CN112958158B - Double-ligand rare earth complex photocatalyst and preparation method and application thereof - Google Patents
Double-ligand rare earth complex photocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112958158B CN112958158B CN202110215734.1A CN202110215734A CN112958158B CN 112958158 B CN112958158 B CN 112958158B CN 202110215734 A CN202110215734 A CN 202110215734A CN 112958158 B CN112958158 B CN 112958158B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- ligand
- photocatalyst
- dual
- hydroxypyrazole
- 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 62
- 239000003446 ligand Substances 0.000 title claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 30
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 25
- FERCTUUKKXAWIL-UHFFFAOYSA-N 5-oxo-1,2-dihydropyrazole-3-carboxylic acid Chemical compound OC(=O)C=1C=C(O)NN=1 FERCTUUKKXAWIL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 15
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000987 azo dye Substances 0.000 claims abstract description 4
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 101150054405 hpcH gene Proteins 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 17
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 17
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 14
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 11
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 11
- 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 description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- -1 rare earth metal salt Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 239000000975 dye Substances 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 229910052746 lanthanum Inorganic materials 0.000 description 21
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 21
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 21
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 11
- 238000001782 photodegradation Methods 0.000 description 10
- 230000031700 light absorption Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 229920001795 coordination polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 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
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/36—Yttrium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/37—Lanthanum
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (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 discloses a dual-ligand rare earth complex photocatalyst and a preparation method and application thereof, wherein the chemical expression of the photocatalyst is { Ln (NO) 3 )(hpcH)(phen)} n hpCH in chemical expression 2‑ Is 5-hydroxypyrazole-3-carboxylic acid organic ligand anion, phen is 1,10-phenanthroline, ln = Gd, la, Y, ln 3+ Through ionic connection with 5-hydroxypyrazole-3-carboxylic acid organic ligand, a two-dimensional layered structure is formed, a phen molecule and NO 3 ‑ The ions are arranged on two sides of the wave layer; the synthesis method of the photocatalyst is simple and convenient, and the reaction condition is mild; the catalyst can be used for efficiently catalyzing and degrading the soluble azo dye under the conditions of normal temperature and visible light, and the catalyst can be recycled and can keep stable structure, so that a new choice is provided for the degradation of organic dye pollutants in water.
Description
Technical Field
The invention belongs to the technical field of coordination compound synthesis, and particularly relates to a dual-ligand rare earth complex photocatalyst as well as a preparation method and application thereof.
Background
With the rapid development of science and technology and industrialization, a plurality of chemicals enter the life of people, and chemical materials also threaten the living environment of human beings to a certain extent while enriching the substance life of people. Among them, the dye compound is one of the most common organic pollutants in industrial wastewater, and has the characteristics of various kinds, complex structure and high stability. In order to effectively suppress the environmental pollution caused by the use of dye compounds, various adsorption, membrane separation and photocatalytic treatment technologies are widely applied and developed. From the standpoint of environmental operating conditions and cost effectiveness, photocatalytic technology can be considered as one of the most effective strategies for the efficient removal of dye contaminants from wastewater.
TiO 2 Semiconductor photocatalysts such as ZnO, cdS and the like have been proved to be capable of efficiently degrading various organic pollutants into molecules with lower toxicity or directly into harmless CO 2 And H 2 However, these semiconductor photocatalysts have the problem of low light Energy utilization rate due to narrow band gap, and are easily corroded under the illumination condition, and metal ions are easy to move into water to cause secondary pollution (see Energy environ, sci.,2014,7,2831-2867). In view of these deficiencies, there has been a continuing improvement in and a great deal of effort to develop new semiconductor materials as photocatalytic materials to degrade different types of organic contaminants.
Coordination Polymers (CPs) are complexes formed by self-assembly of metal ions and organic ligands, have large specific surface area and good thermal stability and chemical stability, and the ordered porous structure can greatly shorten the distance between holes for transmitting photogenerated electrons to the surface and effectively block the photo-electron-hole recombination to a certain extent, thereby improving the photocatalytic performance. Compared with the traditional inorganic material, the synthesis of the coordination polymer can select proper organic ligands, metal ions or reaction conditions to realize the adjustability of the absorption capacity of the coordination polymer to light. Among them, selection of an appropriate organic ligand is the best way to enhance the light absorption ability of the complex semiconductor catalyst.
5-hydroxypyrazole-3-carboxylic acids are multidentate organic ligands having N, O heteroatom-coordinating heterocyclic carboxyl and hydroxyl trifunctional groups. When the complex is formed, the complex can form rich and various spatial structures and has good light absorption coefficient. 1,10-phenanthroline is used as a second ligand, and the structure and the light absorption performance of the complex can be regulated and controlled. Based on the rare earth complex photocatalyst, the invention develops a rare earth complex photocatalyst which takes 5-hydroxypyrazole-3-carboxylic acid and 1,10-phenanthroline as double ligands. The development of the material can make up the defects in the prior art, provide a new solution for the field of photocatalytic degradation of organic dyes and widen the solution of corresponding problems.
Disclosure of Invention
Aiming at the problems in the background technology, the invention aims to provide a dual-ligand rare earth complex photocatalyst and a preparation method and application thereof.
The technical scheme of the invention is as follows: a dual-ligand rare-earth complex photocatalyst has a chemical expression of { Ln (NO) 3 )(hpcH)(phen)} n hpCH in chemical expression 2- Is 5-hydroxypyrazole-3-carboxylic acid organic ligand anion, phen is 1,10-phenanthroline, ln = Gd, la, Y, ln 3+ Through ionic connection with 5-hydroxypyrazole-3-carboxylic acid organic ligand, a two-dimensional layered structure is formed, a phen molecule and NO 3 - The ions are arranged on two sides of the wave layer; the molecular structure is as follows:
further, the photocatalyst belongs to monoclinic system, P2 1 The/c space group.
The preparation method of the dual-ligand rare earth complex photocatalyst comprises the following steps:
1) Dissolving 5-hydroxypyrazole-3-carboxylic acid and 1,10-phenanthroline in a solvent, adding rare earth metal salt according to a certain proportion, and uniformly mixing;
2) Putting the mixture obtained in the step 1) in an oven for solvothermal reaction, and cooling to room temperature after the reaction is finished to obtain the target product.
Further, the rare earth metal salt in the step 1) is gadolinium nitrate, lanthanum nitrate or yttrium nitrate; the solvent is distilled water.
Further, in the step 1), the molar ratio of the 5-hydroxypyrazole-3-carboxylic acid to 1,10-phenanthroline is 1:1-1, and the molar ratio of the 5-hydroxypyrazole-3-carboxylic acid to the rare earth metal salt is 1:2-1:4; the molar volume ratio of the 5-hydroxypyrazole-3-carboxylic acid to the solvent is 0.04mmol (3-5) mL.
Further, the reaction is carried out in an oven, the reaction temperature is 120-130 ℃, and the reaction time is 2-3 days.
The dual-ligand rare earth complex photocatalyst can catalyze and degrade methylene blue and Congo red azo dyes under the condition of visible light irradiation, and can be recycled for multiple times.
Compared with the prior art, the invention has the following advantages:
the preparation method of the dual-ligand rare earth complex photocatalyst disclosed by the invention is simple and convenient, the reaction condition is mild, and the preparation efficiency is high;
the product prepared by the method disclosed by the invention has stable structure and excellent catalytic performance, can be recycled, has basically unchanged catalytic degradation efficiency after repeated cycles, and can still keep the polymer structure stable, thereby providing a new choice for the degradation of organic dye in water;
the double-ligand rare earth complex photocatalyst prepared by the invention can efficiently catalyze and degrade soluble azo dyes under the conditions of normal temperature and visible light, wherein the degradation efficiency of the lanthanum complex photocatalyst of the double-ligand on methylene blue and Congo red respectively reaches 86.19 percent and 71.62 percent, and the degradation efficiency of the yttrium complex photocatalyst of the double-ligand on methylene blue and Congo red respectively reaches 93.60 percent and 87.12 percent.
Drawings
FIG. 1 is a graph of crystallographic data for a biligand gadolinium complex photocatalyst obtained in the example;
FIG. 2 is a diagram of the coordination environment of the dual ligand gadolinium complex photocatalyst obtained in the example;
FIG. 3 is a graph showing a visible light absorption spectrum of methylene blue by the photocatalytic degradation using the lanthanum complex photocatalyst obtained in example 1;
FIG. 4 is a graph showing the rate of change of concentration of methylene blue cyclically 3 times in the photocatalytic degradation by the lanthanum complex photocatalyst obtained in example 1;
FIG. 5 is a graph showing a visible light absorption spectrum of congo red photodegraded by the catalysis of a lanthanum complex photocatalyst obtained in example 1;
FIG. 6 is a graph showing the rate of change of concentration of Congo red after 3 cycles of photocatalytic degradation using the lanthanum complex photocatalyst obtained in example 1;
FIG. 7 is a graph showing a visible light absorption spectrum of methylene blue by the photocatalytic degradation using the yttrium complex photocatalyst obtained in example 1;
FIG. 8 is a graph showing the rate of change of the concentration of methylene blue cyclically 3 times in the photocatalytic degradation by applying the yttrium complex photocatalyst obtained in example 1;
FIG. 9 is a graph showing a visible light absorption spectrum of congo red photodegraded by the yttrium complex photocatalyst obtained in application example 1;
FIG. 10 is a graph of the rate of change of concentration of Congo red catalyzed by the yttrium complex photocatalyst obtained in application example 1 after 3 cycles of photodegradation;
FIG. 11 is a PXRD pattern of catalytic photodegradation cycle of lanthanum complex photocatalyst obtained in application example 1;
FIG. 12 is a PXRD pattern for a photocatalytic photodegradation cycle using the yttrium complex photocatalyst obtained in example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings, but not limited thereto, and any modification or equivalent replacement of the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention shall be covered by the protection scope of the present invention.
Example 1:
a preparation method of a dual-ligand rare earth complex photocatalyst comprises the following steps:
0.0052g of 5-hydroxypyrazole-3-carboxylic acid (0.04 mmol) and 0.0159g of 1, 10-phenanthroline (0.08 mmol) are weighed and dissolved in 2mL of distilled water to prepare an organic ligand solution;
weighing 0.04512g gadolinium nitrate (0.1 mmol) and dissolving in 1mL distilled water to form gadolinium nitrate solution; or 0.04332g lanthanum nitrate (0.1 mmol) is dissolved in 1mL of distilled water to form a lanthanum nitrate solution; or 0.0383g yttrium nitrate (0.1 mmol) is dissolved in 1mL distilled water to form yttrium nitrate solution;
adding a gadolinium nitrate solution or a lanthanum nitrate solution or a yttrium nitrate solution into an organic ligand solution, uniformly mixing to obtain a clear and transparent mixed solution, reacting in a closed oven at 120 ℃ for 3 days, and cooling to room temperature to obtain a light yellow blocky crystal, namely a double-ligand gadolinium complex photocatalyst or lanthanum complex photocatalyst or yttrium complex photocatalyst, with the yield of 30.3%,19.4% and 28.5% respectively.
The infrared spectrum characterization of the product of this example was carried out, and the specific results were:
gadolinium complex IR (KBr, cm) -1 )：3232(m),2364(w),1579(s),1531(s),1438(s),1361(m),1267(w),1159(m),1011(m),850(w),758(m),651(w),570(w),461(w)。
Lanthanum complex IR (KBr, cm) -1 )：3321(w),3103(W),1593(s),1560(s),1506(s),1434(s),1367(s),1281(s),1175(w),1103(w),1010(w),851(m),765(w),725(s),682(s),568(s),487(s)。
Yttrium Complex IR (KBr, cm) -1 )：3323(w),1590(s),1518(s),1494(s),1432(s),1374(m),1296(s),1114(w),1106(w),1014(w),856(m),764(w),713(m),673(w)。
Example 2:
a preparation method of a dual-ligand rare earth complex photocatalyst comprises the following steps:
weighing 0.0052g of 5-hydroxypyrazole-3-carboxylic acid (0.04 mmol) and 0.0159g of 1, 10-phenanthroline (0.08 mmol) and dissolving in 2mL of distilled water to prepare an organic ligand solution;
weighing 0.04512g gadolinium nitrate (0.1 mmol) and dissolving in 1mL distilled water to form gadolinium nitrate solution; or 0.04332g lanthanum nitrate (0.1 mmol) is dissolved in 1mL of distilled water to form a lanthanum nitrate solution; or 0.0383g yttrium nitrate (0.1 mmol) is dissolved in 1mL of distilled water to form yttrium nitrate solution;
adding a gadolinium nitrate solution or a lanthanum nitrate solution or a yttrium nitrate solution into an organic ligand solution, uniformly mixing to obtain a clear and transparent mixed solution, reacting in a sealed oven at 130 ℃ for 2 days, and cooling to room temperature to obtain a light yellow blocky crystal, namely a double-ligand gadolinium complex photocatalyst or lanthanum complex photocatalyst or yttrium complex photocatalyst, wherein the yield is 33.2%,21.3% and 29.4% respectively.
The infrared spectrum characterization of the product obtained in this example was carried out, and the specific results were:
gadolinium complex IR (KBr, cm) -1 )：3232(m),2363(w),1581(s),1532(s),1435(s),1363(m),1264(w),1158(m),1011(m),851(w),756(m),652(w),572(w),460(w)。
Lanthanum complex IR (KBr, cm) -1 )：3320(w),3101(W),1591(s),1559(s),1504(s),1432(s),1368(s),1280(s),1173(w),1105(w),1011(w),850(m),765(w),725(s),681(s),565(s),485(s)。
Yttrium Complex IR (KBr, cm) -1 )：3324(w),1590(s),1517(s),1493(s),1431(s),1375(m),1295(s),1113(w),1105(w),1013(w),857(m),765(w),714(m),674(w)。
Example 3:
a preparation method of a dual-ligand rare earth complex photocatalyst comprises the following steps:
weighing 0.0052g of 5-hydroxypyrazole-3-carboxylic acid (0.04 mmol) and 0.0159g of 1, 10-phenanthroline (0.08 mmol) and dissolving in 2mL of distilled water to prepare an organic ligand solution;
weighing 0.0675g of gadolinium nitrate (0.15 mmol) and dissolving in 1mL of distilled water to form gadolinium nitrate solution; or 0.06498g lanthanum nitrate (0.15 mmol) is dissolved in 1mL of distilled water to form a lanthanum nitrate solution; or 0.0575g of yttrium nitrate (0.15 mmol) is dissolved in 1mL of distilled water to form yttrium nitrate solution;
adding a gadolinium nitrate solution or a lanthanum nitrate solution or a yttrium nitrate solution into an organic ligand solution, uniformly mixing to obtain a clear and transparent mixed solution, reacting in a closed oven at 120 ℃ for 3 days, and cooling to room temperature to obtain a light yellow blocky crystal, namely a double-ligand gadolinium complex photocatalyst or lanthanum complex photocatalyst or yttrium complex photocatalyst, with the yield of 29.8%,19.1% and 27.2% respectively.
The infrared spectrum characterization of the product obtained in this example was carried out, and the specific results were:
gadolinium complex IR (KBr, cm) -1 )：3230(m,2362(w),1578(s),1532(s),1436(s),1360(m),1269(w),1156(m),1010(m),852(w),756(m),652(w),572(w),461(w)。
Lanthanum complex IR (KBr, cm) -1 )：3324(w),3103(W),1592(s),1566(s),1500(s),1436(s),1361(s),1284(s),1175(w),1102(w),1017(w),853(m),764(w),727(s),683(s),565(s),486(s)。
Yttrium Complex IR (KBr, cm) -1 )：3323(w),1590(s),1515(s),1498(s),1434(s),1379(m),1293(s),1118(w),1106(w),1011(w),854m),762(w),717(m),673(w)。
The product prepared in the above example, a double-ligand gadolinium complex photocatalyst, was subjected to X-ray single crystal diffraction test, and the measured crystallographic data are shown in fig. 1.
The chemical expression of the rare earth complex photocatalyst of the dual-ligand is { Ln (NO) according to a single crystal diffraction structure test 3 )(hpcH)(phen)} n (Ln = Gd, la, Y), hpCH in chemical expression 2- Is 5-hydroxypyrazole-3-carboxylic acid organic ligand ion, phen is 1,10-phenanthroline, and the molecular structure is as follows:
each asymmetric unit of the rare earth ion Ln contains 1 3+ 1 deprotonated organic ligand (hpCH) 2- ) 1 phen molecule and 1 NO 3 - Ions; ln 3+ Through ionic connection with 5-hydroxypyrazole-3-carboxylic acid organic ligand, a wave-shaped two-dimensional layered structure is formed, and a phen molecule and NO are 3 - The ions are arranged on both sides of the corrugated layer.
Taking gadolinium as an example, fig. 2 shows the coordination environment diagram of the biligand gadolinium complex photocatalyst, and as can be seen from fig. 2, gd (iii) is in an eight-coordinate system, and coordinates with five oxygen atoms (O1B, O2, O3C, O, O5, O6) and one nitrogen atom (N1).
Application example 1
The lanthanum complex or yttrium complex of the double ligand prepared in the example 1 is used as a photocatalyst, and the visible light is used for catalyzing and degrading methylene blue and Congo red at room temperature, and a xenon lamp is used for simulating a visible light source.
50mL of methylene blue aqueous solution with the concentration of 5mg/L or 50mL of Congo red aqueous solution with the concentration of 50mg/L is placed in a quartz reaction tank, 15mg of the double-ligand lanthanum complex or the double-ligand yttrium complex prepared in the example 1 is added, stirring is carried out for 30min in a dark environment, and sampling is carried out once after adsorption-desorption balance is achieved. And (3) performing photodegradation reaction by using a xenon lamp to simulate a visible light source, sampling once every 10min for 10 times in total, centrifuging the taken suspension at the rotating speed of 10000r/min for 4min, and taking supernatant to measure the visible light absorption spectrum of the supernatant.
The concentration change of the dual-ligand lanthanum complex photocatalyst for catalyzing photodegradation of methylene blue and Congo red is shown in figures 3 and 5, and as can be seen from figure 3, after illumination for 90min, the degradation rate of the dual-ligand lanthanum complex on the methylene blue reaches 86.19%; as can be seen from fig. 5, after the irradiation for 90min, the degradation rate of the dual-ligand lanthanum complex to congo red reaches 71.62%, which indicates that the dual-ligand lanthanum complex photocatalyst prepared in example 1 has high catalytic photodegradation efficiency for both methylene blue and congo red.
The concentration change of the dual-ligand yttrium complex photocatalyst for catalyzing photodegradation of methylene blue and congo red is shown in fig. 7 and fig. 9, and as can be seen from fig. 7, after illumination for 90min, the degradation rate of the dual-ligand yttrium complex on methylene blue reaches 93.60%; as can be seen from fig. 9, after illumination for 90min, the degradation rate of the dual-ligand yttrium complex to congo red reaches 87.12%, which indicates that the dual-ligand yttrium complex photocatalyst prepared in example 1 has high catalytic photodegradation efficiency for both methylene blue and congo red.
The dual-ligand lanthanum complex and the dual-ligand yttrium complex photocatalyst prepared in example 1 are used for carrying out 3 times of cyclic catalytic photodegradation processes on methylene blue and Congo red, and the concentration change rate graphs of the 3 times of cyclic catalytic photodegradation processes are shown in figures 4, 6, 8 and 10.
After 3 cycles of the double-ligand lanthanum complex and the double-ligand yttrium complex photocatalyst prepared in example 1, solid-liquid separation is respectively carried out on the complexes, PXRD (PXRD) tests are carried out on recovered solid parts, and spectrograms are shown in figures 11 and 12, so that the structures of the recovered double-ligand lanthanum complex and the recovered double-ligand yttrium complex are not obviously changed, and the compounds have high stability.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (7)
1. A dual-ligand rare earth complex photocatalyst is characterized in that the chemical expression of the photocatalyst is { Ln (NO) 3 )(hpcH)(phen)} n hpCH in chemical expression 2- Is 5-hydroxypyrazole-3-carboxylic acid organic ligand anion, phen is 1,10-phenanthroline, ln = Gd, la or Y; the molecular structure is as follows:
2. the family of dual ligand rare earth complex photocatalysts of claim 1 wherein the photocatalysts belong to the monoclinic system, P2 1 The/c space group.
3. The preparation method of the dual-ligand rare earth complex photocatalyst according to any one of claims 1-2, characterized by comprising the following steps:
1) Dissolving 5-hydroxypyrazole-3-carboxylic acid and 1,10-phenanthroline in a solvent, adding rare earth metal salt according to a certain proportion, and uniformly mixing;
2) Putting the mixture obtained in the step 1) in an oven for solvothermal reaction, and cooling to room temperature after the reaction is finished to obtain the target product.
4. The method for preparing a type of dual-ligand rare earth complex photocatalyst as claimed in claim 3, wherein the rare earth metal salt in step 1) is gadolinium nitrate, lanthanum nitrate or yttrium nitrate; the solvent is distilled water.
5. The preparation method of a type of dual-ligand rare earth complex photocatalyst according to claim 3, characterized in that, in step 1), the molar ratio of 5-hydroxypyrazole-3-carboxylic acid to 1,10-phenanthroline is 1:1-1, the molar ratio of 5-hydroxypyrazole-3-carboxylic acid to rare earth metal salt is 1:2-1:4; the molar volume ratio of the 5-hydroxypyrazole-3-carboxylic acid to the solvent is 0.04mmol (3-5) mL.
6. The preparation method of a dual-ligand rare earth complex photocatalyst according to claim 3, wherein the reaction is carried out in an oven at a temperature of 120-130 ℃ for 2-3 days.
7. The application of the dual-ligand rare earth complex photocatalyst in the aspect of photocatalytic degradation according to claim 1 is characterized in that the material can be used for catalytically degrading methylene blue and Congo red azo dyes under the condition of visible light irradiation and can be recycled for multiple times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110215734.1A CN112958158B (en) | 2021-02-26 | 2021-02-26 | Double-ligand rare earth complex photocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110215734.1A CN112958158B (en) | 2021-02-26 | 2021-02-26 | Double-ligand rare earth complex photocatalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112958158A CN112958158A (en) | 2021-06-15 |
| CN112958158B true CN112958158B (en) | 2023-03-10 |
Family
ID=76275956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110215734.1A Active CN112958158B (en) | 2021-02-26 | 2021-02-26 | Double-ligand rare earth complex photocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112958158B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316286B (en) * | 2021-11-30 | 2023-06-27 | 北京建筑材料科学研究总院有限公司 | Rare earth metal complex and preparation method and application thereof |
| CN114768874A (en) * | 2022-04-21 | 2022-07-22 | 北京建筑材料科学研究总院有限公司 | Rare earth metal complex, preparation method thereof and photocatalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633823A (en) * | 2012-02-23 | 2012-08-15 | 沈阳化工大学 | Rare-earth metal complex and preparation method thereof |
| CN106589396A (en) * | 2016-11-11 | 2017-04-26 | 吉林师范大学 | Rare earth complex based on mixed ligand of 4-HNCP and terephthalic, preparing method, crystal structure and application thereof |
| CN109320532A (en) * | 2018-10-19 | 2019-02-12 | 江苏理工学院 | Cadmium complex and its preparation method and application with catalysis Photocatalytic Degradation of Azo Dye function |
-
2021
- 2021-02-26 CN CN202110215734.1A patent/CN112958158B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633823A (en) * | 2012-02-23 | 2012-08-15 | 沈阳化工大学 | Rare-earth metal complex and preparation method thereof |
| CN106589396A (en) * | 2016-11-11 | 2017-04-26 | 吉林师范大学 | Rare earth complex based on mixed ligand of 4-HNCP and terephthalic, preparing method, crystal structure and application thereof |
| CN109320532A (en) * | 2018-10-19 | 2019-02-12 | 江苏理工学院 | Cadmium complex and its preparation method and application with catalysis Photocatalytic Degradation of Azo Dye function |
Non-Patent Citations (2)
| Title |
|---|
| Meiling Cheng et al.《Effect of N ancillary ligands on the structure，nuclearity and magnetic behavior of Cu(II)–pyrazolecarboxylate complexes》.2016,第40卷全文. * |
| 翟长伟 等.《以5-甲基-3-吡唑甲酸和菲咯啉为配体的锰和镉的配合物的合成、晶体结构和荧光性能》.2015,第31卷(第31期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112958158A (en) | 2021-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| He et al. | Two 3D metal–organic frameworks based on CoII and ZnII clusters for Knoevenagel condensation reaction and highly selective luminescence sensing | |
| CN112958158B (en) | Double-ligand rare earth complex photocatalyst and preparation method and application thereof | |
| Wang et al. | Fluorescence detection of anilines and photocatalytic degradation of Rhodamine B by a multifunctional metal–organic framework | |
| CN109395761B (en) | Nitrogen-doped BiOIO3Preparation method and application of photocatalyst | |
| Hou et al. | Photocatalytic Application of 4f–5f Inorganic–Organic Frameworks: Influence of Lanthanide Contraction on the Structure and Functional Properties of a Series of Uranyl–Lanthanide Complexes | |
| CN108640934B (en) | Metal cadmium organic framework material and preparation method and application thereof | |
| CN110639610B (en) | Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst | |
| Chen et al. | A [Cu4I] cluster based metal-organic framework to detect F− ions | |
| Su et al. | Significant enhancement of pesticide and organic dyes degradation by ion-exchange within a metal–organic framework | |
| CN115254189B (en) | Iron tailing sand MOF composite photocatalyst and preparation method and application thereof | |
| Guo et al. | Synthesis, structure and photocatalytic property of the 1D oxalate-bridged coordination polymer of manganese (II) | |
| CN111004397B (en) | Metal organic framework molecular material of electron-rich system and application thereof in photocatalytic reduction of heavy metal ions | |
| Yang et al. | An acid–base resistant paddle-wheel Cu (II) coordination polymer for visible-light-driven photodegradation of organic dyes | |
| CN104262275B (en) | A kind of silver-azotetrazole metal-organic framework material and its preparation method and application | |
| CN108424524A (en) | A kind of copper（II）Coordination polymer and the preparation method and application thereof | |
| Guo et al. | Construction of visible‐light‐responsive metal–organic framework with pillared structure for dye degradation and Cr (VI) reduction | |
| Shi et al. | A rigid and porous metal-organic frameworks with 1D rhombus channels and double walls: Selective adsorption of CO2 over N2, iodine capture, and fluorescence | |
| CN106496284A (en) | A kind of isonicotinoyl hydrazone nickel complex photocatalyst and its preparation method and application | |
| Wu et al. | An uncommon 3D (3, 8)-connected metal-organic framework: Luminescence sensing and photocatalytic properties | |
| Qiu et al. | Cd (II) frameworks with tetracarboxylate and imidazole-containing ligands: Syntheses, structures, adsorption and sensing properties | |
| Phengthaisong et al. | The crystal structure and photocatalytic properties of a cobalt (II) coordination polymer based on 4, 4′-oxy (bis) benzoic acid | |
| CN111518282B (en) | Hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye and preparation and application thereof | |
| Luo et al. | Polynuclear Cd (II) coordination polymer with unique configuration for chromium pollutants removal | |
| CN112076793B (en) | In-MOF material based on tricarboxylic acid ligand, preparation method and application | |
| CN111748101B (en) | Hydroxypyrazole manganese carboxylate complex photocatalyst and 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 |