CN115385713B - 一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用 - Google Patents
一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用 Download PDFInfo
- Publication number
- CN115385713B CN115385713B CN202210939694.XA CN202210939694A CN115385713B CN 115385713 B CN115385713 B CN 115385713B CN 202210939694 A CN202210939694 A CN 202210939694A CN 115385713 B CN115385713 B CN 115385713B
- Authority
- CN
- China
- Prior art keywords
- magnetic
- diatomite
- cobalt
- solution
- diatomite composite
- 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.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000004005 microsphere Substances 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000001354 calcination Methods 0.000 claims abstract description 19
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 18
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 18
- 239000000661 sodium alginate Substances 0.000 claims abstract description 18
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 14
- 229940088710 antibiotic agent Drugs 0.000 claims abstract description 12
- 230000000593 degrading effect Effects 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 57
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000010433 feldspar Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 25
- 239000000725 suspension Substances 0.000 claims description 22
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 230000003115 biocidal effect Effects 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 7
- 229960001180 norfloxacin Drugs 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical group [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 5
- 229910020598 Co Fe Inorganic materials 0.000 claims description 4
- 229910002519 Co-Fe Inorganic materials 0.000 claims description 4
- 229910003321 CoFe Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 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
- 239000004098 Tetracycline Substances 0.000 claims description 2
- 239000012984 antibiotic solution Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 229960000282 metronidazole Drugs 0.000 claims description 2
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 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
- 229960002180 tetracycline Drugs 0.000 claims description 2
- 229930101283 tetracycline Natural products 0.000 claims description 2
- 235000019364 tetracycline Nutrition 0.000 claims description 2
- 150000003522 tetracyclines Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 abstract description 2
- 229940072056 alginate Drugs 0.000 abstract description 2
- 235000010443 alginic acid Nutrition 0.000 abstract description 2
- 229920000615 alginic acid Polymers 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 32
- 238000003756 stirring Methods 0.000 description 28
- 238000005303 weighing Methods 0.000 description 28
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
-
- 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
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/636—Polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compounds Of Iron (AREA)
Abstract
本发明公开一种磁性钴铁合金/硅藻土复合陶粒,将Fe3+、Co2+两种离子取代海藻酸钠中的Na+制备海藻酸钴铁微球,并引入硅藻土作为钴铁颗粒的载体,通过煅烧制备负载钴铁合金的硅藻土陶粒,能够高效地降解水中抗生素且方便通过外加磁场进行磁回收再用。磁性钴铁合金/硅藻土复合陶粒催化降解抗生素的效果好,抗生素的降解率可达到96%。
Description
技术领域
本发明涉及一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用,属于污水处理和环境修复材料制备与应用技术领域。
背景技术
抗生素是水环境中的一类有害污染物,由于其对人体健康和水生生态系统的有害影响,已成为广泛关注的环境问题。目前已有吸附、生物降解等多种技术来去除或降解水中的抗生素污染物,但传统的废水处理过程对于某些抗生素组分的降解效果不好,而且存在某些应用上的缺陷,例如用活性炭吸附的方法存在成本较高、吸附容量低、再生性低等问题。因此,迫切需要开发一种更有效、更经济的方法来去除抗生素。目前,基于硫酸根自由基的高级氧化工艺在降解抗生素方面表现出极大的优势。与传统基于羟基自由基的高级氧化工艺相比,硫酸根自由基具有更高的有机物选择性和效率以及更宽的pH范围内的有效性。过渡金属活化的过硫酸盐系统可以实现在温和的操作条件下快速降解污染物,因此更有希望在水处理领域得到广泛应用。如何制备高效、低成本和可重复应用的过渡金属催化剂,成为硫酸根自由基降解抗生素应用的关键。
Fe、Co、Ni是最常见的磁性元素,且其对过硫酸盐有活化作用,而且在完成后可以通过外部磁铁进行磁回收。同时,考虑到粉末催化剂的难回收性和易团聚性,需要一种有效的方法将磁性金属颗粒装饰在载体上。迄今为止,已经研究了多种载体,其中,具有大量多孔结构的三维结构硅藻土已被探索用于环境应用,如吸附、催化、光电催化剂等,相关研究表明利用天然硅藻土的多孔结构和吸附性能,可以提升对有机污染物的降解性能。
发明内容
本发明的目的是制备一种磁性钴铁合金/硅藻土复合陶粒,将Fe3+、Co2+两种离子取代海藻酸钠中的Na+制备海藻酸钴铁微球,并引入硅藻土作为钴铁颗粒的载体,通过煅烧制备负载钴铁合金的硅藻土陶粒,能够高效地降解水中抗生素且方便通过外加磁场进行磁回收再用。
为了实现上述目的,本发明采用如下技术方案:
本发明提供一种磁性钴铁合金/硅藻土陶粒,所述磁性钴铁合金/硅藻土陶粒的制备方法为:
(1)将海藻酸钠和氢氧化钠溶于水A中,得到溶液A;
所述的海藻酸钠与氢氧化钠的质量比为1:0.2~0.25(优选1:0.2);
(2)向步骤(1)所述的溶液A中加入硅藻土和长石粉,20~30℃下均匀分散(水浴超声),得到悬浊液B;
所述的硅藻土、长石粉与溶液A的质量比为1:0.25~1:6~6.5(优选1:0.25:6.5);硅藻土浓度越高,微球的催化性能越好,长石粉浓度越高,微球机械强度越高。长石粉起陶瓷中助熔剂作用,低于本案限定的量太低或不加不会形成微球或微球结构松散。不加硅藻土形成的球体孔道少,催化性能会变低。
(3)取柠檬酸溶于水C中,加入六水硝酸钴和九水硝酸铁,溶解后,得到澄清溶液C;
所述的柠檬酸、六水硝酸钴与九水硝酸铁的质量比为1:3.5~4:10~11(优选1:3.7:10.3);
(4)将步骤(2)所得的悬浊液B逐滴滴入到步骤(3)所得的溶液C中,静置老化得到微球混合物,所述微球混合物经后处理,得到微球D(深黄色);
所述的静置老化的时间为2~4h(实施例中在室温进行,未专门说明温度,本发明推荐20~40℃内进行);
(5)将步骤(4)所得的微球D煅烧,即得所述的磁性钴铁合金/硅藻土陶粒;
所述的煅烧的条件为950~1150℃、空气气氛下煅烧1.5~3h(优选1000℃煅烧2h),空气气氛下煅烧不需要通气、也不需要额外创造真空或惰性气氛环境,对设备要求低、降解制备成本(铁和钴通常情况下都是容易被氧化的,而此申请中,即使在空气气氛下,也能形成钴铁合金,而不是氧化钴、氧化铁或CoFe2O4)。
上述字母都只是为了区分不同阶段的试剂或产物,方便描述,无其它特殊含义。
进一步,步骤(1)中,所述的海藻酸钠与水A的质量比为1:30~40(优选1:40)。
进一步,步骤(3)中所述柠檬酸与水C的质量比为1:50~60(优选1:50),此范围内,柠檬酸浓度越高,微球机械强度越高,六水硝酸钴浓度越高,微球磁性能和催化性能越高,九水硝酸铁浓度越高,微球磁性能越高。
进一步,步骤(4)中所述后处理为:将所述微球混合物过滤,所得滤饼用去离子水洗涤,烘干,得到所述微球D。更进一步,所述烘干的条件为90~100℃下烘干4~6h。
本发明还提供上述的磁性钴铁合金/硅藻土复合陶粒在降解抗生素中的应用。
所述的应用为:将磁性钴铁合金/硅藻土复合陶粒加入到抗生素水溶液中,加入过硫酸盐进行催化降解,其中,所述的抗生素浓度为10~30mg/L;所述的过硫酸盐为过硫酸氢钾、过硫酸钠或过硫酸钾;所述的磁性钴铁合金/硅藻土复合陶粒、过硫酸盐与抗生素溶液的量比为0.3~5g:0.2~5g:1L。
催化降解的时间一般为10~60min。
优选的,所述的过硫酸盐为过硫酸氢钾。
进一步,所述抗生素为诺氟沙星、四环素或甲硝唑等(优选诺氟沙星)。
与现有技术相比,本发明具有如下有益效果:
(1)本发明所涉及的原料广泛、成本低廉,磁性钴铁合金硅藻土复合陶粒的制备过程简便、高效、安全。
(2)磁性钴铁合金/硅藻土复合陶粒的制备过程中,长石的引入有助于提高材料的机械强度。
(3)磁性钴铁合金/硅藻土复合陶粒催化降解抗生素的效果好,抗生素的降解率可达到96%。
(4)磁性钴铁合金/硅藻土复合陶粒的制备过程中,海藻酸钠的引入有助于形成复合陶粒。
附图说明
图1为本发明实施例1制备的磁性钴铁合金/硅藻土复合陶粒的XRD图;
图2为本发明实施例1制备的磁性钴铁合金/硅藻土复合陶粒的照片;
图3为本发明实施例1制备的磁性钴铁合金/硅藻土复合陶粒的SEM图;
图4为本发明实施例1和对比例1、对比例3制备的样品的磁性能测试对比图;
图5为对比例4和对比例5样品在水中的稳定性能照片;
图6为对比例6样品与长石原料的对比XRD图。
具体实施方式
实施例1:
(1)称取1.25g海藻酸钠和0.25g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取8g硅藻土和2g长石粉,加入到步骤(1)所得的溶液A中,超声后置于25℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于50mL水中,加入3.7g六水硝酸钴和10.3g九水硝酸铁,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2.5h得到微球,经过滤、去离子水洗涤,得到黄色微球,将微球置于100℃下烘干6h,得到微球D;
(5)在1000℃、空气气氛下煅烧2h步骤(4)所得的微球D,即得所述的磁性钴铁合金/硅藻土复合陶粒。
该磁性钴铁合金/硅藻土复合陶粒的XRD图如图1所示,该材料的成分包括有石英、Co3Fe7。
该磁性钴铁合金/硅藻土复合陶粒的照片如图2所示。
该磁性钴铁合金/硅藻土复合陶粒的SEM图如图3所示,图3表明磁性钴铁合金/硅藻土复合陶粒存在硅藻土的微观形貌,且硅藻土表面出现熔融玻化形貌。
实施例2:
(1)称取1.5g海藻酸钠和0.3g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取8g硅藻土和4g长石粉,加入到步骤(1)所得的溶液A中,超声后置于20℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于60mL水中,加入4g六水硝酸钴和10g九水硝酸铁,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化3h得到微球,经过滤、洗涤,得到黄色微球,将微球置于90℃下烘干6h,得到微球D;
(5)在950℃、空气气氛下煅烧3h步骤(4)所得的微球D,即得所述的磁性钴铁合金/硅藻土复合陶粒。
实施例3:
(1)称取1.6g海藻酸钠和0.4g氢氧化钠,超声搅拌溶于48mL水中,得到溶液A;
(2)称取8g硅藻土和3g长石粉,加入到步骤(1)所得的溶液A中,超声后置于30℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于60mL水中,加入3.5g六水硝酸钴和11g九水硝酸铁,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2h得到微球,经过滤、洗涤,得到黄色微球,将微球置于100℃下烘干4h,得到微球D;
(5)在1150℃、空气气氛下煅烧1.5h步骤(4)所得的微球D,即得所述的磁性钴铁合金/硅藻土复合陶粒。
对比例1:
(1)称取1.25g海藻酸钠和0.25g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取8g硅藻土和2g长石粉,加入到步骤(1)所得的溶液A中,超声后置于25℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于50mL水中,加入10.3g九水硝酸铁,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2.5h得到微球,经过滤、洗涤,得到黄色微球,将微球置于100℃下烘干6h,得到微球D;
(5)在1000℃、空气气氛下煅烧2h步骤(4)所得的微球D,即得所述的磁性钴铁合金/硅藻土陶粒。
对比例1与实施例1相比,对比例1的步骤(3)中未添加六水硝酸钴。
对比例1的磁性能如图4b所示,图4b表明添加六水硝酸钴有利与提高复合材料的磁回收性能。
对比例2:
(1)称取1.25g海藻酸钠和0.25g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取10g长石粉,加入到步骤(1)所得的溶液A中,超声后置于25℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于50mL水中,加入3.7g六水硝酸钴和10.3g九水硝酸铁,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2.5h得到微球,经过滤、洗涤,得到黄色微球,将微球置于100℃下烘干6h,得到微球D;
(5)在1000℃、空气气氛下煅烧2h步骤(4)所得的微球D,即得所述的磁性钴铁合金/硅藻土陶粒。
对比例2与实施例1相比,对比例2的步骤(2)中未添加硅藻土。
对比例3:
(1)称取1.25g海藻酸钠和0.25g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取8g硅藻土和2g长石粉,加入到步骤(1)所得的溶液A中,超声后置于25℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于50mL水中,加入3.7g六水硝酸钴,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2.5h得到微球,经过滤、洗涤,得到黄色微球,将微球置于100℃下烘干6h,得到深黄色微球D;
(5)在1000℃、空气气氛下煅烧2h步骤(4)所得的深黄色微球D,即得所述的磁性钴铁合金/硅藻土陶粒。
对比例3与实施例1相比,对比例3的步骤(3)中未添加九水硝酸铁。
对比例3的磁性能如图4c所示,图4c表明添加九水硝酸铁有利与提高复合材料的磁回收性能。
对比例4
(1)称取1.25g海藻酸钠和0.25g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取10g硅藻土,加入到步骤(1)所得的溶液A中,超声后置于25℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于50mL水中,加入3.7g六水硝酸钴和10.3g九水硝酸铁,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2.5h得到微球,经过滤、洗涤得到黄色微球,将微球置于100℃下烘干6h,得到微球D;
(5)在1000℃、空气气氛下煅烧2h步骤(4)所得的微球D,即得所述的磁性钴铁合金/硅藻土陶粒。
对比例4在水中稳定性能如图5a所示,图5a表明不添加长石的复合材料稳定性能较差。对比例5:
(1)称取1.25g海藻酸钠和0.25g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取8g硅藻土和2g长石粉,加入到步骤(1)所得的溶液A中,超声后置于25℃水浴中搅拌分散,得到悬浊液B;
(3)称取3.7g六水硝酸钴和10.3g九水硝酸铁溶于50mL水中,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2.5h得到微球,经过滤、洗涤,得到黄色微球,将微球置于100℃下烘干6h,得到微球D;
(5)在1000℃、空气气氛下煅烧2h步骤(4)所得的微球D,即得所述的磁性钴铁合金/硅藻土陶粒。
对比例5在水中稳定性能如图5b所示,图5b表明不添加柠檬酸的复合材料稳定性能较差。
对比例6:
(1)称取1.25g海藻酸钠和0.25g氢氧化钠,超声搅拌溶于50mL水中,得到溶液A;
(2)称取8g硅藻土和2g长石粉,加入到步骤(1)所得的溶液A中,超声后置于90℃水浴中搅拌分散,得到悬浊液B;
(3)称取1g柠檬酸溶于50mL水中,加入3.7g六水硝酸钴和10.3g九水硝酸铁,搅拌分散,得到澄清溶液C;
(4)将步骤(2)所得的悬浊液B用注射器滴到步骤(3)所得的溶液C中,静置老化2.5h得到微球,经过滤、洗涤,得到黄色微球,将微球置于100℃下烘干6h,得到深黄色微球D;
(5)在1000℃、空气气氛下煅烧2h步骤(4)所得的深黄色微球D,即得所述的磁性钴铁合金/硅藻土复合陶粒。
对比例6与实施例1相比,对比例1的步骤(2)中水浴温度为90℃
对比例6的XRD图如图6所示,该复合材料的主要物相成分包括石英、Fe2SiO4。
应用例:过硫酸盐催化降解实验
在石英试管中加入50mL浓度为20mg/L的诺氟沙星水溶液,称取实施例1~3和对比例1~2制备的样品各0.05g加入到上述诺氟沙星水溶液中,随后搅拌加入0.025g过硫酸氢钾,室温下磁力搅拌60min后取上清液离心后测试吸光度,计算上清液中诺氟沙星浓度,从而得到诺氟沙星降解率。
磁回收实验,称取实施例1~3和对比例1~2制备的样品各0.05g放入烧杯中,加入去离子水,然后烧杯侧端放置磁铁,倒出烧杯中的去离子水,根据烧杯中被磁铁吸附留存在样品重量,计算磁回收率(%)。实验结果如表1所示。
表1实施例1~3及对比例1~2样品的检测分析结果
样品 | 降解率(%) | 磁回收率(%) |
实施例1 | 96 | 98 |
实施例2 | 96 | 93 |
实施例3 | 93 | 90 |
对比例1 | 24 | 10 |
对比例2 | 85 | 80 |
通过表1中实施例1与对比例1的降解率可见,实施例加入六水硝酸钴能提高复合材料的催化降解性能。
通过表1中实施例1与对比例2的降解率可见,实施例加入硅藻土能提高复合材料的催化降解性能。
Claims (10)
1.一种磁性钴铁合金/硅藻土复合陶粒,其特征在于所述磁性钴铁合金/硅藻土复合陶粒的制备方法为:
(1)将海藻酸钠和氢氧化钠溶于水A中,得到溶液A;
所述的海藻酸钠与氢氧化钠的质量比为1:0.2~0.25;
(2)向步骤(1)所述的溶液A中加入硅藻土和长石粉,20~30℃下均匀分散,得到悬浊液B;
所述的硅藻土、长石粉与溶液A的质量比为1:0.25~1:6~6.5;
(3)取柠檬酸溶于水C中,加入六水硝酸钴和九水硝酸铁,溶解后,得到溶液C;
所述的柠檬酸、六水硝酸钴与九水硝酸铁的质量比为1:3.5~4:10~11;
(4)将步骤(2)所得的悬浊液B逐滴滴入到步骤(3)所得的溶液C中,静置老化得到微球混合物,所述微球混合物经后处理,得到微球D;
所述的静置老化的时间为2~4h;
(5)将步骤(4)所得的微球D煅烧,即得所述的磁性钴铁合金/硅藻土复合陶粒;
所述的煅烧的条件为950~1150℃、空气气氛下煅烧1.5~3h。
2.如权利要求1所述的磁性钴铁合金/硅藻土复合陶粒,其特征在于:步骤(1)中,所述的海藻酸钠与水A的质量比为1:30~40。
3.如权利要求1所述的磁性钴铁合金/硅藻土复合陶粒,其特征在于:步骤(2)中所述的硅藻土、长石粉与溶液A的质量比为1:0.25:6.5。
4.如权利要求1所述的磁性钴铁合金/硅藻土复合陶粒,其特征在于:步骤(3)中所述柠檬酸与水C的质量比为1:50~60。
5.如权利要求1所述的磁性钴铁合金/硅藻土复合陶粒,其特征在于:步骤(3)中所述的柠檬酸、六水硝酸钴与九水硝酸铁的质量比为1:3.7:10.3。
6.如权利要求1所述的磁性钴铁合金/硅藻土复合陶粒,其特征在于:步骤(4)中所述后处理为:将所述微球混合物过滤,所得滤饼用去离子水洗涤,烘干,得到所述微球D。
7.如权利要求6所述的磁性钴铁合金/硅藻土复合陶粒,其特征在于:所述烘干的条件为90~100℃下烘干4~6h。
8.如权利要求1所述的磁性钴铁合金/硅藻土复合陶粒在降解抗生素中的应用,
所述的应用为:将磁性钴铁合金/硅藻土复合陶粒加入到抗生素水溶液中,加入过硫酸盐进行催化降解,其中,所述的抗生素浓度为10~30mg/L;所述的过硫酸盐为过硫酸氢钾、过硫酸钠或过硫酸钾;所述的磁性钴铁合金/硅藻土复合陶粒、过硫酸盐与抗生素溶液的量比为0.3~5g:0.2~5g:1L。
9.如权利要求8所述的应用,其特征在于:所述的过硫酸盐为过硫酸氢钾。
10.如权利要求8所述的应用,其特征在于:所述抗生素为诺氟沙星、四环素或甲硝唑。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210939694.XA CN115385713B (zh) | 2022-08-05 | 2022-08-05 | 一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210939694.XA CN115385713B (zh) | 2022-08-05 | 2022-08-05 | 一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115385713A CN115385713A (zh) | 2022-11-25 |
CN115385713B true CN115385713B (zh) | 2023-03-31 |
Family
ID=84118713
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210939694.XA Active CN115385713B (zh) | 2022-08-05 | 2022-08-05 | 一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115385713B (zh) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101716488A (zh) * | 2009-12-07 | 2010-06-02 | 浙江工业大学 | 一种硅藻土吸附材料的制备方法 |
CN105481035A (zh) * | 2016-01-26 | 2016-04-13 | 张锐 | 一种高效污水处理剂及其制备方法 |
CN109110907A (zh) * | 2018-08-28 | 2019-01-01 | 浙江正洁环境科技有限公司 | 磁性生物载体材料 |
CN109896639A (zh) * | 2019-04-03 | 2019-06-18 | 深圳市清研环境科技有限公司 | 耐重金属的菌剂、制备方法及其在污水处理中的应用 |
CN111438180A (zh) * | 2019-01-16 | 2020-07-24 | 四川千路环保科技有限责任公司 | 一种土壤修复颗粒剂及其制备方法 |
CN112717893A (zh) * | 2020-12-02 | 2021-04-30 | 青岛科技大学 | 一种污水处理剂及其在重金属废水中的应用 |
CN113083174A (zh) * | 2021-03-17 | 2021-07-09 | 武汉工程大学 | 一种纳米银/硅藻土/海藻酸钙复合抗菌水凝胶微球的制备方法 |
CN114735795A (zh) * | 2022-04-29 | 2022-07-12 | 扬州工业职业技术学院 | 一种海藻酸钠-硅藻土复合磁性絮凝剂及其制备方法 |
CN114751597A (zh) * | 2022-04-29 | 2022-07-15 | 扬州工业职业技术学院 | 一种基于复合磁性絮凝剂的水处理工艺 |
-
2022
- 2022-08-05 CN CN202210939694.XA patent/CN115385713B/zh active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101716488A (zh) * | 2009-12-07 | 2010-06-02 | 浙江工业大学 | 一种硅藻土吸附材料的制备方法 |
CN105481035A (zh) * | 2016-01-26 | 2016-04-13 | 张锐 | 一种高效污水处理剂及其制备方法 |
CN109110907A (zh) * | 2018-08-28 | 2019-01-01 | 浙江正洁环境科技有限公司 | 磁性生物载体材料 |
CN111438180A (zh) * | 2019-01-16 | 2020-07-24 | 四川千路环保科技有限责任公司 | 一种土壤修复颗粒剂及其制备方法 |
CN109896639A (zh) * | 2019-04-03 | 2019-06-18 | 深圳市清研环境科技有限公司 | 耐重金属的菌剂、制备方法及其在污水处理中的应用 |
CN112717893A (zh) * | 2020-12-02 | 2021-04-30 | 青岛科技大学 | 一种污水处理剂及其在重金属废水中的应用 |
CN113083174A (zh) * | 2021-03-17 | 2021-07-09 | 武汉工程大学 | 一种纳米银/硅藻土/海藻酸钙复合抗菌水凝胶微球的制备方法 |
CN114735795A (zh) * | 2022-04-29 | 2022-07-12 | 扬州工业职业技术学院 | 一种海藻酸钠-硅藻土复合磁性絮凝剂及其制备方法 |
CN114751597A (zh) * | 2022-04-29 | 2022-07-15 | 扬州工业职业技术学院 | 一种基于复合磁性絮凝剂的水处理工艺 |
Also Published As
Publication number | Publication date |
---|---|
CN115385713A (zh) | 2022-11-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110732323B (zh) | 催化挥发性有机化合物氧化的α-MnO2催化剂的制备方法 | |
CN111744476B (zh) | 一种赤泥碳基催化剂的制备方法及应用 | |
CN112156752B (zh) | 吸附性可再生的改性活性炭及其在废水处理中的应用 | |
CN107973352B (zh) | 一种铁/铜双金属氧化物降解四环素的方法 | |
CN110694691A (zh) | 一种光芬顿催化剂及制备方法与应用方法 | |
CN110694685B (zh) | 一种由超薄纳米片组装的锰铁钴类普鲁士蓝和锰氧化物复合纳米盒的制备方法及应用 | |
CN114100634B (zh) | 一种磁性多组分铁碳复合类芬顿催化剂的制备方法、产品及应用 | |
CN113457695B (zh) | 一种锰镍铜基水处理催化剂及其制备方法和应用 | |
CN111617770A (zh) | 一种银量子点磁性氧化锌光催化材料及制备方法 | |
CN106892482A (zh) | 一种黑色TiO2纳米材料及其制备方法与应用 | |
WO2012109846A1 (zh) | 一种用于肼降解催化剂的制备和应用方法 | |
CN113198508A (zh) | 一种负载型铁-氮-碳复合材料及其在处理染料废水中的应用 | |
CN111905751B (zh) | 一种利用高温淬火改性LaCoO3-δ材料催化降解水体中苯酚的方法 | |
CN115318300A (zh) | 具有催化和特异性磷吸附性能的磁性生物炭的制备方法 | |
CN110314685B (zh) | 一种用于甲苯低温催化氧化的核壳结构催化剂制备方法 | |
CN111905702A (zh) | 吸附去除水中重金属的负载纳米零价铁多孔颗粒滤料的制备方法 | |
CN113976123A (zh) | 一种氧化铝/铝基尖晶石复合材料及其制备方法与催化应用 | |
CN115385713B (zh) | 一种磁性钴铁合金/硅藻土复合陶粒及其制备方法与应用 | |
CN112547087A (zh) | 一种铁/猛酸镧催化剂的制备方法及应用 | |
CN112110744A (zh) | 一种磁性多孔陶瓷吸附材料及其制备方法和应用 | |
CN111151251A (zh) | 一种Fe-Ni-Co复合类芬顿催化剂及制备方法 | |
CN114870870B (zh) | 协同处理MO和Cr(Ⅵ)污染的磁性环境净化材料及其制备方法 | |
CN111318289B (zh) | 一种Bi-Bi5+/BiOBr自掺杂光催化剂及其制备方法 | |
CN112221512B (zh) | 催化氧化nh4+的活性炭基锰铁氧化膜的制备方法、活性炭基锰铁氧化膜及脱氨应用 | |
CN114558554A (zh) | 一种具有异质结的复合材料其制备和用途及降低水体中总磷浓度的方法 |
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 |