CN111097413B - CuO (copper oxide)xNanocluster and application thereof as ozone catalyst - Google Patents
CuO (copper oxide)xNanocluster and application thereof as ozone catalyst Download PDFInfo
- Publication number
- CN111097413B CN111097413B CN201911365013.8A CN201911365013A CN111097413B CN 111097413 B CN111097413 B CN 111097413B CN 201911365013 A CN201911365013 A CN 201911365013A CN 111097413 B CN111097413 B CN 111097413B
- Authority
- CN
- China
- Prior art keywords
- cuo
- carrier
- reaction
- ozone
- nanoclusters
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title description 40
- 239000005751 Copper oxide Substances 0.000 title description 40
- 229910000431 copper oxide Inorganic materials 0.000 title description 40
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 50
- 229910016553 CuOx Inorganic materials 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 9
- 238000010668 complexation reaction Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002071 nanotube Substances 0.000 claims description 18
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 14
- 230000000536 complexating effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 7
- 238000007306 functionalization reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 description 30
- 229960003760 florfenicol Drugs 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 230000010718 Oxidation Activity Effects 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000010791 quenching Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 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
- B01J23/72—Copper
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
Abstract
The invention discloses a CuOxNanoclusters and their use as ozone catalysts. The CuOxThe nanocluster is obtained by mixing an aminated carrier with a high specific surface area and a copper ion solution, then carrying out a complex reaction, filtering a reaction solution after the reaction is finished to obtain a solid, washing and drying the solid, finally calcining the solid at 300-500 ℃ for 2-8 h, and cooling the solid. The CuO of the present inventionxThe nano-cluster is prepared by firstly carrying out amino functionalization on a carrier, forming an active riveting point which is complexed with copper ions on the surface of the carrier, and then carrying out complexation reaction with the copper ions, thereby controllably carrying out Cu2+Highly and uniformly dispersed on the surface of the carrier to obtain CuO after calcinationxNanoclusters; the CuOxThe preparation process of the nano-cluster is simple and controllable, and the obtained CuOxThe nanoclusters have rich dangling bonds (unsaturated coordination), and can be used as an ozone catalyst to efficiently catalyze ozone to oxidize and degrade organic pollutants.
Description
Technical Field
The invention relates to the technical field of ozone catalytic oxidation and environmental materials, in particular to CuOxNanoclusters and their use as ozone catalysts.
Background
The catalytic ozonation technology is an advanced oxidation method combining the ozone oxidation technology and a catalyst, the catalyst can promote ozone to be rapidly decomposed to generate various active oxygen species (such as hydroxyl radicals, singlet oxygen, surface oxygen atoms and the like), and the catalyst can effectively degrade high-stability and non-degradable organic pollutants which are difficult to be independently oxidized by ozone, so that the aims of deep oxidation and removal of the organic pollutants to the maximum are fulfilled.
Nanoclusters are intermediate single atoms or molecules and assembled from a small number of atoms or moleculesIntermediate structures between the nanomaterials. Compared with single atoms, the catalyst is easier to prepare, and atoms in the nanocluster may have mixed valence states, so that the redox cycle of the catalyst in catalytic reaction is facilitated; compared with nanomaterials, it has more atoms exposed to the outside, and the outer layers of these atoms exposed to the outside have no atoms coordinated thereto and thus have dangling bonds (unsaturated coordination), thereby exhibiting ultra-high catalytic activity. However, the preparation of nanoclusters is still difficult due to their high surface energy and thermodynamic instability, and in particular, nanoclusters of metal oxides are particularly difficult to prepare, and are usually supported on a porous support, but the support has no fixed riveting points, is random, and is very easy to aggregate to form large-particle metal oxides rather than clusters. Considering that the copper oxide has good ozone catalytic activity and the copper ion coordination capacity is strong. Therefore, the invention grafts the active riveting points on the surface of the carrier, controls the complexation of copper ions and the surface complexing points to be uniformly dispersed on the surface of the carrier, and can controllably prepare the CuO through calcinationxThe nano-cluster can be applied to catalyzing ozone to efficiently oxidize organic pollution.
Disclosure of Invention
The invention aims to provide a CuOxA nanocluster. The CuO of the present inventionxThe nano-cluster is prepared by firstly carrying out amino functionalization on a carrier, forming an active riveting point which is complexed with copper ions on the surface of the carrier, and then carrying out complexation reaction with the copper ions, thereby controllably carrying out Cu2+Highly and uniformly dispersed on the surface of the carrier to obtain CuO after calcinationxNanoclusters; the preparation process is simple and controllable, and the obtained CuOxThe nanoclusters have rich dangling bonds (unsaturated coordination), and can be used as an ozone catalyst to efficiently catalyze ozone to oxidize and degrade organic pollutants.
It is another object of the present invention to provide the CuOxApplication of nanoclusters as ozone catalysts.
The above object of the present invention is achieved by the following scheme:
CuO (copper oxide)xNano cluster, mixing aminated high specific surface area carrier with copper ion solutionCarrying out a complexing reaction, filtering the reaction solution after the reaction is finished to obtain a solid, washing, drying, calcining at 300-500 ℃ for 2-8 h, and cooling to obtain CuOxA nanocluster.
In the existing preparation method, because the surface of the carrier is not provided with fixed riveting points (used for fixing copper ions), the positions and the quantity of the copper ions loaded on the carrier have randomness, so that the prepared product is easy to aggregate to form large-particle metal oxide instead of clusters. In order to improve the defect, the surface of the carrier is firstly functionalized by amino, active riveting points of copper ions are formed on the surface of the carrier, and then the active riveting points and the copper ions are subjected to complex reaction, so that the Cu is controllably added2+Highly and uniformly dispersed on the surface of the carrier to obtain CuO after calcinationxNanoclusters; the preparation process is simple and controllable, and the obtained CuOxThe nanoclusters have rich dangling bonds (unsaturated coordination), and can be used as an ozone catalyst to efficiently catalyze ozone to oxidize and degrade organic pollutants.
Preferably, the high specific surface area carrier is mesoporous TiO2Or CeO2。
Preferably, the aminated high specific surface area support is obtained by the following process: adding the carrier with high specific surface area into ethanol, then adding 3-aminopropyltrimethoxysilane for reaction (amination reaction), filtering to obtain a solid after the reaction is finished, and washing and drying to obtain the aminated carrier with high specific surface area.
Preferably, the mass-to-volume ratio of the high specific surface area support to ethanol is: 0.1-1: 1. If the mass-volume ratio of the high specific surface area carrier to the ethanol is too low, the solvent ethanol is wasted; if the mass-to-volume ratio is too high, the viscosity of the formed suspension is too high, which is not beneficial to stirring and mass transfer, and the amino groups at the surface active riveting points are not uniformly distributed.
Preferably, the mass-to-volume ratio of the high specific surface area support to ethanol is: 0.2-0.3: 1; most preferably, it is 0.25: 1.
Preferably, the mass-volume ratio of the high-specific surface area carrier to the 3-aminopropyltrimethoxysilane is 1: 1-10.
In the amination process, if the 3-aminopropyltrimethoxysilane is added too much, a silane reagent is wasted, and the subsequent washing process is more difficult; if the 3-aminopropyltrimethoxysilane is added too little, the riveting points connected to the surface of the carrier are too few, the number of nano-clusters on the obtained carrier per unit mass is too few, and the catalytic activity is reduced. When the mass-volume ratio of the carrier with the high specific surface area to the 3-aminopropyltrimethoxysilane is in the range of the invention, the proper and uniform distribution of the active riveting points on the surface of the aminated carrier can be ensured, and the product is easier to separate and wash after the amination reaction is finished.
Preferably, the mass-to-volume ratio of the high specific surface area carrier to the 3-aminopropyltrimethoxysilane is 1: 2-6.
Preferably, the reaction time of the high-specific surface area carrier and 3-aminopropyltrimethoxysilane is 10-14 h; more preferably, 12 h.
Preferably, the mass ratio of the copper ions in the copper ion solution is 0.1-2%.
Preferably, the mass ratio of copper ions in the copper ion solution is 0.8-1.2%; most preferably, it is 1%.
Preferably, in the complexing reaction, the solid-to-liquid ratio of the aminated high specific surface area carrier to the copper ion solution is 0.005-0.3%.
In the process of complexing reaction, too high solid-to-liquid ratio, too low copper ion concentration and too short complexing time can result in too few nano-clusters on unit mass carrier, and CuO is reducedxCatalytic activity of nanoclusters; however, if the solid-to-liquid ratio is too low, the concentration of copper ions is too high, and the complexing time is too long, CuO particles are formed instead of CuOxAnd (4) clustering.
Preferably, the solid-to-liquid ratio of the aminated high-specific surface area carrier to the copper ion solution is 0.05-0.15%; most preferably, it is 0.1%.
Preferably, the time of the complexation reaction is 10-30 s.
Preferably, the time of the complexation reaction is 20 s.
Preferably, the calcination temperature is 350 ℃ and the calcination time is 3 h. In the process of calcinationIn the process, if the temperature is too low and the time is too short, the precursor including the functionalized organic matter can not be decomposed completely, so that the CuO is reducedxCatalytic activity of nanoclusters; on the contrary, too high calcination temperature and too long calcination time can cause product melt sintering, carrier structure collapse and nanocluster agglomeration, and reduce the catalytic activity of the product.
The invention also protects the CuOxApplication of nanoclusters as ozone catalysts.
Preferably, the CuOxThe nanoclusters are used as a catalyst for catalyzing ozone to degrade organic pollutants in water.
Preferably, the organic contaminants are refractory organics including but not limited to chlorophenols, antibiotics, dyes, and the like.
Compared with the prior art, the invention has the following beneficial effects:
the CuO of the present inventionxThe nano-cluster is prepared by firstly carrying out amino functionalization on a carrier, forming an active riveting point which is complexed with copper ions on the surface of the carrier, and then carrying out complexation reaction with the copper ions, thereby controllably carrying out Cu2+Highly and uniformly dispersed on the surface of the carrier to obtain CuO after calcinationxNanoclusters;
the CuOxThe preparation process of the nano-cluster is simple and controllable, and the obtained CuOxThe nanoclusters have rich dangling bonds (unsaturated coordination), and can be used as an ozone catalyst to efficiently catalyze ozone to oxidize and degrade organic pollutants.
Drawings
FIG. 1 is an electron micrograph of the product prepared in example 1.
FIG. 2 is a high resolution TEM image of the product prepared in example 1.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
Example 1
CuO (copper oxide)xThe nano-cluster is prepared by the following steps:
(1) 0.05g of TiO2Adding the nanotube into 20mL of ethanol, adding 200 mu L of 3-aminopropyltrimethoxysilane while stirring, stirring for reacting for 12h, filtering and washing to obtain a surface aminated carrier;
(2) adding the carrier with the aminated surface into 50mL of copper ion solution with the copper ion concentration of 10mg/L, stirring for reaction for 20s, filtering, washing and drying;
(3) placing the dried material in a muffle furnace, calcining at 350 ℃ for 3h, and cooling to room temperature to obtain CuOxA nanocluster.
The scanning electron microscope of the prepared final product is shown in fig. 1, and only the nanotube structure of the carrier can be seen from fig. 1; the high resolution transmission electron microscope of the final product is shown in FIG. 2, when the scale is 5nm, the diffraction fringes in the product are TiO2Nanotube structure at which CuO cannot be detectedxThe structure of (1) illustrates CuOxIs lower than the nano-scale, and the generated product is CuOxAnd (4) clustering.
Evaluation of catalyst Performance: selecting antibiotic florfenicol but not limiting florfenicol from simulated pollutants, adding 100mL of florfenicol wastewater of 15mg/L and 0.3g/L of TiO into a cylindrical reactor2Nanotube supported CuOxAnd (3) clustering an ozone catalyst, and testing the removal rate of florfenicol to evaluate the ozone catalytic oxidation activity of the catalyst. The ozone concentration is 1.15mg L-1The flow rate is 100mL min-1Quenching the unreacted ozone at the outlet of the reactor with potassium iodide solution, sampling at regular time, and using N to remove the ozone in the solution2After blowing out, filtering, testing the concentration by HPLC, and after reacting for 40min, the florfenicol removal rate reaches 91.3%.
Example 2
CuO (copper oxide)xThe nano-cluster is prepared by the following steps:
(1) 0.05g of CeO2The nanotube is added into 5mL of ethanol, and 500 mu L of 3-aminopropyl trimethoxy is added while stirringStirring silane for reaction for 12h, filtering and washing to obtain a surface aminated carrier;
(2) adding the carrier with the aminated surface into 33mL of copper ion solution with the copper ion concentration of 20mg/L, stirring for reaction for 10s, filtering, washing and drying;
(3) and placing the dried material in a muffle furnace, calcining for 3h at the calcining temperature of 350 ℃, and cooling to room temperature to obtain the CuOx nanocluster.
Evaluation of catalyst Performance: selecting antibiotic florfenicol as a simulated pollutant without limitation to florfenicol, and adding 100mL of florfenicol wastewater of 15mg/L and 0.3g/L of CeO into a cylindrical reactor2Nanotube supported CuOxAnd (3) clustering an ozone catalyst, and testing the removal rate of florfenicol to evaluate the ozone catalytic oxidation activity of the catalyst. The ozone concentration is 1.15mg L-1The flow rate is 100mL min-1Quenching the unreacted ozone at the outlet of the reactor with potassium iodide solution, sampling at regular time, and using N to remove the ozone in the solution2After blowing out, filtering, testing the concentration by HPLC, and after reacting for 40min, the florfenicol removal rate reaches 86.3%.
CuO prepared in this examplexWhen the nano-cluster is used as a catalyst, the catalytic efficiency of the nano-cluster is affected by CuO on a unit mass carrierxNumber of nanoclusters and support and CuOxThe influence of the interaction between them. In the process of amino functionalization treatment on the surface of the carrier, when the carrier is TiO2Or CeO2When the concentration (solid-to-liquid ratio) of the carrier is 1 to 10g/L and the ratio of the mass (g) of the carrier to the volume (mL) of 3-aminopropyltrimethoxysilane is 1:1 to 1:10, the mixture is stirred smoothly and TiO with different hydroxyl group densities on the surface2And CeO2In other words, the surface amino density of the carrier can be maximized, so that more copper ions can be complexed, and more CuO can be generated on the unit mass of the carrierxAnd (4) nano.
In addition, CeO is used2And TiO2The acidity of the catalyst is suitable, so that copper elements cannot form fixed chemical bonds with Ti or Ce elements, and the catalyst is favorable for the redox cycle of Cu ions in catalytic reaction. Selection of SiO2When it is carrier-like, due to copperThe interaction force between the elements and the carrier is too strong, and oxidation-reduction circulation is difficult to occur in the reaction process, so that the catalytic activity is very low.
Example 3
CuO (copper oxide)xThe nano-cluster is prepared by the following steps:
(1) 0.05g of TiO2Adding the nanotube into 20mL of ethanol, adding 200 mu L of 3-aminopropyltrimethoxysilane while stirring, stirring for reacting for 12h, filtering and washing to obtain a surface aminated carrier;
(2) adding the carrier with the aminated surface into 1000mL of copper ion solution with the copper ion concentration of 1mg/L, stirring for reaction for 30s, filtering, washing and drying;
(3) placing the dried material in a muffle furnace, calcining at 350 ℃ for 3h, and cooling to room temperature to obtain CuOxA nanocluster.
Evaluation of catalyst Performance: selecting antibiotic florfenicol but not limiting florfenicol from simulated pollutants, adding 100mL of florfenicol wastewater of 15mg/L and 0.3g/L of TiO into a cylindrical reactor2Nanotube supported CuOxAnd (3) clustering an ozone catalyst, and testing the removal rate of florfenicol to evaluate the ozone catalytic oxidation activity of the catalyst. The ozone concentration is 1.15mg L-1The flow rate is 100mL min-1Quenching the unreacted ozone at the outlet of the reactor with potassium iodide solution, sampling at regular time, and using N to remove the ozone in the solution2After blowing out, filtering, testing the concentration by HPLC, and after reacting for 40min, the florfenicol removal rate reaches 87.3%.
In the preparation process, in the complexing reaction with copper, the concentration of copper ions is too high, the reaction time is too long, the copper ions are uniformly dispersed on the surface of the carrier through the complexing reaction, the copper ions can be physically adsorbed (adsorbed by pores) on the surface of the carrier, the physically adsorbed copper ions are aggregated together, and aggregated CuO particles instead of CuO are formed after calcinationxNanocluster, otherwise, surface complexation is not thorough, and CuO on unit mass of carrier obtained after calcinationxThe number of nanoclusters is small. When the solid-to-liquid ratio of the carrier is 0.05-3 g/L, the concentration of copper ions in the solution is 1-20 mg/L, and the reaction is carried outWhen the time is 10-30 s, more CuO can be generated on the unit mass carrierxNano, no CuO particles are generated, and the catalyst has higher activity.
Example 4
CuO (copper oxide)xThe nano-cluster is prepared by the following steps:
(1) 0.05g of TiO2Adding the nanotube into 20mL of ethanol, adding 200 mu L of 3-aminopropyltrimethoxysilane while stirring, stirring for reacting for 12h, filtering and washing to obtain a surface aminated carrier;
(2) adding the carrier with the aminated surface into 50mL of copper ion solution with the copper ion concentration of 10mg/L, stirring for reaction for 20s, filtering, washing and drying;
(3) and placing the dried material in a muffle furnace, calcining at the calcining temperature of 500 ℃ for 8h, and cooling to room temperature to obtain the CuOx nanocluster.
Evaluation of catalyst Performance: selecting antibiotic florfenicol but not limiting florfenicol from simulated pollutants, adding 100mL of florfenicol wastewater of 15mg/L and 0.3g/L of TiO into a cylindrical reactor2Nanotube supported CuOxAnd (3) clustering an ozone catalyst, and testing the removal rate of florfenicol to evaluate the ozone catalytic oxidation activity of the catalyst. The ozone concentration is 1.15mg L-1The flow rate is 100mL min-1Quenching the unreacted ozone at the outlet of the reactor with potassium iodide solution, sampling at regular time, and using N to remove the ozone in the solution2After blowing out, filtering, testing the concentration by HPLC, and after reacting for 40min, the florfenicol removal rate reaches 82.3%.
In the preparation process, in the process of calcining to generate the CuOx nano cluster, the calcining temperature is too low, the calcining time is too short, the precursor including the functionalized organic matter can not be thoroughly decomposed, and the catalytic activity is reduced; on the contrary, the catalyst is fused and sintered due to the excessively high calcination temperature and the excessively long calcination time, the carrier structure collapses, the nano-clusters are agglomerated, and the catalytic activity is reduced. When the calcination temperature is 300-500 ℃ and the calcination time is 2-8 h, the carrier structure is kept complete, the specific surface area is slightly reduced along with the increase of the temperature, and CuO is generatedxNanometer, high catalyst activity.
Comparative example 1
CuO (copper oxide)xThe nano-cluster is prepared by the following steps:
(1) 0.05g of TiO2Directly adding the nanotube into 50mL of copper ion solution with the copper ion concentration of 10mg/L, stirring for reacting for 20s, filtering, washing and drying;
(2) and placing the dried material in a muffle furnace, calcining for 3h at the calcining temperature of 350 ℃, and cooling to room temperature to obtain a product.
Evaluation of catalyst Performance: selecting antibiotic florfenicol but not limiting florfenicol from simulated pollutants, adding 100mL of florfenicol wastewater of 15mg/L and 0.3g/L of TiO into a cylindrical reactor2Nanotube supported CuOxAnd (3) clustering an ozone catalyst, and testing the removal rate of florfenicol to evaluate the ozone catalytic oxidation activity of the catalyst. The ozone concentration is 1.15mg L-1The flow rate is 100mL min-1Quenching the unreacted ozone at the outlet of the reactor with potassium iodide solution, sampling at regular time, and using N to remove the ozone in the solution2After blowing out, filtering, testing the concentration by HPLC, and after reacting for 40min, the florfenicol removal rate reaches 65.1%.
TiO2The surface of the nano tube is not functionalized by amino, and copper ions are randomly adsorbed on TiO2The surface of the nanotube can cause copper ions to aggregate, and CuO particles in an aggregated state are generated after calcination instead of CuOxNanoclusters other than CuOxNanoclusters, in which atoms inside particles are saturated in coordination and not directly contacted with reactants, cannot catalyze the progress of reactions, thus exhibiting low catalytic activity.
Comparative example 2
CuO (copper oxide)xThe nano-cluster is prepared by the following steps:
(1) 0.05g of TiO2Adding the nanotube into 20mL of ethanol, adding 200 mu L of 3-aminopropyltrimethoxysilane while stirring, stirring for reacting for 12h, filtering and washing to obtain a surface aminated carrier;
(2) adding the surface aminated carrier into 50mL of copper ion solution with copper ion concentration of 100mg/L, stirring for reaction for 2h, filtering, washing and drying;
(3) and placing the dried material in a muffle furnace, calcining for 3h at the calcining temperature of 350 ℃, and cooling to room temperature to obtain a product.
Evaluation of catalyst Performance: selecting antibiotic florfenicol but not limiting florfenicol from simulated pollutants, adding 100mL of florfenicol wastewater of 15mg/L and 0.3g/L of TiO into a cylindrical reactor2Nanotube supported CuOxAnd (3) clustering an ozone catalyst, and testing the removal rate of florfenicol to evaluate the ozone catalytic oxidation activity of the catalyst. The ozone concentration is 1.15mg L-1The flow rate is 100mL min-1Quenching the unreacted ozone at the outlet of the reactor with potassium iodide solution, sampling at regular time, and using N to remove the ozone in the solution2After blowing out, filtering, testing the concentration by HPLC, and after reacting for 40min, the florfenicol removal rate reaches 70.9%.
TiO2In the complex copper ion reaction, the concentration of copper ions is too high, and the copper ions are randomly physically adsorbed (adsorbed by pores) on TiO while the complex reaction is carried out2The surface of the nanotube can cause copper ions to aggregate, and CuO particles in an aggregated state are generated after calcination instead of CuOxNanoclusters other than CuOxNanoclusters, in which atoms inside particles are saturated in coordination and not directly contacted with reactants, cannot catalyze the progress of reactions, thus exhibiting low catalytic activity.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. CuO for catalyzing ozone to degrade organic pollutants in waterxThe nano-cluster is characterized in that after the aminated carrier with high specific surface area is mixed with copper ion solution, the complexing reaction is carried out, and the reaction is carried outAfter the reaction is finished, filtering the reaction solution to obtain a solid, washing, drying, calcining at 300-500 ℃ for 2-8 h, and cooling to obtain CuOxNanoclusters;
the carrier with high specific surface area is TiO2Nanotubes or CeO2A nanotube; the mass ratio of copper ions in the copper ion solution is 0.1-2%, and in the complexing reaction, the solid-to-liquid ratio of the aminated high-specific-surface-area carrier to the copper ion solution is 0.005-0.3%;
the aminated high specific surface area support is obtained by the following process: adding the high specific surface area carrier into ethanol, then adding 3-aminopropyltrimethoxysilane for reaction, filtering to obtain a solid after the reaction is finished, and washing and drying to obtain the aminated high specific surface area carrier.
2. The CuO of claim 1xThe nano-cluster is characterized in that the mass-volume ratio of the high specific surface area carrier to ethanol is as follows: 0.1-1: 1.
3. The CuO of claim 1xThe nano-cluster is characterized in that the mass-volume ratio of the high-specific surface area carrier to the 3-aminopropyltrimethoxysilane is 1: 1-10.
4. The CuO of claim 1xThe nanocluster is characterized in that the time of the complexation reaction is 10-30 s.
5. The CuO according to any one of claims 1 to 4xApplication of nanoclusters as ozone catalysts.
6. The use of claim 5, wherein said CuO isxThe nanoclusters are used as a catalyst for catalyzing ozone to degrade organic pollutants in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911365013.8A CN111097413B (en) | 2019-12-26 | 2019-12-26 | CuO (copper oxide)xNanocluster and application thereof as ozone catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911365013.8A CN111097413B (en) | 2019-12-26 | 2019-12-26 | CuO (copper oxide)xNanocluster and application thereof as ozone catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111097413A CN111097413A (en) | 2020-05-05 |
| CN111097413B true CN111097413B (en) | 2021-05-04 |
Family
ID=70424929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911365013.8A Active CN111097413B (en) | 2019-12-26 | 2019-12-26 | CuO (copper oxide)xNanocluster and application thereof as ozone catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111097413B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259428A (en) * | 2008-04-24 | 2008-09-10 | 福州大学 | Preparation of catalyst for processing industrial wastewater and using method thereof |
| CN110449150A (en) * | 2019-07-04 | 2019-11-15 | 中山大学 | A kind of Carbon Hollow pipe array catalyst of embedded nano metal and its preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8651048B2 (en) * | 2010-04-21 | 2014-02-18 | University Of North Texas | Controlled deposition of metal and metal cluster ions by surface field patterning in soft-landing devices |
-
2019
- 2019-12-26 CN CN201911365013.8A patent/CN111097413B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101259428A (en) * | 2008-04-24 | 2008-09-10 | 福州大学 | Preparation of catalyst for processing industrial wastewater and using method thereof |
| CN110449150A (en) * | 2019-07-04 | 2019-11-15 | 中山大学 | A kind of Carbon Hollow pipe array catalyst of embedded nano metal and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| Simultaneous Control over Lattice Doping and Nanocluster Modification of a Hybrid CuOx/TiO2 Photocatalyst during Flame Synthesis for Enhancing Hydrogen Evolution;Fan Yang etal.;《Sol. RRL》;20181231;Simultaneous Control over Lattice Doping and Nanocluster Modification of a Hybrid CuOx/TiO2 Photocatalyst during Flame Synthesis for Enhancing Hydrogen Evolution * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111097413A (en) | 2020-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109569729B (en) | Supported bimetal advanced oxidation catalyst, preparation method and analysis method of each enhanced function contribution of supported bimetal advanced oxidation catalyst | |
| CN107398269A (en) | High-efficiency multi-stage hole nanocatalyst applied to catalytic removal volatile organic matter and preparation method thereof | |
| CN107597109A (en) | Load type gold catalyst of nano-metal-oxide doping and preparation method and application | |
| CN112264040B (en) | Carbon sphere-graphene oxide catalyst and preparation method and application thereof | |
| JP2022528253A (en) | Metallic nanoparticle catalyst collected on a porous oxide carrier with high activity even at low temperatures | |
| JP5386986B2 (en) | Catalyst-supported carbon nanohorn composite and production method thereof | |
| CN111215123B (en) | Can simultaneously remove COS and H in garbage gasification2S catalyst and preparation method thereof | |
| CN110694619A (en) | Platinum and ruthenium bimetal loaded zirconium oxide nanotube composite material, preparation method thereof and application thereof in low-temperature thermal catalytic treatment of toluene | |
| CN106582651A (en) | Preparation method for porous carrier-loaded nano-cobalt catalyst | |
| CN110523398B (en) | Carbon nano-sheet layer loaded TiO2Molecularly imprinted material and preparation method and application thereof | |
| CN110314685B (en) | Preparation method of core-shell structure catalyst for low-temperature catalytic oxidation of toluene | |
| JPWO2005120708A1 (en) | Method for producing catalyst | |
| CN111097413B (en) | CuO (copper oxide)xNanocluster and application thereof as ozone catalyst | |
| CN110449150B (en) | Hollow carbon tube array catalyst embedded with nano metal and preparation method and application thereof | |
| CN113967477B (en) | Monoatomic transition metal catalyst and preparation method and application thereof | |
| CN106984318B (en) | Bimetal cobalt-based catalyst, preparation method and application | |
| CN110116019B (en) | Nano cobaltosic oxide/alumina @ carrier catalyst and preparation method and application thereof | |
| Liu et al. | Boosting formaldehyde catalytic oxidation of novel Au/mPVB fiber membrane with microreactor-like structure | |
| CN114797847B (en) | Metal doped mesoporous carbon-based catalyst and preparation method and application thereof | |
| CN113457709B (en) | Preparation method and application of magnetic Co@CN nano material | |
| Du et al. | Mechanochemical synthesis of platinum nanoclusters supported cordierite for enhanced catalytic oxidation of toluene | |
| CN108236950A (en) | A kind of preparation method of the Pd-B/C powder as formaldehyde remover | |
| CN111672507B (en) | Preparation method and application of expanded perlite loaded nano-gold particle catalyst | |
| Li et al. | Enhanced catalytic ozonation performance by CuOx nanoclusters/TiO2 nanotube and an insight into the catalytic mechanism | |
| CN114768812B (en) | Heterogeneous Fenton catalyst LaFeO 3 /3DOMCeO 2 Preparation method and application thereof |
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 |