CN109575296A - A kind of transition metal Zn complex and Fe3+The photocatalysis performance of modified composite material - Google Patents
A kind of transition metal Zn complex and Fe3+The photocatalysis performance of modified composite material Download PDFInfo
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- CN109575296A CN109575296A CN201710931976.4A CN201710931976A CN109575296A CN 109575296 A CN109575296 A CN 109575296A CN 201710931976 A CN201710931976 A CN 201710931976A CN 109575296 A CN109575296 A CN 109575296A
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- mof1
- composite material
- rhodamine
- modified composite
- iron ion
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- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 8
- 230000001699 photocatalysis Effects 0.000 title claims description 14
- 150000003624 transition metals Chemical class 0.000 title abstract description 7
- 238000007146 photocatalysis Methods 0.000 title description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 abstract description 22
- 101100131043 Oryza sativa subsp. japonica MOF1 gene Proteins 0.000 claims abstract description 21
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 10
- -1 iron ion Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005070 sampling Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 5
- 238000004847 absorption spectroscopy Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- GDLZGLLSIVMLOL-UHFFFAOYSA-N C(=O)N.C(=O)N.S1C=CC=C1 Chemical compound C(=O)N.C(=O)N.S1C=CC=C1 GDLZGLLSIVMLOL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000000862 absorption spectrum Methods 0.000 claims 1
- 238000013019 agitation Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000013384 organic framework Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
- 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]
-
- B01J35/39—
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
Abstract
The present invention relates to the performance studies that a kind of organic framework material of transition metal zinc and the modified composite material of iron ion have carried out photocatalytic degradation rhodamine B.Result of study shows that the B effect of the photocatalytic degradation rhodamine of independent MOF1 is general, but passes through the modified composite material Fe of iron ion3+The Photocatalytic Degradation Property of@MOF1 be improved significantly, 81% is increased to from original 38% in 2h to the degradation rate of rhodamine B.
Description
Technical field
The present invention relates to the Photocatalytic Performance Studies of a kind of transition metal Zn complex and its iron ion modified composite material
Technical background
Past chemical industry extensive style develops the various environmental problems of bring in intensive outburst nearly ten years.It is with dyeing industry
Example, China's dyeing industry unit product pollutant discharge amount is 1.2~1.8 times of developed country at present.It is used in printing and dyeing industry
Dyestuff be largely artificial synthesized chemical dye, they have the spies such as many kinds of, chemical stability is strong, structure is complicated
Point would become hard to degrade in water body if be drained into, and huge pressure can be caused safely to water body.Traditional waste water treatment process is such as raw
The disadvantages of there are poor processing effects for change method, absorption method, flocculation, chemical oxidization method etc., and energy consumption is high, at high cost.And light is urged
It is turned to a kind of environmentally friendly technology for eliminating pollution, cheap sunlight can be made full use of, thoroughly by organic pollutant
It is decomposed into inorganic molecules.This novel Technologies for Organic Wastewater Treatment due to having many advantages, such as wide spectrum, efficient, cheap, rapidly at
For the hot spot of Recent study.Therefore, develop and select suitable catalyst to become urgent problem to be solved.
Catalyst is also known as catalyst, is that can accelerate chemical reaction speed by providing a lower reaction path of activation energy
Rate, and the substance that the quality of itself, composition and chemical property remain unchanged before and after participating in chemical reaction.Organic-metallic skeleton
Material (MOFs) is because its good thermo-chemical stability and photostability can be applied to the photocatalytic degradation in organic pollutant, especially
It has because it has the characteristics that duct is more, pore size distribution range is big, catalytic site is numerous as the huge of catalyst of new generation
Big potential.Outer metal catalytic site is largely exposed to using MOFs material, it can be in the condition for keeping itself good stability
Effective degradation of contaminant down.However the degradation effect of single MOFs catalysis material synthesized at present passes through doping than relatively limited
It is an effective method that transition metal rice, which improves catalytic performance,.The present invention has been probed into 2,5- bis--(3,5- dicarboxyl benzene
Base) thiophene the diformamide metal organic framework MOF1 and its Fe that are synthesized with transition metal zinc salt3+Modified composite material exists
Application in photocatalytic degradation rhodamine B.
Summary of the invention
The purpose of the present invention is to provide a kind of new techniques of degradable organic dyestuff.Pass through heat of solution method, preparation
Metal organic framework, and using it as photocatalyst applications in the photocatalytic degradation of organic dyestuff.
To achieve the above object, the present invention adopts the following technical solutions:
The present invention is prepared for 2,5- bis--(3,5- dicarboxyphenyi) thiophene diformamide (L) and transition using solvent-thermal method
The metal organic frame MOF1 that metal zinc salt is formed, molecular formula are [Zn2(L) (4,4 '-bpy) (CH3OH)(H2O)2]·
3.5H2O·CH3OH, specific preparation process are as follows:
By Zn (NO3)2·6H2O, the mixed solution of L ligand, 4,4'-Bipyridine, DMF and water is added dropwise few drops of concentrated nitric acids and sets
In polytetrafluoroethylliner liner, isothermal reaction 3 days at 85 DEG C, then cooled to room temperature, is filtered, products therefrom DMF
Washing, drying at room temperature obtain bulk crystals.
A kind of transition metal organic frame is prepared for using above method.
The step of metal of the present invention organic Zn complex MOF1 photocatalytic degradation rhodamine B are as follows: by 80mL 1 ×
10-5The rhodamine B solution of mol/L is placed in quartz beaker, and 0.12g MOF1 is added, and in the dark state, stirring 40min reaches
Adsorption-desorption balance, sampling are primary.Then it is reacted under the irradiation of 300W xenon lamp, it is primary every 1h sampling.Gained sample is carried out
Centrifugation measures sample ultraviolet-visible absorption spectroscopy.
Show that the complex has certain degradation to rhodamine B by the photocatalysis experimental study of MOF1, in 2h
It is interior, degradation rate 38%.In order to improve the photocatalysis performance of complex, we have carried out iron ion doping to complex and have obtained
Fe3+@MOF1 composite material, detailed process is as follows:
It weighs 0.12g MOF1 to be put into dry beaker, adds the Fe (NO of 15mL3)3(0.1M) solution, at room temperature magnetic
It after power stirring for 24 hours, is clarified with distilled water centrifuge washing to supernatant, is dried for 24 hours under the conditions of 80 DEG C.
Similarly, to Fe3+Modified composite material Fe3+@MOF1 has carried out Photocatalytic Performance Study, and experimental procedure is same as above.
It lives all the above experimental results show that being modified by iron ion and complex can be enhanced in the photocatalysis of ultraviolet region
Property, substantially increase the degradation rate of rhodamine B.
Detailed description of the invention
Fig. 1 for institute MOF1 degrade target contaminant rhodamine B ultraviolet-visible spectrogram；
Fig. 2 is institute Fe3+Modified composite material Fe3+The ultraviolet-visible of@MOF1 degradation target contaminant rhodamine B
Spectrogram；
Fig. 3 is the degradation rate figure of rhodamine B under different condition；
Specific embodiment
1 complex [Zn of embodiment2(L) (4,4 '-bpy) (CH3OH)(H2O)2]·3.5H2O·CH3The synthesis of OH (MOF1)
By Zn (NO3)2·6H2O, 2,5- bis--(3,5- dicarboxyphenyi) thiophene diformamide (L), 4,4'-Bipyridine,
DMF, first alcohol and water mixed solution be placed in polytetrafluoroethylliner liner, isothermal reaction 3 days, then naturally cool at 85 DEG C
Room temperature, filtering, products therefrom are washed with DMF, and drying at room temperature obtains bulk crystals C34H37N4O17.5SZn2, yield 71.8%.
Embodiment 2:Fe3+Modified composite material Fe3+The preparation of@MOF1
It weighs 0.12g MOF1 to be put into dry beaker, adds the Fe (NO of 15mL3)3(0.1M) solution, at room temperature magnetic
It after power stirring for 24 hours, is clarified with distilled water centrifuge washing to supernatant, is dried for 24 hours under the conditions of 80 DEG C.
The Photocatalytic Performance Study of embodiment 3:MOF1
By 80mL 1 × 10-5The rhodamine B solution of mol/L is placed in quartz beaker, 0.12g MOF1 is added, in dark shape
Under state, stirring 40min reaches adsorption-desorption balance, and sampling is primary.Then it reacts under the irradiation of 300W xenon lamp, is sampled every 1h
Once.Gained sample is centrifuged, surveys its ultraviolet-visible absorption spectroscopy, as shown in Figure 1, the results showed that MOF1 is in 6h degradation sieve
The ratio of red bright B is 85%.
Embodiment 4:Fe3+The Photocatalytic Performance Study of@MOF1
By 80mL 1 × 10-5The rhodamine B solution of mol/L is placed in quartz beaker, and Fe is added3+@MOF1, in dark shape
Under state, stirring 40min reaches adsorption-desorption balance, and sampling is primary.Then it reacts under the irradiation of 300W xenon lamp, is taken every 20min
Sample is primary.Gained sample is centrifuged, it is as shown in Figure 2 to survey its ultraviolet-visible absorption spectroscopy, the results showed that Fe3+Modified composite wood
Expect Fe3+The ratio of@MOF1 rhodamine B degradation in 2h is 81%.
Embodiment 5:Fe3+The check experiment of@MOF1 Photocatalytic Performance Study
By 80mL 1 × 10-5The rhodamine B solution of mol/L is placed in quartz beaker, is urged respectively in dark, natural light, nothing
It is primary every 30min sampling under the conditions of agent.Gained sample is centrifuged, its ultraviolet-visible absorption spectroscopy, different condition are surveyed
Under degradation rate as shown in figure 3, from figure 3, it can be seen that under dark, natural light, without catalysts conditions, rhodamine B is basic
It is undegraded.In addition, individually time-consuming for MOF1 complex photocatalytic process, but pass through Fe3+Composite material Fe after modification3+@
The ratio of MOF1 rhodamine B degradation in 2h is significantly improved by 38% to 81%, and photocatalysis efficiency greatly improves.This is because iron
Ion has good light reaction ability, successfully improves composite material in the response of ultraviolet region, passes through the association with complex
Same-action effectively improves the photocatalysis performance of complex.
Claims (5)
1. a kind of metal formed by 2,5- bis--(3,5- dicarboxyphenyi) thiophene diformamide (L) and transition metal zinc salt has
Machine frame [Zn2(L) (4,4 '-bpy) (CH3OH)(H2O)2]·3.5H2O·CH3OH (MOF1) and its Fe3+Modified composite material
(Fe3+@MOF1) Photocatalytic Performance Study.Specifically prepare iron ion modified composite material (Fe3+@MOF1) the step of it is as follows: claim
It takes 0.12g MOF1 to be put into dry beaker, the Fe (NO of 15mL is added3)3(0.1M) solution, at room temperature magnetic agitation for 24 hours after,
It is clarified with distilled water centrifuge washing to supernatant liquor, is dried for 24 hours under the conditions of 80 DEG C.
2. MOF1 described in claim 1 and its iron ion doping composite material, the photocatalytic degradation applied to rhodamine B.
3. the specific steps of MOF1 photocatalytic degradation rhodamine B as claimed in claim 2 are as follows: by 80mL 1 × 10-5Sieve of mol/L
Red bright B solution is placed in quartz beaker, and 0.12g MOF1 is added, and in the dark state, it is flat that stirring 40min reaches adsorption-desorption
Weighing apparatus, sampling are primary.Then it is reacted under the irradiation of 300W xenon lamp, it is primary every 1h sampling.Gained sample is centrifuged, its purple is surveyed
Outer visible absorption spectra.
4. the iron ion modified composite material Fe in claim 23+The specific steps of@MOF1 photocatalytic degradation rhodamine B are as follows: will
80mL 1×10-5The rhodamine B solution of mol/L is placed in quartz beaker, and Fe is added3+@MOF1, in the dark state, stirring
40min reaches adsorption-desorption balance, and sampling is primary.Then it is reacted under the irradiation of 300W xenon lamp, it is primary every 20min sampling.It will
Gained sample is centrifuged, its ultraviolet-visible absorption spectroscopy is surveyed.
5. by application described in claim 3,4, MOF1 is 38% to degradation rate of the rhodamine B in 2h as photochemical catalyst,
Through the modified composite material Fe of iron ion3+@MOF1 degradation rate in 2h reaches 81%.
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| CN111203274A (en) * | 2020-01-21 | 2020-05-29 | 上海应用技术大学 | Double-channel mixed metal crystalline catalyst and preparation method and application thereof |
| CN111530501A (en) * | 2020-05-08 | 2020-08-14 | 五邑大学 | Fe/Zn-MOF derived magnetic photocatalytic material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111203274A (en) * | 2020-01-21 | 2020-05-29 | 上海应用技术大学 | Double-channel mixed metal crystalline catalyst and preparation method and application thereof |
| CN111530501A (en) * | 2020-05-08 | 2020-08-14 | 五邑大学 | Fe/Zn-MOF derived magnetic photocatalytic material and preparation method and application thereof |
| CN111530501B (en) * | 2020-05-08 | 2023-07-25 | 五邑大学 | Fe/Zn-MOF-derived magnetic photocatalytic material and preparation method and application thereof |
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