CN114784296B - Preparation method of platinum-ruthenium doped rare earth element ternary alloy nano porous catalyst for efficiently catalyzing oxidation of methanol and ethanol - Google Patents
Preparation method of platinum-ruthenium doped rare earth element ternary alloy nano porous catalyst for efficiently catalyzing oxidation of methanol and ethanol Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 60
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910002058 ternary alloy Inorganic materials 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 4
- 229920002873 Polyethylenimine Polymers 0.000 claims description 4
- 150000003841 chloride salts Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000000956 alloy Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 229910002849 PtRu Inorganic materials 0.000 description 14
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 5
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
- H01M4/88—Processes of manufacture
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a platinum-ruthenium doped rare earth element ternary alloy nano porous catalyst for efficiently catalyzing methanol and ethanol oxidation, which takes composite metal salt as a precursor, carries alloy nano particles synthesized by magnesium-hydrogen reinforced reduction molten salt confinement on a carbon material with high specific surface area, takes anhydrous magnesium chloride and sodium chloride as a confinement agent, and takes magnesium chips-hydrogen and the like as a reducing agent to prepare a carbon-supported platinum-ruthenium doped rare earth element material. The preparation method fully utilizes the advantages of the rare earth element for regulating the catalytic activity of the alloy, and improves the oxygen storage capacity of the catalyst, the lattice oxygen activity of the material and the dispersibility of the active metal on the carrier; greatly improves the methanol oxidation performance, the ethanol oxidation performance, the CO poisoning resistance and the thermal stability of the catalyst.
Description
Technical Field
The invention relates to the research field of platinum-ruthenium doped rare earth element catalysts, in particular to a preparation method of a high-activity platinum-ruthenium catalyst, which can be used for catalyzing methanol and ethanol reaction research.
Background
The fuel sources of methanol and ethanol are wide and low in price, direct Methanol Fuel Cells (DMFCs) and direct ethanol fuel cells (DAFCs) are widely concerned and become reliable alternative clean energy converters for portable and automotive applications, and among platinum-based bimetallic catalysts for MOR and EOR, many researchers have studied platinum binary catalysts containing an aerophilic metal, such as Ru, rh, ir, etc., ptRu bimetallic is currently the most widely used electrocatalyst in DMFCs and DAFCs due to its synergistic effect, ligand effect and strain effect, but its catalytic activity, thermal stability and toxicity resistance still need to be improved in one step. The rare earth element with a 4f orbit is considered as an effective dopant for regulating the catalytic activity of the alloy, and can improve the oxygen storage capacity of the catalyst, the lattice oxygen activity of the material and the dispersibility of the active metal on a carrier; the rare earth elements are doped in the noble metal, so that the consumption of the noble metal can be reduced, and the cost of the catalyst can be reduced; and improves its thermal stability. The method provides a new opportunity for designing and preparing high-performance methanol oxidation and ethanol oxidation noble metal doped rare earth element catalysts.
Disclosure of Invention
The invention aims to provide a preparation method of an efficient methanol and ethanol oxidation catalyst, which reduces the dosage of noble metal platinum ruthenium and greatly improves the methanol oxidation catalytic activity of the catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
(1) Mixing conductive carbon black XC-72 with a Polyethyleneimine (PEI) solution, adding water to dissolve the mixture together, performing ultrasonic treatment on the obtained mixed solution, sufficiently stirring the mixed solution, performing suction filtration on the solution, and finally drying and grinding a suction filtration product to prepare PEI-C;
(2) Ultrasonic treatment is carried out on PEI-C, so that PEI-C is dispersed in pure water and is evenly mixed with precursor solution containing platinum, ruthenium and rare earth elements;
(3) Heating and stirring the mixed solution obtained in the step (2), putting the mixed solution into a freeze dryer for freezing after stirring to be in a mud shape, vacuumizing and drying to obtain a black powdery sample, and finally adding NaCl into the sample for grinding;
(4) Adding anhydrous magnesium chloride and magnesium scraps into the powder ground in the step (3), fully mixing, loading into a molybdenum crucible, and calcining at high temperature in a hydrogen atmosphere;
(5) Adding pure water and acetic acid into the calcined sample in the step (4), carrying out suction filtration after no bubbles are generated, washing the sample with pure water for multiple times to remove excessive acetic acid, and finally drying the product on the suction filtration paper to obtain the ternary alloy nano porous catalyst with platinum-ruthenium doped rare earth elements supported on a carbon carrier.
Preferably, the ultrasonic treatment time of the mixed solution in the step (1) is 0.5-4 hours, the stirring time is 4-12 hours, the suction filtration product is placed in a vacuum oven at 60-70 ℃ for drying for 8-10 hours, and the grinding time is 0.5-1 hour.
Preferably, the content of platinum, ruthenium and rare earth elements in the catalyst is 5-60%.
Preferably, the rare earth element comprises one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium.
Preferably, the precursor solution comprises one or more of chloride salt, nitrate salt, acetylacetonate salt; when the precursor solution is acetylacetonate, the precursor solution is dissolved in ethanol and then mixed with PEI-C dispersed in pure water.
Preferably, the freezing is carried out in the freeze dryer in the step (3) for 24 hours, the vacuum drying is carried out for 24 hours, and the grinding time of adding NaCl is 30 minutes.
Preferably, the high-temperature calcination temperature in the step (4) is 500-900 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-5 hours.
Preferably, the molar ratio of magnesium to the sum of the metal elements in the precursor solution is 5-100:1, the molar ratio of sodium chloride/magnesium chloride is 5-20:1, and the molar ratio of chloride salt to the sum of the metal elements in the precursor solution is 10-100:1.
Preferably, in the step (4), the flow rate of the hydrogen is 10-500ml/min.
Compared with the prior art, the invention has the following effects and advantages:
1. the metal is uniformly dispersed and loaded on the carbon carrier by adopting a thermal stirring method, so that the operation is simple, the efficiency is high, and the dispersion effect is good;
2. the freeze-drying method maintains the basic form of the sample to the greatest extent and maintains the uniform distribution of the particle size;
3. the oxidized metal precursor can be fully reduced by high-temperature calcination under the hydrogen atmosphere;
4. the synthesized platinum ruthenium rare earth element bimetallic catalyst has high methanol oxidation activity and strong stability under acidic conditions.
From the advantages, the invention has important significance for preparing the efficient platinum-ruthenium rare earth element ternary metal catalyst.
Drawings
FIG. 1 is a mass activity diagram of a ternary alloy nano porous catalyst doped with rare earth elements by platinum and ruthenium in different proportions, specifically (A) 0.5. 0.5M H 2 SO 4 +1.0M CH 3 Scanning under the condition of OH solutionAt a rate of 0.05V s -1 (B) at 0.5. 0.5M H 2 SO 4 +1.0M C 2 H 5 Under the condition of OH solution, the scanning speed is 0.05V s -1 ；
FIG. 2 is a graph showing the specific activities of methanol oxidation and ethanol oxidation of a ternary alloy nano porous catalyst doped with rare earth elements by platinum and ruthenium in different proportions;
FIG. 3 is a graph showing the comparison of the stability of the ternary alloy nano porous catalyst doped with rare earth elements by platinum and ruthenium according to different proportions and the commercial PtRu/C catalyst measured by a time-current method, specifically (A) at 0.5V voltage and 0.5M H 2 SO 4 +1M CH 3 Chronoamperometry under OH solution conditions, (B) at a voltage of 0.5V, 0.5. 0.5M H 2 SO 4 +1M C 2 H 5 Timing current method under OH solution condition;
FIG. 4 is a graph showing the carbon monoxide dissolution performance of a ternary alloy nanoporous catalyst doped with rare earth elements and a commercial PtRu/C catalyst with different proportions of Pt and Ru, specifically 0.5M H at CO saturation 2 SO 4 CO dissolution was measured in solution at a scan rate of 0.05V s -1 。
Detailed Description
The following examples are given to illustrate embodiments of the present invention and are not intended to limit the scope of the invention.
Example 1
600ml of pure water is dissolved into 2g of XC-72 and 4g of polyethyleneimine, and after 2 hours of ultrasonic treatment, the mixture is fully stirred, filtered, dried and ground to prepare PEI-C.
30mg of PEI-C was weighed and dispersed in 10mL of pure water by ultrasonic treatment for 2 hours, and 24.12mg of platinum acetylacetonate, 24.44mg of ruthenium acetylacetonate and 28.39mg of RE (acac) dissolved in ethanol in advance were added 3 (Pt: ru: re=1:1:1) stirring at 50 ℃ and 700rpm hot stage for 12 hours until the mixture is in a mud shape, placing the mixture in a freeze dryer for freezing for 24 hours, vacuumizing and drying for 24 hours to obtain a black powdery sample, adding 0.45g of NaCl and grinding for 30 minutes; adding 0.0813g anhydrous magnesium chloride and 0.5g magnesium chips into the ground powder, mixing thoroughly, and loading into molybdenum crucibleCalcining at 700 ℃ in hydrogen atmosphere. And adding pure water and acetic acid to fully react to remove excessive Mg, washing the mixture with pure water for multiple times, filtering to remove excessive acetic acid, and finally drying the product on the filter paper, and then naming the product as a sample 1.
Comparison one: 30mg of PEI-C was weighed and dispersed in 10mL of pure water by ultrasonic treatment for 2 hours, and 20.52mg of platinum acetylacetonate, 20.78mg of ruthenium acetylacetonate and 12.07mg of RE (acac) dissolved in ethanol in advance were added 3 (Pt: ru: re=2:2:1) other experimental procedures were identical to sample 1 and were designated sample 2.
Comparison two: 30mg of PEI-C was weighed and dispersed in 10mL of pure water by ultrasonic treatment for 2 hours, and 19.58mg of platinum acetylacetonate, 19.84mg of ruthenium acetylacetonate and 7.68mg of RE (acac) dissolved in ethanol in advance were added 3 (Pt: ru: re=3:3:1) other experimental procedures were identical to sample 1 and were designated sample 3.
Comparison III: 30mg of PEI-C was weighed and dispersed in 10mL of pure water by ultrasonic treatment for 2 hours, and 29.19mg of platinum acetylacetonate, 29.57mg of ruthenium acetylacetonate and 51.52mg of RE (acac) dissolved in ethanol in advance were added 3 (Pt: ru: re=2:2:3) other experimental procedures were identical to sample 1 and were designated sample 4.
Comparison four: 30mg of PEI-C was weighed and dispersed in 10mL of purified water by ultrasonic treatment for 2 hours, and 15.59mg of platinum acetylacetonate and 15.79mg of ruthenium acetylacetonate (Pt: ru=1:1) dissolved in ethanol in advance were added, and the experimental procedure was the same as that of sample 1 and designated as sample 5.
The electrochemical reaction test is carried out at normal temperature and normal pressure, and the specific performance test operation process comprises the following steps:
weighing 5mL of ethanol, 1.25mL of isopropanol and 100uL of Nafion solution, fully and uniformly mixing the ethanol, weighing 1-2 mg of prepared catalyst samples I to five, dispersing the catalyst samples I to five in the mixed solution, keeping the concentration of the catalyst solution at 2mg/mL, carrying out ultrasonic treatment for 30-60 minutes to obtain uniform ink, taking 10 uL of ink drop on the surface of a glassy carbon electrode, and drying the ink to prepare the working electrode. Meanwhile, an Ag/AgCl electrode is used as a reference electrode, and a platinum sheet electrode is used as a counter electrode to form a three-electrode system for electrochemical test. FIG. 1 (A) shows that the mass activity (Im) of sample 1 Methanol Oxidation (MOR) is as high as 1320mA mg Pt -1 1.28 times and 2.5 times that of commercial PtRu/C and rare earth element-free sample 5, respectively，I f /I b (sample 1) =1.5>I f /I b =1.16 (PtRu/C-JM), sample 1 exhibited better resistance to CO poisoning than commercial PtRu/C; as can be seen from FIG. 1 (B), sample 1 Ethanol Oxidation (EOR) Im was 1305mA mg Pt -1 1.28 times and 2.5 times that of commercial PtRu/C and sample 5 without rare earth doping, respectively; in addition, sample 4 had better methanol oxidation and ethanol oxidation properties than commercial PtRu/C; FIGS. 3 (A), (B) show timing current diagrams in acidic methanol and ethanol electrolytes, respectively, at a voltage of 0.5V, showing that the methanol oxidation Im of sample 1 and PtRu/C-JM, respectively, is 180mA mg, tested for 5000s Pt -1 、105mA mg Pt -1 Ethanol oxidation Im of sample 1 and PtRu/C-JM was 160mA mg, respectively Pt -1 、80mA mg Pt -1 The results show that sample 1, after 5000s chronoamperometric testing, has higher methanol oxidation and ethanol oxidation mass activity than commercial PtRu/C.
This patent uses the CO dissolution method (fig. 4) to calculate the electrochemical active area (ECSA), and uses the following formula for the CO dissolution method calculation, considering that the Pt alloy catalyst has weak adsorptivity to hydrogen (ECSA calculated by hydrogen adsorption is smaller than the actual value):
ECSA＝10 5 ⅹQ/(420ⅹM Pt )
ECSA represents the electrochemically active area (m 2 /g Pt ) Q represents the CO adsorption area (C), 420 represents the number of charges (uC/cm) of adsorbing two charges per unit area of platinum surface 2 )，M Pt The platinum loading (mg) on the working electrode is indicated.
The ECSA for each catalyst was calculated as shown in the following table:
TABLE 1 ECSA of samples 1-5 and PtRu/C-JM
| Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | PtRu/C-JM | |
| ECSA(m 2 /g Pt ) | 47.62 | 43.18 | 40.82 | 52.52 | 36.24 | 64.91 |
The specific activity diagram (figure 2) of methanol oxidation and ethanol oxidation is calculated by mass activity and electrochemical activity area, and the specific activities of MOR and EOR of the sample 1 can be found to be 1.75 times and 2.08 times of commercial PtRu/C-JM respectively; sample 1 has 1.87-fold and 1.83-fold specific MOR and EOR activities as compared to sample 5, which is not doped with rare earth elements. Meanwhile, the specific activity of the samples 2-4 added with rare earth elements in different proportions is greatly improved on the basis of the sample 5 without the rare earth elements
As can be clearly seen from the CO-strip chart (FIG. 4), the initial potential and the peak potential of the different catalysts are respectively 0.32V and 0.45V (which are respectively shifted in the negative direction compared with PtRu/C-JM by 80mV and 45 mV), and the initial potential and the peak potential are respectively shifted in the negative direction compared with sample 5 which is not doped with rare earth elements, which indicates that the sample 1 has excellent CO poisoning resistance.
In conclusion, the methanol oxidation and ethanol oxidation activity of the catalyst can be effectively improved by doping rare earth elements, and the CO poisoning resistance of the catalyst is greatly improved, because the rare earth elements have unique 4f orbit structures, adjustable electronic structures and the like, the catalyst is helpful for adsorbing OH at lower potential ads CO adsorbed to the active site of the catalyst ads Oxidation, and improving catalytic activity. The invention further analyzes the proportion of doped rare earth elements to obtain the optimal proportion (Pt: ru: RE=1:1:1).
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 (7)
1. A preparation method of a platinum-ruthenium doped rare earth element ternary alloy nano porous catalyst for efficiently catalyzing oxidation of methanol and ethanol is characterized by comprising the following steps:
(1) Mixing XC-72 with a polyethyleneimine solution, adding water for dissolving, performing ultrasonic treatment on the obtained mixed solution, sufficiently stirring, performing suction filtration on the solution, and finally drying and grinding a suction filtration product to prepare PEI-C;
(2) Ultrasonic treatment is carried out on PEI-C, so that PEI-C is dispersed in pure water and is evenly mixed with precursor solution containing platinum, ruthenium and rare earth elements;
(3) Heating and stirring the mixed solution obtained in the step (2), putting the mixed solution into a freeze dryer for freezing after stirring to be in a mud shape, vacuumizing and drying to obtain a black powdery sample, and finally adding NaCl into the sample for grinding;
(4) Adding anhydrous magnesium chloride and magnesium chips into the powder ground in the step (3), fully mixing, loading into a molybdenum crucible, and calcining at a high temperature in a hydrogen atmosphere, wherein the high temperature calcining temperature is 500-900 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 1-5 hours; the molar ratio of magnesium to the sum of all metal elements in the precursor solution is 5-100:1, the molar ratio of sodium chloride to magnesium chloride is 5-20:1, and the molar ratio of chloride salt to the sum of all metal elements in the precursor solution is 10-100:1;
(5) Adding pure water and acetic acid into the calcined sample in the step (4), carrying out suction filtration after no bubbles are generated, washing the sample with pure water for multiple times to remove excessive acetic acid, and finally drying the product on the suction filtration paper to obtain the ternary alloy nano porous catalyst with platinum-ruthenium doped rare earth elements supported on a carbon carrier.
2. The method according to claim 1, wherein the ultrasonic treatment time of the mixed solution in the step (1) is 0.5-4 hours, the stirring time is 4-12 hours, the suction filtration product is placed in a vacuum oven at 60-70 ℃ for 8-10 hours, and the grinding time is 0.5-1 hour.
3. The method of claim 1, wherein the catalyst comprises 5-60% of platinum, ruthenium, and rare earth elements.
4. The method of claim 1, wherein the rare earth element comprises one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium.
5. The method of claim 1, wherein the precursor solution comprises one or more of a chloride salt, a nitrate salt, an acetylacetonate salt; when the precursor solution is acetylacetonate, the precursor solution is dissolved in ethanol and then mixed with PEI-C dispersed in pure water.
6. The method of claim 1, wherein the freezing is performed in the freeze dryer in step (3) for 24 hours, the vacuum drying is performed for 24 hours, and the grinding time for adding NaCl is 30 minutes.
7. The method of claim 1, wherein the hydrogen flow rate in step (4) is 10-500ml/min.
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