CN115770589A - Ultra-small stable platinum-cobalt nanoparticle catalyst, preparation method thereof and application thereof in selective hydrogenation - Google Patents
Ultra-small stable platinum-cobalt nanoparticle catalyst, preparation method thereof and application thereof in selective hydrogenation Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 76
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
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- 239000002904 solvent Substances 0.000 claims description 9
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- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 229910002837 PtCo Inorganic materials 0.000 abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
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- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 125000003636 chemical group Chemical group 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000005011 phenolic resin Substances 0.000 abstract 1
- 229920001568 phenolic resin Polymers 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 9
- 229910000531 Co alloy Inorganic materials 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
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- 239000002082 metal nanoparticle Substances 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 3
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 229910002451 CoOx Inorganic materials 0.000 description 1
- 241001092410 Francoa Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229940114055 beta-resorcylic acid Drugs 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to the technical field of nano material preparation, and provides a platinum-cobalt nano particle catalyst, a preparation method and application thereof in selective hydrogenation. The stability of the ultra-small platinum-cobalt nanoparticles in high-temperature high-pressure liquid phase reaction is improved by utilizing the combined action of physical clamping and chemical group adsorption. Phenolic resin spheres were first formed on top of the silica spheres by a sol-gel method, while the reduction of the Pt nanoparticles was carried out. And then coating the silica spheres again, and the silica sphere coating technology can prevent agglomeration of the nanoparticles during the subsequent calcination process. After calcination, the double-layered silica spheres were etched, and the carbon material was etched with nitric acid so that the Pt nanoparticles were sufficiently exposed. And then, co salt soaking is carried out, so that the ultra-small PtCo nano-particle catalyst with excellent catalytic performance is formed.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a platinum-cobalt nano particle catalyst, a preparation method thereof and application thereof in selective hydrogenation.
Background
Today, as petroleum resources are reduced and the demand for petroleum from emerging economies increases, it is critical to develop energy-efficient processes to achieve sustainable production of fuels and chemicals. Biofuel is currently the only sustainable source of organic carbon. Among them, 5-hydroxymethylfurfural (5-HMF) is a biomass molecule which can be efficiently obtained directly from cellulose (total yield of 75%) [1,2] The 2,5-Dimethylfuran (DMF) molecule has the characteristics of high energy density, high octane number, capability of being mixed and dissolved with the existing gasoline fuel and the like [3,4] . Therefore, selective hydrodeoxygenation of HMF to DMF has attracted considerable attention by researchers [5] . However, the catalytic reaction is difficult, and the problems of high reaction temperature, high pressure and low catalytic performance are generally existed, and simultaneously, a large amount of by-products are generated [3] . The design and preparation of the long-acting catalyst with high selectivity and high activity have important practical application value and theoretical significance for realizing the industrial production of DMF (dimethyl formamide) by the hydrogenation and deoxidation of the biomass HMF.
In the process of producing DMF by HMF hydrodeoxygenation, the activity of a non-noble metal catalyst is generally lower, and the process of producing DMF by HMF hydrodeoxygenation on non-noble metals is a reaction which is less explored [6-8] . Noble metal catalysis is a widely developed HMF hydrogenation process [9-11] . Among them, the platinum-based catalyst is the most widely used catalyst in the hydrogenation reaction, and thus is a promising choice due to its excellent activity. And the platinum-cobalt alloy shows the characteristic of selective hydrogenation to carbon-oxygen bonds. Calculation and experiments show that the platinum-cobalt alloy can effectively improve the selective hydrodeoxygenation of carbon-oxygen bonds in the catalytic reaction. The research indicates that the metal oxide layer formed on the outer surface of the platinum-cobalt alloy can reduce the interaction between the catalyst and furan ring and prevent DMF (dimethyl formamide) excessive hydrogenation and secondary ring opening by-product generation [12] . The prior technical proposal mainly adopts>The PtCo alloy with the particle size of 3nm is used for hydrogenation catalysis. In 2008, the 4.8nm PtCo alloy prepared by Shik Chi Tsang by using a solvothermal method shows good selectivity on C = O [16] . In 2014, germany Ma Puxue, ferdiSch fur teaching group of coal chemical institute, encapsulating platinum-cobalt alloy nanoparticles of 3.6 +/-0.7 nm in a carbon shell by using 2,4-dihydroxybenzoic acid and formaldehyde polymeric hollow spheres, and obtaining a catalytic yield of more than 98% by using the catalyst under hydrogen gas of 180 ℃ and 10 atmospheres [17] . In 2018, congWang et al prepared PtCo with a diameter of 4nm 3 The alloy particles are uniform, and transitional hydrogenation is effectively inhibited; research shows that the alloy catalyst can stabilize the adsorption of aldehyde, prevent furan from falling on the surface of the catalyst, and observe that a CoOx monolayer is formed on the surface of the catalyst; the coating inhibits the interaction of furan rings with the catalyst surface [18] 。
The alloy nanoparticles with larger size in the prior art have smaller surface area, cannot expose more active sites, and need higher catalytic conditions. Thus, reducing the size of a nanoparticle to a few nanometers or even sub-nanometers can significantly increase its surface atom to bulk atom ratio, which can affect the overall energy and fundamental properties of the nanoparticle, thereby affecting its catalytic performance in the reaction. Especially when the particle diameter of the metal is reduced to be about 1nm, the electronic state and coordination number of surface atoms of the metal can be greatly changed, so that the chemical adsorption between the metal and a guest molecule is mutated, and the catalytic performance is greatly improved [13-15] .2016 LichengBai et al also showed that the control of ultra-small platinum nanoparticles<3 nm) can realize the optimization of the catalytic activity of the catalyst, and greatly reduce the difficulty of catalytic reaction; the prepared 1.2nm ultra-small platinum particles show quinoline hydrogenation performance with high selectivity and high activity; the catalytic conversion with 99 percent yield can be realized at normal temperature and normal pressure by hydrogenation reaction at high temperature and high pressure [13] . Therefore, designing and preparing the ultra-small PtCo alloy nanoparticle catalyst inevitably reduces the reaction difficulty of preparing DMF (dimethyl formamide) by hydrogenation deoxidation of HMF (high molecular weight) and improves the selectivity of the DMF. However, one of the major challenges with the use of ultra-small metal nanoparticle catalysts is preventing goldThe nano-particles are leached from the carrier, and particularly the growth of the metal nano-particles under severe conditions. It is a key issue how to maintain long-term stability of the catalyst while preparing ultra-small metal nanoparticles to reduce the difficulty of the reaction.
[1]Chen,S.,Wojcieszak,R.,Dumeignil,F.,et al.Chemical Reviews,2018,118(22):11023-11117.
[2]Bozell,J.J.and Petersen,G.R.Green Chemistry,2010,12(4):539-554.
[3]Wang,H.,Zhu,C.,Li,D.,et al.Renewable&Sustainable Energy Reviews,2019,103:227-247.
[4]Daniel,R.,Xu,H.,Wang,C.,et al.Applied Energy,2012,98:59-68.
[5]Huber,G.W.,Iborra,S.,and Corma,A.Chemical Reviews,2006,106(9):4044-4098.
[6]ChenMY,ChenCB,ZadaB,etal.GreenChemistry,2016,18(13):3858-3866.
[7]SolankiBS,RodeCV.GreenChemistry,2019,21(23):6390-6406.
[8]AkmazS,EsenM,SezginE,etal.TheCanadianJournalofChemicalEngineering,2020,98(1):138-146.
[9]TzengTW,LinCY,PaoCW,etal.FuelProcessingTechnology,2020,199:106225.
[10]MhadmhanS,FrancoA,PinedaA,etal.ACSSustainableChemistry&Engineering,2019,7(16):14210-14216.
[11]LiZ,ZhuC,WangH,etal.ACSSustainableChemistry&Engineering,2021,9(18):6355-6369.
[12]Luo,J.,Yun,H.,Mironenko,A.V.,et al.ACS Catalysis,2016,6(7):4095-4104.
[13]Bai,L.,Wang,X.,Chen,Q.,Ye,Y.,et al.Angewandte Chemie International Edition,2016,55:15656-15661.
[14]Bai,L.,Zhang,S.,Chen,Q.,et al.ACS Applied Materials&Interfaces,2017,9(11):9710-9717.
[15]Bai,L.,Wang,X.,Tang,S.,et al.Advanced Materials,2018,30(40):1803641.
[16]Tsang,S.C.,Cailuo,N.,Oduro,W.,et al.ACS Nano,2008,2(12):2547-2553.
[17]Wang,G.H.,Hilgert,J.,Richter,F.H.,et al.Nature Materials,2014,13(3):293-300.
[18]Wang C,Luo J,Liao V,et al.Catalysis Today,2018,302:73-79.
Disclosure of Invention
The invention provides a preparation method of an ultra-small stable platinum-cobalt nanoparticle catalyst, aiming at solving the problem of low efficiency of the selective hydrogenation reaction for catalyzing 5-hydroxymethylfurfural.
The preparation method of the ultra-small stable platinum-cobalt nanoparticle catalyst comprises the following steps:
s1: dispersing silicon dioxide spheres in a solvent, adding resorcinol, formaldehyde and a platinum solution into the solvent, stirring, heating, reacting, centrifuging after reaction, washing, and dispersing in water;
s2: adding water, ethanol and ammonia water into the aqueous solution obtained in the step S1 and tetraethyl silicate to form a mixed solution, stirring, centrifuging, drying, calcining, etching by using strong base to remove silicon dioxide, and cleaning;
s3: dissolving the product obtained in S2 in water, adding CoCl 2 Stirring, heating, reacting, centrifuging, precipitating and washing to obtain the ultra-small stable platinum-cobalt nanoparticle catalyst.
Furthermore, the mass ratio of the resorcinol, the formaldehyde and the platinum in the platinum solution in S1 is (0.5-3.6): (0.4-355): 0.3-130).
Further, the reaction condition in S1 is that the mixture is stirred for 10-12 hours at room temperature, then the temperature is raised to 60-80 ℃, and the mixture is stirred for 8-10 hours.
Furthermore, the mass ratio of the tetraethyl silicate to the absolute ethyl alcohol to the ammonia water is (4.5-9) to (17-42) to (2.6-25.7). The water is a solvent.
Further, the calcination time is 2-6 h, and a mixed gas of nitrogen and hydrogen is used as a protective atmosphere, wherein the volume ratio of the nitrogen to the hydrogen is (80-90): (1-10).
Furthermore, the ratio of the cobalt in S3 to the platinum in the platinum solution in S1 is (0.02-0.5) to (0.001-0.2).
Further, the reaction condition in S3 is that the mixture is heated and stirred for 3 to 7 hours under the condition of 30 to 70 ℃.
The invention aims to provide an ultra-small stable platinum-cobalt nanoparticle catalyst which is prepared by the preparation method of any one of the ultra-small stable platinum-cobalt nanoparticle catalysts.
An object of the invention is to provide an application of the ultra-small stable platinum-cobalt nanoparticle catalyst in selective hydrogenation of 5-hydroxymethylfurfural.
The invention provides an ultra-small stable platinum-cobalt nanoparticle catalyst. Compared with the prior art, the ultra-small stable platinum-cobalt nanoparticle catalyst can realize a hollow spherical structure, can realize ultra-small grain size, and simultaneously realize the stability of platinum-cobalt alloy nanoparticles, thereby avoiding the agglomeration of the nanoparticles in a circulation experiment; the catalytic performance of the material is greatly improved.
Drawings
FIG. 1 is a flow chart of a method for preparing an ultra-small stable platinum-cobalt nanoparticle catalyst provided by the invention;
FIG. 2 is a TEM image of Pt nanoparticles embedded in a hollow carbon layer, provided in examples 1-3 of the present invention, wherein the upper right corner is a distribution graph of particle size;
FIG. 3 is a graph of the hydrogenation performance of the ultra-small stable platinum-cobalt nanoparticle catalysts provided in examples 1-3 of the present invention;
fig. 4 is a graph of hydrogenation performance of ultra-small stable platinum-cobalt nanoparticle catalysts provided in examples 2, four to six of the present invention.
FIG. 5 is a chart of the cyclic hydrogenation performance of the ultra-small stable platinum-cobalt nanoparticle catalyst provided in example 7 of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, specific embodiments accompanied with figures are described in detail below, but the present invention is not to be construed as limiting the implementable range thereof.
Referring to the description of fig. 1, the preparation method of the ultra-small stable platinum-cobalt nanoparticle catalyst comprises the following steps:
s1: dispersing silica spheres in a solvent, adding resorcinol, formaldehyde and a platinum solution into the solvent, stirring, heating, reacting, centrifuging, washing, and dispersing in water, wherein the solvent in S1 is absolute ethyl alcohol and water in a volume ratio of 1: (2-3) mixing to form a mixed solution;
s2: adding water, ethanol and ammonia water into the aqueous solution obtained in the step S1 and tetraethyl silicate to form a mixed solution, stirring, centrifuging, drying, calcining, etching by using strong base to remove silicon dioxide, and cleaning;
s3: and (3) dissolving the product obtained in the step (S2) in water, adding cobalt, stirring, heating, reacting, centrifuging, precipitating and washing to obtain the ultra-small stable platinum-cobalt nanoparticle catalyst.
Examples one to nine examples relate to the following concentrations of substances:
tetraethyl silicate 0.933g/ml; 0.79g/ml of absolute ethyl alcohol; formaldehyde 1.067g/ml; the concentration of Pt in the Pt solution is 0.02g/ml; resorcinol 1.27g/m; 0.91g/ml ammonia water
Example one
(1) Preparation of silica spheres: 10mL of tetraethyl silicate were dissolved in a solution containing 10mL of H 2 O, 30ml of ethanol and 1ml of ammonia water (25-28 percent). After stirring for 12h, the product was collected by centrifugation and dried with ethanol and water, respectively.
(2) Reduction of crosslinked polymer and Pt nanoparticles: 100mg of silica spheres were dispersed in 10ml of ethanol, 30ml of water, followed by addition of 20mg of resorcinol, 100ul of formaldehyde (37 wt%), 0.1ml of Pt (0.1M) solution. The mixed solution is firstly stirred for 12 hours at room temperature, then the temperature is raised to 60-80 ℃, and the stirring is carried out for 8-10 hours. After the reaction, the precipitate was obtained by centrifugation, and washed with water and ethanol and dried.
(3) And (3) calcining the ultra-small Pt nano particles at high temperature: dissolving the crosslinked polymer and Pt nanoparticles obtained in step (2) with 1mL of tetraethyl silicate in 3mL of H 2 O, 10ml of ethanol and 1ml of ammonia water (the mass fraction is 25-28 percent). After stirring for 5h, the product was collected by centrifugation and dried with ethanol and water, respectively. Then calcining, and adopting a mixed gas of nitrogen and hydrogen, wherein the volume ratio of the nitrogen to the hydrogen is 9:1, and the temperature is 600 DEGAnd keeping the temperature for 1h.
(4) Etching of the silicon dioxide balls: and (3) adding 10M NaOH solution into the product obtained in the step (3), stirring for 3 hours, then stirring for 4 hours at 80 ℃, and etching to remove the double-layer silicon dioxide spheres. And cleaning with nitric acid to finally obtain the Pt nano-particles clamped and embedded in the hollow carbon layer.
(5) Co alloying of Pt nanoparticles: the Pt nanoparticles embedded in the hollow carbon layer were dissolved in 3ml of water, and 8mg of CoCl was added 2 And heating and stirring for 6h at 70 ℃, centrifuging to obtain a precipitate after the reaction is finished, washing for 1 time by using water and ethanol, and finally obtaining the PtCo nano-particle catalyst clamped in the hollow carbon layer.
Referring to fig. two a, tem in the specification, it can be seen that a PtCo alloy having an average particle size of 0.9nm was prepared.
Example two
(1) Preparation of silica spheres: 10mL of tetraethyl silicate were dissolved in a solution containing 10mL of H 2 O, 30ml of ethanol and 1ml of ammonia water (25-28 percent). After stirring for 12h, the product was collected by centrifugation and dried with ethanol and water, respectively.
(2) Reduction of crosslinked polymer and Pt nanoparticles: 100mg of silica spheres were dispersed in 10ml of ethanol, 30ml of water, followed by addition of 20mg of resorcinol, 100ul of formaldehyde (37 wt%), 0.6ml of Pt (0.1M) solution. The mixed solution is firstly stirred for 12 hours at room temperature, then the temperature is raised to 60-80 ℃, and the stirring is carried out for 8-10 hours. After the reaction, the precipitate was obtained by centrifugation, and washed with water and ethanol and dried.
(3) High-temperature calcination of ultra-small Pt nanoparticles the crosslinked polymer and Pt nanoparticles obtained in step (2) were dissolved in 3mL of H with 1mL of tetraethyl silicate 2 O, 10ml of ethanol and 1ml of ammonia water (the mass fraction is 25-28 percent). After stirring for 5h, the product was collected by centrifugation and dried with ethanol and water, respectively. Then calcining, adopting mixed gas of nitrogen and hydrogen, wherein the ratio of the nitrogen to the hydrogen is 9:1, and keeping the temperature at 600 ℃ for 1h.
(4) Etching of the silicon dioxide balls: and (3) adding 10M NaOH solution into the product obtained in the step (3), stirring for 3 hours, then stirring for 4 hours at 80 ℃, and etching to remove the double-layer silicon dioxide spheres. And cleaning with nitric acid to finally obtain the Pt nano-particles clamped and embedded in the hollow carbon layer.
(5) Co alloying of Pt nanoparticles: the Pt nanoparticles clipped to the hollow carbon layer were dissolved in 3ml of water, and 50mg of CoCl was added 2 And heating and stirring for 6h at 70 ℃, centrifuging to obtain a precipitate after the reaction is finished, washing for 1 time by using water and ethanol, and finally obtaining the PtCo nano-particle catalyst clamped in the hollow carbon layer.
Referring to the figure b, tem, it can be seen that a PtCo alloy with an average particle size of 1.2nm was prepared.
EXAMPLE III
(1) Preparation of silica spheres: 10mL of tetraethyl silicate were dissolved in a solution containing 10mL of H 2 O, 30ml of ethanol and 1ml of ammonia water (25-28 percent). After stirring for 12h, the product was collected by centrifugation, washed with ethanol and water, and dried.
(2) Reduction of crosslinked polymer and Pt nanoparticles: 100mg of silica spheres were dispersed in 10ml of ethanol, 30ml of water, followed by addition of 20mg of resorcinol, 100ul of formaldehyde (37 wt%), and 1.8ml of Pt (0.1M) solution. The mixed solution is firstly stirred for 12 hours at room temperature, then the temperature is raised to 60-80 ℃, and the stirring is carried out for 8-10 hours. After the reaction, the precipitate was obtained by centrifugation, and washed with water and ethanol and dried.
(3) And (3) calcining the ultra-small Pt nano particles at high temperature: dissolving the crosslinked polymer and Pt nanoparticles obtained in step (2) with 1mL of tetraethyl silicate in 3mL of H 2 O, 10ml of ethanol and 1ml of ammonia water (the mass fraction is 25-28 percent). After stirring for 5h, the product was collected by centrifugation, washed with ethanol and water, and dried. Then calcining, adopting mixed gas of nitrogen and hydrogen, wherein the ratio of nitrogen to hydrogen is 9:1, and keeping the temperature at 600 ℃ for 1h.
(4) Etching of the silicon dioxide balls: and (3) adding 10M NaOH solution into the product obtained in the step (3), stirring for 3 hours, then stirring for 4 hours at 80 ℃, and etching to remove the double-layer silicon dioxide spheres. And cleaning with nitric acid to finally obtain the Pt nano-particles clamped and embedded in the hollow carbon layer.
(5) Co alloying of Pt nanoparticles: the Pt nanoparticles embedded in the hollow carbon layer were dissolved in 3ml of water, and 130mg of CoCl was added 2 Heating and stirring for 6h at 70 ℃, after the reaction is finished,centrifuging to obtain a precipitate, and washing with water and ethanol for 1 time to obtain the PtCo nano-particle catalyst clamped in the hollow carbon layer.
Referring to the figure c of the specification, tem shows that a PtCo alloy having an average particle size of 2.3nm is prepared.
Evaluation of catalyst Performance
The catalysts of examples one to three were compared for performance. The reaction conditions are as follows: 20mg HMF, 80mg platinum cobalt nanoparticle catalyst and 0.2MPa hydrogen for 2 hours, the reaction temperature is controlled at 100 ℃, and the reaction solvent is 1ml toluene.
As a result, as shown in the third figure, it can be seen that the platinum-cobalt nanoparticle catalyst of 1.2nm exhibited the best hydrogenation performance.
Example four:
the same procedure as in example two, with CoCl added 2 Mass 6mg, pt: the molar ratio of Co was 3:1.
Example five:
the same procedure as in example two, with CoCl added 2 Mass 17mg, pt was obtained: the molar ratio of Co was 1:1.
Example six:
the same procedure as in example two, with CoCl added 2 Mass 85mg, pt: the molar ratio of Co was 1:5.
Comparison of catalytic Performance
Example two, four to six were compared for performance. The reaction conditions are as follows: 20mg HMF, 80mg platinum cobalt nanoparticle catalyst and 0.2MPa hydrogen for 2 hours, the reaction temperature is controlled at 100 ℃, and the reaction solvent is 1ml of toluene.
As a result, as shown in the fourth drawing, it can be seen that the particle diameter is 1.2nm, pt: co =1: the catalyst of 3 showed the best catalytic performance.
Example seven:
the cycle hydrogenation test was performed on example two, under the same conditions as described above. The results are shown in FIG. V, particle size 1.2nm, pt: co =1: the catalyst of 3 has little change of performance after five times of circulation and good circulation stability.
The invention provides an ultra-small stable platinum-cobalt nanoparticle catalyst. Compared with the prior art, the ultra-small stable platinum-cobalt nanoparticle catalyst can realize a hollow spherical structure, can realize ultra-small grain size, and simultaneously realizes the clamping and embedding of platinum-cobalt alloy nanoparticles, thereby avoiding the agglomeration of the nanoparticles in a circulation experiment; the catalytic performance of the material is greatly improved.
Claims (10)
1. A preparation method of an ultra-small stable platinum-cobalt nanoparticle catalyst is characterized by comprising the following steps:
s1: dispersing silicon dioxide spheres in a solvent, adding resorcinol, formaldehyde and a platinum solution into the solvent, stirring, heating, reacting, centrifuging after reaction, washing and dispersing in water;
s2: adding water, ethanol and ammonia water into the aqueous solution obtained in the step S1 and tetraethyl silicate to form a mixed solution, stirring, centrifuging, drying, calcining, etching by using strong base to remove silicon dioxide, and cleaning;
s3: dissolving the product obtained in S2 in water, adding CoCl 2 Stirring, heating, reacting, centrifuging, precipitating and washing to obtain the ultra-small stable platinum-cobalt nanoparticle catalyst.
2. The method for preparing the ultra-small stable platinum-cobalt nanoparticle catalyst as claimed in claim 1, wherein the solvent in S1 is absolute ethanol and water in a volume ratio of 1: (2-3) mixing to form a mixed solution.
3. The method of claim 1, wherein the mass ratio of said resorcinol, said formaldehyde and said platinum in said platinum solution in S1 is (0.5-3.6): (0.4-355): (0.3-130).
4. The preparation method of the ultra-small stable platinum-cobalt nanoparticle catalyst as claimed in claim 1, wherein the reaction condition in S1 is stirring at room temperature for 12h, then raising the temperature to 60-80 ℃, and stirring for 8-10 h.
5. The method of claim 1, wherein the amount ratio of the tetraethyl silicate, the absolute ethanol and the ammonia water is (4.5-9): (17-42): (2.6-25.7).
6. The preparation method of the ultra-small stable platinum-cobalt nanoparticle catalyst as claimed in claim 1, wherein the calcination time is 2-6 h, and a mixed gas of nitrogen and hydrogen is used as a protective atmosphere, wherein the volume ratio of the nitrogen to the hydrogen is (80-90): (1-10).
7. The method of claim 1, wherein the ratio of the amount of cobalt in S3 to the amount of platinum in the platinum solution in S1 in S3 is (0.02-0.5) to (0.001-0.2).
8. The method for preparing the ultra-small stable platinum-cobalt nanoparticle catalyst as claimed in claim 1, wherein the reaction condition in S3 is heating and stirring for 3-7 h at 30-70 ℃.
9. An ultra-small stable platinum-cobalt nanoparticle catalyst, which is characterized by being prepared by the preparation method of the ultra-small stable platinum-cobalt nanoparticle catalyst according to any one of claims 1 to 8.
10. Use of the ultrasmall stable platinum-cobalt nanoparticle catalyst according to claim 9 in selective hydrogenation of 5-hydroxymethylfurfural.
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