CN114602514B - Selenium microsphere surface loading Pd 17 Se 15 Alloy catalyst and preparation method and application thereof - Google Patents
Selenium microsphere surface loading Pd 17 Se 15 Alloy catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114602514B CN114602514B CN202210070400.4A CN202210070400A CN114602514B CN 114602514 B CN114602514 B CN 114602514B CN 202210070400 A CN202210070400 A CN 202210070400A CN 114602514 B CN114602514 B CN 114602514B
- Authority
- CN
- China
- Prior art keywords
- selenium
- reaction
- microspheres
- alloy catalyst
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011669 selenium Substances 0.000 title claims abstract description 156
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000004005 microsphere Substances 0.000 title claims abstract description 75
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 57
- 239000000956 alloy Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000011068 loading method Methods 0.000 title claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 107
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 11
- 239000012498 ultrapure water Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 8
- 239000008103 glucose Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 235000019441 ethanol Nutrition 0.000 claims description 29
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 208000001408 Carbon monoxide poisoning Diseases 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000000446 fuel Substances 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 32
- 238000007254 oxidation reaction Methods 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 208000005374 Poisoning Diseases 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 230000008093 supporting effect Effects 0.000 description 3
- 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
- 239000012696 Pd precursors Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 palladium ions Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- MUSFRELEIXGPKU-UHFFFAOYSA-N selanylidenepalladium Chemical compound [Pd]=[Se] MUSFRELEIXGPKU-UHFFFAOYSA-N 0.000 description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003950 stripping voltammetry Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910001370 Se alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/923—Compounds thereof with non-metallic elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
Abstract
The invention discloses a selenium microsphere surface loaded Pd 17 Se 15 Alloy catalyst, and preparation method and application thereof, the method comprises: dispersing selenium dioxide and glucose into ultrapure water, fully stirring to form a suspension, placing the suspension into a reaction kettle for hydrothermal reaction, and after the reaction is finished, washing and drying the product to obtain selenium microspheres; dispersing selenium microspheres into glycol solution, stirring uniformly, dropwise adding aqueous solution of palladium chloride acid, adjusting pH to alkalinity after the dropwise addition is finished, stirring fully, placing the mixed solution into a microwave reactor for microwave reaction, and carrying out suction filtration, washing and drying treatment on the product after the reaction is finished to obtain the selenium microsphere surface-loaded Pd 17 Se 15 Alloy catalyst. The catalyst prepared by the invention has simple preparation conditions, higher carbon monoxide poisoning resistance, catalytic activity and stability in alcohol electrooxidation reaction, and wide application prospect in alcohol fuel cells.
Description
Technical Field
The invention relates to a selenium microsphere surface load Pd 17 Se 15 Alloy catalyst and its preparation process and application, and belongs to the field of alcohol fuel cell technology.
Background
Increasingly depleted fossil fuels and increasingly severe environmental pollution have prompted rapid research into green renewable energy technologies. Alcohol fuel cells have received great attention due to their high energy conversion efficiency and environmental protection. In order to make this technique widely used, it is important to obtain an anode catalyst with high activity and durable electrocatalyst for accelerating the oxidation reaction of alcohols. Platinum-based materials have so far been the most advanced anode electrocatalysts in the field of alcohol oxidation. However, the large-scale application of platinum-based catalysts still faces some dilemmas, such as slow reaction kinetics, active site aggregation, susceptibility to carbon monoxide poisoning, etc. In this case, extensive studies have demonstrated that palladium-based catalysts are, due to their relatively high abundance and high intrinsic catalytic activity, alcohol electro-oxidation catalysts which are expected to replace platinum-based catalysts, especially in alkaline media. Therefore, the search for effective strategies to improve the resistance to carbon monoxide poisoning, catalytic activity and durability of palladium-based catalysts has become a hot spot of research in recent years.
In palladium-based catalyst systems, forming an alloy structure with an parent element is a method for effectively improving catalytic performance. The palladium-based alloy with good design not only can improve the utilization rate of palladium, but also can effectively generate adsorbed hydroxyl in alkaline medium by taking the introduced parent oxygen element as a cocatalyst, and weaken the adsorbed carbon monoxide intermediate, thereby relieving carbon monoxide poisoning. Selenium with the oxygen-philic characteristic can form an alloy with palladium, so that the alcohol electrooxidation activity is effectively improved. In addition, the introduction of a suitable support is also critical to improving the electrocatalytic properties of the catalyst. The palladium with the nano structure is combined with other supporting materials, so that the dispersibility of noble metal can be improved, and the intrinsic activity and stability of the noble metal can be enhanced, thereby improving the electrocatalytic performance of the noble metal in alcohol oxidation reaction. Catalyst supports having more of the oxophilic component are favored by researchers over traditional carbon-based supports. In palladium-based catalyst systems, the semimetallic selenium as a support can provide more oxygen-containing species through the support effect, and the ligand effect between the alloy synergistically adjusts the intrinsic activity and stability of the catalyst. Selenium has been rarely reported in palladium-based systems to promote oxidation of alcohols, although it has been demonstrated to have the potential to promote oxidation of alcohol fuels (chem. Comm.2021,57, 199-202). Therefore, further exploration and development of palladium selenium catalytic systems with high resistance to carbon monoxide poisoning for alcohol fuel cells is challenging, but also attractive.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a selenium microsphere surface loaded Pd 17 Se 15 The alloy catalyst and the preparation method and application thereof can solve the technical problems of active site aggregation and poor carbon monoxide poisoning resistance in the background technology.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a selenium microsphere surface loaded Pd 17 Se 15 The preparation method of the alloy catalyst comprises the following steps:
dispersing selenium dioxide and glucose into ultrapure water, fully stirring to form a suspension, placing the suspension into a reaction kettle for hydrothermal reaction, and after the reaction is finished, washing and drying the product to obtain selenium microspheres;
dispersing selenium microspheres into glycol solution, stirring uniformly, dropwise adding aqueous solution of palladium chloride acid, adjusting pH to alkalinity after the dropwise addition is finished, stirring fully, placing the mixed solution into a microwave reactor for microwave reaction, and carrying out suction filtration, washing and drying treatment on the product after the reaction is finished to obtain the selenium microsphere surface-loaded Pd 17 Se 15 Alloy catalyst.
In some embodiments, the suspension is placed in a reaction vessel to perform the hydrothermal reaction as follows: the suspension is placed in a reaction kettle, and the hydrothermal reaction is carried out for 6 to 12 hours at the reaction temperature of 150 to 200 ℃.
In some embodiments, after the hydrothermal reaction is finished, the product is washed with ultrapure water and absolute ethanol for a plurality of times, and then dried in vacuum for 10 to 12 hours at 60 to 80 ℃ to obtain the selenium microspheres.
In some embodiments, the molar ratio of selenium dioxide to glucose is (1-3): 6.
in some embodiments, the selenium microspheres are calculated as a mass ratio: palladium is (1-2): 1.
in some embodiments, the pH is adjusted with NaOH solution in the range of 9 to 11.
In some embodiments, the mixed solution is placed in a microwave reactor for microwave reaction, wherein the power of the microwave reactor is 650-950W and the time of the microwave reaction is 90-180 s.
In a second aspect, the invention provides a catalyst, which adopts the selenium microspheres to load Pd on the surfaces 17 Se 15 The preparation method of the alloy catalyst is provided.
In a third aspect, the selenium microsphere provided by the invention is loaded with Pd on the surface 17 Se 15 The alloy catalyst is used for catalyzing alcohol oxidation.
In the fourth aspect, pd is loaded on the surface of the selenium microsphere 17 Se 15 The alloy catalyst is applied to the anode of an alcohol fuel cell.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a selenium microsphere surface loaded Pd 17 Se 15 The alloy catalyst can effectively improve the cost effectiveness of the alcohol oxidation catalyst by replacing a platinum-based catalyst with a palladium-based catalyst, the electronic structure of active site palladium is regulated by the alloy structure formed by the alloy catalyst and the selenium serving as an oxygen-related element, the oxidation of a reaction intermediate is accelerated, and the intrinsic activity and the selectivity of the catalyst are regulated by the cooperation of the alloy catalyst and the supporting effect of the selenium microspheres serving as a carrier, so that the carbon monoxide poisoning resistance of the alcohol oxidation catalyst is enhanced, and the activity and the stability of the catalyst are enhanced.
2. The invention provides a selenium microsphere surface loaded Pd 17 Se 15 Alloy catalyst, which uses selenium microsphere as carrier, uses the reduction potential difference between palladium precursor and selenium to drive spontaneous exchange reaction between palladium and selenium, consumes partial selenium atoms on surface and forms positively charged selenium, so that the positively charged selenium and palladium ions in solution are reduced and deposited on the surface of selenium microsphere to form Pd supported by selenium microsphere 17 Se 15 Alloy catalyst.
3. The invention provides a selenium microsphere surface loaded Pd 17 Se 15 The preparation method of the alloy catalyst has simple preparation conditions, can be obtained in one step by a simple microwave method, and has excellent performance in electrocatalytic alcohol oxidation. Has better commercial application potential on the anode side of the alcohol fuel cell.
Drawings
FIG. 1 shows Pd-loaded microspheres of selenium and palladium particles prepared according to an embodiment of the present invention 17 Se 15 XRD spectra of alloy catalysts;
FIG. 2 is an SEM image of selenium microspheres prepared according to an embodiment of the present invention;
FIG. 3 shows a Pd-loaded selenium microsphere surface prepared according to an embodiment of the present invention 17 Se 15 TEM image of alloy catalyst;
FIG. 4 shows the Pd loading on the surface of the selenium microspheres in application example 1 of the present invention 17 Se 15 Cyclic voltammograms of alloy catalyst (a) and self-made palladium-carbon catalyst (b) after different carbon monoxide poisoning times in 1mol/L potassium hydroxide electrolyte;
FIG. 5 shows the Pd loading on the surface of the selenium microspheres in application example 1 of the present invention 17 Se 15 A line graph of carbon monoxide adsorption amounts of the alloy catalyst and the self-made palladium-carbon catalyst in potassium hydroxide electrolyte with the concentration of 1mol/L at different carbon monoxide poisoning times;
FIG. 6 shows the surface loading Pd on the selenium microspheres in application example 1 17 Se 15 A comparison graph of a cyclic voltammogram (a) and a timing current test curve (b) of an alloy catalyst and a self-made palladium-carbon catalyst in a mixed electrolyte of 1mol/L methanol and 1mol/L potassium hydroxide;
FIG. 7 shows the surface loading Pd on selenium microspheres in application example 2 17 Se 15 And (3) comparing the cyclic voltammogram (a) and the timing current test curve (b) of the alloy catalyst and the self-made palladium-carbon catalyst in the mixed electrolyte of ethanol with the concentration of 1mol/L and potassium hydroxide with the concentration of 1 mol/L.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
The experimental methods used in the following examples are not specifically described, but the experimental methods in which specific conditions are not specified in the examples are generally carried out under conventional conditions, and the materials, reagents, etc. used in the following examples are commercially available unless otherwise specified.
The invention provides a selenium microsphere surface loaded Pd 17 Se 15 The preparation method of the alloy catalyst comprises the following steps:
dispersing selenium dioxide and glucose into ultrapure water, the molar ratio of selenium dioxide to glucose in some embodiments being (1-3): and 6, fully stirring to form a suspension, placing the suspension into a reaction kettle for hydrothermal reaction, washing the product with ultrapure water and absolute ethyl alcohol for several times after the hydrothermal reaction is finished, and vacuum drying at 60-80 ℃ for 10-12 h to obtain the selenium microspheres. The suspension is put into a reaction kettle to carry out hydrothermal reaction, and the specific steps are as follows: the suspension is placed in a reaction kettle, and the hydrothermal reaction is carried out for 6 to 12 hours at the reaction temperature of 150 to 200 ℃.
Dispersing selenium microspheres into glycol solution, stirring uniformly, dropwise adding an aqueous solution of palladium chloride acid, and after the dropwise addition is finished, in some embodiments, adjusting the pH to 9-11 by adopting NaOH solution, fully stirring, placing the mixed solution into a microwave reactor for microwave reaction, and in some embodiments, calculating according to the mass ratio, wherein the selenium microspheres are prepared by the following steps: palladium is (1-2): 1, after the reaction is finished, carrying out suction filtration, washing and drying treatment on the product to obtain the selenium microsphere surface loaded Pd 17 Se 15 Alloy catalyst. The mixed solution is placed in a microwave reactor for microwave reaction, wherein the power of the microwave reactor is 650-950W, and the time of the microwave reaction is 90-180 s.
Examples
The preparation steps of the catalyst are as follows:
1. preparation of selenium microspheres
Step (1), 180mg of selenium dioxide and 1.5g of glucose (C 6 H 12 O 6 ) Dispersing into 15mL of ultrapure water, and stirring by magnetic force uniformly.
And (2) transferring the mixed solution obtained in the step (1) into a 50mL hydrothermal reaction kettle, and carrying out hydrothermal reaction for 6h at the temperature of 200 ℃.
And (3) carrying out suction filtration on the mixed solution after the hydrothermal reaction is finished, flushing the product with absolute ethyl alcohol and ultrapure water for several times, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain the selenium microspheres.
2. Pd loaded on surface of selenium microsphere 17 Se 15 Preparation of alloy catalyst
Taking the selenium microspheres prepared in the example as a carrier, and carrying out Pd on the surfaces of the selenium microspheres 17 Se 15 Alloy preparation, namely Pd loaded on the surface of the selenium microsphere is obtained through the reaction between palladium and selenium 17 Se 15 The alloy catalyst comprises the following specific steps:
dispersing 40mg of selenium microspheres in a beaker filled with 100mL of ethylene glycol solution, and magnetically stirring uniformly;
step (2), adding 675 microliters of an aqueous solution of palladium chloride acid dropwise to the mixed solution obtained in the step (1), wherein the concentration of the palladium chloride acid is 40mg/mL, in this case, adjusting the pH to 10 by using an NaOH solution, and stirring thoroughly to obtain a suspension, wherein the NaOH solution can be 0.1M;
step (3), transferring the suspension obtained in the step (2) into a microwave reactor, and carrying out microwave reaction for 90s under the condition of 800W;
step (4), carrying out suction filtration on the solution obtained after the reaction in the step (3), washing the product with absolute ethyl alcohol and ultrapure water for a plurality of times, placing the product at 60 ℃ after washing, and vacuum drying for 12 hours, wherein the obtained product is named Pd 17 Se 15 Se, i.e. Pd supported on the surface of selenium microspheres 17 Se 15 Alloy catalyst.
Comparative example
Step (1), dropwise adding 675 microliters of chloropalladite acid aqueous solution into a beaker filled with 100mL of ethylene glycol solution, wherein the concentration of the chloropalladite acid is 40mg/mL, and magnetically stirring uniformly;
step (2), transferring the suspension obtained in the step (1) into a microwave reactor, and carrying out microwave reaction for 90 seconds under the condition of 800W;
and (3) carrying out suction filtration on the solution obtained after the reaction in the step (2), washing the product with absolute ethyl alcohol and ultrapure water for several times, and vacuum drying the washed product at 60 ℃ for 12 hours, wherein the obtained product is named Pd.
The invention prepares Pd by the method 17 Se 15 Performance tests were performed on the Se and Pd catalysts, including XRD patterns, SEM images, TEM images and electrochemical tests.
Specifically, FIG. 1 shows Pd on the surface of selenium microspheres prepared in the example 17 Se 15 Alloy catalyst Pd 17 Se 15 XRD spectra of the Pd catalyst prepared in the comparative example and Se.
From the figure, the surface load Pd of the selenium microsphere can be seen 17 Se 15 Pd on alloy catalyst 17 Se 15 The diffraction peaks of (2) and selenium, and no obvious characteristic peak of palladium exists, indicating that the selenium microspheres are loaded with Pd 17 Se 15 Successful preparation of alloy catalysts. There is a significant diffraction peak of palladium for the Pd catalyst prepared in the comparative example.
Fig. 2 is an SEM image of the prepared selenium microspheres. The surface of the selenium microsphere is provided with folds, which is favorable for loading palladium-selenium alloy.
FIG. 3 shows Pd on the surface of the prepared selenium microspheres 17 Se 15 Alloy catalyst Pd 17 Se 15 TEM image of/Se, pd, as clearly seen from the image 17 Se 15 TEM image of Se is different from SEM image of Se microsphere, pd 17 Se 15 In TEM image of Se, pd is loaded on the surface of Se microsphere 17 Se 15 And (3) alloy.
Application example 1
The invention loads Pd on the surface of the prepared selenium microsphere 17 Se 15 Alloy catalyst is used for catalyzing alkaline methanol electrooxidation.
In the application example, the methanol oxidation reaction in the catalytic alkaline electrolyte is carried out on an electrochemical workstation, specifically, a standard three-electrode system is adopted, the catalytic alkaline electrolyte is carried out at normal temperature (25 ℃) and is a mixed solution of 1mol/L methanol and 1mol/L potassium hydroxide, the electrolytic solution for carbon monoxide stripping voltammetry test in the alkaline electrolyte is a 1mol/L potassium hydroxide solution, the electrolytic solution for the electro-oxidation of methanol in the catalytic alkaline electrolyte is a mixed solution of 1mol/L methanol and 1mol/L potassium hydroxide, the surface of a glassy carbon electrode polished by alumina is used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a carbon rod is used as a counter electrode.
The specific process is as follows: 2mg of Pd on the surface of the selenium microspheres prepared in the example 17 Se 15 The alloy catalyst and Pd prepared in 1mg of comparative example are respectively added into 950 microliter ethanol and 50 microliter Nafion mixed solution together with 3mg and 4mg of carbon black (Vulcan XC 72), the mixture is uniformly dispersed by ultrasonic, 5 microliter of catalyst ink is added dropwise on the surface of a working electrode, after drying, cyclic voltammetry is adopted, cyclic voltammetry scanning is carried out at a scanning speed of 50mV/s between-1 and 0.2V, and a constant current timing test is carried out for 3600 seconds at a potential of-0.25V vs.
The electrolyte for the carbon monoxide stripping voltammetry test is 1mol/L potassium hydroxide solution, and the specific process is as follows: firstly, introducing carbon monoxide for poisoning for a period of time under the potential of minus 0.8V vs. SCE, then introducing nitrogen, and carrying out cyclic voltammetry scanning at a scanning speed of 20mV/s after removing the carbon monoxide in the solution, wherein the potential range is minus 1.0V to 0.2V.
FIG. 4 is a Pd on selenium microsphere surface loading 17 Se 15 Cyclic voltammograms of alloy catalyst (a) and self-made palladium on carbon (b) after different carbon monoxide poisoning times. As can be seen from FIG. 4, compared with the self-made palladium-carbon catalyst, the selenium microspheres of the present invention have Pd supported on the surface 17 Se 15 The alloy catalyst has no obvious carbon monoxide dissolution peak after the carbon monoxide is poisoned for 15 minutes, and the self-made palladium-carbon generates the obvious carbon monoxide dissolution peak after the poisoning time is 5 minutes. FIG. 5 shows the surface loading Pd of selenium microspheres 17 Se 15 Line graphs of carbon monoxide adsorption amounts of alloy catalyst and self-made palladium-carbon catalyst in potassium hydroxide mixed electrolyte with concentration of 1mol/L at different carbon monoxide poisoning times. From the drawingsAs can be seen, pd was present even at a poisoning time of 60 minutes 17 Se 15 The carbon monoxide dissolution peak of the/Se is still obviously smaller than that of self-made palladium carbon, which indicates Pd 17 Se 15 The Se has high resistance to carbon monoxide poisoning.
FIG. 6 selenium microsphere surface loading Pd 17 Se 15 And (3) comparing the cyclic voltammogram (a) and the timing current test curve (b) of the alloy catalyst and the self-made palladium-carbon catalyst in the mixed electrolyte of 1mol/L methanol and 1mol/L potassium hydroxide. As can be seen from FIG. 6, compared with the self-made palladium-carbon catalyst, the surface of the selenium microsphere of the present invention is supported with Pd 17 Se 15 The alloy catalyst has higher catalytic activity and stability in alkaline methanol electrooxidation.
Application example 2
Pd loaded on surface of selenium microsphere 17 Se 15 The alloy catalyst is applied to catalyzing the electro-oxidation of alkaline ethanol.
In the application example, the ethanol oxidation reaction condition in the catalytic alkaline electrolyte is the same as that of the catalytic methanol oxidation, and the electrolyte is a mixed solution of 1mol/L ethanol and 1mol/L potassium hydroxide.
FIG. 7 selenium microsphere surface loading Pd 17 Se 15 And (3) comparing the cyclic voltammogram (a) and the timing current test curve (b) of the alloy catalyst and the self-made palladium-carbon catalyst in the mixed electrolyte of ethanol with the concentration of 1mol/L and potassium hydroxide with the concentration of 1 mol/L. As can be seen from FIG. 7, compared with the self-made palladium-carbon catalyst, the surface of the selenium microsphere of the present invention is supported with Pd 17 Se 15 The alloy catalyst has higher catalytic activity and stability in alkaline ethanol electrooxidation.
The invention provides a selenium microsphere surface loaded Pd 17 Se 15 Alloy catalyst, which uses selenium microsphere as carrier, uses the reduction potential difference between palladium precursor and selenium to drive spontaneous exchange reaction between palladium and selenium, consumes partial selenium atoms on surface and forms positively charged selenium, so that the positively charged selenium and palladium ions in solution are reduced and deposited on the surface of selenium microsphere to form Pd supported by selenium microsphere 17 Se 15 Alloy catalyst.The palladium-based catalyst is used for replacing the platinum-based catalyst, so that the cost effectiveness of the alcohol oxidation catalyst can be effectively improved, the electronic structure of active site palladium is regulated by the alloy structure formed by the palladium-based catalyst and the selenium as an oxygen-related element, the oxidation of a reaction intermediate is accelerated, and the intrinsic activity and selectivity of the catalyst are regulated in a synergistic way by the supporting effect of the selenium microspheres as a carrier, so that the carbon monoxide poisoning resistance of the alcohol oxidation catalyst can be enhanced, and the activity and stability of the catalyst are further enhanced.
After understanding the essence of the present invention, one skilled in the art can load Pd on the surface of the selenium microsphere 17 Se 15 Alloy catalyst is applied in catalyzing alcohol oxidation, and Pd is loaded on surface of selenium microsphere 17 Se 15 The alloy catalyst has high carbon monoxide poisoning resistance, can be applied to the anode of an alcohol fuel cell, has excellent catalytic activity and stability, and has wide application prospect in the alcohol fuel cell.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and variations could be made by those skilled in the art without departing from the technical principles of the present invention, and such modifications and variations should also be regarded as being within the scope of the invention.
Claims (5)
1. Selenium microsphere surface loading Pd 17 Se 15 The application of the alloy catalyst in catalyzing alkaline methanol electrooxidation or alkaline ethanol electrooxidation is characterized in that Pd is loaded on the surface of the selenium microsphere 17 Se 15 The preparation method of the alloy catalyst comprises the following steps:
dispersing selenium dioxide and glucose into ultrapure water, fully stirring to form a suspension, placing the suspension into a reaction kettle, and performing hydrothermal reaction for 6-12 hours at the reaction temperature of 150-200 ℃; after the hydrothermal reaction is finished, washing the product with ultrapure water and absolute ethyl alcohol for a plurality of times, and vacuum drying at 60-80 ℃ for 10-12 hours to obtain selenium microspheres;
dispersing selenium microspheres into glycol solution, stirring uniformly, and dropwise adding chloropalladateThe aqueous solution is dropwise added, the pH value is regulated to be alkaline, and the aqueous solution is fully stirred, the mixed solution is placed in a microwave reactor for microwave reaction, and after the reaction is finished, the product is subjected to suction filtration, washing and drying treatment, so that the selenium microsphere surface loaded Pd is prepared 17 Se 15 Alloy catalyst.
2. The use according to claim 1, wherein the molar ratio of selenium dioxide to glucose is (1-3): 6.
3. the use according to claim 1, wherein the selenium microspheres, calculated as mass ratio: palladium is (1-2): 1.
4. the use according to claim 1, wherein the pH is adjusted with NaOH solution in the range of 9 to 11.
5. The use according to claim 1, wherein the mixed solution is placed in a microwave reactor for microwave reaction, wherein the power of the microwave reactor is 650-950 w and the time of the microwave reaction is 90-180 s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210070400.4A CN114602514B (en) | 2022-01-21 | 2022-01-21 | Selenium microsphere surface loading Pd 17 Se 15 Alloy catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210070400.4A CN114602514B (en) | 2022-01-21 | 2022-01-21 | Selenium microsphere surface loading Pd 17 Se 15 Alloy catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114602514A CN114602514A (en) | 2022-06-10 |
| CN114602514B true CN114602514B (en) | 2023-10-27 |
Family
ID=81857702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210070400.4A Active CN114602514B (en) | 2022-01-21 | 2022-01-21 | Selenium microsphere surface loading Pd 17 Se 15 Alloy catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114602514B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005105336A (en) * | 2003-09-30 | 2005-04-21 | Mitsubishi Chemicals Corp | Method of coprecipitating chalcogen compound, method of producing platinum group-chalcogen alloy, method of producing platinum group-chalcogen alloy/inorganic porous carried product, and method of producing oxide reaction product |
| CN101667644A (en) * | 2009-09-27 | 2010-03-10 | 西北师范大学 | High-performance low-platinum catalyst for methanol fuel cell and preparation method thereof |
| CN107887618A (en) * | 2017-09-27 | 2018-04-06 | 姚乃元 | A kind of carbon-based platinum silver palladium ternary alloy catalyst and preparation method thereof |
| WO2018179006A1 (en) * | 2017-03-25 | 2018-10-04 | Jawaharlal Nehru Centre For Advanced Scientific Research | Palladium based selenides as highly stable and durable cathode materials in fuel cell for green energy production |
| CN112103520A (en) * | 2020-09-24 | 2020-12-18 | 扬州大学 | Anode catalyst of alcohol fuel cell |
| CN113443610A (en) * | 2021-07-09 | 2021-09-28 | 常州大学 | Ruthenium selenide nanosphere electrocatalyst and preparation method and application thereof |
-
2022
- 2022-01-21 CN CN202210070400.4A patent/CN114602514B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005105336A (en) * | 2003-09-30 | 2005-04-21 | Mitsubishi Chemicals Corp | Method of coprecipitating chalcogen compound, method of producing platinum group-chalcogen alloy, method of producing platinum group-chalcogen alloy/inorganic porous carried product, and method of producing oxide reaction product |
| CN101667644A (en) * | 2009-09-27 | 2010-03-10 | 西北师范大学 | High-performance low-platinum catalyst for methanol fuel cell and preparation method thereof |
| WO2018179006A1 (en) * | 2017-03-25 | 2018-10-04 | Jawaharlal Nehru Centre For Advanced Scientific Research | Palladium based selenides as highly stable and durable cathode materials in fuel cell for green energy production |
| CN107887618A (en) * | 2017-09-27 | 2018-04-06 | 姚乃元 | A kind of carbon-based platinum silver palladium ternary alloy catalyst and preparation method thereof |
| CN112103520A (en) * | 2020-09-24 | 2020-12-18 | 扬州大学 | Anode catalyst of alcohol fuel cell |
| CN113443610A (en) * | 2021-07-09 | 2021-09-28 | 常州大学 | Ruthenium selenide nanosphere electrocatalyst and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Meng Zha等."Efficient alcohol fuel oxidation catalyzed by a novel Pt/Se catalyst".《Chem. Commun.》.2020,第57卷(第199期),199-202. * |
| Xuchuan Jiang等."Template-engaged synthesis of RuSe2 and Pd17Se15 nanotubes by reacting precursor salts with selenium nanowires".《Chemical Physics Letters》.2004,第385卷472-476. * |
| Zhiyong Yu等."Phase-Controlled Synthesis of Pd-Se Nanocrystals for Phase-Dependent Oxygen Reduction Catalysis".《Nano Lett.》.2021,第21卷3805-3812. * |
| 上官文峰等编著.《能源材料原理与应用》.上海交通大学出版社,2017,49-50. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114602514A (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112186207B (en) | Low platinum/non-platinum composite catalyst and preparation method thereof | |
| CN113178582A (en) | Proton exchange membrane fuel cell anti-reversal electrode PtIr/CNT catalyst and preparation method thereof | |
| CN111261886A (en) | Non-noble metal modified platinum-based catalyst for fuel cell and preparation method and application thereof | |
| CN112436158B (en) | Anode catalyst of alcohol fuel cell | |
| CN112103520A (en) | Anode catalyst of alcohol fuel cell | |
| CN110931805A (en) | Platinum alloy catalyst, preparation method thereof and application thereof in fuel cell cathode catalyst | |
| CN113174053B (en) | Mn-MOF based on urotropine and preparation method and application thereof | |
| CN114300693A (en) | Method for improving stability of fuel cell carbon-supported platinum-based catalyst through activation of carbon carrier | |
| CN101176844B (en) | Direct methanol fuel cell anode catalyzer as well as preparation method and application thereof | |
| CN114602514B (en) | Selenium microsphere surface loading Pd 17 Se 15 Alloy catalyst and preparation method and application thereof | |
| CN112397732A (en) | ORR catalyst material and preparation method and application thereof | |
| CN110629248A (en) | Fe-doped Ni (OH)2Preparation method of/Ni-BDC electrocatalyst | |
| CN113774425B (en) | Preparation method and application of Ru-modified FeCo @ NF electrocatalyst | |
| CN113684499B (en) | Preparation method and application of nickel-nitrogen co-doped carbon-based catalyst with high metal loading efficiency | |
| CN113481522B (en) | Organic composite nano metal catalyst and preparation method and application thereof | |
| CN112366327B (en) | rGO-MOF (Al) -supported palladium-bismuth-phosphorus alloy nano catalyst and preparation method thereof | |
| CN114678549A (en) | Fuel cell catalyst with low precious metal content, preparation method and application thereof | |
| CN113410472A (en) | Alcohol fuel cell anode catalyst and preparation method thereof | |
| CN114335576B (en) | CoN/Ti with foamed nickel as substrate 3 C 2 Material preparation method and application | |
| CN115650317B (en) | Amorphous polymetallic boride catalysts and their use | |
| CN115094475B (en) | Electrode material with high-performance oxygen evolution catalytic activity and preparation method thereof | |
| CN113441189B (en) | Na ion modified Bi nano catalyst, preparation method and application thereof | |
| CN116230972A (en) | Monoatomically dispersed PtCo-N-C catalyst, and preparation method and application thereof | |
| CN115584528A (en) | Electrocatalyst for preparing hydrogen by electrolyzing methanol and preparation method thereof | |
| CN105845950A (en) | Preparation method for metal oxide-phosphor-noble metal composite catalyst used for fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |