埃洛石复合材料及其应用 |
| CN115254116B (zh) * | 2022-08-12 | 2023-09-05 | 浙江工业大学 | 改性钴基金属氧化物/埃洛石复合材料及其应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113292086B (zh) | 2022-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110152641A (zh) | 一种具有光催化效应的非晶光子晶体结构色材料及其制备方法 | |
| CN106423153B (zh) | 掺银二氧化钛纳米管的制备方法及氧气指示剂 | |
| CN107511154B (zh) | 一种海胆状CeO2/Bi2S3复合可见光催化剂及其制备方法 | |
| CN108212192A (zh) | 一种光-芬顿催化剂及其制备方法 | |
| CN108620113B (zh) | 一种氮掺杂的碳-铈复合纳米片的制备方法 | |
| CN113292086B (zh) | 一种CoAl2O4纳米粉体、制备方法及应用 | |
| CN102030358B (zh) | 多孔氧化锌纳米棒及其制备方法 | |
| CN110694627A (zh) | 一种三氧化二铁纳米环光催化剂及其制备方法 | |
| CN112387304A (zh) | 一种磁性分子筛负载TiO2复合光催化剂及其制备方法 | |
| CN111085227A (zh) | CeO2-BiOCl纳米材料及其在光催化方面的应用 | |
| CN105056926A (zh) | 一种新型TiO2/WO3包覆的磁性纳米复合粒子及其制备方法和用途 | |
| CN114602508A (zh) | 具有光催化性能的MnS@ZnS核壳空心球制备及其应用 | |
| CN110841686B (zh) | 一种碳包覆亚氧化钛复合氮化碳复合材料及其制法和应用 | |
| CN1285405C (zh) | 具有可见光活性的氧化锌光催化剂及其制备方法 | |
| CN109926085A (zh) | 一种非晶/结晶型催化剂的制备方法 | |
| CN110743522A (zh) | 一种高指数晶面二氧化钛纳米催化剂及其制备方法 | |
| CN113351246A (zh) | 一种水杨醛敏化纳米二氧化钛光触媒的制备方法 | |
| CN114452996A (zh) | 一种g-C3N4/WO3·H2O/Pd三元复合光催化剂及其制备方法与应用 | |
| CN113441156A (zh) | 一种镂空球型结构Cu2O/Cu9S5光催化材料及其制备方法和应用 | |
| CN113511678A (zh) | 一种m相二氧化钒纳米粉体及其制备方法和制备装置 | |
| CN115845878B (zh) | 一种Ni/CdS催化剂及其制备方法和应用 | |
| CN113247950B (zh) | 一种制备ScVO4粉体的方法 | |
| CN111579515A (zh) | 一种以纳米二氧化铈为模拟氧化酶氧化tmb的方法 | |
| CN104591267A (zh) | 一种多功能型单相烧绿石结构的锡酸钕纳米球复合氧化物材料 | |
| CN111530468A (zh) | 一种ZnFe2O4-TiO2-rGO异质结光催化降解材料及其制法 |
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 |