CN116356351A - Preparation method of dye electrocatalytic hydrogenation cathode material for jean - Google Patents
Preparation method of dye electrocatalytic hydrogenation cathode material for jean Download PDFInfo
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- CN116356351A CN116356351A CN202310124391.7A CN202310124391A CN116356351A CN 116356351 A CN116356351 A CN 116356351A CN 202310124391 A CN202310124391 A CN 202310124391A CN 116356351 A CN116356351 A CN 116356351A
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- Prior art keywords
- dye
- salt
- deionized water
- carbon
- manufacturing according
- Prior art date
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- 239000010406 cathode material Substances 0.000 title claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 150000002696 manganese Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 229910000365 copper sulfate Inorganic materials 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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 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 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 abstract description 53
- 238000004043 dyeing Methods 0.000 abstract description 37
- 239000001257 hydrogen Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 63
- 238000006722 reduction reaction Methods 0.000 description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000243 solution Substances 0.000 description 18
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 12
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 9
- 229940097275 indigo Drugs 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 239000000984 vat dye Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 239000000988 sulfur dye Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009423 ventilation Methods 0.000 description 3
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000176 sodium gluconate Substances 0.000 description 2
- 235000012207 sodium gluconate Nutrition 0.000 description 2
- 229940005574 sodium gluconate Drugs 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PGYZAKRTYUHXRA-UHFFFAOYSA-N 2,10-dinitro-12h-[1,4]benzothiazino[3,2-b]phenothiazin-3-one Chemical compound S1C2=CC(=O)C([N+]([O-])=O)=CC2=NC2=C1C=C1SC3=CC=C([N+](=O)[O-])C=C3NC1=C2 PGYZAKRTYUHXRA-UHFFFAOYSA-N 0.000 description 1
- VIFKLIUAPGUEBV-UHFFFAOYSA-N 2-(3-hydroxy-1h-indol-2-yl)-1h-indol-3-ol Chemical compound N1C2=CC=CC=C2C(O)=C1C1=C(O)C2=CC=CC=C2N1 VIFKLIUAPGUEBV-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 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
- 238000010960 commercial process Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010014 continuous dyeing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940032950 ferric sulfate Drugs 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FCKJABJGVFTWPW-UHFFFAOYSA-H iron(3+);trisulfate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FCKJABJGVFTWPW-UHFFFAOYSA-H 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- 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
- C25B3/01—Products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—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
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Abstract
The invention relates to a preparation method of a dye electrocatalytic hydrogenation cathode material for jeans, which comprises the following steps: (1) Pretreating a carbon-based substrate material, and then carrying out surface oxidation and carbonization; (2) Dissolving a reagent containing a molybdenum source and a sulfur source in deionized water, adding metal salt into the solution, and stirring to obtain a uniform solution; (3) Adding the carbon-based substrate material treated in the step (1) into the solution to perform hydrothermal reaction; (4) And naturally cooling to room temperature after the reaction is finished, cleaning the obtained electrode material, and then drying in vacuum to obtain the dye electrocatalytic hydrogenation cathode material for denim. The preparation method is simple, active hydrogen is selectively generated in the alkaline water electrolysis process of the obtained cathode material, the active hydrogen with strong reducibility obviously improves the reduction efficiency of the dye adsorbed on the surface of the electrode, meanwhile, the formation of the active hydrogen can be controlled, the excessive reduction of the dye is avoided, the reduction efficiency of the dye is improved, and the dyeing quality is ensured.
Description
Technical Field
The invention belongs to the field of fabric dyeing and finishing, and particularly relates to a preparation method of a dye electrocatalytic hydrogenation cathode material for jeans.
Background
The conventional denim is dyed by using vat dyes such as indigo, sulfur dyes and the like, and the dyeing can be completed only after the indigo dyes, the sulfur dyes and the like are reduced into leuco bodies due to the characteristics of the dyes, through infiltration, adsorption and oxidation in the air. For example, in the indigo dyeing process, sodium hydrosulfite, caustic soda and the like are added into the indigo dye solution, the indigo is reduced into leuco at a certain temperature, and the dyeing is completed through forming hydrogen bonds with fibers in the yarns, but the dyeing effect requirement can be met through multiple padding. For example, when jean yarn is dyed with indigo, 6-12 dyeing tanks are usually selected according to the requirement of the color shade, and the production process is long. Because leuco indigo is easily oxidized by oxygen in the air during dyeing, excessive indigo mother liquor and dye auxiliary agent are usually added into the dyeing tank to maintain stable dye liquor concentration. Meanwhile, in the dyeing process, the yarn tension is controlled unevenly, and a large amount of flooding on the yarn prevents dye molecules from further penetrating into the fiber, so that the problems of low dye utilization rate, low dye-uptake, poor friction color fastness, color difference in the middle of the edge, head and tail and the like are caused. In addition, a large amount of water, sodium hydrosulfite, sodium sulfide and other dyes are consumed during dyeing, and the dyed waste liquid brings great pollution to the natural environment, so that the waste liquid treatment cost is greatly increased. Therefore, the jean cleaning dyeing technology with short process, low energy consumption, high efficiency, water saving and zero carbon emission is developed, the jean dyeing quality is improved, and the energy consumption and pollutant emission in the production process are reduced, so that the jean cleaning dyeing technology has great significance for sustainable development of jean production.
Aiming at the defects of large using amount of sodium hydrosulfite, difficult storage, environmental pollution and the like, in recent years, people are researching a plurality of novel reduction methods including novel chemical reduction (sodium hydrosulfite regeneration, environment-friendly reducing agents, a two-component system related to ferrous salt and the like), catalytic hydrogenation pre-reduction and electrochemical reduction. The main principle of electrochemical reduction is to replace a reducing agent with electrons, harmful byproducts are not generated in the reaction, and the method becomes a green and environment-friendly dyeing method. From the aspects of high-speed electron transfer speed and certain controllability of applied voltage/current on reaction, the electrochemical technology has the advantages of high-efficiency cleaning and certain adjustability and controllability, which promotes electro-electrochemical reduction dyeing to be a research hot spot nowadays.
Currently, electrochemical reduction methods of dyes for denim are roughly classified into three types: direct electroreduction, indirect electrochemical reduction, and electrocatalytic hydrogenation. Among them, direct electroreduction mainly involves two mechanisms, direct electron transfer between the dye and the electrode in two solid phases and reduction by dye radicals. Due to the limited interface between the cathode material and the dye particles and the low concentration of free radicals, the concentration of dye required to obtain the same hue is higher than that required for conventional reduction processes. Thus, the efficiency of direct electroreduction is not high, whereas indirect electrochemical reduction and electrocatalytic hydrogenation are the most likely commercial processes. The indirect electrochemical reduction method uses reversible redox pair added into the dye liquor as electron carrier, although the method has the advantages of small usage amount of chemical reagent, easy control of dyeing condition, small waste water amount, and cyclic use of the dye liquor, etc., the continuous dyeing technology needs to add additional mediator feed to compensate mediator loss caused by liquid discharge amount proportional to fabric or yarn amount, and filtering in the recovery of the dye liquor increases cost and adds a few technical problems.
Electrocatalytic hydrogenation by nickel or similar high surface area conductive catalytically active materials with low hydrogen overvoltage is a potential electrocatalytic reduction process and has been successfully used in numerous organic reactions. The electrocatalytic hydrogenation of vat dye is mainly characterized in that the vat dye on the low hydrogen evolution overpotential conductive catalytic metal is reduced into a soluble leuco body by utilizing active hydrogen generated in situ by electrolytic water, the raw materials are easy to obtain, the method is green and environment-friendly, and the trouble of electrochemical hydrogen production and then chemical catalytic hydrogenation is avoided. The hydrogen evolution side reaction is reduced by applying an appropriate voltage, thereby optimizing the hydrogenation process. It is considered that vat dyes and sulfur dyes are mostly solid particles insoluble in water and have poor contact effect with catalysts, so that people have to select and develop electrocatalytically active materials for a long time, and the materials mainly used are platinum group elements and transition metals, but platinum group metals (platinum, ruthenium, palladium and the like) are high in price and easy to deactivate; the transition metal (iron, cobalt, nickel, molybdenum, tungsten, etc.) has high overpotential and poor current efficiency; to achieve an industrially viable reduction rate, a huge electrode surface is still required. Therefore, development of a novel electrode material and an electrochemical reduction dyeing method for improving reduction efficiency, current efficiency and dyeing effect in electrocatalytic reduction of dye is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a dye electrocatalytic hydrogenation cathode material for jean, which can selectively generate active hydrogen in the alkaline water electrolysis process of the obtained cathode material, and the active hydrogen with strong reducibility can obviously improve the reduction efficiency of the dye adsorbed on the surface of an electrode, can control the formation of the active hydrogen, avoid excessive reduction of the dye, improve the reduction efficiency of the dye and ensure the dyeing quality.
The invention provides a preparation method of dye electrocatalytic hydrogenation cathode material for jeans, which comprises the following steps:
(1) Pretreating a carbon-based substrate material, and then carrying out surface oxidation and carbonization;
(2) Dissolving a reagent containing a molybdenum source and a sulfur source in deionized water, adding metal salt into the solution, and stirring to obtain a uniform solution;
(3) Adding the carbon-based substrate material treated in the step (1) into the solution to perform hydrothermal reaction;
(4) And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the obtained electrode material with deionized water and ethanol, and then drying in a vacuum oven to obtain the dye electrocatalytic hydrogenation cathode material for jean.
The carbon-based substrate material in the step (1) is at least one of carbon cloth, carbon paper, carbon felt and graphite felt.
The pretreatment method in the step (1) comprises the following steps: soaking the carbon-based substrate material in an acetone solution for 8-18 hours to remove surface impurities; and then washing with deionized water and drying.
The oxidation in the step (1) is specifically: placing the carbon-based substrate material into dilute acid for oxidation (hydrophilic) treatment, then washing the material with deionized water, and drying the material; wherein the dilute acid is sulfuric acid with the volume fraction of 5-15% or nitric acid with the volume fraction of 10-30%; the temperature of the oxidation process is 30-75 ℃, and the treatment time is 30-120 min.
The carbonization in the step (1) specifically comprises the following steps: and nitrogen is introduced for protection, the carbonization treatment temperature is 500-900 ℃, and the carbonization treatment time is 30-120 min.
The reagent containing the molybdenum source in the step (2) is at least one of sodium molybdate, ammonium molybdate and ammonium tetrathiomolybdate, and the mass ratio of the reagent containing the molybdenum source to deionized water is 1:20-1:30; the sulfur source-containing reagent is one or more of thiourea, thioacetamide and ammonium tetrathiomolybdate, and the mass ratio of the sulfur source-containing reagent to deionized water is 1:5-1:15.
The metal salt in the step (2) is at least one of ferric salt, cobalt salt, nickel salt, copper salt and manganese salt.
The ferric salt is one of ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric chloride and ferrous chloride, and the mass ratio of the ferric salt to deionized water is 1:800-1:2000; the cobalt salt is one of cobalt nitrate and cobalt chloride, and the mass ratio of the cobalt salt to deionized water is 1:1000-1:3000; the nickel salt is one of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, and the mass ratio of the nickel salt to deionized water is 1:750-1:2500; the copper salt is one of copper nitrate and copper sulfate, and the mass ratio of the copper salt to deionized water is 1:500-1:2000; the manganese salt is manganese sulfate, and the mass ratio of the manganese salt to deionized water is 1:750-1:1500.
The hydrothermal reaction kettle in the step (3) is a stainless steel autoclave lined with polytetrafluoroethylene, and the volume is 20-100 mL; the hydrothermal reaction temperature is 180-220 ℃ and the reaction time is 6-20 hours.
The vacuum drying temperature in the step (4) is 50-80 ℃ and the vacuum drying time is 6-12 hours.
The invention also provides a construction method of the dye liquid flow electrochemical efficient reduction device for the jean, which comprises the following steps:
as shown in fig. 1, the dye liquid flow electrochemical high-efficiency reduction device for denim comprises a cathode catalytic electrode, a cathode chamber, a grid, an anode electrode, an anode chamber and a diaphragm; wherein the cathode catalytic electrode uses the dye electrocatalytic hydrogenation cathode material for jean; the anode electrode is any one of a graphite electrode and a stainless steel electrode; the membrane is a cation exchange membrane; (1) Adding auxiliary electrolyte into alkali liquor, and uniformly stirring to obtain anode electrolyte;
(2) Adding dye into alkali liquor, and uniformly stirring to obtain a catholyte;
(3) Under the protection of protective gas, respectively introducing the cathode electrolyte and the anode electrolyte into a cathode chamber and an anode chamber in a liquid flow electrolytic cell at room temperature for electrolytic reduction.
The auxiliary electrolyte in the step (1) is any one of sodium sulfate and sodium chloride, and the alkali liquor is sodium hydroxide. The sodium sulfate content is 0.05-0.2 mol/L, the sodium chloride content is 0.1-0.4 mol/L, and the sodium hydroxide content is 0.5-1 mol/L.
The concentration of dye in the catholyte in the step (2) is 0.0038-0.228 mol/L, wherein the dye is any one of indigo, vat yellow F3GC, vat blue RS, vat red FBB and sulfur black BR, and the pH of the catholyte is adjusted to 11-14 by alkali liquor. The alkali liquor is sodium hydroxide.
The protective gas in the step (3) is nitrogen or argon, the electrolysis voltage is 1-30V, and the reduction time is 15-150 min.
Advantageous effects
Firstly, the invention uses the carbon-based substrate material (such as carbon felt) with good electron transmission and ion conduction characteristics, high porosity, light and thin quality, high elasticity and low cost as the substrate material, the three-dimensional structure of the carbon felt has higher surface adsorption performance on active hydrogen, and has certain affinity to dye molecules, which is beneficial to the hydrogenation reduction of the active hydrogen to the dye molecules.
Secondly, the invention adopts a one-step hydrothermal method to grow the molybdenum disulfide-based electrocatalyst with the nano heterostructure on the carbon felt, and applies the molybdenum disulfide-based electrocatalyst to the electro-catalytic hydrogenation reduction dyeing of vat dyes. The molybdenum disulfide-based electrocatalyst with the nano structure has low price and large specific surface area, and the catalyst structure is optimized by the heterogeneous and synergistic effect of active sites between metal and nonmetal, so that the adsorption capacity of the catalyst on active hydrogen and dye molecules is enhanced, the contact and reaction of the active hydrogen and the dye molecules are promoted, and the electrocatalytic hydrogenation reduction reaction rate of the dye is improved.
And thirdly, sodium sulfate, sodium chloride and the like are used as auxiliary substances in the anolyte to increase the conductivity of the electrolyte solution, and meanwhile, the electron transfer rate of the whole system is improved under the combined action of an external power supply.
Fourthly, the preparation method of the dye electrocatalytic hydrogenation cathode material for denim provided by the invention is simple, active hydrogen is selectively generated in the alkaline water electrolysis process of the obtained electrode material, the active hydrogen with strong reducibility obviously improves the reduction efficiency of the dye adsorbed on the surface of the electrode, meanwhile, the formation of the active hydrogen can be controlled, the excessive reduction of the dye is avoided, the reduction efficiency of the dye is improved, and the dyeing quality is ensured.
Fifth, the electrochemical reduction equipment provided by the invention is simple and convenient, the process completely abandons the use of sodium hydrosulfite, the dosage of chemical reagents can be effectively reduced without adding any medium, a large amount of high-concentration salt can not be produced, the dye liquor can be recycled, the reduction dyeing process is cleaner and environment-friendly, the reaction condition is mild, the hydrogenation process is easy to control, and obvious ecological benefit and economic benefit are realized.
Drawings
FIG. 1 is a schematic diagram of an electrochemical high-efficiency reduction device for jean dye liquid flow.
Fig. 2 shows the electrocatalytic reduction process and mechanism of dye for denim.
Fig. 3 is a scanning electron microscope image of the cathode material prepared in example 1.
Fig. 4 is an LSV curve and Tafel plot of the cathode material prepared in example 1.
Fig. 5 is a photograph of indigo-dyed fabric using the cathode material prepared in example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
And (3) testing:
the catalytic activity of the cathode electrode was evaluated by linear sweep voltammetry (LSV test) and the catalytic efficiency was evaluated by comparing the overpotential with the Tafel slope. The current density was 10mA/cm 2 The potential at this time is an overpotential, and the lower the overpotential is, the higher the catalytic activity is. And converting the LSV curve according to a Tafel empirical formula to obtain a Tafel curve so as to study the electrode surface dynamics process.
η＝a+blog j；
Wherein eta is the overpotential and a is when the current density is 1mA/cm 2 Is the current density, and b is the Tafel slope.
Dye conversion (reduction): the dye was weighed and dissolved in 1.0M caustic soda solution at concentrations of 1g/L, 2g/L, 3g/L, 4g/L and 5g/L, respectively, and then reduced to dye leuco with excess sodium hydrosulfite or sodium sulfide. Using an ultraviolet spectrophotometer, the maximum absorption wavelength of the dye leuco is determined and a concentration versus absorbance standard curve is made. And taking out the catholyte after electrochemical reduction of the liquid flow, testing the concentration of the catholyte, and calculating the dye conversion rate.
Dye conversion = C/Co;
faraday current efficiency= (m×n×f)/Q;
wherein Co is the concentration of dye solution, and C is the concentration of dye leuco. Q is total electric quantity, m is mole number of dye leuco, n is electron number required for reducing one dye molecule, and F is Faraday constant.
Reduction potential ORP: referring to the measuring method of the oxidation-reduction potential of the industrial standard SL94-1994, a reduction potentiometer is put into a dye liquor at normal temperature by using the oxidation-reduction potentiometer, and after the value is stable, the reduction potential value is read.
K/S value: the sample was folded 4 layers (opaque) and tested using a Color-i5 computer Color measuring and matching instrument (X-Rite, usa). The average value was taken at different positions 3.
Example 1
A preparation method of dye electrocatalytic hydrogenation cathode material for jean and liquid flow electrochemical high-efficiency reduction equipment. The method comprises the following steps:
(1) The carbon felt is put into acetone solution for soaking for 8 hours, then washed and dried by deionized water, then is put into 10% dilute nitric acid for treatment at 60 ℃ for 40 minutes, and then is heated and carbonized in a tube furnace (600 ℃ for 60 minutes and nitrogen protection).
(2) 1.235g of ammonium molybdate tetrahydrate and 2.218g of thiourea are dissolved in 30mL of deionized water, 0.0215g of nickel sulfate hexahydrate is added, and the mixture is stirred to obtain a uniform solution, then the pretreated carbon felt is added into the solution, and the solution is transferred into a hydrothermal reaction kettle, and reacted for 8 hours at 200 ℃ in a vacuum oven. The resulting cathode material was further repeatedly washed with distilled water and ethanol, and then dried in an oven under vacuum. Obtaining the dye electrocatalytic hydrogenation cathode material for jean.
(3) The dye electrocatalytic hydrogenation cathode material for denim prepared by the method is used as a cathode, the concentration of indigo in a catholyte is 0.019mol/L, the pH is regulated to 13 by alkali liquor, the anode is a graphite electrode, and the electrolyte consists of 0.5mol/L sodium hydroxide and 0.1mol/L sodium sulfate. The membrane is a sulfonic acid type cation exchange membrane. And (3) carrying out electrolytic reduction under the condition of nitrogen protection at room temperature, wherein the electrolytic voltage is 6V, and the time is 30min. Electrochemical reduction staining: adding pure cotton semi-bleached coarse-grained oblique cloth which is wetted by distilled water in advance into the catholyte solution obtained in the step (3), wherein the bath ratio is 1:20, and the dyeing time is 1min; after dyeing, ventilation oxidation is carried out, and after-dyeing treatment is finished through soap boiling and water washing, and the color depth K/S value of the finally obtained fabric is tested.
Tested; the cathode material obtained in example 1 had an overpotential of 145.65mV, a Tafel slope of 100.53mV/dev, a dye conversion of 48%, a current efficiency of 15.5%, a catholyte reduction potential of-821 mV after electrolysis, and a K/S value of 16.23 for the dyed sample.
Example 2
The preparation method of the cathode material in the embodiment comprises the following steps:
(1) The carbon felt is put into acetone solution for soaking for 10 hours, then washed and dried by deionized water, then put into 10% dilute sulfuric acid for treatment at 70 ℃ for 30 minutes, and then heated and carbonized in a tube furnace (500 ℃ for 90 minutes and nitrogen protection).
(2) 0.785g of sodium molybdate dihydrate and 1.786g of thioacetamide were dissolved in 20mL of deionized water, and 0.0185g of ferric sulfate nonahydrate was added thereto, stirred to obtain a uniform solution, and then the pretreated carbon felt was added to the above solution, transferred to a hydrothermal reaction vessel, and reacted in a vacuum oven at 180℃for 10 hours. The resulting cathode material was further repeatedly washed with distilled water and ethanol, and then dried in an oven under vacuum. Obtaining the dye electrocatalytic hydrogenation cathode material for jean.
(3) The dye electrocatalytic hydrogenation cathode material for denim prepared by the method is used as a cathode, the concentration of indigo in a catholyte is 0.019mol/L, the pH is regulated to 13 by alkali liquor, the anode is a graphite electrode, and the electrolyte consists of 0.5mol/L sodium hydroxide and 0.1mol/L sodium sulfate. The membrane is a sulfonic acid type cation exchange membrane. And (3) carrying out electrolytic reduction under the condition of nitrogen protection at room temperature, wherein the electrolytic voltage is 5V, and the time is 25min. Electrochemical reduction staining: adding pure cotton semi-bleached coarse-grained oblique cloth which is wetted by distilled water in advance into the catholyte solution obtained in the step (3), wherein the bath ratio is 1:20, and the dyeing time is 1min; after dyeing, ventilation oxidation is carried out, and after-dyeing treatment is finished through soap boiling and water washing, and the color depth K/S value of the finally obtained fabric is tested.
Tested; the cathode material obtained in example 2 had an overpotential of 176.43mV, a Tafel slope of 121.14mV/dev, a dye conversion of 44.5%, a current efficiency of 13.7%, a catholyte reduction potential of-812 mV after electrolysis, and a K/S value of 15.84 for the dyed sample.
Comparative example
An electrolytic system for indirect electrochemical dyeing of vat dye and an indirect electrochemical dyeing process:
(1) Dye electrochemical reduction and dissolution: and adding a complexing system obtained by fully mixing ferric sulfate and sodium gluconate, indigo dye and sodium borohydride into 0.0625mol/L caustic soda solution, and fully stirring to obtain the catholyte. Wherein, iron ion is 0.004mol/L, sodium gluconate is 0.012mol/L, indigo dye is 0.019mol/L, and sodium borohydride is 0.016mol/L. Iron ions in the anolyte are 0.25mol/L, and anhydrous sodium sulphate content is 0.2112mol/L. The cathode is an iron electrode, the anode is a graphite electrode, the electrolysis voltage is 7.5V, and the anode is electrified and reduced for 50min at room temperature under the protection of nitrogen. And after the reduction is finished, placing a reduction potentiometer into the dye liquor at normal temperature, and reading the reduction potential value after the value is stable.
(2) Electrochemical reduction staining: adding pure cotton semi-bleaching coarse-grain oblique cloth which is wetted by distilled water in advance into the solution in the step (1), wherein the bath ratio is 1:20, and the dyeing time is 1min; after dyeing, ventilation oxidation is carried out, and after-dyeing treatment is finished through soap boiling and water washing, and the color depth K/S value of the finally obtained fabric is tested.
After the reduction is finished, the lowest reduction potential of the dye liquor reaches-807 mV, and the color depth K/S value of the dyed cloth sample after washing and soaping is 15.56.
Compared with the traditional indirect electrochemical reduction dyeing method, the electrocatalytic reduction dyeing method provided by the invention has the advantages of fewer chemical reagents, lower electrolysis voltage, shorter electrolysis time, better dyeing effect, and higher energy-saving and environment-friendly benefits as shown in the embodiment 1 and the embodiment 2.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A preparation method of dye electrocatalytic hydrogenation cathode material for jean comprises the following steps:
(1) Pretreating a carbon-based substrate material, and then carrying out surface oxidation and carbonization;
(2) Dissolving a reagent containing a molybdenum source and a sulfur source in deionized water, adding metal salt into the solution, and stirring to obtain a uniform solution;
(3) Adding the carbon-based substrate material treated in the step (1) into the solution to perform hydrothermal reaction;
(4) And naturally cooling to room temperature after the reaction is finished, repeatedly cleaning the obtained electrode material with deionized water and ethanol, and then drying in a vacuum oven to obtain the dye electrocatalytic hydrogenation cathode material for jean.
2. The method of manufacturing according to claim 1, characterized in that: the carbon-based substrate material in the step (1) is at least one of carbon cloth, carbon paper, carbon felt and graphite felt.
3. The method of manufacturing according to claim 1, characterized in that: the pretreatment method in the step (1) comprises the following steps: soaking the carbon-based substrate material in an acetone solution for 8-18 hours to remove surface impurities; and then washing with deionized water and drying.
4. The method of manufacturing according to claim 1, characterized in that: the oxidation in the step (1) is specifically: placing the carbon-based substrate material into dilute acid for oxidation treatment, then washing with deionized water and drying; wherein the dilute acid is sulfuric acid with the volume fraction of 5-15% or nitric acid with the volume fraction of 10-30%; the temperature of the oxidation process is 30-75 ℃, and the treatment time is 30-120 min.
5. The method of manufacturing according to claim 1, characterized in that: the carbonization in the step (1) specifically comprises the following steps: and nitrogen is introduced for protection, the carbonization treatment temperature is 500-900 ℃, and the carbonization treatment time is 30-120 min.
6. The method of manufacturing according to claim 1, characterized in that: the reagent containing the molybdenum source in the step (2) is at least one of sodium molybdate, ammonium molybdate and ammonium tetrathiomolybdate, and the mass ratio of the reagent containing the molybdenum source to deionized water is 1:20-1:30; the sulfur source-containing reagent is one or more of thiourea, thioacetamide and ammonium tetrathiomolybdate, and the mass ratio of the sulfur source-containing reagent to deionized water is 1:5-1:15.
7. The method of manufacturing according to claim 1, characterized in that: the metal salt in the step (2) is at least one of ferric salt, cobalt salt, nickel salt, copper salt and manganese salt.
8. The method of manufacturing according to claim 7, wherein: the ferric salt is one of ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, ferric chloride and ferrous chloride, and the mass ratio of the ferric salt to deionized water is 1:800-1:2000; the cobalt salt is one of cobalt nitrate and cobalt chloride, and the mass ratio of the cobalt salt to deionized water is 1:1000-1:3000; the nickel salt is one of nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, and the mass ratio of the nickel salt to deionized water is 1:750-1:2500; the copper salt is one of copper nitrate and copper sulfate, and the mass ratio of the copper salt to deionized water is 1:500-1:2000; the manganese salt is manganese sulfate, and the mass ratio of the manganese salt to deionized water is 1:750-1:1500.
9. The method of manufacturing according to claim 1, characterized in that: the hydrothermal reaction kettle in the step (3) is a stainless steel autoclave lined with polytetrafluoroethylene, and the volume is 20-100 mL; the hydrothermal reaction temperature is 180-220 ℃ and the reaction time is 6-20 hours.
10. The method of manufacturing according to claim 1, characterized in that: the vacuum drying temperature in the step (4) is 50-80 ℃ and the vacuum drying time is 6-12 hours.
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