CN118136867A - Double single atom doped carbon coupled Pt3Zn intermetallic compound and preparation method and application thereof - Google Patents
Double single atom doped carbon coupled Pt3Zn intermetallic compound and preparation method and application thereof Download PDFInfo
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- CN118136867A CN118136867A CN202410300086.3A CN202410300086A CN118136867A CN 118136867 A CN118136867 A CN 118136867A CN 202410300086 A CN202410300086 A CN 202410300086A CN 118136867 A CN118136867 A CN 118136867A
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- intermetallic compound
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- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 89
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000011701 zinc Substances 0.000 claims abstract description 141
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 34
- 230000008878 coupling Effects 0.000 claims abstract description 30
- 238000010168 coupling process Methods 0.000 claims abstract description 30
- 238000005859 coupling reaction Methods 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- 150000003751 zinc Chemical class 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000013110 organic ligand Substances 0.000 claims abstract description 18
- -1 transition metal salt Chemical class 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 229910021399 diatomic carbon Inorganic materials 0.000 claims abstract description 11
- LBVWYGNGGJURHQ-UHFFFAOYSA-N dicarbon Chemical compound [C-]#[C+] LBVWYGNGGJURHQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 103
- 239000012621 metal-organic framework Substances 0.000 description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 238000000197 pyrolysis Methods 0.000 description 15
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000004321 preservation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002149 hierarchical pore Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
- 229910019041 PtMn Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 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
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to the technical field of catalyst preparation, in particular to a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing zinc salt, transition metal salt, organic ligand and solvent, purifying the obtained mixed solution to obtain MOF precursor powder; performing heat treatment on MOF precursor powder in an inert atmosphere, mixing the obtained diatomic carbon doped with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture; and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound. The preparation method can prepare the intermetallic compound catalyst with lower cost and simpler process, has the advantages of high specific surface area, high conductivity, superfine size of intermetallic compound and the like, has a synergistic effect, greatly improves the activity and stability of the catalyst, and is beneficial to improving the performance of devices.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, a preparation method and application thereof.
Background
The proton exchange membrane fuel cell (Proton exchange membrane fuel cell, PEMFC) adopts clean hydrogen as fuel, is a high-efficiency energy conversion technology, and has the advantages of high efficiency, high power density and the like. The oxygen reduction reaction (Oxygen reduction reaction, ORR) efficiency determines the PEMFC output performance, and in order to accelerate the ORR kinetics of the PEMFC, a highly active and stable catalyst needs to be used on the cathode side. Currently, platinum and platinum-based alloy catalysts have proven to have excellent ORR catalytic activity; however, the high price and poor stability of commercial Pt-based catalysts limit the commercial application of PEMFCs. On the premise of not reducing the catalytic activity and stability, the reduction of the use amount of noble metal Pt or partial utilization of non-noble metal materials to replace Pt is the focus of research. Researchers often increase the atomic utilization and intrinsic activity of Pt by reducing the size of the Pt nanostructure, surface strain, alloying, or building specific nanostructures with rich Pt surfaces, thereby achieving the goal of reducing Pt loading. In addition, the carrier of the commercial Pt/C catalyst is carbon black (Vulcan XC-72). The bonding between Pt nanoparticles and carbon black support is weak, resulting in dissolution or particle agglomeration of Pt nanoparticles. Carbon black carriers can undergo carbon corrosion in harsh strong acid environments, poisoning Pt nanoparticles, and thus catalyst deactivation.
The martial university Mu et al report that highly dispersed Mn atom doped carbon as a carrier coupled with ultra-fine Pt nanoparticles, the catalyst shows excellent mass activity, good long-term stability and methanol resistance in acidic media. Furthermore, alloying of Pt with transition metals (M, mainly transition metals Fe, co, ni) can enhance the intrinsic ORR activity of Pt. Huang et al, university of california, los Angeles division designed a graphene-nano-pocket-wrapped PtCo nanocatalyst with good ORR performance at the required ultra-low Pt loading due to the non-contact shell of the graphene nano-pocket. Wu et al, university of chinese science and technology, adopted a special mesoporous carbon limiting strategy to obtain ultra-small size Pt-based intermetallic compounds (Pt 3 Co, ptCo and Pt 3 Ti) that exhibited excellent mass activity and ORR durability. The PtMn nanodendrite catalyst is synthesized by Guo et al at Beijing university using solvothermal method, and strain control caused by Mn shrinkage induces simultaneous increase of ORR activity and stability. However, the yield of the solvothermal synthesized material is relatively low, and the solvothermal synthesis method is not suitable for large-scale application.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound, a preparation method and application thereof, and aims to solve the problems that the intrinsic activity of the existing catalyst is low, the yield of a solvothermal synthesized material is low and the like.
The technical scheme of the invention is as follows:
a preparation method of a double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound comprises the following steps:
Mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution;
Purifying the mixed solution to obtain MOF precursor powder;
Performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon;
Mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture;
And calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound.
The preparation method of the diatomic carbon-doped coupling Pt 3 Zn intermetallic compound comprises the step of preparing a zinc salt, wherein the zinc salt is one or more of zinc acetate, zinc nitrate, zinc sulfate, zinc chloride and zinc oxide; the transition metal salt is selected from one of ferric salt, cobalt salt, nickel salt and manganese salt.
The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound comprises the step of preparing a double monatomic carbon-doped coupled Pt 3 Zn intermetallic compound, wherein the ferric salt is one or more selected from ferric acetate, ferric nitrate, ferric sulfate, ferric chloride and ferric acetylacetonate; the cobalt salt is one or more selected from cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetylacetonate; the nickel salt is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetylacetonate; the manganese salt is selected from one or more of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride and manganese acetylacetonate.
The preparation method of the double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound comprises the step of preparing a double single-atom doped carbon-coupled Pt 3 Zn intermetallic compound, wherein the organic ligand is selected from one or more of imidazole, 2-methylimidazole, 2-nitroimidazole and benzimidazole; and/or the solvent is selected from one or more of methanol, ethanol and deionized water.
The preparation method of the diatomic carbon-doped coupling Pt 3 Zn intermetallic compound comprises the steps of (1) the mass ratio of zinc salt to transition metal salt (0.002-0.06); and/or the mass ratio of the total mass of the zinc salt and the transition metal salt to the organic ligand is 1 (0.5-10).
The preparation method of the diatomic carbon-doped coupling Pt 3 Zn intermetallic compound comprises the step of (4-5) and (1-2) of the mass ratio of the diatomic carbon-doped to the chloroplatinic acid in the chloroplatinic acid aqueous solution.
The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound comprises the steps of heating at a heating rate of 2 ℃/min-20 ℃/min, heating at 800-1100 ℃ and heating for 0.5-10 h.
The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound comprises the steps of heating up at a speed of 2 ℃/min-20 ℃/min, calcining at a temperature of 700 ℃ -1100 ℃ and calcining for 0.5h-3h.
A diatomic carbon-doped coupled Pt 3 Zn intermetallic compound is prepared by a preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound.
The application of double single-atom doped carbon coupling Pt 3 Zn intermetallic compound in proton exchange membrane fuel cell.
The beneficial effects are that: the invention provides a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, a preparation method and application thereof, and the preparation method of the double single-atom doped carbon coupling Pt 3 Zn intermetallic compound comprises the following steps: mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution; purifying the mixed solution to obtain MOF precursor powder; performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon; mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture; and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound. According to the invention, the morphology and the size of the MOF are regulated and controlled through the selection of a solvent in the synthesis process, then the MOF precursor powder is subjected to high-temperature pyrolysis, a corresponding Zn-based diatomic carbon-doped carrier material can be derived, and then the superfine Pt 3 Zn intermetallic compound nano particles are anchored on the diatomic carbon-doped through a dipping-reducing atmosphere calcination method, so that the diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound is obtained. The preparation method can prepare the double single-atom doped carbon-coupled superfine Pt 3 Zn intermetallic compound catalyst with lower cost and simpler process, and has the advantages of high specific surface area, high conductivity, superfine size intermetallic compound and the like. In addition, the catalyst has a synergistic effect, greatly improves the activity and stability of the catalyst, and is more beneficial to improving the performance of devices.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a diatomic carbon-doped coupled Pt 3 Zn intermetallic compound according to the present invention;
FIG. 2 is an XRD pattern of an N-doped carbon anchored Fe/Zn diatomic species prepared in example 1;
FIG. 3 is a TEM image of an N-doped carbon-anchored Fe/Zn diatomic group prepared in example 1;
FIG. 4 is an XRD pattern of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound obtained in example 5;
FIG. 5 is a TEM image of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound obtained in example 5;
FIG. 6 is a graph showing the particle size distribution of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound obtained in example 5;
FIG. 7 is an ORR polarization curve of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound prepared in example 5.
Detailed Description
The invention provides a double single-atom doped carbon coupling Pt 3 Zn intermetallic compound, a preparation method and application thereof, and aims to make the purposes, technical schemes and effects of the invention clearer and more definite, and the invention is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The Metal-organic framework (Metal-organic framework, MOF) becomes an ideal material conversion platform for constructing single/double-atom doped carbon by virtue of the diversity of Metal ions and functional organic ligands (containing N, P, S and other elements) and the diversity of topological structures and sizes. The MOF is used as a reaction template or a precursor derived carbon-based material, and has the advantages of high specific surface area, porous morphology, adjustment and high dispersion of doped metal elements, controllable graphitization degree, high stability and the like. After pyrolysis, the active metal species supported on the MOF framework are converted to monoatomic sites, which are immobilized on the support by formation of coordination bonds with the coordination atoms (N, S, P, O, etc.) on the carbon support. The construction of the double single-atom doped carbon system is regulated and controlled through reasonable design of the composition, structure and morphology of the MOF precursor.
Based on the above, as shown in fig. 1, the present invention provides a preparation method of a diatomic doped carbon coupled Pt 3 Zn intermetallic compound, comprising the steps of:
step S10: mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution;
Step S20: purifying the mixed solution to obtain MOF precursor powder;
Step S30: performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon;
step S40: mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture;
Step S50: and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound.
In the embodiment, the double-single-atom doped carbon prepared by utilizing the pyrolysis of the MOF precursor can improve the bonding effect between the carrier and Pt and improve the stability; meanwhile, double single-atom doped carbon (N-doped carbon anchored double single atoms) can provide a Zn source, and the Zn source is alloyed with Pt nano particles to form the Pt 3 Zn intermetallic compound with high intrinsic activity. The whole preparation process is simple, efficient and environment-friendly, and more importantly, the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound prepared by the preparation method shows excellent ORR performance.
Further, the diatomic carbon-doped coupling intermetallic compound prepared by the preparation method has high specific surface area, high conductivity and ultra-fine size intermetallic compound, and the high specific surface area and the high conductivity are naturally obtained by deriving MOF precursors in the heat treatment process without additional post-treatment; and ultrafine sized intermetallic compounds are formed mainly due to the high specific surface area and the confinement effect of the rich nitrogen coordinating atoms. In addition, the prepared double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound has a synergistic effect, greatly improves the activity and stability of the catalyst, is more beneficial to the improvement of the performance of the device, and simultaneously shows excellent ORR performance.
Specifically, the MOF precursor has excellent structural characteristics of large specific surface area, high porosity and the like, after pyrolysis at high temperature, organic coordination is converted into N-doped carbon, so that the conductivity is improved, metal Zn is evaporated to form a microporous structure, and meanwhile, the structure of the MOF does not collapse, so that the MOF precursor has high specific surface area and a porous structure; after pyrolysis, the active metal species loaded on the MOF framework are converted into monoatomic sites, and the monoatomic sites are fixed on a carrier through coordination bonds formed by coordination atoms (N, S, P, O and the like) on a carbon carrier, so that double monoatoms are formed. Zn in the Zn-rich diatomic doped carbon carrier derived from the MOF precursor diffuses in the calcination process of the reducing atmosphere and combines with Pt to form Pt 3 Zn intermetallic compound.
The PtM intermetallic compound nano particles are prepared independently, and then are loaded on the carbon carrier, so that the metal particles obtained by the method and the carbon carrier mainly depend on physical adsorption, have weak interaction and have low stability. In the double monoatomic doped carbon coupling ultrafine Pt 3 Zn intermetallic compound prepared by the method, a strong coupling effect exists between the Pt 3 Zn intermetallic compound and double monoatomic sites in the carbon carrier, so that interaction between the Pt 3 Zn intermetallic compound and Pt 3 Zn nano particles in the ORR process can be enhanced. Meanwhile, the double monoatomic sites weaken oxygen adsorption on Pt 3 Zn, thereby enhancing intrinsic activity.
In some embodiments, the zinc salt is selected from, but is not limited to, one or more of zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc oxide; the transition metal salt is selected from one of iron salt, cobalt salt, nickel salt and manganese salt. And performing heat treatment on MOF precursor powder prepared by mixing zinc salt, transition metal salt, organic ligand and solvent to obtain the Zn-based diatomic doped carbon carrier material.
In some embodiments, in the step S20, the purification treatment includes centrifugation, washing, and drying; the mixed solution is purified to obtain MOF precursor powder with single component.
In some embodiments, in the step S10 and the step S20, the method specifically includes the steps of: dissolving zinc salt and transition metal salt in a solvent to obtain a first mixed solution; dissolving an organic ligand in a solvent to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution, fully stirring for 12 hours at the temperature of 25-80 ℃, standing for 10 hours, centrifuging to realize solid-liquid separation, repeatedly washing with a solvent, and drying to obtain powder which is MOF precursor powder.
In some embodiments, the iron salt is selected from, but not limited to, one or more of iron acetate, iron nitrate, iron sulfate, iron chloride, iron acetylacetonate; the cobalt salt is selected from one or more of cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetylacetonate; the nickel salt is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetylacetonate; the manganese salt is selected from one or more of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride and manganese acetylacetonate.
Specifically, when the transition metal is ferric salt, preparing Fe-ZIF-8 precursor; when the transition metal is cobalt salt, a Co-ZIF-8 (ZIF-67) precursor is prepared; when the transition metal is nickel salt, preparing a Ni-ZIF-8 precursor; when the transition metal is manganese salt, mn-ZIF-8 precursor is prepared.
In some embodiments, the zeolitic imidazolate framework-8 (ZIF-8) employed may also be replaced with other MOF precursors, such as MOF-5, MOF-74, uiO-66-NH 2, and the like
In some embodiments, the organic ligand is selected from, but not limited to, one or more of imidazole, 2-methylimidazole, 2-nitroimidazole, benzimidazole; and/or the solvent is selected from one or more of methanol, ethanol, deionized water, but not limited to. The imidazole organic ligand contains N, MOF precursor powder obtained by mixing the imidazole organic ligand with zinc salt and transition metal salt is subjected to heat treatment, and then the ligand is decomposed and converted into N-doped carbon; after pyrolysis, the diatomic atom coordinates with N, and can exist stably. And the type of the solvent can regulate the morphology and the size of the MOF.
In some embodiments, the mass ratio of the zinc salt to the transition metal salt is 1 (0.002-0.06); and/or the mass ratio of the total mass of the zinc salt and the transition metal salt to the organic ligand is 1 (0.5-10).
In some embodiments, the ratio of the mass of the diatomic carbon doped to the mass of chloroplatinic acid in the chloroplatinic acid solution is (4-5): 1-2.
In some embodiments, the step S40 specifically includes the steps of: dispersing the diatomic doped carbon in deionized water to obtain a diatomic doped carbon solution with the concentration of 0.25mg/mL-10 mg/mL; and mixing the diatomic carbon doped solution with chloroplatinic acid solution, and freeze-drying to obtain a mixture.
In some embodiments, the chloroplatinic acid solution is an aqueous solution of chloroplatinic acid; the concentration of the chloroplatinic acid aqueous solution is 1mg/mL-50mg/mL.
In some embodiments, the inert atmosphere includes, but is not limited to, one of nitrogen, argon, a mixture of hydrogen and nitrogen, a mixture of hydrogen and argon.
Specifically, the MOF precursor powder is placed in a porcelain boat, transferred into a tube furnace, introduced with inert atmosphere for 1h, discharged with redundant air in the tube furnace, and then subjected to heat treatment.
In some embodiments, the heat treatment has a heating rate of 2 ℃/min to 20 ℃/min, a temperature of 800 ℃ to 1100 ℃, and a time of 0.5h to 10h. The doping amount of double single atoms, the hierarchical pore structure of the carbon carrier, the graphitization degree and the like can be adjusted by changing the temperature and the time of the heat treatment.
Specifically, the imidazole organic ligand contains N element, pyrolysis is carried out at the temperature of 800-1100 ℃, the ligand is decomposed and converted into N-doped carbon, the higher the temperature is, the more unstable the N is, and the content of N is reduced along with the increase of the pyrolysis temperature; after pyrolysis, the diatomic atoms coordinate with N to exist stably, so the content of N determines the content of the diatomic atoms; the more N indicates a lower degree of graphitization, and the less N indicates a higher degree of graphitization. In the pyrolysis stage, zn volatilizes, the boiling point of Zn is 907 ℃, micropores are generated after Zn volatilizes, and therefore, the hierarchical pore structure can be changed by changing the temperature and time of heat treatment.
In some embodiments, the temperature rise rate of the calcination treatment is 2 ℃/min to 20 ℃/min, the temperature of the calcination treatment is 700 ℃ to 1100 ℃, and the time of the calcination treatment is 0.5h to 3h. The size, crystallinity, order, etc. of Pt 3 Zn can be adjusted by changing the temperature and time of the calcination treatment.
Specifically, the invention adopts dipping-reducing atmosphere calcination, certain mass of diatomic doped carbon is dispersed into deionized water, and a certain amount of chloroplatinic acid aqueous solution is added; the mass part of Pt can be realized by controlling the addition amount of chloroplatinic acid; and then ultrasonic dispersion is carried out to enable Pt ions to be adsorbed on the surface of the double monoatomic doped carbon as soon as possible, then room-temperature stirring is carried out, after freeze drying treatment, the dried precursor powder is calcined in inert atmosphere, the heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, and the heat preservation time is set to 1h. And naturally cooling to obtain black powder, namely the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound.
In some embodiments, the reducing atmosphere includes, but is not limited to, one of a different ratio of hydrogen/argon mixture, a different ratio of hydrogen/nitrogen mixture; preferably, the volume ratio of the hydrogen in the mixed gas is 1% -50%.
In addition, the invention also provides a diatomic carbon-doped coupled Pt 3 Zn intermetallic compound, which is prepared by the preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound.
In the embodiment, the MOF is used as a reaction template or a precursor derived carbon-based material, and the preparation method has the advantages of high specific surface area, porous morphology, adjustment and high dispersion of doped metal elements, controllable graphitization degree, high stability and the like. Meanwhile, the MOF-derived Zn-based diatomic can provide a Zn source for the formation of the superfine Pt 3 Zn intermetallic compound, and the Zn source is not required to be additionally introduced; and the double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound can produce a synergistic effect, so that the activity and stability of Pt 3 Zn are improved. Namely, the MOF-derived high specific surface area, zn-rich diatomic and superfine Pt 3 Zn intermetallic compound are utilized to generate a synergistic effect, so that the activity and stability of the catalyst are improved. Meanwhile, the preparation method can realize multiplied production, and has the advantages of simple process, adjustable components and excellent performance.
In addition, the invention also provides application of the double single-atom doped carbon coupling Pt 3 Zn intermetallic compound in a proton exchange membrane fuel cell.
In this embodiment, the application of the diatomic carbon doped coupled Pt 3 Zn intermetallic compound in the electrocatalytic reaction of the exchange membrane fuel cell exhibits excellent performance in electrocatalytic ORR.
The following examples are further given to illustrate the invention in detail. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
The preparation of the N-doped carbon-anchored Fe/Zn diatomic structure in this example comprises the following steps:
50mg of iron acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is Fe-ZIF-8 precursor. Placing the Fe-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Fe/Zn diatomic.
Example 2
The preparation of the N-doped carbon-anchored Co/Zn diatomic includes the following steps:
100mg of cobalt acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is the Co-ZIF-8 precursor. Placing a Co-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Co/Zn diatomic.
Example 3
The preparation of the N-doped carbon-anchored Ni/Zn diatomic includes the following steps:
100mg of nickel acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is the Ni-ZIF-8 precursor. Placing the Ni-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Ni/Zn diatomic.
Example 4
The preparation of the N-doped carbon-anchored Mn/Zn diatomic includes the following steps:
100mg of manganese acetate and 3.0g of zinc nitrate were weighed into 270mL of methanol, and 2.78g of 2-methylimidazole was weighed into 30mL of methanol; and then the two solutions are fully mixed, stirred for 12 hours at 60 ℃ under the oil bath condition, and then kept stand for 10 hours. Centrifuging to realize solid-liquid separation, and repeatedly washing with methanol; the powder obtained after drying is Mn-ZIF-8 precursor. Placing the Mn-ZIF-8 precursor in a tube furnace, and introducing argon for 1h; then carrying out heating heat treatment (the heating rate is set to be 3 ℃/min, the pyrolysis temperature is set to be 1100 ℃, the heat preservation time is set to be 3 h), and naturally cooling to obtain black powder which is N-doped carbon anchored Mn/Zn diatomic.
Example 5
The Fe/Zn diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound prepared in the embodiment comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Fe/Zn diatomic doped carbon (N-doped carbon-anchored Fe/Zn diatomic) prepared in example 1 was weighed into 10mL of deionized water, and then 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, the heat preservation time is set to 1h, and the obtained black powder is the Fe/Zn diatomic carbon-doped superfine Pt 3 Zn intermetallic compound.
Example 6
The preparation method of the Co/Zn diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Co/Zn diatomic doped carbon (N-doped carbon-anchored Co/Zn diatomic) prepared in example 2 was weighed into 10mL of deionized water, and 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The temperature rising rate is set to 10 ℃/min, the calcination temperature is set to 900 ℃, and the heat preservation time is set to 1h. The black powder is Co/Zn double single-atom doped carbon coupling superfine Pt 3 Zn intermetallic compound.
Example 7
The preparation method of the Ni/Zn diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Ni/Zn diatomic doped carbon (N-doped carbon-anchored Ni/Zn diatomic) prepared in example 3 was weighed into 10mL of deionized water, and 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, the heat preservation time is set to 1h, and the obtained black powder is the Ni/Zn diatomic carbon-doped superfine Pt 3 Zn intermetallic compound.
Example 8
The Mn/Zn diatomic carbon doped coupling superfine Pt 3 Zn intermetallic compound is prepared in the embodiment, and comprises the following steps:
The mass fraction of Pt in the target catalyst was set to 10wt%. 50mg of the Mn/Zn diatomic doped carbon (N-doped carbon-anchored Mn/Zn diatomic) prepared in example 4 was weighed into 10mL of deionized water, and 4.5mL of an aqueous solution of chloroplatinic acid (4 mg mL -1) was added thereto, followed by ultrasonic dispersion for 1min and stirring at room temperature for 24 hours. After freeze-drying, the sample was subjected to calcination treatment in a hydrogen/argon mixed atmosphere. The heating rate is set to 10 ℃/min, the calcining temperature is set to 900 ℃, the heat preservation time is set to 1h, and the obtained black powder is the Mn/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound.
Characterization of the N-doped carbon-anchored Fe/Zn diatomic and Fe/Zn diatomic carbon-coupled ultrafine Pt 3 Zn intermetallic compound prepared in example 1 was performed as follows:
The XRD pattern of the N-doped carbon-anchored Fe/Zn diatomic structure obtained in example 1 is shown in FIG. 2, from which it is clear that the N-doped carbon-anchored Fe/Zn diatomic structure obtained in example 1 does not have any diffraction peaks of metal particles and metal compounds, indicating that Fe/Zn is highly dispersed; the TEM image of the N-doped carbon-anchored Fe/Zn diatomic is shown in fig. 3, and no metal particles and metal compounds were observed with the TEM electron microscope, which is typical of diatomic doped carbon.
The XRD pattern of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound prepared in example 5 is shown in figure 4, and diffraction peaks in XRD are matched with characteristic peaks of standard Pt 3 Zn, which indicates that Pt 3 Zn exists in the sample; the TEM image of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound is shown in FIG. 5, the nano particles observed by using a TEM electron microscope are Pt 3 Zn, and the particle size is relatively uniform; the particle size distribution diagram of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound is shown in figure 6, and the particle size statistics shows that the size of the Pt 3 Zn nano-particles in figure 5 is concentrated between 2.5nm and 4.5 nm; the ORR polarization curve of the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound is shown in FIG. 7, and the ORR polarization curve shows that the Fe/Zn diatomic carbon-doped ultrafine Pt 3 Zn intermetallic compound has excellent ORR activity.
In summary, the preparation method and application of the double-single-atom doped carbon-coupled Pt 3 Zn intermetallic compound provided by the invention comprise the following steps: mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution; purifying the mixed solution to obtain MOF precursor powder; performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon; mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture; and calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound. According to the invention, the morphology and the size of the MOF are regulated and controlled through the selection of a solvent in the synthesis process, then the MOF precursor powder is subjected to high-temperature pyrolysis, a corresponding Zn-based diatomic carbon-doped carrier material can be derived, and then the superfine Pt 3 Zn intermetallic compound nano particles are anchored on the diatomic carbon-doped through a dipping-reducing atmosphere calcination method, so that the diatomic carbon-doped coupling superfine Pt 3 Zn intermetallic compound is obtained. The preparation method can prepare the double single-atom doped carbon-coupled superfine Pt 3 Zn intermetallic compound catalyst with lower cost and simpler process, and has the advantages of high specific surface area, high conductivity, superfine size intermetallic compound and the like. In addition, the catalyst has a synergistic effect, greatly improves the activity and stability of the catalyst, and is more beneficial to improving the performance of devices.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. The preparation method of the diatomic carbon-doped coupled Pt 3 Zn intermetallic compound is characterized by comprising the following steps:
Mixing zinc salt, transition metal salt, organic ligand and solvent to obtain mixed solution;
Purifying the mixed solution to obtain MOF precursor powder;
Performing heat treatment on the MOF precursor powder in an inert atmosphere to obtain diatomic doped carbon;
Mixing the diatomic doped carbon with chloroplatinic acid solution and water, and freeze-drying to obtain a mixture;
And calcining the mixture in a reducing atmosphere to obtain the double single-atom doped carbon coupling ultrafine Pt 3 Zn intermetallic compound.
2. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the zinc salt is selected from one or more of zinc acetate, zinc nitrate, zinc sulfate, zinc chloride, zinc oxide; the transition metal salt is selected from one of ferric salt, cobalt salt, nickel salt and manganese salt.
3. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 2, wherein the iron salt is one or more selected from the group consisting of iron acetate, iron nitrate, iron sulfate, iron chloride, and iron acetylacetonate; the cobalt salt is one or more selected from cobalt acetate, cobalt nitrate, cobalt sulfate, cobalt chloride and cobalt acetylacetonate; the nickel salt is selected from one or more of nickel acetate, nickel nitrate, nickel sulfate, nickel chloride and nickel acetylacetonate; the manganese salt is selected from one or more of manganese acetate, manganese nitrate, manganese sulfate, manganese chloride and manganese acetylacetonate.
4. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the organic ligand is selected from one or more of imidazole, 2-methylimidazole, 2-nitroimidazole, benzimidazole; and/or the solvent is selected from one or more of methanol, ethanol and deionized water.
5. The method for preparing the diatomic carbon doped coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the mass ratio of the zinc salt to the transition metal salt is 1 (0.002-0.06); and/or the mass ratio of the total mass of the zinc salt and the transition metal salt to the organic ligand is 1 (0.5-10).
6. The method for producing a diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the mass ratio of the diatomic doped carbon to chloroplatinic acid in the chloroplatinic acid solution is (4-5): 1-2.
7. The method for preparing the diatomic carbon doped coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the heating rate of the heat treatment is 2 ℃/min-20 ℃/min, the temperature of the heat treatment is 800 ℃ -1100 ℃, and the time of the heat treatment is 0.5h-10h.
8. The method for preparing the diatomic doped carbon coupled Pt 3 Zn intermetallic compound according to claim 1, wherein the temperature rise rate of the calcination treatment is 2 ℃/min-20 ℃/min, the temperature of the calcination treatment is 700 ℃ -1100 ℃, and the time of the calcination treatment is 0.5h-3h.
9. A diatomic carbon doped coupled Pt 3 Zn intermetallic compound prepared using the method of preparing a diatomic carbon doped coupled Pt 3 Zn intermetallic compound as defined in any one of claims 1 to 8.
10. Use of a diatomic carbon doped coupled Pt 3 Zn intermetallic compound as defined in claim 9 in a proton exchange membrane fuel cell.
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