CN112403471A - Preparation method and application of hydrangea-shaped nickel oxide microsphere catalyst - Google Patents
Preparation method and application of hydrangea-shaped nickel oxide microsphere catalyst Download PDFInfo
- Publication number
- CN112403471A CN112403471A CN202011369976.8A CN202011369976A CN112403471A CN 112403471 A CN112403471 A CN 112403471A CN 202011369976 A CN202011369976 A CN 202011369976A CN 112403471 A CN112403471 A CN 112403471A
- Authority
- CN
- China
- Prior art keywords
- hydrangea
- nickel oxide
- catalyst
- shaped nickel
- preparation
- 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
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 36
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 239000004005 microsphere Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 23
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000004913 activation Effects 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- -1 sulfate radicals Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003911 water pollution 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method and application of hydrangea-shaped nickel oxide microsphere catalyst, which is characterized in that nickel nitrate hexahydrate is used as a raw material, a mixed solution of dimethyl formamide, ethanol and water is used as a solvent, isonicotinic acid is used as a morphology regulator, hydrothermal reaction is carried out at the temperature of 150 ℃, a prepared precursor is subjected to pyrolysis reaction at the temperature of 450 ℃, and a micron-grade hydrangea-shaped nickel oxide material is prepared. Compared with the prior art, the invention has the advantages of rich catalytic sites, good catalytic effect and low preparation cost, and is a persulfate activation catalyst with excellent performance.
Description
Technical Field
The invention relates to the technical field of application of activated persulfate to degradation of organic pollutants, in particular to a preparation method of a micron-sized hydrangea-shaped nickel oxide catalyst and application of the micron-sized hydrangea-shaped nickel oxide catalyst to degradation of organic pollutants by activated persulfate.
Background
The problems of water pollution and water resource shortage due to economic and social development have prompted the continuous upgrade of wastewater treatment technologies in recent years. The advanced oxidation technology based on sulfate radicals has wide application potential in the field of wastewater treatment due to the characteristics of high speed, high efficiency, wide application range and the like. Persulfate can generate sulfate radicals with strong oxidizing property under the activation conditions of introducing heat, light, transition metal, alkali, electricity, complexing agent and the like, and can be used for degrading organic pollutants. The method for generating sulfate radical free radical by activating persulfate through transition metal ions has a very strong application prospect due to the fact that the reaction system is simple, the reaction condition is mild, the energy consumption is low, and no external energy is needed.
Nickel oxide is widely used in the fields of catalysis, sensing, and the like as a widely used p-type semiconductor, and nickel oxide has the advantages of being inexpensive and readily available as a transition metal oxide compared to noble metals. The application of nickel oxide in catalyzing and activating persulfate to rapidly and effectively degrade organic pollutants is not reported at present.
Disclosure of Invention
The invention aims to provide a preparation method and application of a hydrangea-shaped nickel oxide microsphere catalyst, aiming at the defects of the prior art, the micron-sized hydrangea-shaped nickel oxide microsphere catalyst is prepared by using nickel nitrate hexahydrate as a substrate and adopting a hydrothermal synthesis method, the appearance of the material is adjusted by adding isonicotinic acid, the catalytic performance is improved, the persulfate is promoted to decompose and degrade pollutants, the hydrabamate is applied to catalytically activated persulfate, the bisphenol A organic pollutants in water can be rapidly and effectively degraded, the catalytic sites are rich, the catalytic effect is good, the preparation cost is low, the persulfate activated catalyst is a persulfate activated catalyst with excellent performance, the preparation method is simple and convenient, the reaction condition is mild, the energy consumption is low, no additional energy is needed, and the catalyst is cheap and efficient and has a very strong application prospect.
The specific technical scheme for realizing the purpose of the invention is as follows: a preparation method of hydrangea-shaped nickel oxide microsphere catalyst is characterized in that nickel nitrate hexahydrate is used as a matrix, the shape of the material is adjusted by adding isonicotinic acid, and a micron-sized hydrangea-shaped nickel oxide catalyst is synthesized by a hydrothermal method, and the preparation method specifically comprises the following steps:
a. mixing dimethylformamide, ethanol and deionized water according to the volume ratio of 5-10: 2-6: 1 to prepare solution A for later use;
b. nickel nitrate hexahydrate, isonicotinic acid and A solution are mixed according to the proportion of 1-2 mmol: 1-2 mmol: 1.5 g of the mixture is mixed into a solution B according to a molar volume ratio;
c. keeping the temperature of the solution B at 120-160 ℃ for 4-6 hours, and cooling to room temperature;
d. respectively cleaning the material obtained in the step c with deionized water and ethanol for 3 times, and then freeze-drying for 12-24 hours to prepare a precursor of the nickel oxide material;
e. pyrolyzing the precursor at 400-450 ℃ for 2-4 hours under the protection of argon gas to obtain the product, namely, the hydrangea-shaped nickel oxide microsphere catalyst.
The application of the hydrangea-shaped nickel oxide microsphere catalyst is characterized in that the hydrangea-shaped nickel oxide microsphere catalyst is used for activating persulfate to degrade bisphenol A in organic wastewater, and the adding amount of the catalyst is 0.1-0.5 g/L; the concentration of the persulfate is 5 g/L, and the adding amount of the persulfate is 5-15 mL/L; the concentration of bisphenol A in the sewage is 10-20 mg/L; the degradation reaction time is 20-30 minutes, and the degradation temperature is room temperature.
Compared with the prior art, the invention has the following beneficial effects:
1) the hydrangea-shaped nickel oxide material mainly takes nickel nitrate hexahydrate as a raw material, presents the appearance of hydrangea-shaped microspheres under the regulation and control of isonicotinic acid, has large specific surface area and rich active sites, can quickly catalyze persulfate to decompose in persulfate advanced oxidation reaction, and improves the degradation effect on pollutants.
2) In the process of synthesizing the nickel oxide catalyst, the appearance is regulated by adding the isonicotinic acid, so that the nickel oxide catalyst has uniform size and shape, good stability of the material appearance and difficult collapse.
3) The catalyst has good stability and can be repeatedly used.
4) The cheap nickel nitrate hexahydrate is used as a raw material, and the preparation cost is low.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention;
FIG. 2 is a scanning electron microscope image of hydrangeal-shaped nickel oxide microspheres prepared in example 1;
FIG. 3 is a graph showing embroidery ball-shaped nickel oxide microspheres and a graph showing degradation of bisphenol A by catalytically activating persulfate with nickel oxide.
Detailed Description
Referring to the attached figure 1, the invention takes nickel nitrate hexahydrate as a substrate, adjusts the morphology of the material by adding isonicotinic acid, adopts a hydrothermal synthesis micron-sized hydrangea-shaped nickel oxide catalyst, and comprises the following steps:
a. mixing dimethylformamide, ethanol and deionized water according to the volume ratio of 5-10: 2-6: 1 to prepare solution A for later use;
b. nickel nitrate hexahydrate, isonicotinic acid and A solution are mixed according to the proportion of 1-2 mmol: 1-2 mmol: 1.5 g of the mixture is mixed into a solution B according to a molar volume ratio;
c. keeping the temperature of the solution B at 120-160 ℃ for 4-6 hours, and cooling to room temperature;
d. respectively cleaning the material obtained in the step c with deionized water and ethanol for 3 times, and then freeze-drying for 12-24 hours to obtain a material serving as a precursor;
e. pyrolyzing the precursor at 400-450 ℃ for 2-4 hours under the protection of argon gas to obtain the product, namely, the hydrangea-shaped nickel oxide microsphere catalyst.
The invention is further described in the following with reference to the drawings and the specific examples of the description, but without thereby limiting the scope of protection of the invention. Unless otherwise indicated, all reagents, methods and materials used in the present invention are conventional in the art.
Example 1
a. Mixing dimethylformamide, ethanol and deionized water according to the volume ratio of 9:5:1 to obtain a uniform solution;
b. respectively weighing 0.2 mmol of nickel nitrate hexahydrate and 0.1 mmol of isonicotinic acid, pouring into a mixed solution of dimethylformamide, ethanol and deionized water, and ultrasonically mixing uniformly;
c. transferring the mixed solution obtained in the step b into a reaction kettle, putting the reaction kettle into an oven, preserving the heat at the temperature of 150 ℃ for 4 hours, and then cooling to room temperature;
d. respectively cleaning the material obtained by the hydrothermal synthesis with deionized water and ethanol for three times, and freeze-drying for 15 hours to obtain a precursor of the nickel oxide material;
e. putting the obtained precursor material into a tube furnace, and pyrolyzing the precursor material at the temperature of 450 ℃ for 2 hours at the heating rate of 2 ℃/min under the protection of argon to obtain the product, namely the hydrangea-shaped nickel oxide microsphere catalyst.
Referring to the attached figure 2, the product presents the shape of a hydrangea-shaped microsphere through a scanning electron microscope, the specific surface area is large, and active sites are rich.
Example 2
The hydrangea-shaped nickel oxide catalyst prepared in example 1 is applied to catalytic activation of persulfate, and taking the treatment of typical non-degradable organic pollutant bisphenol A as an example, the catalyst dosage added at room temperature is 0.1 g/L, the concentration of persulfate is 5 g/L, the addition amount is 8 mL/L, the concentration of degraded bisphenol A is 20 mg/L, the reaction time is 30 minutes, and the degradation rate of bisphenol A reaches 100%.
Referring to the attached figure 3, the embroidery ball-shaped nickel oxide prepared by the invention can degrade the organic sewage with the bisphenol A concentration of 20 mg/L, the degradation rate can reach 100%, and the degradation rate of the organic sewage with the bisphenol A concentration of 20 mg/L, which is degraded by the nickel oxide supplied by the market, is 40%.
The performance test result shows that the hydrangea-shaped nickel oxide prepared by the method can rapidly catalyze the decomposition of persulfate in the persulfate advanced oxidation reaction, and the degradation effect on pollutants is improved.
The invention has been described in further detail in the foregoing for the purpose of illustration and not of limitation, and the equivalent implementations calculated without departing from the spirit and scope of the inventive concept are intended to be covered by the claims set forth at the end of this patent.
Claims (2)
1. A preparation method of hydrangea-shaped nickel oxide microsphere catalyst is characterized in that nickel nitrate hexahydrate is used as a matrix, the morphology of the material is adjusted by adding isonicotinic acid, and the micron-sized hydrangea-shaped nickel oxide catalyst is synthesized by adopting hydrothermal method, and the preparation method specifically comprises the following steps:
a. mixing dimethylformamide, ethanol and deionized water according to the volume ratio of 5-10: 2-6: 1 to prepare solution A for later use;
b. nickel nitrate hexahydrate, isonicotinic acid and A solution are mixed according to the proportion of 1-2 mmol: 1-2 mmol: 1.5 g of the mixture is mixed into a solution B according to a molar volume ratio;
c. keeping the temperature of the solution B at 120-160 ℃ for 4-6 hours, and cooling to room temperature;
d. respectively cleaning the material obtained in the step c with deionized water and ethanol for 3 times, and then freeze-drying for 12-24 hours to obtain a material serving as a precursor;
e. pyrolyzing the precursor at 400-450 ℃ for 2-4 hours under the protection of argon gas to obtain the product, namely, the hydrangea-shaped nickel oxide microsphere catalyst.
2. The application of the catalyst prepared by the preparation method of the hydrangea-shaped nickel oxide microsphere catalyst according to claim 1 is characterized in that the hydrangea-shaped nickel oxide microsphere catalyst is used for activating persulfate to degrade bisphenol A in organic wastewater, and the adding amount of the catalyst is 0.1-0.5 g/L; the concentration of the persulfate is 5 g/L, and the adding amount of the persulfate is 5-15 mL/L; the concentration of bisphenol A in the organic wastewater is 10-20 mg/L; the degradation reaction time is 20-30 minutes, and the degradation temperature is room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011369976.8A CN112403471A (en) | 2020-11-30 | 2020-11-30 | Preparation method and application of hydrangea-shaped nickel oxide microsphere catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011369976.8A CN112403471A (en) | 2020-11-30 | 2020-11-30 | Preparation method and application of hydrangea-shaped nickel oxide microsphere catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112403471A true CN112403471A (en) | 2021-02-26 |
Family
ID=74830504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011369976.8A Pending CN112403471A (en) | 2020-11-30 | 2020-11-30 | Preparation method and application of hydrangea-shaped nickel oxide microsphere catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112403471A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188156A (en) * | 2016-06-27 | 2016-12-07 | 宿州学院 | A kind of 3 hydroxyl 2 pyridine carboxylic acid nickel coordination polymers and preparation method thereof |
| CN108455718A (en) * | 2018-03-13 | 2018-08-28 | 上海交通大学 | A kind of biodegrading process of organic pollution |
| CN109999815A (en) * | 2019-04-15 | 2019-07-12 | 江苏师范大学 | A kind of three-dimensional NiO porous ball and its synthetic method of porous chips assembling |
-
2020
- 2020-11-30 CN CN202011369976.8A patent/CN112403471A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188156A (en) * | 2016-06-27 | 2016-12-07 | 宿州学院 | A kind of 3 hydroxyl 2 pyridine carboxylic acid nickel coordination polymers and preparation method thereof |
| CN108455718A (en) * | 2018-03-13 | 2018-08-28 | 上海交通大学 | A kind of biodegrading process of organic pollution |
| CN109999815A (en) * | 2019-04-15 | 2019-07-12 | 江苏师范大学 | A kind of three-dimensional NiO porous ball and its synthetic method of porous chips assembling |
Non-Patent Citations (1)
| Title |
|---|
| ZHIBIN WU: ""Enhanced heterogeneous activation of persulfate by NixCo3–xO4 for oxidative degradation of tetracycline and bisphenol A"", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN108671907B (en) | Platinum/titanium dioxide nanoflower composite material and preparation method and application thereof | |
| CN107983387B (en) | Preparation method and application of carbon nitride/bismuth selenate composite material | |
| CN113042090B (en) | Nonmetallic photocatalyst with charge transfer chain and preparation method and application thereof | |
| CN108295881A (en) | A kind of Co4The hollow nanocages composite material and preparation method of N/N doped carbons and application | |
| CN113368905B (en) | Method for synthesizing Co monoatomic atom by using chitosan as substrate and application of Co monoatomic atom in efficient activation of persulfate to degrade organic pollutants | |
| CN114011413A (en) | Method for preparing ferrum-cobalt bimetallic single-atom anchoring nitrogen-doped graphene cocatalyst and application thereof | |
| CN113663704B (en) | Indium zinc sulfide/graphite phase carbon nitride composite material and preparation and application thereof | |
| CN107876093B (en) | Method for regulating and controlling metal valence state in metal carbide organic framework material by using alkaline N | |
| CN111359652A (en) | Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof | |
| CN111889127B (en) | In-situ growth preparation of beta-Bi 2 O 3 /g-C 3 N 4 Method for preparing nano composite photocatalyst | |
| CN109046466A (en) | A kind of photochemical catalyst and its preparation method and application that the derivative carbon-based material of ZIF-8 is CdS-loaded | |
| CN113813944B (en) | Monoatomic rhodium catalyst and preparation method and application thereof | |
| CN109158114B (en) | Method for preparing CdS @ C composite photocatalyst by one-step method | |
| CN111974436B (en) | Graphite-phase carbon nitride and preparation method thereof, and method for producing hydrogen by photocatalytic water | |
| CN111229200B (en) | Bismuth oxide modified Ti 3+ Self-doping TiO 2 Preparation method of heterojunction photocatalyst | |
| CN114950437B (en) | Preparation, product and application of supported Cu-Co bimetallic-based ZIF-derived Cu/Co-C ozone catalyst | |
| CN112403471A (en) | Preparation method and application of hydrangea-shaped nickel oxide microsphere catalyst | |
| CN112058291A (en) | Microspherical composite visible-light-driven photocatalyst and rapid preparation method and application thereof | |
| CN113856717B (en) | Super-stable photocatalytic material accelerator and preparation method thereof | |
| CN112871174A (en) | Preparation method and application of hexagonal flaky nano nickel oxide catalyst | |
| CN107486194A (en) | A kind of preparation method of the load cerium tin oxide composite microsphere photocatalyst of aquiculture waste water processing | |
| CN109772401B (en) | Carbon ring/carbon nitride/titanium dioxide composite material, and preparation method and application thereof | |
| CN110961136A (en) | Fe with three-dimensional continuous structure3N-coated FeNCN compound and preparation method thereof | |
| CN110354885A (en) | A kind of neodymium oxide doping carbon nitride photocatalyst and preparation method 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210226 |