CN114405544B - Conjugated polymer supported metal platinum nanoparticle, preparation method thereof and application thereof in photocatalytic hydrogen evolution - Google Patents
Conjugated polymer supported metal platinum nanoparticle, preparation method thereof and application thereof in photocatalytic hydrogen evolution Download PDFInfo
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title abstract description 127
- 229910052697 platinum Inorganic materials 0.000 title abstract description 73
- 239000002105 nanoparticle Substances 0.000 title abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910052751 metal Inorganic materials 0.000 title abstract description 8
- 239000002184 metal Substances 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 229930192474 thiophene Natural products 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 7
- ZKBKRTZIYOKNRG-UHFFFAOYSA-N 1,3,6,8-tetrabromopyrene Chemical compound C1=C2C(Br)=CC(Br)=C(C=C3)C2=C2C3=C(Br)C=C(Br)C2=C1 ZKBKRTZIYOKNRG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 claims description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 22
- 239000008139 complexing agent Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
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- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
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- 238000011068 loading method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 229910000510 noble metal Inorganic materials 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 10
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- SFLGSKRGOWRGBR-UHFFFAOYSA-N phthalane Chemical compound C1=CC=C2COCC2=C1 SFLGSKRGOWRGBR-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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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
- 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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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C—CHEMISTRY; METALLURGY
- 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
- C01B3/04—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a conjugated polymer supported metal platinum nanoparticle, a preparation method thereof and application thereof in photocatalytic hydrogen evolution. By adding DMF during the synthesis, pt nanoparticles can be successfully loaded on conjugated polymers. DMF is used as a solvent, a protective agent and a reducing agent in the process, and Pt nano particles are stably loaded on a polymer under the condition of not adding a complexing agent. In addition, the load of Pt nano particles and the D-A function of the conjugated polymer are utilized, so that photo-generated electron-hole pairs are effectively separated, the visible light response is increased, the photocatalytic performance is improved, and the obtained material has strong visible light catalytic hydrogen production performance. In addition, the preparation method has lower requirements on equipment, so that the investment cost for mass production is low, and the method is beneficial to practical application.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and relates to conjugated polymer supported metal platinum nano particles, a preparation method thereof and application thereof in photocatalytic hydrogen evolution.
Background
Renewable energy sources are urgently sought due to the ever-increasing energy demands and environmental hazards created by fossil fuel combustion. Wherein hydrogen (H) 2 ) Zero emissions and high energy are considered as major alternative resources to fossil fuels. At H 2 In a plurality of conversion methods, sunlight is utilized to drive photocatalytic water decomposition to produce H 2 As a solution to the problem of the ringThe strategies that solve the environmental problems and energy problems have attracted great interest.
The conjugated polymer not only has the characteristics of high chemical stability and adjustable photoelectron performance, but also is a novel low-cost organic material with higher heteroatom content, and the conjugated structure can effectively promote the separation of photogenerated charge carriers. In theory, all photocatalytic reactions are driven by charge carriers, whose behavior can be divided into charge generation, separation, migration and surface reactions. The efficiency of charge utilization in each step determines the overall performance of the photocatalyst. The loading of the noble metal cocatalyst can effectively improve the photocatalytic activity, but the modification of the conjugated polymer by using the noble metal cocatalyst still has challenges at present.
Therefore, further studies on how to smoothly load the noble metal co-catalyst onto the conjugated polymer and stably exist in order to effectively improve the photocatalytic efficiency and charge separation have been required.
In recent years, the loading of noble metal cocatalysts onto conjugated polymers has been achieved by a variety of methods, including loading palladium (Pd) or Pt with the microporous structure and coordination bonds of the polymer, loading Pt onto the end of the polymer with a complexing agent, anchoring Pt with unsaturated coordinated nitrogen (N) atoms of the polymer itself, and loading Pt nanoparticles with electrostatic adsorption.
For example, chinese patent application No. cn202010877354.X discloses a method of loading Pd or Pt onto a polymer. In the loading process, the heteropoly acid plays an important role as a complexing agent, and the heteropoly acid is firstly loaded in the polymer by utilizing the micropore structure of the polymer and then forms a coordination bond with Pd or Pt, so that Pd or Pt can stably exist in the polymer. Also disclosed in the chinese patent application No. CN201911243610.3 is a method for preparing a polymer supported Pt catalyst. According to the invention, a polymer with large molecular weight is introduced on the surface of the carrier, and Pt is loaded at the tail end of the polymer by using a complexing agent so as to reduce steric hindrance and increase the compatibility of a system, so that the loading of the noble metal cocatalyst on the polymer is successfully realized. Except for the use of complexing agents as described aboveIn addition, polyvinyl pyrrolidone (PVP) may be used as a complexing agent. By ultrasound of a mixed solution containing PVP, pt and a polymer, pt matched with PVP enters micropores of the polymer, and PVP is shed off in a plasma etching mode, so that Pt can be successfully loaded into the polymer (ACS appl. Nano Mater 2021, 4,4, 4070-4076). In addition, the Chinese patent with the application number of CN201410212520.9 discloses a preparation method of the coordination polymer supported Pt nano catalyst. The method firstly utilizes N anchoring on Pt and 4, 4-bipyridine to change the electronic structure of the polymer, so that the charge density of the metal is delocalized, and proton adsorption is promoted. Then in H 2 Pt is reduced to Pt nanoparticles under the condition that the Pt nanoparticles are stably supported on the polymer. Also, for example, chinese patent application No. CN201310457005.2 discloses a method for loading Pt nanoparticles with cationic polymer. The invention utilizes positive charges uniformly distributed on the surface of cationic polymer graphene to make the chloroplatinic acid radical ion (PtCl) with negative charges 6 2- ) Through electrostatic adsorption, the graphene particles are uniformly adsorbed and distributed on the surface of graphene.
The prior art has the main defects that:
(1) Most polymers do not have a microporous structure. This results in the inability of the noble metal promoter to be directly supported on the polymer by the pores.
(2) The coordination bond has weak acting force and is easy to fall off. Because of the inherent nature between the noble metal promoter and the polymer, there is no strong interaction between the noble metal promoter and the polymer, but a large amount of the noble metal promoter exists in the solution, and the loading is greatly reduced.
(3) Some polymers have no unsaturated coordinated N atoms anchored Pt themselves. This results in the inability to support Pt on the polymer surface without the addition of a complexing agent.
(4) Most polymers are neutral organic molecules, and the loading of noble metal promoters cannot be achieved by electrostatic adsorption.
Based on this, it is important to develop a novel process to achieve a stable loading of noble metal promoters on the polymer surface.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a conjugated polymer supported metal platinum (Pt) nanoparticle, a preparation method thereof and application thereof in photocatalytic hydrogen evolution. By adding DMF during the synthesis, pt nanoparticles can be successfully loaded on conjugated polymers. DMF is used as a solvent, a protective agent and a reducing agent in the process, and Pt nano particles are stably loaded on a polymer under the condition of not adding a complexing agent. In addition, the loading of Pt nano particles and the action of Donor-Accept (D-A) of the conjugated polymer are utilized, so that photo-generated electron-hole pairs are effectively separated, the visible light response is increased, the photocatalytic performance is improved, and the obtained material has strong visible light catalytic hydrogen production performance.
In order to solve the problems in the prior art, the technical scheme adopted by the invention is as follows:
the preparation method of the conjugated polymer supported metal platinum nano-particle comprises the following steps:
(1) Adding raw material dithiophene [3,2-B:2',3' -D ] thiophene and m-chloroperoxybenzoic acid into a round bottom flask, adding anhydrous dichloromethane, heating, cooling, performing column chromatography, and vacuum drying to obtain DTDO;
(2) At N 2 Adding the DTDO, 1,3,6, 8-tetrabromopyrene, anhydrous potassium carbonate, tris (dibenzylideneacetone) dipalladium, pivalic acid, tris (o-methoxyphenyl) phosphorus and anhydrous o-phthaloyl dimethyl ether obtained in the step (1) under the condition, heating, cooling, washing and drying to obtain PyDTDO-3;
(3) Adding deionized water and chloroplatinic acid into the PyDTDO-3,N,Ndimethylformamide @N, N-dimethyl formamide (DMF), heating, cooling, washing, drying and annealing under Ar gas atmosphere to obtain the conjugated polymer supported Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3.
Preferably, in the step (1), the molar ratio of the raw material dithiophene [3,2-B:2',3' -D ] thiophene and the m-chloroperoxybenzoic acid is (1-10): (10-20); 20-50 of mL of anhydrous methylene dichloride is added to 1 mmol of total raw materials, wherein the total raw materials comprise dithiophene [3,2-B:2',3' -D ] thiophene and m-chloroperoxybenzoic acid.
Preferably, in the step (1), the heating temperature is 10-40 ℃ and the heating time period is 20-30h; the column chromatography is carried out according to the volume ratio (1-5): petroleum ether of (1-5): dichloromethane is a eluent; the vacuum drying temperature is 20-80 ℃ and the drying time is 20-30h.
Preferably, the molar ratio of DTDO, 1,3,6, 8-tetrabromopyrene, anhydrous potassium carbonate, tris (dibenzylideneacetone) dipalladium, pivalic acid, tris (o-methoxyphenyl) phosphorus in step (2) is: (0.1-0.8): (0.1-0.5): (1-3): (0.01-0.03): (0.1-0.5): (0.01-0.05), adding 5-15. 15 mL anhydrous o-phthaloyl ether into 1 mmol total raw material, wherein the total raw material comprises dithiophene [3,2-B:2',3' -D ] thiophene and m-chloroperoxybenzoic acid.
Preferably, the heating temperature in the step (2) is 80-150 ℃ and the heating time period is 60-80 h; the washing is carried out by using 10-30 mL deionized water; the vacuum drying temperature is 20-80 ℃ and the drying time is 20-30h.
Preferably, in the step (3), the addition amount of the PyDTDO-3 is 20-60 mg, the addition amount of the deionized water is 5-20 mL, the addition amount of the chloroplatinic acid is 1-5 mL, and the addition amount of the DMF is 5-20 mL; the heating temperature is 50-100 ℃, and the heating time is 5-15 h; the washing is carried out by using 10-30 mL deionized water; the temperature of the vacuum drying is 20-80 ℃ and the drying time is 20-30h; the annealing temperature of the Ar gas atmosphere is 80-150 ℃ and the annealing time is 0.5-2 h.
The conjugated polymer loaded Pt photocatalysis hydrogen evolution material Pt/PyDTDO-3 prepared based on any one of the above methods.
The application of the conjugated polymer supported Pt photocatalysis hydrogen evolution material Pt/PyDTDO-3 in preparing hydrogen evolution photocatalyst.
The beneficial effects are that:
compared with the prior art, the conjugated polymer supported metal platinum (Pt) nanoparticle, the preparation method and the application thereof in photocatalytic hydrogen evolution are provided, and the method is to prepare a series of visible light responsive Pt/PyDYDO-3 photocatalytic materials with higher activity by utilizing the method of coordinating DMF with a noble metal cocatalyst and then supporting the DMF on the conjugated polymer. The photocatalytic water splitting hydrogen production result shows that the visible light catalytic activity of the 7% Pt/PyDYDO-3 material is obviously enhanced, and the hydrogen production rate is 2.3 times that of the pure PyDYDO-3 material. And has good photocatalytic cycle stability and certain application value in the aspect of hydrogen production by photocatalytic decomposition of water. The photocatalytic material prepared by the preparation method has high photocatalytic efficiency and good visible light catalytic water decomposition effect. In addition, the preparation method has lower requirements on equipment, so that the investment cost for mass production is low, and the method is beneficial to practical application. The method is specifically as follows:
(1) Compared with the prior art, no additional complexing agent is needed, and the method is suitable for loading the noble metal cocatalyst on the neutral organic high polymer without the microporous structure and unsaturated coordination N atoms, greatly expands the application range of loading the noble metal cocatalyst on the surface of the polymer, and has universality;
(2) The conjugated polymer supported Pt photocatalytic material prepared by the invention has wide light absorption and narrower band gap, in addition, pi-stacking interaction in the conjugated polymer can promote migration and transfer of carriers along a plane and a stacking direction, and can effectively prevent the recombination of photo-generated electrons and holes, thereby greatly improving the photocatalytic activity, and the hydrogen yield of a 7% Pt/PyDTDO-3 sample can reach 3.91 mmol.g -1 ·h -1 Compared with the pure PyDTDO-3, the method has the advantages that the yield is improved by 2.3 times, and in addition, the hydrogen prepared by the method is green hydrogen, so that the method is environment-friendly and pollution-free, and has a wide application prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of PyDTDO-3, 3% Pt/PyDTDOO-3, 5% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3, 9% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3-DF prepared in comparative example 1, comparative example 2, example 1, example 2, example 3 and example 4;
FIG. 2 (a) is an image of a PyDTDO-3 Scanning Electron Microscope (SEM) prepared in comparative example 1 at 10 ten thousand magnification;
FIG. 2 (b) is an image of 7% Pt/PyDTDOO-3 Scanning Electron Microscope (SEM) prepared in example 3 at 10 ten thousand magnification;
FIG. 2 (c) is an image of a 7% Pt/PyDTDOO-3-DF Scanning Electron Microscope (SEM) at 10 thousand magnification;
FIGS. 2 (d) -2 (f) are Transmission Electron Microscope (TEM) images of PyDTDO-3 prepared in comparative example 1;
FIGS. 2 (g) -2 (i) are Transmission Electron Microscope (TEM) images of 7% Pt/PyDTDOO-3 prepared in example 3;
FIG. 3 is a Fourier transform infrared spectrum (FTIR) of PyDTDO-3, 3% Pt/PyDTDOO-3, 5% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3, 9% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3-DF prepared in comparative example 1, comparative example 2, example 1, example 2, example 3 and example 4 of the present invention;
FIG. 4 is a total X-ray electron spectrum (XPS-Survey) of PyDTDO-3, 7% Pt/PyDTDOO-3 and 7% Pt/PyDTDOO-3-DF prepared in comparative example 1, example 3 and comparative example 2;
FIG. 5 is a high resolution XPS plot of PyDTDO-3, 7% Pt/PyDTDOO-3, and 7% Pt/PyDTDOO-3-DF prepared in comparative examples 1,3, and 2 of the present invention, wherein (a) is a high resolution XPS O1S spectrum, (b) is an XPS C1S spectrum, (C) is an XPS S S2 p spectrum, and (d) is an XPS Pt 4f spectrum;
FIG. 6 is an ultraviolet-visible absorption spectrum (UV-Vis DRS) of PyDTDO-3, 3% Pt/PyDTDOO-3, 5% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3, 9% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3-DF prepared in comparative example 1, comparative example 2, example 1, example 2, example 3 and example 4;
FIG. 7 shows photocatalytic performance test patterns of PyDTDO-3, 3% Pt/PyDTDOO-3, 5% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3, 9% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3-DF prepared in comparative examples 1, 2, 3 and 4, wherein, (a) is a photocatalytic hydrogen production curve change chart, (b) is a hydrogen production efficiency chart, (c) is a 5-cycle experiment test chart, and (d) is an XRD chart before and after photocatalytic reaction;
FIG. 8 is a FTIR chart of the invention prepared in comparative example 1 and example 3 before and after photocatalytic reaction of PyDTDO-3 and 7% Pt/PyDTDOO-3.
Detailed Description
The following examples will provide those skilled in the art with a more complete understanding of the invention, but are not intended to limit the invention in any way.
Example 1
5 mmol of dithiophene [3,2-B:2',3' -D ] thiophene and 15 mmol of m-chloroperoxybenzoic acid were weighed according to the molar ratio, added into a round bottom flask, 30 mL of anhydrous dichloromethane was added, heated at 20 ℃ for 24 h, and cooled to room temperature. Petroleum ether in a volume ratio of 2:1: column chromatography was performed with methylene chloride and dried under vacuum at 50℃for 24 h to give DTDO.
0.5 mmol of DTDO, 0.25 mmol of 1,3,6, 8-tetrabromopyrene, 1.5 mmol of anhydrous potassium carbonate, 0.015 mmol of tris (dibenzylideneacetone) dipalladium, 0.3 mmol of pivalic acid, 0.03 mmol of tris (o-methoxyphenyl) phosphorus and 10 mL of anhydrous o-xylylene ether are weighed according to the molar ratio. 120. And heating 72-h at the temperature and cooling to the room temperature. Washing with 15 mL deionized water, and vacuum drying at 60deg.C for 24. 24 h to obtain PyDTDO-3.
40 mg of PyDTDO-3 was weighed, 10 mL of deionized water, 1.2 mL of chloroplatinic acid, 10 mL of DMF and 70 ℃ of heating 10 h and cooling to room temperature. Washing with 15 mL deionized water, vacuum drying at 60 ℃ for 24 hours, and annealing at 125 ℃ in Ar atmosphere for 1 h to obtain 3% Pt/PyDTDO-3.
Example 2
Similar to example 1, except that 2 mL chloroplatinic acid was taken, the resulting sample was designated 5% Pt/PyDTDO-3.
Example 3
Similar to example 1, except that 2.8. 2.8 mL chloroplatinic acid was taken, the resulting sample was designated 7% Pt/PyDTDO-3.
Example 4
Similar to example 1, except that chloroplatinic acid was taken at 3.6. 3.6 mL, the resulting sample was designated 9% Pt/PyDTDO-3.
Comparative example 1
5 mmol of dithiophene [3,2-B:2',3' -D ] thiophene and 15 mmol of m-chloroperoxybenzoic acid were weighed according to the molar ratio, added into a round bottom flask, 30 mL of anhydrous dichloromethane was added, heated at 20 ℃ for 24 h, and cooled to room temperature. Petroleum ether in a volume ratio of 2:1: column chromatography was performed with methylene chloride and dried under vacuum at 50℃for 24 h to give DTDO.
0.5 mmol of DTDO, 0.25 mmol of 1,3,6, 8-tetrabromopyrene, 1.5 mmol of anhydrous potassium carbonate, 0.015 mmol of tris (dibenzylideneacetone) dipalladium, 0.3 mmol of pivalic acid, 0.03 mmol of tris (o-methoxyphenyl) phosphorus and 10 mL of anhydrous o-xylylene ether are weighed according to the molar ratio. 120. And heating 72-h at the temperature and cooling to the room temperature. Washing with 15 mL deionized water, and vacuum drying at 60deg.C for 24. 24 h to obtain PyDTDO-3.
Comparative example 2
5 mmol of dithiophene [3,2-B:2',3' -D ] thiophene and 15 mmol of m-chloroperoxybenzoic acid were weighed according to the molar ratio, added into a round bottom flask, 30 mL of anhydrous dichloromethane was added, heated at 20 ℃ for 24 h, and cooled to room temperature. Petroleum ether in a volume ratio of 2:1: column chromatography was performed with methylene chloride and dried under vacuum at 50℃for 24 h to give DTDO.
0.5 mmol of DTDO, 0.25 mmol of 1,3,6, 8-tetrabromopyrene, 1.5 mmol of anhydrous potassium carbonate, 0.015 mmol of tris (dibenzylideneacetone) dipalladium, 0.3 mmol of pivalic acid, 0.03 mmol of tris (o-methoxyphenyl) phosphorus and 10 mL of anhydrous o-xylylene ether are weighed according to the molar ratio. 120. And heating 72-h at the temperature and cooling to the room temperature. Washing with 15 mL deionized water, and vacuum drying at 60deg.C for 24. 24 h to obtain PyDTDO-3.
40 mg PyDTDO-3 was weighed, added with 20 mL deionized water and 2.8 mL chloroplatinic acid, heated to 70℃for 10 h, and cooled to room temperature. Washing with 15 mL deionized water, vacuum drying at 60deg.C for 24 h, and Ar atmosphere annealing at 125deg.C for 1 h to obtain 7% Pt/PyDTDO-3 without DMF (denoted as 7% Pt/PyDTDO-3-DF).
Characterization of materials
XRD spectrum results:
FIG. 1 is an XRD pattern for samples of each component, and it was observed that all samples except 9% Pt/PyDTDO-3 had more pronounced diffraction peaks at about 26℃representing pi-pi stacking between conjugated polymers. However, the diffraction peak of about 26℃for 9% Pt/PyDTDO is significantly reduced or eliminated from other samples due to the inhibition of pi-pi conjugation in the structure by the addition of excess chloroplatinic acid. In addition, no diffraction peaks as evident as crystals were observed in all samples, indicating that the synthesized conjugated polymer was amorphous.
SEM, TEM pictures:
FIG. 2 is an SEM of the prepared PyDTDO-3 (FIG. 2 (a)), 7% Pt/PyDTDO-3 (FIG. 2 (b)), 7% Pt/PyDTDO-3-DF (FIG. 2 (c)), and photocatalytic materials. As shown in the figure, pure PyDTDO-3 shows a morphology of mixed rod-and-sphere growth, and compared with other SEM images, the loading of Pt has no influence on the morphology of PyDTDO-3. In addition, images of mixed growth of rods and spheres were observed from TEM images of PyDTDO-3 (FIG. 2 (d) -FIG. 2 (f)) and 7% Pt/PyDTDO-3 (FIGS. 2 (g) - (i)). The HRTEM plot of 7% Pt/PyDTDO-3 (FIG. 2 (i)) clearly shows the Pt loading.
FTIR spectrum results:
FIG. 3 is a FTIR spectrum of a sample of each component used to determine the material composition and surface functionality of the photocatalyst. As shown, there are mainly four types of peaks, 2917 and cm respectively -1 、1655 cm -1 、1473 cm -1 、1312 cm -1 And 1136 cm -1 . Wherein 2917 and 2917 cm -1 A C-H bond stretching vibration peak, 1655 and 1655 cm -1 Is the stretching vibration peak of aromatic ring (C=C), 1473 and 1473 cm -1 Belongs to the telescopic vibration of thiophene (C-S-C), 1312 and 1312 cm -1 And 1136 cm -1 Stretching vibration attributed to sulfone group (o=s=o). A further 9% Pt/PyDTDO-3 sample was observed at 1022 cm -1 Peaks appear, belonging to Pt-OH, which also correspond to those in XRD. In addition, it can be seen from the figure that different proportions of Pt/PyDTDO-3 show similar stretching and bending vibrations as the support PyDTDO-3, indicating that the loading of Pt hardly affects the architecture of PyDTDO-3.
XPS spectrum results:
FIG. 4 is XPS spectrum, which can be used to characterize the material composition and valence state of a photocatalytic material. XPS spectra of PyDTDO-3, 7% Pt/PyDTDO-3 and 7% Pt/PyDTDO-3-DF were analyzed to confirm the chemical state of the elements therein. It can be seen from fig. 4 that C, O, S and Br elements were present in all samples, and that Br elements were present indicating incomplete polymerization and the presence of Br end groups. The presence of Pt element can be seen from the full spectra of 7% Pt/PyDTDO-3 and 7% Pt/PyDTDO-3-DF, further demonstrating the successful loading of Pt.
FIG. 5 is a high resolution spectrum of PyDTDO-3, 7% Pt/PyDTDO-3, and 7% Pt/PyDTDO-3-DF. (a) The figure shows an O1S XPS spectrum, with the peak at 532.1 eV representing the presence of an o=s bond. (b) The figure shows the XPS spectrum of C1 s, with the peak at 284.9 eV representing the presence of c=c, indicating the presence of an aromatic ring backbone in CPs. (c) Panel S2 p spectra, which can be divided into three groups of peaks. 169 Peaks around eV correspond to s=o bonds, the peak of 168 eV corresponds to C-S-C in thiophene, and the peaks in 165 and 164 eV are S2 p (3 d, respectively 3/2 ) And S2 p (3 d) 5/2 ) All belonging to S-S cross-linking. (d) FIG. 7% Pt/PyDTDO-3 and 7% Pt/PyDTDO-3-DF Pt 4f XPS spectra. In 7% Pt/PyDTDO-3, two peaks appear at binding energies 74.9 and 71.6 eV, indicating the formation of Pt-O coordination bonds. In 7% Pt/PyDTDO-3-DF, in addition to the Pt-O coordination bonds of 78.4 and 72.7 eV, there are 75.6 and 70.8 eV Pt-Pt bonds present, as well as Pt during the reaction 4+ Pt produced by precursor reduction 0 Corresponding to each other. These results all correspond to those in FTIR.
Fifth, DRS spectrogram result:
FIG. 6 is a UV-Vis DRS spectrum showing a broad UV visible absorption range of 250 to 800 nm for all CPs due to the high degree of conjugation of the support PyDTDO-3, which creates numerous electron delocalized orbital overlaps between Py and DTDO units. In a series of Pt-loaded samples, the absorption intensity in the visible region increased with increasing Pt content, indicating that they had better light absorption characteristics. The 9% loading of PyDTDO-3 may result in a decrease in its absorption strength over 7% loading of PyDTDO-3 due to a decrease in its atom utilization. In addition, the Pt is loaded, so that the visible light absorption intensity can be enhanced, and the visible light photolysis water hydrogen production activity can be improved. At the same time, the high content of DTDO in PyDTDO-3 is also responsible for its narrower band gap.
Performance testing
20 mg Pt/PyDTDO-3 prepared in the above examples was added to a reaction flask, 90 mL deionized water, 10 mL DMF and 17 g ascorbic acid (sacrificial reagent) were added, ar gas was introduced into the flask for 30 min, and after magnetic stirring for about 30 min, ar gas was closed to seal the flask. The gas in the reaction flask was pumped out and injected into the gas chromatograph at intervals of 60 min for detection.
Fig. 7 is a graph of hydrogen production performance of the photolysis water of each component, and fig. 7 (a) shows that the hydrogen production of the material is gradually increased along with the extension of illumination time, and the linear growth trend is shown. FIG. 7 (b) shows the H of PyDTDO-3, 3% Pt/PyDTDO-3, 5% Pt/PyDTDO-3, 7% Pt/PyDTDO-3-DF and 9% Pt/PyDTDO-3 2 The production rates were 1.72, 2.16, 2.44, 3.91, 2.42 and 3.45 mmol.g, respectively -1 ·h -1 . The binding diagram shows that when the Pt loading reaches 7%, the photocatalytic activity of the material is highest and is 2.3 times and 1.6 times that of PyDTDO-3 and 7% Pt/PyDTDO-3-DF respectively. However, when the Pt loading is insufficient or exceeds 7%, the activity increases significantly slowly, which may be due to a decrease in the utilization of Pt atoms. In addition, under the condition of optimal load, DMF is not added in the synthesis process, so that the influence on the hydrogen production is great, and the important effect of DMF in the Pt atom load process is demonstrated. FIG. 7 (c) is a graph of 7% Pt/PyDTDO-3 hydrogen production cycle, and it can be seen that after 30h (5) cycles of experiments, 7% Pt/PyDTDO-3 hydrogen production is not significantly reduced and remains stable. And as can be seen from fig. 7 (d) and fig. 8, XRD and FTIR patterns of 7% Pt/PyDTDO-3 were hardly changed before and after the photocatalytic reaction, further demonstrating that 7% Pt/PyDTDO-3 has a certain stability.
In the foregoing, the protection scope of the present invention is not limited to the preferred embodiments of the present invention, and any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention disclosed in the present invention fall within the protection scope of the present invention.
Claims (6)
1. The application of the conjugated polymer supported Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3 in photolysis of water to hydrogen production is characterized by comprising the following steps of:
adding raw material dithiophene [3,2-B:2',3' -D ] thiophene and m-chloroperoxybenzoic acid into a round bottom flask, adding anhydrous dichloromethane, heating, cooling, performing column chromatography, and vacuum drying to obtain DTDO;
at N 2 Adding the DTDO, 1,3,6, 8-tetrabromopyrene, anhydrous potassium carbonate, tris (dibenzylideneacetone) dipalladium, pivalic acid, tris (o-methoxyphenyl) phosphorus and anhydrous o-phthaloyl dimethyl ether obtained in the step (1) under the condition, heating, cooling, washing and drying to obtain PyDTDO-3;
adding deionized water and chloroplatinic acid into the PyDTDO-3,N,Nand (3) heating, cooling, washing, drying and annealing at 80-150 ℃ under Ar gas atmosphere for 0.5-2 h to obtain the conjugated polymer supported Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3.
2. The use according to claim 1, wherein in step (1), the starting dithiophene [3,2-B:2',3' -D ] thiophene, m-chloroperoxybenzoic acid has a molar ratio of (1-10): (10-20); 20-50 of mL of anhydrous methylene dichloride is added to 1 mmol of total raw materials, wherein the total raw materials comprise dithiophene [3,2-B:2',3' -D ] thiophene and m-chloroperoxybenzoic acid.
3. The use according to claim 1, wherein in step (1) the heating is carried out at a temperature of 10-40 ℃ for a period of 20-30h; the column chromatography is carried out according to the volume ratio (1-5): petroleum ether of (1-5): dichloromethane is a eluent; the vacuum drying temperature is 20-80 ℃ and the drying time is 20-30h.
4. The use according to claim 1, wherein the molar ratio of DTDO, 1,3,6, 8-tetrabromopyrene, anhydrous potassium carbonate, tris (dibenzylideneacetone) dipalladium, pivalic acid, tris (o-methoxyphenyl) phosphorus in step (2) is: (0.1-0.8): (0.1-0.5): (1-3): (0.01-0.03): (0.1-0.5): (0.01-0.05), adding 5-15. 15 mL anhydrous o-phthaloyl ether into 1 mmol total raw material, wherein the total raw material comprises dithiophene [3,2-B:2',3' -D ] thiophene and m-chloroperoxybenzoic acid.
5. The use according to claim 1, wherein the heating in step (2) is at a temperature of 80-150 ℃ for a period of 60-80 h; the washing is carried out by using 10-30 mL deionized water; the vacuum drying temperature is 20-80 ℃ and the drying time is 20-30h.
6. The use according to claim 1, wherein in step (3), the amount of PyDTDO-3 added is 20-60 mg, the amount of deionized water added is 5-20 mL, the amount of chloroplatinic acid added is 1-5 ml, and the amount of dmf added is 5-20 mL; the heating temperature is 50-100 ℃, and the heating time is 5-15 h; the washing is carried out by using 10-30 mL deionized water; the vacuum drying temperature is 20-80 ℃ and the drying time is 20-30h.
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