CN114678551A - Preparation method of rare earth element modified platinum-ruthenium nanoparticles - Google Patents
Preparation method of rare earth element modified platinum-ruthenium nanoparticles Download PDFInfo
- Publication number
- CN114678551A CN114678551A CN202210224723.4A CN202210224723A CN114678551A CN 114678551 A CN114678551 A CN 114678551A CN 202210224723 A CN202210224723 A CN 202210224723A CN 114678551 A CN114678551 A CN 114678551A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- platinum
- ruthenium
- salt
- nanoparticles
- 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.)
- Pending
Links
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 30
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical class [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 11
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 150000003057 platinum Chemical class 0.000 claims abstract description 5
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- 229910002849 PtRu Inorganic materials 0.000 claims description 15
- 239000002086 nanomaterial Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 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 claims 1
- 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 claims 1
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- 229910052693 Europium Inorganic materials 0.000 claims 1
- 229910052688 Gadolinium Inorganic materials 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 229910052772 Samarium Inorganic materials 0.000 claims 1
- 229910052769 Ytterbium Inorganic materials 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 150000002910 rare earth metals Chemical class 0.000 abstract description 15
- 238000011056 performance test Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000691 Re alloy Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical group [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical group S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003320 CeOx Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910000929 Ru alloy Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical group [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical group [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical group [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 1
Images
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
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The invention provides a preparation method of rare earth element modified platinum-ruthenium nanoparticles, which comprises the following steps: (1) preparing a mixed solution of rare earth metal salt, ruthenium salt and platinum salt, adding the mixed solution into DMF, fully and uniformly stirring (2) introducing hydrogen, reacting at the temperature of 120-160 ℃, then standing and cooling to room temperature, and centrifuging, washing and drying reactants to obtain rare earth oxide modified ruthenium-platinum nanoparticles; (3) and uniformly mixing the obtained catalyst and carbon black, drying after uniform ultrasonic treatment, and then carrying out heat treatment to obtain the PtRu-REE/C for electrochemical performance test. Wherein, Pt1Ru1‑Er2O3/C、Pt1Ru1‑EuOxThe HOR performance of the/C nanoparticles under alkaline conditions exceeds commercial Pt/C. The invention is simple, the experimental process is short, and the condition is mild; in thatTrace rare earth is introduced into a platinum ruthenium system, and the fine combination of characteristic structures is generated by combining a solvothermal synthesis technology, so that the obtained rare earth oxide modified ruthenium platinum nano-particles show excellent HOR performance, and are very suitable for mass production.
Description
Technical Field
The invention relates to a preparation method and application of rare earth element modified platinum-ruthenium nanoparticles, belonging to the technical field of inorganic material preparation.
Background
From the viewpoint of structure-function relationship, electrocatalysts having a specific surface structure or electronic effect, etc., may significantly affect intermediates and trace impurities (e.g., H, OH and CO), thereby changing their HOR performance. For example, in the case of a liquid,
the HOR of the surface of low-index Pt in the alkaline medium is studied, and the correlation between the activity and the crystal face is found in the ranges from (111) to (100)<<(110) Zhumng et al demonstrated that in alkaline media, the PtRu/C nanocatalyst indeed had higher HOR activity than Pt/C, and that the activation energies of PtRu/C and Pt/C, obtained from the AMmhenMus formula, were 14.6MJ mMl, respectively-1And 35.2MJ mMl-1。
Despite the great advantages of Pt-RE alloy catalysts, obstacles to Pt-RE alloy catalysts exist from a synthesis point of view. The solution synthesis of these alloys is a huge challenge to the scientific community due to the extremely low reduction potential of lanthanides. The rare earth metal and platinum alloy have an energy of about 4eM, while the rare earth metal and platinum oxide have an energy of about 10 eM. Thus, during synthesis, oxides are more readily formed when the rare earth element is contacted with any oxidizing agent. The rare earth components will appear as oxides/hydroxides. This results in the formation of a heterogeneous phase between the Pt in the metallic state and the RE in the oxide, forming a Pt/oxide phase separation.
The surface chemical property of the nano catalyst can be optimized by adjusting the near-surface component of the PtRu alloy, and the slow H in the alkaline electrolyte is further improved2The electrooxidation performance of (1). However, there are still significant obstacles to overcome to build alloy nanomaterials of precise near-surface composition and smaller particle size.
The different compositional ratios have an effect on the electrochemical performance of the product. The surfactant is removed by high temperature calcination to obtain inorganic materials with specific morphology and structure. The solvothermal method is to rapidly mix a mixed salt solution of metal ions and a precipitator into nuclei, and trace rare earth elements are introduced in the process, so that the electronic structure of the platinum-ruthenium alloy is possibly changed, and the performance is improved.
Disclosure of Invention
In view of the problems in the prior art, an object of the present invention is to provide a method for preparing rare earth element modified platinum-ruthenium nanoparticles, so as to improve the catalytic activity of the catalyst, and to reduce the amount of expensive noble metal Pt and reduce the cost by a preparation process. A practical material with excellent performance is found by combining rare earth metal and noble metal. The ultra-small PtRu-REE ternary nanoparticles prepared by the method are uniform and dispersed in appearance, and the particle size is less than 3 nm.
The invention adopts the following technical scheme.
A preparation method of rare earth element modified platinum-ruthenium nano-particles comprises the following steps:
(1) preparing a mixed solution of rare earth metal salt, ruthenium salt and platinum salt, adding the mixed solution into DMF, and fully and uniformly stirring;
(2) then introducing hydrogen, reacting for 3-5 hours at the temperature of 120-160 ℃, cooling to room temperature, and centrifuging, washing and drying to obtain the ruthenium-platinum nanoparticles modified by the rare earth oxide;
(3) mixing the obtained catalyst and carbon black uniformly, ultrasonically homogenizing, drying, and performing heat treatment for 1 hr
The PtRu-REE/C is obtained at the temperature of 150-450 ℃ and is used for electrochemical performance test.
The invention adopts in-situ synthesis atmosphere regulation and control, hydrogen and sodium borohydride are used as reducing agents, and a series of PtRu nano materials modified by different rare earth elements are prepared by a simple hydrothermal synthesis method. The catalyst has high performance and high stability under alkaline conditions.
The prepared catalyst PtRu-REE/C takes carbon black as a carrier and PtRu-REE as an active component of the catalyst;
the nano material is uniform and dispersed in appearance, and nano particles with the particle size less than 3nm are uniformly distributed on the surface of the carbon black.
Pt1Ru1-EM2O3/C、Pt1Ru1-EuOxHOR performance of/C nanoparticles under alkaline conditions far surpasses commercial Pt/C. The HOR performance of the two under alkaline conditions corresponds to a current density of 2.55mA cm under a potential of 50mV (Ms.RHE) -2 dMsMAnd 2.5mA cm-2 dMsM. And the catalyst has better stability under alkaline conditions.
The reaction temperature in step (2) is 120 ℃ to 160 ℃, for example, 120 ℃, 130 ℃, 140 ℃,150 ℃ and 160 ℃. The hydrothermal reaction temperature is too low, which results in low crystallinity of the catalyst product, and the reaction temperature is too high, which results in easy agglomeration of the catalyst, unfavorable performance and resource waste.
The heat treatment temperature in the step (3) is 150 ℃ to 450 ℃, for example, 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃ and 450 ℃. Too low a heat treatment temperature does not completely leave the surface impurities, and too high a heat treatment temperature wastes resources and causes agglomeration of the catalyst.
The preparation method of the rare earth modified PtRu nanoparticle catalyst with high performance and high stability under the alkaline condition is exemplified. The method comprises the following steps:
(1) preparing a mixed solution of rare earth metal salt, ruthenium salt and platinum salt, adding the mixed solution into DMF, and fully and uniformly stirring;
(2) then introducing hydrogen, reacting for 3-5 hours at the temperature of 120-160 ℃, then standing and cooling to room temperature, and centrifuging, washing and drying reactants to obtain the ruthenium-platinum nanoparticles modified by the rare earth oxide;
(3) mixing the obtained catalyst and carbon black uniformly, ultrasonically homogenizing, drying, and performing heat treatment for 1 hr
The PtRu-REs/C is obtained at the temperature of 150-450 ℃ and is used for electrochemical performance test.
Catalyst Pt prepared1Ru1-EM2O3/C、Pt1Ru1-EuOxHOR performance under alkaline conditions of/C far surpassed commercial Pt/C. The HOR performance of the two under alkaline conditions corresponds to a current density of 2.55mA cm under a potential of 50mV (Ms.RHE)-2 dMsMAnd 2.5mA cm-2 dMsM. And the catalyst has better stability under alkaline conditions.
The second purpose of the invention is to provide the rare earth modified PtRu nano-particles prepared by the method. The catalyst prepared by the method has high HOR performance and excellent stability.
It is a further object of the present invention to provide the use of the high performance and high stability rare earth modified PtRu nanoparticles as described above for anodes in hydrogen-oxygen fuel cells.
Compared with the prior art, the invention has the following effects:
(1) the invention adopts reducing atmosphere H2Compared with the PtRu nano-material synthesized by the prior art, the synthetic method is simple and convenient, and the synthesized nano-material has monodispersity and uniform particle size distribution.
(2) Compared with commercial Pt/C, the rare earth modified PtRu nanoparticles synthesized by our method have excellent HOR performance and stability.
(3) The invention adopts a hydrothermal method for synthesis, and the preparation process is simple and convenient.
Characterization and performance analysis of PtRu-REs/C.
FIGS. 1A and B show Pt prepared in examples 1 and 2, respectively1Ru1-EM2O3/C、Pt1Ru1-EuOxTEM image of/C, the morphology of which is monodisperse nanoparticles. As can be seen from the figure, the two materials are monodisperse and have very uniform particle sizes distributed in the copper mesh, which illustrates that the method can synthesize rare earth modified PtRu nanoparticles with very regular morphology and good dispersibility; FIGS. 2A and B show Pt prepared in examples 1 and 2, respectively1Ru1-EM2O3/C、Pt1Ru1-EuOxXRD pattern of/C. From the XRD patterns, it can be seen that hcp PtRu-REE was formed. Therefore, we can pass this simple reducing atmosphere H2The PtRu nano-particles modified by rare earth and a strong oxidant are synthesized by double reduction, which is very beneficial to practical application.
FIG. 3 shows Pt1Ru1-EM2O3/C、Pt1Ru1-EuOxHOR performance graph measured by the rare earth doped catalyst of/C series under alkaline condition. As can be seen from the performance diagram, the prepared catalyst Pt1Ru1-EM2O3/C、Pt1Ru1-EuOxThe activity of the catalyst/C is much higher than that of a commercial Pt/C catalyst under alkaline conditions, and the corresponding current density of HOR performance under the alkaline conditions under the potential of 50mV (Ms.RHE) respectively reaches 2.55mA cm -2 dMsMAnd 2.5mA cm-2 dMsM。
The rare earth modified PtRu nano-particles prepared by the method have important application in the aspect of anode reaction catalysis of hydrogen-oxygen fuel cells. The electrochemical activity was tested in the following manner: a three-electrode system is adopted, a reference electrode is a saturated calomel electrode, a counter electrode is a carbon rod, and a working electrode is a glassy carbon electrode. The electrolyte used under alkaline conditions was a 0.1M KOH solution. Mixing the catalyst to be detected with ethanol, adding a certain amount of NMfMMn solution, performing ultrasonic uniform, dripping the solution on the surface of the glassy carbon electrode, and naturally drying to obtain the working electrode. Before the test, hydrogen gas 30mMn was introduced to saturate the solution with oxygen, and the sweep interval was-1.2 to-0.2V (Ms SCE) for the test, and the sweep rate was 10mV/s for the HOR performance test.
As can be seen from FIG. 3, Pt1Ru1-EM2O3/C、Pt1Ru1-EuOxThe activity of the catalyst/C is much higher than that of a commercial Pt/C catalyst under alkaline conditions, and the corresponding current density of HOR performance under the alkaline conditions under the potential of 50mV (Ms.RHE) respectively reaches 2.55mA cm-2 dMsMAnd 2.5mA cm-2 dMsM。
Drawings
FIGS. 1A and B show Pt prepared in examples 1 and 2, respectively1Ru1-EM2O3/C、Pt1Ru1-EuOxTEM image of/C.
FIGS. 2A and B show Pt supported on carbon black as catalysts synthesized in examples 1 and 2, respectively1Ru1-EM2O3/C、Pt1Ru1-EuOxXRD pattern of/C.
FIG. 3 is Pt synthesized in example 11Ru1-EM2O3TEM images of nanoparticles.
FIG. 4 shows PtRu/C, Pt1Ru1-EM2O3/C、Pt1Ru1-EuOxHOR performance diagram measured under alkaline conditions.
FIG. 5 shows a graph of HOR performance of the catalysts synthesized in examples 1, 10, 11, 12 and 13, measured under basic conditions.
FIG. 6 shows HOR performance plots for commercial Pt/C.
Detailed Description
Example 1
The preparation method of the high-performance high-stability rare earth modified PtRu nano-particle catalyst simultaneously acts through double reducing agents under the alkaline condition, and the Ru nano-material is 2-3nm nano-particles with uniform morphology dispersion.
The method comprises the following steps:
(1) mixing 0.2ml of 10mmMl/L erbium nitrate solution, 1ml of 100mmMl/L ruthenium chloride solution, 1ml of 100mmMl/L chloroplatinic acid solution and 0.5ml of 10mg/ml sodium nitrate solution in 10ml of DMF, and stirring at room temperature for 30mMn, wherein the molar ratio of erbium ions, platinum ions and ruthenium ions in the mixed solution is 0.02:1: 1;
(2) adding 26mg of sodium borohydride, stirring for 20mMn, introducing hydrogen to enable the air pressure in the quartz tube to be 0.3MpM, reacting for 3 hours at 150 ℃, cooling to room temperature, centrifugally washing for 3 times by using acetone, and drying for 6 hours to obtain erbium-modified ruthenium platinum nanoparticles;
(3) uniformly mixing the obtained catalyst and carbon black, drying after ultrasonic uniform treatment, and then carrying out heat treatment at 200 ℃ for 2 hours in a muffle furnace to obtain Pt 1Ru1-EM2O3/C。
Example 2
The procedure of example 1 was repeated except that erbium nitrate was replaced with europium nitrate to obtain Pt1Ru1-EuOx/C。
Example 3
Otherwise, the same procedure as in example 1 was repeated except that erbium nitrate was replaced with cerium nitrate to obtain Pt1Ru1-CeOx/C。
Example 4
The same procedure as in example 1 was repeated except that erbium nitrate was replaced with lanthanum nitrate to obtain Pt1Ru1-LMOx/C。
Example 5
The same procedure as in example 1 was repeated except that erbium nitrate was replaced with ytterbium nitrate to obtain Pt1Ru1-YbOx/C。
Example 6
The same procedure as in example 1 was repeated except that erbium nitrate was replaced with yttrium nitrate to obtain Pt1Ru1-YOx/C。
Example 7
The same procedure as in example 1 was repeated except that erbium nitrate was changed to samarium nitrate to obtain Pt1Ru1-SmOx/C。
Example 8
The same procedure as in example 1 was repeated except that erbium nitrate was replaced with gadolinium nitrate to obtain Pt1Ru1-GdOx/C。
Example 9
Otherwise, as in example 1, except that erbium nitrate was changed to praseodymium nitrate, Pt was obtained1Ru1-PMOx/C。
Example 10
The procedure was repeated as in example 1 except that the molar ratio of platinum to ruthenium was changed to 2: 1.
Example 11
The process is the same as example 1 except that the molar ratio of platinum to ruthenium is changed to 3: 1.
Example 12
The process was the same as example 1 except that the molar ratio of platinum to ruthenium was changed to 4: 1.
Example 13
The procedure was repeated as in example 1 except that the molar ratio of platinum to ruthenium was changed to 1: 2.
TABLE 1 HOR performance of different rare earth modified Ru/Pt nanoparticles.
TABLE 2 HOR performance of the synthesized ruthenium platinum nanoparticles for different platinum-ruthenium composition ratios.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (5)
1. A preparation method of rare earth element modified platinum-ruthenium nanoparticles is characterized by comprising the following steps:
(1) preparing a mixed solution of rare earth metal salt, ruthenium salt and platinum salt, adding the mixed solution into DMF, and fully and uniformly stirring; the feeding molar ratio of platinum to ruthenium is 1:0.25-1: 2; the feeding molar ratio of the rare earth ions to the platinum ions in the liquid is 0.02: 1;
(2) then introducing hydrogen, reacting at the temperature of 120-160 ℃ for 3 hours, cooling to room temperature, centrifuging, washing and drying to obtain the ruthenium-platinum nano particles modified by the rare earth oxide;
(3) and uniformly mixing the obtained catalyst and carbon black, performing ultrasonic uniform treatment, drying, and performing heat treatment at 150-400 ℃ for 2h to obtain the PtRu-REE/C.
2. The method according to claim 1, wherein the ruthenium salt is selected from any one of ruthenium chloride and ruthenium acetylacetonate.
3. The method according to claim 1, wherein the platinum salt is selected from any one of chloroplatinic acid and platinum acetylacetonate.
4. The method of claim 1, wherein: the rare earth metal salt is nitrate of Ce, La, Eu, Yb, Sm, Gd, Pr, Y or Er.
5. Use of the rare earth-modified platinum ruthenium PtRu nanomaterial prepared by the method of claim 1 as a catalyst for hydrogen oxidation reaction of an anode in a hydrogen-oxygen fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210224723.4A CN114678551A (en) | 2022-03-07 | 2022-03-07 | Preparation method of rare earth element modified platinum-ruthenium nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210224723.4A CN114678551A (en) | 2022-03-07 | 2022-03-07 | Preparation method of rare earth element modified platinum-ruthenium nanoparticles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114678551A true CN114678551A (en) | 2022-06-28 |
Family
ID=82072447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210224723.4A Pending CN114678551A (en) | 2022-03-07 | 2022-03-07 | Preparation method of rare earth element modified platinum-ruthenium nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114678551A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132069A (en) * | 2007-09-22 | 2008-02-27 | 太原理工大学 | Method for manufacturing carbon-carrying platinum-ruthenium alloy electrode doped with rare earth elements of La series |
| CN101299461A (en) * | 2008-07-03 | 2008-11-05 | 昆明贵金属研究所 | Method for preparing platinum ruthenium doping La series rare earth element polyphase catalysts |
| CN101740786A (en) * | 2009-12-14 | 2010-06-16 | 浙江大学 | PtRu/graphene nano electro-catalyst and preparation method thereof |
| CN110350213A (en) * | 2019-07-25 | 2019-10-18 | 常州北化澳联环保科技有限公司 | Difunctional fuel battery anode catalyst of efficient PtRu/C and preparation method thereof |
| CN110745856A (en) * | 2019-11-27 | 2020-02-04 | 云南大学 | Preparation method of nano-granular cerium oxide composite ruthenium platinum palladium oxide |
| CN112103520A (en) * | 2020-09-24 | 2020-12-18 | 扬州大学 | Anode catalyst of alcohol fuel cell |
| CN114023976A (en) * | 2021-09-27 | 2022-02-08 | 华东理工大学 | Nano platinum-rare earth alloy and preparation method and application thereof |
-
2022
- 2022-03-07 CN CN202210224723.4A patent/CN114678551A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101132069A (en) * | 2007-09-22 | 2008-02-27 | 太原理工大学 | Method for manufacturing carbon-carrying platinum-ruthenium alloy electrode doped with rare earth elements of La series |
| CN101299461A (en) * | 2008-07-03 | 2008-11-05 | 昆明贵金属研究所 | Method for preparing platinum ruthenium doping La series rare earth element polyphase catalysts |
| CN101740786A (en) * | 2009-12-14 | 2010-06-16 | 浙江大学 | PtRu/graphene nano electro-catalyst and preparation method thereof |
| CN110350213A (en) * | 2019-07-25 | 2019-10-18 | 常州北化澳联环保科技有限公司 | Difunctional fuel battery anode catalyst of efficient PtRu/C and preparation method thereof |
| CN110745856A (en) * | 2019-11-27 | 2020-02-04 | 云南大学 | Preparation method of nano-granular cerium oxide composite ruthenium platinum palladium oxide |
| CN112103520A (en) * | 2020-09-24 | 2020-12-18 | 扬州大学 | Anode catalyst of alcohol fuel cell |
| CN114023976A (en) * | 2021-09-27 | 2022-02-08 | 华东理工大学 | Nano platinum-rare earth alloy and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tan et al. | Pd-around-CeO 2− x hybrid nanostructure catalyst: three-phase-transfer synthesis, electrocatalytic properties and dual promoting mechanism | |
| CN105431230A (en) | Method for forming noble metal nanoparticles on a support | |
| CN112281176B (en) | Nitrogen-doped carbon-coated Ru nano catalyst and application thereof in electrochemical deuterium evolution reaction | |
| CN114522706A (en) | Carbide-supported noble metal monatomic catalyst, and preparation and application thereof | |
| CN112044461A (en) | Lignin-based bimetallic functionalized carbon material and preparation method and application thereof | |
| CN114023976A (en) | Nano platinum-rare earth alloy and preparation method and application thereof | |
| CN109686988A (en) | A kind of carbon carrying transition metal atom pair elctro-catalyst and the preparation method and application thereof | |
| CN112103520A (en) | Anode catalyst of alcohol fuel cell | |
| CN109638300A (en) | The preparation method of special appearance rare earth cerium oxide | |
| CN109585865A (en) | A kind of extra small monodisperse PtCu alloy catalyst and the preparation method and application thereof | |
| CN114855208A (en) | Nano iridium oxide electrocatalyst with high crystal water content and preparation method thereof | |
| Hebié et al. | Electrochemical reactivity at free and supported gold nanocatalysts surface | |
| CN113621988A (en) | High-efficiency oxygen precipitation high-entropy amorphous oxide nano catalyst and preparation method and application thereof | |
| CN110416561B (en) | Bifunctional Pt-IrO2Nano-wire electro-catalyst, preparation method thereof and fuel cell | |
| CN112725828A (en) | IrRu-based multicomponent alloy metal precipitation catalyst and preparation method thereof | |
| CN110961101A (en) | Platinum-based catalyst, preparation method and application thereof | |
| CN114678551A (en) | Preparation method of rare earth element modified platinum-ruthenium nanoparticles | |
| CN110061246A (en) | The preparation method of core-shell structure Te@metal electro-oxidizing-catalyzing agent | |
| JP2000067877A (en) | Manufacture of electrode catalyst | |
| CN115172783A (en) | Carbon-base-free loaded high-entropy alloy particle and preparation method and application thereof | |
| Yang et al. | PdCu nanoalloys deposited on porous carbon as a highly efficient catalyst for ethanol oxidation | |
| CN115557469B (en) | Amorphous noble metal oxide material and preparation method and application thereof | |
| CN114988411B (en) | Pure phase W with high specific surface area 2 C nano material and preparation method and application thereof | |
| CN115074774B (en) | Rhodium-based hollow porous microsphere/nickel foam electrode and preparation method and application thereof | |
| CN117161374A (en) | Nitrogen-doped porous carbon-loaded multielement ordered metal alloy nanoparticle and preparation method thereof |
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 |