CN115999613A - Nitrogen and transition metal doped titanium dioxide particles, method for the production and use thereof - Google Patents
Nitrogen and transition metal doped titanium dioxide particles, method for the production and use thereof Download PDFInfo
- Publication number
- CN115999613A CN115999613A CN202310101578.5A CN202310101578A CN115999613A CN 115999613 A CN115999613 A CN 115999613A CN 202310101578 A CN202310101578 A CN 202310101578A CN 115999613 A CN115999613 A CN 115999613A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- nitrogen
- titanium dioxide
- solvent
- doped titanium
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 46
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 title claims abstract description 41
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 29
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 11
- 229960003405 ciprofloxacin Drugs 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 9
- 229940043267 rhodamine b Drugs 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000975 dye Substances 0.000 claims description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 26
- 229910010413 TiO 2 Inorganic materials 0.000 description 23
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000008187 granular material Substances 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 8
- 239000004202 carbamide Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052755 nonmetal Inorganic materials 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000002122 magnetic nanoparticle Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The invention provides nitrogen and transition metal doped titanium dioxide particles, a preparation method and application thereof. The nitrogen and transition metal doped titanium dioxide particles consist of a core, an inner shell coating the core and an outer shell coating the inner shell, wherein the core is a magnetic carrier, the inner shell is silicon dioxide, the outer shell is nitrogen and transition metal doped titanium dioxide, and the core and the inner shell form a composite magnetic carrier. Wherein the nitrogen content is 3.34 to 11.8% and the transition metal content is 0.7 to 3% based on 100% by mass of the nitrogen and the transition metal doped titanium dioxide particle surface element.
Description
Technical Field
The invention relates to the field of photocatalysis, in particular to titanium dioxide particles doped with nitrogen and transition metal, a preparation method and application thereof.
Background
In recent years, with the random emission of organic dyes, global pollution is increasingly serious, and photodegradation of catalytic materials has been a hot spot of research. Some domestic and foreign researches show that the photocatalysis method has good removal effect on hydrocarbons, carboxylic acid, dye, nitrogen-containing organic matters, phenols, chlorine-containing organic matters and the like in water, and has very important significance especially on organic pollutants which are difficult to degrade and photocatalysis. Among the photocatalysts commonly used, tiO 2 Is one of the most important types currently. TiO (titanium dioxide) 2 The method is an excellent research object because of the advantages of low cost, no toxicity, large specific surface area, high catalytic activity, corrosion resistance and the like. TiO (titanium dioxide) 2 Is an n-type semiconductor catalyst, has a low-energy valence band and a high-energy conduction band, has a forbidden band with a width of 3.2eV in the middle, and when the energy of illumination is greater than or equal to the forbidden band width, electrons on the valence band transition to the conduction band, leaving holes (h + ) Hole-electron pairs with high activity are generated. During photocatalysis, the holes (h + ) Has extremely strong capability of acquiring electrons, and TiO 2 The hole redox potential on the valence band is +2.7eV. It can convert OH - And H 2 O molecules are converted into hydroxyl radical OH with extremely high oxidizing ability and reactivity and adsorbed on TiO 2 Free oxygen in the surface material or solvent traps electrons to form 0 2 And (3) an equal high activity free radical. Can catalytically degrade organic pollutants into CO 2 、H 2 And inorganic small molecules such as O and the like are finally thoroughly purified. Domestic and foreign TiO 2 There are many reports on the use as photocatalysts, but in practical applications, there are several problems that restrict TiO 2 Application of the photocatalyst: (1) narrow spectral response range. Anatase TiO 2 Is of forbidden bandwidth (E) 0 =3.2 eV) can only absorb uv light with a wavelength less than or equal to 387 nm. While ultraviolet light only accounts for 3% to 4% of sunlight, which makes its light energy utilization lower. (2) Is not easy to recycle and heavyThe reuse rate is low. Therefore, how to develop a photocatalyst which can respond to visible light and can be easily recycled becomes a hot spot of current research.
Doping is TiO 2 A modification method commonly used is shown by researches, and the research shows that for TiO 2 Doping of nonmetallic or transition metal ions is carried out, so that hybridization of electron cloud is possibly changed, forbidden bands are narrowed, absorption bands are red shifted, and activity of visible light is improved. TiO (titanium dioxide) 2 The doping of (a) can be classified into metal ion doping and nonmetal ion doping, wherein the doping of metal ions such as Sn (II), nb (V), co (II), cu (II), ru (III) and the like can improve the visible light activity, and the nonmetal ions are mainly N, B, C, S. In recent years, metal-nonmetal N double doped TiO 2 There is also growing interest in the research of metal-nonmetal synergism which may increase its catalytic activity. Currently, metal-nonmetal N double doped TiO 2 Urea (urea) is generally used as the N source and the corresponding metal salt for the preparation, but the visible light catalytic properties of the product are generally low.
Disclosure of Invention
One of the present invention provides a nitrogen and transition metal doped titanium dioxide particle consisting of a core, an inner shell coating the core, and an outer shell coating the inner shell, wherein the core is a magnetic carrier, the inner shell is silica, the outer shell is nitrogen and transition metal doped titanium dioxide, wherein the core and the inner shell constitute a composite magnetic carrier.
In one embodiment, the composite magnetic carrier has a particle size of 100 to 1000nm.
In one embodiment, the composite magnetic carrier has a particle size of 200 to 500nm.
In one embodiment, the transition metal is at least one of cobalt, iron, and copper.
In a specific embodiment, the nitrogen content is 3.34% to 11.8% and the transition metal content is 0.7% to 3% based on 100% by mass of the nitrogen and transition metal doped titanium dioxide particle surface elements. The surface elements of the titanium dioxide particles doped with nitrogen and transition metals are obtained by EDS element analysis, for example, by Hitachi SU8100 emission Scanning Electron Microscope (SEM) EDS element analysis.
In a specific embodiment, the nitrogen content is 3.34% to 7.23% and the transition metal content is 0.9% to 3% based on 100% by mass of the nitrogen and transition metal doped titanium dioxide particle surface elements. The surface elements of the titanium dioxide particles doped with nitrogen and transition metals are obtained by EDS element analysis, for example, by Hitachi SU8100 emission Scanning Electron Microscope (SEM) EDS element analysis.
The second invention provides a process for preparing nitrogen-and transition metal-doped titanium dioxide particles according to any one of the invention, comprising the steps of:
1) Mixing and dispersing the composite magnetic carrier, the first solvent and tetrabutyl titanate to obtain a first dispersion liquid;
2) Mixing the second solvent, the third solvent and the surfactant, then mixing with the first dispersing agent, and regulating the pH value to be acidic to obtain a second dispersing liquid;
3) Adding a nitrate of a transition metal or a hydrate of a nitrate of a transition metal to the second dispersion to form a sol;
4) Separating out solid components from the sol, washing and drying to obtain a solid product;
5) Calcining the solid product to obtain the titanium dioxide particles doped with nitrogen and transition metal.
In one embodiment, the first solvent and the third solvent are independently absolute ethanol and the second solvent is water.
In a specific embodiment, the surfactant is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
In a specific embodiment, in step 1), the mass ratio of the composite magnetic carrier to tetrabutyl titanate is (0.1 to 1.2): 100.
in a specific embodiment, in step 2), the surfactant is added in such an amount that the molar ratio of surfactant to titanium (element) is (2 to 3): 50, e.g., a molar ratio of surfactant to titanium (element) of 2.36:50.
in a specific embodiment, in step 3), the nitrate of a transition metal or the hydrate of the nitrate of a transition metal is added in such an amount that the molar ratio of transition metal ions to titanium (element) is (1 to 2): 100, for example, the molar ratio of transition metal ions to titanium (element) is 1:100.
in a specific embodiment, in step 2), the pH is adjusted to a value of 2 to 4.
In a specific embodiment, in step 1), mixing the composite magnetic carrier and the first solvent, uniformly dispersing by ultrasonic, then adding tetrabutyl titanate, and uniformly stirring to obtain a first dispersion liquid;
in the step 2), the second solvent, the third solvent and the surfactant are mixed, then the mixture is dripped into the first dispersing agent, and the pH is regulated to be acidic by nitric acid, so as to obtain second dispersing liquid;
in step 3), a nitrate of a transition metal or a hydrate of a nitrate of a transition metal is added to the second dispersion, and the mixture is stirred continuously at an ambient temperature for 2 to 4 hours and then left at the ambient temperature for 8 to 12 hours to form a sol.
In a specific embodiment, in step 4), the solid component is separated from the sol by centrifugation or magnetic adsorption.
In a specific embodiment, in step 5), the calcination is carried out at a temperature of 450 to 500 ℃ for a time of 120 to 180 minutes.
The third invention provides the application of the nitrogen and transition metal doped titanium dioxide particles prepared by the method according to any one of the first invention or any one of the second invention in photocatalytic degradation of antibiotics and/or dyes.
In a specific embodiment, the use is for photocatalytic degradation of ciprofloxacin and/or rhodamine B.
The invention has the beneficial effects that:
introduction of Fe 3 O 4 Although the magnetic core can make the catalyst easy to recover and the absorption band red-shift, it is reported that if Fe is added 3 O 4 Directly wrap TiO 2 Which tends to result in a decrease in its catalytic efficiency. Therefore, the invention adopts nitrate of transition metal as N source and transition metal ion source to TiO 2 The doping of N and transition metal can effectively improve the ratio of transition metal/N content of the product and increase the visible light catalytic performance of the product. At the same time adopt SiO 2 Layer will Fe 3 O 4 The magnetic cores are separated, so that TiO at high temperature can be prevented 2 The magnetic core can be acted as an adhesive to adsorb TiO more 2 The catalytic effect is better. Then coating hydroxyl SiO by chemical method 2 The surface of the magnetic particle of the layer is coated with the above-mentioned N and transition metal element doped TiO with high transition metal/N ratio 2 And the layer is used for preparing the magnetic nano catalyst with a visible light response and a double-layer shell-core structure. The magnetic nanocatalyst is coated on the one hand with surface-coated doped TiO with a high transition metal/N ratio 2 A layer of TiO 2 The defect position is introduced or the crystallinity is changed, so that the energy required for exciting electrons can be reduced, and the visible light catalytic activity is improved. At the same time introduce Fe 3 O 4 The magnetic core can enable the catalyst to be easily recovered and reused through an external magnetic field. In addition Fe 3 O 4 Magnetic core surface SiO 2 The layer can prevent the damage of high temperature and acid environment to magnetic core and reduce TiO of magnetic core 2 Effect of layer photocatalytic efficiency.
The titanium dioxide particles doped with nitrogen and transition metal show higher visible light catalytic efficiency when used for catalytic degradation of the antibiotic wastewater and the organic dye rhodamine B under the visible light condition, and the degradation efficiency of the antibiotic wastewater and the rhodamine dye solution can reach 99.7 percent and 98.8 percent respectively. Meanwhile, the method is convenient for separation, recovery and cyclic utilization, and has good application prospects in the aspects of catalyzing water pollution, air pollution and the like.
Drawings
FIG. 1 shows N/Co-TiO prepared in example 1 2 @SiO 2 @Fe 3 O 4 With Fe 3 O 4 Particles and TiO 2 XRD contrast pattern of particles.
FIG. 2 shows N/Cu-TiO prepared in example 3 2 @SiO 2 @Fe 3 O 4 EDS elemental analysis map of the particles.
Fig. 3 shows the kinetics of the visible light-catalyzed degradation of ciprofloxacin aqueous solutions for the granular products prepared in examples 1 to 3 and comparative examples 1 and 2.
Fig. 4 shows the kinetics of the catalytic degradation of aqueous rhodamine B solutions by visible light for example 1, comparative example 1 and comparative example 2.
Detailed Description
The invention is further illustrated below with reference to the examples, which are merely illustrative of the invention and do not constitute a limitation of the invention in any way.
Example 1
N/Co-TiO 2 @SiO 2 @Fe 3 O 4 Preparation of granules
1) 40mL of absolute ethanol and 54mg of 200-500nm SiO 2 @Fe 3 O 4 Adding magnetic nano particles into a 250mL three-necked flask, uniformly dispersing the magnetic nano particles in an ultrasonic cleaner, then adding 0.05mol of tetrabutyl titanate, and mechanically stirring for 30min to obtain a first dispersion liquid;
2) 9mL of deionized water, 25mL of absolute ethanol and 2.36mmol of SDS are mixed, then the mixture is slowly added into the first dispersion liquid in a dropwise manner, and the pH value is adjusted to 3.0 by nitric acid, so that a second dispersion liquid is obtained;
3) To the second dispersion was added 0.5mmol Co (NO) 3 ) 2 ·6H 2 O, continuously stirring for 2 hours at the ambient temperature, and standing at the ambient temperature for one night to form sol;
4) Centrifuging the sol at 8000rpm for 3min, removing supernatant after centrifuging, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying at 100deg.C for 4h to obtain solid product;
5) The solid product was placed in a muffle furnace and heated to 450℃in an air atmosphereCalcining for 120min to obtain N/Co-TiO 2 @SiO 2 @Fe 3 O 4 And (3) particles.
Detection of N/Co-TiO using an X-ray powder diffractometer (Co target, bruker, germany) model D8 ADVANCE 2 @SiO 2 @Fe 3 O 4 XRD of particles, with Fe 3 O 4 Particles and TiO 2 The particles serve as a control, see figure 1.
As can be seen from the results of FIG. 1, N/Co-TiO 2 @SiO 2 @Fe 3 O 4 Particles at 2θ=25.4°,37.8 °,48.1 °,53.9 °,54.3 ° and 62.8 ° respectively exhibit corresponding anatase TiO 2 (101) of (a); (004); (200); (105) Diffraction peaks, explaining TiO 2 Has been successfully coated on SiO 2 @Fe 3 O 4 Outer core layer, and Fe at 2θ=35.6 ° (311) and 57.2 ° (511) 3 O 4 The characteristic peak of (2) is significantly reduced.
N/Co-TiO pairs using Hitachi SU8100 emission scanning electron microscope 2 @SiO 2 @Fe 3 O 4 As a result of EDS elemental analysis of the granular product, N/Co-TiO was analyzed by Hitachi SU 8100-type emission scanning electron microscope EDS elemental analysis 2 @SiO 2 @Fe 3 O 4 The total mass of the surface elements of the particles was taken as 100%, the N content was 7.23% and the Co content was 0.91%.
Example 2
N/Fe-TiO 2 @SiO 2 @Fe 3 O 4 Preparation of granules
0.14552g Co(NO 3 ) 2 ·6H 2 O is replaced by 0.20200g Fe (NO) 3 ) 3 ·9H 2 O, N/Fe-TiO is obtained 2 @
SiO 2 @Fe 3 O 4 And (3) particles.
Otherwise, the same as in example 1 was conducted.
N/Fe-TiO pairs using Hitachi SU8100 emission scanning electron microscope 2 @SiO 2 @Fe 3 O 4 As a result of EDS elemental analysis of the granular product, N/Fe-TiO was analyzed by Hitachi SU 8100-type emission scanning electron microscope EDS elemental analysis 2 @SiO 2 @Fe 3 O 4 The total mass of the surface elements of the particles was taken as 100%, wherein the N content was 3.34% and the Fe content was 2.98%.
Example 3
N/Cu-TiO 2 @SiO 2 @Fe 3 O 4 Preparation of granules
0.14552g Co(NO 3 ) 2 ·6H 2 O is replaced by 0.09378g Cu (NO) 3 ) 2 ·xH 2 O, N/Cu-TiO is obtained 2 @
SiO 2 @Fe 3 O 4 And (3) particles.
Otherwise, the same as in example 1 was conducted.
N/Cu-TiO pairs using Hitachi SU8100 emission scanning electron microscope 2 @SiO 2 @Fe 3 O 4 EDS elemental analysis of the particulate product was performed, and the results are shown in FIG. 2. As can be seen from FIG. 2, N/Cu-TiO was analyzed by Hitachi SU8100 type emission scanning electron microscope EDS elemental analysis 2 @SiO 2 @Fe 3 O 4 The total mass of the surface elements of the particles was taken as 100%, wherein the N content was 6.14% and the Cu content was 0.96%.
Comparative example 1
1) 60mg of SiO 2 @Fe 3 O 4 Mixing magnetic nanoparticles with 40mL of deionized water), adding the mixture into a 250mL three-necked flask, and uniformly dispersing the mixture in an ultrasonic cleaner to obtain a first dispersion;
2) 0.84g of urea is dissolved in 5mL of deionized water to obtain urea aqueous solution;
3) Slowly adding urea aqueous solution and 5mL tetrabutyl titanate into the first dispersion liquid which is vigorously stirred in sequence, keeping at 40 ℃ for 2 hours, and then carrying out ultrasonic treatment at 40 ℃ for 40 minutes to obtain a second dispersion liquid;
4) Centrifuging the second dispersion liquid at 8000rpm for 3min, removing supernatant after centrifuging, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying at 100deg.C for 4h to obtain solid product;
5) Calcining the solid product in a muffle furnace in an air atmosphere at 450 ℃ for 120min to obtain TiO 2 @SiO 2 @Fe 3 O 4 And (3) particles.
Comparative example 2
1) 60mg of SiO 2 @Fe 3 O 4 Mixing magnetic nanoparticles with 40mL of deionized water), adding the mixture into a 250mL three-necked flask, and uniformly dispersing the mixture in an ultrasonic cleaner to obtain a first dispersion;
2) 0.84g of urea is dissolved in 5mL of deionized water to obtain urea aqueous solution;
3) 3.3g of CoCl 2 ·6H 2 O is dissolved in 5mL of water to obtain CoCl 2 An aqueous solution;
4) Urea aqueous solution, coCl 2 Slowly adding the aqueous solution and 5mL of tetrabutyl titanate into the vigorously stirred first dispersion liquid in sequence, keeping at 40 ℃ for 2 hours, and then carrying out ultrasonic treatment at 40 ℃ for 40 minutes to obtain a second dispersion liquid;
5) Centrifuging the second dispersion liquid at 8000rpm for 3min, removing supernatant after centrifuging, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, and drying at 100deg.C for 4h to obtain solid product;
6) Calcining the solid product in a muffle furnace in air at 450 ℃ for 120min to obtain N/Co-TiO 2 @SiO 2 @Fe 3 O 4 And (3) particles.
N/Co-TiO pairs using Hitachi SU8100 emission scanning electron microscope 2 @SiO 2 @Fe 3 O 4 As a result of EDS elemental analysis of the granular product, N/Co-TiO was analyzed by Hitachi SU 8100-type emission scanning electron microscope EDS elemental analysis 2 @SiO 2 @Fe 3 O 4 The total mass of the surface elements of the particles was taken as 100%, where the N content was 21.84% and the Co content was 1.78%.
Performance measurement
1. Visible light catalytic degradation of ciprofloxacin
3mg of the pellets prepared in examples 1 to 3 and comparative examples 1 and 2 were added to 3mL of 0.017mmoll, respectively -1 In ciprofloxacin aqueous solution, a xenon lamp is turned on to carry out illumination reaction while a stirring device is turned on, sampling is carried out every half hour, and the reaction is finished after 3 hours. Wherein, the samples of each time are centrifugally separated, and the supernatant is taken after the centrifugation is finished to measure the ultraviolet spectrum, and the result is shown in figure 4.
As can be seen from fig. 3, for the granules prepared in comparative examples 1 and 2 added to ciprofloxacin aqueous solution, the degradation rates to ciprofloxacin after irradiation with visible light for 3 hours were only 26.6% and 42.2%, respectively; in contrast, after the granules prepared in examples 1 to 3 were added, the degradation rate of ciprofloxacin under irradiation of visible light was significantly increased, and ciprofloxacin was substantially completely degraded within 3 hours, and the degradation rates of the granules prepared in examples 1 to 3 were 99.13%, 91.56% and 99.67%, respectively, in this order. The degradation rate of the granules prepared in the examples 1 and 3 is very fast in the first 1h, and the degradation rate of ciprofloxacin can reach 86.43% and 98.91% respectively in sequence, so that the granules show higher visible light catalytic activity.
2. Visible light catalytic degradation rhodamine B
50g of the pellets prepared in example 1, comparative example 1 and comparative example 2 were added to 50mL of 4mg/L rhodamine B aqueous solution, respectively, a xenon lamp was turned on while a stirring device was turned on, the timing was started, continuous light was performed, sampling was performed every half hour, and the reaction was completed after 3 hours. Wherein, the samples were subjected to centrifugal separation, and the supernatant was taken after the centrifugation was completed to measure the ultraviolet absorption, and the result is shown in FIG. 4.
As can be seen from fig. 4, the degradation rates of rhodamine B after irradiation with visible light for 3 hours were only 59.5% and 72.1% for comparative example 1 and comparative example 2, respectively. In contrast, the granule prepared in example 1 significantly increased the degradation rate of rhodamine B under visible light irradiation, and the granule prepared in example 1 was able to degrade rhodamine B substantially completely in 3 hours, and the degradation rate reached 98.8%, thus showing higher visible light catalytic activity.
Although the invention has been described with reference to specific embodiments, those skilled in the art will appreciate that various modifications might be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of materials, and method to the essential scope, spirit, and scope of the present invention. All such modifications are intended to be included within the scope of this invention as defined in the following claims.
Claims (10)
1. The nitrogen and transition metal doped titanium dioxide particles consist of a core, an inner shell coating the core and an outer shell coating the inner shell, wherein the core is a magnetic carrier, the inner shell is silicon dioxide, the outer shell is nitrogen and transition metal doped titanium dioxide, and the core and the inner shell form a composite magnetic carrier.
2. The nitrogen-and transition metal-doped titanium dioxide particles of claim 1, wherein the transition metal is at least one of cobalt, iron, and copper.
3. The nitrogen-and transition metal-doped titanium dioxide particles according to claim 1, wherein the nitrogen content is 3.34% to 11.8% and the transition metal content is 0.7% to 3% based on the mass of the surface elements of the nitrogen-and transition metal-doped titanium dioxide particles as 100%;
preferably, the nitrogen content is 3.34 to 7.23% and the transition metal content is 0.9 to 3% based on 100% by mass of the nitrogen and transition metal doped titanium dioxide particle surface elements.
4. A process for preparing nitrogen-and transition metal-doped titanium dioxide particles according to any one of claims 1 to 3, comprising the steps of:
1) Mixing and dispersing the composite magnetic carrier, the first solvent and tetrabutyl titanate to obtain a first dispersion liquid;
2) Mixing the second solvent, the third solvent and the surfactant, then mixing with the first dispersing agent, and regulating the pH value to be acidic to obtain a second dispersing liquid;
3) Adding a nitrate of a transition metal or a hydrate of a nitrate of a transition metal to the second dispersion to form a sol;
4) Separating out solid components from the sol, washing and drying to obtain a solid product;
5) Calcining the solid product to obtain the titanium dioxide particles doped with nitrogen and transition metal.
5. The method of claim 4, wherein the first solvent and the third solvent are independently absolute ethanol and the second solvent is water; and/or
The surfactant is sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate.
6. The method according to claim 4, wherein in step 1), the mass ratio of the composite magnetic carrier and tetrabutyl titanate is (0.1 to 1.2): 100; and/or
In step 2), the surfactant is added in such an amount that the molar ratio of surfactant to titanium is (2 to 3): 50; and/or
In step 3), the nitrate of the transition metal or the hydrate of the nitrate of the transition metal is added in such an amount that the molar ratio of the transition metal ion to titanium is (1 to 2): 100.
7. the method according to claim 4, wherein in step 2), the pH is adjusted to 2 to 4.
8. The method according to claim 4, wherein in step 1), the composite magnetic carrier and the first solvent are mixed, dispersed by ultrasound uniformly, and then tetrabutyl titanate is added and stirred uniformly to obtain a first dispersion;
in the step 2), the second solvent, the third solvent and the surfactant are mixed, then the mixture is dripped into the first dispersing agent, and the pH is regulated to be acidic by nitric acid, so as to obtain second dispersing liquid;
in step 3), a nitrate of a transition metal or a hydrate of a nitrate of a transition metal is added to the second dispersion, and the mixture is stirred continuously at an ambient temperature for 2 to 4 hours and then left at the ambient temperature for 8 to 12 hours to form a sol.
9. The method according to claim 4, characterized in that in step 4) the solid components are separated from the sol by centrifugation or magnetic adsorption; and/or
In step 5), the calcination temperature is 450 to 500 ℃ and the calcination time is 120 to 180 minutes.
10. Use of the nitrogen and transition metal doped titanium dioxide particles according to any one of claims 1 to 3 or prepared by the method of any one of claims 4 to 9 for photocatalytic degradation of antibiotics and/or dyes;
preferably, the use is for photocatalytic degradation of ciprofloxacin and/or rhodamine B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310101578.5A CN115999613A (en) | 2023-02-10 | 2023-02-10 | Nitrogen and transition metal doped titanium dioxide particles, method for the production and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310101578.5A CN115999613A (en) | 2023-02-10 | 2023-02-10 | Nitrogen and transition metal doped titanium dioxide particles, method for the production and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115999613A true CN115999613A (en) | 2023-04-25 |
Family
ID=86034026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310101578.5A Pending CN115999613A (en) | 2023-02-10 | 2023-02-10 | Nitrogen and transition metal doped titanium dioxide particles, method for the production and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115999613A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118002126A (en) * | 2024-04-07 | 2024-05-10 | 西南交通大学 | Titanium dioxide hollow sphere loaded nano copper photocatalyst and preparation method and application thereof |
-
2023
- 2023-02-10 CN CN202310101578.5A patent/CN115999613A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118002126A (en) * | 2024-04-07 | 2024-05-10 | 西南交通大学 | Titanium dioxide hollow sphere loaded nano copper photocatalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lei et al. | ZIF-8 derived hollow CuO/ZnO material for study of enhanced photocatalytic performance | |
| CN106824213B (en) | Cobalt oxide doped bismuth subcarbonate/bismuth oxychloride photocatalyst and preparation method thereof | |
| Li et al. | Facile synthesis of ZnO/g-C3N4 composites with honeycomb-like structure by H2 bubble templates and their enhanced visible light photocatalytic performance | |
| Yang et al. | One step solvothermal synthesis of Bi/BiPO4/Bi2WO6 heterostructure with oxygen vacancies for enhanced photocatalytic performance | |
| Khanmohammadi et al. | Insights into mesoporous MCM-41-supported titania decorated with CuO nanoparticles for enhanced photodegradation of tetracycline antibiotic | |
| US10933406B2 (en) | Method of preparing large-size high-porosity Fe-doped photocatalytic porous magnetic microspheres and uses thereof | |
| Lavand et al. | Synthesis, characterization, and visible light photocatalytic activity of nanosized carbon doped zinc oxide | |
| CN110227453B (en) | Preparation method of AgCl/ZnO/GO composite visible light catalyst | |
| CN103172030A (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN112844484B (en) | Boron nitride quantum dot/porous metal organic framework composite photocatalytic material and preparation method and application thereof | |
| CN107469804A (en) | A kind of titania-based composite photocatalyst material of nano particle bismuth load and its preparation method and application | |
| CN106902890B (en) | Cu-BTC/bismuth vanadate/SWCNTs ternary heterostructure photocatalyst and preparation method and application thereof | |
| CN115999613A (en) | Nitrogen and transition metal doped titanium dioxide particles, method for the production and use thereof | |
| Jamila et al. | Pivotal role of N and Bi doping in CQD/Mn 3 O 4 composite structure with outstanding visible photoactivity | |
| Shi et al. | Synergistic effect of oxygen vacancies and built-in electric field in GdCrO3/BiVO4 composites for boosted photocatalytic reduction of nitrate in water | |
| Li et al. | Visible-light photocatalytic activity of Fe and/or Ni doped ilmenite derived-titanium dioxide nanoparticles | |
| CN108837840B (en) | A kind of Ag/g-C3N4Modify bismuth tungstate mixed crystal composite material and preparation method and application | |
| Hou et al. | A three-dimensional nano-network WO 3/F-TiO 2-{001} heterojunction constructed with OH-TiOF 2 as the precursor and its efficient degradation of methylene blue | |
| Ahmad et al. | A review on versatile metal vanadates photocatalysts for energy conversion and environmental remediation | |
| Jin et al. | Preparation of flower-like Bi 2 WO 6/ZnO heterojunction photocatalyst with improved photocatalytic performance | |
| Chen et al. | RETRACTED ARTICLE: Visible-Light-Driven Mitigation of Rhodamine B and Disinfection of E. coli Using Magnetic Recyclable Copper–Nitrogen Co-doped Titania/Strontium Ferrite/Diatomite Heterojunction Composite | |
| CN111266114A (en) | Metallic iron/zinc oxide/carbon ternary nano composite visible light catalyst and preparation method and application thereof | |
| Shang et al. | Oxygen vacancy induced bismuth basic nitrate with excellent photocatalytic activity | |
| CN114471707B (en) | Hydrogel sphere containing catalyst, preparation method thereof and application thereof in photocatalytic treatment of organic pollutants | |
| Xue et al. | Construction of Cu 2+-doped CeO 2 nanocrystals hierarchical hollow structure and its enhanced photocatalytic performance |
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 |