CN114733574B - Preparation method of Au nanorod-modified PCN-222 (Cu) catalyst - Google Patents
Preparation method of Au nanorod-modified PCN-222 (Cu) catalyst Download PDFInfo
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- 239000013097 PCN-222 Substances 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
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- 238000003756 stirring Methods 0.000 claims description 20
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 17
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims description 7
- 101710134784 Agnoprotein Proteins 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 7
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- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
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- 230000003213 activating effect Effects 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
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- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- 239000001257 hydrogen Substances 0.000 abstract description 19
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- 239000010931 gold Substances 0.000 description 64
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 21
- 235000019253 formic acid Nutrition 0.000 description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
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- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000019254 sodium formate Nutrition 0.000 description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C01—INORGANIC CHEMISTRY
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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Abstract
The invention belongs to the technical field of research of nano catalytic materials, and relates to a preparation method of an Au nanorod modified PCN-222 (Cu) catalyst. The Au/PCN-222 (Cu) composite material is constructed in an in-situ growing manner of the Au nanorods, the agglomeration phenomenon of the Au nanorods in the post-synthesis process is avoided, the dispersity of the Au nanorods is improved, the photocatalytic hydrogen production efficiency is further improved, the plasma resonance Au nanorods have a remarkable photo-thermal effect, and the Au in the composite material generates high-energy thermal electrons in the photocatalytic process to promote the photo-generated electron hole separation and transfer of the PCN-222 (Cu).
Description
Technical Field
The invention belongs to the technical field of research of nano catalytic materials, and relates to a preparation method of an Au nanorod modified PCN-222 (Cu) catalyst.
Background
In recent years, with the excessive consumption of energy, CO in the atmosphere 2 Is becoming one of the key factors causing global climate change. Therefore, people urgently seek a clean and green method to solve the problem of excessive energy consumption, thereby greatly lightening the problem of environmental pollution. Solar energy is the most abundant renewable energy source on earth, and research on efficiently converting solar energy into chemical energy for storage is being pursued. The document Adv Mater,2021,33 (22) mentions that the conversion of solar energy into chemical energy by means of photocatalytic processes is one of the possible solutions to solve the future energy crisis. Hydrogen has been used in various fields as an important clean fuel instead of fossil fuel. However, as reviewed in Fuel Processing Technology 87 (2006) 461-472, conventional methods for producing hydrogen, such as energy supply and synthesis conditions, are often not a green route, resulting in difficulties in achieving "net" carbon dioxide emissions during the production process. A low carbon "green" hydrogen production route would be a key factor in determining future hydrogen energy technologies. Following this concept, it is desirable to store and release H using a green, efficient route 2 . ACS Catalysis,2015,5 (8): 4772-4782, reported that formic acid (FA, HCOOH) is considered as Liquid Organic Hydrogen Carrier (LOHCs) that can release H by selective dehydrogenation 2 . Therefore, hydrogen production by photocatalytic decomposition of formic acid provides possibility for 'green' hydrogen production.
Metal-organic frameworks (MOFs) are porous crystalline materials composed of organic ligands and metal node coordination, have adjustable pore structures and large specific surface areas compared with traditional semiconductor photocatalysts, and have been widely used in the fields of gas adsorption, storage and separation, catalysis, drug delivery, and the like. The literature reports that metal-metalloporphyrin frameworks (MMFs) in MOFs are also widely applied to photocatalytic conversion of various small molecules due to their excellent photoactive properties, as reported in angelw.chem.int.ed.2012, 51, 10307-10310. The documents adv, mater, 2014,26,5274-5309 report that gold nanorods (AuNRs) are a typical surface plasmon resonance material, have an obvious photothermal enhancement effect, and therefore have potential application prospects in photocatalysis of HCOOH dehydrogenation.
Disclosure of Invention
Therefore, the invention designs an in-situ growth strategy, successfully constructs a plasma resonance AuNRs photo-thermal enhanced PCN-222 (Cu) composite material Au/PCN-222 (Cu) (PCN = multiaxial coordination network), and improves the efficiency of decomposing formic acid and dehydrogenating by utilizing a photo-thermal enhanced method so as to realize clean and efficient high-selectivity photocatalytic formic acid hydrogen production. The invention opens up a way for the production and the use of high-efficiency solar energy fuel.
The technical scheme of the invention is as follows:
a preparation method of Au nanorod modified PCN-222 (Cu) catalyst is characterized in that AuNRs are loaded on the surface of the PCN-222 (Cu) to prepare a composite material Au/PCN-222 (Cu), and the preparation method comprises the following steps:
the method comprises the following steps: synthesis of PCN-222 (Cu)
Reacting ZrCl 4 And benzoic acid in N, N-diethylformamide to obtain solution A, in which ZrCl is present 4 And benzoic acid in a molar ratio of 1: 70-1: 80; adding Cu-H 2 TCPP is dissolved in N, N-diethylformamide to obtain solution B, the solution A and the solution B are respectively ultrasonically dissolved for 20min to 30min, and then the solution A and the solution B are mixed to obtain solution C, wherein ZrCl is contained in the solution C 4 With Cu-H 2 The mass ratio of TCPP is 1:1 to 2:1; zrCl 4 The concentration of the C solution is 0.02 mol/L-0.04 mol/L; carrying out ultrasonic treatment on the solution C for 10-20 min, reacting for 12-48 h at the temperature of 120-130 ℃, after the reaction is finished, carrying out centrifugal separation on the product, washing for 3-5 times by using N, N-diethylformamide respectively,washing with ethanol for 3-5 times, and drying under vacuum condition for 10-12 h.
Step two: PCN-222 (Cu) activation treatment
Heating the PCN-222 (Cu) obtained in the step one for 4-12 h at the temperature of 200-250 ℃, removing the volatile solvent, and activating the material.
Step three: in-situ growth synthesis of Au nanorod-loaded PCN-222 (Cu)
Under vigorous stirring, naBH 4 Ice water solution (Ice Water bath treatment) was added to HAuCl 4 In aqueous solution, wherein NaBH 4 With HAuCl 4 The molar ratio is 1:4 to 1:5, changing the solution from yellow to brown, and continuously stirring for 10-20 min to obtain a solution containing Au nano seed crystals;
dispersing the PCN-222 (Cu) obtained in the step two into a hexadecyl trimethyl ammonium bromide aqueous solution under an ultrasonic condition, wherein after dispersion, the concentration of the PCN-222 (Cu) is 2 mg/mL-4 mg/mL; and then adding a solution containing Au nano-crystal seeds under an ultrasonic condition, wherein the mass ratio of the Au nano-crystal seeds to PCN-222 (Cu) is kept to be 1:20 to 3:20; continuing to perform ultrasonic treatment for 5-10 min, keeping the solution in a static state, and standing for 30-60 min to obtain a PCN-222 (Cu) solution loaded with Au nano crystal seeds;
mixing CTAB aqueous solution and AgNO 3 Aqueous solution, HAuCl 4 Mixing the aqueous solution and the ascorbic acid aqueous solution, and violently stirring for 30-60 s to obtain a solution D, wherein CTAB and HAuCl 4 The molar ratio is 700:1 to 500:1,AgNO 3 With HAuCl 4 In a molar ratio of 1:10 to 3:10, ascorbic acid with HAuCl 4 The molar ratio is 1:1.1 to 1:1.2; adding a solution containing Au nano-seed supported PCN-222 (Cu) to the solution D to mix, wherein HAuCl is maintained 4 The mass ratio of the copper powder to PCN-222 (Cu) is 2:5 to 4:5, stirring for 30-60 s, storing in dark place, and standing overnight at 28-30 ℃; and centrifuging the obtained composite material, washing the composite material for 3 to 5 times by using deionized water, and drying the composite material for 10 to 12 hours under a vacuum condition to obtain the PCN-222 (Cu) loaded by the Au nanorod.
The invention has the beneficial effects that: the Au/PCN-222 (Cu) composite material is constructed in an in-situ growing Au nanorod mode, the agglomeration phenomenon of the Au nanorod in the post-synthesis process is avoided, the dispersity of the Au nanorod is improved, the photocatalytic hydrogen production efficiency is further improved, the plasma resonance Au nanorod has a remarkable photo-thermal effect, and the Au in the composite material generates high-energy thermal electrons in the photocatalytic process to promote the photo-generated electron hole separation and transfer of the PCN-222 (Cu).
Drawings
FIG. 1 is a schematic diagram of the synthetic route of the preparation method of the Au nanorod-modified PCN-222 (Cu) catalyst.
FIG. 2 shows XRD patterns of templates PCN-222, PCN-222 (Cu), au/PCN-222 (Cu).
FIG. 3 is SEM images of different resolutions, wherein a and b are PCN-222 (Cu) SEM images of different resolutions, and c and d are Au/PCN-222 (Cu) -1SEM images of example 1 of different resolutions.
FIG. 4 is SEM images of different resolutions, wherein a and b are Au/PCN-222 (Cu) -2SEM images of example 2 of different resolutions, and c and d are Au/PCN-222 (Cu) -3SEM images of example 3 of different resolutions.
FIG. 5 is a graph showing the hydrogen evolution rates of different catalytic systems, i.e., PCN-222 (Cu), au/PCN-222 (Cu) -1, au/PCN-222 (Cu) -2, and Au/PCN-222 (Cu) -3, for decomposing formic acid by photocatalysis.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
0.3mmol of ZrCl 4 0.026mol of benzoic acid was dissolved in 7.5mLN, N-diethylformamide and identified as solution A; then 70mgCu-H 2 Dissolving TCPP in 7.5ml DEF, marking as solution B, performing ultrasonic dissolution on A and B for 20min respectively to obtain solution C, performing ultrasonic dissolution on the solution C for 20min, putting the solution C into a hydrothermal kettle with a polytetrafluoroethylene lining, heating to 120 ℃ for reaction for 12h, after the reaction is finished, performing centrifugal separation on the product, washing with DEF for 3 times and ethanol for 3 times respectively, and drying at 75 ℃ for 10h under a vacuum condition.
Passing the obtained PCN-222 (Cu) through a tube furnace in N 2 Heating at 200 deg.C for 4h, removing volatile solvent, and activating the material.
The XRD pattern of FIG. 2 shows that the diffraction peak positions of the experimentally obtained PCN-222 (Cu) and the simulated PCN-222 are consistent, indicating the successful synthesis of the powder PCN-222 (Cu). The successful synthesis of rod-like PCN-222 (Cu) can be seen by SEM images of a and b in FIG. 3.
Au/PCN-222 (Cu) -1 is synthesized by adopting a method of growing Au NRs in situ. 10mg of PCN-222 (Cu) was ultrasonically dispersed in 5mL of cetyltrimethylammonium bromide (concentration: 0.1 mmol. Multidot.L) -1 ) In aqueous solution. Under vigorous stirring, 0.3125mL of NaBH 4 Ice-water solution (Ice-water bath treatment) (concentration 10 mmol. Multidot.L) -1 ) Add to 5mL of HAuCl 4 (concentration: 0.25 mmol. Multidot.L -1 ) And hexadecyltrimethylammonium bromide (concentration 0.1 mmol. L) -1 ) And (2) in the mixed aqueous solution, changing the solution from yellow to brown, continuously stirring for 10min, standing for 15min to obtain Au nano seed crystals, adding 96 mu L of seed crystal solution into hexadecyl trimethyl ammonium bromide solution for dispersing PCN-222 (Cu) in the ultrasonic process, performing ultrasonic treatment for 5min, standing for 30min, and keeping the temperature at 30 ℃ in the standing process. 10mL of cetyltrimethylammonium bromide (concentration 0.1 mmol. Multidot.L) was added into the round-bottomed flask -1 ) Aqueous solution, 0.2mL AgNO 3 (concentration 10 mmol. Multidot.L) -1 ) Aqueous solution, 2mL HAuCl was added 4 Aqueous solution (concentration 10 mmol. L) -1 ) 0.23mL of an aqueous ascorbic acid solution (concentration: 100 mmol. Multidot.L) was added -1 ) And stirring for 30s, finally adding the mixed solution of the Au seed crystal-loaded PCN-222 (Cu), stirring for 30s, storing at 28 ℃ in a dark place, standing overnight, washing with water for 3-5 times, and drying under a vacuum condition for 10h to obtain Au/PCN-222 (Cu) -1.
The XRD of the composite Au/PCN-222 (Cu) -1 of FIG. 2 clearly shows the corresponding PCN-222 (Cu) and Au diffraction peaks, indicating that the Au/PCN-222 (Cu) -1 composite structure is successfully synthesized. The position and intensity of the diffraction peaks in the composite did not change relative to the individual components, revealing that the components retained the crystalline structure that would be intact. According to the c and d SEM images in FIG. 3, au NRs are uniformly supported on the surface of PCN-222 (Cu), and the rod-like crystal structure of PCN-222 (Cu) is still maintained.
The Au nanorod modified PCN-222 (Cu) catalyst is used as a photocatalyst, and is applied to dehydrogenation by photocatalytic decomposition of formic acid: 5mg of photocatalystThe reagent powder was dispersed in 5mL of HCOOH (concentration 1 mol. L) -1 ) And HCOONa (concentration of 1 mol. L) -1 ) The mixed aqueous solution is dispersed by ultrasonic for 10min, the catalytic system is placed in a quartz catalyst, and Ar gas is introduced for 20min. Under continuous magnetic stirring at room temperature, using a 300W xenon lamp (. Lamda.)>400nm，100mW·cm -2 ) Visible light irradiates a photocatalytic reaction for 4 hours. The gas product is detected by gas chromatography (GC 7900), figure 5 is a photo-catalytic hydrogen evolution yield chart of Au/PCN-222 (Cu) -1, and the hydrogen production rate is 1.38 mmol-g from figure 5 -1 ·h -1 。
Example 2
0.3mmol of ZrCl 4 0.023mmol of benzoic acid is dissolved in 4mLN of N-diethylformamide and is marked as solution A; then 50mgCu-H 2 TCPP, dissolved in 4mLN, N-diethylformamide, was designated as solution B. Respectively ultrasonically dissolving the solution A and the solution B for 25min to obtain a solution C, ultrasonically dissolving the solution C for 25min, mixing, putting the solution C into a hydrothermal kettle with a polytetrafluoroethylene lining, heating to 125 ℃ for reacting for 24h, after the reaction is finished, centrifugally separating a product, respectively washing with DEF for 3 times and ethanol for 3 times, and keeping the temperature of 80 ℃ under a vacuum condition for drying for 11h.
Passing the obtained PCN-222 (Cu) through a tube furnace in N 2 Heating at 230 deg.C for 6h to remove volatile solvent, and activating the material.
Au/PCN-222 (Cu) -2 is synthesized by adopting a method of growing Au NRs in situ. Dispersing 15mg PCN-222 (Cu) in 5mL hexadecyl trimethyl ammonium bromide (concentration 0.1 mmol. L) by ultrasonic -1 ) In aqueous solution. Under vigorous stirring, 0.3mL of NaBH 4 Ice water solution (ice water bath treatment) (concentration 10 mmol. Multidot.L) -1 ) Added to 5mL of HAuCl 4 (concentration: 0.25 mmol. Multidot.L -1 ) And hexadecyltrimethylammonium bromide (concentration 0.1 mmol. Multidot.L) -1 ) And (2) in the mixed aqueous solution, changing the solution from yellow to brown, continuously stirring for 15min, standing for 30min to obtain Au nano seed crystals, taking 144 mu L of the seed crystals, adding the seed crystals into a hexadecyl trimethyl ammonium bromide solution for dispersing PCN-222 (Cu) in an ultrasonic process, performing ultrasonic treatment for 6min, standing for 45min, and keeping the temperature at 29 ℃ in the standing process. Into a round-bottomed flask was added 14mL of cetyltrimethylammonium bromide (concentration 0.1 mmol. L.) -1 ) Aqueous solution and 0.4mL AgNO 3 (concentration 10 mmol. Multidot.L) -1 ) Aqueous solution, 2mL HAuCl was added 4 Aqueous solution (concentration 10 mmol. Multidot.L) -1 ) 0.22mL of an aqueous ascorbic acid solution (concentration: 100 mmol. Multidot.L) was added thereto -1 ) Vigorously stirring for 45s, finally adding the Au seed crystal-loaded PCN-222 (Cu) mixed solution, stirring for 45s, storing at 29 ℃ in dark place, standing overnight, washing with water for 3-5 times, and drying under vacuum condition for 11h to obtain Au/PCN-222 (Cu) -2.
The a and b Au/PCN-222 (Cu) -2SEM images in FIG. 4 show that Au NRs are uniformly loaded on the surface of PCN-222 (Cu) and the PCN-222 (Cu) still retains the rod-like crystal structure, and the surface of the composite Au/PCN-222 (Cu) -2 in FIG. 4 is loaded with more Au NRs than the Au/PCN-222 (Cu) -1 of example 1, which is caused by the variation of the amount of Au seed added during the synthesis of the composite.
The Au nanorod modified PCN-222 (Cu) catalyst is used as a photocatalyst, and is applied to dehydrogenation by photocatalytic decomposition of formic acid: 5mg of Au/PCN-222 (Cu) catalyst was dispersed in 5mL of HCOOH (concentration 1 mol. L) -1 ) And HCOONa (concentration of 1 mol. L) -1 ) The mixed aqueous solution is dispersed by ultrasonic for 10min, the catalytic system is placed in a quartz catalyst, and Ar gas is introduced for 20min. Under continuous magnetic stirring at room temperature, using 300W xenon lamp (. Lamda.)>400nm，100mW·cm -2 ) The visible light irradiates a photocatalytic reaction, the reaction lasts for 4h, and the gas product is detected by gas chromatography (GC 7900). FIG. 5 is a graph showing the photocatalytic hydrogen evolution yield of Au/PCN-222 (Cu) -2, in which the photocatalytic hydrogen production rate is the highest because Au NRs are uniformly dispersed and the supported amount is larger than that of Au/PCN-222 (Cu) -1, and the hydrogen production rate is 2.33 mmol/g as can be seen from FIG. 5 -1 ·h -1 。
Example 3
0.3mmol of ZrCl 4 0.024mmol of benzoic acid in 3.75mLN, N-diethylformamide as solution A; then 35mgCu-H 2 TCPP, dissolved in 3.75mLN, N-diethylformamide, was identified as solution B. Respectively ultrasonically dissolving the solution A and the solution B for 30min to obtain a solution C, ultrasonically dissolving the solution C for 30min, mixing, putting into a hydrothermal kettle with a polytetrafluoroethylene lining, heating to 130 ℃ for reacting for 48h, after the reaction is finished, centrifugally separating the product, and washing with N, N-diethylformamide respectivelyWashing with ethanol for 3 times, and vacuum drying at 80 deg.C for 12 hr.
Passing the obtained PCN-222 (Cu) through a tube furnace in N 2 Heating for 12h at 250 ℃, removing the volatile solvent, and activating the material.
Au/PCN-222 (Cu) -3 is synthesized by adopting a method of growing Au NRs in situ. Ultrasonic dispersing 20mg PCN-222 (Cu) in 5mL hexadecyltrimethylammonium bromide (with the concentration of 0.1 mmol. L) -1 ) In aqueous solution. Under vigorous stirring, 0.25mL of NaBH 4 Ice-water solution (Ice-water bath treatment) (concentration 10 mmol. Multidot.L) -1 ) Added to 5mL of HAuCl 4 (concentration: 0.25 mmol. Multidot.L) -1 ) And hexadecyltrimethylammonium bromide (concentration 0.1 mmol. Multidot.L) -1 ) Changing the solution from yellow to brown in the mixed aqueous solution, continuously stirring for 20min, standing for 60min to obtain Au nano seed crystals, adding 192 mu L of the seed crystals into a hexadecyl trimethyl ammonium bromide solution dispersing PCN-222 (Cu) in an ultrasonic process, performing ultrasonic treatment for 10min, standing for 60min, and keeping the temperature at 30 ℃ in the standing process. Into a round-bottomed flask was added 12mL of cetyltrimethylammonium bromide (concentration: 0.1 mmol. Multidot.L) -1 ) Aqueous solution and 0.6mL AgNO 3 (concentration 10 mmol. Multidot.L) -1 ) Aqueous solution, 2mL HAuCl was added 4 Aqueous solution (concentration 10 mmol. Multidot.L) -1 ) 0.24mL of an aqueous ascorbic acid solution (concentration: 100 mmol. Multidot.L) was added -1 ) Vigorously stirring for 60s, adding the mixed solution of PCN-222 (Cu) loaded with Au seed crystal, stirring for 60s, storing at 30 deg.C in dark place, standing overnight, washing with water for 3-5 times, and drying under vacuum for 12h.
C and d in FIG. 4 are Au/PCN-222 (Cu) -3SEM images showing that Au NRs are concentrated on the surface of PCN-222 (Cu), because the Au NRs are agglomerated with the increase of the amount of Au seeds in example 3 and are not well dispersed on the surface of PCN-222 (Cu), so that the control of the dispersion degree of the seeds is important in the synthesis of Au/PCN-222 (Cu).
The Au nanorod modified PCN-222 (Cu) catalyst is used as a photocatalyst, and is applied to dehydrogenation by photocatalytic decomposition of formic acid: 5mg of Au/PCN-222 (Cu) catalyst was dispersed in 5mL of HCOOH (concentration 1 mol. L) -1 ) And HCOONa (concentration 1 mol. L) -1 ) Mixed aqueous solution ofAnd (3) performing ultrasonic dispersion for 10min, placing the catalytic system in a quartz catalyst, and introducing Ar gas for 20min. Under continuous magnetic stirring at room temperature, using a 300W xenon lamp (. Lamda.)>400nm，100mW·cm -2 ) The visible light irradiates a photocatalytic reaction, the reaction lasts for 4h, and the gas product is detected by gas chromatography (GC 7900). FIG. 5 is a graph showing the photocatalytic hydrogen evolution yield of Au/PCN-222 (Cu) -3, and the SEM analysis of FIG. 4 shows that Au NRs are agglomerated on the surface of PCN-222 (Cu) and therefore have a low photocatalytic hydrogen production rate, and FIG. 5 shows that the hydrogen production rate is 0.87 mmol-g -1 ·h -1 . From FIG. 5, it can be seen that in the Au/PCN-222 (Cu) -2 catalytic system, H 2 The highest precipitation rate. In contrast, PCN-222 (Cu) and Au NRs, alone, exhibited lower photocatalytic activity. Therefore, au NRs in the composite material can improve the photocatalytic capability of PCN-222 (Cu).
Claims (1)
1. A preparation method of an Au nanorod modified PCN-222 (Cu) catalyst is characterized by comprising the following steps:
the method comprises the following steps: synthesis of PCN-222 (Cu)
Reacting ZrCl 4 And benzoic acid in N, N-diethylformamide to obtain solution A, in which ZrCl is present 4 And benzoic acid in a molar ratio of 1:70 to 1:80; adding Cu-H 2 TCPP is dissolved in N, N-diethylformamide to obtain a solution B, the solution A and the solution B are respectively ultrasonically dissolved for 2 to 30min, and then the solution A and the solution B are mixed to obtain a solution C, wherein ZrCl is contained in the solution C 4 With Cu-H 2 The mass ratio of TCPP is 1:1 to 2:1; zrCl 4 The concentration of the C solution is 0.02-0.04 mol/L; performing ultrasonic treatment on the solution C for 10min to 2 min, putting the solution C into a hydrothermal kettle with a polytetrafluoroethylene lining, heating the solution C at the temperature of 120-130 ℃ for reaction for 12h to 48h, after the reaction is finished, performing centrifugal separation on a product, washing the product with N, N-diethylformamide for 3-5 times, washing the product with ethanol for 3-5 times, and drying the product under a vacuum condition for 1h to 12h;
step two: PCN-222 (Cu) activation treatment
Heating the PCN-222 (Cu) obtained in the first step at 200-250 ℃ for 4-12h, removing a volatile solvent, and activating the material;
step three: in-situ growth synthesis of Au nanorod-loaded PCN-222 (Cu)
Under vigorous stirring, naBH 4 Ice-water solution to HAuCl 4 In aqueous solution, in which NaBH is present 4 With HAuCl 4 The molar ratio is 1:4 to 1:5, changing the yellow color of the solution into brown color, and continuously stirring for 10min to 2 min to obtain a solution containing the Au nano seed crystal;
dispersing the PCN-222 (Cu) obtained in the step two into a hexadecyl trimethyl ammonium bromide aqueous solution under an ultrasonic condition, wherein after dispersion, the concentration of the PCN-222 (Cu) is 2 mg/mL-4 mg/mL; and then adding a solution containing Au nano seed crystals under an ultrasonic condition, wherein the mass ratio of the Au nano seed crystals to the PCN-222 (Cu) is kept to be 1:20 to 3:20; continuing ultrasonic treatment for 5min to 10min, keeping the solution static, and standing for 30min to 60min to obtain a PCN-222 (Cu) solution loaded with Au nano seed crystals;
mixing CTAB aqueous solution and AgNO 3 Aqueous solution, HAuCl 4 Mixing the aqueous solution and the ascorbic acid aqueous solution, and stirring vigorously for 30s to 60s to obtain a solution D, wherein CTAB and HAuCl are added 4 The molar ratio is 700:1 to 500:1,AgNO 3 With HAuCl 4 In a molar ratio of 1:10 to 3:10, ascorbic acid with HAuCl 4 The molar ratio is 1:1.1 to 1:1.2; adding a solution containing Au nano-seed supported PCN-222 (Cu) to the solution D to mix, wherein HAuCl is maintained 4 The mass ratio of the copper powder to PCN-222 (Cu) is 2:5 to 4:5, stirring for 30s to 60s, storing in a dark place, and standing overnight at the temperature of 28-30 ℃; and centrifuging the obtained composite material, washing the composite material with deionized water for 3 to 5 times, and drying the composite material for 10h to 12h under a vacuum condition to obtain the Au nanorod-loaded PCN-222 (Cu).
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