CN112473661A - Carbon-doped palladium interstitial nano alloy catalyst and synthesis method thereof - Google Patents
Carbon-doped palladium interstitial nano alloy catalyst and synthesis method thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
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Abstract
The invention discloses a carbon-doped palladium interstitial nano alloy catalyst and a synthesis method thereof, and relates to the technical field of palladium catalysts. The method comprises the following steps of mixing a palladium source, a carbon source and a carbon carrier according to the weight ratio of 1: 1.2-1.5, adding the mixture into an organic solvent for reaction, wherein the reaction temperature is 110-130 ℃; and centrifugally washing and drying the reaction product to obtain the carbon-doped palladium interstitial nano alloy catalyst. The prepared catalyst has extremely high FAOR catalytic performance, and simultaneously has excellent catalytic performance stability and catalyst structure stability. The catalyst can be applied to the anode of a formic acid fuel cell, and can be used as a catalyst to improve the electrooxidation efficiency of formic acid and increase the power density of the formic acid fuel cell; considering that the palladium-based catalyst has wide catalytic performance, the catalyst also has application prospect as a catalyst in industrial organic hydrogenation/dehydrogenation reactions and the like.
Description
Technical Field
The invention relates to the technical field of palladium catalysts, in particular to a carbon-doped palladium interstitial nano alloy catalyst and a synthesis method thereof.
Background
Formic Acid Fuel Cells (FAFCs) are an electrochemical energy conversion device with a high prospect of application in the future. Which has a number of advantages that are associated with,[1]among the many types of fuel cells, the FAFCs have the highest theoretical electromotive force (1.41V); formic acid is a renewable raw material, has the characteristics of low cost, cleanness, no toxicity, low electrolyte membrane permeability and safe storage and transportation, and is an ideal battery fuel; the energy output density of FAFCs is high and is the highest among all types of fuel cells except for hydrogen fuel cells. Currently, the FAFCs still face many technical bottlenecks, and among them, the more prominent problem is the anode electrocatalytic efficiency and stability. Researches find that the palladium-based interstitial nano alloy has higher formic acid electrocatalytic oxidation (FAOR) activity and good stability, and is a FAOR catalyst with high practical value.
At present, the research on palladium-based interstitial type nano-alloy catalyst mainly comprises boron-palladium alloy[2]And phosphorus palladium alloy[3]The two catalysts are mature in synthesis, the FAOR performance of the two catalysts is greatly improved compared with palladium, but the stability of the catalytic performance and the stability of the catalyst structure still have a space for improvement. Carbon atoms and boron/phosphorus atoms have the same properties and can form interstitial alloys with palladium. Because of less selectable carbon dopants, the research on the carbon-palladium gap type alloy is less, and the synthesis method of the carbon-palladium gap type alloy is not common. There is a literature that uses glucose as a carbon source,[4]after being mixed with carbon-supported palladium, the carbon-supported palladium composite nano-alloy is sintered at high temperature to release a small amount of carbon source through glucose decomposition so as to achieve the purpose of doping, thereby synthesizing the carbon-palladium interstitial nano-alloy catalyst. Because the method adopts higher temperature and carbon atoms are unstable in palladium crystal lattices at high temperature, the method is difficult to synthesize the palladium alloy with high carbon phase; furthermore, high temperatures tend to cause agglomeration of the catalyst, resulting in loss of catalytic sites.
Reference documents:
1.A.L.Dicks,D.A.J.Rand.Fuel Cell Systems Explained[M].Hoboken:John Wiley&Sons Ltd,2018.
2.K.Jiang,J.Chang,H.Wang,S.Brimaud,W.Xing,R.J.Behm and W.B.Cai,ACS Appl.Mater.Interfaces,2016,8,7133-7138.
3.G.Yang,Y.Chen,Y.Zhou,Y.Tang and T.Lu,Electrochem.Commun.,2010,12,492-495.
4.C.W.Chan,Y.Xie,N.Cailuo,K.M.Yu,J.Cookson,P.Bishop and S.C.Tsang,Chem.Commun.,2011,47,7971-7973.
disclosure of Invention
The invention aims to solve the technical problem that the carbon-palladium gap type nano alloy catalyst obtained by the existing synthesis method has poor structural stability and catalytic stability.
In order to solve the above problems, the present invention proposes the following technical solutions:
in a first aspect, the invention provides a method for synthesizing a carbon-doped palladium interstitial nano alloy catalyst, which comprises the following steps:
s1, mixing a mixture of a palladium source and a carbon carrier according to the weight ratio of 1: 1.2-1.5, adding the mixture into an organic solvent for reaction, wherein the reaction temperature is 110-130 ℃;
and S2, centrifugally washing and drying the reaction product of S1 to obtain the carbon-doped palladium interstitial nano alloy catalyst.
The further technical proposal is that the dosage of the organic solvent is 0.8 to 1.5 times of the total mass of reactants.
The further technical proposal is that the palladium source is selected from palladium acetate.
The further technical proposal is that the carbon carrier is selected from activated carbon.
The further technical proposal is that the organic solvent is selected from diethylene glycol.
The further technical proposal is that the carbon source is selected from palladium acetate.
The technical scheme is that in the step S1, the specific operation is that palladium acetate and activated carbon are mixed according to a weight ratio of 1: 1.2-1.5, adding the mixture into diethylene glycol, firstly carrying out ultrasonic treatment for 0.5-2h, and then heating the mixture to 110 ℃ and 130 ℃ for reaction.
The further technical proposal is that the ultrasonic frequency is 38-42 kHz; the reaction time is 6-10 h.
The further technical scheme is that the weight ratio of palladium acetate to active carbon is 1: 1.5.
in a second aspect, the invention provides a carbon-doped palladium interstitial nano alloy catalyst, which is prepared by the synthesis method of the carbon-doped palladium interstitial nano alloy catalyst in the first aspect, and the carbon-doped palladium interstitial nano alloy catalyst is applied to anode catalysts of formic acid fuel cells and industrial organic matter hydrogenation/dehydrogenation catalysts.
Compared with the prior art, the invention can achieve the following technical effects:
in the synthesis method of the carbon-doped palladium interstitial nano alloy catalyst, the carbon-palladium interstitial alloy catalyst can be successfully prepared. The catalyst has uniform nano particles, the average particle size of 4.3nm and good monodispersity. The doping amount of carbon in the alloy reaches 0.15 (carbon-palladium atomic ratio). Tests show that the catalyst prepared by the scheme has extremely high FAOR catalytic performance, and simultaneously has excellent catalytic performance stability and catalyst structure stability.
The carbon-doped palladium gap nano alloy catalyst provided by the invention can be applied to the anode of a formic acid fuel cell, and can be used as a catalyst to improve the electrooxidation efficiency of formic acid and increase the power density of the formic acid fuel cell; considering that the palladium-based catalyst has wide catalytic performance, the catalyst also has application prospect as a catalyst in industrial organic hydrogenation/dehydrogenation reactions and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic flow chart of a method for synthesizing a carbon-doped palladium interstitial nanoalloy catalyst according to an embodiment of the present invention;
FIG. 2 is a XRD test spectrum of the catalyst of example 1 of the present invention and a commercial palladium catalyst;
FIG. 3 is a formic acid oxidation curve test result of the catalyst of example 1 of the present invention and a commercial palladium catalyst;
FIG. 4 is the results of I-t curve testing of the catalyst of example 1 of the present invention versus a commercial palladium catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification and the appended claims, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
It is also to be understood that the terminology used in the description of the embodiments of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the embodiments of the invention. As used in the description of embodiments of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
Example 1
Referring to fig. 1, adding palladium acetate (10mg), activated carbon (15mg) and diethylene glycol (20ml) into a round-bottom flask, carrying out ultrasonic treatment for 1h, heating at 120 ℃ for a certain time to carry out reaction, and after the reaction is finished, centrifugally washing and drying a reaction product to obtain the carbon-doped palladium interstitial nano-alloy catalyst.
Wherein the ultrasonic frequency is 40 kHz; the reaction time was 8 h.
It should be noted that, in the preparation process of this embodiment, diethylene glycol is used as a dispersant and a reducing agent, and palladium acetate is both a metal precursor and a carbon doping source. During the heating process, the diethylene glycol can slowly reduce palladium acetate, a large amount of palladium cores are formed in the solution in the early stage of the growth of the palladium nanoparticles, and acetate ions can be decomposed on the surfaces of the palladium cores to form methyl free radicals (CH)3)。·CH3The carbon-hydrogen bonds in the palladium core are further decomposed to form carbon atoms, and the carbon atoms decomposed from the acetate ions can penetrate into the crystal lattice of the palladium core at a proper temperature to form the carbon-palladium gap type alloy nanoparticles. In the scheme, the inventor creatively finds an effective carbon doping source, namely palladium acetate, and the reagent can be used as a metal precursor to obtain palladium nanoparticles and can also be used as a carbon doping source to dope carbon.
The carbon-doped palladium interstitial nano alloy catalyst prepared by the embodiment has uniform nano particles, the average particle size of 4.3nm and good monodispersity. The doping amount of carbon in the alloy reaches 0.15 (carbon-palladium atomic ratio).
The carbon-doped palladium interstitial nanoalloy catalyst prepared in example 1 was now subjected to XRD testing separately from the commercially available commercial palladium catalyst, and the results are shown in fig. 2.
The commercial palladium catalyst is commercially available from Bokel technologies, Inc., Guangzhou at 10% Pd/C.
As can be seen from fig. 2, the XRD diffraction peak of the carbon-doped palladium interstitial nano alloy catalyst of example 1 is shifted to a small angle with respect to the XRD diffraction peak of the commercial palladium catalyst, which indicates that the carbon atoms of the carbon-doped palladium interstitial nano alloy catalyst prepared in this example successfully enter into the crystal lattice of the palladium nanoparticles.
Performance test 2
The carbon-doped palladium interstitial nanoalloy catalyst prepared in example 1 was subjected to formic acid oxidation electrochemical tests separately from a commercially available palladium catalyst.
The test instrument employed the CHI electrochemical workstation of Shanghai Chenghua, Inc.
The test method is as follows:
about 3mg of each catalyst sample was weighed out to prepare a catalyst ink of 2.5mg/ml, and the solution for preparing the ink was nafion membrane solution (D520, 5% by mass, dupont, usa). And ultrasonically treating the prepared ink until the ink is uniformly dispersed. An 8. mu.l portion of the catalyst ink was applied to a glassy carbon electrode, dried by an infrared lamp, and subjected to an electrochemical test in an aqueous solution containing 0.1M perchloric acid and 2M formic acid.
The test results are shown in fig. 3-4.
The formic acid oxidation polarization curve of fig. 3 shows that the carbon-doped palladium interstitial nanoalloy catalyst of this example has excellent formic acid oxidation catalytic activity with a maximum current 16 times that of the commercial palladium catalyst.
The catalyst i-t curve results of fig. 4 show that the carbon-doped palladium interstitial nanoalloy catalyst of this example has higher stability than the commercial palladium catalyst.
Tests show that the catalyst prepared by the embodiment has extremely high FAOR catalytic performance, and simultaneously has excellent catalytic performance stability and catalyst structure stability.
In conclusion, the carbon-doped palladium interstitial nano alloy catalyst of the embodiment has excellent formic acid oxidation catalytic activity, the doping amount of carbon in the alloy reaches 0.15 (carbon-palladium atomic ratio), and the carbon-doped palladium interstitial nano alloy catalyst can be applied to an anode of a formic acid fuel cell, can be used as a catalyst to improve the formic acid electro-oxidation efficiency, and can increase the power density of the formic acid fuel cell. Considering that the palladium-based catalyst has wide catalytic performance, the catalyst of the embodiment has application prospect in catalysts for industrial organic hydrogenation/dehydrogenation and other reactions.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A synthetic method of a carbon-doped palladium gap nano alloy catalyst is characterized by comprising the following steps:
s1, mixing a mixture of a palladium source and a carbon carrier according to the weight ratio of 1: 1.2-1.5, adding the mixture into an organic solvent for reaction, wherein the reaction temperature is 110-130 ℃;
and S2, centrifugally washing and drying the reaction product of S1 to obtain the carbon-doped palladium interstitial nano alloy catalyst.
2. The method for synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 1, wherein the amount of the organic solvent is 0.8-1.5 times of the total mass of the reactants.
3. The method of synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 2 wherein the palladium source is selected from palladium acetate.
4. The method of synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 3 wherein the carbon support is selected from activated carbon.
5. The method of synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 4, wherein the organic solvent is selected from diethylene glycol.
6. The method of synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 5, wherein the carbon source is selected from palladium acetate.
7. The method for synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 6, wherein in step S1, the specific operation is that palladium acetate and activated carbon are mixed according to the weight ratio of 1: 1.2-1.5, adding the mixture into diethylene glycol, firstly carrying out ultrasonic treatment for 0.5-2h, and then heating the mixture to 110 ℃ and 130 ℃ for reaction.
8. The method of synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 7 wherein the ultrasonic frequency is 38-42 kHz; the reaction time is 6-10 h.
9. The method of synthesizing a carbon-doped palladium interstitial nanoalloy catalyst as claimed in claim 7, wherein the weight ratio of palladium acetate to activated carbon is 1: 1.5.
10. a carbon-doped palladium interstitial nanoalloy catalyst, which is prepared by the synthesis method of the carbon-doped palladium interstitial nanoalloy catalyst as claimed in any one of claims 1 to 8, and is applied to anode catalysts of formic acid fuel cells and industrial organic hydrogenation/dehydrogenation catalysts.
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