CN117587444B - Method for preparing indium-based electrocatalyst by using waste liquid crystal display material, indium-based electrocatalyst and application of indium-based electrocatalyst - Google Patents
Method for preparing indium-based electrocatalyst by using waste liquid crystal display material, indium-based electrocatalyst and application of indium-based electrocatalyst Download PDFInfo
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- 229910052738 indium Inorganic materials 0.000 title claims abstract description 119
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 38
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 239000012769 display material Substances 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 235000021110 pickles Nutrition 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000002386 leaching Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 230000000536 complexating effect Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 61
- 239000011521 glass Substances 0.000 claims description 44
- 239000000758 substrate Substances 0.000 claims description 43
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
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- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
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- 238000001816 cooling Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 2
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 230000001404 mediated effect Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- 239000003495 polar organic solvent Substances 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 15
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- 239000003223 protective agent Substances 0.000 abstract description 6
- 238000004904 shortening Methods 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 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 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100317222 Borrelia hermsii vsp3 gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- -1 Fe are extracted Chemical class 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000010793 electronic waste Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001449 indium ion Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
-
- 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
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B3/26—Reduction of carbon dioxide
Abstract
The invention provides a method for preparing an indium-based electrocatalyst by using a waste liquid crystal display material, the indium-based electrocatalyst and application thereof, and belongs to the field of electrocatalyst and solid waste disposal. The method comprises the following steps: (1) Sequentially carrying out pretreatment and acid leaching treatment on the waste liquid crystal display material to obtain indium-containing pickle liquor; (2) Mixing the indium-containing pickle liquor and organic amine liquor to obtain a solution containing a coordination compound, then mixing the solution containing the coordination compound with a nonpolar organic solvent, and carrying out separation treatment to obtain a complex liquor; (3) And mixing the complexing solution with a carbon carrier, and performing hydrothermal reaction to obtain the indium-based electrocatalyst. The invention provides the organic amine as the extractant in the recovery process and the protective agent in the electrocatalyst synthesis process, so that the extraction separation of indium is coupled with the electrocatalyst application of the catalyst, the purposes of shortening the flow, reducing the cost and reducing the environmental pollution are achieved, and a new idea is provided for recycling waste resources.
Description
Technical Field
The invention belongs to the field of electrocatalysis and solid waste disposal, and particularly relates to a method for preparing an indium-based electrocatalyst by using a waste liquid crystal display material, the indium-based electrocatalyst and application thereof.
Background
In the past decades, liquid Crystal Display Panels (LCDPs) have been widely used in electronic products, such as PC displays, notebook computers, tablet computers, mobile phones, televisions, etc., due to their light weight, high resolution, small size, low power consumption, etc., but they have been subject to a large amount of electronic waste to be managed due to their short service lives (3-8 years) and rapid technological updates. As early as 2012 the european union committee classified LCDPs as Waste Electronic and Electrical Equipment (WEEE), which has a complex structure and contains a variety of compounds including toxic substances such as aromatic rings, cyano groups, fluorine, chlorine, and bromine. However, the presence of components of LCDPs that contain great recycling potential, such as plastics, glass, steel, rare noble metals, and circuit boards, and the like, particularly Indium Tin Oxide (ITO), an optoelectronic material that has the properties of being transparent to visible light, conductive, and reflective to heat, has led to the interest of numerous researchers. In addition, with the rapid development of the photovoltaic industry, the limited indium native resources have failed to meet the rapidly growing indium demand.
Therefore, efficient and economical recovery of indium from secondary sources, especially discarded LCDPs, is of great importance for sustainable development and ecological environmental protection.
Compared with the pyrometallurgical technology, the hydrometallurgical technology has the advantages of high flexibility, less energy consumption, low production cost and the like, and can be effectively applied to extracting and recycling indium from waste LCDPs. Hydrometallurgical recovery processes typically consist of several basic procedures by leaching with acidic or basic reagents to completely dissolve indium, then metal separation by solvent extraction, adsorption or ion exchange, followed by further purification by precipitation, cementation or electrolysis, etc. for reuse. However, the whole process from waste recovery treatment to reuse is long, the operation flow is complicated, and more toxic or corrosive chemical reagents are used, so that the environmental pollution and other problems occur in the process of wastewater treatment. In addition, only through the way of extraction separation, certain impurity components are inevitably remained, the quality of reutilization is difficult to achieve, and further purification can improve the purity of metal, but more time and effort are required. Therefore, if the process from indium separation to recycling can be integrated, the whole process is shortened, the recycling efficiency is improved, the production cost is reduced, the use of organic reagents is reduced, and the harm to the environment is reduced.
CO 2 The electrochemical reduction technology is that CO can be reduced by green power 2 Technology for conversion into valuable chemicals and fuels is hopefully an effective solution to the problem of environmental pollution due to excessive industrial carbon dioxide emissions. However, the development of the existing product is seriously hindered by the problems of low selectivity, poor stability in the electrochemical synthesis process and the like. Therefore, there is an urgent need to develop a high-performance, low-cost electrocatalyst to meet the current density and faraday efficiency required for industry for stable production. Indium-based catalyst has oxygen-philic property and CO-scavenging property 2 The nature of the transformation of the OCHO intermediate is of great interest.
In summary, in the face of the current situation that the worldwide reserves of metal indium are extremely deficient, how to extract indium from waste LCDPs and CO 2 The electrocatalytic technology is coupled, so that a new way for utilizing secondary resources is established, and the key direction of research is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing an indium-based electrocatalyst by using a waste liquid crystal display material, the indium-based electrocatalyst and application thereof. The invention provides an indium extraction technology of waste liquid crystal display material and an indium-based electrocatalyst in CO by taking organic amine as an extractant in hydrometallurgy recovery process and a protective agent in electrocatalyst synthesis process 2 The application of the electrocatalytic reduction reaction is coupled, the purposes of shortening the indium extraction flow, reducing the extraction cost and reducing the environmental pollution are achieved, and a new idea is provided for recycling waste resources.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an indium-based electrocatalyst from a spent liquid crystal display material, the method comprising the steps of:
(1) Sequentially carrying out pretreatment and acid leaching treatment on the waste liquid crystal display material to obtain indium-containing pickle liquor;
(2) Mixing the indium-containing pickle liquor and organic amine liquor to obtain a solution containing a coordination compound, then mixing the solution containing the coordination compound with a nonpolar organic solvent, and carrying out separation treatment to obtain a complex liquor;
(3) And mixing the complexing solution with a carbon carrier, and performing hydrothermal reaction to obtain the indium-based electrocatalyst.
The invention provides an indium extraction technology of waste liquid crystal display material and an indium-based electrocatalyst in CO by taking organic amine as an extractant in hydrometallurgy recovery process and a protective agent in electrocatalyst synthesis process 2 The application of the electrocatalytic reduction reaction is coupled, the purposes of shortening the indium extraction flow, reducing the extraction cost and reducing the environmental pollution are achieved, and a new idea is provided for recycling waste resources.
In the present invention, the purpose of the acid leaching treatment is to leach the metallic indium in an acid solution.
As a preferred technical scheme of the invention, the specific steps of the pretreatment in the step (1) comprise:
(a) Crushing and disassembling the waste liquid crystal display material to obtain a glass substrate containing an ITO film;
(b) And sequentially carrying out water bath heating and acetone soaking treatment on the glass substrate containing the ITO film so as to remove the polarizing film and the liquid crystal.
In the invention, since the waste liquid crystal display material contains plastics, metal frames, circuit boards and the like, the glass substrate containing an ITO film (indium tin oxide film) can be effectively removed by a multi-crushing and disassembling mode.
Preferably, the temperature of the water bath heating is 60-100deg.C, such as 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C or 100deg.C, and the time is 0.5-1.5h, such as 0.5h, 1h or 1.5 h.
Preferably, the specific steps of the acetone soaking treatment comprise:
the glass substrate heated in the water bath is cut into pieces, and then is soaked in a container containing an acetone solution for 1-5 hours (for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc.).
Preferably, the area of the chips is 0.5X0.5 cm or more 2 For example, it may be 0.5X0.5 cm 2 、1×1cm 2 、1.5×1.5cm 2 Or 2X 2cm 2 Etc.
As a preferable technical scheme of the invention, the acid leaching treatment in the step (1) is accompanied by ultrasonic, and the power of the ultrasonic is 200-400W, for example, 200W, 250W, 300W, 350W or 400W, etc.
Preferably, the acid solution used in the acid leaching process of step (1) comprises any one or a combination of at least two of aqueous hydrochloric acid, aqueous sulfuric acid or aqueous nitric acid.
Preferably, the concentration of the acid solution used in the acid leaching treatment in the step (1) is 0.1 to 5mol/L, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, etc.
Preferably, the acid leaching treatment in the step (1) is performed for 30-120min, for example, 30min, 50min, 70min, 90min or 110min, etc.
As a preferred embodiment of the present invention, the organic amine solution in step (2) includes any one or a combination of at least two of a dodecylamine solution, a hexadecylamine solution and an octadecylamine solution, and is preferably a dodecylamine solution.
In the invention, the dodecylamine solution can be better used as an extractant in the hydrometallurgical recovery process and a protective agent in the indium-based electrocatalyst synthesis process.
Preferably, the liquid-solid ratio of the organic amine in the organic amine liquid in step (2) to the ITO film-containing glass substrate is 2 to 100. Mu.L/g, and may be, for example, 2. Mu.L/g, 5. Mu.L/g, 15. Mu.L/g, 25. Mu.L/g, 50. Mu.L/g, 75. Mu.L/g, 100. Mu.L/g, or the like.
In the present invention, the liquid-solid ratio refers to the ratio of the volume of the organic amine to the mass of the glass substrate containing the ITO film. If the liquid-solid ratio of the organic amine to the glass substrate containing the ITO film is too small, namely the consumption of the organic amine is too small, the metal indium in the pickling liquid cannot be completely extracted; if the liquid-solid ratio of the organic amine to the glass substrate containing the ITO film is too large, i.e., the amount of the organic amine used is too large, not only too much extraction of impurity metals such as Al, fe, etc. is caused, but also waste of reagents is caused.
Preferably, in the process of mixing the pickle liquor and the organic amine liquid in the step (2), the pH value of the mixed solution is controlled to be 6-9, and can be 6, 6.5, 7, 7.5, 8, 8.5 or 9, for example.
In the invention, the pH value of the mixed solution is controlled to be 6-9, so that the coordination compound formed by the metal indium ions and the organic amine in the pickle liquor can be realized.
Preferably, the pH adjustor comprises an inorganic base.
Preferably, the inorganic base comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide, ammonia water, calcium hydroxide, calcium oxide, potassium oxide or sodium oxide.
As a preferred embodiment of the present invention, the nonpolar organic solvent in the step (2) includes any one or a combination of at least two of n-hexane, chloroform, toluene, p-xylene, dichloromethane, carbon tetrachloride, cyclohexane, isooctane, oleylamine, and oleic acid.
In the present invention, the complex compound can be separated from the solution by using the above-mentioned type of nonpolar organic solvent.
Preferably, the volume ratio of the solvent to the nonpolar organic solvent in the solution containing the coordination compound in the step (2) is (0.2-5): 1, for example, may be 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, or the like.
In the invention, if the volume ratio of the solvent to the nonpolar organic solvent in the solution containing the coordination compound is too small, namely the dosage of the nonpolar organic solvent is too large, the waste of the reagent can be caused; if the volume ratio of the solvent to the nonpolar organic solvent in the solution containing the complex is too large, i.e. the amount of nonpolar organic solvent used is too small, the phase transfer efficiency of the metal complex formed in the pickling solution is affected.
As a preferred embodiment of the present invention, the carbon carrier in step (3) includes activated carbon or carbon paper.
Preferably, when the carbon carrier in the step (3) is activated carbon, the mass ratio of the activated carbon to the indium metal in the indium-containing pickle liquor is (1-4): 1, for example, 1:1, 2:1, 3:1, 4:1 or the like.
In the invention, if the addition amount of the activated carbon is excessive, the metal load per gram of the catalyst is less, so that the activity of the catalyst is lower; if the amount of activated carbon is too small, the metal cannot be effectively and completely loaded.
As a preferable technical scheme of the invention, stirring is carried out during the mixing process in the step (3).
Preferably, before the hydrothermal reaction in the step (3), the mixture obtained by mixing the complexing solution and the carbon carrier is subjected to standing, precipitation and separation.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 90-220 ℃, for example, 90 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃ or 220 ℃ and the like, and the time is 1-24 hours, for example, 1 hour, 6 hours, 12 hours, 18 hours or 24 hours and the like.
In the invention, too low or high temperature of the hydrothermal reaction affects the shape and size of the catalyst, thereby deteriorating the catalytic performance.
As a preferred technical solution of the present invention, the method comprises the steps of:
taking a waste liquid crystal display as a raw material, manually crushing and disassembling to obtain a glass substrate containing an ITO film, then heating the glass substrate containing the ITO film in a water bath at 60-100 ℃ for 0.5-1.5 hours to obtain a glass substrate with a polarizing film removed, cutting the glass substrate with the polarizing film removed into fragments, and soaking in a solution containing acetone for 1-5 hours to obtain a glass substrate with liquid crystal removed;
(II) stirring and mixing the glass substrate with the liquid crystal removed and the acid solution with the concentration of 0.1-5mol/L for 30-120min, and simultaneously performing ultrasonic treatment with ultrasonic power of 200-400W to obtain an indium-containing pickle liquor;
(III) stirring and mixing the indium-containing pickle liquor and the ethanol-mediated dodecylamine solution, and controlling the pH value of the mixed solution to be 6-9 to obtain an aqueous solution containing a coordination compound;
wherein the liquid-solid ratio of the dodecyl amine in the dodecyl amine solution to the glass substrate containing the ITO film is 2-100 mu L/g;
adding a nonpolar organic solvent into the aqueous solution containing the coordination compound, and separating to obtain a complex solution;
wherein the volume ratio of water to the nonpolar organic solvent in the aqueous solution containing the coordination compound is (0.2-5) 1;
(V) stirring and mixing the complexing solution and the active carbon, standing, precipitating and separating to obtain the active carbon loaded with indium, placing the active carbon loaded with indium in a reaction kettle containing water and ethanol for carrying out hydrothermal reaction at 90-220 ℃ for 1-24 hours, naturally cooling to room temperature after the reaction is finished, taking out, centrifuging, washing and drying to obtain the indium-based electrocatalyst;
wherein the mass ratio of the active carbon to the indium metal in the indium-containing pickle liquor is (1-4): 1, and the volume ratio of the ethanol to the water is (0.5-2): 1 (for example, 0.5:1, 1:1, 1.5:1 or 2:1, etc.).
The room temperature is not particularly limited, and may be, for example, 25±5 ℃, such as 20 ℃, 25 ℃, 30 ℃, or the like.
In a second aspect, the present invention provides an indium-based electrocatalyst prepared by the method according to the first aspect, the indium-based electrocatalyst comprising a support and an active component, the support being a carbon support and the active component comprising indium.
In a third aspect, the present invention provides the use of an indium-based electrocatalyst according to the second aspect, the indium-based catalyst being for use in CO 2 The field of electrocatalytic reduction.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention combines the hydrometallurgical process of waste liquid crystal display material with CO 2 The preparation process of the indium-based electrocatalyst in electrochemical reduction is coupled, so that valuable metal indium in the waste liquid crystal display material can be applied to electrocatalytic carbon dioxide reduction reaction.
(2) The invention provides the organic amine as the extractant in the hydrometallurgical recovery process and the protective agent in the electrocatalyst synthesis process, so that the extraction and separation of indium are coupled with the application of an indium-based catalyst in the electrocatalyst, the purposes of shortening the indium extraction flow, reducing the extraction cost and reducing the environmental pollution are achieved, and a new thought is provided for the reuse of waste resources.
Drawings
Fig. 1 is a bar graph showing the change in the content of indium metal and other elements in the leachate after dissolution of aqua regia in the waste liquid crystal display used in example 1 and the leachate obtained in the different treatment stages of example 1.
Fig. 2 is an XRD pattern of the indium-based electrocatalyst prepared in example 1 according to the invention.
Fig. 3 is a TEM image of an indium-based electrocatalyst prepared in example 1 according to the invention.
Fig. 4 is a LSV test chart of the indium-based electrocatalyst prepared in example 1 according to the invention.
Fig. 5 is a graph showing faraday efficiencies of the indium-based electrocatalyst prepared in example 1 according to the invention at different potentials.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The room temperature hereinafter means 25 ℃.
Example 1
The embodiment provides a method for preparing an indium-based electrocatalyst by using a waste liquid crystal display material, which comprises the following steps:
(1) Manually crushing and disassembling a waste liquid crystal display (Dell Inc. E170 Sc) to obtain 20g of glass substrate containing an ITO film, and then subjecting the glass substrate containing the ITO film toHeating the plate in water bath at 90deg.C for 1 hr, tearing off the polarizing film to obtain a polarizing film-removed glass substrate, and cutting the polarizing film-removed glass substrate into pieces with dimensions of 2×2cm 2 Is placed in 20mL of solution containing acetone for soaking for 3h, and a glass substrate with liquid crystal removed is obtained;
(2) Stirring and mixing the glass substrate with liquid crystal removed and 30mL of 1mol/L hydrochloric acid aqueous solution for 90min, and performing ultrasonic treatment at the ultrasonic power of 300W to obtain an indium-containing pickle liquor;
(3) Adding 0.5mL of dodecylamine into 30mL of ethanol solvent, stirring uniformly to obtain dodecylamine solution, stirring and mixing the dodecylamine solution and the indium-containing pickle liquor, and controlling the pH value of the mixed solution to be 6.5-7.5 by adding sodium hydroxide to obtain aqueous solution containing coordination compound;
wherein the liquid-solid ratio of the dodecylamine solution to the glass substrate containing the ITO film is 25 mu L/g;
(4) Adding 30mL of n-hexane into the aqueous solution containing the coordination compound, stirring and mixing for 5min, and then transferring to a separating funnel for separation treatment to obtain a complex solution;
wherein the volume ratio of water to normal hexane in the aqueous solution containing the coordination compound is 1:1;
(5) Stirring and mixing the complexing liquid and the active carbon, standing, precipitating and separating to obtain the active carbon loaded with indium, then placing the active carbon loaded with indium into a reaction kettle containing 10mL of water and 10mL of ethanol for hydrothermal reaction at 120 ℃ for 12 hours, naturally cooling to room temperature after the reaction is finished, taking out, and centrifuging, washing and drying to obtain the indium-based electrocatalyst;
wherein the mass ratio of the active carbon to the indium metal in the indium-containing pickle liquor is 1.5:1, and the volume ratio of the ethanol to the water is 1:1.
Fig. 1 shows a column statistical chart of the content changes of metal indium and other elements in the leachate after the aqua regia is dissolved in the waste liquid crystal display adopted in example 1 and the leachate obtained in different treatment stages in example 1, and it is clear from the figure that the method in example 1 can be used for preparing the indium-based catalyst by efficiently obtaining the metal indium from the waste liquid crystal display, but the extract liquid does not obtain a high-purity indium solution, and mainly contains metal impurity components such as Sn, al, fe and the like.
Fig. 2 shows the XRD pattern of the indium-based electrocatalyst prepared in this example, and as shown, the characteristic peaks of the indium-based electrocatalyst and the characteristic peaks of the standard card may well correspond (PDF # 17-0549).
Fig. 3 shows a TEM image of the indium-based electrocatalyst prepared in this example, wherein fig. (a) is a transmission electron microscope image, fig. (b) is a high resolution transmission electron microscope image, and fig. (c) -fig. (h) are element distribution diagrams. As can be seen from fig. (a), the indium-based electrocatalyst prepared in this example is polyhedral in morphology, and the average particle size is about 15.4nm; further, it was found from graph (b) that the lattice spacing of the individual metal nanoparticles was 0.341nm, which corresponds well to InOOH (110); as can be seen from fig. (c) -fig. (h), the impurities in each InOOH nanoparticle were uniformly doped.
FIG. 4 shows LSV test patterns of the indium-based electrocatalyst prepared in this example, which shows that the catalyst performs in CO compared to that tested in Ar gas flow 2 Having a greater current density in the atmosphere, the catalyst being specific to CO 2 Has better catalytic activity.
Fig. 5 shows the faraday efficiency plot of the indium-based electrocatalyst prepared in this example at different potentials, and it can be found that the indium-based electrocatalyst exhibits relatively good formate selectivity over a wide voltage range (-0.77-1.17V vs. RHE), with a faraday efficiency of formic acid above 85%, and in particular, with a highest efficiency of formic acid of 90.23% at-0.97V vs. RHE.
Example 2
The embodiment provides a method for preparing an indium-based electrocatalyst by using a waste liquid crystal display material, which comprises the following steps:
(1) Manually crushing and disassembling a waste liquid crystal display (Dell Inc. E170 Sc) to obtain 50g of glass substrate containing an ITO film, and then heating the glass substrate containing the ITO film in a water bath at 90 ℃ for a period of time1h, tearing off the polarizing film to obtain a polarizing film-removed glass substrate, and then cutting the polarizing film-removed glass substrate into a size of 2X 2cm 2 Is placed in 20mL of solution containing acetone for soaking for 3h, and a glass substrate with liquid crystal removed is obtained;
(2) Stirring and mixing the glass substrate with liquid crystal removed and 30mL of hydrochloric acid aqueous solution with the concentration of 2mol/L for 90min, and performing ultrasonic treatment at the ultrasonic power of 240W to obtain an indium-containing pickle liquor;
(3) Adding 0.5mL of dodecylamine into 30mL of ethanol solvent, stirring uniformly to obtain dodecylamine solution, stirring and mixing the dodecylamine solution and the indium-containing pickle liquor, and controlling the pH value of the mixed solution to be 7.5-8.5 by adding sodium hydroxide to obtain aqueous solution containing coordination compound;
wherein the liquid-solid ratio of the dodecylamine solution to the glass substrate containing the ITO film is 10 mu L/g;
(4) Adding 30mL of toluene into the aqueous solution containing the coordination compound, stirring and mixing for 10min, and then transferring to a separating funnel for separation treatment to obtain a complex solution;
wherein the volume ratio of water to toluene in the aqueous solution containing the coordination compound is 1:1;
(5) Stirring and mixing the complexing liquid and the active carbon, standing, precipitating and separating to obtain the active carbon loaded with indium, then placing the active carbon loaded with indium into a reaction kettle containing 10mL of water and 10mL of ethanol for hydrothermal reaction at 150 ℃ for 6 hours, naturally cooling to room temperature after the reaction is finished, taking out, and centrifuging, washing and drying to obtain the indium-based electrocatalyst;
wherein the mass ratio of the active carbon to the indium metal in the indium-containing pickle liquor is 1.5:1, and the volume ratio of the ethanol to the water is 1:1.
Example 3
This example is different from example 1 in that the addition amount of dodecylamine in step (3) was adjusted so that the liquid-solid ratio of dodecylamine in the dodecylamine solution to the glass substrate containing an ITO film was 2. Mu.L/g.
The remaining methods and parameters remain the same as in example 1.
Example 4
This example is different from example 1 in that the addition amount of dodecylamine in step (3) was adjusted so that the liquid-solid ratio of dodecylamine in the dodecylamine solution to the glass substrate containing an ITO film was 100. Mu.L/g.
The remaining methods and parameters remain the same as in example 1.
Example 5
This example differs from example 1 in that the mass ratio of activated carbon to indium metal in the indium-containing pickle liquor is 0.8:1.
The remaining methods and parameters remain the same as in example 1.
Example 6
This example differs from example 1 in that the mass ratio of activated carbon to indium metal in the indium-containing pickle liquor is 5:1.
The remaining methods and parameters remain the same as in example 1.
Example 7
This example differs from example 1 in that the temperature of the hydrothermal reaction in step (5) is 50 ℃.
The remaining methods and parameters remain the same as in example 1.
Example 8
This example differs from example 1 in that the temperature of the hydrothermal reaction in step (5) is 250 ℃.
The remaining methods and parameters remain the same as in example 1.
Comparative example 1
This comparative example differs from example 1 in that in step (3) the dodecylamine is replaced by tetraoctylammonium bromide.
The remaining methods and parameters remain the same as in example 1.
Catalyst preparation and electrochemical Performance testing
The electrocatalytic carbon dioxide reduction performance tests on the indium-based electrocatalysts prepared in the examples and comparative examples above were performed using a standard three-electrode test system at a Bio-logic VMP3 type electrochemical workstation (equipped with EC-lab software, version 9.56). Wherein the reference isThe electrode is Ag/AgCl electrode (KCl saturation), and the counter electrode is platinum sheet electrode (1X 1 cm) 2 ) The working electrode is prepared by the indium-based electrocatalyst through surface treatment. Firstly, dispersing 5mg of catalyst powder into 1mL of solution containing 0.8mL of ethanol, 0.18mL of ultrapure water and 0.02mL of Nafion, and fully mixing the solution into a viscous slurry mixture by ultrasonic treatment; a certain amount of the slurry mixture was uniformly dropped onto the surface of a glassy carbon electrode having a diameter of 8mm, and then the electrode was dried in a stream of hot air at 70 ℃ for 1 hour to obtain a working electrode. After the working electrode is prepared, a standard three-electrode test system is formed by the working electrode, the reference electrode and the counter electrode. All potentials were converted to values referenced to the Reversible Hydrogen Electrode (RHE) using E (V vs RHE) =e (V vs Ag/AgCl) +0.1989v+0.0591v×ph.
Before electrochemical measurement, at 10mL min -1 Will CO 2 Passing into 0.5M KHCO 3 The solution (ph=7.3) was kept for 30 minutes and then at 10mV s -1 Next, linear Sweep Voltammetry (LSV) was performed from 0V to-1.17V, and the gas product of the cathode chamber was analyzed using gas chromatography (SRI 8610C) equipped with a heat conduction detector (TCD) and a Helium Ionization Detector (HID), and the carrier gas was high purity helium (99.999%) with the faraday efficiency calculation formula of the gas product as follows:
wherein Z is CO or H 2 V (mL/min) is CO as measured by a S48-32 mass flow controller (HORIBA) 2 Inlet flow, I (mA) is the total current during the reaction, T(s) is the time at which the gas sample was taken, here 60s, F= 96485C mol -1 ，P=1.01×10 5 Pa，R=8.314J mol -1 K -1 t=298.15K. The liquid product was analyzed using a BRUKER AVANCE III MHz nuclear magnetic resonance spectrometer and the 1H NMR spectrum was determined using the water inhibition method. 0.5mL of sample was added to 0.1. 0.1mLD 2 In a mixture of O and 10 μL of the MSO solution (6 mM) as an internal standard, the product content in the sample was calculated from the following formula:
wherein I is product And I DMSO Integration of product peak and DMSO peak, respectively, N product And N DMSO The number of protons corresponding to the product peak and the DMSO peak, M product And M DMSO For the molar mass of the product and DMSO, m DMSO N=30 mL/0.5 ml=60 for DMSO mass.
The faraday efficiency of the liquid product is calculated as follows:
wherein F is Faraday constant (F= 96485C mol) -1 ) N is the molar quantity generated, Q is the total charge quantity, and e is the number of transferred electrons.
The above test results are shown in table 1.
TABLE 1
Analysis:
as can be seen from the above table, the present invention proposes that organic amine is used as extractant in hydrometallurgical recovery process and protective agent in electrocatalyst synthesis process, so that the indium extraction technology of waste liquid crystal display material and indium-based electrocatalyst in CO 2 The application of the electrocatalytic reduction reaction is coupled, the purposes of shortening the indium extraction flow, reducing the extraction cost and reducing the environmental pollution are achieved, and a new idea is provided for recycling waste resources. In addition, the indium-based electrocatalyst prepared by the invention has excellent catalytic activity and formate selectivity.
As is clear from examples 1 and 3 to 4, if the liquid-solid ratio of dodecylamine in the dodecylamine solution to the glass substrate containing the ITO film is too small, i.e., the amount of dodecylamine used is too small, the amount of indium extracted is small, resulting in a low current density of the catalyst; if the liquid-solid ratio of the dodecylamine solution to the glass substrate containing the ITO film is too large, that is, if the amount of dodecylamine is too large, a large amount of impurity metals such as Fe are extracted, resulting in a decrease in the faraday efficiency of the catalyst.
From examples 1 and 5-6, it is known that too small an amount of activated carbon can cause aggregation of catalyst particles, and agglomeration during the reaction process, which affects the activity and stability of the catalyst; if the amount of the activated carbon is too large, the catalyst metal component is reduced, and the activity of the catalyst is reduced.
As is clear from examples 1 and 7-8, if the temperature of the hydrothermal reaction is too low, the metal in the catalyst cannot be reduced sufficiently to affect the growth of the catalyst, resulting in a decrease in catalytic activity; if the temperature of the hydrothermal reaction is too high, the catalyst particles are seriously agglomerated and cannot be sufficiently dispersed, resulting in a decrease in catalytic activity.
From example 1 and comparative example 1, it is understood that if dodecylamine is replaced with tetraoctylammonium bromide, the phase transfer efficiency of indium is lowered, resulting in a decrease in current density during electrocatalytic carbon dioxide reduction.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for preparing an indium-based electrocatalyst from a spent liquid crystal display material, the method comprising the steps of:
(1) Sequentially carrying out pretreatment and acid leaching treatment on the waste liquid crystal display material to obtain indium-containing pickle liquor;
(2) Mixing the indium-containing pickle liquor and organic amine liquor to obtain a solution containing a coordination compound, then mixing the solution containing the coordination compound with a nonpolar organic solvent, and carrying out separation treatment to obtain a complex liquor;
(3) Mixing the complex solution with a carbon carrier, and performing hydrothermal reaction to obtain the indium-based electrocatalyst;
the organic amine liquid in the step (2) comprises any one or a combination of at least two of a dodecylamine solution, a hexadecylamine solution and an octadecylamine solution.
2. The method according to claim 1, wherein the specific step of preprocessing in step (1) comprises:
(a) Crushing and disassembling the waste liquid crystal display material to obtain a glass substrate containing an ITO film;
(b) And sequentially carrying out water bath heating and acetone soaking treatment on the glass substrate containing the ITO film so as to remove the polarizing film and the liquid crystal.
3. The method of claim 1, wherein the acid leaching treatment of step (1) is accompanied by ultrasound, the power of the ultrasound being 200-400W;
the acid solution used in the acid leaching treatment process in the step (1) comprises any one or a combination of at least two of hydrochloric acid aqueous solution, sulfuric acid aqueous solution and nitric acid aqueous solution;
the concentration of the acid solution used in the acid leaching treatment process of the step (1) is 0.1-5mol/L;
the acid leaching treatment time in the step (1) is 30-120min.
4. The method according to claim 2, wherein the liquid-solid ratio of the organic amine in the organic amine liquid and the ITO film-containing glass substrate in step (2) is 2 to 100 μl/g;
in the step (2), the pH value of the mixed solution is controlled to be 6-9 in the process of mixing the pickle liquor and the organic amine liquor;
the pH regulator comprises inorganic base.
5. The method of claim 1, wherein the non-polar organic solvent of step (2) comprises any one or a combination of at least two of n-hexane, chloroform, toluene, p-xylene, methylene chloride, carbon tetrachloride, cyclohexane, isooctane, oleylamine, or oleic acid;
the volume ratio of the solvent to the nonpolar organic solvent in the solution containing the coordination compound in the step (2) is (0.2-5): 1.
6. The method of claim 1, wherein the carbon support of step (3) comprises activated carbon or carbon paper;
when the carbon carrier in the step (3) is active carbon, the mass ratio of the active carbon to indium metal in the indium-containing pickle liquor is (1-4): 1.
7. The method of claim 1, wherein the mixing of step (3) is accompanied by agitation;
before the hydrothermal reaction in the step (3), standing, precipitating and separating a mixture obtained by mixing the complexing liquid and the carbon carrier;
the temperature of the hydrothermal reaction in the step (3) is 90-220 ℃ and the time is 1-24h.
8. The method according to claim 1, characterized in that it comprises the steps of:
taking a waste liquid crystal display as a raw material, manually crushing and disassembling to obtain a glass substrate containing an ITO film, then heating the glass substrate containing the ITO film in a water bath at 60-100 ℃ for 0.5-1.5 hours to obtain a glass substrate with a polarizing film removed, cutting the glass substrate with the polarizing film removed into fragments, and soaking in a solution containing acetone for 1-5 hours to obtain a glass substrate with liquid crystal removed;
(II) stirring and mixing the glass substrate with the liquid crystal removed and the acid solution with the concentration of 0.1-5mol/L for 30-120min, and simultaneously performing ultrasonic treatment with ultrasonic power of 200-400W to obtain an indium-containing pickle liquor;
(III) stirring and mixing the indium-containing pickle liquor and the ethanol-mediated dodecylamine solution, and controlling the pH value of the mixed solution to be 6-9 to obtain an aqueous solution containing a coordination compound;
wherein the liquid-solid ratio of the dodecyl amine in the dodecyl amine solution to the glass substrate containing the ITO film is 2-100 mu L/g;
adding a nonpolar organic solvent into the aqueous solution containing the coordination compound, and separating to obtain a complex solution;
wherein the volume ratio of water to the nonpolar organic solvent in the aqueous solution containing the coordination compound is (0.2-5) 1;
(V) stirring and mixing the complexing solution and the active carbon, standing, precipitating and separating to obtain the active carbon loaded with indium, placing the active carbon loaded with indium in a reaction kettle containing water and ethanol for carrying out hydrothermal reaction at 90-220 ℃ for 1-24 hours, naturally cooling to room temperature after the reaction is finished, taking out, centrifuging, washing and drying to obtain the indium-based electrocatalyst;
wherein the mass ratio of the active carbon to the indium metal in the indium-containing pickle liquor is (1-4): 1, and the volume ratio of the ethanol to the water is (0.5-2): 1.
9. An indium-based electrocatalyst obtainable by the process according to any one of claims 1 to 8, characterised in that the indium-based electrocatalyst comprises a support and an active component, the support being a carbon support and the active component comprising indium.
10. Use of an indium-based electrocatalyst according to claim 9, wherein the indium-based catalyst is used for CO 2 The field of electrocatalytic reduction.
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