CN114405544A - Conjugated polymer loaded metal platinum nano-particles, preparation method thereof and application thereof in photocatalytic hydrogen evolution - Google Patents
Conjugated polymer loaded metal platinum nano-particles, preparation method thereof and application thereof in photocatalytic hydrogen evolution Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 79
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 31
- 239000001257 hydrogen Substances 0.000 title claims abstract description 31
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 13
- 239000002184 metal Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229930192474 thiophene Natural products 0.000 claims description 16
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- 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
- 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 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 2
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 13
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- 238000011068 loading method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 17
- 229910000510 noble metal Inorganic materials 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 11
- 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
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
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- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 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
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- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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- 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
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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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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
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Abstract
The invention discloses a conjugated polymer loaded metal platinum nanoparticle, a preparation method thereof and application thereof in photocatalytic hydrogen evolution. By adding DMF in the synthesis process, Pt nano-particles can be successfully loaded on the conjugated polymer. In the process, DMF is used not only as a solvent, but also as a protective agent and a reducing agent, and Pt nano particles are stably supported on the polymer under the condition of not adding a coordination agent. In addition, the load of Pt nano particles and the D-A function of the conjugated polymer are utilized to effectively separate photoproduction electron-hole pairs, the visible light response is increased, the photocatalytic performance is improved, and the obtained material has stronger visible light catalysis hydrogen production performance. In addition, the preparation method has low requirements on equipment, so that the investment cost of mass production is low, and the preparation method is favorable for practical application.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and relates to a conjugated polymer loaded metal platinum nanoparticle, a preparation method thereof and application thereof in photocatalytic hydrogen evolution.
Background
Renewable energy sources are urgently sought due to the ever-increasing energy demand and the environmental hazards created by the burning of fossil fuels. Wherein hydrogen (H)2) It is considered as a major alternative resource to fossil fuels due to zero emission and high energy. At H2In the conversion method, the sunlight is used to drive the photocatalytic water decomposition to produce H2Great interest has been raised as a strategy to solve both environmental and energy problems.
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 of the conjugated polymer can effectively promote the separation of photo-generated 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 load of the noble metal cocatalyst can effectively improve the photocatalytic activity, but the modification of the conjugated polymer by utilizing the load of the noble metal cocatalyst is still challenging at present.
Therefore, in order to effectively improve the photocatalytic efficiency and charge separation, how to smoothly load and stabilize the noble metal cocatalyst on the conjugated polymer is still under study.
In recent years, researchers have implemented the loading of noble metal promoters on conjugated polymers by various methods, including loading palladium (Pd) or Pt by using the microporous structure and coordination bonds of the polymer, loading Pt at the end of the polymer by using a coordination agent, anchoring Pt by using unsaturated coordinated nitrogen (N) atoms of the polymer itself, and loading Pt nanoparticles by electrostatic adsorption.
For example, application No. CN20201087735X, discloses a method of loading Pd or Pt onto a polymer. The heteropoly acid plays an important role as a coordination agent in the loading process, and the heteropoly acid is loaded in the polymer by utilizing the microporous structure of the polymer, and then the heteropoly acid and Pd or Pt form a coordination bond, so that the Pd or Pt can stably exist in the polymer. Also, the chinese patent application No. CN201911243610.3 discloses a preparation method of a polymer supported Pt catalyst. According to the invention, a polymer with large molecular weight is introduced on the surface of a carrier, and Pt is loaded on the tail end of the polymer by using a coordination agent so as to reduce steric hindrance and increase the compatibility of a system, thereby successfully realizing the loading of a noble metal cocatalyst on the polymer. In addition to the use of the complexing agents described above, polyvinylpyrrolidones (PVP) can also be used as complexing agents. Pt matched with PVP is enabled to enter micropores of the polymer by ultrasonic treatment of a mixed solution containing the PVP, the Pt and the polymer, and the PVP is enabled to be stripped in a plasma etching mode, so that the Pt can be successfully loaded into the polymer (ACS appl. Nano Mater. 2021, 4,4, 4070-4076). In addition, the invention has a Chinese patent with the application number of CN201410212520.9, and discloses a preparation method of a coordination polymer supported Pt nano catalyst. The method firstly utilizes Pt and N anchoring on 4, 4-bipyridine to change the electronic structure of the polymer, so that the charge density of metal is delocalized, thereby promoting proton adsorption. Then H is added2The Pt is reduced into Pt nano particles under the condition and stably supported on the polymer. For another example, chinese patent application No. CN201310457005.2 discloses a method for loading Pt nanoparticles with cationic polymer. The invention utilizes the positive charges uniformly distributed on the surface of the cationic polymer graphene to carry out the preparation of the chloroplatinic acid radical ion (PtCl) with negative charges6 2-) Through the electrostatic adsorption effect, the uniform adsorption is distributed on the surface of the graphene.
The prior art mainly has the following defects:
(1) most polymers do not have a microporous structure. This results in the inability of the noble metal promoter to be supported directly on the polymer by virtue of the pores.
(2) The coordination bond has a weak action force and is easy to fall off. Due to the inherent property between the noble metal cocatalyst and the polymer, the noble metal cocatalyst and the polymer do not have strong interaction, but exist in a solution in a large amount, and the loading amount is greatly reduced.
(3) There are polymers that do not have unsaturated coordinated N atoms to anchor the Pt itself. 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 the noble metal cocatalyst cannot be realized by utilizing electrostatic adsorption.
Based on this, it is important to develop a novel method to achieve stable loading of the noble metal promoter on the polymer surface.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a conjugated polymer loaded metal platinum (Pt) nanoparticle, a preparation method thereof and application thereof in photocatalytic hydrogen evolution. By adding DMF in the synthesis process, Pt nano-particles can be successfully loaded on the conjugated polymer. In the process, DMF is used not only as a solvent, but also as a protective agent and a reducing agent, and Pt nano particles are stably supported on the polymer under the condition of not adding a coordination agent. In addition, the load of Pt nano particles and the Donor-Accept (D-A) function of the conjugated polymer are utilized to effectively separate photo-generated electron-hole pairs, so that the visible light response is increased, the photocatalytic performance is improved, and the obtained material has stronger visible light catalytic hydrogen production performance.
In order to solve the problems of the prior art, the technical scheme adopted by the invention is as follows:
a preparation method of conjugated polymer supported metal platinum nanoparticles comprises the following steps:
(1) adding dithiophene [3,2-B:2 ', 3' -D ] thiophene and m-chloroperoxybenzoic acid serving as raw materials into a round-bottom flask, adding anhydrous dichloromethane, heating, cooling, carrying out column chromatography, and carrying out vacuum drying to obtain DTDO;
(2) in N2Adding the DTDO, the 1,3,6, 8-tetrabromopyrene, the anhydrous potassium carbonate and the tri (dibenzylidene) obtained in the step (1) under the conditionAcetone), dipalladium, pivalic acid, tri (o-methoxyphenyl) phosphorus and anhydrous o-dimethyl ether, heating, cooling, washing and drying to obtain PyDTDO-3;
(3) adding deionized water and chloroplatinic acid into the PyDTDO-3,N,N-dimethylformamide (f)N, NDimethyl formamide, DMF), heating, cooling, washing, drying, and annealing in Ar atmosphere to obtain the conjugated polymer loaded Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3.
Preferably, in the step (1), the molar ratio of the dithiophene [3,2-B:2 ', 3' -D ] thiophene to the m-chloroperoxybenzoic acid is (1-10): (10-20); adding 20-50 mL of anhydrous dichloromethane into 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 is 20-30 h; the column chromatography is carried out according to the volume ratio (1-5): petroleum ether of (1-5): dichloromethane is eluent; the temperature of the vacuum drying is 20-80 ℃, and the drying time is 20-30 h.
Preferably, the molar ratio of DTDO, 1,3,6, 8-tetrabromopyrene, anhydrous potassium carbonate, tris (dibenzylideneacetone) dipalladium, pivalic acid and tris (o-methoxyphenyl) phosphorus in the step (2) is as follows: (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 mL of anhydrous o-dimethyl ether into 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, the heating temperature in the step (2) is 80-150 ℃, and the heating time is 60-80 h; washing with 10-30 mL of deionized water; the temperature of the vacuum drying is 20-80 ℃, and the drying time is 20-30 h.
Preferably, in the step (3), the adding amount of PyDTDO-3 is 20-60 mg, the adding amount of deionized water is 5-20 mL, the adding amount of chloroplatinic acid is 1-5 mL, and the adding amount of DMF is 5-20 mL; the heating temperature is 50-100 ℃, and the heating time is 5-15 h; 10-30 mL of deionized water is used for washing; the temperature of the vacuum drying is 20-80 ℃, and the drying time is 20-30 h; the annealing temperature in the Ar gas atmosphere is 80-150 ℃, and the annealing time is 0.5-2 h.
The conjugated polymer prepared by any one of the methods is loaded with a Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3.
The conjugated polymer loaded Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3 is applied to preparation of a hydrogen evolution photocatalyst.
Has the advantages that:
compared with the prior art, the conjugated polymer loaded metal platinum (Pt) nano-particles, the preparation method thereof and the application thereof in photocatalytic hydrogen evolution have the advantages that DMF and a noble metal cocatalyst are coordinated, and then the Pt/PyDYDO-3 photocatalytic materials with high activity and visible light response are prepared by the method of loading the DMF and the noble metal cocatalyst on the conjugated polymer. The hydrogen production result by photocatalytic water decomposition 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 of that of pure PyDYDO-3. And has good photocatalytic cycle stability and certain application value in the aspect of hydrogen production by photocatalytic water decomposition. The photocatalytic material prepared by the preparation method has high photocatalytic efficiency and good effect of decomposing water by visible light catalysis. In addition, the preparation method has low requirements on equipment, so that the investment cost of mass production is low, and the preparation method is favorable for practical application. The details are as follows:
(1) compared with the prior art, no coordination agent is additionally added, and the method is suitable for loading the noble metal cocatalyst on the neutral organic high molecular polymer which does not contain a microporous structure and does not contain unsaturated complex N atoms, so that the application range of the noble metal cocatalyst loaded on the surface of the polymer is greatly expanded, and the method has universality;
(2) the Pt-loaded conjugated polymer photocatalytic material prepared by the invention has wide light absorption and narrower band gap, in addition, the pi-stacking interaction in the conjugated polymer can promote the migration and transfer of carriers along the plane and the stacking direction, and the recombination of photogenerated electrons and holes can be effectively prevented, so that the photocatalytic activity is greatly improved, and the hydrogen production of a 7% Pt/PyDTDO-3 sample can reach 3.91 mmol/g-1·h-1Compared with the pure sample PyDTDO-3, the yield is improved2.3 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 according to the present invention;
FIG. 2 (a) is a PyDTDO-3 Scanning Electron Microscope (SEM) image prepared in comparative example 1 at a magnification of 10 ten thousand;
FIG. 2 (b) is a 7% Pt/PyDTDOO-3 Scanning Electron Microscope (SEM) image prepared in example 3 at a magnification of 10 ten thousand;
FIG. 2 (c) is a 7% Pt/PyDTDOO-3-DF Scanning Electron Microscope (SEM) image at 10 ten thousand times magnification;
FIG. 2 (d) -FIG. 2 (f) are Transmission Electron Microscope (TEM) images of PyDTDO-3 prepared in comparative example 1;
FIG. 2 (g) -FIG. 2 (i) is a Transmission Electron Microscope (TEM) image of 7% Pt/PyDTDOO-3 prepared in example 3;
FIG. 3 is a Fourier Transform Infrared (FTIR) spectrum 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 according to the present invention;
FIG. 4 is an X-ray electron spectroscopy total 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 according to the present invention;
FIG. 5 is a high resolution XPS map of PyDTDO-3, 7% Pt/PyDTDOO-3 and 7% Pt/PyDTDOO-3-DF prepared in comparative example 1, example 3 and comparative example 2 of the present invention, wherein (a) is a high resolution XPS O1S spectrum, (b) is an XPS C1S spectrum, (C) is an XPS S2 p spectrum, and (d) is an XPS Pt 4f spectrum;
FIG. 6 is a UV-VIS 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 according to the present invention;
FIG. 7 is a graph showing the results of testing photocatalytic performance of PyDTDO-3, 3% Pt/PyDTDOO-3, 5% Pt/PyDTDOO-3, 7% Pt/PyDTDOO-3, 9% Pt/PyDTDOO-3, and 7% Pt/PyDTDOO-3-DF prepared in comparative example 1, comparative example 2, example 1, example 2, example 3, and example 4 according to the present invention, wherein (a) is a graph showing the change in photocatalytic hydrogen production curve, (b) is a graph showing the hydrogen production efficiency, (c) is a graph showing the test of 5-cycle experiment, and (d) is an XRD graph showing the results before and after photocatalytic reaction;
FIG. 8 is an FTIR chart of PyDTDO-3 and 7% Pt/PyDTDOO-3 prepared in comparative example 1 and example 3 of the present invention before and after photocatalytic reaction.
Detailed Description
The following examples are presented to enable one of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Example 1
Weighing 5 mmol of dithiophene [3,2-B:2 ', 3' -D ] thiophene and 15 mmol of m-chloroperoxybenzoic acid according to a molar ratio, adding the dithiophene [3,2-B:2 ', 3' -D ] thiophene and the m-chloroperoxybenzoic acid into a round-bottom flask, adding 30 mL of anhydrous dichloromethane, heating at 20 ℃ for 24 hours, and cooling to room temperature. Petroleum ether in a volume ratio of 2: 1: and carrying out column chromatography on dichloromethane, and carrying out vacuum drying at 50 ℃ for 24 h to obtain 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-phenylether were weighed in terms of molar ratio. Heating at 120 deg.C for 72 h, and cooling to room temperature. Washed by 15 mL of deionized water and dried in vacuum at 60 ℃ for 24 h to obtain PyDTDO-3.
40 mg of PyDTDO-3 was weighed, 10 mL of deionized water, 1.2 mL of chloroplatinic acid, and 10 mL of DMF were added, heated at 70 ℃ for 10 h, and cooled to room temperature. Washing with 15 mL of deionized water, vacuum drying at 60 ℃ for 24 h, and annealing at 125 ℃ for 1 h in an Ar atmosphere to obtain 3% Pt/PyDTDO-3.
Example 2
Similar to example 1, except that 2 mL of chloroplatinic acid was measured out, the obtained sample was named 5% Pt/PyDTDO-3.
Example 3
Similar to example 1, except that 2.8 mL of chloroplatinic acid was measured out, the obtained sample was named 7% Pt/PyDTDO-3.
Example 4
Similar to example 1, except that 3.6 mL of chloroplatinic acid was measured out, the obtained sample was named 9% Pt/PyDTDO-3.
Comparative example 1
Weighing 5 mmol of dithiophene [3,2-B:2 ', 3' -D ] thiophene and 15 mmol of m-chloroperoxybenzoic acid according to a molar ratio, adding the dithiophene [3,2-B:2 ', 3' -D ] thiophene and the m-chloroperoxybenzoic acid into a round-bottom flask, adding 30 mL of anhydrous dichloromethane, heating at 20 ℃ for 24 hours, and cooling to room temperature. Petroleum ether in a volume ratio of 2: 1: and carrying out column chromatography on dichloromethane, and carrying out vacuum drying at 50 ℃ for 24 h to obtain 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-phenylether were weighed in terms of molar ratio. Heating at 120 deg.C for 72 h, and cooling to room temperature. Washed by 15 mL of deionized water and dried in vacuum at 60 ℃ for 24 h to obtain PyDTDO-3.
Comparative example 2
Weighing 5 mmol of dithiophene [3,2-B:2 ', 3' -D ] thiophene and 15 mmol of m-chloroperoxybenzoic acid according to a molar ratio, adding the dithiophene [3,2-B:2 ', 3' -D ] thiophene and the m-chloroperoxybenzoic acid into a round-bottom flask, adding 30 mL of anhydrous dichloromethane, heating at 20 ℃ for 24 hours, and cooling to room temperature. Petroleum ether in a volume ratio of 2: 1: and carrying out column chromatography on dichloromethane, and carrying out vacuum drying at 50 ℃ for 24 h to obtain 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-phenylether were weighed in terms of molar ratio. Heating at 120 deg.C for 72 h, and cooling to room temperature. Washed by 15 mL of deionized water and dried in vacuum at 60 ℃ for 24 h to obtain PyDTDO-3.
40 mg of PyDTDO-3 was weighed, 20 mL of deionized water and 2.8 mL of chloroplatinic acid were added, heated at 70 ℃ for 10 h, and cooled to room temperature. Washing with 15 mL of deionized water, drying in vacuum at 60 ℃ for 24 h, and annealing at 125 ℃ for 1 h under Ar atmosphere to obtain DMF-free 7% Pt/PyDTDO-3 (noted as 7% Pt/PyDTDO-3-DF).
Material characterization
The result of XRD spectrum is as follows:
FIG. 1 is an XRD pattern of the component samples, and it can be observed that all samples except 9% Pt/PyDTDO-3 have a relatively distinct diffraction peak at about 26 deg., which represents pi-pi stacking between conjugated polymers. However, the diffraction peak of 9% Pt/PyDTDO at about 26 ℃ is obviously reduced or disappeared compared with other samples, which is caused by that the pi-pi conjugation in the structure is hindered by adding excessive chloroplatinic acid. In addition, no diffraction peak as distinct as a crystal was observed in all samples, indicating that the conjugated polymer synthesized was amorphous.
SEM and TEM pictures:
FIG. 2 shows SEM images of the prepared PyDTDO-3 (FIG. 2 (a)), 7% Pt/PyDTDO-3 (FIG. 2 (b)), and 7% Pt/PyDTDO-3-DF (FIG. 2 (c)) photocatalytic materials. As shown in the figure, pure PyDTDO-3 presents a form of rod-shaped and spherical mixed growth, and compared with other SEM pictures, the Pt loading has no influence on the appearance of the PyDTDO-3. In addition, images of mixed growth of the rods and spheres were observed from the TEM images of PyDTDO-3 (FIG. 2 (d) -FIG. 2 (f)) and 7% Pt/PyDTDO-3 (FIGS. 2 (g) - (i)). The Pt loading is clearly seen in the HRTEM image of 7% Pt/PyDTDO-3 (FIG. 2 (i)).
FTIR spectrum results:
FIG. 3 is an FTIR spectrum of a sample of components used to determine the material composition and surface functional groups of a photocatalyst. As shown, there are mainly four types of peaks, 2917 cm each-1、1655 cm-1、1473 cm-1、1312 cm-1And 1136 cm-1. Wherein 2917 cm-11655 cm, which is the stretching vibration peak of C-H bond-1Is the stretching vibration peak of aromatic ring (C = C), 1473 cm-1Belongs to the stretching vibration of thiophene (C-S-C), 1312 cm-1And 1136 cm-1Stretching vibration attributed to sulfone group (O = S = O). Another 9% Pt/PyDTDO-3 sample was observed at 1022 cm-1 A peak was present, belonging to Pt-OH, which also corresponds to the results in XRD. In addition from the figureIt can be observed that different ratios of Pt/PyDTDO-3 and the support PyDTDO-3 show similar stretching and bending vibrations, indicating that the Pt loading hardly affects the architecture of PyDTDO-3.
XPS spectrum result:
FIG. 4 is an XPS spectrum that may be used to characterize the composition of matter and valence states 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 status of the elements therein. It can be seen from FIG. 4 that C, O, S and Br elements were present in all samples, and the presence of Br elements indicates incomplete polymerization and the presence of Br end groups. The presence of Pt element can be seen from the full spectrum of 7% Pt/PyDTDO-3 and 7% Pt/PyDTDO-3-DF, further illustrating the successful loading of Pt.
FIG. 5 shows high resolution spectra of PyDTDO-3, 7% Pt/PyDTDO-3 and 7% Pt/PyDTDO-3-DF. (a) The figure is an O1S XPS spectrum with the peak at 532.1 eV representing the presence of an O = S bond. (b) The figure is a C1 s XPS spectrum with the peak at 284.9 eV representing the presence of C = C, indicating the presence of aromatic ring backbone in the CPs. (c) The graph is an S2 p spectrum, which can be divided into three groups of peaks. Peaks around 169 eV correspond to the S = O bond, 168 eV to C-S-C in thiophene, and 165 and 164 eV to S2 p (3 d)3/2) And S2 p (3 d)5/2) All belong to S-S cross-links. (d) The graphs show XPS spectra for 7% Pt/PyDTDO-3 and 7% Pt/PyDTDO-3-DF Pt 4 f. In 7% Pt/PyDTDO-3, two peaks appear at binding energies of 74.9 and 71.6 eV, indicating the formation of Pt-O coordination bonds. Whereas in 7% Pt/PyDTDO-3-DF, in addition to the Pt-O coordination bonds of 78.4 and 72.7 eV, there were also Pt-Pt bonds of 75.6 and 70.8 eV which were associated with Pt during the reaction4+Pt produced by reduction of precursor0And correspondingly. These results all corresponded to the results in FTIR.
DRS spectrogram result:
FIG. 6 is a UV-Vis DRS spectrum in which all CPs exhibit a broad UV-visible absorption range of 250 to 800 nm due to the high conjugation of the support PyDTDO-3, which creates a large electron delocalized orbital overlap 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 have better light absorption characteristics. The 9% loading of PyDTDO-3 may result in a decrease in the absorption strength as compared to the 7% loading of PyDTDO-3 due to a decrease in its atomic utilization. In addition, the Pt is loaded, so that the absorption intensity of visible light can be enhanced, and the activity of hydrogen production by visible light photolysis can be improved. While a high level of DTDO in PyDTDO-3 is also responsible for its narrower band gap.
Performance testing
Adding 20 mg of Pt/PyDTDO-3 prepared in different embodiments into a reaction bottle, adding 90 mL of deionized water, 10 mL of DMF and 17 g of ascorbic acid (sacrificial reagent), introducing Ar gas into the reaction bottle for 30 min, magnetically stirring for about 30 min, and closing the Ar gas to seal the reaction bottle. Pumping out gas in the reaction bottle every 60 min, and introducing the gas into a gas chromatograph for detection.
Fig. 7 is a graph of the performance of photolyzing water to produce hydrogen of each component, and fig. 7(a) shows that the hydrogen production of the material is gradually increased along with the increase of the illumination time, and shows a linear increasing trend. FIG. 7(b) shows the H for PyDTDO-3, 3% Pt/PyDTDO-3, 5% Pt/PyDTDO-3, 7% Pt/PyDTDO-3-DF and 9% Pt/PyDTDO-32The formation rates were 1.72, 2.16, 2.44, 3.91, 2.42 and 3.45 mmol. multidot.g, respectively-1·h-1. The combined graphs show that when the Pt loading reaches 7%, the photocatalytic activity of the material is the highest, which is 2.3 times and 1.6 times 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 availability of Pt atoms. In addition, under the condition of optimal loading, the effect of no DMF in the synthesis process on the hydrogen production is also great, which shows the important function of DMF in the Pt atom loading process. FIG. 7(c) is a hydrogen generation cycle chart of 7% Pt/PyDTDO-3, and it can be observed that the hydrogen generation performance of 7% Pt/PyDTDO-3 is not greatly reduced and remains stable after 30h (5 times) of cycle experiments. And it can be observed from fig. 7(d) and fig. 8 that XRD and FTIR patterns of 7% Pt/PyDTDO-3 before and after the photocatalytic reaction are hardly changed, further proving that 7% Pt/PyDTDO-3 has a certain stability.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications 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 are within the scope of the present invention.
Claims (8)
1. A preparation method of conjugated polymer loaded metal platinum nanoparticles is characterized by comprising the following steps:
adding dithiophene [3,2-B:2 ', 3' -D ] thiophene and m-chloroperoxybenzoic acid serving as raw materials into a round-bottom flask, adding anhydrous dichloromethane, heating, cooling, carrying out column chromatography, and carrying out vacuum drying to obtain DTDO;
in N2Under the condition, adding the DTDO, the 1,3,6, 8-tetrabromopyrene, the anhydrous potassium carbonate, the tris (dibenzylideneacetone) dipalladium, the pivalic acid, the tris (o-methoxyphenyl) phosphorus and the anhydrous o-dimethyl ether obtained in the step (1), heating, cooling, washing and drying to obtain PyDTDO-3;
adding deionized water and chloroplatinic acid into the PyDTDO-3,N,Nand (2) heating, cooling, washing, drying and annealing in an Ar atmosphere to obtain the Pt/PyDTDO-3 material for photocatalytic hydrogen evolution of the conjugated polymer loaded Pt.
2. The method for preparing the conjugated polymer supported metal platinum nanoparticles as claimed in claim 1, wherein in the step (1), the molar ratio of the bithiophene [3,2-B:2 ', 3' -D ] thiophene to the m-chloroperoxybenzoic acid is (1-10): (10-20); adding 20-50 mL of anhydrous dichloromethane into 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 method for preparing the conjugated polymer supported metal platinum nanoparticles as claimed in claim 1, wherein in the step (1), the heating temperature is 10-40 ℃ and the heating time is 20-30 h; the column chromatography is carried out according to the volume ratio (1-5): petroleum ether of (1-5): dichloromethane is eluent; the temperature of the vacuum drying is 20-80 ℃, and the drying time is 20-30 h.
4. The method for preparing the conjugated polymer supported metal platinum nanoparticle as claimed in claim 1, wherein the molar ratio of DTDO, 1,3,6, 8-tetrabromopyrene, anhydrous potassium carbonate, tris (dibenzylideneacetone) dipalladium, pivalic acid and tris (o-methoxyphenyl) phosphorus in step (2) is as follows: (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 mL of anhydrous o-dimethyl ether into 1 mmol of total raw materials, wherein the total raw materials comprise dithiophene [3,2-B:2 ', 3' -D ] thiophene and m-chloroperoxybenzoic acid.
5. The method for preparing the conjugated polymer supported metal platinum nanoparticles as claimed in claim 1, wherein the heating temperature in the step (2) is 80-150 ℃, and the heating time is 60-80 h; washing with 10-30 mL of deionized water; the temperature of the vacuum drying is 20-80 ℃, and the drying time is 20-30 h.
6. The method 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; 10-30 mL of deionized water is used for washing; the temperature of the vacuum drying is 20-80 ℃, and the drying time is 20-30 h; the annealing temperature in the Ar gas atmosphere is 80-150 ℃, and the annealing time is 0.5-2 h.
7. The conjugated polymer supported Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3 prepared based on any one of the methods of claims 1-6.
8. Use of the conjugated polymer supported Pt photocatalytic hydrogen evolution material Pt/PyDTDO-3 according to claim 1 or claim 7 for the preparation of a hydrogen evolution photocatalyst.
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