CN117638112A - Nd-doped FeNC catalyst and preparation method thereof - Google Patents
Nd-doped FeNC catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000000197 pyrolysis Methods 0.000 claims abstract description 18
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 69
- 239000002243 precursor Substances 0.000 claims description 67
- 150000003839 salts Chemical class 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 8
- 150000003384 small molecules Chemical class 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- 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 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 claims description 2
- LOXWVAXWPZWIOO-UHFFFAOYSA-N 7-bromo-1-chloronaphthalene Chemical compound C1=C(Br)C=C2C(Cl)=CC=CC2=C1 LOXWVAXWPZWIOO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001206 Neodymium Chemical class 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 2
- VQVDTKCSDUNYBO-UHFFFAOYSA-N neodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VQVDTKCSDUNYBO-UHFFFAOYSA-N 0.000 claims description 2
- GPHQHTOMRSGBNZ-UHFFFAOYSA-N pyridine-4-carbonitrile Chemical compound N#CC1=CC=NC=C1 GPHQHTOMRSGBNZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- 238000006276 transfer reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000010757 Reduction Activity Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 49
- 239000010453 quartz Substances 0.000 description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 42
- 238000003756 stirring Methods 0.000 description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 238000000227 grinding Methods 0.000 description 21
- 239000000843 powder Substances 0.000 description 21
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000000967 suction filtration Methods 0.000 description 14
- 238000005303 weighing Methods 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000002390 rotary evaporation Methods 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000010183 spectrum analysis Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 229910002556 Fe–N4 Inorganic materials 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- SEQUALWBCFCDGP-UHFFFAOYSA-N [C].[N].[Fe] Chemical compound [C].[N].[Fe] SEQUALWBCFCDGP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 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
Abstract
The application provides an Nd-doped FeNC catalyst and a preparation method thereof. The catalyst comprises an organic metal framework compound carrier formed by doping N with C, nd and Fe loaded on the carrier, and an electronic structure of Fe sites is regulated and controlled through abundant underfilling orbits of an Nd atom 4f layer, so that the adsorption strength of Fe centers on oxygen reduction intermediates is reduced, and the free energy of a fast-stepping is optimized. Compared with the traditional Fenc catalyst, the synthesized Nd-doped Fenc catalyst has higher oxygen reduction activity, the Fenton effect of the catalyst is reduced due to the addition of Nd, the two-electron transfer reaction and the four-electron transfer reaction of oxygen on the surface of the catalyst are fewer, the reaction efficiency is improved, the hydrogen peroxide yield is reduced, and the durability of the catalyst is improved. The preparation method provided by the application is simple in condition, the selected Nd and Fe elements are low in price, and the preparation method is higher in performance compared with the one-time pyrolysis preparation method, and is expected to become a fuel cell non-noble metal catalyst with application prospect.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a Nd-doped FeNC catalyst and a preparation method thereof.
Background
The reduction of fossil energy use is becoming a major concern due to the advent of the "two carbon" goal. The proton exchange membrane fuel cell has the advantages of high energy conversion efficiency, cleanness and reproducibility, and is an energy technology with future prospect. The cost of the catalyst in the current fuel cell cost occupies a large proportion, and noble metals such as platinum in the noble metal catalysts used in the current business are an important reason for high catalyst cost, so that the research on the replacement catalysts of the noble metal catalysts with low price is significant for promoting the large-scale application of the fuel cells.
Currently, the non-noble metal catalysts are mainly based on an atomic supported catalyst on an N-doped carbon substrate (Singh, s.k. adv. mater 2019, 31, (13), 1804297), wherein the nitrogen-doped carbon catalyst supported by iron atoms is represented by its excellent performance, and is attracting attention of researchers. Li et al (Li, Z.Adv. Mater.2022, 35, (9), e 2209644.) prepared a single atom Fe catalyst on a mesoporous nitrogen-doped carbon catalyst using a combination of polymer coating, wet chemical adsorption, ammonia treatment and pyrolysis using a pyrolysis process with ZIF-8 as a precursor, and had good catalytic performance at all pH conditions. Peng et al (Peng, L.adv Mater2022, 34, (29), e 2202544.) functionalize MOF-74 as a precursor by synthesizing Fe-N4 sites on the surface of the carbon substrate using a microwave-assisted pyrolysis method. The synthesis method forms a stable hierarchical porous structure and rich FeN4-O active sites, and the alkaline medium shows remarkable ORR catalytic activity.
However, the catalytic activity of iron nitrogen carbon catalysts is still not as good as noble metal catalysts, and it was found in studies that the presence of a two electron transfer path during the reaction of FenC catalysts, the resulting free radical induced Fenton effect accelerates the performance decay of the catalysts (Kumar, K. Chemical Reviews 2023, 123, (15), 9265-9326.). Therefore, higher four-electron transfer path selectivity is needed to reduce catalyst deactivation, which is beneficial for future applications.
Therefore, providing a better catalyst is a technical problem to be solved in the art.
Disclosure of Invention
The application aims to provide a better catalyst, in particular to an Nd-doped FeNC catalyst and a preparation method thereof.
The scheme that this application was used for solving above-mentioned technical problem is:
an Nd-doped FeNC catalyst comprises an organometallic framework compound carrier formed by N-doping C, and Nd and Fe supported on the carrier.
Further, based on elemental simple substance, the mass percent of Fe is 0.3% -3%, the mass percent of Nd is 0.2% -1.5%, and the mass percent of N in the carrier is 5% -20%.
The second scheme for solving the technical problems is as follows:
a preparation method of an Nd-doped FeNC catalyst comprises the following steps:
s1: complexing a solution containing M salt and Fe salt with an organic ligand solution containing N to form crystals of an organic metal framework, washing and drying to obtain a first precursor; wherein, the M salt is a salt of a metal which can be used as an organic metal frame node; preferably, the M salt is selected from at least one of Zr salt, ce salt, zn salt, fe salt, cu salt, V salt, in salt, cr salt, hf, mg salt; more preferably, the M salt is a Zn salt.
S2: carrying out pyrolysis treatment on the first precursor obtained in the step S1 in an inert atmosphere to obtain a second precursor;
s3: fully mixing the second precursor obtained in the step S2, the N-containing small molecules and Nd salt in a solution, and removing the solvent to obtain a third precursor;
s4: and (3) carrying out pyrolysis treatment on the third precursor obtained in the step (S3) in an argon-hydrogen atmosphere to obtain the Nd-doped FeNC catalyst.
Further, in step S1: the Fe salt is at least one of ferric nitrate, ferric nitrate nonahydrate, ferric trichloride hexahydrate and ferric acetylacetonate.
Further, in step S1: the N-containing organic ligand is at least one of 2-methylimidazole, 2-formaldehyde and 4-cyanopyridine, preferably 2-methylimidazole.
Further, step S1 is: respectively dissolving M salt, fe salt and an N-containing organic ligand in a solvent, wherein the mixing sequence is that firstly adding Fe salt solution into the N-containing organic ligand solution, fully mixing, and then adding the M salt solution for mixing reaction for 12-24 hours to obtain a first precursor; wherein, the molar ratio of Fe salt, M salt and N-containing organic ligand is 9: (70-200): (300-1000).
Further, the Zn salt is at least one of zinc nitrate, zinc nitrate hexahydrate, zinc sulfate heptahydrate, zinc acetylacetonate, zinc acetate and zinc chloride.
Further, in step S1: the solvent is independently selected from at least one of methanol, ethanol, isopropanol, and water, preferably methanol.
Further, in the step S2, the inert gas is nitrogen or argon, preferably argon, and the pyrolysis temperature is 800-1000 ℃, preferably 950-1000 ℃; the pyrolysis treatment time is 0.5h-3h, preferably 1h-2h; the heating rate is 2 ℃/min-15 ℃/min, preferably 5-10 ℃/min.
Further, the step S3 specifically includes: dispersing the second precursor, nd salt and N-containing small molecules in a solvent, uniformly dispersing the second precursor, nd salt and N-containing small molecules by ultrasonic treatment for 0.5-1 h, stirring the mixture at room temperature for 6-12h, and removing the solvent to obtain a third precursor.
Further, the Nd salt in step S3 is at least one of neodymium chloride, neodymium chloride hexahydrate, neodymium acetate, neodymium nitrate hexahydrate, and neodymium acetylacetonate.
Further, the N-containing small molecules in step S3 are: at least one of urea, dicyandiamide, melamine and phenanthroline.
Further, the solvent in step S3 is independently selected from at least one of methanol, ethanol, isopropanol, and water, preferably methanol.
Further, in step S3, the mass ratio of the second precursor to the N-containing small molecule and neodymium salt is 1000: (1000-5000): (5-200).
Further, the atmosphere used in the pyrolysis in the step S4 is a mixed gas of argon and hydrogen; wherein, the volume ratio of the hydrogen is 3-15%, preferably 5-10%, and the balance is argon; the pyrolysis temperature used is 800 ℃ to 1000 ℃, preferably 950 ℃ to 1000 ℃. The pyrolysis treatment time is 0.5-3 h, preferably 1-2h, and the heating rate is 2-15 ℃/min, preferably 5-10 ℃/min.
Further, step S2 further includes performing acid leaching treatment on the second precursor Nd-doped FeNC catalyst.
Further, step S4 further includes acid leaching the Nd-doped FeNC catalyst.
Further, the acid leaching treatment specifically comprises: dispersing the second precursor or the Nd-doped FeNC catalyst in 0.5-3mol/L acid solution for soaking for 4-24 hours, preferably 12-20 hours; then washed with water, preferably suction filtered. Washing with water for 1-3 times, and drying at 25-60deg.C, preferably 50-60deg.C for 4-12 hr, preferably 8-10 hr.
The beneficial effects of this application lie in:
1. the application provides an Nd-doped FeNC catalyst. The catalyst comprises an organic metal framework compound carrier formed by doping N with C, nd and Fe loaded on the carrier, and an electronic structure of Fe sites is regulated and controlled through abundant underfilling orbits of an Nd atom 4f layer, so that the adsorption strength of Fe centers on oxygen reduction intermediates is reduced, and the free energy of a fast-stepping is optimized. Compared with the traditional Fenc catalyst, the synthesized Nd-doped Fenc catalyst has higher oxygen reduction activity, the Fenton effect of the catalyst is reduced due to the addition of Nd, the two-electron transfer reaction and the four-electron transfer reaction of oxygen on the surface of the catalyst are fewer, the reaction efficiency is improved, the hydrogen peroxide yield is reduced, and the durability of the catalyst is improved.
2. The preparation method provided by the invention has simple conditions, and the selected Nd and Fe elements have low price, and the preparation method has higher performance compared with the one-time pyrolysis preparation method, and is expected to become a fuel cell non-noble metal catalyst with application prospect.
3. The catalyst obtained by the preparation method provided by the invention has a regular polyhedral structure, nd and Fe elements exist on the surface of the catalyst, the catalyst mainly comprises N doped C, and the elements are uniformly distributed on the surface of the catalyst. The catalyst mainly exists in the form of graphite carbon, and Fe and Nd in the catalyst are doped with the dispersion degree of single atom level. Nd is mainly Nd 3+ In the form of (2) the catalyst is free of Nd clusters.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention. In the drawings, like reference numerals are used to identify like elements. The drawings, which are included in the description, illustrate some, but not all embodiments of the invention. Other figures can be derived from these figures by one of ordinary skill in the art without undue effort.
FIG. 1 is a scanning electron microscope image of an embodiment of the present invention;
FIG. 2 is a transmission electron microscope image of one embodiment of the present invention;
FIG. 3 is a surface element profile of one embodiment of the present invention;
FIG. 4 is an X-ray diffraction analysis chart of one embodiment of the present invention;
FIG. 5 is an X-ray photoelectron spectrum of an embodiment of the invention;
FIG. 6 is a graphical representation of a linear sweep voltammetric test result arrangement in accordance with one embodiment of the present invention;
FIG. 7 is a graph showing the results of calculation of hydrogen peroxide yield and electron transfer number according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, weighing 40 mmol of 2-methylimidazole by using an electronic balance, dissolving in 80mL of methanol, stirring for 0.5h, adding a methanol solution containing 30mg of ferric chloride, and stirring for 0.5h to obtain a yellow transparent solution A; 8mmol of zinc nitrate was weighed out and dissolved in 40mL of methanol and stirred for 0.5h to give a clear solution B. Adding the solution B into the solution A, uniformly mixing, stirring for 24 hours, centrifuging, washing with ethanol, repeating for three times to obtain a light yellow solid, drying in a 50 ℃ oven for 10 hours, and grinding in a mortar until the light yellow solid is completely light yellow powder, namely the first precursor.
S2, placing the first precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12h, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10h, and collecting the obtained black powder to obtain the iron-doped carbon carrier, namely the second precursor.
S3, weighing 100mg of a second precursor by using an electronic balance, dispersing in 40mL of ethanol, adding 200mg of dicyandiamide, adding a solution containing 20 mu mol of neodymium chloride, fully stirring for 12 hours, and removing the solvent by rotary evaporation to obtain a black solid, namely a third precursor.
S4, placing the third precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed atmosphere containing 10% hydrogen, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the Nd-doped FeNC catalyst of the embodiment 1.
Comparative example 1
A Nd-free catalyst was prepared in substantially the same manner as in example 1 except that: nd salt is not added in step S3.
The Nd-doped FeNC catalyst of example 1 was subjected to scanning electron microscope characterization, and the result is shown in fig. 1, and it can be seen that the catalyst has a regular polyhedral structure.
The catalyst of example 1 was subjected to transmission electron microscopy characterization, and the results are shown in fig. 2, so that the catalyst composition and structure are relatively uniform, and no obvious particle aggregation or agglomeration phenomenon exists on the surface.
The distribution of the elements on the surface of the catalyst is represented as shown in figure 3, and the result shows that Nd and Fe elements exist on the surface of the catalyst, the catalyst mainly comprises N doped C, and the elements are uniformly distributed on the surface of the catalyst.
As a result of X-ray diffraction analysis of the catalyst obtained in example 1, as shown in FIG. 4, it was found that the catalyst was mainly in the form of graphite carbon, indicating that Fe and Nd were mainly in the form of atomic dispersion in the catalyst.
As a result of X-ray photoelectron spectroscopy analysis of the catalyst obtained in example 1, as shown in FIG. 5, nd in Nd-doped FeNC was mainly represented by Nd 3+ Also indicating that the catalyst is free of Nd clusters.
The catalyst obtained in example 1 was used in a catalyst of 1mol/L HClO 4 The linear sweep voltammetric test was performed in solution and compared with comparative example 1, and the results are shown in fig. 6, and it can be seen that the Nd doped FeNC catalyst has better catalytic performance than comparative example 1.
The hydrogen peroxide yield and the electron transfer number were calculated for the catalyst obtained in example 1 and compared with those of comparative example 1, and as shown in fig. 6, it can be seen that the hydrogen peroxide yield of the catalyst was lower than that of the comparative sample, and that the electron transfer number was closer to 4 electrons than that of comparative example 1.
Example 2
S1, at room temperature, 80 mmol of 2-methylimidazole is weighed by using an electronic balance and dissolved in 120 mL methanol, the mixture is stirred for 0.5h, a methanol solution containing 60 mg ferric chloride is added, and the mixture is stirred for 0.5h to obtain yellow transparent solution A; 16 mmol of zinc nitrate was weighed out and dissolved in 60mL of methanol and stirred for 0.5h to give a clear solution B. Adding the solution B into the solution A, uniformly mixing, stirring for 24 hours, centrifuging, washing with ethanol, repeating for three times to obtain a light yellow solid, drying in a 50 ℃ oven for 10 hours, and grinding in a mortar until the light yellow solid is completely light yellow powder, namely the first precursor.
S2, placing the first precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12h, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10h, and collecting the obtained black powder to obtain the iron-doped carbon carrier, namely the second precursor.
S3, weighing 100mg of a second precursor by using an electronic balance, dispersing in 40mL of ethanol, adding 200mg of dicyandiamide, adding a solution containing 20 mu mol of neodymium chloride, fully stirring for 12 hours, and removing the solvent by rotary evaporation to obtain a black solid, namely a third precursor.
S4, placing the third precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed atmosphere containing 10% hydrogen, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the Nd-doped FeNC catalyst.
The Nd-doped FeNC catalyst obtained in example 2 was subjected to electron microscopic characterization, X-ray diffraction spectrum analysis, X-ray photoelectron spectroscopy analysis and electrochemical performance test, and the results were similar to those of example 1.
Example 3
S1, weighing 40 mmol of 2-methylimidazole by using an electronic balance, dissolving in 80mL methanol, stirring for 0.5h, adding a methanol solution containing 30mg ferric chloride, and stirring for 0.5h to obtain a yellow transparent solution A; 8mmol of zinc nitrate was weighed out and dissolved in 40mL methanol and stirred for 0.5h to give a clear solution B. Adding the solution B into the solution A, uniformly mixing, stirring for 24 hours, centrifuging, washing with ethanol, repeating for three times to obtain a light yellow solid, drying in a 50 ℃ oven for 10 hours, and grinding in a mortar until the light yellow solid is completely light yellow powder, namely the first precursor.
S2, placing the first precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 60 ℃ oven for drying treatment for 12 hours, and collecting the obtained black powder to obtain the iron-doped carbon carrier, namely the second precursor.
S3, weighing 100mg of a second precursor by using an electronic balance, dispersing in 40mL of ethanol, adding 200mg of dicyandiamide, adding a solution containing 40 mu mol of neodymium chloride, fully stirring for 12 hours, and removing the solvent by rotary evaporation to obtain a black solid, namely a third precursor.
S4, placing the third precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed atmosphere containing 10% hydrogen, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the Nd-doped FeNC catalyst.
The Nd-doped FeNC catalyst obtained in example 3 was subjected to electron microscopic characterization, X-ray diffraction spectrum analysis, X-ray photoelectron spectroscopy analysis and electrochemical performance test, and the results were similar to those of example 1.
Example 4
S1, at room temperature, 45 mmol of 2-methylimidazole is weighed by using an electronic balance and dissolved in 80mL methanol, the mixture is stirred for 0.5h, a methanol solution containing 30mg ferric chloride is added, and the mixture is stirred for 0.5h, so that a yellow transparent solution A is obtained; 9 mmol of zinc nitrate was weighed out and dissolved in 60mL of methanol and stirred for 0.5h to give a clear solution B. Adding the solution B into the solution A, uniformly mixing, stirring for 24 hours, centrifuging, washing with ethanol, repeating for three times to obtain a light yellow solid, drying in a 50 ℃ oven for 10 hours, and grinding in a mortar until the light yellow solid is completely light yellow powder, namely the first precursor.
S2, placing the first precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 12 hours, and collecting the obtained black powder to obtain the iron-doped carbon carrier, namely the second precursor.
S3, weighing 100mg of a second precursor by using an electronic balance, dispersing in 40mL of isopropanol, adding 300mg of dicyandiamide, adding a solution containing 15 mu mol of neodymium chloride, fully stirring for 12 hours, and removing the solvent by rotary evaporation to obtain a black solid, namely a third precursor.
S4, placing the third precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed atmosphere containing 5% hydrogen, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the Nd-doped FeNC catalyst.
The Nd-doped FeNC catalyst obtained in example 4 was subjected to electron microscopic characterization, X-ray diffraction spectrum analysis, X-ray photoelectron spectroscopy analysis and electrochemical performance test, and the results were similar to those of example 1.
Example 5
S1, weighing 75 mmol of 2-methylimidazole by using an electronic balance, dissolving in 100 mL methanol, stirring for 0.5h, adding a methanol solution containing 50 mg ferric chloride, and stirring for 0.5h to obtain a yellow transparent solution A; 13 mmol of zinc nitrate was weighed out and dissolved in 60mL of methanol and stirred for 0.5h to give a clear solution B. Adding the solution B into the solution A, uniformly mixing, stirring for 24 hours, centrifuging, washing with ethanol, repeating for three times to obtain a light yellow solid, drying in a 60 ℃ oven for 10 hours, and grinding in a mortar until the light yellow solid is completely light yellow powder, namely the first precursor.
S2, placing the first precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in a hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 60 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the iron-doped carbon carrier, namely the second precursor.
S3, weighing 100mg of a second precursor by using an electronic balance, dispersing in 40mL of methanol, adding 200mg of melamine, adding a solution containing 20 mu mol of neodymium chloride, fully stirring for 12 hours, and removing the solvent by rotary evaporation to obtain a black solid, namely a third precursor.
S4, placing the third precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed atmosphere containing 10% hydrogen, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the Nd-doped FeNC catalyst.
The Nd-doped FeNC catalyst obtained in example 5 was subjected to electron microscopic characterization, X-ray diffraction spectrum analysis, X-ray photoelectron spectroscopy analysis and electrochemical performance test, and the results were similar to those of example 1.
Example 6
S1, weighing 40 mmol of 2-methylimidazole by using an electronic balance, dissolving in 80mL methanol, stirring for 0.5h, adding a methanol solution containing 40 mg ferric acetylacetonate, and stirring for 0.5h to obtain a yellow transparent solution A; 8mmol of zinc nitrate was weighed out and dissolved in 40mL of methanol and stirred for 0.5h to give a clear solution B. Adding the solution B into the solution A, uniformly mixing, stirring for 24 hours, centrifuging, washing with ethanol, repeating for three times to obtain a light yellow solid, drying in a 50 ℃ oven for 10 hours, and grinding in a mortar until the light yellow solid is completely light yellow powder, namely the first precursor.
S2, placing the first precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12h, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10h, and collecting the obtained black powder to obtain the iron-doped carbon carrier, namely the second precursor.
S3, weighing 100mg of a second precursor by using an electronic balance, dispersing in 40mL of ethanol, adding 200mg of dicyandiamide, adding a solution containing 20 mu mol of neodymium chloride, fully stirring for 12 hours, and removing the solvent by rotary evaporation to obtain a black solid, namely a third precursor.
S4, placing the third precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed atmosphere containing 10% hydrogen, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the Nd-doped FeNC catalyst.
The Nd-doped FeNC catalyst obtained in example 6 was subjected to electron microscopic characterization, X-ray diffraction spectrum analysis, X-ray photoelectron spectroscopy analysis and electrochemical performance test, and the results were similar to those of example 1.
Example 7
S1, at room temperature, 80 mmol of 2-methylimidazole is weighed by using an electronic balance and dissolved in 120 mL methanol, the mixture is stirred for 0.5h, a methanol solution containing 60 mg ferric chloride is added, and the mixture is stirred for 0.5h to obtain yellow transparent solution A; 16 mmol of zinc nitrate was weighed out and dissolved in 60mL of methanol and stirred for 0.5h to give a clear solution B. Adding the solution B into the solution A, uniformly mixing, stirring for 24 hours, centrifuging, washing with ethanol, repeating for three times to obtain a light yellow solid, drying in a 50 ℃ oven for 10 hours, and grinding in a mortar until the light yellow solid is completely light yellow powder, namely the first precursor.
S2, placing the first precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12h, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10h, and collecting the obtained black powder to obtain the iron-doped carbon carrier, namely the second precursor.
S3, weighing 100mg of a second precursor by using an electronic balance, dispersing in 40mL of ethanol, adding 200mg of dicyandiamide, adding a solution containing 20 mu mol of neodymium acetylacetonate, fully stirring for 12 hours, and removing the solvent by rotary evaporation to obtain a black solid, namely a third precursor.
S4, placing the third precursor in a quartz boat, placing the quartz boat in a heating center of a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 5 ℃/min under an argon-hydrogen mixed atmosphere containing 10% hydrogen, and then maintaining 950 ℃ for 1h, so that the quartz boat is naturally cooled to room temperature, and a black solid is obtained. Grinding the black solid, dispersing in hydrochloric acid solution with the concentration of 1mol/L, fully mixing, stirring for 12 hours, carrying out suction filtration, washing with deionized water, repeating for three times, then placing in a 50 ℃ oven for drying treatment for 10 hours, and collecting the obtained black powder to obtain the Nd-doped FeNC catalyst.
The Nd-doped FeNC catalyst obtained in example 7 was subjected to electron microscopic characterization, X-ray diffraction spectrum analysis, X-ray photoelectron spectroscopy analysis and electrochemical performance test, and the results were similar to those of example 1.
In each of examples 1 to 7, zinc nitrate was used as the M salt in step S1. The M salt is used for forming an organic metal frame together with the Fe salt in the invention, and can be used as the M salt as the metal salt of the organic metal frame node, so that the M salt can be selected by a person skilled in the art according to the needs, and the achievement of the purpose of the invention is not affected, and therefore the M salt is not listed.
The above description may be implemented alone or in various combinations and these modifications are within the scope of the present invention.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific examples described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (10)
1. An Nd-doped FeNC catalyst is characterized by comprising an organic metal framework compound carrier formed by N-doped C, and Nd and Fe supported on the carrier.
2. The Nd-doped FeNC catalyst according to claim 1, characterized in that the mass percentage of Fe is 0.3% -3%, the mass percentage of Nd is 0.2% -1.5% and the mass percentage of N in the carrier is 5% -20% based on elemental substance.
3. A process for the preparation of a catalyst according to claim 1 or 2, comprising the steps of:
s1: complexing a solution containing M salt and Fe salt with an organic ligand solution containing N to form crystals of an organic metal framework, washing and drying to obtain a first precursor; wherein, the M salt is a salt of a metal which can be used as an organic metal frame node;
s2: carrying out pyrolysis treatment on the first precursor obtained in the step S1 in an inert atmosphere to obtain a second precursor;
s3: fully mixing the second precursor obtained in the step S2, the N-containing small molecules and Nd salt in a solution, and removing the solvent to obtain a third precursor;
s4: and (3) carrying out pyrolysis treatment on the third precursor obtained in the step (S3) in an argon-hydrogen atmosphere to obtain the Nd-doped FeNC catalyst.
4. A method according to claim 3, wherein in step S1: the Fe salt is at least one of ferric nitrate, ferric nitrate nonahydrate, ferric trichloride hexahydrate and ferric acetylacetonate; the N-containing organic ligand is at least one of 2-methylimidazole, 2-formaldehyde and 4-cyanopyridine.
5. A method according to claim 3, wherein step S1 is: respectively dissolving M salt, fe salt and an N-containing organic ligand in a solvent, wherein the mixing sequence is that firstly adding Fe salt solution into the N-containing organic ligand solution, fully mixing, and then adding the M salt solution for mixing reaction for 12-24 hours to obtain a first precursor; wherein, the molar ratio of Fe salt, M salt and N-containing organic ligand is 9: (70-200): (300-1000).
6. The method according to claim 3, wherein in step S2, the inert gas is nitrogen or argon, and the pyrolysis temperature is 800 ℃ to 1000 ℃; the pyrolysis treatment time is 0.5h-3h; the temperature rising rate is 2 ℃/min-15 ℃/min.
7. The method according to claim 3, wherein the Nd salt in step S3 is at least one of neodymium chloride, neodymium chloride hexahydrate, neodymium acetate, neodymium nitrate hexahydrate, and neodymium acetylacetonate; the N-containing small molecules are as follows: at least one of urea, dicyandiamide, melamine and phenanthroline; the solvents used were: at least one of ethanol, methanol, isopropanol and water; in the step S3, the mass ratio of the second precursor to the N-containing small molecules and neodymium salt is 1000: (1000-5000): (5-200).
8. The method according to claim 3, wherein in the argon-hydrogen atmosphere in the step S4, the volume ratio of hydrogen is 3% -15%, and the balance is argon; the pyrolysis temperature is 800-1000 ℃, the pyrolysis treatment time is 0.5-3 h, and the heating rate is 2-15 ℃/min.
9. The method according to claim 3, wherein step S2 further comprises acid leaching the second precursor; and step S4, carrying out acid leaching treatment on the Nd-doped FeNC catalyst.
10. The method according to claim 9, wherein the acid leaching treatment is specifically: dispersing the second precursor or the Nd-doped FeNC catalyst in 0.5-3mol/L acid solution for soaking for 4-24 h, and then washing with water; the drying condition is 25-60 ℃ and the time is 4-12 h.
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