CN110201718B - Preparation and application of red phosphorus/iron-based metal organic framework composite material - Google Patents
Preparation and application of red phosphorus/iron-based metal organic framework composite material Download PDFInfo
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- CN110201718B CN110201718B CN201910456079.1A CN201910456079A CN110201718B CN 110201718 B CN110201718 B CN 110201718B CN 201910456079 A CN201910456079 A CN 201910456079A CN 110201718 B CN110201718 B CN 110201718B
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000013082 iron-based metal-organic framework Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000013179 MIL-101(Fe) Substances 0.000 claims abstract description 48
- 239000004098 Tetracycline Substances 0.000 claims abstract description 30
- 229960002180 tetracycline Drugs 0.000 claims abstract description 30
- 229930101283 tetracycline Natural products 0.000 claims abstract description 30
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 30
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000011941 photocatalyst Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 239000002689 soil Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 239000006228 supernatant Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a red phosphorus/iron-based metal organic framework composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1: dissolving commercial red phosphorus in deionized water, transferring the red phosphorus into a reaction kettle, heating at constant temperature, cooling to room temperature, washing an obtained product, and centrifugally drying to obtain purified red phosphorus; step 2: dissolving ferric trichloride hexahydrate and terephthalic acid in an N, N-dimethylformamide organic solvent, carrying out ultrasonic treatment, uniformly mixing, cooling to room temperature after reaction, centrifuging, washing with deionized water and absolute ethyl alcohol, and drying to obtain MIL-101 (Fe); and step 3: respectively dissolving purified RP and MIL-101 (Fe) in absolute ethyl alcohol, mixing, carrying out hydrothermal reaction, cooling to room temperature, centrifuging, and drying the obtained solid to obtain the RP/MIL-101 (Fe) composite material. The RP/MIL-101 (Fe) composite material obtained by the invention has the degradation performance of simply, quickly and efficiently removing tetracycline waste water.
Description
Technical Field
The invention relates to preparation and application of a red phosphorus/iron-based metal organic framework composite material for efficiently adsorbing-photocatalytic degrading tetracycline, and belongs to the technical field of pharmaceutical wastewater treatment.
Background
With the rapid development of economy and the rapid improvement of the living standard of people, environmental protection and management are very important. In recent years, due to the increasing concern of people on antibiotic pollution caused by frequent detection of antibiotics in underground water, drinking water, surface water, sediments and farmland soil, china has become the world first antibiotic use and production country according to statistics. At present, environmental pollution caused by abuse of antibiotics and ecological toxicological effects thereof become one of the major environmental problems faced by China. As one of the representative antibiotics frequently used, the wastewater pollution treatment of tetracycline is also a hot problem to be solved urgently, so that the development of a simple, effective, economic and rapid method for removing tetracycline is widely concerned and paid attention by more and more researchers, which has a great significance for environmental protection and medical industry.
At present, tetracycline wastewater treatment is mainly divided into physical treatment technology, chemical treatment technology, biological treatment technology, photocatalytic technology, combined treatment of various methods and the like. The photocatalysis technology has the characteristics of high efficiency, environmental protection, low price and the like, is a green method which saves resources and is environment-friendly, and is increasingly favored by people in the aspect of tetracycline wastewater treatment.
The metal organic framework Material (MOFs) has a porous network structure consisting of metal oxide clusters and organic ligands, so that the MOFs can be used as a good adsorbent and an excellent catalyst, the porous characteristic means that a catalytic reaction can occur on a larger surface, and the energy band structure of the MOFs material can be adjusted by modifying organic matters or inorganic matters in the synthesis process, so that the MOFs material can be used as a photocatalyst for treating environmental pollutants. While the iron-based metal organic framework material (MIL-101 (Fe)) is the most representative one of MOFs, research reports have confirmed that it is a good photocatalyst, but it does not belong to the wide photoresponse range of photocatalysts because of its limited photocatalytic capability.
In recent years, elemental red phosphorus is found to be a photocatalytic material with very excellent performance, and if a proper amount of red phosphorus is loaded on an iron-based metal organic framework material with a large specific surface area to prepare a composite material, the problem of small photoresponse of the iron-based metal organic framework material can be solved, and meanwhile, the synergistic effect of adsorption and photocatalysis can be fully utilized to improve the removal effect of environmental pollutants. So far, no report of the invention patent of the red phosphorus/iron-based metal organic framework composite material and the preparation method thereof for degrading tetracycline wastewater is found.
Disclosure of Invention
The invention aims to provide a material with better photocatalytic degradation performance on tetracycline wastewater, and preparation and application thereof.
In order to achieve the aim, the invention provides a preparation method of a red phosphorus/iron-based metal organic framework composite material, which is characterized by comprising the following steps:
step 1: dissolving Red Phosphorus (RP) in deionized water to obtain a suspension, transferring the suspension into a reaction kettle, heating at a constant temperature, cooling to room temperature, repeatedly washing the obtained product with the deionized water and absolute ethyl alcohol after suction filtration for many times, centrifuging, and drying to obtain purified red phosphorus;
step 2: ferric chloride hexahydrate (FeCl) 3 ·6H 2 O) and terephthalic acid (H) 2 BDC) is dissolved in an organic solvent, the mixture is mixed evenly by ultrasonic to obtain a suspension, the mixed suspension is moved into a reaction kettle for constant temperature reaction, the obtained product is filtered, washed by absolute ethyl alcohol for a plurality of times and dried to obtain a product, which is marked as MIL-101 (Fe);
and step 3: and (3) respectively dissolving the purified Red Phosphorus (RP) obtained in the step (1) and the MIL-101 (Fe) obtained in the step (2) in absolute ethyl alcohol, then mixing the two suspensions, transferring the mixture to a reaction kettle for hydrothermal reaction, cooling to room temperature after the reaction is finished, centrifuging, and drying to obtain the RP/MIL-101 (Fe) composite material, namely the red phosphorus/iron-based metal organic framework composite material.
Preferably, the concentration of red phosphorus in the suspension in step 1 is 1.5-2.5M.
Preferably, the constant temperature heating temperature in the step 1 is 190-210 ℃, and the heating time is 10-12 h.
Preferably, the mole ratio of ferric trichloride hexahydrate to terephthalic acid in step 2 is 2.
Preferably, the organic solvent in step 2 is N, N-Dimethylformamide (DMF).
Preferably, the concentration of ferric chloride hexahydrate in the suspension in the step 2 is 0.04-0.05 g/mL.
Preferably, the concentration of terephthalic acid in the suspension in the step 2 is 0.013-0.014 g/mL.
Preferably, the constant temperature reaction temperature in the step 2 is 100-130 ℃, and the reaction time is 18-22 h.
Preferably, the weight ratio of the red phosphorus purified in the step 3 to the MIL-101 (Fe) is 1 (3-9).
More preferably, the weight ratio of the red phosphorus purified in the step 3 to the MIL-101 (Fe) is 1 (5-7)
Preferably, the temperature of the hydrothermal reaction in the step 3 is 75-85 ℃, and the reaction time is 3-5 h.
The invention also provides the red phosphorus/iron-based metal organic framework composite material prepared by the preparation method.
The invention also provides application of the red phosphorus/iron-based metal organic framework composite material in treatment of tetracycline wastewater.
Preferably, the application of the red phosphorus/iron-based metal organic framework composite material in the treatment of tetracycline waste water is characterized in that the red phosphorus/iron-based metal organic framework composite material is placed in the waste water containing tetracycline, and is subjected to photophobic reaction to reach adsorption-desorption balance, and then illumination is performed to degrade the tetracycline.
The invention adopts a solvothermal method to prepare the target compound MIL-101 (Fe). Synthesizing the RP/MIL-101 (Fe) composite material by a low-temperature hydrothermal method. The preparation of the photocatalyst with specific composition and morphology plays a key role in improving the photocatalytic performance. Octahedron MIL-101 (Fe) can be used as a good adsorbent and also can be used as a good photocatalyst. And further adjusting the energy band structure of MIL-101 (Fe) by subsequently loading RP to obtain the composite photocatalyst, thereby achieving higher photocatalytic efficiency. So far, the invention patent reports of RP/MIL-101 (Fe) composite materials for photocatalytic degradation of tetracycline wastewater and preparation methods thereof are not found.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method is scientific, reasonable and easy to implement, low in cost and high in repeatability, and the obtained red phosphorus/iron-based metal organic framework composite material has the degradation performance of simply, quickly and efficiently removing tetracycline waste water, so that the red phosphorus/iron-based metal organic framework composite material has potential application prospects.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of purified red phosphorus;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of MIL-101 (Fe);
FIG. 3 is a scanning electron micrograph of the RP (15 wt.%)/MIL-101 (Fe) composite;
FIG. 4 is an X-ray powder diffraction pattern of the RP (15 wt.%)/MIL-101 (Fe) composite;
FIG. 5 is a UV-visible diffuse reflectance spectrum of an RP (15 wt.%)/MIL-101 (Fe) composite;
FIG. 6 is a graph of the adsorption-photocatalytic performance of the RP (15 wt.%)/MIL-101 (Fe) composite on tetracycline.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a preparation method of a red phosphorus/iron-based metal organic framework composite material, which comprises the following specific preparation steps:
step 1: purification treatment of commercial red phosphorus:
2g of commercial red phosphorus (purchased from Aladdin, AR 98.5%) is ground and dissolved in 20mL of deionized water to obtain a suspension, the prepared suspension is transferred to a reaction kettle and kept at a constant temperature of 200 ℃ for 12h, the suspension is cooled to room temperature after the reaction is finished, the obtained product is subjected to suction filtration, is repeatedly washed with deionized water and absolute ethyl alcohol for multiple times, and is finally centrifugally collected and dried at 50 ℃ for 12h to obtain purified RP for later use;
step 2: preparation of iron-based metal organic framework material (MIL-101 (Fe)):
0.675g of FeCl 3 ·6H 2 O (purchased from Aladdin, AR ≥ 99%) and 0.206g H 2 BDC (purchased from Aladdin, AR is more than or equal to 99 percent) is dissolved in 15mL DMF, the mixture is subjected to ultrasonic treatment for 15min and is uniformly mixed to obtain mixed suspension, the mixed suspension is moved to a 50mL reaction kettle to react for 20h at 110 ℃, after the reaction is finished, the obtained brown solid is filtered out, the crude product is washed for 2 times by adopting absolute ethyl alcohol at 60 ℃, and finally, the product MIL-101 (Fe) is obtained after freeze drying for 12h at 50 ℃ below zero for standby;
and step 3: preparation of RP/MIL-101 (Fe) composite:
respectively dissolving 0.03g of the purified RP obtained in the step 1 and 0.17g of MIL-101 (Fe) obtained in the step 2 in 15mL of absolute ethanol, performing ultrasonic homogenization, then uniformly mixing the two suspensions, moving the mixture into a 50mL reaction kettle to react for 4h at 80 ℃, and then centrifuging the obtained product, collecting the product at-50 ℃, and performing freeze drying for 12h to obtain an RP (15 wt.%)/MIL-101 (Fe) composite material;
and 4, step 4: adsorption-photocatalytic performance experiment:
placing 0.05g of the RP (15 wt.%)/MIL-101 (Fe) composite material obtained in the step 3 in 100mL of 50mg/L Tetracycline (TC) solution, and reacting for 60min in a dark place to achieve adsorption-desorption equilibrium; simulating sunlight irradiation by using Pofely 300WXe xenon lamp as light source, centrifuging 4mL samples at 5-10min intervals after the start of the irradiation, placing the supernatant in a cuvette, measuring the absorption value of tetracycline by using an Shimadzu UV-2550 ultraviolet spectrophotometer, and measuring the absorption value by using C/C 0 To evaluate the degradation rate, wherein C is the concentration of tetracycline in the sample after a certain period of light irradiation, C 0 Is the initial tetracycline concentration of the sample.
FIG. 1 is a Scanning Electron Micrograph (SEM) of the purified RP prepared in this example. It can be seen that the resulting RP is a nanoparticle with a size around 10 nm.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the iron-based metal organic framework material (MIL-101 (Fe)) prepared in the example. It can be seen that the prepared sample is an octahedron with a concave surface, the size of the octahedron is about 200nm, and the distribution of the octahedron is relatively uniform.
FIG. 3 is a Scanning Electron Microscope (SEM) illustration of the resulting RP (15 wt.%)/MIL-101 (Fe) composite prepared in this example, and it can be seen that the nanoparticles RP are supported on the surface of the octahedral MIL-101 (Fe).
FIG. 4 is an X-ray powder diffraction (XRD) pattern of the RP (15 wt.%)/MIL-101 (Fe) composite prepared according to the example. As can be seen, the XRD spectrum of the RP (15 wt%)/MIL-101 (Fe) composite material is the superposition of the RP characteristic absorption peak and the MIL-101 (Fe) characteristic absorption peak, and no other impurity peaks appear in the composite material, which indicates that the purity of the synthesized RP (15 wt%)/MIL-101 (Fe) composite material is higher.
FIG. 5 is a graph of the ultraviolet-visible diffuse reflectance spectrum (UV-Vis DRS) of the RP (15 wt.%)/MIL-101 (Fe) composite prepared in this example, which shows that the composite has excellent ultraviolet and visible light absorption properties and can be used as a photocatalyst.
Fig. 6 is an adsorption-photocatalytic performance curve of the RP (15 wt.%)/MIL-101 (Fe) composite material prepared by the present example to tetracycline, and experimental results show that the RP (15 wt.%)/MIL-101 (Fe) composite material has very fast and efficient performance for photocatalytic degradation of tetracycline, the adsorption rate to tetracycline with an initial concentration of 50mg/L reaches 47.4% within 60min, and the degradation rate to tetracycline reaches 86.8% within 60min after light is turned on, so that the adsorption and photocatalytic degradation of tetracycline are integrated, and the RP (15 wt.%)/MIL-101 (Fe) composite material can be used as an efficient adsorbent or photocatalyst for application in the field of environmental protection.
Example 2
This example differs from example 1 in that in step 3, an RP (10 wt.%)/MIL-101 (Fe) composite is obtained, which is otherwise the same as example 1.
Example 3
This example differs from example 1 in that in step 3, an RP (20 wt.%)/MIL-101 (Fe) composite is obtained, which is otherwise the same as example 1.
Example 4
This example differs from example 1 in that in step 3, an RP (25 wt.%)/MIL-101 (Fe) composite was obtained, which was otherwise the same as example 1.
The results of the experiments show that the photocatalytic effect of the composite samples of RP (10 wt.%)/MIL-101 (Fe), RP (15 wt.%)/MIL-101 (Fe), RP (20 wt.%)/MIL-101 (Fe), and RP (25 wt.%)/MIL-101 (Fe) on tetracycline is 85.9%, 86.8%, 85.73%, 85.58%, respectively, with the 15wt.% RP content of the composite sample being the best photocatalytic effect on tetracycline.
Claims (3)
1. The application of the red phosphorus/iron-based metal organic framework composite material in the treatment of tetracycline wastewater is characterized in that the red phosphorus/iron-based metal organic framework composite material is placed in the tetracycline-containing wastewater, and is subjected to photophobic reaction to achieve adsorption-desorption balance, and then illumination is performed to degrade tetracycline;
the preparation method of the red phosphorus/iron-based metal organic framework composite material comprises the following steps:
step 1: dissolving red phosphorus in deionized water to obtain a suspension, transferring the suspension into a reaction kettle, heating at a constant temperature, cooling to room temperature, repeatedly washing the obtained product with deionized water and absolute ethyl alcohol after suction filtration for many times, centrifuging, and drying to obtain purified red phosphorus;
and 2, step: dissolving ferric trichloride hexahydrate and terephthalic acid in an organic solvent, uniformly mixing by ultrasonic waves to obtain a suspension, transferring the suspension into a reaction kettle for constant-temperature reaction, washing the obtained product with absolute ethyl alcohol for multiple times after suction filtration, and drying to obtain a product, wherein the product is marked as MIL-101 (Fe); the molar ratio of ferric trichloride hexahydrate to terephthalic acid is 2; the constant temperature reaction temperature is 100-130 ℃, and the reaction time is 18-22 h;
and step 3: respectively dissolving the purified red phosphorus obtained in the step 1 and the MIL-101 (Fe) obtained in the step 2 in absolute ethyl alcohol, wherein the weight ratio of the purified RP to the MIL-101 (Fe) is 1 (3-9); and then mixing the two suspensions, transferring the mixture into a reaction kettle for hydrothermal reaction at 75-85 ℃ for 3-5 h, cooling to room temperature after the reaction is finished, centrifuging, and drying to obtain the RP/MIL-101 (Fe) composite material, namely the red phosphorus/iron-based metal organic framework composite material.
2. The use of a red phosphorus/iron-based metal organic framework composite material according to claim 1, wherein the concentration of red phosphorus in the suspension in step 1 is 1.5-2.5M; the constant heating temperature is 190-210 ℃, and the heating time is 10-12 h.
3. The use of a red phosphorus/iron-based metal organic framework composite material according to claim 1, wherein the organic solvent in step 2 is N, N-dimethylformamide; the concentration of ferric trichloride hexahydrate in the suspension is 0.04-0.05 g/mL; the concentration of terephthalic acid in the suspension is 0.013-0.014 g/mL.
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| CN104525266A (en) * | 2014-12-30 | 2015-04-22 | 河南理工大学 | Preparation method of metal-organic framework material photocatalyst and application |
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| CN104525266A (en) * | 2014-12-30 | 2015-04-22 | 河南理工大学 | Preparation method of metal-organic framework material photocatalyst and application |
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