CN113265061A - Preparation method and application of Ru/Cu-BTC metal organic framework material - Google Patents
Preparation method and application of Ru/Cu-BTC metal organic framework material Download PDFInfo
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- 239000013148 Cu-BTC MOF Substances 0.000 title claims abstract description 58
- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NOSIKKRVQUQXEJ-UHFFFAOYSA-H tricopper;benzene-1,3,5-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1.[O-]C(=O)C1=CC(C([O-])=O)=CC(C([O-])=O)=C1 NOSIKKRVQUQXEJ-UHFFFAOYSA-H 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 19
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 3
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- 230000007062 hydrolysis Effects 0.000 abstract description 3
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- 229910019891 RuCl3 Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
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- 239000002184 metal Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 238000006467 substitution reaction Methods 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
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- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
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- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 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 preparation method of a metal organic framework material (Ru/Cu-BTC) with enhanced water stability and photocatalytic activity and application of the metal organic framework material in photocatalytic hydrolysis hydrogen evolution. The preparation process of the water-unstable Cu-BTC material and the enhanced stable material Ru/Cu-BTC thereof is as follows: (1) adding Cu (NO)3)3﹒3H2O (0.725g) and H3BTC (0.420g) was ultrasonically dispersed in a mixed solution of water and ethanol, and then transferred to a reaction vessel to react at 150 ℃ for 24 hours. After cooling, the blue solid product obtained was centrifuged and washed several times with deionized water and ethanol and finally dried under vacuum at 80 ℃ for 12 h. (2) Dispersing the prepared Cu-BTC into water, and then adding a certain amount of RuCl3And stirring for 12h, then centrifuging and drying in vacuum to obtain the product Ru/Cu-BTC. R prepared by the inventionThe u/Cu-BTC material not only can enhance the stability of Cu-BTC in water, but also can improve the photocatalytic activity and promote the hydrogen evolution of photocatalytic hydrolysis, and the hydrogen evolution rate of the u/Cu-BTC material is improved by 50 percent compared with that of pure Cu-BTC and reaches 15814.8 mu mol g‑1·h‑1。
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a preparation method and application of Ru/Cu-BTC metal organic framework Materials (MOFs).
Background
The massive use of fossil fuels brings a great crisis to the environment and energy, and for human beings, it is important to find clean and sustainable energy to replace fossil fuels. Hydrogen energy is a renewable energy source and produces no other pollutants after combustion. However, hydrogen energy is currently obtained primarily by fossil fuel conversion. According to the latest plan of European Union, the hydrogen production method by hydrogen evolution through hydrolysis is a necessary substitute for the hydrogen production method by fossil fuel. And the photolysis water can directly convert solar energy into hydrogen energy, so that the cheap and effective photocatalyst is especially important to find.
Metal Organic Frameworks (MOFs) assembled from organic linkers and metal nodes have been widely used in many fields due to their unique properties and catalytic properties. Particularly, metal nodes uniformly dispersed in the MOFs can be used as independent active sites to participate in photocatalytic reaction. It is known that the uniformly dispersed metal nodes in the original MOFs tend to have very high atom utilization efficiency due to their large specific surface area and high porosity. In addition, the chemical environment of these metal nodes is easily modulated by the doped atoms or ions, and the modulating effect of the heteroatom dopant tends to change the electronic structure of the metal nodes. Therefore, it is very valuable to adopt abundant metal nodes in the original MOFs as a co-catalyst for photocatalytic hydrogen evolution.
Many MOFs have been developed as photocatalysts, but exhibit only limited hydrogen evolution photocatalytic activity even with noble metal (e.g., Pt, Au, etc.) nanoparticles as promoters. This is because the pore opening size of the MOFs is small, the promoter particles are difficult to deposit in the pores of the MOFs, and the hydrophobicity of the organic linking group also causes the promoter particles to be difficult to deposit in the pores of the MOFs, so that the release of photocatalytic hydrogen can only occur at the reaction centers near the outer surface of the bulk MOFs, and the photogenerated charge carriers must travel a long distance to reach the reaction centers, so that the transfer rate and separation efficiency of the photogenerated carriers are low, resulting in low photocatalytic efficiency. Cu-BTC is MOFs which can be prepared on a large scale and has low cost, but is rarely used for hydrogen production by water photolysis because of structural damage caused by adsorption of small molecules such as water and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the problems of unstable catalyst, high cost in the preparation process of the catalyst and low photocatalytic efficiency caused by low transfer rate and separation efficiency of a photon-generated carrier in the prior art, and provides a method for enhancing the stability of MOFs and enhancing the photocatalytic activity of the MOFs and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing M-BTC (M: Cu, Zn, Co, Ce, Bi) and Ru/Cu-BTC material with enhanced water stability comprises the following steps:
(1) Cu-BTC: adding Cu (NO)3)3﹒3H2O (0.725g) and H3BTC (0.420g) was dispersed in 12ml of a mixed solution of water and ethanol by sonication, and then transferred to a reaction vessel to react at 150 ℃ for 24 hours. After cooling, washing with deionized water and ethanol for multiple times, and finally vacuum drying at 80 ℃ for 12 h.
(2) Zn-BTC, Co-BTC: adding 12mmol of Zn (NO)3)2·6H2O and 8mmol H3BTC is dispersed into 200ml of mixed solution of ethanol and water, 24mmol of NaOH is added after full dissolution, stirring is carried out for 30min, and finally washing is carried out for multiple times by deionized water and ethanol, and vacuum drying is carried out for 12h at 80 ℃.
(3) Ce-BTC: adding 10mmol of Ce (NO)3)3·6H2O and 3mmol H3BTC was dissolved in 50ml DMF, then transferred to a reaction kettle to react at 130 ℃ for 24h, cooled and washed with DMF and ethanol several times, and finally dried under vacuum at 80 ℃ for 12 h.
(4) Bi-BTC: 0.49mmol of Bi (NO)3)3·5H2O and 0.920mmol H3BTC is dispersed into a mixed solution of DMF and MeOH, is stirred uniformly and then is transferred into a reaction kettle to react for 45h at 120 ℃, is washed with DMF and methanol for a plurality of times after being cooled, and is finally dried for 12h under vacuum at 80 ℃.
(5) A preparation method of a Cu-BTC metal organic framework material with enhanced water stability is characterized by comprising the following steps:
the prepared 400mg of Cu-BTC was dispersed in water, and then a certain amount of RuCl was added3(the mass ratio of Ru to Cu-BTC is 3 percent), stirring for 12 hours, then centrifuging and drying in vacuum to obtain the product Ru/Cu-BTC with enhanced water stability.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the Ru/Cu-BTC material with enhanced water stability provided by the invention is simple to operate, simple in equipment, low in price, good in repeatability and high in popularization value.
2. The M-BTC (M: Cu, Zn, Co, Ce, Bi) and the Ru/Cu-BTC material with enhanced water stability are prepared by the method, wherein the Cu-BTC has a wide light absorption range under the irradiation of visible light, and a metal organic framework adopts a Cu-O oxo cluster as a reaction site. But has poor water stability, but the stability of the Cu-BTC alloy is greatly improved after partial Cu substitution in Ru.
3. In the M-BTC series materials prepared by the invention, the Cu-BTC material has the highest photocatalytic hydrogen evolution activity, and the Ru/Cu-BTC material with enhanced water stability has the hydrogen evolution rate as high as 15814.8 mu mol g-1·h-1The catalytic activity of the material is improved by 50 percent compared with that of a pure Cu-BTC material.
Drawings
FIG. 1 is an X-ray diffraction pattern of M-BTC (M: Zn, Co, Ce, Bi) prepared in examples 2 to 4 of the present invention.
FIG. 2 is an X-ray diffraction pattern of Cu-BTC and Ru/Cu-BTC prepared in examples 1 and 5 of the present invention.
FIG. 3 shows H existing in water for a long time2X-ray diffraction patterns of O/Cu-BTC and Cu-BTC prepared in example 1 of the present invention.
FIG. 4 shows Cu-BTC (a), Ru/Cu-BTC (b) and H in the present invention2Scanning electron microscope image of O/Cu-BTC (c).
FIG. 5 is a graph comparing the hydrogen production of catalysts prepared in examples 1-5 of the present invention.
FIG. 6 is a hydrogen production cycle test chart of the Ru/Cu-BTC catalyst prepared in example 5 of the invention.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Preparation of M-BTC (M: Cu, Zn, Co, Ce, Bi) and Ru/Cu-BTC material with enhanced stability
Example 1
Preparation of Cu-BTC:
adding Cu (NO)3)3﹒3H2O (0.725g) and H3BTC (0.420g) was dispersed in 12ml of a mixed solution of water and ethanol by sonication, and then transferred to a reaction vessel to react at 150 ℃ for 24 hours. After cooling, washing with deionized water and ethanol for multiple times, and finally vacuum drying at 80 ℃ for 12 h.
Example 2
Preparation of Zn-BTC and Co-BTC:
adding 12mmol of Zn (NO)3)2·6H2O and 8mmol H3BTC is dispersed into 200ml of mixed solution of ethanol and water, 24mmol of NaOH is added after full dissolution, stirring is carried out for 30min, and finally washing is carried out for multiple times by deionized water and ethanol, and vacuum drying is carried out for 12h at 80 ℃.
Example 3
Preparation of Ce-BTC:
adding 10mmol of Ce (NO)3)3·6H2O and 3mmol H3BTC was dissolved in 50ml DMF and then transferred to a reaction kettle to react at 130 ℃ for 24h, after cooling, washed several times with DMF and ethanol and finally dried under vacuum at 80 ℃ for 12 h.
Example 4
Preparation of Bi-BTC:
0.49mmol of Bi (NO)3)3·5H2O and 0.920mmol H3BTC is dispersed into a mixed solution of DMF and MeOH, is stirred uniformly and then is transferred into a reaction kettle to react for 45h at 120 ℃, is washed with DMF and methanol for a plurality of times after being cooled, and is finally dried for 12h under vacuum at 80 ℃.
Example 5
Preparation of Ru/Cu-BTC:
the prepared 400mg of Cu-BTC was dispersed in water, and then a certain amount of RuCl was added3(the mass ratio of Ru to Cu-BTC is 3 percent), stirring for 12 hours, then centrifuging and drying in vacuum to obtain the product Ru/Cu-BTC with enhanced water stability.
The M-BTC (M: Cu, Zn, Co, Ce, Bi) prepared in examples 1-5 and the Ru/Cu-BTC material with enhanced stability were analyzed and tested accordingly, and the test results are shown in FIGS. 1-3. Wherein fig. 1 and 2 are their corresponding X-ray diffraction patterns. As can be seen from the figure, the corresponding material has been successfully prepared, and FIG. 2 further shows that the Ru substitution of part of Cu in Cu-BTC does not change the overall structure, and the main peak is shifted, which can also prove the substitution of Ru for part of Cu in Cu-BTC. FIG. 3 is H after Cu-BTC was present in water for a long period of time (12H)2XRD pattern of O/Cu-BTCIt can be seen that the results are quite different from that of Cu-BTC. FIG. 4 shows Cu-BTC, Ru/Cu-BTC and H2SEM images of O/Cu-BTC further illustrate that substitution of Ru for a portion of Cu in Cu-BTC enhances its stability.
Secondly, measurement of catalytic characteristics
5ml triethanolamine as electronic sacrificial agent, 30mg eosin as photosensitizer, 25ml H were added to the quartz reactor2O as a proton source, and 10mg of each of the catalysts obtained in examples 1 to 5 were added. Introducing N during the stirring process2Degassing the hydrogen-producing photocatalyst in about 30min, introducing the hydrogen-producing photocatalyst into the hydrogen-producing photocatalyst system, and circulating condensed water at 10 deg.c. And vacuumizing the hydrogen production photocatalytic system connected with the quartz reactor. Placing a xenon lamp light source with a filter with a wavelength of 420nm at a position of 5cm above the quartz reactor, sampling once every 30min, passing through a hydrogen production photocatalysis system, entering a gas chromatograph, and detecting the amount of hydrogen. The results are shown in Table 1.
TABLE 1 comparison of hydrogen production for catalysts prepared in examples 1-5
FIG. 5 is a diagram of the photocatalytic hydrogen evolution of M-BTC materials composed of different metals and trimesic acid, and it can be seen that the Cu-BTC material has the best effect. And after the Ru replaces part of Cu, the photocatalytic performance of the material is further improved by 50%. FIG. 6 is a graph of a photocatalytic hydrogen evolution cycle test of Ru/Cu-BTC, which shows better stability.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (3)
1. A preparation method of M-BTC (M: Cu, Zn, Co, Ce, Bi) metal organic framework material is characterized by comprising the following steps:
(1) Cu-BTC: adding Cu (NO)3)3﹒3H2O (0.725g) and H3BTC (0.420g) was dispersed in 12ml of a mixed solution of water and ethanol by sonication, and then transferred to a reaction vessel to react at 150 ℃ for 24 hours. After cooling, washing with deionized water and ethanol for multiple times, and finally vacuum drying at 80 ℃ for 12 h.
(2) Zn-BTC, Co-BTC: adding 12mmol of Zn (NO)3)2·6H2O and 8mmol H3BTC is dispersed into 200ml of mixed solution of ethanol and water, 24mmol of NaOH is added after full dissolution, stirring is carried out for 30min, and finally washing is carried out for multiple times by deionized water and ethanol, and vacuum drying is carried out for 12h at 80 ℃. (3) Ce-BTC: adding 10mmol of Ce (NO)3)3·6H2O and 3mmol H3BTC was dissolved in 50ml DMF and then transferred to a reaction kettle to react at 130 ℃ for 24h, after cooling, washed several times with DMF and ethanol and finally dried under vacuum at 80 ℃ for 12 h.
(4) Bi-BTC: 0.49mmol of Bi (NO)3)3·5H2O and 0.920mmol H3BTC is dispersed into a mixed solution of DMF and MeOH, is stirred uniformly and then is transferred into a reaction kettle to react for 45h at 120 ℃, is washed with DMF and methanol for a plurality of times after being cooled, and is finally dried for 12h under vacuum at 80 ℃.
2. A preparation method of a Cu-BTC metal organic framework material with enhanced water stability is characterized by comprising the following steps:
the prepared 400mg of Cu-BTC was dispersed in water, and then a certain amount of RuCl was added3(the mass ratio of Ru to Cu-BTC is 3 percent), stirring for 12 hours, then centrifuging and drying in vacuum to obtain the product Ru/Cu-BTC with enhanced water stability.
3. Use of the water-stable product Ru/Cu-BTC metal-organic framework material, characterized in that the M-BTC (M: Cu, Zn, Co, Ce, Bi) metal-organic framework material prepared according to any of claims 1-2 and the water-stable Ru/Cu-BTC are used for photocatalytic hydrogen production.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113856763A (en) * | 2021-10-29 | 2021-12-31 | 福州大学 | Biphenyl covalent organic framework copper-loaded material, preparation method thereof and application of copper-loaded material in photocatalytic hydrogen production |
| CN115260513A (en) * | 2022-07-29 | 2022-11-01 | 广东石油化工学院 | Hierarchical porous MOFs material containing CuRu bimetal and preparation method and application thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113856763A (en) * | 2021-10-29 | 2021-12-31 | 福州大学 | Biphenyl covalent organic framework copper-loaded material, preparation method thereof and application of copper-loaded material in photocatalytic hydrogen production |
| CN113856763B (en) * | 2021-10-29 | 2023-02-28 | 福州大学 | Biphenyl covalent organic framework copper-loaded material, preparation method thereof and application of copper-loaded material in photocatalytic hydrogen production |
| CN115260513A (en) * | 2022-07-29 | 2022-11-01 | 广东石油化工学院 | Hierarchical porous MOFs material containing CuRu bimetal and preparation method and application thereof |
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