CN112547078B - 一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法 - Google Patents
一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法 Download PDFInfo
- Publication number
- CN112547078B CN112547078B CN202011408378.7A CN202011408378A CN112547078B CN 112547078 B CN112547078 B CN 112547078B CN 202011408378 A CN202011408378 A CN 202011408378A CN 112547078 B CN112547078 B CN 112547078B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- bismuth
- sillenite
- nano
- scale
- 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
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000010941 cobalt Substances 0.000 title claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004729 solvothermal method Methods 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001621 bismuth Chemical class 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052851 sillimanite Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 31
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 abstract 1
- 150000002989 phenols Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- 239000000047 product Substances 0.000 description 10
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229960000907 methylthioninium chloride Drugs 0.000 description 6
- 230000000052 comparative effect Effects 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
- 238000003756 stirring Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910002115 bismuth titanate Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920006389 polyphenyl polymer Polymers 0.000 description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 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 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910002116 Bi12TiO20 Inorganic materials 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- QWAUSPYZWIWZPA-UHFFFAOYSA-N [Co].[Bi] Chemical compound [Co].[Bi] QWAUSPYZWIWZPA-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/39—Photocatalytic 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- C01G51/40—Cobaltates
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法，属于环境科学与无机材料制备领域。本发明采用溶剂热法制备一种纳米级钴基软铋矿高效光催化剂Bi25CoO40。本发明利用铋盐和钴盐在特定的碱液体系中沉淀，然后在一定温度与适宜时间下进行溶剂热反应，制得纳米级钴基软铋矿高效光催化。本发明方法成本低、工艺简单、易于控制，为其他类似结构的纳米级软铋矿光催化剂制备提供借鉴；所得催化剂有颗粒粒径小、活性高的特点，对染料和酚类等水中有机污染物表现出良好的可见光催化降解活性，在可见光有机污染物降解领域拥有广泛的潜在应用前景。
Description
技术领域
本发明涉及一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法，属于环境科学与无机材料制备领域。
背景技术
光催化作为高效和低能耗的环境治理技术，近年来得到广泛的研究。半导体光催化剂的性能受到催化剂颗粒粒径的影响，颗粒粒径小则具有相对较大的比表面积和较短的光生电子传输路径，有利于污染物的扩散和光生电子较快转移至催化剂表面进行反应。将新型、大尺寸光催化剂纳米化，是目前光催化研究的热点方向。
铋盐是无机半导体光催化剂中较常见的一类。软铋矿是近年来刚发现的铋盐光催化剂的一种，对其光催化性能的研究具有较大意义。目前软铋矿光催化剂的制备多采用水热合成、高温固相反应等方法，颗粒粒径多处在微米级，其可见光活性仍具有较大的提升空间。例如中国专利CN105129850A提出了一种水热法制备钒酸铋软铋矿的方法，但钒酸铋软铋矿的颗粒粒径为1-2μm，活性较差，添加硼氢化钠情况下，80min分钟内还未完全降解4-氨基苯酚。中国专利CN101147859A提出一种溶剂热法合成钛酸铋软铋矿的方法，虽使用溶剂热方法，但颗粒粒径为5-20μm，粒径仍不能有效减小。美国专利US20110155971A1提出一种水热法合成钛酸铋软铋矿的方法，其粒径虽处在纳米级，但钛酸铋禁带宽度大于3.0eV，不能有效利用太阳光。印度专利IN201841028670A提出一种水热法合成铁酸铋软铋矿的方法，其铁位缺陷较多，且颗粒粒径为1mm。除已发表的专利外，目前文献上也多采用水热反应或高温固相方法合成新型软铋矿光催化剂(比如：Wang Pei et al.Ultrason.Sonochem.38,2017,289–297，Zhang Lei et al.CrystEngComm.2015,17,6527-6537，Hu Jin Song etal.RSC Adv.2015,5,78457)，同样普遍存在粒径过大、可见光活性低的问题。
发明内容
为了解决上述问题，本发明首次提出一种新型溶剂发制备纳米级钴基软铋矿Bi25CoO40光催化剂的方法，所得催化剂的颗粒粒径小、降解污染物活性好，有很好的环境化学应用前景。
本发明的第一个目的是提供一种制备纳米级钴基软铋矿Bi25CoO40光催化剂的方法，所述方法包括如下步骤：
(1)利用强碱溶于溶剂中，配置1～3mol/L的碱液A；
(2)将铋盐和钴盐加入到碱液A中，形成固体沉淀，分离、收集固体沉淀；然后置于反应容器中进行溶剂热反应，反应结束后，固液分离，收集固体沉淀，洗涤、干燥。
在本发明的一种实施方式中，所述步骤(1)溶剂为乙醇，或者水和乙醇的混合体系。
在本发明的一种实施方式中，所述步骤(1)溶剂中水和乙醇的体积比为(0:30)～(22.5:7.5)。
在本发明的一种实施方式中，所述步骤(1)中强碱包括如下任意一种或多种：氢氧化钠、氢氧化钾。
在本发明的一种实施方式中，所述步骤(2)中铋盐与钴盐中Bi3+与Co2+的摩尔比为(1.2～2.5)：0.1。
在本发明的一种实施方式中，所述步骤(2)中铋盐相对碱液A的摩尔浓度为0.04～0.1mol/L；优选0.04～0.083mol/L。
在本发明的一种实施方式中，所述步骤(2)中铋盐选自如下任意一种或多种：硝酸铋、氯化铋、醋酸铋。
在本发明的一种实施方式中，所述步骤(2)中钴盐选自如下任意一种或多种：硝酸钴、六水合硝酸钴、醋酸钴、氯化钴。
在本发明的一种实施方式中，所述步骤(2)中形成固体沉淀的过程是在10-40℃下进行的。
在本发明的一种实施方式中，所述步骤(2)中溶剂热反应中的溶剂同步骤(1)中的溶剂。
在本发明的一种实施方式中，所述步骤(2)中溶剂热反应的反应温度为100℃～180℃。
在本发明的一种实施方式中，所述步骤(2)中溶剂热反应的反应时间为6～48h。
在本发明的一种实施方式中，所述步骤(2)中洗涤是将固体沉淀洗涤至中性。
在本发明的一种实施方式中，所述步骤(2)中干燥是采用60℃鼓风烘箱干燥。
在本发明的一种实施方式中，上述纳米级钴基软铋矿高效光催化剂Bi25CoO40的制备方法具体包括如下步骤：
(1)碱溶液配制：用30ml去离子水和乙醇混合溶液将0.03～0.09mol强碱溶解得到碱液A；碱液A浓度为1～3mol/L；
(2)铋-钴混合盐溶液配制：将1.2～2.5mmol铋盐和0.1mmol钴盐加入碱液A中，得到混合溶液B；溶液B搅拌30min后，将得到的黄褐色沉淀转移至对位聚苯(PPL)内衬的反应釜内，100℃～180℃溶剂热反应6～48h；离心、用去离子水和乙醇洗涤步骤3得到的固体颗粒至pH为7，转移至60℃鼓风烘箱干燥即得产物。
本发明的第二个目的是利用上述方法提供一种纳米级钴基软铋矿高效光催化剂Bi25CoO40。
在本发明的一种实施方式中，该催化剂的颗粒粒径为80-300nm。
本发明的第三个目的是将上述的纳米级钴基软铋矿高效光催化剂Bi25CoO40应用于降解有机污染物中。
有益效果：
与现有技术相比，本发明提出的纳米级钴基软铋矿高效光催化剂Bi25CoO40具有如下优点：本发明合成的光催化剂具有颗粒粒径小、活性高等优点。本发明的纳米级钴基软铋矿高效光催化剂Bi25CoO40颗粒粒径显著小于已有报道的软铋矿光催化剂，如Bi25VO40(1-2μm)、Bi12TiO20(1-1.8μm)等。本发明的纳米级光催化剂在可见光下3h能完全降解MB，此外对无色有机污染物如苯酚、4-氯苯酚等同样表现出一定的降解活性。
本发明提出制备钴基软铋矿高效光催化剂Bi25CoO40的方法是溶剂热法，相较于水热和高温固相反应，本发明的方法所需温度较低，能很好地控制所制得催化剂的形貌和颗粒粒径大小，避免颗粒的团聚。本发明为其它类似纳米级软铋矿光催化剂的制备提供了借鉴。
附图说明
图1为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40的X射线衍射谱图；
图2为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40的扫描电子显微镜图像；
图3为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40的紫外-可见光漫反射吸收光谱；(其中对比实验微米颗粒的制备采用高温水热法，参考文献ZhangLei et al.CrystEngComm.2015,17,6527-6537。)
图4为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40可见光催化降解亚甲基蓝曲线；(其中对比实验微米颗粒的制备采用高温水热法，参考文献ZhangLei et al.CrystEngComm.2015,17,6527-6537。)
图5为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40对亚甲基蓝、罗丹明B(2×10-5mol/L、100ml)、4-氯苯酚(5ppm、50ml)、苯酚(5ppm、50ml)染料的去除率(统一采用300W氙灯，酚类检测采用超高效液相色谱)。
具体实施方式
实施例1：
将0.03mol NaOH溶于15ml去离子水和15ml乙醇混合溶液中(即体积比1:1，浓度1M)，加入2.5mmol的Bi(NO3)3·5H2O(即0.083M)和0.1mmol的Co(NO3)2·6H2O(即0.0033M)，搅拌30min，将黄褐色沉淀转移至50mL对位聚苯(PPL)内衬的反应釜内(溶剂1:1水：乙醇)，在180℃溶剂热6h，冷却至室温，产物离心，用去离子水和乙醇洗涤至pH为7，在60℃烘干，即得到产物Bi25CoO40。
实施例2：
将0.06mol NaOH溶于22.5ml去离子水和7.5ml乙醇混合溶液中(即体积比3:1，浓度2M)，加入1.2mmol的(CH3CO2)3Bi(即0.04M)和0.1mmol的CoCl2(即0.0033M)，搅拌30min，将黄褐色沉淀转移至50mL对位聚苯(PPL)内衬的反应釜内(溶剂3:1水：乙醇)，在150℃溶剂热24h，冷却至室温，产物离心，用去离子水和乙醇洗涤至pH为7，在60℃烘干，即得到产物Bi25CoO40。
实施例3：
将0.09mol KOH溶于30ml乙醇中(浓度3M)，加入1.6mmol的BiCl3(即0.053M)和0.1mmol的C4H6CoO4(即0.0033M)，搅拌30min，将黄褐色沉淀转移至50mL对位聚苯(PPL)内衬的反应釜内(溶剂为乙醇)，在100℃溶剂热48h，冷却至室温，产物离心，用去离子水和乙醇洗涤至pH为7，在60℃烘干，即得到产物Bi25CoO40。
对实施例1-3所得催化剂进行结构表征：
图1为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40的X射线衍射谱图，X射线衍射是分析样品的晶型和结晶性的技术。由X射线衍射结果可以看出，所制得催化剂Bi25CoO40结晶性好，无不纯相，对应于PDF No.39-0871。
图2为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40的扫描电子显微镜图像，扫描电子显微镜是分析催化剂形貌和颗粒粒径大小的技术。由扫描结果可以看出，催化剂颗粒粒径处于80-300nm之间，呈现出块状结构，并且颗粒分散性较高。
图3为实施例1制备的宽光谱响应软铋矿基纳米级高效光催化剂Bi25CoO40的紫外-可见光漫反射吸收光谱，漫反射图谱是分析物质吸光特性。其中，对比实验微米颗粒的制备采用高温水热法，参考文献Zhang Lei et al.CrystEngComm.2015,17,6527-6537。由图3中结果可以看出，相较于微米级颗粒，纳米级颗粒的吸光范围发生明显的向低波数移动(蓝移)趋势，原因在于纳米颗粒的量子尺寸效应的影响，尺寸下降带隙变宽，被电子占据分子轨道能级与未被占据分子轨道能级之间的宽度随颗粒直径减小而增大。
实施例2-3所得催化剂的结构表征结果与实施例1基本相同。
实施例4
以亚甲基蓝为典型污染物代表：准确称取0.05g实施例1所得催化剂粉末，将其加入到100ml浓度为2×10-5mol/L的亚甲基蓝水溶液中，超声波作用下制成悬浮液，黑暗下搅拌处理30min，达到吸附平衡，用300W氙灯作为光源，420nm截止滤光片滤除紫外光，可见光照射下进行反应。开始前1h每30min取4ml的样品，此后1h取4ml样品，离心去除催化剂，用紫外分光光度计分析剩余溶液的亚甲基蓝浓度。
采用相同的方法，将2×10-5mol/L的亚甲基蓝分别替换为罗丹明B(2×10-5mol/L、100ml)、4-氯苯酚(5ppm、50ml)、苯酚(5ppm、50ml)，测定相应目标污染物的去除效果。
结果如图4、5所示，具体结果见表1。
表1该光催化剂以及微米颗粒对四种目标污染物的降解去除效果
其中，去除率的含义为：C/Co(C表示取点时样品浓度；Co表示污染物初始浓度)
实施例2和3的降解结果与实施例1基本相同。
对比例1探究碱液浓度对催化剂的影响
参照实施例1，将NaOH的浓度分别替换为0.1M、5M，其他条件不变，制备不出相应的复合光催化剂。在0.1M NaOH浓度下，存在较多的CoO杂相；在5M NaOH浓度下铋盐容易被乙醇还原为铋单质。
参照实施例4中的应用过程，结果发现：在同等条件下降解MB，0.1M和5M的去除率分别为15％和12％。
对比例2
参照实施例1，将Co(NO3)2·6H2O的替换等摩尔量的为克钛酸四丁酯(Ti(OC4H9)4)，其他条件不变，制得相应的钛酸铋复合氧化物光催化剂。
所得催化剂虽然其颗粒尺寸在纳米级50－100nm，但其禁带宽度大于3eV，因而不能对可见光有响应。
参照实施例4中的应用过程，结果发现：在同等可见光条件下降解MB，去除率为0％，没有光催化活性。
Claims (5)
1.一种制备纳米级钴基软铋矿Bi25CoO40光催化剂的方法，其特征在于，所述方法包括如下步骤：
(1)将强碱溶于溶剂中，配置1～3mol/L的碱液A；所述溶剂为水和乙醇的混合体系；其中，水与乙醇的体积比为(0:30)～(22.5:7.5)；
(2)将铋盐和钴盐按照Bi3+与Co2+摩尔比为(1.2～2.5)：0.1加入到碱液A中，形成固体沉淀，分离、收集固体沉淀；然后置于反应容器中100℃～180℃下进行溶剂热反应6～48h，反应结束后，固液分离，收集固体沉淀，洗涤、干燥；其中铋盐选自如下任意一种或多种：硝酸铋、氯化铋、醋酸铋。
2.根据权利要求1所述的方法，其特征在于，所述步骤(2)中铋盐相对碱液A的摩尔浓度为0.04～0.1mol/L。
3.根据权利要求1所述的方法，其特征在于，所述步骤(2)中钴盐选自如下任意一种或多种：硝酸钴、六水合硝酸钴、醋酸钴、氯化钴。
4.权利要求1-3任一项所述方法制得的一种纳米级钴基软铋矿高效光催化剂Bi25CoO40。
5.权利要求4所述的纳米级钴基软铋矿高效光催化剂Bi25CoO40在降解有机污染物中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011408378.7A CN112547078B (zh) | 2020-12-03 | 2020-12-03 | 一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011408378.7A CN112547078B (zh) | 2020-12-03 | 2020-12-03 | 一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112547078A CN112547078A (zh) | 2021-03-26 |
| CN112547078B true CN112547078B (zh) | 2022-02-01 |
Family
ID=75048275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011408378.7A Active CN112547078B (zh) | 2020-12-03 | 2020-12-03 | 一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112547078B (zh) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582118B (zh) * | 2022-09-15 | 2023-08-08 | 江南大学 | 铬掺杂三氧化二铋软铋矿纳米片的制备方法及在光催化co2还原中的应用 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723467A (zh) * | 2009-12-22 | 2010-06-09 | 上海大学 | 水热法合成软铋矿相Bi25FeO40的方法 |
| CN102826608A (zh) * | 2012-08-24 | 2012-12-19 | 华南理工大学 | 一种溶剂热法制备铁酸铋粉体的方法 |
| CN105129850A (zh) * | 2015-08-27 | 2015-12-09 | 安徽理工大学 | 一种软铋矿相Bi25VO40立方块及其合成方法 |
| CN106587162A (zh) * | 2016-10-31 | 2017-04-26 | 宝鸡文理学院 | 一种常压水相法制备软铋矿Bi25FeO40纳米粉体的方法 |
| CN108483612A (zh) * | 2018-03-21 | 2018-09-04 | 四川大学 | 一种利用还原性有机弱酸强化铁酸铋光催化还原六价铬的方法 |
| CN108546992A (zh) * | 2018-04-11 | 2018-09-18 | 福州大学 | 一种钴铁掺杂的软铋矿型磁光晶体及其制备方法与应用 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SK288485B6 (sk) * | 2014-10-09 | 2017-08-02 | Slovenská Technická Univerzita V Bratislave | Mäkká spájka na báze bizmut-striebro s prídavkom lantánu |
-
2020
- 2020-12-03 CN CN202011408378.7A patent/CN112547078B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723467A (zh) * | 2009-12-22 | 2010-06-09 | 上海大学 | 水热法合成软铋矿相Bi25FeO40的方法 |
| CN102826608A (zh) * | 2012-08-24 | 2012-12-19 | 华南理工大学 | 一种溶剂热法制备铁酸铋粉体的方法 |
| CN105129850A (zh) * | 2015-08-27 | 2015-12-09 | 安徽理工大学 | 一种软铋矿相Bi25VO40立方块及其合成方法 |
| CN106587162A (zh) * | 2016-10-31 | 2017-04-26 | 宝鸡文理学院 | 一种常压水相法制备软铋矿Bi25FeO40纳米粉体的方法 |
| CN108483612A (zh) * | 2018-03-21 | 2018-09-04 | 四川大学 | 一种利用还原性有机弱酸强化铁酸铋光催化还原六价铬的方法 |
| CN108546992A (zh) * | 2018-04-11 | 2018-09-18 | 福州大学 | 一种钴铁掺杂的软铋矿型磁光晶体及其制备方法与应用 |
Non-Patent Citations (2)
| Title |
|---|
| O. Jankovsky＇et al..Phase diagram of the pseudobinary system Bi-Co–O.《Journal of the European Ceramic Society》.2013,第33卷第2699-2704页. * |
| 软铋矿基微纳米材料的设计合成及其在光催化中的应用;曹秀军等;《化学进展》;20191219;第32卷;第262-273页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112547078A (zh) | 2021-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tong et al. | Convenient fabrication of BiOBr ultrathin nanosheets with rich oxygen vacancies for photocatalytic selective oxidation of secondary amines | |
| Bafaqeer et al. | Well-designed ZnV2O6/g-C3N4 2D/2D nanosheets heterojunction with faster charges separation via pCN as mediator towards enhanced photocatalytic reduction of CO2 to fuels | |
| CN111672497B (zh) | 一种原位合成二氧化铈/石墨相氮化碳复合光催化材料的方法 | |
| Liu et al. | Solvothermal fabrication of Bi2MoO6 nanocrystals with tunable oxygen vacancies and excellent photocatalytic oxidation performance in quinoline production and antibiotics degradation | |
| Labib | Preparation, characterization and photocatalytic properties of doped and undoped Bi2O3 | |
| Sun et al. | Synthesizing and comparing the photocatalytic properties of high surface area rutile and anatase titania nanoparticles | |
| JIA et al. | Preparation and photocatalytic performance of porous ZnO microrods loaded with Ag | |
| CN101940933B (zh) | CdS量子点敏化Zn1-xCdxS光解水制氢可见光光催化剂制备方法 | |
| Bajorowicz et al. | Preparation of CdS and Bi 2 S 3 quantum dots co-decorated perovskite-type KNbO 3 ternary heterostructure with improved visible light photocatalytic activity and stability for phenol degradation | |
| Shahini et al. | Immobilization of plasmonic Ag-Au NPs on the TiO2 nanofibers as an efficient visible-light photocatalyst | |
| CN108855131B (zh) | 一种银-镍双金属掺杂二氧化钛纳米复合材料的制备和应用 | |
| Wang et al. | Plasmon mediated Fe–O in an octahedral site of cuprospinel by Cu NPs for photocatalytic hydrogen evolution | |
| CN103055903B (zh) | 能带可调型BiOI-AgI球形固溶体可见光光催化材料的制备方法 | |
| Chen et al. | Plasmonic Ag@ SiO2 core/shell structure modified g-C3N4 with enhanced visible light photocatalytic activity | |
| Sanjini et al. | Effect of precursors on the synthesis of CuO nanoparticles under microwave for photocatalytic activity towards methylene blue and rhodamine B dyes | |
| CN108452787B (zh) | 一种高可见光活性的二氧化钛空心微球及其制备方法和应用 | |
| Xiao et al. | Vis-NIR responsive Bi24O31Br10 and corresponding composite with up-conversion phosphor towards efficient photocatalytic oxidation | |
| Segovia-Guzmán et al. | Green Cu2O/TiO2 heterojunction for glycerol photoreforming | |
| CN111085227A (zh) | CeO2-BiOCl纳米材料及其在光催化方面的应用 | |
| Wang et al. | Fabrication of monodispersed plasmonic photocatalysts on activated carbon with the carbon source and reduction property of sewage sludge | |
| Wang et al. | Ag doped Bi 2 O 2.33 microrods: photocatalytic activity investigation | |
| CN112547078B (zh) | 一种低温溶剂热制备纳米级钴基软铋矿高效光催化剂的方法 | |
| Liu et al. | Biomass assisted synthesis of 3D hierarchical structure BiOX (X Cl, Br)-(CMC) with enhanced photocatalytic activity | |
| CN107008337B (zh) | 一种非化学计量比铋酸铜纳米材料及其制备方法和应用 | |
| Yang et al. | ZnO hierarchical structures with tunable oxygen vacancies for high performance in photocatalytic degradation of phenol |
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 |