CN114588947A - Preparation method and application of Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst - Google Patents
Preparation method and application of Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
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- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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- 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]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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Abstract
The invention discloses a preparation method of a Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst, which comprises the following steps: A1) putting Zr-MOF-s (Pt) (Zr/Ti) in a vacuum drying oven at the temperature of 80-120 ℃ for drying for 8-12h to obtain a Zr-MOF-s (Pt) (Zr/Ti) solid material; A2) the solid material of Zr-MOF-s (Pt) (Zr/Ti) in the step A1) is subjected to H at the temperature of 150-250 DEG C2Reducing for 1-3h in the atmosphere to obtain the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst. The invention also discloses application of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst prepared by the preparation method. The Zr-MOF-s (Pt) (Zr/Ti) ion-exchange resin provided by the inventionThe preparation method of the R photocatalyst and the prepared Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst have the advantages that the mixed cluster of Zr/Ti-oxo and the Pt NPs generated in situ greatly promote the charge transfer and separation rate, so that the effects of simultaneously enhancing the removal of photocatalytic NO and the generation of hydrogen are achieved.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a preparation method and application of a Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst.
Background
With the rapid combustion of fossil fuels, energy crisis and environmental pollution gradually become two global problems that restrict the sustainable development of human civilization, so that the rapid development of various environment-friendly technologies is urgently required to cope with these challenges. Photocatalysis is an efficient and environment-friendly technology, and is considered to be one of the most effective ways to solve the problems of energy and environmental pollution. The photocatalysis technology is widely applied to hydrogen production (a clean and sustainable energy source) and removal of harmful pollutants (particularly nitrogen oxides) in the environment by fully utilizing inexhaustible solar energy. The photocatalyst is the core of the photocatalysis technology, but many existing photocatalysts have inherent defects of poor light stability, fast carrier recombination, slow electron transfer rate and the like. Therefore, it is very important to find a high-efficiency photocatalyst which can promote the removal of harmful pollutants and the hydrogen production by photolysis of water.
Metal Organic Frameworks (MOFs) are an emerging class of crystalline and porous materials with two-or three-dimensional structures assembled from metal ions (or metal clusters) and organic linkers. Porphyrin can be used as a connecting ligand of MOFs, and porphyrin organic ligands have a tetrapyrrole macrocyclic conjugated structure with 18 pi electrons, have excellent light absorption capacity in a visible light region, and can expand the absorption spectrum of MOFs to the visible light region. Meanwhile, metal ions or metal clusters (particularly Zr (iv) metals) with high valence state often can effectively improve the physical and chemical stability of MOFs, so a series of Zr-based porphyrins MOFs (such as a series of PCNs) have been reported. However, the lower carrier transfer efficiency of porphyrins to zr (iv) metal clusters still prevents their application in the field of photocatalysis. Moreover, if proton reduction cannot be performed to obtain hydrogen, photoelectrons generated through the LMCT pathway are gradually accumulated in the metal cluster nodes of the MOFs, further resulting in very low separation efficiency.
Therefore, how to find a more convenient and efficient method for preparing the MOFs photocatalyst to improve the catalytic effect thereof is the research direction of those skilled in the art.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention mainly aims to provide a preparation method of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst, which has the advantages of simple process, environmental protection and safety, and the prepared Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst has high catalytic activity and is used for catalytically removing nitrogen oxides.
The purpose of the invention is realized by the following technical scheme:
in a first aspect: a preparation method of Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst comprises the following steps:
A1) putting Zr-MOF-s (Pt) (Zr/Ti) in a vacuum drying oven at the temperature of 80-120 ℃ for drying for 8-12h to obtain a Zr-MOF-s (Pt) (Zr/Ti) solid material;
A2) the Zr-MOF-s (Pt) (Zr/Ti) solid material in the step A1) is subjected to H at the temperature of 150 ℃ and 250 DEG C2Reducing for 1-3h in the atmosphere to obtain the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst.
Further wherein the Zr-MOF-s (Pt) (Zr/Ti) is obtained by the following preparation method:
B1) cp is2TiCl2And Zr-MOF-s (Pt) are dissolved in the DMF solution, react for 60 to 80 hours at the temperature of 100-150 ℃, and are cooled to the room temperature to obtain a mixed solution;
B2) and C, centrifuging, washing and vacuum drying the mixed solution obtained in the step B1) to obtain the Zr-MOF-s (Pt) (Zr/Ti) material.
Further, in the step B2), after the mixed solution is centrifuged, the separated solid precipitate is respectively immersed in DMF, ethanol and acetone for purification and washing three times; the vacuum drying conditions are as follows: vacuum drying at 40-60 deg.c for 8-16 hr to obtain Zr-MOF-s (Pt) (Zr/Ti) material.
Further wherein in said step B1), said Cp2TiCl2The addition amount of the Zr-MOF-s (Pt) is between 35 and 45mg, and the addition amount of the DMF is between 6 and 10 mL.
Further wherein the Zr-MOF-s (Pt) is obtained by the following preparation method:
C1) reacting ZrCl4Formic acid and H2O is mixed in DMF, then PtTCPP is added, magnetic stirring is carried out for 10min at room temperature, and the obtained evenly mixed solution reacts for 12-36h at the temperature of 100-150 ℃ to obtain a mixture;
C2) and C1) centrifuging, washing and vacuum drying the mixture to obtain the Zr-MOF-s (Pt) material.
Further, in the step C2), after the mixture is centrifuged, the separated product is immersed into ethanol and acetone respectively for purification and washing three times; the vacuum drying conditions are as follows: vacuum drying at 40-60 deg.c for 6-18 hr to obtain Zr-MOF-s (Pt) material.
Further, wherein in the step C1), the ZrCl is added4The addition amount of (A) is 45-55mg, the addition amount of PtTCPP is 35-45mg, the addition amount of formic acid is 1.0-1.5mL, and the H is2The addition amount of O is 200-300 mu L, and the addition amount of DMF is 5-15 mL.
In a second aspect: application of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst obtained according to the preparation method in photocatalytic decomposition of water for hydrogen production and NO removal.
Compared with the prior art, the invention has at least the following advantages:
1) according to the preparation method of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst, Ti (IV) is used for replacing part of Zr (IV) on the basis of original Zr-based porphyrin MOFs, and limited domain Pt NPs with relatively small size are generated in situ in a cavity, so that the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst can be prepared, and the prepared Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst is prepared, wherein the charge transfer and separation rate are greatly promoted by the mixed cluster of Zr/Ti-oxo and the Pt NPs generated in situ, and the effects of simultaneously enhancing photocatalytic NO removal and hydrogen generation are achieved.
2) The hydrogen production amount of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst obtained by the preparation method reaches 10180.43 mu mol g within 4h under the irradiation of visible light-1(original Zr-MOF-s (Pt)) has a hydrogen production effect of 887.33. mu. mol g-1) (ii) a And the NO removal rate is improved by nearly 6 times compared with the original Zr-MOF-s (Pt).
3) The preparation method of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst provided by the invention has the advantages of simple operation, mild condition and low equipment requirement, is an environment-friendly and simple preparation method, and is convenient for popularization and application.
Drawings
In order to more clearly illustrate the embodiments of the present invention, reference will now be made briefly to the embodiments or to the accompanying drawings that are needed in the description of the prior art.
FIG. 1 is an XRD spectrum of Zr-MOF-s (Pt) material, Zr-MOF-s (Pt) (Zr/Ti) material and Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst according to examples 1-3 of the present invention;
FIG. 2 is an SEM image of Zr-MOF-s (Pt) material (a), Zr-MOF-s (Pt) (Zr/Ti) material (b) and Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst (c) of examples 1-3 of the present invention;
FIG. 3 is a TEM image of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst of example 3 of the present invention;
FIG. 4 is an IR spectrum of a Zr-MOF-s (Pt) material, a Zr-MOF-s (Pt) (Zr/Ti) material and a Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst according to examples 1 to 3 of the present invention;
FIG. 5 is a diagram of photocatalytic hydrogen production of Zr-MOF-s (Pt) material, Zr-MOF-s (Pt) (Zr/Ti) material and Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst according to examples 1 to 3 of the present invention;
FIG. 6 is a graph of the photocatalytic NO oxidation performance of the Zr-MOF-s (Pt) materials and the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalysts of examples 1 and 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the following drawings and examples, which are illustrative only and not intended to be limiting, and the scope of the present invention is not limited thereby.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or upper and lower limit of the preferred value, it is to be understood that any range where any pair of upper limit or preferred value and any lower limit or preferred value of the range is combined is specifically disclosed, regardless of whether the range is specifically disclosed. Unless otherwise indicated, numerical range values set forth herein are intended to include the endpoints of the range, and all integers and fractions within the range.
The materials, methods, and examples herein are illustrative and, unless otherwise specified, should not be construed as limiting; the raw materials and the detection equipment used in this example, not specifically described, are commercially available.
Wherein R in Zr-MOF-s (Pt) (Zr/Ti) -R expresses reduction.
Example 1 preparation of Zr-MOF-s (Pt)
A preparation method of Zr-MOF-s (Pt) comprises the following steps:
C1) reacting ZrCl4(50mg), formic acid (1.2mL) and H2Mixing O (250 mu L) in DMF (10mL) to obtain a mixed solution, adding 42mg of platinum porphyrin (PtTCPP) into the mixed solution, magnetically stirring at room temperature for 10min, transferring the obtained uniformly mixed solution into an autoclave with a PTFE lining, and reacting at 120 ℃ for 24h to obtain a mixture;
C2) centrifuging the mixture obtained in the step C1), respectively soaking the separated product into ethanol and acetone for purification and washing for three times, and then performing vacuum drying for 12h at the temperature of 50 ℃ to obtain the Zr-MOF-s (Pt) material.
Example 2 preparation of Zr-MOF-s (Pt) (Zr/Ti)
The preparation method of the Zr-MOF-s (Pt) (Zr/Ti) material comprises the following steps:
B1) cp is2TiCl2(46mg) and Zr-MOF-s (Pt) (42mg) were dissolved in a DMF (7.3ml) solution, reacted at a temperature of 120 ℃ for 72 hours, and then cooled to room temperature to give a mixed solution;
B2) centrifuging the mixed solution obtained in the step B1), and respectively soaking the separated solid precipitate into DMF, ethanol and acetone for purification and washing for three times; and then vacuum drying for 12h at the temperature of 50 ℃ to prepare the Zr-MOF-s (Pt) (Zr/Ti) material.
Wherein Zr-MOF-s (Pt) can be obtained by the preparation method in example 1.
Example 3 preparation of Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst
The Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst specifically comprises the following steps:
A1) putting the Zr-MOF-s (Pt) (Zr/Ti) obtained in the example 2 into a vacuum drying oven at 100 ℃ for drying for 10h to obtain a Zr-MOF-s (Pt) (Zr/Ti) solid material;
A2) h of the Zr-MOF-s (Pt) (Zr/Ti) solid material in the step A1) at 200 DEG C2Reducing for 2h in the atmosphere to obtain the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst.
The Zr-MOF-s (Pt) (Zr/Ti) used in this example can be obtained by the method of example 2.
Measurement of Performance
1) Determination of catalytic Activity
The present application carried out analytical tests on the Zr-MOF-s (Pt) material obtained in example 1, the Zr-MOF-s (Pt) (Zr/Ti) material obtained in example 2, and the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst obtained in example 3, wherein XRD spectra of the Zr-MOF-s (Pt), the Zr-MOF-s (Pt) (Zr/Ti) and the Zr-MOF-s (Pt) (Zr/Ti) -R material are shown in FIG. 1, SEM image is shown in FIG. 2, TEM image is shown in FIG. 3, and IR spectrum is shown in FIG. 4; as can be seen from FIGS. 1 to 4, the morphology structure of Zr-MOF-s (Pt) (Zr/Ti) -R is substantially consistent with that of original MOF, which shows that the MOF has good structural stability after Ti is doped and Pt NPs are generated in situ, and simultaneously the catalytic performance is improved.
2) Photocatalytic hydrogen production performance test
In a quartz reactor, 5mg of the Zr-MOF-s (Pt), Zr-MOF-s (Pt) (Zr/Ti) and Zr-MOF-s (Pt) (Zr/Ti) -R materials obtained in examples 1-3 were suspended in 50mL of a mixed solution containing 50mL of deionized water and 880mg of ascorbic acid as a sacrificial agent; covering the quartz reactor, introducing nitrogen for bubbling, and deoxidizing for 20 min; then, the hydrogen production photocatalysis system is accessed, and the circulating condensed water is kept at 6 ℃; vacuumizing a hydrogen production photocatalytic system connected with a quartz reactor; placing a xenon lamp light source at the position 5cm above the quartz reactor, starting the light source, sampling every half hour, entering a gas chromatograph through a hydrogen production photocatalytic system, and detecting the amount of hydrogen; the specific hydrogen production of MOF materials prepared in examples 1-3 over 4h is shown in figure 5 and table 1.
TABLE 1 hydrogen production in 4h of MOF materials prepared in examples 1-3
| Examples | Hydrogen production (umol. g)-1) | Hydrogen yield (uL. g)-1) |
| Example 1 | 887.33 | 19876.192 |
| Example 2 | 2320.30 | 51974.72 |
| Example 3 | 10180.43 | 228041.632 |
As is clear from Table 1, the hydrogen production amount in example 1 was 887.33umol g-1In example 3, the hydrogen production amount was 10180.43umol g-1Compared with the hydrogen production amount of Zr-MOF-s (Pt) in example 1, the hydrogen production amount of Zr-MOF-s (Pt) (Zr/Ti) -R in example 3 is obviously improved and is 11.47 times of the hydrogen production amount of Zr-MOF-s (Pt) in example 1; the significant increase in hydrogen production of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst is attributable to enhanced visible light absorption and the formation of novel electron transfer pathways.
3) Performance testing of photocatalytic NO removal
The Zr-MOF-s (Pt) materials prepared in examples 1 and 3 and Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst (0.1g) were placed in two glass dishes with a diameter of 12cm, and 10mL of ethanol was added for ultrasonic dispersion; the glass dish was then dried at 60 ℃ until all the solvent had evaporated; after cooling to room temperature, the two dried glass dishes were used for further photocatalytic NO removal experiments. By NO-NO2-NOxThe analyser (Thermo Scientific, 42iTL) tested photocatalytic NO oxidation, which was carried out in a continuous flow reactor with two common LED lamps (12W) placed vertically above the reactor. In thatDuring each test, NO (initial concentration 100ppm) was first fed and then the air generator was turned on to dilute the NO concentration to 530 ppb; after the gas reaches the adsorption-desorption balance, turning on a lamp to start the illumination reaction; after the NO concentration is stabilized, turning on the light source, examining the sample every 1min, and passing NOxThe analyzer records the results. The NO removal rate (. eta.) was calculated by the following formula.
η(％)＝(1-C/C0)*100％
Wherein C and C0The NO concentration in the outlet and feed streams, respectively.
As shown in FIG. 6, the NO removal rate of the Zr-MOF-s (Pt) material of example 1 is 8.07%, which is much lower than that of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst of example 3, and the optimal removal rate of the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst can reach 46.6%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (8)
1. A preparation method of Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst is characterized by comprising the following steps:
A1) putting Zr-MOF-s (Pt) (Zr/Ti) in a vacuum drying oven at the temperature of 80-120 ℃ for drying for 8-12h to obtain a Zr-MOF-s (Pt) (Zr/Ti) solid material;
A2) the Zr-MOF-s (Pt) (Zr/Ti) solid material in the step A1) is subjected to H at the temperature of 150 ℃ and 250 DEG C2Reducing for 1-3h in the atmosphere to obtain the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst.
2. The method of preparing Zr-MOF-s (pt) (Zr/Ti) -R photocatalyst according to claim 1, wherein said Zr-MOF-s (pt) (Zr/Ti) is obtained by the following method:
B1) cp is2TiCl2And Zr-MOF-s (Pt) are dissolved in a DMF solution, react for 60 to 80 hours at the temperature of 100-150 ℃, and are cooled to room temperature to obtain a mixed solution;
B2) and C, centrifuging, washing and vacuum drying the mixed solution obtained in the step B1) to obtain the Zr-MOF-s (Pt) (Zr/Ti) material.
3. The method for preparing Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst according to claim 2, wherein in the step B2), after the mixed solution is centrifuged, the separated solid precipitate is respectively immersed in DMF, ethanol and acetone for purification and washing three times; the vacuum drying conditions are as follows: vacuum drying at 40-60 deg.c for 8-16 hr to obtain Zr-MOF-s (Pt) (Zr/Ti) material.
4. A process for the preparation of Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst according to claim 3, characterized in that in said step B1), said Cp2TiCl2The addition amount of the Zr-MOF-s (Pt) is between 35 and 45mg, and the addition amount of the DMF is between 6 and 10 mL.
5. The method of preparing Zr-MOF-s (pt) (Zr/Ti) -R photocatalyst according to claim 2, wherein said Zr-MOF-s (pt) is obtained by the following method:
C1) reacting ZrCl4Formic acid and H2O is mixed in DMF, then PtTCPP is added, magnetic stirring is carried out for 10min at room temperature, and the obtained uniformly mixed solution reacts for 12-36h at the temperature of 100-150 ℃ to obtain a mixture;
C2) and C1) centrifuging, washing and vacuum drying the mixture to obtain the Zr-MOF-s (Pt) material.
6. The method for preparing Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst in accordance with claim 5, wherein in the step C2), after the mixture is centrifuged, the separated product is purified and washed three times by immersing in ethanol and acetone respectively; the vacuum drying conditions are as follows: vacuum drying at 40-60 deg.c for 6-18 hr to obtain Zr-MOF-s (Pt) material.
7. The method of claim 6, wherein the ZrCl is present in the Zr-MOF-s (Pt) (Zr/Ti) -R photocatalyst in the step C1)4The addition amount of (A) is 45-55mg, the addition amount of PtTCPP is 35-45mg, the addition amount of formic acid is 1.0-1.5mL, and the H is2The addition amount of O is 200-300 mu L, and the addition amount of DMF is 5-15 mL.
8. Use of the Zr-MOF-s (pt) (Zr/Ti) -R photocatalyst obtained by the preparation method according to any one of claims 1 to 7, for photocatalytic decomposition of water to produce hydrogen and for NO removal.
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