CN105731514B - Cubic nano CeO2 and application thereof in degrading o-aminophenol - Google Patents
Cubic nano CeO2 and application thereof in degrading o-aminophenol Download PDFInfo
- Publication number
- CN105731514B CN105731514B CN201610057876.9A CN201610057876A CN105731514B CN 105731514 B CN105731514 B CN 105731514B CN 201610057876 A CN201610057876 A CN 201610057876A CN 105731514 B CN105731514 B CN 105731514B
- Authority
- CN
- China
- Prior art keywords
- aminophenol
- ceo
- degradation rate
- degrading
- ceo2
- 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.)
- Expired - Fee Related
Links
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims description 46
- 230000000593 degrading effect Effects 0.000 title abstract description 9
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title description 28
- 230000010355 oscillation Effects 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 230000015556 catabolic process Effects 0.000 abstract description 38
- 238000006731 degradation reaction Methods 0.000 abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 229910001868 water Inorganic materials 0.000 abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 13
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 13
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 abstract description 12
- 239000004202 carbamide Substances 0.000 abstract description 12
- 239000002243 precursor Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 238000004925 denaturation Methods 0.000 abstract description 2
- 230000036425 denaturation Effects 0.000 abstract description 2
- 102000004316 Oxidoreductases Human genes 0.000 abstract 4
- 108090000854 Oxidoreductases Proteins 0.000 abstract 4
- 229910004631 Ce(NO3)3.6H2O Inorganic materials 0.000 abstract 1
- 230000003278 mimic effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 18
- 238000002835 absorbance Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 11
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 9
- 108090000790 Enzymes Proteins 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 238000004088 simulation Methods 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000009514 concussion Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 102000003992 Peroxidases Human genes 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 108700020962 Peroxidase Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003593 chromogenic compound Substances 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000007491 morphometric analysis Methods 0.000 description 1
- 238000011527 multiparameter analysis Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 230000036186 satiety Effects 0.000 description 1
- 235000019627 satiety Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
-
- 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
-
- 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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of water treatment, and particularly relates to a cubic nano cerium oxide (CeO2) and application thereof as a mimic oxidase in degrading o-aminophenol. In the CeO2 preparation process, Ce(NO3)3.6H2O is used as a cerium source, urea is used as a precipitant, and CTAB (cetyltrimethylammonium bromide) is used as a surfactant. A precursor is firstly prepared, and the precursor is calcined to obtain the CeO2. Compared with the natural oxidase, the cerium oxide provided by the invention has the advantages of high stability, low denaturation tendency, wide application range and high reutilization ratio, is easy for storage and transportation, also has high-efficiency oxidase catalytic activity, and thus, can well substitute the existing natural oxidase. When the cerium oxide provided by the invention is used in degrading o-aminophenol, the maximum degradation rate can reach 70% or above.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to a kind of cubic nanometer ceria（CeO2）And its as mould
Intend application of the oxidizing ferment in o-aminophenol degraded.
Background technology
Enzyme is efficient biocatalyst, almost participates in biological all of reaction in vivo.Enzyme have high efficiency, selectivity,
The characteristics of diversity and mildness.Native enzyme has great reality in medicine, chemical industry, food processing, environmental protection and agricultural
Apply on border.But native enzyme has the shortcomings that mutability inactivation, expensive, purification difficult, storage and use cost are high, and this is all limited
Their extensive application is made.Therefore, simulate native enzyme to the molecular recognition of substrate and the research of the analogue enztme of efficient catalytic into
For the task of top priority.
Find that ferroferric oxide nano granules have the catalysis of peroxidase first from 2007 Nian Yanxiyun research groups
Since activity, the exploration of nano material mimetic enzyme catalysis activity causes at once highest attention.Later, people had found successively various
Nano material such as golden nanometer particle, Co3O4, carbon quantum dot, FeS, V2O5Deng the work for being also found to have similar peroxidase
Property, but these analogue enztmes nearly all will could occur catalytic reaction by oxidant of hydrogen peroxide, which greatly limits these materials
Expect potential application prospect.2009, Perez team found CeO2Nano particle does not need the presence of hydrogen peroxide, it is possible to
Oxidation substrates, with the oxidasic activity of simulation, but with regard to CeO2Application still lack further research.
Phenol wastewater be it is a kind of quite serious to harm and and the industrial wastewater of generally existing, to phenol wastewater
Administering common processing method has Physical, chemical method and bioanalysis etc., but is all difficult to meet the requirement that thoroughly degraded is removed.
2- amino phenols, is commonly called as o-aminophenol, is a kind of using more extensive fine-chemical intermediate, in medicine production, dyestuff system
There is relatively broad purposes in the fields such as standby, rubber synthesis, feed, oil；Thus the pollutant effluents containing o-aminophenol
It is a kind of more typical phenol wastewater.Due to the height of the production waste strength containing o-aminophenol, colourity depth, difficult degradation, can
Biochemical is poor, and with very big toxicity, the method for dealing with cumbersome, general treatment classification waste water is all difficult effectively place
Reason amino phenols waste water.And the oxidasic process for appearing as phenol wastewater of new nanometer simulation provides a kind of new solution party
Case, but have not yet to see the report for preferably combining both.
The content of the invention
The invention provides a kind of specific cubic nanometer ceria material and preparation method thereof, and carry based on this
A kind of new water process side of application of cubic nanometer ceria as simulation oxidizing ferment in o-aminophenol degraded is supplied
Method.
The technical solution used in the present invention is described in detail as follows.
A kind of cubic nanometer CeO2, it is prepared from using following steps：
（1）With Ce (NO3)3·6H2O as cerium source, using urea as precipitating reagent, with CTAB（Cetyl trimethyl bromination
Ammonium）As surfactant；By Ce (NO3)3·6H2O, CTAB, urea are dissolved in deionized water, ultrasonic wave dissolving, until solution
Become colorless and transparent；
Each material is with molar ratio computing, Ce (NO3)3·6H2O ︰ CTAB ︰ urea=2.28 ~ 2.32：0.24~0.30：9.03~
9.37；Optimum ratio is, 2.3：0.27：9.2；
（2）By step（1）Middle solution is transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), 160 DEG C ~
200 DEG C of 18 ~ 36h of reaction, preferably 180 DEG C 24 h of reaction, naturally cool to room temperature；
（3）By step（2）Reactant liquor centrifugation after middle cooling, preferred 10000r/min is centrifuged 5 minutes, takes out precipitation
Alternately washing 3 times of thing, sediment absolute ethyl alcohol and deionized water, oven drying, 60 DEG C ~ 80 DEG C 3 ~ 6h of drying, preferably 70 DEG C
Be dried 5h, obtain cerium oxide precursor body；
（4）By step（3）Middle cerium oxide precursor body roasting in Muffle furnace, 400 DEG C ~ 600 DEG C 10 ~ 15h of roasting, preferably
The h of roasting 12 at 500 DEG C, obtains light yellow powder cubic nanometer ceria.
Cubic nanometer CeO2Preparation method, specifically include following steps：
（1）With Ce (NO3)3·6H2O as cerium source, using urea as precipitating reagent, with CTAB（Cetyl trimethyl bromination
Ammonium）As surfactant；By Ce (NO3)3·6H2O, CTAB, urea are dissolved in deionized water, ultrasonic wave dissolving, until solution
Become colorless and transparent；
Each material is with molar ratio computing, Ce (NO3)3·6H2O ︰ CTAB ︰ urea=2.28 ~ 2.32：0.24~0.30：9.03~
9.37；Optimum ratio is, 2.3：0.27：9.2；
（2）By step（1）Middle solution is transferred in the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE), 160 DEG C ~
200 DEG C of 18 ~ 36h of reaction, naturally cool to room temperature；
（3）By step（2）Reactant liquor centrifuge after middle cooling, takes out sediment, sediment absolute ethyl alcohol
Alternately wash and be centrifuged 3 times with deionized water, 60 DEG C in an oven ~ 80 DEG C 3 ~ 6h of drying obtain cerium oxide precursor body；
（4）By step（3）Middle cerium oxide precursor body 400 DEG C ~ 600 DEG C 10 ~ 15h of roasting in Muffle furnace, obtain light yellow
Powder cubic nanometer ceria.
Cubic nanometer CeO2Application in o-aminophenol degraded, cubic nanometer CeO2Play as analogue enztme and make
With, using when, concrete proportioning is：
When o-aminophenol concentration is 10 ~ 70 mg/L, 20mL, CeO2Addition be 10 ~ 70mg, pH=2 ~ 10,0 ~ 300
R/min, 1 ~ 6h of constant temperature oscillation；
Proportion optimizing is：
When o-aminophenol concentration is 40 mg/L, 20mL, CeO2Addition not less than 30mg, pH=3,25 DEG C, 225
R/min constant temperature oscillation 3h.
The invention provides a kind of specific cubic nanometer ceria, this ceria can be as analogue enztme so as to urging
Change and degrade and adsorb o-aminophenol., compared to Native Oxide enzyme, its stability is high, be difficult for ceria provided by the present invention
Generation denaturation, it is applied widely, be easy to store and transport, and recycling degree is high, and equally there is efficient oxidizing ferment to urge
Change activity, thus can preferably substitute the application of existing day thermal oxide enzyme.Ceria provided by the present invention compared to
Other Mimetic Peroxidases, it is not necessary to which hydrogen peroxide is thus easy to use as oxidant, in o-aminophenol degraded,
Highest degradation rate is up to more than 70%.In general, the cubic nanometer ceria in the present invention, its preparation process is simple can be grasped
The property made is strong, and has preferably application prospect in o-aminophenol process, thus with preferable application value.
Description of the drawings
Fig. 1 is cube nano Ce O prepared by embodiment 12SEM figure；
Fig. 2 is cube nano Ce O prepared by embodiment 12XRD spectrum figure；
Fig. 3 is cube nano Ce O prepared by embodiment 12FT-IR figure；
Fig. 4 is cube nano Ce O prepared by embodiment 12TMB lab diagrams, wherein a is to be not added with CeO2（It is colourless）, b is
Plus CeO2（Become blue）, c is that acid adding stops（Turn yellow）；
Fig. 5 is o-aminophenol concentration-absorbance standard curve；
Fig. 6 is the abosrption spectrogram of o-aminophenol under condition of different pH；
Fig. 7 is illumination for o-aminophenol degradation rate affects；
Fig. 8 is addition H2O2Impact to degradation rate；
Fig. 9 is impact of the oscillation rate to degradation rate；
Figure 10 is impacts of the pH to degradation rate；
Figure 11 is CeO2Impact of the addition to degradation rate；
Figure 12 is impact of the concussion time to degradation rate；
Figure 13 is impact of the o-aminophenol initial concentration to degradation rate.
Specific embodiment
Technical scheme is further described with reference to embodiment as follows.Before introducing specific embodiment, to this
The situation of partial material used and experimental provision is briefly discussed below in invention.
Material used is common experimental medicine in laboratory in the present invention, and purity is pure for analysis；
Involved major experimental instrument has：
SEM (SEM), Q250 F, FEI Co. of the U.S.；
X-ray diffractometer（XRD）, XD-3, Beijing Puxi General Instrument Co., Ltd；
Fourier transformation infrared spectrometer, Nicolet iS 10, Thermo Fisher Scientific companies of the U.S.；
Multi parameter analysis instrument, DZS-708, Shanghai Precision Scientific Apparatus Co., Ltd；
Ultraviolet-uisible spectrophotometer, T6 new centuries, Beijing Puxi General Instrument Co., Ltd.
Embodiment 1
Before specific embodiment is introduced, first to preparing CeO in the present invention2Know-why be briefly discussed below.
The present invention is with Ce (NO3)3·6H2O as cerium source, using urea as precipitating reagent, using CTAB as surfactant,
First CeO is prepared by hydro-thermal method2Presoma, then the calcining preparation of this presoma lived to obtain CeO again2.Concrete reaction mechanism is such as
Under：
First, in reaction mixture, urea decomposes generation ammonium ion and cyanic acid ion：
H2N-CO-NH2→NH4 + + OCN-；
When in acid condition, cyanic acid ion occurs rapidly following reaction：
OCN- + 2H+ + H2O → CO2 + NH4 + ；
When under neutral or basic conditions, it will following reaction occurs：
OCN- + OH- + H2O → NH3 + CO3 2- ；
Due to Ce3+It is charge with alkalescent and height, will there is strong aquation, specifically：
Ce3+Hydrolysis and with hydrone or OH-Complexing：
Ce3+ + yH2O→[Ce(OH)(H2O)n−1]2+ + H3O+；
With the rising and the lengthening in reaction time of reaction temperature, the hydrolysis rate of urea is accelerated, CO3 2- With H3O+Start
It is a large amount of to generate, finally obtain CeO2Presoma：
[Ce(OH)(H2O)n−1]2+ + CO3 2- = CeOHCO3(CeCO3OH)+(n-1)H2O；
And presoma CeOHCO3CeO can be thermally decomposed to generate under 500 DEG C of high temperature2：
4CeCO3OH + O2→4CeO2 + 2H2O + 4CO2。
The cubic nanometer ceria prepared by the present invention is specifically described as follows with reference to embodiment.
The cubic nanometer ceria that the present embodiment is provided, is prepared from using following steps：
（1）By Ce (NO3)3·6H2O、CTAB（Cetyl trimethylammonium bromide）, urea be dissolved in the deionized water of 10 mL
In, ultrasonic wave dissolving, until solution becomes colorless and transparent；
The concrete consumption of each material is：Ce(NO3)3·6H2O ︰ CTAB ︰ urea=2.3mmol：0.27 mmol：9.2mmol；
（2）By step（1）Middle solution is transferred in the stainless steel autoclave of 20 mL inner liner polytetrafluoroethylenes, sealing
Afterwards, it is placed in baking oven, 180 DEG C of 24 h of reaction naturally cool to room temperature；
（3）By step（2）Reactant liquor after the middle cooling centrifuge 5 minutes of 10000r/min, takes out sediment,
Alternately washing 3 times of sediment absolute ethyl alcohol and deionized water, 5h are dried in 70 DEG C of baking oven and obtain cerium oxide precursor body；
（4）By step（3）The h of roasting 12 in Muffle furnace of the middle cerium oxide precursor body at 500 DEG C, obtains buff powder
Shape cubic nanometer ceria.
For prepared CeO2, inventor further carried out SEM morphology analysis, XRD scanning, fourier-transform infrared
The Morphometric analysis such as analysis, correlated process is briefly discussed below.
SEM morphology analysis
When SEM is scanned, it is specifically configured to：During high vacuum pattern, 3.0nm when 1.0nm, 1kv during 30kv；Low-vacuum mode
When, 3.0nm when 1.4nm, 3kv during 30kv；During environment vacuum pattern, 2.5nm during 30kv.Multiplication factor is under the pattern of high-altitude
14x-1000000x, multiplication factor error is less than 3%.
As a result it is as shown in Figure 1.
CeO2Crystal morphology change mechanism be：With the rising of reaction temperature, crystal satiety in one side reaction system
Reduce with degree；On the other hand, crystal face is more smooth-out, because the growth tendency of nano particle is usually to be intended to three from one-dimensional
Dimension development, that is to say, that the particle diameter of product slowly diminishes, when reacted between reach one timing, the size of sample particle diameter is with reaction
The rising of temperature and reduce.From figure 1 it appears that the CeO prepared by the present embodiment2Particle diameter between 200 ~ 300nm, category
In nanometer materials.
XRD analysis
X-ray diffraction analysis is to determine crystal structure, the analysis of thing phase of material, by the diffraction maximum position to sample
Compare the crystalline phase that can obtain sample after being normalized with intensity with standard powder diffraction PDF cards, so as to realize determining for sample
Property facies analysis.CeO prepared by the present embodiment2The concrete test condition of sample is：Using curved product graphite monochromator and Cu under room temperature
K alpha rays (λ=0.154056nm), Ni optical filters, operating voltage be 36 kV, operating current be 20 mA, 2 ° of sweep speed/
Min, step-length is 0.02, and scanning angle of diffraction 2 θ is 10-90 °.
As a result it is as shown in Figure 2.In fig. 2, the height and width at peak represents the size of crystal grain and the height of degree of crystallinity, peak
More narrow higher, it is bigger to represent crystal grain, crystallizes more perfect；Otherwise peak is more wide shorter, it may be possible to which crystal grain is smaller, poor causing is crystallized
's.From figure 2 it can be seen that 30 degree, 35 degree, 45 degree, the peak at 58 degree it is all higher, it is only shorter individually, illustrate system
It is higher for the degree of crystallinity for going out.
FT-IR（Fourier-transform infrared light splitting）Analysis
Infrared spectrum collection is carried out to sample using pellet technique.Test condition is：Wave-number range is 4000-400
cm-1, scanning times are 32 times, and resolution ratio is 4.Sample preparation methods are：First cerium oxide powder and KBr are pressed into one
Certainty ratio is ground, and then carries out compressing tablet, you can tested.
As a result it is as shown in Figure 3.In figure 3,3300-3500 cm-1Strong absworption peak be due to sample surfaces physical absorption
What the stretching vibration of the O-H in water and the crystallization water caused；1600 cm-1- the H that neighbouring absworption peak can belong to the crystallization water is curved
Qu Zhendong；1300 cm-1、1093 cm-1And 400 cm-1Three neighbouring absworption peaks correspond to CeO2。
CeO2 analogue enztme activities are identified（TMB colour developing checkings）
CeO is verified using TMB2Whether there is analogue enztme activity.Detailed process is：
Substrate colour developing A liquid is prepared first：The g of sodium acetate 13.6, the g of citric acid 1.6, distilled water adds to 500 mL；
Prepare chromogenic substrate B liquid：The g of disodium ethylene diamine tetraacetate 0.2, the g of citric acid 0.95, the mL of glycerine 50, then take 0.15
GTMB is dissolved in 3mL ethanol solutions, and distilled water adds to 500mL；
A liquid, B liquid note keeping in dark place；
During checking, A liquid, each 0.5mL of B liquid are taken, add 5mg CeO2, after being well mixed, colour developing situation is observed after 10min.
As a result it is as shown in Figure 4.Figure 4, it is seen that CeO2Can act on TMB, there is blue reaction, illustrate CeO2Tool
There is the oxidasic activity of simulation.
Embodiment 2
Due in the present invention in solution o-aminophenol concentration mensuration Main Basiss concentration and absorbance relation determine,
Thus the present invention is as follows firstly the need of o-aminophenol concentration calibration curve corresponding with absorbance, detailed process is drawn：
0 mg/L, 10 mg/L, 20 mg/L, 30 mg/L, 40 mg/L, 50 mg/L, 60 mg/L, 70mg/L are prepared respectively
O-aminophenol solution, using distilled water as blank, regulation Detection wavelength is 280nm, uses spectrophotometry
Meter difference mensuration absorbance, and draw calibration curve.
As a result it is as shown in Figure 5.In Figure 5, ordinate Y represents absorbance（Abs）, abscissa X represents in solution adjacent amino
Mass concentration c of phenol（mg/L）, in addition as seen from the figure, the equation of linear regression of o-aminophenol is Y=0.0346X-
0.0144, linearly dependent coefficient R2=0.9991。
Due under condition of different pH, the absorbing wavelength of o-aminophenol is different, thus for adjacent amino in Accurate Determining solution
The absorbance of phenol, inventor has done o-aminophenol absorbing wavelength measure work under condition of different pH, specially：
Using the o-aminophenol solution of 40 mg/L, with the quartz colorimetric utensil of 1cm, blank reference is done with distilled water, in purple
On outer spectrophotometer from the nm of wavelength 190 to 330 nm, every 10 nm determine an absorbance, with wavelength as abscissa, inhale
Luminosity is ordinate, draws o-aminophenol absorption spectrum curve, the absorbing wavelength corresponding to absworption peak is found out, if multiple
Absorbing wavelength, which then compares again is affected smaller by pH, so as to select optimal absorption wavelength.
As a result it is as shown in Figure 6.From fig. 6 it can be seen that the abosrption spectrogram change of PH=2, PH=3, PH=4.5 tri- becomes
Gesture is similar.Wavelength corresponding to maximum absorption band is respectively：230 nm and 275 nm, absworption peak when wavelength is 230 nm be by
What the amino on o-aminophenol was caused, wavelength is affected less when being 275 nm by pH, therefore can be used as maximum absorption wavelength.
The clearance of o-aminophenol（）It is calculated as follows：
；
A in formula0For initial absorbance, A is absorbance after degraded.
Using CeO2During catalytic degradation o-aminophenol, due to pH value of solution, CeO may be subject to2Consumption, illumination, adjacent aminobenzene
The Multiple factors such as phenol concentration affect, so that inquire into optimum response being equipped with, correlation test process is briefly discussed below.
Impact of the light to o-aminophenol of degrading
Detailed process is：Simulation neighbour's ammonia that 20 mL concentration are 40 mg/L is separately added in the conical flask of four 50 mL
Base phenolic waste water, wherein No. 1 conical flask is not added with CeO2；No. 2 conical flasks add 30mg CeO2；No. 3 conical flasks are encased with masking foil, no
Plus CeO2；No. 4 conical flasks are encased with masking foil, plus 30 mgCeO2, then pH=2 be put into 25 DEG C, 300 r/ in isothermal vibration device
Min vibrates 3 h.After reaction terminates, sand core funnel is filtered, and mensuration absorbance calculates degradation rate.
As a result it is as shown in Figure 7.From figure 7 it can be seen that having light and the unglazed impact to degradation rate less, CeO is illustrated2Degraded
O-aminophenol is not photocatalysis.
The impact that H2O2 degrades to o-aminophenol
Detailed process is：The H of 0,1,2,3,4,10 mL mass fractions 15% is separately added in five conical flasks2O2, then
The CeO of o-aminophenol simulated wastewater that 20 mL concentration are 40 mg/L and 30 mg is added in each conical flask2, pH=2 puts
Enter 25 DEG C in isothermal vibration device, the h of 300 r/min oscillating reactions 3.After reaction terminates, sand core funnel is filtered, mensuration absorbance meter
Calculate degradation rate.
As a result it is as shown in Figure 8.From figure 8, it is seen that with addition H2O2The increase of amount, degradation rate dramatic decrease, explanation
CeO2In there is no a peroxide root, degradation is not peroxide catalysis.
Impact of the concussion speed to o-aminophenol of degrading
Detailed process is：The o-aminophenol simulation that 20 mL concentration are 40 mg/L is separately added in five conical flasks useless
Water and 30 mg CeO2, pH=2, in being individually placed to the constant temperature oscillator that speed is 0,75,150,225,300 r/min, 25 DEG C are shaken
Swing 3 h of reaction.After reaction terminates, sand core funnel is filtered, and mensuration absorbance calculates degradation rate.
As a result it is as shown in Figure 9.It can be seen in figure 9 that as the increase of speed, degradation rate are gradually increased, finally tending to
Balance.Its reason is that when rotating speed increases, dissolved oxygen increases, due to nano Ce O2There is the storage oxygen function of uniqueness, work as rotating speed
Increase, nano Ce O2Storage oxygen is more and more, Ce3+Become Ce4+, increase degradation rate.When speed be 225 r/min when degradation rate
Reach most preferably, now degradation rate is 58%.
Impacts of the pH to o-aminophenol of degrading
Detailed process is：The o-aminophenol simulation that 20 mL concentration are 40 mg/L is separately added in 9 conical flasks useless
Water, it is 2,2.5,3,3.5,4,5,6,8,10 that pH is adjusted respectively, is subsequently adding 30 mgCeO2, be put into 25 DEG C in isothermal vibration device,
225 r/min vibrate 3 h.After reaction terminates, sand core funnel is filtered, and mensuration absorbance calculates degradation rate.
As a result it is as shown in Figure 10.It can be seen from fig. 10 that pH is at 2-3, as the increase degradation rate of PH is raised, when
When pH is more than 3, with the increase of pH, degradation rate is more and more lower.Therefore, as pH=3, preferably, now degradation rate is degradation effect
64.9%。
Impact of the dosage of CeO2 to o-aminophenol of degrading
Detailed process is：The o-aminophenol simulation that 20 mL concentration are 40 mg/L is separately added in 7 conical flasks useless
Water, is then respectively adding 10mg, 20 mg, 30 mg, 40 mg, 50 mg, 60 mg, the CeO of 70 mg2, regulation pH=3,25 DEG C,
The h of 225 r/min constant temperature oscillations 3.After reaction terminates, sand core funnel is filtered, and mensuration absorbance calculates degradation rate.
As a result it is as shown in figure 11.It can be seen from fig. 11 that with dosage be continuously increased when, degraded take the lead in increase then
Slowly tend towards stability, when dosage is more than 30 mg, degradation rate is almost unchanged, remains 58%.Therefore, optimum dosage is 30
mg。
Impact of the concussion time to o-aminophenol of degrading
Detailed process is：The o-aminophenol simulated wastewater that 20 mL concentration are 40 mg/L is added in 6 conical flasks, so
The CeO of 30 mg is added afterwards2, adjust pH=3,25 DEG C, 225 r/min constant temperature oscillations, duration of oscillation be respectively set to 1h, 2h, 3h,
4h、5h、6 h.After reaction terminates, sand core funnel is filtered, and mensuration absorbance calculates degradation rate.
As a result it is as shown in figure 12.In figure 12 it can be seen that after the concussion time 4 h is more than, with the increasing of concussion time
Plus, degradation rate is slowly reduced on the contrary, it may be said that bright CeO2Not only there is oxidation catalytic degradation o-aminophenol, there is also absorption and make
With when overlong time is shaken, the rate of adsorption is less than desorption rate, reduces degradation rate.Therefore, the optimal concussion time is 3 h,
Now degradation rate is 62.7%.
Impact of the initial concentration to o-aminophenol of degrading
Detailed process is：20 mL concentration are separately added in 7 conical flasks for 10,20,30,40,50,60,70 mg/L
O-aminophenol simulated wastewater and 30 mg CeO2, adjust pH=3,25 DEG C, 225 r/min constant temperature oscillation 3h.Reaction terminates
Afterwards, sand core funnel is filtered, and mensuration absorbance calculates degradation rate.
As a result it is as shown in figure 13.It can be observed from fig. 13 that when concentration be 40 mg/L when, degradation rate be it is best, now
For 68.4%.
O-aminophenol degradation rate under the conditions of optimal proportion
On the basis of above-mentioned optimal conditions, inventor has further carried out experimental verification, concrete to arrange as follows：
O-aminophenol simulated wastewater and 30 mg CeO that 20 mL concentration are 40 mg/L are added in conical flask2, adjust
PH=3,25 DEG C, 225 r/min constant temperature oscillation 3h.After reaction terminates, sand core funnel is filtered, and mensuration absorbance calculates degradation rate.Knot
Fruit shows that now degradation rate is up to 71%.
Claims (2)
1. cubic nanometer CeO2Application in o-aminophenol degraded, it is characterised in that cubic nanometer CeO2Send out as analogue enztme
The effect of waving, using when, concrete proportioning is：
When o-aminophenol concentration is 10 ~ 70 mg/L, 20mL, CeO2Addition be 10 ~ 70mg, pH=2 ~ 10,0 ~ 300 r/
Min, 1 ~ 6h of constant temperature oscillation.
2. cubic nanometer CeO as claimed in claim 12Application in o-aminophenol degraded, it is characterised in that when applying, tool
Body proportioning is：
When o-aminophenol concentration is 40 mg/L, 20mL, CeO2Addition is not less than 30mg, pH=3,25 DEG C, 225 r/min
Constant temperature oscillation 3h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057876.9A CN105731514B (en) | 2016-01-28 | 2016-01-28 | Cubic nano CeO2 and application thereof in degrading o-aminophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610057876.9A CN105731514B (en) | 2016-01-28 | 2016-01-28 | Cubic nano CeO2 and application thereof in degrading o-aminophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105731514A CN105731514A (en) | 2016-07-06 |
| CN105731514B true CN105731514B (en) | 2017-05-17 |
Family
ID=56246842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610057876.9A Expired - Fee Related CN105731514B (en) | 2016-01-28 | 2016-01-28 | Cubic nano CeO2 and application thereof in degrading o-aminophenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105731514B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106044837B (en) * | 2016-07-25 | 2017-11-07 | 湖北师范大学 | A kind of low-temperature synthetic method of peach-pit shape ceria |
| CN106268758A (en) * | 2016-07-31 | 2017-01-04 | 国家海洋局第海洋研究所 | A kind of CeVO4analogue enztme material and its preparation method and application |
| CN106883108B (en) * | 2017-02-07 | 2019-06-07 | 江南大学 | The method for being converted into aldehyde based on iridium nanoparticulate selective catalysis oxidation alcohol |
| CN107445212B (en) * | 2017-07-27 | 2019-08-16 | 武汉工程大学 | A kind of magnetic Fe3O4@CeO2The preparation method and applications of composite nano particle |
| CN112499660A (en) * | 2019-08-26 | 2021-03-16 | 山西开辰鑫科技有限公司 | Preparation method and electrochemical application of octahedral nano cerium dioxide |
| CN110702837A (en) * | 2019-09-19 | 2020-01-17 | 上海工程技术大学 | Simple and low-cost cerium dioxide catalytic performance characterization method |
| CN112209422B (en) * | 2020-10-15 | 2021-11-23 | 东北大学 | Method for preparing cerium oxide nanospheres |
| CN114195179B (en) * | 2021-10-25 | 2023-07-25 | 华南农业大学 | Method for detecting bacillus cereus by non-diagnostic double-antibody sandwich enzyme-linked immunosorbent assay |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU1621001A (en) * | 1999-11-17 | 2001-05-30 | Cabot Corporation | Ceria composition and process for preparing same |
| CN101734707A (en) * | 2009-12-24 | 2010-06-16 | 中国科学院生态环境研究中心 | High-stability nano cerium oxide material for catalyzing and oxidizing ortho-xylene at low temperature and application thereof |
| CN103449496A (en) * | 2012-12-31 | 2013-12-18 | 深圳信息职业技术学院 | Nano cerium oxide and preparation method thereof |
-
2016
- 2016-01-28 CN CN201610057876.9A patent/CN105731514B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN105731514A (en) | 2016-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105731514B (en) | Cubic nano CeO2 and application thereof in degrading o-aminophenol | |
| CN105731515B (en) | A kind of mesoporous flower-shaped CeO2, preparation method and applications | |
| Li et al. | Surface effect of natural zeolite (clinoptilolite) on the photocatalytic activity of TiO2 | |
| Zhang et al. | Synthesis of CeO2 nanoparticles with different morphologies and their properties as peroxidase mimic | |
| CN103951833B (en) | The method of houghite photocatalytic degradation xylogen | |
| Šoštarič et al. | Studies on the growth of Chlorella vulgaris in culture media with different carbon sources | |
| Wang et al. | Synthesis of CdSe quantum dots using selenium dioxide as selenium source and its interaction with pepsin | |
| Li et al. | Reduced graphene oxide on a dumbbell-shaped BiVO4 photocatalyst for an augmented natural sunlight photocatalytic activity | |
| CN111939963B (en) | Preparation method of Bi-metal Sm and Bi co-doped graphite phase carbon nitride composite photocatalyst material and application of Bi-metal Sm and Bi co-doped graphite phase carbon nitride composite photocatalyst material in photocatalytic degradation | |
| CN103754921A (en) | Preparation method of monodisperse cerium oxide loose nanospheres | |
| CN107790163A (en) | A kind of photochemical catalyst In2O3/g‑C3N4B preparation and application | |
| CN109364958A (en) | A kind of Bi4O5BrxI2-xThe preparation method of mischcrystal photocatalyst | |
| CN108313993B (en) | Synthesis method of nitric acid | |
| CN108786849A (en) | A kind of preparation and application of artificial gold/composite titania material | |
| WO2019109597A1 (en) | Sulfur-doped s-c3n4 ammonia synthesis catalyst with graphene-like structure and preparation method therefor | |
| Cheng et al. | Morphology-dependent photocatalytic activity of Bi5O7I: Different charge separation efficiencies caused by facet synergy and internal electric field | |
| Hossain et al. | Crystallographic characterization of bio-waste material originated CaCO3, green-synthesized CaO and Ca (OH) 2 | |
| CN103785425B (en) | A kind of flower-shaped Bi 2o (OH) 2sO 4the preparation method of photochemical catalyst and application | |
| CN113120973B (en) | Preparation method of copper-doped nickel-aluminum layered double hydroxide, obtained product and application | |
| CN110961125A (en) | TiO22/TiOF2Preparation method of photocatalyst and application of photocatalyst in treatment of antibiotic wastewater | |
| Priya et al. | Synthesis of intense red light-emitting β-Ca2SiO4: Eu3+ phosphors for near UV-excited light-emitting diodes utilizing agro-food waste materials | |
| CN108671956A (en) | A kind of preparation method of ion filled graphite phase carbon nitride nanometer sheet | |
| Caldas et al. | Fabrication of CN-HAp heterostructures from eggshells with improved photocatalytic performance in degrading of mixing dyes under sunlight | |
| CN109482209A (en) | Utilize the method for the double Z shaped photochemical catalyst catalytic elimination antibiotic of silver orthophosphate/bismuth sulfide/bismuth oxide | |
| CN110669500B (en) | Preparation of terbium-based rare earth crystalline material and application of terbium-based rare earth crystalline material in fluorescence detection of antibiotics in water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170517 Termination date: 20180128 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |