CN109967092A - A kind of metal-doped indium sulfide nanometer sheet, preparation method and application - Google Patents
A kind of metal-doped indium sulfide nanometer sheet, preparation method and application Download PDFInfo
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- CN109967092A CN109967092A CN201910367622.0A CN201910367622A CN109967092A CN 109967092 A CN109967092 A CN 109967092A CN 201910367622 A CN201910367622 A CN 201910367622A CN 109967092 A CN109967092 A CN 109967092A
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- China
- Prior art keywords
- nanometer sheet
- doped
- indium
- metal
- indium sulfide
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Links
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 26
- 150000002471 indium Chemical class 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012990 dithiocarbamate Substances 0.000 claims abstract description 17
- 150000001412 amines Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 235000019253 formic acid Nutrition 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 4
- 229950004394 ditiocarb Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910003320 CeOx Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- AXHBQUDQEYGJPJ-UHFFFAOYSA-N [Na].C(N)(O)=S Chemical compound [Na].C(N)(O)=S AXHBQUDQEYGJPJ-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000004119 disulfanediyl group Chemical group *SS* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- -1 salt compound Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/33—
-
- 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
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/806—Electrocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
Abstract
The present invention provides a kind of preparation methods of metal-doped indium sulfide nanometer sheet, comprising: S1) by indium salts, doped metal salt and dialkyl dithiocarbamate hybrid reaction in organic solvent, obtain precursor complexes;S2) precursor complexes are heated in amine solvent to reaction, obtain metal-doped indium sulfide nanometer sheet.Compared with prior art; the present invention is introduced in indium sulfide nanometer sheet using regulation precursor synthesis with thermal decomposition metal-doped; preparation process is simple and convenient, can magnanimity preparation; presoma ratio is controllable; Doped ions concentration can be adjusted precisely; and ion is introduced with universality; resulting nanometer sheet thickness is uniform, good dispersion; improve its catalytic activity in electroreduction carbon dioxide; this preparation method in addition to the nanometer sheet for preparing additive Mn can also scale magnanimity prepare other ion-doped nano pieces, have wide application prospect.
Description
Technical field
The invention belongs to two-dimension nano materials technical field, more particularly to a kind of metal-doped indium sulfide nanometer sheet, its
Preparation method and application.
Background technique
The modern economic heavy dependence fossil resource of global energy, and the burning of fossil resource can bring CO2 emission to draw
The environmental problems such as greenhouse effects are played, in order to meet the pollution mitigated while the energy demand of long-term economic growth to environment,
We are badly in need of developing a kind of sustainable alternative energy source.Consideration is transformed into the renewable electric power such as wind energy and solar energy entirely
Ball energy supply is one of promising mode, however, the intermittent feature of these resources itself causes storage to generate
Power cost is high.It by carbon dioxide reduction to carbon-based chemicals is most possibly to mitigate this worry in a manner of electric energy, together
When alleviate Atmospheric CO2The problem of concentration rises.The reaction using renewable electric power as input, carbon dioxide and water as raw material,
It is sustainable by CO2It is converted into fuel and industrial chemical.In carbon dioxide electroreduction, reaction efficiency largely by
The limitation of the high energy barrier of carbon dioxide activation, the step need the overpotential relative to standard hydrogen -1.9V.To reduce the reaction
Barrier is reacted, all kinds of catalyst materials are widely used in electroreduction carbon dioxide reaction process, to accelerate reaction rate.
It in recent years, is the New Two Dimensional nano material of representative because of its unique structure and excellent electrochemistry using graphene
Can, it is widely used in energy catalytic field.Two-dimension nano materials can promote electro-catalysis anti-with its high specific surface area
High-efficient contact during answering between catalytic media, to realize, quick charge transfer provides guarantee between interface, to be expected to
It designs to obtain the electroreduction carbon dioxide reaction catalyst of Cheap highly effective by specific structure based on this.As a special dictionary
The two-dimension nano materials of type, two-dimentional In2S3Nanometer sheet largely exposed active site and is being urged with its unique architectural characteristic
Good stability causes the interest of more and more researchers during change.Meanwhile the electronic structure of catalyst is in electroreduction
Also have the function of during carbon dioxide reaction particularly important.Excellent electronic structure can improve the absorption to gas molecule
Ability adjusts the adsorption strength that differential responses intermediate in interface is catalyzed during electrocatalytic reaction, so that it is guaranteed that efficiently
Journal of Molecular Catalysis transformation efficiency.And the property of nano material and the structure of catalyst, surface topography and component are closely bound up, therefore,
It how probes by two-dimentional In2S3The regulation of nanometer sheet electronic structure realizes it for CO2The active promotion of Journal of Molecular Catalysis has
Very important meaning.
However, still having in terms of the Electronic Structure Design of two-dimension nano materials and performance regulation at present many urgently to be resolved
Problem.For example, " American Chemical Society " (J.Am.Chem.Soc.139,5652-5655,2017) reports building Au/CeOxBoundary
Face can improve to Au/CeOxCO2Absorption and activation, to improve to Au or CeOxCO2Electroreduction activity and selection
Property;In addition, " German applied chemistry " (Angewandte Chemie International Edition57,6054-6059,
2018) it reports, introduces Lacking oxygen and the electronics near valence band is caused to increase, electronic transfer process is promoted, to promote
Oxygen-enriched defect ZnO nano on piece electroreduction CO2To CO product.These methods are focused on by interface or surface defect
Reason improves catalytic activity, needs to use the noble metal catalysts such as Au and preparation process is complicated, while being also required to special installation
And instrument is unfavorable for large scale preparation, and electronic-controlled effect is limited, needs to find accuracy controlling so that reaction cost is very high
The regulation method of component.
Up to the present, there has been no document reports under simple condition, and quick magnanimity is prepared ingredient controllable precise, is had
The two-dimentional In of good electronic structure and excellent catalytic activity2S3The method of nanometer chip architecture.
Summary of the invention
In view of this, doping component is adjustable, has the technical problem to be solved in the present invention is that providing a kind of structural integrity
Metal-doped indium sulfide nanometer sheet, preparation method and the application of good electronic structure and excellent catalytic performance.
The present invention provides a kind of preparation methods of metal-doped indium sulfide nanometer sheet, comprising:
S1 it) by indium salts, doped metal salt and dialkyl dithiocarbamate hybrid reaction in organic solvent, obtains
Precursor complexes;
S2) precursor complexes are heated in amine solvent to reaction, obtain metal-doped indium sulfide nanometer sheet.
Preferably, the indium salts are selected from one of inidum chloride, indium nitrate, indium sulfate and indium acetate or a variety of;It is described to mix
Miscellaneous metal salt be selected from manganese salt, be preferably selected from one of manganese chloride, protochloride manganese, manganese nitrate, acetic acid Asia manganese and manganese sulfate or
It is a variety of;The organic solvent is selected from methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, diglycol, glycerine, poly- second
One of glycol, acetone, formamide and n,N-Dimethylformamide are a variety of;The dialkyl dithiocarbamate choosing
From in dialkyldithiocarbamacompositions sodium, dialkyldithiocarbamacompositions ammonium and dialkyldithiocarbamacompositions diethyl ammonium
It is one or more;The amine solvent is selected from one of octylame, decyl amine, lauryl amine, tetradecy lamine, cetylamine and oleyl amine or more
Kind.
Preferably, the indium salts and the molar ratio of dialkyl dithiocarbamate are 1:(1~5);The presoma
The mass ratio of complex and amine solvent is (0.005~0.1): 1;Phosphide element and metal member in doped metal salt in the indium salts
The molar ratio of element is 100:(1~10).
Preferably, the step S1) specifically:
Indium salts, doped metal salt are mixed with organic solvent, obtain the first mixed solution;Indium salts in first mixed liquor
Concentration be 0.05~0.5mmol/ml;
Dialkyl dithiocarbamate is mixed with organic solvent, obtains the second mixed solution;Second mixing
The concentration of dialkyl dithiocarbamate is 0.05~0.5mmol/ml in liquid;
By first mixed solution and the second mixed solution hybrid reaction, precursor complexes are obtained.
Preferably, the step S1) in hybrid reaction temperature be 20 DEG C~40 DEG C;The time of hybrid reaction be 20~
200min;
The step S2) in heating reaction temperature be 200 DEG C~320 DEG C;Heating reaction time be 100~
200min。
The present invention also provides the metal-doped indium sulfide nanometer sheets prepared by the above method.
Preferably, the average-size of the indium sulfide nanometer sheet of the additive Mn is 50~100nm;Average thickness be 0.6~
2nm。
Preferably, the metal-doped indium sulfide nanometer sheet is the indium sulfide nanometer sheet of additive Mn.
Preferably, the surface crystal face of the indium sulfide nanometer sheet of the additive Mn is (022).
The present invention also provides application of the above-mentioned metal-doped indium sulfide nanometer sheet in carbon dioxide electro-catalysis reduction.
The present invention provides a kind of preparation methods of metal-doped indium sulfide nanometer sheet, comprising: S1) by indium salts, doping
Metal salt and dialkyl dithiocarbamate hybrid reaction in organic solvent, obtain precursor complexes;It S2) will be described
Precursor complexes heat reaction in amine solvent, obtain metal-doped indium sulfide nanometer sheet.Compared with prior art, originally
Invention introduces in indium sulfide nanometer sheet metal-doped with thermally decomposing using regulation precursor synthesis, preparation process is simple and convenient,
Can magnanimity preparation, presoma ratio is controllable, and Doped ions concentration can be adjusted precisely, and introduce ion have universality, it is resulting
Nanometer sheet thickness is uniform, good dispersion, improves its catalytic activity in electroreduction carbon dioxide, this preparation method is except preparation
Outside the nanometer sheet of additive Mn can also scale magnanimity prepare other ion-doped nano pieces, have wide application prospect.
Experiment shows Mn-In provided by the invention2S3Ultrathin nanometer piece uniform component distribution, electronic structure is controllable,
Under relative standard's hydrogen electrode -1.0V overpotential, it is simple In that current density, which is 42 milliamps per square centimeter,2S3The electricity of nanometer sheet
2 times of current density.Moreover, for the primary product (formic acid) of electroreduction, Mn-In2S3Ultrathin nanometer piece and pure In2S3Nanometer sheet
Faradic efficiency be respectively 80.2% and 42.0%.In addition, Mn-In of the present invention2S3Ultrathin nanometer piece can be directly as catalyst
During electroreduction carbon dioxide reaction, and excellent catalytic activity in catalytic reaction process is shown, had non-
Often big advantage.
Detailed description of the invention
Fig. 1 is Mn-In obtained in the embodiment of the present invention 12S3The transmission electron microscope picture of ultrathin nanometer piece;
Fig. 2 is Mn-In obtained in the embodiment of the present invention 12S3Ultrathin nanometer piece and the X-ray of pure indium sulfide nanometer sheet are spread out
Penetrate map;
Fig. 3 is Mn-In obtained in the embodiment of the present invention 12S3The X-ray light of ultrathin nanometer piece and pure indium sulfide nanometer sheet
Electronic energy spectrum;
Fig. 4 is the Mn-In of the embodiment of the present invention 32S3Ultrathin nanometer piece is electric under different overpotentials from pure indium sulfide nanometer sheet
Current density curve;
Fig. 5 is the Mn-In of the embodiment of the present invention 32S3Ultrathin nanometer piece first under different overpotentials from pure indium sulfide nanometer sheet
The faradic efficiency column diagram of acid;
Fig. 6 is the Fe-In of the embodiment of the present invention 32S3Ultrathin nanometer piece has under different overpotentials from pure indium sulfide nanometer sheet
Imitate the faradic efficiency curve of carbon product;
Fig. 7 is the Co-In of the embodiment of the present invention 32S3Ultrathin nanometer piece has under different overpotentials from pure indium sulfide nanometer sheet
Imitate the faradic efficiency curve of carbon product;
Fig. 8 is the Ni-In of the embodiment of the present invention 32S3Ultrathin nanometer piece has under different overpotentials from pure indium sulfide nanometer sheet
Imitate the faradic efficiency curve of carbon product;
Fig. 9 is that the overpotential in relative standard's hydrogen electrode of the embodiment of the present invention 3 is Mn-In under -1.0V2S3Ultrathin nanometer
The current density of piece and pure indium sulfide nanometer sheet changes over time figure;
Figure 10 is that the overpotential in relative standard's hydrogen electrode of the embodiment of the present invention 3 is Mn-In under -1.0V2S3It is ultra-thin to receive
Rice piece and the formic acid faradic efficiency of pure indium sulfide nanometer sheet change over time figure.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of metal-doped indium sulfide nanometer sheet, comprising: S1) by indium salts, doping
Metal salt and dialkyl dithiocarbamate hybrid reaction in organic solvent, obtain precursor complexes;It S2) will be described
Precursor complexes heat reaction in amine solvent, obtain metal-doped indium sulfide nanometer sheet.
The application is not particularly limited the source of all raw materials, is commercially available.
Wherein, the indium salts are preferably one of inidum chloride, indium nitrate, indium sulfate and indium acetate or a variety of;It is described to mix
Miscellaneous metal salt is that other in addition to indium salts can be used as the salt compound of doping metals in indium sulfide nanometer sheet, preferably ferrous
One of salt, cobalt salt, nickel salt and manganese salt are a variety of, more preferably nickel chloride, cobalt chloride, frerrous chloride, nickel nitrate, nitric acid
Cobalt, ferrous nitrate, nickel acetate, cobalt acetate, ferrous acetate, nickel sulfate, cobaltous sulfate, ferrous sulfate, manganese chloride, protochloride manganese, nitre
One of sour manganese, acetic acid Asia manganese and manganese sulfate are a variety of;The dialkyl dithiocarbamate is preferably alkyl two
One of thiocarbamic acid sodium, dialkyldithiocarbamacompositions ammonium and dialkyldithiocarbamacompositions diethyl ammonium are more
Kind;The organic solvent is preferably methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, diglycol, glycerine, poly- second
One of glycol, acetone, formamide and n,N-Dimethylformamide are a variety of;The amine solvent is preferably C8~C20's
One of amine solvent, more preferably octylame, decyl amine, lauryl amine, tetradecy lamine, cetylamine and oleyl amine are a variety of.
By indium salts, doped metal salt and dialkyl dithiocarbamate hybrid reaction in organic solvent;The indium
The molar ratio of salt and doped metal salt is preferably 100:(1~10), more preferably 100:(1~8), further preferably for 100:(2~
6) it is further preferably, 100:(3~5), most preferably 100:(3~4);The indium salts and dialkyl dithiocarbamate rub
You are than being preferably 1:(1~5), more preferably 1:(2~4), it is further preferably 1:3;In the present invention, this step is preferred specifically:
Indium salts, doped metal salt are mixed with organic solvent, obtain the first mixed solution;The concentration of indium salts is excellent in first mixed liquor
It is selected as 0.05~0.5mmol/ml, more preferably 0.1~0.4mmol/ml, is further preferably 0.2~03mmol/ml;By dialkyl group
Dithiocar-bamate is mixed with organic solvent, obtains the second mixed solution;Dialkyl dithio in second mixed liquor
The concentration of carbaminate is preferably 0.05~0.5mmol/ml, more preferably 0.1~0.4mmol/ml, further preferably for 0.2~
0.4mmol/ml, most preferably 0.3mmol/ml;By first mixed solution and the second mixed solution hybrid reaction;It is described mixed
The temperature for closing reaction is preferably 20 DEG C~40 DEG C, and more preferably 25 DEG C~35 DEG C, further preferably to react at room temperature;The mixing is anti-
The time answered is preferably 20~200min, more preferably 30~150mi, is further preferably 30~120min;The hybrid reaction is excellent
Choosing carries out under stirring conditions.Doping metals are introduced directly into presoma in the present invention.It is introduced directly into presoma
Mode, which can be adjusted effectively, introduces content and elemental constituent, to prepare the metal-doped of uniform component distribution and non-split-phase
Indium sulfide nanometer sheet.
After hybrid reaction, organic solvent washing is preferably used, centrifugation obtains precursor complexes after dry;It is described organic molten
Agent is preferably methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, diglycol, glycerine, polyethylene glycol, acetone, formyl
One of amine and n,N-Dimethylformamide are a variety of.
The precursor complexes are heated to reaction in amine solvent;The matter of the precursor complexes and amine solvent
Amount is than being preferably (0.005~0.1): 1, more preferably (0.01~0.08): 1, be further preferably (0.01~0.06): 1, further preferably
For (0.02~0.04): 1, most preferably (0.028~0.03): 1;The temperature of the heating reaction is preferably 200 DEG C~320
℃;The time of the heating reaction is preferably 100~200min, more preferably 120~180min, further preferably for 150~
180min;The heating reaction carries out preferably in protective atmosphere;The protective atmosphere is preferably nitrogen;In the present invention, this
Step is preferred specifically: the precursor complexes mixed with amine solvent, it is closed in protective atmosphere to carry out heating reaction,
It is preferred that being first heated to the reaction of the first temperature, second temperature insulation reaction is then heated to;First temperature is preferably 150
DEG C~250 DEG C, more preferably 180 DEG C~220 DEG C, be further preferably 200 DEG C;The time of first temperature reaction is preferably
10~40min, more preferably 20~40min are further preferably 30min;The second temperature is preferably 260 DEG C~320 DEG C, more excellent
280 DEG C~320 DEG C are selected as, is further preferably 300 DEG C;The time of the second temperature insulation reaction is preferably 60~190min, more
Preferably 100~160min is further preferably 120min.
After heating reaction, preferably with after organic solvent washing, centrifugation, drying, metal-doped indium sulfide nanometer sheet is obtained;
The organic solvent is preferably acetone and/or chloroform.
The present invention introduces metal-doped, preparation process using regulation precursor synthesis and thermal decomposition in indium sulfide nanometer sheet
It is simple and convenient, can magnanimity preparation, presoma ratio is controllable, and Doped ions concentration can be adjusted precisely, and introduce ion have it is pervasive
Property, resulting nanometer sheet thickness is uniform, good dispersion, improves its catalytic activity in electroreduction carbon dioxide, this preparation
Method in addition to the nanometer sheet for preparing additive Mn can also scale magnanimity prepare other ion-doped nano pieces, have wide application
Prospect.
The present invention also provides a kind of metal-doped indium sulfide nanometer sheets of above method preparation;It is described metal-doped
The average-size of indium sulfide nanometer sheet is preferably 50~100nm;Average thickness is preferably 0.6~2nm;Ultra-thin structure can be sudden and violent
Reveal surface atom abundant, reaction molecular comes into full contact with catalyst during facilitating electroreduction carbon dioxide reaction, accelerates
Reaction carries out.
The metal-doped indium sulfide nanometer sheet is preferably the indium sulfide nanometer sheet of additive Mn;The vulcanization of the additive Mn
The surface crystal face of indium nanometer sheet is preferably (022).
The present invention also provides application of the above-mentioned metal-doped indium sulfide nanometer sheet in carbon dioxide electro-catalysis reduction.
By the way that in the synthesis process, controllable precise doping component is effectively improved its electronic structure, In is promoted2S3Ultrathin nanometer piece is gone back in electricity
Catalytic activity in former carbon dioxide reaction, and catalytic selectivity is high, stability is good.
In order to further illustrate the present invention, the indium sulfide metal-doped to one kind provided by the invention with reference to embodiments
Nanometer sheet, preparation method and application are described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
3mmol sodium diethyldithiocarbamate is dissolved in 10mL methanol, 5mL is added and contains 1mmol inidum chloride
And the methanol solution of 0.03mmol manganese chloride, stirring, which is sufficiently placed under 25 DEG C of room temperature, to be kept for 120 minutes, is washed later with ethyl alcohol
It washs, is centrifuged, is dried to obtain InMn-DDTC presoma.
0.112g InMn-DDTC presoma is added in 4g lauryl amine, logical nitrogen kept closed after 15 minutes, heated
30 minutes are kept the temperature to 200 DEG C, then rises to 300 DEG C and keeps the temperature 2 hours.Acetone and chloroform are used later, and centrifugation is dried to obtain Mn-
In2S3Ultrathin nanometer piece.
Using transmission electron microscope to Mn-In obtained in embodiment 12S3Ultrathin nanometer piece is detected, and obtains it thoroughly
The sub- microscope photograph of radio is as shown in Figure 1, as shown in Figure 1, Mn-In obtained in embodiment 12S3The average ruler of ultrathin nanometer piece
Very little is 50~100nm, and average thickness is 0.6~2nm.
Using X-ray to Mn-In obtained in embodiment 12S3Ultrathin nanometer piece is detected with pure indium sulfide nanometer sheet,
It is as shown in Figure 2 to obtain its X ray diffracting spectrum;It is as shown in Figure 3 to obtain its x-ray photoelectron spectroscopy figure.
Embodiment 2
Mn-In2S3Elctro-catalyst and electroreduction carbon dioxide test condition of the ultrathin nanometer piece as effective component.
By 0.2mg Mn-In2S3Ultrathin nanometer piece, the Nafion solution of 0.8mg active carbon and 15 μ L5% mass fractions
It is scattered in 1mL ethyl alcohol, ultrasonic 1h is to obtain a uniform solution.Then, above-mentioned solution is taken uniformly to brush in 1cm × 0.5cm
Carbon paper on.Using the carbon paper as working electrode, silver/silver chloride electrode is used as reference electrode, graphite rod to electrode.Electricity is also
Former carbon dioxide reaction electrolyte is that 40mL concentration is 0.1mol/L potassium bicarbonate aqueous solution, and logical 30min is at least needed before reaction
Carbon dioxide drive other gases away.Catalysis reaction carries out in H-type electrolytic cell, which is handed over by 115 proton of Nafion
It changes film and separates anode and cathode;Pass through the additional overpotential of electrochemical workstation and detection current density.The hydrogen that catalysis generates passes through gas
The detection of phase chromatography, the formic acid of generation are detected with nuclear-magnetism.
Embodiment 3
Mn-In2S3Current density and gas selectivity of product of the ultrathin nanometer piece in the test of electroreduction carbon dioxide are surveyed
Examination.
Under the reaction condition of embodiment 2, constant potential is taken to test.Be arranged relative standard's hydrogen electrode overpotential be-
0.6V, constant potential are tested 40 minutes.During the reaction, it needs to be continually fed into carbon dioxide with the speed of 10mL/min.Reaction
The oxygen that Anodic generates is discharged into air.Pass through online gas-chromatography within the gaseous product generated in reaction process every 8 minutes
Thermal conductivity cell detector detection, the formic acid of generation are detected with nuclear-magnetism.After the completion of test, overpotential is changed to -0.7V, -0.8V, -
0.9V, -1.0V are utilized respectively identical process and are tested.Mn-In2S3Ultrathin nanometer piece current density under these overpotentials is shown in
The faradic efficiency of Fig. 4, formic acid are shown in Fig. 5.
Embodiment 4
3mmol sodium diethyldithiocarbamate is dissolved in 10mL methanol, 5mL is added and contains 1mmol inidum chloride
And the methanol solution of 0.03mmol frerrous chloride, stirring, which is sufficiently placed under 25 DEG C of room temperature, to be kept for 120 minutes, is washed later with ethyl alcohol
It washs, is centrifuged, is dried to obtain InFe-DDTC presoma.
0.112g InFe-DDTC presoma is added in 4g lauryl amine, logical nitrogen kept closed after 15 minutes, heated
30 minutes are kept the temperature to 200 DEG C, then rises to 300 DEG C and keeps the temperature 2 hours.Acetone and chloroform are used later, and centrifugation is dried to obtain Fe-
In2S3Ultrathin nanometer piece.
Under the conditions of the test condition of the electroreduction carbon dioxide of embodiment 2 and the product detection of embodiment 3, respectively
It is tested using identical process, Fe-In2S3Ultrathin nanometer piece faradic efficiency of effective carbon product under these overpotentials is shown in
Fig. 6.
Embodiment 5
3mmol sodium diethyldithiocarbamate is dissolved in 10mL methanol, 5mL is added and contains 1mmol inidum chloride
And the methanol solution of 0.03mmol cobalt chloride, stirring, which is sufficiently placed under 25 DEG C of room temperature, to be kept for 120 minutes, is washed later with ethyl alcohol
It washs, is centrifuged, is dried to obtain InCo-DDTC presoma.
0.112g InCo-DDTC presoma is added in 4g lauryl amine, logical nitrogen kept closed after 15 minutes, heated
30 minutes are kept the temperature to 200 DEG C, then rises to 300 DEG C and keeps the temperature 2 hours.Acetone and chloroform are used later, and centrifugation is dried to obtain Co-
In2S3Ultrathin nanometer piece.
Under the conditions of the test condition of the electroreduction carbon dioxide of embodiment 2 and the product detection of embodiment 3, respectively
It is tested using identical process, Co-In2S3Ultrathin nanometer piece faradic efficiency of effective carbon product under these overpotentials is shown in
Fig. 7.
Embodiment 6
3mmol sodium diethyldithiocarbamate is dissolved in 10mL methanol, 5mL is added and contains 1mmol inidum chloride
And the methanol solution of 0.03mmol nickel chloride, stirring, which is sufficiently placed under 25 DEG C of room temperature, to be kept for 120 minutes, is washed later with ethyl alcohol
It washs, is centrifuged, is dried to obtain InNi-DDTC presoma.
0.112g InNi-DDTC presoma is added in 4g lauryl amine, logical nitrogen kept closed after 15 minutes, heated
30 minutes are kept the temperature to 200 DEG C, then rises to 300 DEG C and keeps the temperature 2 hours.Acetone and chloroform are used later, and centrifugation is dried to obtain Ni-
In2S3Ultrathin nanometer piece.
Under the conditions of the test condition of the electroreduction carbon dioxide of embodiment 2 and the product detection of embodiment 3, respectively
It is tested using identical process, Ni-In2S3Ultrathin nanometer piece faradic efficiency of effective carbon product under these overpotentials is shown in
Fig. 8.
Embodiment 7
Under the conditions of the overpotential of relative standard's hydrogen electrode is -1.0V, Mn-In2S3Ultrathin nanometer piece is in electroreduction titanium dioxide
The activity and stability test of carbon production formic acid.
Under the reaction condition of embodiment 2, constant potential is taken to test.Be arranged relative standard's hydrogen electrode overpotential be-
1.0V, constant potential are tested 8 hours.During the reaction, it needs to be continually fed into carbon dioxide with the speed of 10mL/min.In reaction
The oxygen that anode generates is discharged into air.The every 8 minutes heat by online gas-chromatography of the gaseous product generated in reaction process
Pool detector detection is led, the formic acid of generation is detected with nuclear-magnetism.Mn-In2S3Ultrathin nanometer piece passes through electrochemistry work under the current potential
Work station record current density changes over time figure and sees Fig. 9.Figure 10 is seen by the variation that nuclear-magnetism detects formic acid selectivity.
The Mn-In that the present invention obtains2S3Ultrathin nanometer piece is compared with other catalysis materials are in catalysis reaction, in the present invention
The catalyst choice used is high, and stability is good, this is because Mn-In2S3Ultrathin nanometer piece is with its special two-dimensional nanostructure
Largely exposed In atom has unique advantage in terms of electro-catalysis carbon dioxide reduction.The present invention is with In2S3It is ultra-thin to receive
A small amount of Mn ion is introduced into In as basic structure, while by the method for direct precursor body regulation doping by rice piece2S3Crystalline substance
In body structure, the structural intergrity of two-dimensional nano piece itself can be not only maintained, but also can use the manganese ion of introducing to In2S3Electricity
The regulating and controlling effect of minor structure, so that the Mn-In with excellent electronic structure2S3Ultrathin nanometer piece is expected to play in catalytic field aobvious
Works is used.
Claims (10)
1. a kind of preparation method of metal-doped indium sulfide nanometer sheet characterized by comprising
S1) by indium salts, doped metal salt and dialkyl dithiocarbamate hybrid reaction in organic solvent, forerunner is obtained
Body complex;
S2) precursor complexes are heated in amine solvent to reaction, obtain metal-doped indium sulfide nanometer sheet.
2. preparation method according to claim 1, which is characterized in that the indium salts are selected from inidum chloride, indium nitrate, indium sulfate
With one of indium acetate or a variety of;The doped metal salt be selected from manganese salt, be preferably selected from manganese chloride, protochloride manganese, manganese nitrate,
One of acetic acid Asia manganese and manganese sulfate are a variety of;The organic solvent is selected from methanol, ethyl alcohol, isopropanol, n-butanol, second two
One of alcohol, diglycol, glycerine, polyethylene glycol, acetone, formamide and n,N-Dimethylformamide are a variety of;
The dialkyl dithiocarbamate be selected from dialkyldithiocarbamacompositions sodium, dialkyldithiocarbamacompositions ammonium with
One of dialkyldithiocarbamacompositions diethyl ammonium is a variety of;The amine solvent is selected from octylame, decyl amine, lauryl amine, ten
One of tetramine, cetylamine and oleyl amine are a variety of.
3. preparation method according to claim 1, which is characterized in that the indium salts and dialkyl dithiocarbamate
Molar ratio be 1:(1~5);The mass ratio of the precursor complexes and amine solvent is (0.005~0.1): 1;The indium
The molar ratio of phosphide element and metallic element in doped metal salt is 100:(1~10 in salt).
4. preparation method according to claim 1, which is characterized in that the step S1) specifically:
Indium salts, doped metal salt are mixed with organic solvent, obtain the first mixed solution;Indium salts is dense in first mixed liquor
Degree is 0.05~0.5mmol/ml;
Dialkyl dithiocarbamate is mixed with organic solvent, obtains the second mixed solution;In second mixed liquor
The concentration of dialkyl dithiocarbamate is 0.05~0.5mmol/ml;
By first mixed solution and the second mixed solution hybrid reaction, precursor complexes are obtained.
5. preparation method according to claim 1, which is characterized in that the step S1) in hybrid reaction temperature be 20
DEG C~40 DEG C;The time of hybrid reaction is 20~200min;
The step S2) in heating reaction temperature be 200 DEG C~320 DEG C;The time of heating reaction is 100~200min.
6. metal-doped indium sulfide nanometer sheet prepared by Claims 1 to 5 any one.
7. metal-doped indium sulfide nanometer sheet according to claim 6, which is characterized in that the indium sulfide of the additive Mn
The average-size of nanometer sheet is 50~100nm;Average thickness is 0.6~2nm.
8. metal-doped indium sulfide nanometer sheet according to claim 6, which is characterized in that the metal-doped vulcanization
Indium nanometer sheet is the indium sulfide nanometer sheet of additive Mn.
9. the indium sulfide nanometer sheet of additive Mn according to claim 8, which is characterized in that the indium sulfide of the additive Mn is received
The surface crystal face of rice piece is (022).
10. metal-doped indium sulfide nanometer sheet or claim 6~9 prepared by Claims 1 to 5 any one are any one
Application of the metal-doped indium sulfide nanometer sheet in carbon dioxide electro-catalysis reduction described in.
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