CN111841559A - Sr, Ni and Cr co-doped LaAlO3Application of photocatalyst in organic wastewater treatment - Google Patents
Sr, Ni and Cr co-doped LaAlO3Application of photocatalyst in organic wastewater treatment Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 27
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 27
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 26
- 238000004065 wastewater treatment Methods 0.000 title abstract description 8
- 239000011651 chromium Substances 0.000 claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002244 LaAlO3 Inorganic materials 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 14
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims abstract description 7
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 20
- 230000001699 photocatalysis Effects 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 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 6
- 229940043267 rhodamine b Drugs 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000013067 intermediate product Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 230000015556 catabolic process Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 3
- 229940012189 methyl orange Drugs 0.000 claims description 3
- 229960003742 phenol Drugs 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 20
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- -1 lanthanum aluminate Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/866—Nickel and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
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- 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
Abstract
The invention relates to Sr, Ni and Cr co-doped LaAlO3Application of photocatalyst in organic wastewater treatment, wherein the photocatalyst is La according to chemical formulaaSrbNicAldCreO3Wherein a is 0.7 to 0.9, b is 0.05 to 0.15, c is 0.05 to 0.15, d is 0.7 to 0.9, e is 0.1 to 0.3, strontium nitrate, nickel nitrate, chromium nitrate, lanthanum nitrate and aluminum nitrate are weighed, dissolved in water, then a certain amount of urea is added, ultrasonic dispersion is carried out, microwave heating is carried out, drying, roasting and grinding are carried out,the photocatalyst is pressed and molded, calcined for a certain time and ground again to obtain a product, the forbidden band width of the photocatalyst is 1.31-1.35 eV, organic pollutants in organic wastewater can be efficiently degraded under the condition of visible light, the repeatability is good, secondary pollution cannot be caused, the photocatalyst can be widely used, and the photocatalyst has the advantages of good practical application prospect.
Description
1.1.1 technical field
The invention belongs to the field of organic wastewater treatment, and particularly relates to a method for co-doping LaAlO with Sr, Ni and Cr3Application of photocatalyst in organic wastewater treatment.
1.1.2 background Art
At present, the problem of environmental pollution has become one of the focus problems of global attention, and the quality of the environmental environment seriously affects the living standard of people and the sustainable development of society. The development and utilization of the photocatalysis technology are one of effective ways for solving the problem of environmental pollution.
LaAlO3The photocatalyst is a perovskite type semiconductor, is a novel photocatalyst which is low in price, stable in chemical property and non-toxic and harmless to the environment, has the forbidden bandwidth of 3.23eV, and does not correspond to visible light. To LaAlO3The method has the advantages that the forbidden bandwidth is reduced by ion doping, so that the method can be widely researched under visible light, and common doping elements such as Fe and Cr greatly improve the photocatalytic performance of the lanthanum aluminate photocatalyst, so that the lanthanum aluminate photocatalyst can respond under visible light, and the utilization rate of sunlight is further improved. However, the above research does not consider the influence of the preparation method of the lanthanum aluminate photocatalyst on other performances, and the development of the photocatalyst with higher visible light utilization rate and the reduction of the forbidden bandwidth value still remain the problems to be solved at present.
1.1.3 summary of the invention
The technical problem to be solved by the invention is to provide a method for co-doping LaAlO by Sr, Ni and Cr aiming at the defects in the prior art3The photocatalyst is applied to organic wastewater treatment, has the forbidden band width of 1.31-1.35 eV, can efficiently degrade organic pollutants in the organic wastewater under the condition of visible light, has good repeatability, does not bring secondary pollution, can be widely used, and has good practical application prospect.
The invention adopts the following technical scheme:
sr, Ni and Cr co-doped LaAlO3The application of the photocatalyst in the organic wastewater treatment adopts Sr, Ni and Cr co-doped LaAlO under the irradiation of visible light3The photocatalyst photocatalytically degrades organic pollutants in the organic wastewater, the removal rate of the organic pollutants in the wastewater can reach 99%, and the removal rate can still reach more than 95% after 5 times of repetition; the Sr, Ni and Cr are codoped with LaAlO3The chemical formula of the photocatalyst is LaaSrbNicAldCreO3Wherein a is 0.7-0.9, b is 0.05-0.15, c is 0.05-0.15, d is 0.7-0.9, and e is 0.1-0.3.
Preferably, the Sr, Ni and Cr are codoped with LaAlO3The preparation method of the photocatalyst comprises the following steps:
1) according to the chemical formula LaaSrbNicAldCreO3The stoichiometric ratio of (a) is 0.7-0.9, b is 0.05-0.15, c is 0.05-0.15, d is 0.7-0.9, e is 0.1-0.3, strontium nitrate, nickel nitrate, chromium nitrate, lanthanum nitrate and aluminum nitrate are weighed and put into a beaker, and a proper amount of distilled water is added to fully stir and dissolve;
2) adding a certain amount of urea into a beaker under the condition of stirring, performing ultrasonic dispersion, then performing microwave heating, and evaporating to obtain an intermediate product A;
3) putting the product A into a drying oven for drying, then grinding the dried sample, then putting the sample into a muffle furnace for roasting, taking out the sample, cooling to room temperature, and then fully grinding to obtain loose powder;
4) then placing the loose powder into a mold, pressing and molding the loose powder under the pressure of 100-150 MPa, sintering the loose powder in the air atmosphere at 1400-1700 ℃ for 1-3 h, and grinding the obtained product to obtain Sr, Ni and Cr codoped LaAlO3A photocatalyst.
Preferably, in the step 2), the addition amount of the urea is 1 to 1.5 times of the total molar amount of the metal ions.
Preferably, in the step 2), the ultrasonic dispersion time is 1-3 hours, the microwave heating temperature is 70-90 ℃, and the heating time is 1-3 hours.
Preferably, in the step 3), the drying temperature is 100-140 ℃, the drying time is 10-16 h, the roasting temperature is 1100-1300 ℃, and the roasting time is 1-3 h.
Preferably, the organic contaminant is rhodamine B, methyl orange or phenol.
Preferably, the specific operation steps of the application are as follows: taking 100mL of 10mg/L organic pollutants as degradation objects, adding a photocatalyst to carry out dark adsorption for 20-30 min, wherein the concentration of the catalyst is 1g/L, and carrying out a photocatalytic experiment under the irradiation of a 300W xenon lamp.
Compared with the prior art, the invention has at least the following beneficial effects:
1) the Sr, Ni and Cr co-doped LaAlO provided by the invention3Application of photocatalyst in organic wastewater treatment, wherein the photocatalyst is La according to chemical formulaaSrbNicAldCreO3The stoichiometric ratio of (a) is 0.7-0.9, b is 0.05-0.15, c is 0.05-0.15, d is 0.7-0.9, e is 0.1-0.3, strontium nitrate, nickel nitrate, chromium nitrate, lanthanum nitrate and aluminum nitrate are weighed, dissolved in water, then a certain amount of urea is added, ultrasonic dispersion, microwave heating, drying, roasting, grinding, compression molding, calcining for a certain time, and grinding again to obtain the product, wherein the forbidden band width of the photocatalyst is 1.31-1.35 eV, the photocatalyst can efficiently degrade organic pollutants in organic wastewater under the condition of visible light, has good repeatability, does not bring secondary pollution, can be widely used, and has good practical application prospect.
2) Doping Sr, Ni and Cr into LaAlO3In the crystal lattice, the synergistic effect of the three elements promotes LaAlO3The photocatalytic performance of the photocatalyst is obviously improved, impurity energy levels are formed in the forbidden band of the material due to the doping of elements, and the impurity energy levels corresponding to electronic transition are located in a near infrared spectrum region, so that the forbidden band width value is reduced.
3) La is synthesized by two steps by using an ultrasonic-microwave auxiliary self-combustion methodaSrbNicAldCreO3Wherein a is 0.7-0.9, b is 0.05-0.15, c is 0.05-0.15, d is 0.7-0.9, and e is 0.1-0.3, so that the porosity of the photocatalyst is obviously reduced, the compactness is improved, the reduction of forbidden band width value is promoted, and the photocatalytic performance is improved.
In conclusion, the Sr, Ni and Cr co-doped LaAlO prepared by the invention3The photocatalyst has good compactness, excellent photocatalytic performance and small forbidden bandwidth value, and is an ideal material for photocatalytic degradation of organic pollutants.
The technical solution of the present invention is further described in detail by the following examples.
1.1.4 detailed description of the invention
The Sr, Ni and Cr co-doped LaAlO provided by the invention3The preparation method of the photocatalyst comprises the following steps:
1) according to the chemical formula LaaSrbNicAldCreO3The stoichiometric ratio of (a) is 0.7-0.9, b is 0.05-0.15, c is 0.05-0.15, d is 0.7-0.9, e is 0.1-0.3, strontium nitrate, nickel nitrate, chromium nitrate, lanthanum nitrate and aluminum nitrate are weighed and put into a beaker, and a proper amount of distilled water is added to fully stir and dissolve;
2) adding urea which is 1-1.5 times of the total molar amount of metal ions into a beaker under the condition of stirring, ultrasonically dispersing for 1-3 hours, then carrying out microwave heating for 1-3 hours at 70-90 ℃ in a microwave chemical reactor, and evaporating to obtain an intermediate product A;
3) drying the product A in a drying oven at 100-140 ℃ for 10-16 h, grinding the dried sample, roasting in a muffle furnace at 1100-1300 ℃ for 1-3, taking out the sample, cooling to room temperature, and fully grinding to obtain loose powder;
4) then placing the loose powder into a mold, pressing and molding the loose powder under the pressure of 100-150 MPa, sintering the loose powder in the air atmosphere at 1400-1700 ℃ for 1-3 h, and grinding the obtained product to obtain Sr, Ni and Cr codoped LaAlO3A photocatalyst.
Co-doping the Sr, Ni and Cr with LaAlO3The specific operation steps of applying the photocatalyst to photocatalytic degradation of organic wastewater are as follows: taking 100mL of 10mg/L organic pollutants as degradation objects, adding a photocatalyst to carry out dark adsorption for 20-30 min, wherein the concentration of the catalyst is 1g/L, and carrying out a photocatalytic experiment under the irradiation of a 300W xenon lamp.
Preferably, the organic contaminant is rhodamine B, methyl orange or phenol.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Sr, Ni and Cr co-doped LaAlO3The preparation method of the photocatalyst comprises the following steps:
1) according to the chemical formula LaaSrbNicAldCreO3The stoichiometric ratio of (a) is 0.8, b is 0.1, c is 0.1, d is 0.8, and e is 0.2, strontium nitrate, nickel nitrate, chromium nitrate, lanthanum nitrate and aluminum nitrate are weighed and put into a beaker, and a proper amount of distilled water is added to be fully stirred and dissolved;
2) adding urea which is 1.5 times of the total mole amount of metal ions into a beaker under the condition of stirring, ultrasonically dispersing for 2 hours, then heating for 2 hours in a microwave chemical reactor at 85 ℃ by microwave, and evaporating to obtain an intermediate product A;
3) drying the product A in a drying oven at 120 ℃ for 14h, grinding the dried sample, roasting in a muffle furnace at 1250 ℃ for 2h, taking out the sample, cooling to room temperature, and fully grinding to obtain loose powder;
4) then putting the loose powder into a die, pressing and molding the loose powder under the pressure of 120MPa, sintering the loose powder in the air atmosphere at 1600 ℃ for 2h, and grinding the obtained product to obtain Sr, Ni and Cr codoped LaAlO3A photocatalyst.
Example 2
Sr, Ni and Cr co-doped LaAlO3The preparation method of the photocatalyst comprises the following steps:
1) according to the chemistryFormula LaaSrbNicAldCreO3The stoichiometric ratio of (1), wherein a is 0.8, b is 0.15, c is 0.05, d is 085, and e is 0.15, strontium nitrate, nickel nitrate, chromium nitrate, lanthanum nitrate and aluminum nitrate are weighed and put into a beaker, and a proper amount of distilled water is added to be fully stirred and dissolved;
2) adding urea which is 1 time of the total mole amount of metal ions into a beaker under the condition of stirring, carrying out ultrasonic dispersion for 3 hours, then carrying out microwave heating for 3 hours at 75 ℃ in a microwave chemical reactor, and evaporating to obtain an intermediate product A;
3) putting the product A into a drying oven to be dried for 16h at 100 ℃, then grinding the dried sample, then putting the sample into a muffle furnace to be roasted for 1h at 1300 ℃, taking out the sample, cooling to room temperature, and then fully grinding to obtain loose powder;
4) then putting the loose powder into a die, pressing and molding the loose powder under the pressure of 100MPa, sintering the loose powder in an air atmosphere at 1500 ℃ for 3h, and grinding the obtained product to obtain Sr, Ni and Cr codoped LaAlO3A photocatalyst.
Comparative example
Comparative examples 1 to 6 according to the formula LaaSrbNicAldCreO3Wherein the total amount of doping elements is the same, except that a, b, c, d, e are different, and the other preparation conditions and parameters are the same as in example 1.
Comparative example 7 the microwave-assisted mode was omitted and the other preparation conditions and parameters were the same as in example 1.
A Lambda 750S type ultraviolet-visible-near infrared spectrophotometer and a barium sulfate integrating sphere attached to the spectrophotometer are adopted to test the spectral absorption rate of a sample at 760-2500 nm and the spectral absorption curve at 200-800 nm. Specific parameters are shown in table 1:
specific values of tables 1 a, b, c, d, e
| a | b | c | d | e | |
| Example 1 | 0.8 | 0.1 | 0.1 | 0.8 | 0.2 |
| Comparative example 1 | 0.8 | 0.2 | 0 | 0.8 | 0.2 |
| Comparative example 2 | 0.8 | 0 | 0.2 | 0.8 | 0.2 |
| Comparative example 3 | 0.8 | 0.1 | 0.1 | 1 | 0 |
| Comparative example 4 | 0.8 | 0.2 | 0 | 1 | 0 |
| Comparative example 5 | 0.8 | 0 | 0.2 | 1 | 0 |
| Comparative example 6 | 1 | 0 | 0 | 0.8 | 0.2 |
| Comparative example 7 | 0.8 | 0.1 | 0.1 | 0.8 | 0.2 |
The same application conditions for photocatalytic degradation of organic pollutants were applied to the photocatalysts of examples 1-2 and comparative examples 1-7, and specifically the following were applied: the method comprises the steps of taking 100mL and 10mg/L rhodamine B as a degradation object, adding a photocatalyst to carry out dark adsorption on the rhodamine B for 30min, enabling the concentration of the catalyst to be 1g/L, carrying out a photocatalytic experiment under the irradiation of a 300W xenon lamp, taking 2mL of turbid liquid every 2min, carrying out centrifugal separation, taking supernate, detecting the supernate at the wavelength of 550nm by using a spectrophotometer, recording data, measuring the concentration of the rhodamine B after 10min, and further obtaining the photocatalytic degradation rate through calculation. The photodegradation rate was tested in 5 replicates under the same conditions.
TABLE 2 LaAlO3Photocatalytic degradation test results of photocatalyst
| Forbidden band width eg (eV) | Photodegradation ratio (%) | Photodegradation ratio (%). of repeat 5) | |
| Example 1 | 1.31 | 99.5 | 95.2 |
| Example 2 | 1.35 | 98.9 | 95 |
| Comparative example 1 | 1.53 | 93.5 | 88.6 |
| Comparative example 2 | 1.51 | 94.2 | 88.9 |
| Comparative example 3 | 1.59 | 93.8 | 88.8 |
| Comparative example 4 | 2.16 | 89.9 | 81.3 |
| Comparative example 5 | 2.04 | 89.5 | 80.9 |
| Comparative example 6 | 2.36 | 89.6 | 81.1 |
| Comparative example 7 | 1.41 | 96.4 | 92.1 |
In conclusion, the Sr, Ni and Cr co-doped LaAlO prepared by the invention3The photocatalyst has good compactness, excellent photocatalytic performance and small forbidden bandwidth value, is an ideal material for photocatalytic degradation of organic pollutants, and can promote LaAlO through the synergistic action of Sr, Ni and Cr elements through comparison between the example 1 and the comparative examples 1-63The forbidden band width value of the photocatalyst becomes small, and the photocatalytic performance is improvedThe improvement is obtained; it can be seen from a comparison of example 1 and comparative example 7 that photocatalytic performance is also improved by the microwave-assisted self-combustion method.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. Sr, Ni and Cr co-doped LaAlO3The application of the photocatalyst in the treatment of organic wastewater is characterized in that Sr, Ni and Cr are codoped with LaAlO under the irradiation of visible light3The photocatalyst photocatalytically degrades organic pollutants in the organic wastewater, the removal rate of the organic pollutants in the wastewater can reach 99%, and the removal rate can still reach more than 95% after 5 times of repetition; the Sr, Ni and Cr are codoped with LaAlO3The chemical formula of the photocatalyst is LaaSrbNicAldCreO3Wherein a is 0.7-0.9, b is 0.05-0.15, c is 0.05-0.15, d is 0.7-0.9, and e is 0.1-0.3.
2. The use according to claim 1, wherein the Sr, Ni and Cr co-doped LaAlO3The preparation method of the photocatalyst comprises the following steps:
1) according to the chemical formula LaaSrbNicAldCreO3The stoichiometric ratio of (a) is 0.7-0.9, b is 0.05-0.15, c is 0.05-0.15, d is 0.7-0.9, e is 0.1-0.3, strontium nitrate, nickel nitrate, chromium nitrate, lanthanum nitrate and aluminum nitrate are weighed and put into a beaker, and a proper amount of distilled water is added to fully stir and dissolve;
2) adding a certain amount of urea into a beaker under the condition of stirring, performing ultrasonic dispersion, then performing microwave heating, and evaporating to obtain an intermediate product A;
3) putting the product A into a drying oven for drying, then grinding the dried sample, then putting the sample into a muffle furnace for roasting, taking out the sample, cooling to room temperature, and then fully grinding to obtain loose powder;
4) then placing the loose powder into a mold, pressing and molding the loose powder under the pressure of 100-150 MPa, sintering the loose powder in the air atmosphere at 1400-1700 ℃ for 1-3 h, and grinding the obtained product to obtain Sr, Ni and Cr codoped LaAlO3A photocatalyst.
3. Use according to claim 2, characterized in that: in the step 2), the addition amount of the urea is 1-1.5 times of the total mole amount of the metal ions.
4. Use according to any one of claims 2-3, characterized in that: in the step 2), the ultrasonic dispersion time is 1-3 h, the microwave heating temperature is 70-90 ℃, and the heating time is 1-3 h.
5. Use according to claim 2, characterized in that: in the step 3), the drying temperature is 100-140 ℃, the drying time is 10-16 h, the roasting temperature is 1100-1300 ℃, and the roasting time is 1-3 h.
6. Use according to claim 1, characterized in that: the organic pollutants are rhodamine B, methyl orange or phenol.
7. Use according to claim 1, characterized in that: the specific operation steps of the application are as follows: taking 100mL of 10mg/L organic pollutants as degradation objects, adding a photocatalyst to carry out dark adsorption for 20-30 min, wherein the concentration of the catalyst is 1g/L, and carrying out a photocatalytic experiment under the irradiation of a 300W xenon lamp.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101982418A (en) * | 2010-10-29 | 2011-03-02 | 北京化工大学 | Preparation method of perovskite LnCrO3 and LnAlO3 nanomaterials |
| US20180154345A1 (en) * | 2016-12-01 | 2018-06-07 | GM Global Technology Operations LLC | NUCLEATION LAYERS FOR ENHANCING PHOTOCATALYTIC ACTIVITY OF TITANIUM DIOXIDE (TiO2) COATINGS |
| CN109879305A (en) * | 2019-03-27 | 2019-06-14 | 东北大学 | It is a kind of to prepare micron size LaAlO3:xMm+The method of spheric granules |
| CN110465303A (en) * | 2019-08-28 | 2019-11-19 | 玉林师范学院 | A kind of LaNiO of calcium analysis3The preparation method and application of perovskite type photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101982418A (en) * | 2010-10-29 | 2011-03-02 | 北京化工大学 | Preparation method of perovskite LnCrO3 and LnAlO3 nanomaterials |
| US20180154345A1 (en) * | 2016-12-01 | 2018-06-07 | GM Global Technology Operations LLC | NUCLEATION LAYERS FOR ENHANCING PHOTOCATALYTIC ACTIVITY OF TITANIUM DIOXIDE (TiO2) COATINGS |
| CN109879305A (en) * | 2019-03-27 | 2019-06-14 | 东北大学 | It is a kind of to prepare micron size LaAlO3:xMm+The method of spheric granules |
| CN110465303A (en) * | 2019-08-28 | 2019-11-19 | 玉林师范学院 | A kind of LaNiO of calcium analysis3The preparation method and application of perovskite type photocatalyst |
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