CN106975490A - Iron compound particle, the method for the manufacture iron compound particle and the oxidation catalyst using the iron compound particle - Google Patents
Iron compound particle, the method for the manufacture iron compound particle and the oxidation catalyst using the iron compound particle Download PDFInfo
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- CN106975490A CN106975490A CN201611204147.8A CN201611204147A CN106975490A CN 106975490 A CN106975490 A CN 106975490A CN 201611204147 A CN201611204147 A CN 201611204147A CN 106975490 A CN106975490 A CN 106975490A
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- Prior art keywords
- iron compound
- compound particle
- ions
- beyond
- metallic element
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- 150000002506 iron compounds Chemical class 0.000 title claims abstract description 201
- 239000002245 particle Substances 0.000 title claims abstract description 172
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 65
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 238000005259 measurement Methods 0.000 claims abstract description 36
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract description 6
- 238000002296 dynamic light scattering Methods 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- 150000002500 ions Chemical class 0.000 claims description 72
- 229910003153 β-FeOOH Inorganic materials 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 26
- 229910021645 metal ion Inorganic materials 0.000 claims description 23
- 239000011164 primary particle Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- 229910002588 FeOOH Inorganic materials 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 125
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 51
- 230000000052 comparative effect Effects 0.000 description 46
- 230000003197 catalytic effect Effects 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 229910002651 NO3 Inorganic materials 0.000 description 21
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 21
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 238000009616 inductively coupled plasma Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000004993 emission spectroscopy Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- -1 citrate.In addition Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 241000931526 Acer campestre Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical class [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- UWTNZVZEAHSTRO-UHFFFAOYSA-N azane;ethane-1,2-diamine Chemical compound N.NCCN UWTNZVZEAHSTRO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/862—Iron and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Abstract
The present invention relates to iron compound particle, the method for the manufacture iron compound particle and the oxidation catalyst using the iron compound particle.The iron compound particle is comprising β FeOOH crystalline phases and for the metallic element beyond the Fe for the β FeOOH crystalline phases of adulterating, wherein the metallic element beyond the Fe is selected from least one of following element metallic element：Al；And 3d the and 4d transition metal belonged to beyond the Fe of the race of periodic table the 4th~12, metallic element beyond the Fe is 0.001~0.5 to the atomic ratio (metallic element/Fe elements beyond Fe) of Fe elements, and the iron compound particle meets at least one of (A) and (B) claimed below：(A) crystallite diameter with 1~60nm when by X-ray diffraction measurement；(B) average grain diameter with 1~600nm in the dynamic light scattering measurement in by solvent.
Description
Technical field
The present invention relates to the method for the iron compound particle with β-FeOOH crystalline phases, the manufacture iron compound particle
And use the oxidation catalyst of the iron compound particle.
Background technology
The solution of the problem of as on global environment and exhausted fossil fuel, notice has been concentrated on hydrogen
The utilization and carbon dioxide fixation of energy are technical.Firstly, it is desirable at normal temperatures and pressures that water decomposition is anti-for the water-splitting of hydrogen and oxygen
Cleaning energy production method should be used as with the carbon dioxide reduction reaction that water is used as to electron source.These reactions are inevitably required
Water should carry out oxidation reaction：
2H2O→O2+4H++4e-, 1.23V (relative to RHE)
However, because reaction efficiency is low, it is therefore desirable to promote the catalyst of water oxidation reaction.Urged as such water oxygen
Agent, including the oxide of cobalt oxide, ruthenium-oxide, yttrium oxide etc. is conventionally known.
Iron compound such as Fe is utilized in addition, also reporting recently2O3Or FeOOH water oxidation catalyst.If however, all
Such as Fe2O3Or FeOOH iron compound is unbodied, then this causes oxidation catalyst to have compared with other oxide catalysts
The problem of having low activity.
Therefore, W.D.Chemelewski etc., J.Mater.Chem A (materials chemistry magazine A), 2014, the 2nd phase, the
The amorphous FeOOH doped with Ni elements has been proposed as oxidation catalyst in page 14957~14962 (non-patent literatures 1).
Although Ni doping improves catalytic activity, the oxidation catalyst does not always have sufficiently high catalytic activity.
In addition, A.E.Tufo etc., Hyperfine Interact (hyperfine interaction), 2014, volume 224, the
Page 239~250 (non-patent literatures 2) propose the β-FeOOH doped with Mn elements or Co elements.
The content of the invention
However, β-the FeOOH doped with Co elements proposed as examining in non-patent literature 2 result, the present inventor
It was found that being used as the active low of oxidation catalyst.
In view of above-mentioned problem of the conventional art and complete the present invention.It is an object of the invention to provide with excellent oxidation
The iron compound particle of catalytic activity and the method for the manufacture iron compound particle.
Because the FeOOH doped with Ni elements described in non-patent literature 1 is unbodied, therefore FeOOH can not fill
Ground is divided to be used as oxidation catalyst.In addition, being prepared under the conditions of pH of the catalyst more than 7 so that Fe hydroxide and Ni hydrogen
Oxide is deposited independently of one another, so as to reduce the uniformity as catalyst.For these reasons, the present inventor speculates, no
Sufficiently high oxidation catalytic activity can be obtained.Meanwhile, the β doped with Mn elements or Co elements described in non-patent literature 2-
FeOOH particle diameter is big.Due to the reason, the present inventor speculates, it is impossible to obtain sufficiently high oxidation catalytic activity.
Therefore, present inventor has performed further investigate to realize above-mentioned purpose.As a result, the inventors discovered that, when will contain
The material solution of metal ion beyond Fe ions and Fe ions is with the solution containing nertralizer to cause pH as 1.8~5.0
When mode is mixed, this allows to obtain the iron compound with the β-FeOOH crystalline phases doped with the metallic element beyond Fe
Particle, and at least one of average grain diameter and crystallite diameter diminish.In addition, the inventors have discovered that the iron compound
Particle has excellent oxidation catalytic activity.These discoveries cause to complete the present invention.
Specifically, it is the iron compound particle, the oxidation catalyst of the present invention and manufacture iron of the invention of the present invention herein
The method of compound particles.
[1] iron compound particle, the iron compound particle comprising β-FeOOH crystalline phases and for the β that adulterates-
Metallic element beyond the Fe of FeOOH crystalline phases, wherein
Metallic element beyond the Fe is selected from least one of following element metallic element：Al and belong to the cycle
3d and 4d transition metal beyond the Fe of the race of table the 4th~12,
Metallic element beyond the Fe is 0.001 to the atomic ratio (metallic element/Fe elements beyond Fe) of Fe elements
~0.5, and
The iron compound particle meets at least one of (A) and (B) claimed below：
(A) crystallite diameter with 1~60nm when by X-ray diffraction measurement；With
(B) average grain diameter with 1~600nm in the dynamic light scattering measurement in by solvent.
[2] according to the iron compound particle of [1] above, wherein relative to the content of whole iron compound crystalline phases, it is described
The content of β-FeOOH crystalline phases is 50~100mol%.
[3] according to the iron compound particle of [1] or [2] above, wherein meeting requirement both (A) and (B).
[4] according to the iron compound particle of any one of [1]~[3] above, wherein
Its primary particle to be bar-shaped,
The average length of the major axis of the primary particle is 1~50nm, and
The major axis is 3~10 to the average specific (major axis/minor axis) of short axle in terms of length.
[5] according to the iron compound particle of any one of [1]~[4] above, wherein
Metallic element beyond the Fe is selected from following at least one metallic element：Ni elements, Co elements, Mn members
Element, Cr elements, Zn elements and Al elements.
[6] a kind of oxidation catalyst, the oxidation catalyst includes the iron chemical combination of any one of [1]~[5] more than
Thing particle.
[7] a kind of method for manufacturing iron compound particle, methods described include by will containing Fe ions and Fe ions with
The material solution A of outer at least one metal ion is mixed to prepare pH as 1.8~5.0 with the material solution B containing nertralizer
Colloidal solution so that obtain with doped with the metallic element beyond Fe β-FeOOH crystalline phases iron compound particle, its
Described at least one metal ion beyond Fe ions be selected from Al ions and belong to the Fe ions of the race of periodic table the 4th~12 with
Outer 3d and 4d transition metal ions.
[8] according to the method for the manufacture iron compound particle of [7] above, wherein
Metal ion beyond the Fe ions is selected from following at least one metal ion：Ni ions, Co ions, Mn
Ion, Cr ions, Zn ions and Al ions.
[9] according to the method for the manufacture iron compound particle of [7] or [8] above, wherein
The nertralizer is alkali compounds.
Note, although the reason for oxidation catalytic activity of imprecise clear iron compound particle of the present invention is excellent, this
Inventor is presumed as follows.Specifically, in the iron compound particle of the present invention, β-FeOOH crystalline phases are doped with the gold beyond Fe
Belong to element, so as to change the electronic state at Fe sites.For example, in water oxidation reaction, this allows to easily from hydrogen-oxygen
Electronics is extracted in root, or promotes the absorption of reaction intermediate.The present inventor speculates, for these reasons, and undoped with any
β-FeOOH the crystalline phases of metallic element are compared, and iron compound particle of the invention readily facilitates oxidation reaction.
The invention enables can obtain the iron compound particle with excellent oxidation catalytic activity.
Brief description of the drawings
Fig. 1 is to show that the solution obtained in using embodiment 3, comparative example 1 and comparative example 3 is each supported on carbon paper
The figure of the X-ray diffraction pattern measured on sample.
Fig. 2 is the scanning transmission electron microscope photo of the iron compound particle obtained in embodiment 1.
Fig. 3 is the scanning transmission electron microscope photo of the iron compound particle obtained in comparative example 1.
Fig. 4 shows that display carries out energy dispersion X-ray spectrum analysis to the iron compound particle obtained in embodiment 3
As a result electron micrograph.
Fig. 5 is the schematic diagram of oxidation catalyst activity evaluating apparatus for showing to use in embodiment.
Fig. 6 is the Current-potential curve of iron compound particle for showing to obtain in embodiment 1~3,6 and comparative example 1
Figure.
Fig. 7 be the gas flow that produces in the water-splitting reaction for the iron compound particle for being shown with obtaining in embodiment 3 with
The figure of time change.
Fig. 8 be the gas flow that produces in the water-splitting reaction for the iron compound particle for being shown with obtaining in comparative example 1 with
The figure of time change.
Fig. 9 is the electric current in the water-splitting reaction for the iron compound particle for being shown with obtaining in embodiment 3 and comparative example 1
The figure that density is changed over time.
Figure 10 is the figure of the Current-potential curve of iron compound particle for showing to obtain in embodiment 16~18.
Figure 11 is the gas flow produced in the water-splitting reaction for the iron compound particle for being shown with obtaining in embodiment 17
The figure changed over time.
[label list]
C：To electrode
P：Power supply
R：Reference electrode
S：Measure sample
Embodiment
Hereinafter, it will be described in detail based on the preferred embodiment of the present invention.
First, the iron compound particle of the present invention is illustrated.The iron compound particle of the present invention is tied comprising β-FeOOH
Crystalline phase.In addition, the iron compound particle of the present invention can include other iron compounds beyond β-FeOOH crystalline phases.It is this other
The example of iron compound includes other Iron oxyhydroxides crystalline phases such as alpha-feooh, γ-FeOOH, δ-FeOOH and hydrated ferric oxide
(ferrihydrite), ferriferous oxide such as FeO, Fe2O3And Fe3O4, hydroxide, contained component in iron rust, and its it is amorphous
Component.
In the iron compound particle of the present invention, relative to the content of whole iron compound crystalline phases, the β-FeOOH knots
The content of crystalline phase is preferably 50~100mol%, more preferably 70~100mol%, particularly preferred 80~100mol%.If β-
The content of FeOOH crystalline phases is less than lower limit, then oxidation catalyst activity is tended to low.Note, in the present invention, β-FeOOH knots
The content of crystalline phase refers to the intensity by the peak with maximum intensity from each iron compound or the peak with the second high intensity
Than obtained value, wherein to each described iron chemical combination under 2 θ=30~40 ° in the X-ray diffraction pattern of iron compound particle
Thing is observed.
In addition, the iron compound particle of the present invention includes the metallic element beyond the Fe for β-FeOOH crystalline phases of adulterating.
Thus, compared with the β-FeOOH crystalline phases undoped with any metallic element, oxidation catalytic activity is improved.In addition, beyond the Fe
Metallic element it is a part of can be supported on around β-FeOOH crystalline phases rather than its doping.According to the Fe of the present invention
Metallic element in addition is selected from least one of following element metallic element：Al and belong to the race of periodic table the 4th~12
3d and 4d transition metal beyond Fe.Because these metallic elements have the atomic radius similar to the atomic radius of Fe elements,
It is therefore contemplated that, the metallic element easily replaces Fe elements or is easily introduced into β-FeOOH lattices or grain boundary
In.In addition, from the viewpoint of higher oxidation catalytic activity is obtained, in these metallic elements, preferably Ni elements, Co are first
Element, Mn elements, Cr elements, Zn elements and Al elements；More preferably Ni elements, Co elements and Al elements；Particularly preferred Ni elements.
In the iron compound particle of the present invention, the metallic element beyond this Fe is to the atomic ratio of Fe elements (beyond Fe
Metallic element/Fe elements) be 0.001~0.5.If the ratio of metallic element/Fe elements beyond Fe is less than lower limit, oxygen
Change catalytic activity step-down.On the other hand, if the ratio of metallic element/Fe elements beyond Fe exceedes the upper limit, β-FeOOH knots
The growth of crystalline phase is suppressed；In addition, becoming difficult with the metallic element Uniform Doped beyond Fe so that oxidation catalytic activity is obtained
Less than raising.From can with the metallic element Uniform Doped beyond Fe and from the viewpoint of obtaining high oxidation catalytic activity, Fe with
The ratio of outer metallic element/Fe elements is preferably 0.002~0.45, and more preferably 0.005~0.4.Note, in the present invention, " Fe
The ratio of metallic element in addition/Fe elements " can pass through inductively coupled plasma (ICP) emission spectrum, energy dispersion X-ray
Spectrum (SEM-EDX), x-ray photoelectron power spectrum (XPS) etc. are determined.
In addition, the iron compound particle of the present invention meets at least one of (A) and (B) claimed below：
(A) crystallite diameter with 1~60nm when by X-ray diffraction measurement；With
(B) average grain diameter with 1~600nm when the dynamic light scattering measurement in by solvent (preferably water).
Meet and require that at least one of (A) and (B) iron compound particle have excellent oxidation catalytic activity.In addition,
From the viewpoint of more high oxidation catalytic activity is obtained, both above-mentioned requirements (A) and (B) are preferably met.Note, in the present invention
In, although it is preferred that both crystallite diameter and average grain diameter are measured, if being difficult to the dispersion (glue for preparing iron compound particle
Liquid solution), then it can only measure crystallite diameter；Or if be difficult to the iron compound in solution being recovered as solid or be difficult to solid
Determine iron compound, then can only measure average grain diameter.
In the present invention, if the crystallite diameter of iron compound particle outside the above range, oxidation catalytic activity become
It is low.In addition, from the viewpoint of more high oxidation catalytic activity is obtained, the crystallite diameter of iron compound particle is preferably 1~30nm,
More preferably 1~15nm.
In addition, in the present invention, if the average grain diameter of iron compound particle is outside the above range, oxidation catalysis is lived
Property step-down.Moreover, from the viewpoint of more high oxidation catalytic activity is obtained, the average grain diameter of iron compound particle is preferably 1~
300nm, more preferably 1~150nm.
With the iron compound particle undoped with any metallic element and the iron compound knot wherein beyond β-FeOOH crystalline phases
Crystalline phase is compared doped with the iron compound particle of metallic element, and this iron compound particle of the invention is used under lower overvoltage
The stability for making electrochemical oxidation catalyst and oxidation catalytic activity is more excellent.
In addition, in the iron compound particle of the present invention, its primary particle is preferably bar-shaped.In such bar-shaped iron
In compound primary particle, the average length of its major axis is preferably 1~50nm, more preferably 5~25nm.If the major axis of primary particle
Average length be less than lower limit, then crystallinity tend to low so that high catalytic activity can not be obtained.On the other hand, if flat
Equal length exceedes the upper limit, then specific surface area is tended to small so that oxidation catalytic activity step-down, or can not obtain stable colloid
The aqueous solution so that load is coated with and dried difficult and makes it impossible to easily assign the function.
In addition, in bar-shaped iron compound primary particle, average specific (major axis/minor axis) of the major axis to short axle in terms of length
(average axle ratio) is preferably 3~10, and more preferably 3~7.If the average axle ratio of primary particle is less than lower limit, sexual orientation is crystallized
In low, so as to cannot get high catalytic activity.On the other hand, if average axle ratio exceedes the upper limit, specific surface area tend to it is small,
So that oxidation catalytic activity step-down, or stable colloid aqueous solution can not be obtained so that load coating and dry difficulty simultaneously make
The function can not possibly easily be assigned by obtaining.
Note, the major axis of iron compound primary particle and this length of short axle for example can be schemed in TEM image or STEM
Measured as in.Moreover, in the present invention, " average length of the major axis of primary particle " refers to by TEM image or STEM
It is worth obtained from the length of the major axis of the iron compound primary particle of more than 50 of grab sample is averaging in image, and "
Average specific (major axis/minor axis) (average axle ratio) of the major axis to short axle in terms of length " refers to by more than 50 of grab sample
Iron compound primary particle length in terms of by major axis to the ratio between short axle (major axis/minor axis) be averaging obtained from be worth.
Next, the method to the manufacture iron compound particle of the present invention is illustrated.The manufacture iron chemical combination of the present invention
The method of thing particle includes：By the way that the material solution A containing the metal ion beyond Fe ions and Fe ions is neutralized with containing
The material solution B of agent is mixed to prepare pH as 1.8~5.0 colloidal solution, so as to obtain with doped with the metal beyond Fe
The iron compound particle of the β-FeOOH crystalline phases of element.
The Fe ions used in the method for the manufacture iron compound particle of the present invention can be divalence Fe ions (Fe2+) or
Trivalent Fe ions (Fe3+).However, from the viewpoint of the bar-shaped β-iron compound particle of formation, Fe3+It is preferred.
In addition, the metal ion beyond the Fe ions used in the method for the manufacture iron compound particle of the present invention is choosing
From following at least one metal ion：Al ions and 3d the and 4d mistakes belonged to beyond the Fe ions of the race of periodic table the 4th~12
Cross metal ion.Because these metal ions beyond Fe ions have the atomic radius similar with the atomic radius of Fe ions,
It is therefore envisaged that the metallic element easily replaces Fe elements or is easily introduced into β-FeOOH lattices or grain boundary.Separately
Outside, from the viewpoint of more high oxidation catalytic activity is obtained, in the metal ion beyond these Fe ions, preferably Ni ions,
Co ions, Mn ions, Cr ions, Zn ions and Al ions；More preferably Ni ions, Co ions and Al ions；Particularly preferred Ni from
Son.
In the method for the manufacture iron compound particle of the present invention, mole of metal ion beyond Fe ions to Fe ions
It is preferably 0.2/100~80/100 than (metal ion/Fe ions beyond Fe ions), more preferably 0.5/100~80/100, it is special
Not preferably 1/100~75/100.If " ratio of metal ion/Fe ions beyond Fe ions " is less than lower limit, oxidation is urged
Change activity is tended to low.On the other hand, if " ratio of metal ion/Fe ions beyond Fe ions " exceedes the upper limit, deposit
The trend not improved further in oxidation catalytic activity.
The concentration of Fe ions is not particularly limited in material solution A, but preferably 0.01~1mol/L.In addition, raw material is molten
The concentration of metal ion in liquid A beyond Fe ions is not particularly limited, preferably 0.0001~0.8mol/L.
Gold beyond the source of the Fe ions used in the method for the manufacture iron compound particle of the present invention and Fe ions
The source of category ion is not particularly limited, as long as they dissolve in a solvent.The example in the source includes：Inorganic salts,
Such as hydrochloride, nitrate and sulfate；And organic salt, such as citrate.In addition, solvent is not particularly limited, as long as it can
Dissolving ion is originated.The example of solvent includes water, water-miscible organic solvent (such as methanol, ethanol, propyl alcohol, isopropanol, fourth
Alcohol, acetone, acetonitrile and dimethylformamide), and water and water-miscible organic solvent mixed solvent.
It is not particularly limited for the nertralizer in the method for the manufacture iron compound particle of the present invention, as long as it is that have
The alkali compounds of neutralization.The example of nertralizer includes：Inorganic alkaline compound such as sodium hydroxide, potassium hydroxide and
Ammonia；With organic basic compound such as ethylenediamine, hydrazine, MEA, diethanol amine and triethanolamine.Neutralization in material solution B
The concentration of agent is not particularly limited, but preferably 0.01~1mol/L.
In addition, the present invention manufacture iron compound particle method can use as needed such as aminocaproic acid, ε-oneself
The dispersant of lactams.Such dispersant can be added in any one of material solution A and B, but be preferably added to original
Expect in solution B.
In the method for the manufacture iron compound particle of the present invention, material solution A as described above and material solution B are mixed
It is combined thus to prepare colloidal solution.In this case, make it that the pH of colloidal solution will in the way of 1.8~5.0
Material solution A is mixed with material solution B.If the pH of colloidal solution is less than lower limit, do not occur Fe3+The formation of hydroxide,
So that β-FeOOH crystalline phases are not formed, and oxidation catalytic activity step-down.On the other hand, if the pH of colloidal solution is more than upper
Limit, then the average particle diameter became of iron compound particle is very big, and oxidation catalytic activity step-down.Moreover, from ensuring had
From the viewpoint of the iron compound particle for having β-FeOOH crystalline phases and small average grain diameter, the pH of colloidal solution is preferably 1.9~
4.0, more preferably 2.0~3.0.
In the method for the manufacture iron compound particle of the present invention, when material solution A is mixed with material solution B, temperature
Degree is not particularly limited.The mixing is carried out preferably below 50 DEG C under (more preferably 10~30 DEG C).If mixing temperature exceedes
The length tendency of the upper limit, the then crystallite diameter and average grain diameter of iron compound particle and the major axis of bar-shaped primary particle and short axle
In increase so that oxidation catalytic activity step-down.Moreover, the method that material solution A is mixed with material solution B is not limited especially
System, as long as methods described allows to be sufficiently stirred for.
There is the β-FeOOH crystalline phases doped with the metallic element beyond Fe by iron compound particle obtained above, and
And also there is small crystallite diameter and/or small average grain diameter.This iron compound particle has excellent oxidation catalytic activity.
Note, a part of of the metallic element beyond Fe can be supported on around β-FeOOH crystalline phases rather than its doping.
[embodiment]
Hereinafter, the present invention will be further illustrated based on embodiment and comparative example.However, the invention is not restricted to
Following examples.
(embodiment 1)
In beaker, by FeCl3·6H2O (27.30g, 101mmol) and Zn (NO3)2·6H2O (1.25g, 4.20mmol)
It is dissolved in ion exchange water (500ml).Thus, the aqueous solution of raw material (material solution A) containing metal ion is prepared, it is described molten
The Fe ion concentrations of liquid are 0.2mol/L.Moreover, in beaker, 1/2 ethylenediamine solution will be diluted to ion exchange water
(11ml) is dissolved in ion exchange water (500ml).Thus, the aqueous solution of raw material (material solution B) containing nertralizer is prepared.In room
Under warm (25 DEG C) stirring rod (rotary speed is used using magnetic stirring apparatus：400rpm) material solution A and B are mixed in beaker
And stir 30 minutes together.Thus, the colloidal solution of iron compound is prepared.By using pH meter, gained colloidal solution is determined
PH and it is found to be 2.2.
(embodiment 2)
The colloidal solution of iron compound is prepared in the same manner as in example 1, and difference is to use Co
(NO3)2·6H2O (1.22g, 4.19mmol) replaces Zn (NO3)2·6H2O.The pH of gained colloidal solution is 2.2.
(embodiment 3)
The colloidal solution of iron compound is prepared in the same manner as in example 1, and difference is to use Ni
(NO3)2·6H2O (1.21g, 4.16mmol) replaces Zn (NO3)2·6H2O.The pH of gained colloidal solution is 2.2.
(embodiment 4)
The colloidal solution of iron compound is prepared in the same manner as in example 1, and difference is to use Mn
(NO3)2·6H2O (1.21g, 4.22mmol) replaces Zn (NO3)2·6H2O.The pH of gained colloidal solution is 2.4.
(embodiment 5)
The colloidal solution of iron compound is prepared in the same manner as in example 1, and difference is to use CrCl3·
6H2O (1.21g, 4.54mmol) replaces Zn (NO3)2·6H2O.The pH of gained colloidal solution is 2.5.
(embodiment 6)
The colloidal solution of iron compound is prepared in the same manner as in example 1, and difference is to use Al
(NO3)2·9H2O (1.56g, 4.16mmol) replaces Zn (NO3)2·6H2O.The pH of gained colloidal solution is 2.4.
(comparative example 1)
The colloidal solution of iron compound is prepared in the same manner as in example 1, and difference is without using Zn
(NO3)2·6H2O.The pH of gained colloidal solution is 2.4.
(comparative example 2)
According to Hyperfine Interact (hyperfine interaction), volume 224, institute in the 239-250 pages in 2014
The method stated, prepares the β-FeOOH powder of Co- doping.Specifically, by FeCl3·6H2O (2.69g, 9.95mmol), CoCl2·
6H2O (0.298g, 1.25mmol) and urea (2.40g, 40.0mmol) are added in pure water (100ml), and by room temperature (25
DEG C) under using magnetic stirring apparatus use stirring rod (rotary speed：10 minutes 400rpm) are stirred to be dissolved in wherein.By using pH
Test paper, measures the pH of resulting solution and is found to be about 1.The solution is transferred to the container prepared by TEFLON (registration mark)
In.After container air-tightness is sealed, gains are stood 48 hours at a temperature of 70 DEG C.It is collected by filtration and is consequently formed
Precipitation, and again and again repeat filter and using purification water washing.Gained solid constituent is dried 48 at 40 DEG C
Hour simultaneously and then uses mortar grinder.Thus, iron compound powder is obtained.
(comparative example 3)
In beaker, by Ni (NO3)2·6H2O (1.25g, 4.20mmol) is dissolved in ion exchange water (500ml).By
This, prepares aqueous solution of raw material (material solution A, the Fe ion concentration containing Ni ions：0mol/L).Moreover, preparing 0.01mol/L
Hydrochloric acid (500ml) be used as material solution B.Under room temperature (25 DEG C) stirring rod (rotary speed is used using magnetic stirring apparatus：
400rpm) material solution A and B are mixed in beaker and stirred 30 minutes together.By using pH meter, measurement resulting solution
PH is simultaneously found to be 2.3.
(comparative example 4)
In beaker, by FeCl3·6H2O (27.30g, 101mmol) and Ni (NO3)2·6H2O (1.25g, 4.20mmol)
It is dissolved in ion exchange water (500ml).Thus, the aqueous solution of raw material containing metal ion, the Fe ions of the solution are prepared
Concentration is 0.2mol/L.Under room temperature (25 DEG C) stirring rod (rotary speed is used using magnetic stirring apparatus：400rpm) this is contained
The aqueous solution of raw material for having metal ion is stirred 30 minutes.Thus, it is prepared for the colloidal solution of iron compound.Gained colloidal solution
PH is 1.7.
(comparative example 5)
In beaker, the ethylenediamine solution (11ml) that 1/2 is diluted to ion exchange water is dissolved in ion exchange water
In (500ml).Thus, the aqueous solution of ethylenediamine is prepared.Under room temperature (25 DEG C) stirring rod (rotation is used using magnetic stirring apparatus
Speed：400rpm) ethylenediamine solution is stirred 30 minutes.
<The evaluation of iron compound particle properties>
(i) average grain diameter is measured
Using Size Distribution Analyzer (by Nikkiso the Co., " Nanotrac of Ltd. (Nikkiso Company Limited) manufactures
UPA250EX ", optical maser wavelength：780nm, measurement range：0.8~6000nm), by dynamic light scattering measurement embodiment and compare
The particle diameter distribution of the solution obtained in example, and the volume mean diameter (MV) of calculating is taken as being averaged for corresponding iron compound particle
Particle diameter.Table 1 shows result.Incidentally, the iron compound powder obtained in comparative example 2 is separated out in the solution, so as to be difficult to
Measure particle diameter distribution.In addition, not obtaining the particle diameter distribution of solution obtained in comparative example 3 in above-mentioned measurement range.
(ii) X-ray diffraction measurement
The solution obtained in embodiment and comparative example is each added drop-wise on carbon paper, spontaneously dried, then using water and
0.1M KOH aqueous solution washing.Thus, it is prepared for measuring sample.Note, the iron compound powder obtained in comparative example 2 is straight
Connect as measurement sample.(manufactured using powder x-ray diffraction device by Rigaku Corporation (company of Ricoh)
" Ultima IV ") X-ray diffraction (XRD) measurement is carried out to these measurement samples under following measuring condition：Tube voltage：40kV,
Tube current：40mA, X-ray：CuK α radiate (wavelength).Fig. 1 is shown by using embodiment 3, comparative example
1 and comparative example 3 in the X-ray diffraction pattern of measurement sample for preparing of obtained solution.In addition, in resulting each X-ray
In diffraction pattern, the peak from β-FeOOH crystalline phases is checked for, and crystallization is calculated according to the peak ratio from crystalline phase
The ratio of β-FeOOH crystalline phases in iron compound.In addition, the half-peak breadth using Scherrer equations by the peak from crystalline phase is true
Determine crystallite diameter.Table 1 shows these results.
[table 1]
Result shown in table 1 shows that the colloidal solution (embodiment 3 and comparative example 1) prepared by using Fe ions is contained
There is the iron compound particle with β-FeOOH crystalline phases, and it is unrelated with Ni doping.Moreover, in these iron compound particles not
It was observed that from other iron compounds (such as alpha-feooh, γ-FeOOH and Fe2O3) crystalline phase any peak.On the other hand,
The peak for indicating there is crystalline phase is not observed in the solution (comparative example 3) prepared using only Ni ions.
Result shown in table 1 shows, is prepared by using Fe ions and with the colloidal solution of 2.2~2.5 pH scopes
(embodiment 1~6 and comparative example 1) comprising average grain diameter be 11nm~19nm iron compound particle, and with the presence or absence of doping
Agent is unrelated.Also, it was found that in these iron compound particles, whole crystalline phases are all made up of β-FeOOH crystalline phases, and crystallite is straight
Footpath is 6~10nm.
On the other hand, the iron compound powder obtained in comparative example 2 has big particle diameter so that particle is complete in the solution
Separate out.Moreover, whole crystalline phases of the iron compound powder are all made up of β-FeOOH crystalline phases, but with embodiment 1~6
More than 6 times big crystallite diameters (64nm) of crystallite diameter of obtained iron compound particle.Meanwhile, prepared from using only Ni ions
Solution (comparative example 3) in do not obtain particle diameter distribution；In addition, indicating there is knot because not observed in X-ray diffraction pattern
The peak of crystalline phase, therefore supposition does not form nickel compound particle, and Ni ions exist with its parent form.In addition, unused nertralizer
Prepare and pH has and the iron that is obtained in embodiment 1~6 for the iron compound particle contained by 1.7 colloidal solution (comparative example 4)
The almost identical average grain diameter (11nm) of the average grain diameters of compound particles；Moreover, in the X-ray diffractogram of iron compound particle
The peak for indicating there is crystallization iron compound is not observed in case.Note, further acknowledged in ethylenediamine solution (comparative example 5) not
There is colloidal particle and crystalline compounds.
(iii) electron microscope observation
It is right using transmission electron microscope (" JEM-2100F " that is manufactured by JEOL Ltd. (Jeol Ltd.))
Iron compound particle in the colloidal solution obtained in embodiment and comparative example carries out STEM observations.Fig. 2 and Fig. 3 are respectively illustrated
The STEM images of the iron compound particle obtained in embodiment 1 and comparative example 1.Result shown in Fig. 2 and 3 shows, by passing through
Prepared using Fe ions and pH scopes for 2.2~2.5 colloidal solution obtained iron compound particle (embodiment 1 and comparative example
1) there is thin and long shape, it is unrelated with the presence or absence of dopant.
(iv) energy dispersion X-ray spectroscopic methodology
The colloidal solution obtained in embodiment is each added drop-wise on carbon paper, spontaneously dried, then with water and 0.1M KOH
The aqueous solution is washed.Thus, it is prepared for measuring sample.Use SEM (" SU3500 types ", by Hitachi High-
Technologies Corporation (high and new technology company of Hitachi) are manufactured) the progress SEM observations of measurement sample and EDX are painted
Figure.Fig. 4 shows that the SEM image and EDX of the measurement sample prepared by using the colloidal solution obtained in embodiment 3 are drawn and tied
Really.Ni, which does not localize, to be shown to the EDX mapping results of nickel, and is generally evenly distributed in iron compound.Note, to the EDX of carbon
Mapping result shows that the fibrous matter in SEM image is the carbon fiber of carbon paper.
(v) oxidation catalytic activity evaluation
The colloidal solution obtained in embodiment and comparative example is each added drop-wise on carbon paper, spontaneously dried, then using water
Washed with the 0.1M KOH aqueous solution.Thus, measurement sample is prepared.Measurement sample is placed on shown in Fig. 5 as working electrode
Oxidation catalytic activity evaluating apparatus in (S in Fig. 5).Using being used as the platinum line to electrode C, the Ag/ as reference electrode R
AgCl and 0.1M as the solution KOH aqueous solution (pH：12.8) Current-potential curve, has been obtained.In this case, weight
Multiple scanning several times, untill current value is stable.
Fig. 6 shows the measurement sample prepared by using the colloidal solution obtained in embodiment 1~3,6 and comparative example 1
Current-potential curve.Result shown in Fig. 6 shows, is attributed to the take-off potential of anode current of water oxidation reaction with institute
Add the type of metallic element and change.Moreover, based on resulting Current-potential curve, it is determined that when current density difference
For 0.5mA/cm2、2mA/cm2And 5mA/cm2When current potential (E, unit：V, relative to RHE).Table 2 shows result.
[table 2]
Result shown in table 2 shows, with the iron compound particle (comparative example 1) undoped with any metallic element and doping
There are Co elements and compared with big average grain diameter with the iron compound powder (comparative example 2) of big crystallite diameter, beyond Fe
Metallic element and iron compound particle (embodiment 1~6) with small average grain diameter and small crystallite diameter allows electric current low
Flowed under voltage.Especially, find doped with Co elements (embodiment 2), Ni elements (embodiment 3) or Al elements (embodiment 6)
Iron compound particle allow electric current flow at lower voltages.Further, it was found that in 0.5mA/cm2~5.0mA/cm2Wide model
In enclosing, have doped with the iron compound particle (embodiment 3) of Ni elements than the iron compound grain undoped with any metallic element
Overvoltage (overpotential) low 100~110mV of sub (comparative example 1) overvoltage, and be excellent electrochemical catalysis
Agent.It moreover has been found that there is steep initial current slope doped with the iron compound particle (embodiment 6) of Al elements and oxygen is used as
It is excellent to change catalyst.
(embodiment 7)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is Ni (NO3)2·
6H2O quantitative change is 0.59g (2.03mmol).The pH of gained colloidal solution is 2.2.
(embodiment 8)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to use NiCl2·
8H2O (0.99g, 4.20mmol) replaces Ni (NO3)2·6H2O.The pH of gained colloidal solution is 2.2.
(embodiment 9)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is Ni (NO3)2·
6H2O quantitative change is 2.53g (8.70mmol).The pH of gained colloidal solution is 2.3.
(embodiment 10)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is Ni (NO3)2·
6H2O quantitative change is 5.54g (19.1mmol).The pH of gained colloidal solution is 2.4.
<The evaluation of iron compound particle properties>
Colloidal solution obtained by use, carries out average grain diameter measurement, X-ray to iron compound particle according to the above method and spreads out
Penetrate measurement and oxidation catalytic activity evaluation.Moreover, according to following methods, implementing ICP emission spectroscopy measurements.Table 3 shows this
A little results.
(vi) ICP emission spectroscopy measurements
The colloidal solution obtained in embodiment and comparative example is each added drop-wise on carbon paper and is loaded with preparing thereon
The measurement sample of colloidal particle.(manufactured using ICP emission spectrometers by Rigaku Corporation (company of science)
" CIROS-120EOP ") ICP emission spectroscopy measurements are carried out to measurement sample, to determine the metallic element beyond Fe to Fe elements
Atomic ratio (metallic element/Fe elements beyond Fe).
[table 3]
Result shown in table 3 shows, even if changing Ni addition, and it is 12~37nm's to remain to access average grain diameter
Iron compound particle.Further, it was found that when Ni addition is below 4mol%, Ni addition is more, the electricity of electric current flowing
Pressure is lower, therefore improves oxidation catalytic activity.However, when Ni addition more than about 4mol% and be about 19mol% with
When lower, the further reduction of overvoltage is barely perceivable.
In addition, Ni/Fe atomic ratios in gained iron compound particle are 0.012 (embodiment 3), 0.003 (embodiment 7),
0.016 (embodiment 8), 0.020 (embodiment 9) and 0.029 (embodiment 10).In view of Ni2+PH of the hydroxide more than 6.2
Lower deposition and Fe3+Hydroxide is deposited under 2.5~2.1 pH, thus it is speculated that introduce 29 during β-FeOOH crystalline phases are formed
Atom % (embodiment 3), 15 atom % (embodiment 7), 38 atom % (embodiment 8), 23 atom % (embodiment 9) and 15 are former
The Ni ions added of sub- % (embodiment 10).
(embodiment 11)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to change ethylenediamine
Amount cause colloidal solution pH be 2.6.
(embodiment 12)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to change ethylenediamine
Amount cause colloidal solution pH be 2.8.
(comparative example 6)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to change ethylenediamine
Amount cause colloidal solution pH be 1.6.
(comparative example 7)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to change ethylenediamine
Amount cause colloidal solution pH be 6.8.
(comparative example 8)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to change ethylenediamine
Amount cause colloidal solution pH be 8.1.
<The evaluation of iron compound particle properties>
Colloidal solution obtained by use, carries out average grain diameter measurement, X-ray to iron compound particle according to the above method and spreads out
Penetrate measurement and oxidation catalytic activity evaluation.Table 4 shows result.
[table 4]
Result shown in table 4 shows that average grain diameter, crystallization facies type and the crystallite diameter of iron compound particle are depended on
The pH of colloidal solution.Specifically, when the pH of colloidal solution is 2.2~2.8 (embodiment 3,11 and 12), gained iron compound grain
The average grain diameter of son is 13~230nm and crystallite diameter is 5~6nm, wherein whole crystalline phases are all by β-FeOOH crystalline phase structures
Into.On the other hand, when the pH of colloidal solution is 1.6 (comparative example 6), the average grain diameter of gained iron compound particle is 11nm,
But crystalline phase is not present in iron compound particle.Moreover, when the pH of colloidal solution is 6.8 (comparative example 7), gained iron
The average grain diameter of polymer particle is 770nm and crystallite diameter is 26nm, wherein whole crystalline phases are all by alpha-feooh crystalline phase structure
Into；However, not obtaining including the iron compound particle of β-FeOOH crystalline phases.In addition, (comparing when the pH of colloidal solution is 8.1
Example 8), the average grain diameter of gained iron compound particle is 1200nm and crystallite diameter is 24nm, and wherein crystalline phase is by alpha-feooh knot
Crystalline phase and α-Fe2O3Constitute；However, not obtaining including the iron compound particle of β-FeOOH crystalline phases.
In addition, it is found that with by pH scopes for less than 1.8 or more than 5.0 colloidal solution (comparative example 6~8) prepare iron
Polymer particle is compared, and the iron compound particle by pH scopes for 2.2~2.8 colloidal solution (embodiment 3,11 and 12) preparation is permitted
Perhaps electric current flows and with excellent oxidation catalytic activity at lower voltages.
(embodiment 13)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to replace using ammonia
Ethylenediamine.The pH of gained colloidal solution is 2.1.
(embodiment 14)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to use hydroxide
Sodium replaces ethylenediamine.The pH of gained colloidal solution is 2.1.
(embodiment 15)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is to use monoethanol
Amine replaces ethylenediamine.The pH of gained colloidal solution is 2.2.
<The evaluation of iron compound particle properties>
Colloidal solution obtained by use, carries out average grain diameter measurement, X-ray to iron compound particle according to the above method and spreads out
Penetrate measurement, ICP emission spectroscopy measurements and oxidation catalytic activity evaluation.Table 5 shows result.
[table 5]
Result shown in table 5 shows, even if (embodiment 3,13~15), gained iron when changing the type of nertralizer
The average grain diameter of polymer particle is 13~17nm.In addition, in 2.0mA/cm2Under current potential change with the type of nertralizer, and
And oxidation catalytic activity depends on the type of nertralizer.Even if however it has been found that when using any nertralizer when (embodiment 3,13~
15), compared with the iron compound particle (comparative example 1) undoped with any metallic element, Ni doping allows electric current at lower voltages
Flow and improve oxidation catalytic activity.Moreover, when only loading ethylenediamine (comparative example 5) on carbon paper, in 2.0mA/cm2Under
Current potential it is at a relatively high, and nertralizer hardly shows oxidation catalytic activity.Thus speculate, the iron chemical combination obtained in embodiment
In thing particle, the β-FeOOH crystalline phases doped with metallic element contribute to oxidation catalytic activity.
In addition, the Ni/Fe atomic ratios in gained iron compound particle are 0.021 (embodiment 13), 0.038 (embodiment 14)
With 0.030 (embodiment 15).These values show that β-FeOOH crystalline phases are doped with 51 atom % (embodiment 13), 92 atom %
The Ni ions of (embodiment 14) and 73 atom % (embodiment 15) addition.In view of Ni2+Under pH of the hydroxide more than 6.2
Deposit and Fe3+Hydroxide is deposited under 2.5~2.1 pH, thus it is speculated that during β-FeOOH crystalline phases are formed, and introduces 51 former
The Ni ions of the addition of sub- % (embodiment 13), 92 atom % (embodiment 14) and 73 atom % (embodiment 15).
(vii) water-splitting activity rating
The colloidal solution obtained in embodiment and comparative example is each added drop-wise on carbon paper, spontaneously dried, then using water
Washed with the 0.1M KOH aqueous solution.Thus, measurement sample is prepared.Using measurement sample as working electrode, under an argon atmosphere
Water-splitting reaction is carried out in the battery of airtight sealing.Platinum line is used as, to electrode C, Ag/AgCl to be used as into reference electrode R,
And by the 0.1M KOH aqueous solution (pH：12.8) it is used as solution.Application+0.6V is (relative to Ag/AgCl, equivalent in RHE
Voltage 1.58V), and product is quantified with gas chromatography.Fig. 7 and Fig. 8 show result.
As shown in Figure 7, in the iron compound particle (embodiment 3) doped with Ni elements, with the time substantially with change
Metering is learned than producing hydrogen and oxygen, and current efficiency substantially achieves 100%.It was accordingly found that by with iron compound particle
Water oxidation reaction and oxygen is produced on iron compound particle, while the electronics produced and proton on the Pt to electrode are anti-
Should, so as to produce hydrogen so that water-splitting reaction is carried out.On the other hand, as shown in Figure 8, undoped with any metallic element
Iron compound particle (comparative example 1) in, water-splitting reaction is slightly carried out, but 3 hours after reaction starts, the oxygen of generation
Amount be doped with Ni elements iron compound particle (embodiment 3) about 1/15, show that catalytic activity is at a fairly low.
Moreover, Fig. 9 shows that current density changes with time in water-splitting reaction.As shown in Figure 9, doped with
In the iron compound particle (embodiment 3) of Ni elements, during voltage 4 hours is applied, current density is tended to stable and slightly
Increase；Meanwhile, in the iron compound particle (comparative example 1) undoped with any metallic element, during voltage is applied 3 hours,
Current density is gradually reduced.These results indicate that doped with metallic element iron compound particle catalytic activity stability
Aspect is also excellent.
(embodiment 16)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is Ni (NO3)2·
6H2O quantitative change is 7.28g (25.0mmol).The pH of gained colloidal solution is 2.1.
(embodiment 17)
To prepare the colloidal solution of iron compound with mode same in embodiment 3, difference is Ni (NO3)2·
6H2O quantitative change is 14.55g (50.0mmol).The pH of gained colloidal solution is 2.1.
(embodiment 18)
The colloidal solution of iron compound is prepared in mode in the same manner as in Example 3, difference is Ni (NO3)2·
6H2O quantitative change is 21.83g (75.1mmol).The pH of gained colloidal solution is 2.2.
<The evaluation of iron compound particle properties>
Colloidal solution obtained by use, carries out average grain diameter measurement, X-ray to iron compound particle according to the above method and spreads out
Penetrate measurement and ICP emission spectroscopy measurements.Table 6 shows result.Moreover, the colloidal solution obtained by use, according to the above method pair
Iron compound particle carries out oxidation catalytic activity evaluation.Figure 10 shows molten by using the colloid obtained in embodiment 16~18
The Current-potential curve of measurement sample prepared by liquid.Based on obtained Current-potential curve, it is determined that when current density is
2mA/cm2When current potential (E, unit：V, relative to RHE).Table 6 shows result.In addition, the colloidal solution obtained by use, root
Water-splitting activity rating is carried out to iron compound particle according to the above method.Figure 11 shows result.
[table 6]
Result shown in table 6 shows, even in Ni addition is increased into more than 20mol% (embodiment 16~18)
When, still obtain the iron compound particle that average grain diameter is 9~11nm.Also, it was found that in these iron compound particles, all tying
Crystalline phase is all made up of β-FeOOH crystalline phases, and crystallite diameter is 4~5nm, and Ni/Fe atomic ratios are 0.11~0.38.In addition, it is found that
Compared with the iron compound particle (comparative example 1) undoped with any metallic element, these iron compound particles allow electric current low
Flowed under voltage, the overvoltage with 160~210mV of reduction, and be excellent electrochemical catalyst.
In addition, as shown in Figure 11, in the iron compound particle (embodiment 17) doped with Ni elements, with time base
Hydrogen and oxygen are produced with stoichiometric proportion on this.Consequently found that, by with the iron compound particle with increased Ni/Fe atomic ratios
Water oxidation reaction, also produce oxygen on iron compound particle, while produce electronics with to the proton on the Pt of electrode
Reaction, thus produces hydrogen so that water-splitting reaction is carried out.Especially, the iron compound particle that Ni/Fe atomic ratios are 0.29 is found
(embodiment 17) is produced using the 10 times big amount of amount for being about Ni/Fe atomic ratios as 0.012 iron compound particle (embodiment 3)
Oxygen, and with a relatively high water-splitting activity.
(viii) shape observation and dimensional measurement
Seen using transmission electron microscope (" JEM-2100F " that is manufactured by JEOL Ltd. (Jeol Ltd.))
Examine the iron compound particle in the colloidal solution obtained in embodiment.In each obtained DF-STEM images, to grab sample
The shape of the iron compound primary particle of more than 50 observed.Moreover, to these more than 50 iron compounds once
The major axis and minor axis length of particle are measured.Thus, the average length of major axis is determined.In addition, calculating length of the major axis to short axle
Spend than (major axis/minor axis) to determine its average value (average axle ratio).Table 7 shows these results.
[table 7]
As shown in Table 7, it can be verified that, by using Fe3+Iron compound particle (the embodiment of the invention of preparation
1st, 2,16, in 17), primary particle is the shape of nanometer rods, and major axis has 14~17nm average length, and average axle ratio is (long
Axle/short axle) it is 4.5~5.0.
As described above, the invention enables can be readily derived the iron compound particle with excellent oxidation catalytic activity.
Furthermore, it is possible to obtain the iron compound particle of the present invention in the form of colloidal solution.Thus, applied when with the colloidal solution of the present invention
During cloth carrier (for example, conductive material, semi-conducting material, insulating materials) etc., iron compound particle of the invention is easily fixed to
On carrier so that carrier can be assigned and acted on oxidation catalyst.
In addition, the iron compound particle of the present invention can use cheap material to manufacture at normal temperatures, without using special
The production equipment of door.Therefore, it is possible to expect to develop purposes in wide scope.Moreover, except as electro-chemical water oxidation catalysis
Outside agent, additionally it is possible to expect the iron compound particle of the present invention with such as photochemical catalyst combination application in artificial photosynthesis system
System.
Claims (9)
1. iron compound particle, the iron compound particle is comprising β-FeOOH crystalline phases and for the β-FeOOH crystallizations of adulterating
Metallic element beyond the Fe of phase, wherein
Metallic element beyond the Fe is selected from least one of following element metallic element：Al and belong to periodic table
3d and 4d transition metal beyond the Fe of 4~12 races,
Metallic element beyond the Fe to the atomic ratios (metallic element/Fe elements beyond Fe) of Fe elements for 0.001~
0.5, and
The iron compound particle meets at least one of (A) and (B) claimed below：
(A) crystallite diameter with 1~60nm when by X-ray diffraction measurement；With
(B) average grain diameter with 1~600nm in the dynamic light scattering measurement in by solvent.
2. iron compound particle according to claim 1, wherein relative to the content of whole iron compound crystalline phases, it is described
The content of β-FeOOH crystalline phases is 50~100mol%.
3. iron compound particle according to claim 1 or 2, wherein meeting requirement both (A) and (B).
4. iron compound particle according to claim 1 or 2, wherein
Its primary particle to be bar-shaped,
The average length of the major axis of the primary particle is 1~50nm, and
The major axis is 3~10 to the average specific (major axis/minor axis) of short axle in terms of length.
5. iron compound particle according to claim 1 or 2, wherein
Metallic element beyond the Fe is selected from following at least one metallic element：Ni elements, Co elements, Mn elements, Cr
Element, Zn elements and Al elements.
6. a kind of oxidation catalyst, the oxidation catalyst includes the iron compound particle according to claim 1 or 2.
7. it is a kind of manufacture iron compound particle method, methods described include by by containing beyond Fe ions and Fe ions extremely
The material solution A of few metal ion species is mixed with the material solution B containing nertralizer to prepare pH as 1.8~5.0 colloid
Solution, so that the iron compound particle with the β-FeOOH crystalline phases doped with the metallic element beyond Fe is obtained, wherein described
At least one metal ion beyond Fe ions is selected from the 3d beyond Al ions and the Fe ions for belonging to the race of periodic table the 4th~12
With 4d transition metal ions.
8. the method for manufacture iron compound particle according to claim 7, wherein
Metal ion beyond the Fe ions is selected from following at least one metal ion：Ni ions, Co ions, Mn from
Son, Cr ions, Zn ions and Al ions.
9. the method for the manufacture iron compound particle according to claim 7 or 8, wherein
The nertralizer is alkali compounds.
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| CN109999845A (en) * | 2019-03-26 | 2019-07-12 | 中国科学院化学研究所 | A kind of iron-based oxygen-separating catalyst and the preparation method and application thereof entirely |
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| JP2019127646A (en) * | 2018-01-26 | 2019-08-01 | 株式会社豊田中央研究所 | Electrolysis system and artificial photosynthesis system |
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| CN109351357A (en) * | 2018-10-16 | 2019-02-19 | 华中科技大学 | A kind of effective universal method for promoting perovskite catalyst catalytic performance |
| TWI732454B (en) * | 2019-02-14 | 2021-07-01 | 日商日本曹達股份有限公司 | Adsorption material particles and manufacturing method thereof |
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| CN109999845A (en) * | 2019-03-26 | 2019-07-12 | 中国科学院化学研究所 | A kind of iron-based oxygen-separating catalyst and the preparation method and application thereof entirely |
| CN109999845B (en) * | 2019-03-26 | 2020-05-26 | 中国科学院化学研究所 | All-iron-based oxygen evolution catalyst and preparation method and application thereof |
| CN114921806A (en) * | 2022-05-16 | 2022-08-19 | 中国科学技术大学 | Zinc ferrite photoanode with ultralow water oxidation photocurrent initial potential, preparation method and application |
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