CN113019374B - NiO/ZrO 2 Preparation method of nano composite photocatalyst and application of catalyst - Google Patents
NiO/ZrO 2 Preparation method of nano composite photocatalyst and application of catalyst Download PDFInfo
- Publication number
- CN113019374B CN113019374B CN202110276894.7A CN202110276894A CN113019374B CN 113019374 B CN113019374 B CN 113019374B CN 202110276894 A CN202110276894 A CN 202110276894A CN 113019374 B CN113019374 B CN 113019374B
- Authority
- CN
- China
- Prior art keywords
- zro
- nio
- solution
- composite photocatalyst
- nano composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 83
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 title abstract description 14
- 238000006731 degradation reaction Methods 0.000 claims abstract description 48
- 230000015556 catabolic process Effects 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000005286 illumination Methods 0.000 claims abstract description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000005406 washing Methods 0.000 abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 4
- 239000001569 carbon dioxide Substances 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 77
- 239000000243 solution Substances 0.000 description 55
- 229960000907 methylthioninium chloride Drugs 0.000 description 34
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 239000000706 filtrate Substances 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 10
- 238000011160 research Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- -1 p-Methylene Chemical group 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005303 weighing 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to lightThe technical field of catalysts, in particular to NiO/ZrO 2 A preparation method of a nano composite photocatalyst and application of the catalyst. Reacting NaBH 4 ZrOCl is added into the solution 2 ·8H 2 Forming white sol in the O solution, and stirring until a precipitate is generated; filtering, washing, drying, adding (NH) 4 ) 2 CO 3 Solution and Ni (NO) 3 ) 2 ·6H 2 In O solution, ultrasonic dispersion, drying, roasting and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst. NiO/ZrO prepared by the invention 2 The nano composite photocatalyst has high catalytic activity and good dispersibility. NiO/ZrO 2 The nanometer composite photocatalyst is added into organic wastewater, and is subjected to degradation reaction under the illumination condition, toxic and harmful substances can be directly degraded into water and carbon dioxide, and the degradation rate is over 99.8%, so that the degradation treatment of organic matters in the organic wastewater is realized.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to NiO/ZrO 2 A preparation method of a nano composite photocatalyst and application of the catalyst.
Background
The printing and dyeing wastewater is one of the main industrial wastewater sources in China at present, has deep color, more organic poisons, large discharge amount, difficult biodegradation and high heavy metal content, is treated by physical, chemical and biological methods generally, but has low efficiency, incomplete treatment, easy generation of secondary pollution and the like. Photocatalytic oxidation degradation of pollutants is a green technology developed in recent years, organic pollution sources can be thoroughly degraded into carbon dioxide, water and the like by the aid of a photocatalyst at normal temperature and normal pressure, operation is simple, efficiency is high, secondary pollution is avoided, and the photocatalytic oxidation degradation technology has great application potential in the field of printing and dyeing wastewater treatment.
In recent years, semiconductor photocatalytic oxidation methods have low energy consumption, easy operation and no secondary pollution, and become a new hotspot of wastewater treatment research. At present, the photocatalyst is modified by methods such as surface modification, addition of other semiconductor oxides, deposition of metal ions and the like, for example, the kaolin is used for modifying nano ZnO, and the specific method is as follows: soaking a certain amount of kaolin in a nitric acid aqueous solution, heating in a water bath, stirring, performing vacuum filtration, washing, drying and grinding for later use; weighing a certain amount of modified kaolin and placing the modified kaolin into a three-neck flaskAdding appropriate amount of distilled water, stirring, heating in water bath, and dripping Zn (CH) with a micro burette at a certain dripping speed 3 COO) 2 ·2H 2 O solution, reacting for 30min, and then (NH) is added dropwise 4 ) 2 CO 3 And (3) adjusting the pH value of the dilute solution to 7-8, continuously heating and stirring, filtering, washing, drying, roasting in a muffle furnace, cooling and grinding to obtain the Kaolin/ZnO nano photocatalyst powder.
ZrO 2 Is a P-type semiconductor oxide, has the characteristics of good acid-base property and good oxidation-reduction property, and is easy to generate oxygen holes. Nano-size ZrO 2 Large specific surface area, many surface oxygen vacancies and strong ion exchange capacity, is an excellent photocatalyst and can directly degrade toxic and harmful substances into water, carbon dioxide and the like. But ZrO 2 The forbidden band width (5.65ev) is wider, and the defects of high requirement on a light source, easy agglomeration, need to improve the catalytic activity and the like exist. At present, the research is more carried out by doping other components for composite modification, for example, the energy level difference among different semiconductors is utilized to improve the photocatalytic activity, and simultaneously, the agglomeration phenomenon can be reduced, so that the semiconductor is easier to suspend in waste water, and the catalytic reaction is facilitated. And the forbidden band width of nickel oxide (NiO) is 3.50ev, and the nickel oxide is also an excellent P-type semiconductor material and is widely applied to the aspect of photocatalytic degradation.
Currently, for preparing ZrO by modifying nano NiO 2 The research on the composite photocatalyst is rarely reported.
Disclosure of Invention
The invention aims to provide NiO/ZrO with high catalytic activity and good dispersity 2 A preparation method of a nano composite photocatalyst; the invention simultaneously provides NiO/ZrO 2 Application of the nano composite photocatalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the NiO/ZrO of the invention 2 The preparation method of the nano composite photocatalyst comprises the following steps: reacting NaBH 4 ZrOCl is added into the solution 2 ·8H 2 Forming white sol in the O solution, and stirring until precipitate is generated; filtering, washing, drying, adding (NH) 4 ) 2 CO 3 Solution and Ni (NO) 3 ) 2 ·6H 2 In O solution, ultrasonic dispersion, drying, roasting and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst.
Wherein:
the NaBH 4 Solution and ZrOCl 2 ·8H 2 The volume ratio of the O solution is 1-1.5: 1.
The NaBH 4 The concentration of the solution is 0.1-0.2mol/L, ZrOCl 2 ·8H 2 The concentration of the O solution is 0.1-0.2 mol/L.
Said (NH) 4 ) 2 CO 3 Solution, Ni (NO) 3 ) 2 ·6H 2 O solution and ZrOCl 2 ·8H 2 The volume ratio of the O solution is 1-5:0.5-1: 4-10.
Said (NH) 4 ) 2 CO 3 The concentration of the solution is 0.5-1.0mol/L, Ni (NO) 3 ) 2 ·6H 2 The concentration of O is 0.1-0.2 mol/L.
Vacuum drying is adopted after the ultrasonic dispersion, and the vacuum drying is carried out for 8-10h at the temperature of 80-90 ℃.
The roasting temperature is 350-400 ℃, and the roasting time is 2-4 h.
Said addition of (NH) 4 ) 2 CO 3 Solution and Ni (NO) 3 ) 2 ·6H 2 Stirring the O solution for 20-30min, then ultrasonically dispersing for 20-25min, standing for 2-4h, drying, roasting and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst.
NiO/ZrO prepared by the preparation method of the invention 2 The application of the nano composite photocatalyst comprises the following steps: NiO/ZrO 2 The nano composite photocatalyst is added into the organic wastewater and undergoes degradation reaction under the illumination condition, thereby realizing the degradation treatment of organic matters in the organic wastewater.
Wherein: NiO/ZrO 2 The dosage ratio of the nano composite photocatalyst to the organic wastewater is 0.4-0.6:1, wherein NiO/ZrO 2 The nano composite photocatalyst is calculated by g, and the organic wastewater is calculated by L.
The illumination condition is ultraviolet irradiation or sunlight irradiation. When the ultraviolet light is irradiated, the degradation reaction time is 1.0-1.5 h; when the solar light irradiates, the degradation reaction time is 1.5-2.5 h.
The invention has the following beneficial effects:
(1) NaBH is added to the invention 4 Adding ZrOCl into the solution 2 ·8H 2 Reacting in O solution to form white sol, stirring until Zr (OH) 4 Generating a precipitate; zr (OH) 4 Adding (NH) in the precipitate 4 ) 2 CO 3 Solution and Ni (NO) 3 ) 2 ·6H 2 In the mixed solution of the O solution, Zr (OH) is enabled by ultrasonic 4 The precipitate is uniformly dispersed in (NH) 4 ) 2 CO 3 Solution and Ni (NO) 3 ) 2 ·6H 2 Zr (OH) in the mixture of O solution 4 Precipitation with (NH) 4 ) 2 CO 3 Reaction to form ZrO (OH) 2 ，ZrO(OH) 2 With Ni (NO) 3 ) 2 ·6H 2 Roasting O to generate NiO/ZrO 2 A nano composite photocatalyst. The invention is in ZrO (OH) 2 Before generation, Ni (NO) 3 ) 2 ·6H 2 Adding O solution into the reaction system, ZrO (OH) 2 While forming, the resulting ZrO (OH) is dispersed in the system 2 Uniformly dispersed in Ni (NO) 3 ) 2 ·6H 2 O solution, and then roasting to generate NiO/ZrO 2 NiO and ZrO in nano composite photocatalyst 2 Also in a uniformly dispersed state.
The XRD spectrogram can show that diffraction peaks of 2 theta in the XRD spectrogram respectively correspond to crystal faces of cubic phase NiO, the peak pattern is clear, the intensity is high, the half-peak width is small, and the crystallization performance of NiO in the composite catalyst is good; however, ZrO was not observed 2 Characteristic peak, which indicates ZrO calcined at 350-400 DEG C 2 Mainly in an amorphous state. NiO/ZrO can be seen from the SEM spectrogram 2 The nano composite photocatalyst consists of microspheres with different sizes. The NiO/ZrO can be known by combining an XRD spectrogram and an SEM spectrogram 2 In the nano composite photocatalyst, ZrO 2 And NiO exists in the form of respective compounds, and NiO is uniformly dispersed in ZrO 2 Surface of (2) using NiO to ZrO 2 Composite modification to NiO/ZrO 2 The nano composite photocatalyst has high catalytic activity and dispersionThe performance is good.
(2) The invention leads NiO/ZrO 2 The nanometer composite photocatalyst is added into organic wastewater, and is subjected to degradation reaction under the illumination condition, toxic and harmful substances can be directly degraded into water and carbon dioxide, and the degradation rate is over 99.8%, so that the degradation treatment of organic matters in the organic wastewater is realized.
Drawings
FIG. 1 is a NiO/ZrO example 1 of the present invention 2 XRD pattern of the nano composite photocatalyst;
FIG. 2 is a NiO/ZrO layer in example 1 of the present invention 2 SEM atlas of the nanometer composite photocatalyst;
FIG. 3 is NiO/ZrO in example 1 of the present invention 2 EDS spectrum of the nano composite photocatalyst;
FIG. 4 is a graph showing the amount of Ni added versus NiO/ZrO 2 A catalytic performance diagram of the nano composite photocatalyst;
FIG. 5 is a NiO/ZrO layer of the present invention 2 The influence curve diagram of the dosage of the nano composite photocatalyst on the catalytic performance of the nano composite photocatalyst;
FIG. 6 is a graph of reaction time vs. NiO/ZrO for the present invention 2 The influence curve diagram of the catalytic performance of the nano composite photocatalyst;
FIG. 7 is a NiO/ZrO layer of the present invention 2 A pseudo-first order kinetic model diagram of the catalytic reaction of the nano composite photocatalyst.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
5L of 0.2mol/L NaBH 4 The solution was added dropwise with 5L of 0.1mol/L ZrOCl 2 ·8H 2 Forming white sol in the O solution, and stirring strongly until precipitate is generated; then filtering and washing until the filtrate is neutral, filtering and drying for 6h at 80 ℃; the precipitate was added to 5L of 0.5mol/L (NH) 4 ) 2 CO 3 Solution and 0.9L of 0.1mol/L Ni (NO) 3 ) 2 ·6H 2 Stirring for 20min in O solution, ultrasonic dispersing for 20min, standing for 3h, vacuum drying at 80 deg.C for 8h, calcining at 350 deg.C for 3h, and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst. Wherein NiThe molar fraction of the addition was 15%.
The NiO/ZrO 2 The application of the nano composite photocatalyst comprises the following steps: preparing 60mg/L p-Methylene Blue (MB) solution as simulated wastewater, and adding NiO/ZrO 2 Adding the nano composite photocatalyst into MB solution to obtain NiO/ZrO 2 The dosage of the nano composite photocatalyst is 0.6 g/L; and carrying out degradation reaction for 1.2h under the ultraviolet irradiation condition. Samples were taken at regular intervals from the start of the ultraviolet light irradiation, centrifuged, and the absorbance of MB in the filtrate was measured to calculate the degradation rate D ═ 1- ρ/ρ according to the following formula 0 ) X 100%, where ρ 0 And ρ is the absorbance at the initial and time t, respectively. The degradation rate D is 100%.
Example 2
5L of 0.2mol/L NaBH 4 4L of 0.1mol/L ZrOCl is added dropwise into the solution 2 ·8H 2 Forming white sol in the O solution, and stirring strongly until precipitate is generated; then filtering and washing until the filtrate is neutral, filtering and drying for 5h at 90 ℃; the precipitate was added to 2L of 0.5mol/L (NH) 4 ) 2 CO 3 Solution and 1L of 0.1mol/L Ni (NO) 3 ) 2 ·6H 2 Stirring for 25min in O solution, performing ultrasonic dispersion for 25min, standing for 2h, vacuum drying at 85 deg.C for 9h, calcining at 380 deg.C for 3h, and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst. Wherein the molar fraction of Ni is 20%.
The NiO/ZrO was subjected to 2 The application of the nano composite photocatalyst comprises the following steps: preparing 60mg/L p-Methylene Blue (MB) solution as simulated wastewater, and adding NiO/ZrO 2 Adding the nano composite photocatalyst into MB solution to obtain NiO/ZrO 2 The dosage of the nano composite photocatalyst is 0.6 g/L; and carrying out degradation reaction for 1.5h under the ultraviolet irradiation condition. Samples were taken at regular intervals from the start of the ultraviolet light irradiation, centrifuged, and the absorbance of MB in the filtrate was measured to calculate the degradation rate D ═ 1- ρ/ρ according to the following formula 0 ) X 100%, where ρ 0 ρ is the absorbance at the initial and t times, respectively. The degradation rate is 99.95%.
Example 3
6L of 0.2mol/L NaBH 4 4.5L of 0.2mol/L ZrOCl is added dropwise into the solution 2 ·8H 2 Forming white sol in the O solution, and stirring strongly until precipitate is generated; then filtering and washing until the filtrate is neutral, filtering and drying for 6h at 80 ℃; the precipitate was added to 3L of 1.0mol/L (NH) 4 ) 2 CO 3 Solution and 1L of 0.1mol/L Ni (NO) 3 ) 2 ·6H 2 Stirring in O solution for 30min, ultrasonic dispersing for 20min, standing for 4 hr, vacuum drying at 90 deg.C for 8 hr, calcining at 400 deg.C for 2 hr, and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst. Wherein the molar fraction of Ni is 10%.
The NiO/ZrO was subjected to 2 The application of the nano composite photocatalyst comprises the following steps: preparing 60mg/L p-Methylene Blue (MB) solution as simulated wastewater, and adding NiO/ZrO 2 Adding the nano composite photocatalyst into MB solution to obtain NiO/ZrO 2 The dosage of the nano composite photocatalyst is 0.6 g/L; the degradation reaction is carried out for 1.0h under the condition of ultraviolet irradiation. Samples were taken at regular intervals from the start of the ultraviolet light irradiation, centrifuged, and the absorbance of MB in the filtrate was measured to calculate the degradation rate D ═ 1- ρ/ρ according to the following formula 0 ) X 100%, where ρ 0 And ρ is the absorbance at the initial and time t, respectively. The degradation rate was 99.93%.
Example 4
10L of 0.1mol/L NaBH 4 The solution was added dropwise with 9.5L of 0.1mol/L ZrOCl 2 ·8H 2 Forming white sol in the O solution, and stirring strongly until precipitate is generated; then filtering and washing until the filtrate is neutral, filtering and drying for 6h at 80 ℃; the precipitate was added to 4L of 1.0mol/L (NH) 4 ) 2 CO 3 Solution and 0.5L of 0.1mol/L Ni (NO) 3 ) 2 ·6H 2 Stirring for 30min in O solution, ultrasonic dispersing for 20min, standing for 4h, vacuum drying at 90 deg.C for 10h, calcining at 400 deg.C for 2h, and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst. Wherein the molar fraction of Ni is 5%.
The NiO/ZrO was subjected to 2 The application of the nano composite photocatalyst comprises the following steps: preparing 60mg/L p-Methylene Blue (MB) solution as simulated wastewater, and adding NiO/ZrO 2 Adding the nano composite photocatalyst into MB solution to obtain NiO/ZrO 2 The dosage of the nano composite photocatalyst is 0.6 g/L; in the sunDegradation reaction occurs for 2.5h under the condition of light irradiation. Samples were taken at regular intervals from the start of the solar light irradiation, centrifuged, and the absorbance of MB in the filtrate was measured to calculate the degradation rate D ═ 1- ρ/ρ according to the following formula 0 ) X 100%, where ρ 0 And ρ is the absorbance at the initial and time t, respectively. The degradation rate is 99.85%.
Comparative example 1
Firstly preparing ZrO 2 Precursor, then ZrO is added 2 Precursor and Ni (NO) 3 ) 2 ·6H 2 The catalyst is prepared by roasting the O solution, and the method comprises the following specific steps:
5L of 0.2mol/L NaBH 4 5L of 0.1mol/L ZrOCl is added into the solution 2 ·8H 2 Forming white sol in the O solution, and stirring strongly until precipitate is generated; then filtering and washing until the filtrate is neutral, filtering and drying, and then adding 0.5mol/L (NH) 4 ) 2 CO 3 The solution is placed in a reaction kettle of a self-made Teflon liner after being subjected to ultrasonic treatment and uniform dispersion, is kept at 180 ℃ for 10 hours in an oven, is naturally cooled to room temperature, is washed, dried and ground to obtain ZrO 2 A precursor;
subjecting the above-mentioned ZrO to heat treatment 2 The precursor is dispersed into 0.9L of 0.1mol/L Ni (NO) 3 ) 2 ·6H 2 Stirring for 20min in O solution, ultrasonic dispersing for 20min, standing for 3h, vacuum drying at 80 deg.C for 8h, calcining at 350 deg.C for 3h, and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst.
The NiO/ZrO was subjected to 2 The application of the nano composite photocatalyst comprises the following steps: preparing 60mg/L p-Methylene Blue (MB) solution as simulated wastewater, and adding NiO/ZrO 2 Adding the nano composite photocatalyst into MB solution to obtain NiO/ZrO 2 The dosage of the nano composite photocatalyst is 0.6 g/L; and carrying out degradation reaction for 1.2h under the ultraviolet irradiation condition. Samples were taken at regular intervals from the start of the ultraviolet light irradiation, centrifuged, and the absorbance of MB in the filtrate was measured to calculate the degradation rate D ═ 1- ρ/ρ according to the following formula 0 ) X 100%, where ρ 0 And ρ is the absorbance at the initial and time t, respectively. The degradation rate was 60.31%.
NiO/ZrO treated by the invention 2 Catalysis of nano composite photocatalystThe chemical properties were studied:
(1) the invention researches the addition amount of Ni on NiO/ZrO 2 Influence of the catalytic performance of the nano composite photocatalyst:
NiO/ZrO preparation with Ni addition mole fractions of 5%, 10%, 15% and 20%, respectively 2 The nanometer composite photocatalyst is examined for the degradation effect of the nanometer composite photocatalyst on Methylene Blue (MB) with the initial mass concentration of 60mg/L when the nanometer composite photocatalyst is used in an amount of 0.4g/L and is irradiated by ultraviolet light (254nm) for 1 hour, and the result is shown in figure 4. As shown in FIG. 4, the addition of a proper amount of Ni can improve the nano-ZrO 2 The photocatalytic performance is improved, the degradation rate is gradually increased along with the increase of the addition amount of Ni, and when the molar fraction of Ni is 15%, the degradation rate can reach 99.76 percent at most; when the amount of Ni added continues to increase, the degradation rate becomes smaller instead. Therefore, when the Ni addition mole fraction is 15%, NiO/ZrO 2 The nano composite photocatalyst has the best degradation performance.
For further research on NiO/ZrO 2 The nano composite photocatalyst is prepared by adding NiO/ZrO with the mole fraction of 15% to Ni 2 The nano composite photocatalyst is subjected to XRD, SEM and EDS spectrum analysis, and NiO/ZrO is investigated 2 ZrO in nano composite photocatalyst 2 And the crystalline phase structure and the micro-morphology of NiO, as shown in FIG. 1, FIG. 2 and FIG. 3. As can be seen from the XRD spectrum of FIG. 1, compared with a standard spectrum (JCPDS No 47-1049), diffraction peaks with 2 theta of 38.08 degrees, 43.12 degrees, 62.98 degrees and 75.28 degrees respectively correspond to crystal faces (111), (200), (220) and (311) of cubic phase NiO, the peak type is clear, the intensity is high, and the half-peak width is small, which indicates that the NiO in the composite catalyst has good crystallization performance; however, ZrO was not observed 2 Characteristic peaks indicating the calcination of ZrO at 350 ℃ 2 Mainly in an amorphous state. NiO/ZrO as can be seen from the SEM spectrum of FIG. 2 2 The nano composite photocatalyst consists of microspheres with different sizes, wherein the large size of the microspheres is 100nm-1 mu m, and the small size of the microspheres is 30-60 nm. As can be seen from the EDS spectrum of FIG. 3, the compositional contents of three elements Zr, Ni, O were analyzed according to the micro-regions, as shown in Table 1, which illustrates NiO/ZrO 2 The nano composite photocatalyst is pure ZrO 2 And NiO compound.
TABLE 1NiO/ZrO 2 Of Zr, Ni and O in nano composite photocatalystData on the contents of ingredients
(2) The invention also researches the illumination condition on NiO/ZrO 2 Influence of the catalytic performance of the nano composite photocatalyst:
by investigating three light sources of no illumination, ultraviolet light (254nm) and simulated sunlight for NiO/ZrO 2 The influence of the nano composite photocatalyst on the catalytic degradation of MB with the initial mass concentration of 60mg/L and NiO/ZrO 2 The dosage of the nano composite photocatalyst is 0.4g/L, and the result is shown in Table 2. As can be seen from Table 2, the MB degradation rates were all below 24.01% when only the catalyst was used without irradiation; when the MB is irradiated by ultraviolet light, the decolorizing effect of the MB is best, the degradation reaction rate is fastest, and the MB is almost completely degraded within about 1.0 h; NiO/ZrO under simulated sunlight 2 The photocatalytic degradation rate of the nano composite photocatalyst to MB is lower than that of ultraviolet light, but the degradation rate can reach more than 95% when the light is irradiated for 2.0 hours. Thus, NiO/ZrO 2 The nano composite photocatalyst has high activity under ultraviolet light, also has certain photocatalytic activity under simulated sunlight, and finally can achieve the degradation effect almost the same as that of the ultraviolet light if the illumination time allows.
TABLE 2 different illumination conditions for NiO/ZrO 2 Influence data table of catalytic performance of nano composite photocatalyst
(3) The invention also researches NiO/ZrO 2 The influence of the using amount of the nano composite photocatalyst on the catalytic performance is as follows:
MB is 60mg/L in initial mass concentration, the catalyst dosage is 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0g/L respectively, the centrifugal operation is carried out when the simulated sun is irradiated for 60min, the MB concentration of the filtrate is measured, and the degradation rate D is calculated, as shown in figure 5. As can be seen from fig. 5: the MB degradation rate was only up to 0.03% without catalyst addition, with increasing catalyst loading to 0.6g/LThe degradation rate rapidly increased to 68.78%, and when the catalyst level was increased further, the degradation rate curve was essentially a horizontal straight line and no longer varied. Thus, NiO/ZrO was used 2 When the dosage of the nano composite photocatalyst is 0.6g/L, the catalytic effect is good.
(4) The invention also researches the reaction time on NiO/ZrO 2 Influence of the catalytic performance of the nano composite photocatalyst:
the initial mass concentration of MB is still 60mg/L, the dosage of the catalyst is 0.6g/L, the MB in the filtrate is measured after the experiment is respectively carried out for 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0h under the simulated sunlight, and the degradation rate D is calculated, as shown in figure 6. As can be seen from FIG. 6, the degradation rate rapidly increases to 88.39% in 0-1.5h, the reaction rate of the degradation rate becomes slow in 1.5-2.5h, the degradation rate reaches the maximum value of 100% in 2.5h, the curve maintains a horizontal straight line basically, and the degradation rate does not change any more. Therefore, under the experimental conditions, 2.5h is the appropriate time for simulating the solar photocatalysis.
According to the experimental results of FIG. 6, ln (ρ) was used 0 Performing pseudo first-order reaction equation kinetic simulation on experimental data by using k as a pseudo first-order rate constant (h) in the equation of rho) kt -1 ) The results of the experimental fitting are shown in fig. 7. From the experimental data of FIG. 7, NiO/ZrO 2 The photocatalytic degradation process of the nano composite photocatalyst on MB conforms to a first-order kinetic equation, and the reaction constant of the rate of photodegradation is 1.52h -1 。
Claims (3)
1. NiO/ZrO 2 The preparation method of the nano composite photocatalyst is characterized by comprising the following steps: reacting NaBH 4 ZrOCl is added into the solution 2 •8H 2 Forming white sol in the O solution, and stirring until a precipitate is generated; filtering, drying, adding (NH) 4 ) 2 CO 3 Solution and Ni (NO) 3 ) 2 •6H 2 In the O solution, firstly stirring for 20-30min, then carrying out ultrasonic dispersion for 20-25min, standing for 2-4h, then drying, roasting and grinding to obtain NiO/ZrO 2 A nano composite photocatalyst;
NaBH 4 solution and ZrOCl 2 •8H 2 The volume ratio of the O solution is 1-1.5: 1;
NaBH 4 the concentration of the solution is 0.1-0.2mol/L, ZrOCl 2 •8H 2 The concentration of the O solution is 0.1-0.2 mol/L;
(NH 4 ) 2 CO 3 solution, Ni (NO) 3 ) 2 •6H 2 O solution and ZrOCl 2 •8H 2 The volume ratio of the O solution is 1-5:0.5-1: 4-10;
(NH 4 ) 2 CO 3 the concentration of the solution is 0.5-1.0mol/L, Ni (NO) 3 ) 2 •6H 2 The concentration of O is 0.1-0.2 mol/L;
vacuum drying is adopted after ultrasonic dispersion, and vacuum drying is carried out for 8-10h at the temperature of 80-90 ℃;
the roasting temperature is 350-400 ℃, and the roasting time is 2-4 h.
2. NiO/ZrO prepared by the method of claim 1 2 The application of the nano composite photocatalyst is characterized in that: NiO/ZrO 2 The nanometer composite photocatalyst is added into the organic wastewater to carry out degradation reaction under the illumination condition, thereby realizing the degradation treatment of the organic matters in the organic wastewater.
3. The NiO/ZrO of claim 2 2 The application of the nano composite photocatalyst is characterized in that: NiO/ZrO 2 The dosage ratio of the nano composite photocatalyst to the organic wastewater is 0.4-0.6:1, wherein NiO/ZrO 2 The nano composite photocatalyst is counted by g, the organic wastewater is counted by L, and the degradation reaction time is 1.0-2.5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276894.7A CN113019374B (en) | 2021-03-15 | 2021-03-15 | NiO/ZrO 2 Preparation method of nano composite photocatalyst and application of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276894.7A CN113019374B (en) | 2021-03-15 | 2021-03-15 | NiO/ZrO 2 Preparation method of nano composite photocatalyst and application of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113019374A CN113019374A (en) | 2021-06-25 |
| CN113019374B true CN113019374B (en) | 2022-09-02 |
Family
ID=76470541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110276894.7A Active CN113019374B (en) | 2021-03-15 | 2021-03-15 | NiO/ZrO 2 Preparation method of nano composite photocatalyst and application of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113019374B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116282144B (en) * | 2023-02-15 | 2024-04-12 | 吕梁学院 | Preparation method of zirconium dioxide |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3276679B2 (en) * | 1992-07-15 | 2002-04-22 | 財団法人石油産業活性化センター | Steam reforming catalyst and hydrogen production method |
| CN105056951A (en) * | 2015-08-11 | 2015-11-18 | 雅本化学股份有限公司 | Heterogeneously catalyzed and ozonized nano-composite catalyst and preparation method thereof |
| CN105536800B (en) * | 2015-12-04 | 2018-08-17 | 南昌大学 | A kind of Ni/ZrO2The application of the synthetic method of hydrogenation catalyst and the catalyst in hydrogenation catalyst reaction |
| CN108579749A (en) * | 2018-04-08 | 2018-09-28 | 浙江工业大学 | A kind of high defect monoclinic phase nano zircite load nickel-metal catalyst and its preparation and application |
-
2021
- 2021-03-15 CN CN202110276894.7A patent/CN113019374B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113019374A (en) | 2021-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Enhanced photocatalytic activity of Fe2O3 decorated Bi2O3 | |
| CN103172030A (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN109250755A (en) | A kind of bismuth oxide photocatalyst and preparation method thereof of the different crystal phases containing bismuth defect | |
| CN104056619B (en) | One utilizes WO3with rare-earth metals La to photocatalyst TiO2the method being modified | |
| An et al. | Preparation and visible-light photocatalytic properties of the floating hollow glass microspheres–TiO 2/Ag 3 PO 4 composites | |
| CN110479341A (en) | A kind of hydrogenation modification pucherite/class graphite phase carbon nitride composite photo-catalyst and preparation method thereof | |
| CN113731430B (en) | Double Z-type CuO/CuBi 2 O 4 /Bi 2 O 3 Composite photocatalyst, preparation method and application thereof | |
| CN108298591B (en) | synthesis method and application of hexagonal iron titanate nanosheet material | |
| CN113941357A (en) | Si-TiO2/g-C3N4Ternary composite photocatalytic material and preparation method thereof | |
| CN113019374B (en) | NiO/ZrO 2 Preparation method of nano composite photocatalyst and application of catalyst | |
| CN111632619A (en) | Copper-nitrogen co-doped titanium dioxide photocatalytic material, preparation method and application | |
| Eranjaneya et al. | Solution combustion synthesis of nano ZnWO4 photocatalyst | |
| CN113426461B (en) | Preparation method of silver-doped polycrystalline zinc ferrite photocatalytic nano material | |
| CN108837840B (en) | A kind of Ag/g-C3N4Modify bismuth tungstate mixed crystal composite material and preparation method and application | |
| CN112028119B (en) | Anatase TiO with co-exposed {101}, {100} and {111} -crystal faces 2 Nanocrystal | |
| CN109772293B (en) | Antimony bismuth indium oxide photocatalytic material and preparation and application thereof | |
| CN107308960A (en) | A kind of niobic acid tellurium catalysis material and its preparation method and application | |
| Shi et al. | Hollow sphere manganese–ceria solid solution enhances photocatalytic activity in tetracycline degradation | |
| CN107812519B (en) | Preparation and application of powder catalytic material and SiO 2-containing aerogel composite porous nano catalytic material | |
| CN102786080A (en) | Indium tin oxide compound, its preparation method and its photocatalytic application | |
| CN113058630B (en) | Preparation method and application of photocatalyst suitable for efficiently removing formaldehyde at room temperature | |
| CN106984323A (en) | A kind of barium niobate photochemical catalyst and preparation method thereof | |
| CN113578368A (en) | g-C3N4/Ag3PO4/BiFeO3Preparation method and application of composite visible-light-driven photocatalyst | |
| Aritonang et al. | Photocatalytic Bacterial Inactivation Using Bi-doped TiO2/Kaolinite Under Visible Light Irradiation | |
| CN112588302B (en) | alpha-MnO-containing 2 Photocatalytic system, 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230704 Address after: 230000 B-2704, wo Yuan Garden, 81 Ganquan Road, Shushan District, Hefei, Anhui. Patentee after: HEFEI LONGZHI ELECTROMECHANICAL TECHNOLOGY Co.,Ltd. Address before: No.30 Mishan Road, Zhoucun District, Zibo City, Shandong Province 255300 Patentee before: SHANDONG VOCATIONAL College OF LIGHT INDUSTRY |
|
| TR01 | Transfer of patent right |