CN111977708B - Preparation method of nitrogen-doped transition metal sulfide and application of nitrogen-doped transition metal sulfide in water electrolysis - Google Patents
Preparation method of nitrogen-doped transition metal sulfide and application of nitrogen-doped transition metal sulfide in water electrolysis Download PDFInfo
- Publication number
- CN111977708B CN111977708B CN202010580661.1A CN202010580661A CN111977708B CN 111977708 B CN111977708 B CN 111977708B CN 202010580661 A CN202010580661 A CN 202010580661A CN 111977708 B CN111977708 B CN 111977708B
- Authority
- CN
- China
- Prior art keywords
- transition metal
- nitrogen
- chloride
- sulfate
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- -1 transition metal sulfide Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 title description 5
- 239000000243 solution Substances 0.000 claims abstract description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 18
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 26
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims description 2
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims description 2
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000003568 thioethers Chemical class 0.000 abstract 2
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 description 16
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 8
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 150000004763 sulfides Chemical class 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/70—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/30—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Geology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of composite material synthesis, relates to preparation of sulfides, and in particular relates to a preparation method of nitrogen-doped transition metal sulfides, which comprises the following steps: deionized water is used as a solvent to prepare transition metal salt solutions with the molar concentration of 0.05-0.2 mol/L and hydrazine hydrate solutions with the mass percentage concentration of 2 percent respectively; according to the volume ratio of the transition metal salt solution to the hydrazine hydrate solution of 3-1: 1, mixing and standing for 3-4 hours to form sol and centrifuging; transferring the precursor into a crucible, placing the crucible into an upper air port of a tube furnace, placing sublimated sulfur into a lower air port of the tube furnace, heating to 300-500 ℃, calcining for 30-60 min in an inert atmosphere, and naturally cooling to room temperature to obtain the catalyst. The operation process is simple and feasible, the prepared material electrode has better electrochemical performance and stability, the raw materials are cheap and easy to obtain, the material electrode is nontoxic, the condition is mild and controllable, the material electrode is suitable for large-scale industrial production, can be directly used as an electrode for electrocatalytic decomposition water oxygen evolution reaction, and can also be suitable for preparation of other nitrogen doped sulfides.
Description
Technical Field
The invention belongs to the technical field of composite material synthesis, relates to sulfide preparation, and in particular relates to a preparation method of nitrogen-doped transition metal sulfide and application of the nitrogen-doped transition metal sulfide in electrolysis of water.
Background
Hydrogen is a future clean energy source, and electrolyzed water is a high-efficiency, low-cost and environment-friendly hydrogen production method, and mainly comprises an electrocatalytic Hydrogen Evolution Reaction (HER) and an Oxygen Evolution Reaction (OER), wherein OER is a rapid control step and is a bottleneck for limiting the hydrogen production conversion efficiency of electrolyzed water. The key to improve the conversion efficiency is to introduce a high-efficiency OER catalyst, reduce the reaction potential energy and improve the catalytic reaction rate. Current noble metal IrO 2 、RuO 2 Still being the best OER catalysts, but limited by their high cost and low reserves, make water electrolysis hydrogen production technology impractical for large scale commercial application.
With the intensive research of electrolyzed water, the transition metal-based (iron, cobalt, nickel and the like) electrocatalytic material has the advantages of environmental friendliness, no toxicity, rich reserves, thermodynamic stability and low cost, and is widely applied to the field of electrolyzed water. Single transition metal sulfides have proven to perform poorly and doping is considered an effective method of improving OER performance of single transition metal sulfides because doping can optimize the electronic structure, enhancing conductivity and charge transfer capability. However, the current doping methods involve high temperature calcination and use of some highly polluting chemicals as nitrogen sources. Therefore, it is important to find a nitrogen doping method with mild conditions and controllable reaction.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to disclose a preparation method of nitrogen-doped transition metal sulfide.
A preparation method of nitrogen-doped transition metal sulfide comprises the following steps:
A. deionized water is used as a solvent to prepare transition metal salt solutions with the molar concentration of 0.05-0.2 mol/L and hydrazine hydrate solutions with the mass percentage concentration of 2 percent respectively;
B. according to the volume ratio of the transition metal salt solution to the hydrazine hydrate solution of 3-1: 1, preferably 2:1, pouring the hydrazine hydrate solution into a transition metal salt solution, standing for 3-4 h to form sol, centrifuging, and drying the obtained precursor for later use;
C. transferring the precursor into a crucible, placing the crucible into an upper air port of a tube furnace, placing sublimated sulfur into a lower air port of the tube furnace, heating to 300-500 ℃ at a speed of 10 ℃/min, calcining and preserving heat for 30-60 min under the protection of inert gas, and naturally cooling to room temperature to obtain the nitrogen-doped transition metal sulfide, wherein the mass ratio of the precursor to the sublimated sulfur is 1:2-10, preferably 1:5.
in a preferred embodiment of the present invention, the transition metal salt in the step a is a nitrate, chloride or sulfate of a transition metal.
Further, the nitrate is nickel nitrate, cobalt nitrate, ferric nitrate, copper nitrate, aluminum nitrate, zinc nitrate, vanadium nitrate, molybdenum nitrate, chromium nitrate and the like; the chloride salt is nickel chloride, cobalt chloride, ferric chloride, cupric chloride, aluminum chloride, zinc chloride, vanadium chloride, molybdenum chloride, chromium chloride and the like; the sulfate is nickel sulfate, cobalt sulfate, ferric sulfate, copper sulfate, aluminum sulfate, zinc sulfate, vanadium sulfate, molybdenum sulfate, chromium sulfate, etc.
In the preferred embodiment of the invention, the rotating speed in the step B is 5000-8000 r/min.
In a preferred embodiment of the present invention, the inert gas in the step C is high-purity nitrogen or argon.
The nitrogen doped transition metal sulfide prepared by the method has the morphology of coarse solid pellets of 20-30 nm, and is easy to disperse in water and ethanol.
Sulfides are prone to forming oxyhydroxide during the course of vigorous electrochemical oxidation, which is considered an active species for electrocatalytic oxygen evolution, and studies have shown that the activity of directly synthesized oxyhydroxide is much lower than sulfide conversion. The nitrogen doping can change the electron cloud density of metal atoms and reduce the energy barrier in the oxygen desorption process.
Another object of the present invention is to apply the prepared nitrogen-doped transition metal sulfide to a positive electrode material for water electrolysis.
Electrocatalytic activity experiments of transition metal nitrogen doped sulfides:
(1) The concentration is 1 mol.L -1 KOH solution, seal and place in dark;
（2）adopts CHI660 electrochemical workstation (Shanghai Chen Hua instruments Co., ltd.) in a three-electrode system, platinum sheet as counter electrode, mercury/oxidized mercury electrode (Hg/HgO) as reference electrode, and composite material as working electrode at 1 mol.L -1 The electrochemical performance of transition metal nitrogen doped sulfides was tested in KOH electrolyte using Linear Sweep Voltammetry (LSV).
Advantageous effects
The invention uses hydrazine hydrate as nitrogen source to carry out coordination reaction with metal in room temperature liquid phase, which is suitable for doping various transition metals. When used as a water oxidation catalyst, a lower overpotential can be obtained. The operation process is simple and feasible, the prepared material electrode has better electrochemical performance and stability, the raw materials are cheap and easy to obtain, the material electrode is nontoxic, the condition is mild and controllable, the material electrode is suitable for large-scale industrial production, and the material electrode can be directly used as an electrode for the electrocatalytic decomposition water oxygen evolution reaction. The preparation method of the nitrogen-doped sulfide disclosed by the invention is also suitable for preparing other nitrogen-doped sulfides.
Drawings
Figure 1 XRD pattern of nitrogen doped cobalt sulphide,
figure 2 XRD pattern of nitrogen doped nickel sulfide,
figure 3 linear voltammograms of nitrogen doped nickel sulfide and cobalt sulfide,
fig. 4 active areas of nitrogen doped nickel sulfide and cobalt sulfide.
Detailed Description
The present invention will be described in detail with reference to the following examples, so that those skilled in the art can better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be interpreted to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
A method for preparing a nitrogen-doped transition metal sulfide, comprising:
weighing 0.0015 mol of cobalt chloride solution, dissolving in 20mL of deionized water, and magnetically stirring until the cobalt chloride solution is completely dissolved to form a solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, setting 5000r/min, centrifuging for 5min, transferring the obtained precipitate into a crucible after centrifuging, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 400 ℃, calcination is carried out under the protection of inert gas, the temperature is kept for 60min, and after the material is naturally cooled to room temperature, the nitrogen doped cobalt sulfide is obtained.
As can be seen from fig. 1, the diffraction peaks are not aligned, demonstrating successful doping of nitrogen element;
as can be seen from fig. 2, the diffraction peaks are not aligned, demonstrating successful doping of the nitrogen element;
the excellent electrochemical water oxidation performance is demonstrated by fig. 3;
the active areas of nickel sulfide and cobalt sulfide are doped with nitrogen from fig. 4.
The prepared nitrogen doped cobalt sulfide is applied to an electrolyzed water anode material, and the current density is 10 mA.cm -2 The time overpotential reaches 270mV, and the Tafil slope is 43 mV -1 。
Example 2
A method for preparing a nitrogen-doped transition metal sulfide, comprising:
weighing 0.0015 mol of nickel chloride solution, dissolving in 20mL of deionized water, and magnetically stirring until the nickel chloride solution is completely dissolved to form a solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, setting 5000r/min, centrifuging for 5min, transferring the obtained precipitate into a crucible after centrifuging, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 350 ℃, calcination is carried out under the protection of inert gas, the temperature is kept for 40min, and after the material is naturally cooled to room temperature, the nitrogen-doped nickel sulfide is obtained.
The prepared nitrogen doped cobalt sulfide is applied to an electrolyzed water anode material, and the current density is 10 mA.cm -2 The time overpotential reaches 275mV, and the Tafil slope is 47 mV -1 。
Example 3
A method for preparing a nitrogen-doped transition metal sulfide, comprising:
weighing 0.003 mol of ferric chloride solution, dissolving in 20mL of deionized water, and magnetically stirring until the ferric chloride solution is completely dissolved to form a solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, and centrifuging for 5min at 5000 r/min. After centrifugation is completed, transferring the obtained precipitate into a crucible, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 500 ℃, calcination is carried out under the protection of inert gas, the temperature is kept for 30 min, and after the material is naturally cooled to room temperature, the nitrogen-doped ferric sulfide is obtained.
The prepared nitrogen doped cobalt sulfide is applied to water electrolysisThe positive electrode material had a current density of 10 mA.cm -2 The time overpotential reaches 260mV, and the Tafil slope is 63 mV.dec -1 。
Example 4
A method for preparing a nitrogen-doped transition metal sulfide, comprising:
weighing 0.001 mol of nickel chloride and 0.001 mol of ferric chloride solution, dissolving in 20mL of deionized water, and magnetically stirring until the nickel chloride and the ferric chloride are fully dissolved to form solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, and centrifuging for 5min at 5000 r/min. After centrifugation is completed, transferring the obtained precipitate into a crucible, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 500 ℃, calcination is carried out under the protection of inert gas, the heat is preserved for 30 min, and after the nitrogen doped ferronickel sulfide is naturally cooled to room temperature, the nitrogen doped ferronickel sulfide is obtained.
The prepared nitrogen doped cobalt sulfide is applied to an electrolyzed water anode material, and the current density is 10 mA.cm -2 The time overpotential reaches 210mV, and the Tafil slope is 57 mV -1 。
Example 5
A method for preparing a nitrogen-doped transition metal sulfide, comprising:
weighing 0.003 mol of nickel nitrate solution, dissolving in 20mL of deionized water, and magnetically stirring until the solution is completely dissolved to form solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, and centrifuging for 5min at 5000 r/min. After centrifugation is completed, transferring the obtained precipitate into a crucible, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 500 ℃, calcination is carried out under the protection of inert gas, the temperature is kept for 30 min, and after the material is naturally cooled to room temperature, the nitrogen-doped nickel sulfide is obtained.
The prepared nitrogen-doped nickel sulfide is applied to an electrolytic water positive electrode material, and the current density is 10 mA.cm -2 The time overpotential reaches 275mV, and the Tafil slope is 58 mV -1 。
Example 6
Weighing 0.003 mol of copper sulfate solution, dissolving in 20mL of deionized water, and magnetically stirring until the copper sulfate solution is completely dissolved to form a solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, and centrifuging for 5min at 5000 r/min. After centrifugation is completed, transferring the obtained precipitate into a crucible, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 500 ℃, calcination is carried out under the protection of inert gas, the heat is preserved for 30 min, and after the material is naturally cooled to room temperature, the nitrogen-doped copper sulfide is obtained.
The prepared nitrogen-doped copper sulfide is applied to an electrolytic water positive electrode material, and the current density is 10 mA.cm -2 The time overpotential reaches 310mV, and the Tafil slope is 75mV -1 。
Example 7
Weighing 0.002 mol of zinc sulfate solution, dissolving in 20mL of deionized water, and magnetically stirring until the solution is completely dissolved to form solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, and centrifuging for 5min at 5000 r/min. After centrifugation is completed, transferring the obtained precipitate into a crucible, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 500 ℃, calcination is carried out under the protection of inert gas, the temperature is kept for 30 min, and after the material is naturally cooled to room temperature, the nitrogen-doped zinc sulfide is obtained.
The prepared nitrogen doped zinc sulfide is applied to an electrolytic water positive electrode material, and the current density is 10 mA.cm -2 The time overpotential reaches 310mV, and the Tafil slope is 75mV -1 。
Example 8
Weighing 0.002 mol of chromium sulfate solution, dissolving in 20mL of deionized water, and magnetically stirring until the chromium sulfate solution is completely dissolved to form a solution A;
10mL of deionized water is measured, and 20uL of 30% hydrazine hydrate is added to the solution to form a solution B;
pouring the obtained solution B into the solution A, and standing for about 4 hours at room temperature to form a liquid sol C;
transferring the sol C into a centrifuge tube, and centrifuging for 5min at 5000 r/min. After centrifugation is completed, transferring the obtained precipitate into a crucible, and drying in an oven; transferring the obtained precipitate into a crucible, and drying in an oven;
after drying, 0.1g of precursor is transferred into a crucible and placed at an upper air port of a tube furnace, then 0.5g of sublimed sulfur is weighed and placed at a lower air port of the crucible, then the tube furnace is arranged, the temperature is kept at a programmed temperature of 10 ℃/min to 500 ℃, calcination is carried out under the protection of inert gas, the temperature is kept for 30 min, and after the material is naturally cooled to room temperature, the nitrogen-doped chromium sulfide is obtained.
The prepared nitrogen doped chromium sulfide is applied to the electrolytic water positive pole materialThe material has a current density of 10 mA.cm -2 The time overpotential reaches 290mV, and the Tafil slope is 65 mV -1 。
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (8)
1. The preparation method of the nitrogen-doped transition metal sulfide is characterized by comprising the following steps of:
A. deionized water is used as a solvent to prepare transition metal salt solutions with the molar concentration of 0.05-0.2 mol/L and hydrazine hydrate solutions with the mass percentage concentration of 2 percent respectively;
B. pouring the hydrazine hydrate solution into the transition metal salt solution according to the volume ratio of the transition metal salt solution to the hydrazine hydrate solution of 3-1:1, standing for 3-4 h to form sol, centrifuging, and drying the obtained precursor for later use;
C. transferring the precursor into a crucible, placing the crucible into an upper air port of a tube furnace, placing sublimated sulfur into a lower air port of the tube furnace, heating to 300-500 ℃ at a speed of 10 ℃/min, calcining under the protection of inert gas, preserving heat for 30-60 min, and naturally cooling to room temperature to obtain the nitrogen-doped transition metal sulfide, wherein the mass ratio of the precursor to the sublimated sulfur is 1:2-10.
2. The method for producing a nitrogen-doped transition metal sulfide according to claim 1, wherein: the transition metal salt in the step A is nitrate, chloride or sulfate of transition metal.
3. The method for producing a nitrogen-doped transition metal sulfide according to claim 2, characterized in that: and (C) the nitrate in the step A is nickel nitrate, cobalt nitrate, ferric nitrate, copper nitrate, aluminum nitrate, zinc nitrate, vanadium nitrate, molybdenum nitrate and chromium nitrate.
4. The method for producing a nitrogen-doped transition metal sulfide according to claim 2, characterized in that: and the chloride salt in the step A is nickel chloride, cobalt chloride, ferric chloride, cupric chloride, aluminum chloride, zinc chloride, vanadium chloride, molybdenum chloride and chromium chloride.
5. The method for producing a nitrogen-doped transition metal sulfide according to claim 2, characterized in that: the sulfate in the step A is nickel sulfate, cobalt sulfate, ferric sulfate, copper sulfate, aluminum sulfate, zinc sulfate, vanadium sulfate, molybdenum sulfate and chromium sulfate.
6. The method for producing a nitrogen-doped transition metal sulfide according to claim 1, wherein: and B, the volume ratio of the transition metal salt solution to the hydrazine hydrate solution is 2:1.
7. The method for producing a nitrogen-doped transition metal sulfide according to claim 1, wherein: and C, the inert gas is high-purity nitrogen or argon.
8. The method for producing a nitrogen-doped transition metal sulfide according to claim 1, wherein: and C, the mass ratio of the precursor to the sublimated sulfur is 1:5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010580661.1A CN111977708B (en) | 2020-06-23 | 2020-06-23 | Preparation method of nitrogen-doped transition metal sulfide and application of nitrogen-doped transition metal sulfide in water electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010580661.1A CN111977708B (en) | 2020-06-23 | 2020-06-23 | Preparation method of nitrogen-doped transition metal sulfide and application of nitrogen-doped transition metal sulfide in water electrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111977708A CN111977708A (en) | 2020-11-24 |
| CN111977708B true CN111977708B (en) | 2023-05-09 |
Family
ID=73441995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010580661.1A Active CN111977708B (en) | 2020-06-23 | 2020-06-23 | Preparation method of nitrogen-doped transition metal sulfide and application of nitrogen-doped transition metal sulfide in water electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111977708B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114016053B (en) * | 2021-12-10 | 2023-11-14 | 福州大学 | Method for improving stability of transition metal sulfide catalyst |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110240108A1 (en) * | 2010-04-02 | 2011-10-06 | Matt Law | Method To Synthesize Colloidal Iron Pyrite (FeS2) Nanocrystals And Fabricate Iron Pyrite Thin Film Solar Cells |
| TW201331123A (en) * | 2012-01-18 | 2013-08-01 | Lextar Electronics Corp | Method for producing the powders of copper-zinc-tin-chalcogenide by sol-gel method |
| CN108574106B (en) * | 2017-03-08 | 2021-12-10 | 中国科学技术大学 | Self-supporting nitrogen-doped metal catalyst and preparation method thereof |
| CN107321372B (en) * | 2017-06-06 | 2019-12-03 | 江苏大学 | CoS nano particle/N doping RGO liberation of hydrogen composite material preparation method |
| CN108823597B (en) * | 2018-05-14 | 2020-06-26 | 江苏大学 | Method for preparing nitrogen-doped nickel sulfide hydrogen evolution catalyst by annealing method and application thereof |
| CN110201697B (en) * | 2019-05-29 | 2020-08-04 | 浙江大学 | Three-dimensional nitrogen-doped transition metal oxide/nickel sulfide composite catalyst, and preparation method and application thereof |
-
2020
- 2020-06-23 CN CN202010580661.1A patent/CN111977708B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 韩凯 ; 诸辞 ; 李俊杰 ; .纳米硫化锌颗粒制备工艺与研究进展.世界有色金属.2016,(第13期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111977708A (en) | 2020-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112005413B (en) | ZIF-8-based nickel-iron-nitrogen-doped carbon material three-function electrocatalyst and preparation method and application thereof | |
| CN107803207B (en) | Carbon-based bimetallic composite material, preparation and application thereof | |
| CN107267124B (en) | MOFs (metal-organic frameworks) nitrogen-containing graphitized carbon material containing Ni/Fe bimetal | |
| CN107670679B (en) | MoS2Preparation method and application of/rGO-CN composite material | |
| CN111659401B (en) | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof | |
| CN108754531B (en) | Preparation method of Co-and Ru-containing bimetallic carbon nano composite electro-catalytic material | |
| CN112481653B (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| CN110085879A (en) | A kind of Co9S8/ sulphur nitrogen is co-doped with carbon composite and preparation method thereof | |
| CN108315758B (en) | Catalyst for producing hydrogen by electrolyzing water and preparation method thereof | |
| CN108212194A (en) | A kind of nitrogen-doped carbon nickel coat composite Nano carbon electrolysis water catalyst and preparation method thereof | |
| CN111569907A (en) | Bimetal composite material and preparation method and application thereof | |
| CN113113623A (en) | Synthesis method of carbon-supported platinum-based intermetallic compound nano material and electrocatalysis application thereof | |
| CN111977708B (en) | Preparation method of nitrogen-doped transition metal sulfide and application of nitrogen-doped transition metal sulfide in water electrolysis | |
| CN113802139B (en) | Nickel sulfide based electrocatalytic material with core-shell structure and preparation method and application thereof | |
| CN110828834A (en) | One-pot synthesis of non-noble metal double-effect electrocatalyst for oxygen reduction and oxygen desorption | |
| CN113772644A (en) | Bimetallic phosphide and preparation method and application thereof | |
| CN115074771B (en) | Nitrogen-doped carbon nanotube-coated Ni 3 ZnC 0.7 Ni heterogeneous nanoparticle electrocatalyst and preparation method thereof | |
| CN114892206B (en) | Multi-metal nitride heterojunction nanorod array composite electrocatalyst and preparation method and application thereof | |
| CN111394748B (en) | For CO2Electrolytic iron-nickel alloy in-situ desolventizing layered perovskite cathode material | |
| CN109913897B (en) | Preparation method of three-dimensional integral transition metal compound electrode | |
| CN115763845B (en) | Preparation method of chromium-based inorganic matter coupled transition metal nitrogen-doped carbon catalyst | |
| CN113968592B (en) | Few-layer graphene modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN113388860B (en) | Preparation method of ferric oxide/CuCo-MOF/carbon cloth oxygen evolution composite electrocatalytic film | |
| CN113769769B (en) | Nickel-iron phosphide/graphene/nickel composite material, and preparation method and application thereof | |
| CN117702171A (en) | Polarization electric field mediated CN@AC@O-C=O full-pH water electrolysis hydrogen production catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |