CN108654647B - Preparation method of gold nanoparticle/molybdenum disulfide compound and application of gold nanoparticle/molybdenum disulfide compound as hydrogen evolution reaction catalyst - Google Patents
Preparation method of gold nanoparticle/molybdenum disulfide compound and application of gold nanoparticle/molybdenum disulfide compound as hydrogen evolution reaction catalyst Download PDFInfo
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- 239000010931 gold Substances 0.000 title claims abstract description 66
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 64
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 50
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 50
- -1 molybdenum disulfide compound Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- 239000007809 chemical reaction catalyst Substances 0.000 title abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 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 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229920000587 hyperbranched polymer Polymers 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- DJZHBCSMUWDWQC-UHFFFAOYSA-N 3-azido-2,2-bis(azidomethyl)propan-1-ol Chemical compound [N-]=[N+]=NCC(CO)(CN=[N+]=[N-])CN=[N+]=[N-] DJZHBCSMUWDWQC-UHFFFAOYSA-N 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 238000010898 silica gel chromatography Methods 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 238000013375 chromatographic separation Methods 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 229910052961 molybdenite Inorganic materials 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 description 5
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- WHVWKYKHOGPDQQ-UHFFFAOYSA-N 3-azido-2-(azidomethyl)-2-methylpropan-1-ol Chemical compound [N-]=[N+]=NCC(CO)(C)CN=[N+]=[N-] WHVWKYKHOGPDQQ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229920013746 hydrophilic polyethylene oxide Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a preparation method of a gold nanoparticle/molybdenum disulfide compound and application of the gold nanoparticle/molybdenum disulfide compound as a hydrogen evolution reaction catalyst, wherein gold nanoparticles take thiazole ring star polymers as ligands, and gold nanoparticles with a certain proportion are loaded on MoS2After the last step, the electron microscope atlas shows that the gold nanoparticles are uniformly loaded on the MoS2Surface and exhibits an advantage over MoS2Electrocatalytic performance of. The gold nanoparticle/molybdenum disulfide compound can be used as a catalyst for catalytic hydrogen evolution reaction, can exist stably and be used repeatedly, and the catalytic effect is not influenced by repeated use; catalyst and pure MoS of the invention2Compared with the prior art, the catalyst has higher catalytic activity.
Description
Technical Field
The invention relates to a preparation method of a gold nanoparticle/molybdenum disulfide compound and application of the gold nanoparticle/molybdenum disulfide compound as a hydrogen evolution reaction catalyst.
Background
Hydrogen is considered as an important source of the next generation of clean and renewable energy due to its high energy density and environmental friendliness. Hydrogen production by electrolysis of water is currently the most efficient and continuous method of producing hydrogen. Common hydrogen evolution catalysts are Pt, Pd, Rh, and the like. The rarity and high cost of these noble metals limits their practical application in hydrogen evolution reactions. The search for new catalyst alternatives is imminent. Theoretical and experimental results reveal that the two-dimensional layered molybdenum disulfide can be called as a potential hydrogen evolution catalyst due to its edge unsaturated sulfur atom pair H2Due to the ideal adsorption. However, the unmodified molybdenum disulfide has poor electron transport performance, so that high overvoltage needs to be overcome in the hydrogen evolution reaction to obtain equivalent electrocatalytic performance.
In recent years, some researches have reported that molybdenum disulfide is modified from the following three aspects, so that the electrocatalytic performance of the molybdenum disulfide is improved. 1. Increasing its active site (J.Am.chem.Soc.2013,135, 17881); 2. enhancing its intrinsic activity (j.am. chem. soc.2013,135, 10274); 3. facilitate electron transport rates (j.am. chem. soc.2011,133, 7296).
Recently, studies have been reported that the hybridization of molybdenum disulfide with metals or carbon can improve its electrocatalytic properties. Yi Shi et al suggest that hot electrons generated by the plasmon resonance effect of these metal nanostructures can be injected from the inside of the metal nanoparticles into the molybdenum disulfide layered structure by overcoming the lower Schottky barrier, thereby suppressing MoS2The recombination of electron-hole in the structure improves the electrocatalytic performance. There are problems that the supported gold nanoparticles aggregate to cause a decrease in catalytic efficiency (j.am. chem. soc.2015,137, 7365).
Disclosure of Invention
The invention aims to provide a preparation method of a gold nanoparticle/molybdenum disulfide compound and application of the gold nanoparticle/molybdenum disulfide compound as a hydrogen evolution reaction catalyst. The hydrogen evolution reaction result shows that the novel catalyst has better catalytic performance than pure molybdenum disulfide, and is particularly reflected in lower overpotential and Tafel slope.
The gold nanoparticle/molybdenum disulfide compound of the invention is characterized in that the gold nanoparticle is hyperbranched poly (thiazole) ring polymer (HS- (AB)3)150@PEO17) As a ligand, gold nanoparticles are stabilized in the inner core of the star-shaped polymer of the polythiazole ring.
The preparation method of the gold nanoparticle/molybdenum disulfide compound comprises the following steps:
step 1: preparation of thiazole ring star polymer ligand
1a, thiazole ring AB3Preparation of monomers
3-azido 2, 2-bis (azidomethyl) propan-1-ol (8.0g, 37.9mmol), 4-pentanoic acid (3.9g, 39.8mmol), 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC. HCL) (14.7g, 75.8mmol), 4-dimethylaminopyridine (DMAP, 1.6g, 13.3mmol) and 100mL of anhydrous dichloromethane are sequentially added into a 250mL round-bottomed flask, the reaction is stirred at room temperature for 8-12h, after the reaction is finished, water (2 × 100mL) and saturated saline (100mL) are sequentially washed, anhydrous magnesium sulfate is dried, the solvent is rotationally evaporated, and the crude product is separated by silica gel chromatography (the eluent is n-hexane and ether in a volume ratio of 1: 1) to obtain colorless thiazole ring AB3Monomer (10.5g, 90% yield).
1b hyperbranched Polymer HB- (AB)3Preparation of (e) -150)
To a 25mL reaction flask were added copper sulfate pentahydrate (50.0mg,0.2mmol), 3-azido 2, 2-bis (azidomethyl) propan-1-ol (10.2mg,0.02mmol), thiazole ring AB in that order3Monomer (0.873g,3.0mmol) and 6mL DMF solvent, freezing, vacuumizing and introducing nitrogen for three times, immediately adding ascorbic acid (52.8mg,0.6mmol) into the reaction system, reacting for 50 minutes at 45 ℃ under vacuum condition, stopping the reaction, adding N, N, N' -pentamethyldiethylenetriamine into the reaction system to extract catalyst copper salt in the system, passing the crude reaction product through an aluminum oxide column, and precipitating in methanol to obtain colorless hyperbranched polymer HB- (AB) HB3150) (yield about 70%).
1c, thiazole Ring Star Polymer HS- (AB)3-150)@PEO17Preparation of
The hyperbranched polymer HB- (AB) is added into a 10mL reaction bottle in sequence3-150)(0.2g，1.37mmol of-N3) Alkynyl polyethylene oxide ay-EO17(1.0g, 2.1mmol), copper sulfate pentahydrate (5mg, 0.02mmol) and 5mL of DMF, freezing the reaction system, vacuumizing, introducing nitrogen repeatedly for three times, immediately adding ascorbic acid (17.6mg, 0.1mmol) into the reaction system, reacting for 4 hours at 45 ℃ under vacuum, stopping the reaction, adding N, N, N' -pentamethyldiethylenetriamine into the system to extract catalyst copper salt in the system, passing the crude reaction product through an aluminum oxide column, and precipitating in diethyl ether to obtain colorless thiazolocystane polymer HS- (AB)3-150)@PEO17(yield about 80%).
Step 2: preparation of gold nano-complex
Adding 25mg of thiazole ring star polymer into 50 mu L of chloroauric acid aqueous solution with the concentration of 50mM, stirring and reacting for 30min at room temperature, then cooling the reaction system to 0 ℃, adding 1ml of aqueous solution containing 5mg of sodium borohydride while stirring, and reacting for 4 h at 0 ℃ to obtain a gold nano complex;
the thiazole ring star polymer core contains a large amount of N atoms and can be mixed with chloroauric acid Au3+Coordinated in NaBH4With a reducing agent asWith the method, the gold nanoparticles wrapped by the polymer can be obtained. On one hand, the gold nanoparticle has the function of stabilizing the gold nanoparticles and preventing the aggregation phenomenon; on the other hand, due to the steric hindrance of the polymer, the formed gold nanoparticles still have active points and can be used for catalytic reaction.
And step 3: preparation of gold nanoparticle/molybdenum disulfide compound
Weighing 10-20mg of molybdenum disulfide, and uniformly dispersing in isopropanol by ultrasonic; weighing 1mg of gold nano complex to prepare a gold nano complex aqueous solution; mixing the isopropanol solution of molybdenum disulfide and the gold nano complex aqueous solution, stirring for 1 hour at room temperature, centrifugally collecting precipitates, and drying to obtain the target product.
Loading gold nanoparticles with a certain proportion on MoS2After the last step, the electron microscope atlas shows that the gold nanoparticles are uniformly loaded on the MoS2Surface and exhibits an advantage over MoS2Electrocatalytic performance of.
The gold nanoparticle/molybdenum disulfide compound is used as a catalyst for catalyzing hydrogen evolution, and comprises the following steps:
1. weighing 4mg of gold nanoparticle/molybdenum disulfide compound and 10 mu L of Nafion solution (the mass concentration is 5%) to be dispersed in 1mL of ethanol, and obtaining a dispersion solution after uniform ultrasonic dispersion; uniformly coating 10 mu L of dispersion liquid on a glassy carbon electrode, and drying at room temperature to obtain a catalyst-loaded glassy carbon electrode;
2. a three-electrode system was used, and the electrochemical workstation used was CH 660D. And (2) taking a 0.5mol/L dilute sulfuric acid solution as an electrolyte solution, taking the catalyst-loaded glassy carbon electrode obtained in the step (1) as a working electrode, taking a Pt sheet as a counter electrode, and taking Ag/AgCl as a reference electrode, and carrying out catalytic hydrogen evolution. All electrodes were calibrated to reversible hydrogen electrodes.
Compared with the prior art, the invention has the following advantages:
1. the catalyst of the invention can exist stably and be used repeatedly, and the repeated use has no influence on the catalytic effect.
2. Catalyst and pure MoS of the invention2Compared with the prior art, the catalyst has higher catalytic activity.
Drawings
FIG. 1 is a hyperbranched polymeric core HB- (AB)3-150) and star polymer HS- (AB)3-150)@PEO17The SEC profile (a) and DLS profile (b) of (a). As can be seen from FIG. 1, the hyperbranched polymer core HB- (AB)3-150) and star polymer HS- (AB)3-150)@PEO17Has narrow molecular weight distribution and size distribution, and has hyperbranched polymer nucleus HB- (AB)3-150) and star polymer HS- (AB)3-150)@PEO17Apparent molecular weights of 23.5 × 10 respectively3g/mol and 52.6 × 103g/mol, dynamic light scattering test results show that the average sizes of the polymer particles in the THF solution are 4.9nm and 10.1nm, respectively.
FIG. 2 is an electron microscope atlas of gold nanoparticles with thiazole ring star polymer as ligand. As can be seen from FIG. 2, the gold nanoparticles have a uniform size distribution and an average particle diameter of 5.44. + -. 1.48 nm.
FIG. 3 is a distribution diagram of the particle size of gold nanoparticles with thiazole ring star polymers as ligands. As can be seen from FIG. 3, the gold nanoparticles have a uniform size distribution and an average particle diameter of 5.44. + -. 1.48 nm.
FIG. 4 is a graph of gold nanoparticles loaded on MoS2The electron microscope map (a) above and the electrochemical performance tests (b), (c) and (d) of the composite. As can be seen from FIG. 4a, gold nanoparticles are uniformly loaded on MoS2No agglomeration occurs. As can be seen from the graphs (b), (c) and (d), gold nanoparticles are supported on MoS2Top and back of the shoe is pure MoS2In contrast, it showed higher catalytic activity. The specific characteristics are that the initial potential is low (289mV), the tafel slope is low (68mV/dec), and the exchange current density is high (50.60 mA/cm)2) The electric double layer capacitance is large (5.21 mF).
Detailed Description
The invention is further described below with reference to the following examples:
the preparation method of the gold nanoparticle/molybdenum disulfide composite in this example is as follows:
1. thiazole ring AB3Preparation of monomers
A250 mL round bottom flask was charged with 3-stacks in sequenceN-based 2, 2-bis (azidomethyl) propan-1-ol (8.0g, 37.9mmol), 4-pentanoic acid (3.9g, 39.8mmol), 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride (EDC. HCL) (14.7g, 75.8mmol), 4-dimethylaminopyridine (DMAP, 1.6g, 13.3mmol) and anhydrous dichloromethane (100mL) are stirred and reacted for 8-12h at room temperature, after the reaction is finished, the reaction product is washed by water (2 × 100mL) and saturated saline (100mL) in sequence, dried by anhydrous magnesium sulfate, the solvent is evaporated in a rotary manner, and the crude product is separated by silica gel chromatography (the eluent is n-hexane and ether, the volume ratio is 1: 1) to obtain colorless thiazole ring AB3Monomer 10.5g, 90% yield.
500MHz1H NMR Spectrum (, CDCl)3Solvent) 4.04ppm (s,2H, OCH)2C(CH2N3)3),3.39ppm(s,6H,OCH2C(CH2N3)3),2.60ppm(m,2H,OCH2CH2),2.53ppm(m,2H,OCH2CH2),and 2.01ppm(m,1H,CHCH2CH2).
2. Hyperbranched Polymer HB- (AB)3Preparation of (e) -150)
To a 25mL reaction flask were added copper sulfate pentahydrate (50.0mg,0.2mmol), 3-azido 2, 2-bis (azidomethyl) propan-1-ol (10.2mg,0.02mmol), thiazole ring AB in that order3Monomer (0.873g,3.0mmol) and 6mL DMF solvent, freezing, vacuumizing and introducing nitrogen for three times, immediately adding ascorbic acid (52.8mg,0.6mmol) into the reaction system, reacting for 50 minutes at 45 ℃ under vacuum condition, stopping the reaction, adding N, N, N' -pentamethyldiethylenetriamine into the reaction system to extract catalyst copper salt in the system, passing the crude reaction product through an aluminum oxide column, and precipitating in methanol to obtain colorless hyperbranched polymer HB- (AB) HB3150) in a yield of 70%.
3. Thiazole ring star polymer HS- (AB)3-150)@PEO17Preparation of
The hyperbranched polymer HB- (AB) is added into a 10mL reaction bottle in sequence3)150(0.2g，1.37mmol of-N3) Alkynyl polyethylene oxide ay-EO17(1.0g, 2.1mmol), copper sulfate pentahydrate (5mg, 0.02mmol) and 5mL DMF, the reaction was frozen-evacuating and introducing nitrogen repeatedly three times, immediately adding ascorbic acid (17.6mg, 0.1mmol) into the reaction system, reacting at 45 ℃ for 4 hours under vacuum, stopping the reaction, adding N, N, N' -pentamethyldiethylenetriamine into the system to extract catalyst copper salt in the system, passing the crude reaction product through an aluminum oxide column, and precipitating in diethyl ether to obtain colorless thiazolylostellate polymer HS- (AB)3-150)@PEO17The yield was 80%.
Thiazole Ring Polymer HS- (AB) synthesized in this example3-150)@PEO17Is a water-soluble core-shell structure, and the core is a hydrophobic hyperbranched polymer HB- (AB) containing thiazole rings3150), and the Dynamic Light Scattering (DLS) test result shows that the size of the inner core is about 5nm, the shell is hydrophilic polyethylene oxide (PEO), and the size of the formed core-shell polymer is 10 nm.
4. Preparation of gold nano-complex
Adding 25mg of thiazole ring star polymer into 50 mu L of chloroauric acid aqueous solution with the concentration of 50mM, stirring and reacting for 30min at room temperature, then cooling the reaction system to 0 ℃, adding 1ml of aqueous solution containing 5mg of sodium borohydride while stirring, and reacting for 4 h at 0 ℃ to obtain a gold nano complex;
the thiazole ring star polymer core contains a large amount of N atoms and can be mixed with chloroauric acid Au3+Coordinated in NaBH4Under the action of a reducing agent, the gold nanoparticles wrapped by the polymer can be obtained. On one hand, the gold nanoparticle has the function of stabilizing the gold nanoparticles and preventing the aggregation phenomenon; on the other hand, due to the steric hindrance of the polymer, the formed gold nanoparticles still have active points and can be used for catalytic reaction.
5. Preparation of gold nanoparticle/molybdenum disulfide compound
Weighing 10-20mg of molybdenum disulfide, and uniformly dispersing in isopropanol by ultrasonic; weighing 1mg of gold nano complex to prepare a gold nano complex aqueous solution; mixing the isopropanol solution of molybdenum disulfide and the gold nano complex aqueous solution, stirring for 1 hour at room temperature, centrifugally collecting precipitates, and drying to obtain the target product.
Loading gold nanoparticles with a certain proportion on MoS2After the last step, the electron microscope atlas shows that the gold nanoparticles are uniformly loaded on the MoS2Surface and exhibits an advantage over MoS2Electrocatalytic performance of.
The gold nanoparticle/molybdenum disulfide compound prepared in the embodiment is used as a catalyst for catalytic hydrogen evolution, and the method comprises the following steps:
1. weighing 4mg of gold nanoparticle/molybdenum disulfide compound and 10 mu L of Nafion solution (the mass concentration is 5%) to be dispersed in 1mL of ethanol, and obtaining a dispersion solution after uniform ultrasonic dispersion; uniformly coating 10 mu L of dispersion liquid on a glassy carbon electrode, and drying at room temperature to obtain a catalyst-loaded glassy carbon electrode;
2. a three-electrode system was used, and the electrochemical workstation used was CH 660D. And (2) taking a 0.5mol/L dilute sulfuric acid solution as an electrolyte solution, taking the catalyst-loaded glassy carbon electrode obtained in the step (1) as a working electrode, taking a Pt sheet as a counter electrode, and taking Ag/AgCl as a reference electrode, and carrying out catalytic hydrogen evolution. All electrodes were calibrated to reversible hydrogen electrodes.
Claims (5)
1. A preparation method of a gold nanoparticle/molybdenum disulfide compound is characterized by comprising the following steps:
step 1: preparation of thiazole ring star polymer ligand
1a, thiazole ring AB3Preparation of monomers
Adding 8.0g of 3-azido 2, 2-bis (azidomethyl) propane-1-ol, 3.9g of 4-pentanoic acid, 14.7g of 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride, 1.6g of 4-dimethylaminopyridine and anhydrous dichloromethane into a reactor in sequence, and stirring for reacting for 8-12 hours at room temperature; washing with water and saturated saline water in sequence after the reaction is finished, drying with anhydrous magnesium sulfate, rotary evaporating solvent, and separating the crude product by silica gel chromatography to obtain colorless thiazole ring AB3A monomer;
1b hyperbranched Polymer HB- (AB)3Preparation of (e) -150)
50.0mg of copper sulfate pentahydrate, 10.2mg of 3-azido 2, 2-bis (azidomethyl) propan-1-ol and 10.2mg of thiazole ring AB are sequentially added to the reactor30.873g of monomer and DMF (dimethyl formamide) solvent, and a reaction systemFreezing, vacuumizing, introducing nitrogen for three times, immediately adding 52.8mg of ascorbic acid into the reaction system, reacting at 45 ℃ for 50 minutes under vacuum condition, stopping the reaction, adding N, N, N' -pentamethyldiethylenetriamine into the reaction system to extract catalyst copper salt in the system, passing the crude reaction product through an aluminum oxide column, and precipitating in methanol to obtain colorless hyperbranched polymer HB- (AB)3-150)；
1c, thiazole Ring Star Polymer HS- (AB)3-150)@PEO17Preparation of
Sequentially adding hyperbranched polymer HB- (AB) into a reactor3-150)0.2g of alkynyl polyethylene oxide, 1.0g of alkynyl polyethylene oxide, 5mg of copper sulfate pentahydrate and DMF (dimethyl formamide) as a solvent, freezing the reaction system, vacuumizing, introducing nitrogen repeatedly for three times, immediately adding 17.6mg of ascorbic acid into the reaction system, reacting for 4 hours at 45 ℃ under vacuum, stopping the reaction, adding N, N, N' -pentamethyldiethylenetriamine into the system to extract catalyst copper salt in the system, passing the crude reaction product through an aluminum oxide column, and precipitating in diethyl ether to obtain a colorless thiazolocytarlic polymer HS- (AB)3-150)@PEO17；
Step 2: preparation of gold nano-complex
Adding 25mg of thiazole ring star polymer into 50 mu L of chloroauric acid aqueous solution with the concentration of 50mM, stirring and reacting for 30min at room temperature, then cooling the reaction system to 0 ℃, adding 1ml of aqueous solution containing 5mg of sodium borohydride while stirring, and reacting for 4 h at 0 ℃ to obtain a gold nano complex;
and step 3: preparation of gold nanoparticle/molybdenum disulfide compound
Mixing the isopropanol solution of molybdenum disulfide and the gold nano complex aqueous solution, stirring for 1 hour at room temperature, centrifugally collecting precipitates, and drying to obtain the target product.
2. The method of claim 1, wherein:
in the step 1a, the eluent used in the chromatographic separation of silica gel is n-hexane and diethyl ether, and the volume ratio is 1: 1.
3. the method of claim 1, wherein:
in the step 3, the mass ratio of the gold nano complex to the molybdenum disulfide is 1: 10-20.
4. Use of gold nanoparticle/molybdenum disulfide composites prepared according to claim 1, characterized in that: the gold nanoparticle/molybdenum disulfide compound is used as a catalyst to perform catalytic hydrogen evolution reaction.
5. Use according to claim 4, characterized in that it comprises the following steps:
step 1: weighing 4mg of gold nanoparticle/molybdenum disulfide compound and 10 mu L of Nafion solution with the mass concentration of 5% and dispersing in 1mL of ethanol, and obtaining a dispersion solution after uniform ultrasonic dispersion; uniformly coating 10 mu L of dispersion liquid on a glassy carbon electrode, and drying at room temperature to obtain a catalyst-loaded glassy carbon electrode;
step 2: a three-electrode system is adopted, a 0.5mol/L dilute sulfuric acid solution is used as an electrolyte solution, the catalyst-loaded glassy carbon electrode obtained in the step 1 is used as a working electrode, a Pt sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode, and catalytic hydrogen evolution is carried out; all electrodes were calibrated to reversible hydrogen electrodes.
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