CN114160165B - High-entropy alloy/NiIn 2 S 4 Preparation method of composite photocatalyst - Google Patents
High-entropy alloy/NiIn 2 S 4 Preparation method of composite photocatalyst Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 229910006119 NiIn Inorganic materials 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 150000002471 indium Chemical class 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- JIRRNZWTWJGJCT-UHFFFAOYSA-N carbamothioylthiourea Chemical compound NC(=S)NC(N)=S JIRRNZWTWJGJCT-UHFFFAOYSA-N 0.000 claims description 2
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims description 2
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 239000003242 anti bacterial agent Substances 0.000 abstract description 5
- 229940088710 antibiotic agent Drugs 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000001782 photodegradation Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000011056 performance test Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 6
- 239000002082 metal nanoparticle Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229960000907 methylthioninium chloride Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- -1 transition metal sulfide Chemical class 0.000 description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- YLZGECKKLOSBPL-UHFFFAOYSA-N indium nickel Chemical compound [Ni].[In] YLZGECKKLOSBPL-UHFFFAOYSA-N 0.000 description 1
- AJAXZLXLXZWIIE-UHFFFAOYSA-N indium;hydrochloride Chemical compound Cl.[In] AJAXZLXLXZWIIE-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/39—
Abstract
The invention discloses a high-entropy alloy/NiIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps: s1, weighing a metal source comprising 5 metal ions, a surfactant and a reducing agent, adding the metal source, the surfactant and the reducing agent into a solvent A, and fully stirring and dissolving to form a high-entropy alloy precursor solution; s2, performing ultrasonic reduction on the high-entropy alloy precursor solution by adopting an ultrasonic auxiliary method to obtain a high-entropy alloy; s3, weighing nickel salt, indium salt and sulfur source, adding into the solvent B, and fully stirring for dissolving to form NiIn 2 S 4 Is a precursor solution of (a); s4, niIn above 2 S 4 Adding high-entropy alloy into the precursor solution of (1), reacting in a high-pressure reaction kettle, and cleaning and drying after the reaction is finished to obtain NiIn 2 S 4 High entropy alloy composite. Compared with the prior art, the method has the advantages that the synthesis process is simple, the batch preparation is easy, the obtained composite material has a Z-type heterojunction structure, the separation efficiency of photo-generated carriers is improved, and the method has higher catalytic efficiency on various antibiotics and organic pollutants in sewage.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a high-entropy alloy/NiIn for photodegradation of water antibiotics and organic pollutants 2 S 4 A preparation method of a composite photocatalyst.
Background
Along with the rapid development of society, organic dyes and antibiotics cause serious water and soil pollution, cause serious threat to the health of human bodies, animals and plants, effectively treat the pollution of organic pollutants and antibiotics, protect the living environment of human beings, and are an important problem to be solved for a long time. Under the background of carbon neutralization, the solar photocatalytic degradation technology is considered as a key green and environment-friendly means for solving the important problem. To date, expert scholars have explored various semiconductor materials including metal oxides, sulfides, oxyhalides, oxynitrides, organometallic framework materials, and the like, for photocatalytic degradation. Among all the photocatalysts that have been reported, metal sulfides are considered as good candidates for photocatalysis due to their strong absorption in the visible region. As an important ternary transition metal sulfide, sulfur spinel (a II B III 2 S VI 4 Such as ZnIn 2 S 4 、CoIn 2 S 4 、NiIn 2 S 4 、FeIn 2 S 4 Etc.) has been shownThe feasibility of photocatalysis is shown, as well as potential applications in optoelectronics, light modulators and photodetectors. Wherein NiIn 2 S 4 Has narrow band gap and excellent photocatalytic activity, and has wide application in the field of solar cells.
Ag. The reason why the Au plasma has remarkable photocatalytic activity is that: 1) The electron conduction of the metal nano particles can obtain irradiation energy, so that high-energy electrons are generated on the surfaces of the metal nano particles, and the oxidation of organic pollutant molecules adsorbed on the surfaces of the metal nano particles is facilitated. 2) Metal nanoparticles have better affinity for organic contaminant molecules than semiconductors; 3) The electron density of the surface of the metal nano particle is far higher than that of the semiconductor, so that the reaction of organic pollutant molecules on the surface of the metal nano particle is enhanced. Common Au and Ag nanoparticles are often used as cocatalysts for photocatalysis. The high-entropy alloy containing multiple metal elements has the advantages of excellent catalytic activity, high strength, good corrosion resistance and the like due to coordination, geometric effect and the like.
Xia et al (In situ grown NiIn) 2 S 4 nanosheets as counter electrode for bifacial quasi-solid-state dye-sensitized solar cells) growth of NiIn on FTO conductive glass by hydrothermal growth 2 S 4 The interconnected network-shaped nano-sheets are applied to solar cells.
Fu et al (Superior Oxygen Electrocatalysis on Nickel Indium Thiospinels for Rechargeable Zn-Air Batteries) hydrothermally grown Niln with carbon nanofibers as a carrier 2 S 4 The nano sheet has better catalytic activity in Zn-Air batteries.
Invention patent CN 113181922A adopts high entropy CoMgNiZnCuO x And the silver quantum dots are deposited on the surface of the carrier, so that the efficiency of photodegradation of dye wastewater is improved.
Patent CN 111573775A employs AI x E y Fe z Ni u G v The dye (rhodamine B) is degraded by photochemical-electrochemical bonding as an electrode.
Wang et al (Development of a novel (Ni) 40 Fe 30 Co 20 Al 10 ) 90 Ti 10 high-entropy alloy with excellent photocatalytic performance) was prepared using high energy ball milling-high temperature calcination (Ni) 40 Fe 30 Co 20 Al 10 ) 90 Ti 10 The high entropy alloy promotes electron transfer at the interface between different phases and generates lattice distortion, so that the high entropy alloy has high-efficiency degradation performance on methyl blue in visible light.
Liu et al synthesized a high entropy CoCrFeMnNi/C composite material by impregnation-adsorption-calcination with activated carbon as a carrier, and showed excellent catalytic performance for methylene blue degradation without any peroxide addition.
NiIn is not used in the prior art 2 S 4 The high-entropy alloy composite photocatalytic material is used for photodegradation of antibiotics, and the current photocatalytic material has low separation efficiency of photogenerated carriers.
Disclosure of Invention
The invention aims at: provides a high-entropy alloy/NiIn 2 S 4 A preparation method of a composite photocatalyst.
In order to achieve the above purpose, the present invention adopts the following technical scheme: high-entropy alloy/NiIn 2 S 4 The preparation method of the composite photocatalyst comprises the following steps:
s1, weighing a metal source comprising 5 metal ions, a surfactant and a reducing agent, adding the metal source, the surfactant and the reducing agent into a solvent A, and fully stirring and dissolving to form a high-entropy alloy precursor solution;
s2, performing ultrasonic reduction on the high-entropy alloy precursor solution by adopting an ultrasonic auxiliary method under the condition that the ultrasonic power is 300-1500W, wherein the ultrasonic time is 5-60min, and the temperature is 20-60 ℃ to obtain the high-entropy alloy;
s3, weighing nickel salt, indium salt and sulfur source, adding into the solvent B, and fully stirring and dissolving the nickel salt, the indium salt and the sulfur source to form NiIn, wherein the molar ratio of the nickel salt to the indium salt to the sulfur source is 1:2:4 2 S 4 Is a precursor solution of (a);
s4, niIn above 2 S 4 Adding high-entropy alloy into the precursor solution of (1), reacting for 6-48h at 160-220 ℃ in a high-pressure reaction kettle, and cleaning and drying after the reaction is finished to obtain NiIn 2 S 4 High entropy alloy composite.
As a further description of the above technical solution:
in the step S1, the metal source is five of Co, fe, ni, cu, mn, cr, au, ag, pt, pd, ir, rh hydrochloride, nitrate, sulfate and acetate, the molar ratio of 5 metal ions is 1:1:1:1, and the molar concentration of the total metal ions is 1-1000mmol/L.
As a further description of the above technical solution:
in step S1, the surfactant is one or both of CTAB, PVP, SDS, P and F127.
As a further description of the above technical solution:
in step S1, the reducing agent is one of ethylene glycol, ethylenediamine, ascorbic acid, sodium borohydride, and triethylamine.
As a further description of the above technical solution:
in step S1, the solvent a is one or two of water, ethanol, ethylene glycol, glycerol, and isopropanol.
As a further description of the above technical solution:
in step S3, the nickel salt is one of hydrochloride, sulfate, nitrate, oxalate, and acetate of nickel.
As a further description of the above technical solution:
in step S3, the indium salt is one of indium hydrochloride, nitrate, sulfate, acetate.
As a further description of the above technical solution:
in step S3, the sulfur source is one of thiourea, thioacetamide, sodium sulfide, ethylenediamine, thiosemicarbazide, sodium thiosulfate, ammonium thiosulfate, thioacetic acid, dithioacetamide, and dithiobiuret.
As a further description of the above technical solution:
in the step S3, the solvent B is one or two of water, ethanol, glycol, N-dimethylformamide and N, N-dimethylacetamide, and the mass ratio of the nickel salt to the solvent B is 1:50-200.
As a further description of the above technical solution:
in step S4, the high-entropy alloy is mixed with NiIn 2 S 4 The theoretical mass ratio of (2) is 10:1-1:10.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. in the invention, the high-entropy alloy with narrow particle size range and uniform size can be prepared by adopting the acoustic cavitation effect of ultrasonic irradiation, and the method has the advantages of high synthesis speed, easiness in mass production and the like;
2. in the invention, the high-entropy alloy has the advantages of good visible light transmittance, strong light absorption capacity, good heat resistance, corrosion resistance and the like, and the surface effect and the quantum effect presented by the high-entropy alloy improve the catalytic activity of the composite material;
3. in the invention, niIn is coated or grown on the surface of the high-entropy alloy by utilizing hydrothermal synthesis 2 S 4 The nano material can form a compact Z-type heterojunction structure between the nano material and the nano material, which is favorable for separating photogenerated carriers and improves the photocatalytic activity.
Detailed Description
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Example 1
S1, respectively weighing precursors of silver chloride, cobalt chloride, nickel chloride, copper chloride and palladium chloride according to the mol ratio of Ag: co, ni, cu, pd =1:1:1:1:1, dissolving the precursors in ethylene glycol (the mol concentration of total metal ions is 5 mmol/L), adding a surfactant CTAB, and fully stirring and dissolving to obtain a high-entropy alloy precursor solution;
s2, carrying out ultrasonic reduction on the solution for 30 minutes at the power of 750W and the room temperature in a cell grinder, and cleaning and drying to obtain the high-entropy AgCoNiCuPd alloy;
s3, weighing 1.0mmol of nickel chloride hexahydrate, 2.0mmol of indium trichloride and 8.0mmol of thiourea, adding into 70ml of a mixed solvent of N, N-dimethylformamide and ethylene glycol (volume ratio of 1:1), and fully stirring for dissolving to form NiIn 2 S 4 Is a precursor solution of (a);
s4, transferring the solution into a high-pressure reaction kettle, adding 0.1g of high-entropy AgCoNiCuPd alloy, performing hydrothermal reaction at 180 ℃ for 12 hours, cleaning and drying to obtain NiIn 2 S 4 AgCoNiCuPd composite.
For the NiIn prepared 2 S 4 The AgCoNiCuPd composite material is subjected to photodegradation performance test.
Example two
S1, respectively weighing precursors of silver nitrate, cobalt nitrate, nickel nitrate, copper nitrate and palladium nitrate according to the mol ratio of Ag: co, ni, cu, pd =1:1:1:1:1, dissolving the precursors in ethylene glycol (the mol concentration of total metal ions is 5 mmol/L), adding a surfactant SDS, and fully stirring and dissolving to obtain a high-entropy alloy precursor solution;
s2, carrying out ultrasonic reduction on the solution for 40 minutes at the power of 800W and the room temperature in a cell grinder, and cleaning and drying to obtain the high-entropy AgCoNiCuPd alloy;
s3, weighing 1.0mmol of nickel chloride hexahydrate, 2.0mmol of indium trichloride and 8.0mmol of thiourea, adding into 70ml of a mixed solvent of N, N-dimethylformamide and ethylene glycol (volume ratio of 1:1), and fully stirring for dissolving to form NiIn 2 S 4 Is a precursor solution of (a);
s4, transferring the solution into a high-pressure reaction kettle, adding 0.1g of high-entropy AgCoNiCuPd alloy, performing hydrothermal reaction at 180 ℃ for 12 hours, cleaning and drying to obtain NiIn 2 S 4 AgCoNiCuPd composite.
For the NiIn prepared 2 S 4 The AgCoNiCuPd composite material is subjected to photodegradation performance test.
Example III
S1, respectively weighing precursors of cobalt chloride, chromium chloride, ferric chloride, manganese chloride and nickel chloride according to the mol ratio of Co: cr, fe, mn, ni =1:1:1:1:1, dissolving the precursors in ethylene glycol (the mol concentration of total metal ions is 5 mmol/L), adding a surfactant CTAB, and fully stirring and dissolving to obtain a high-entropy alloy precursor solution;
s2, carrying out ultrasonic reduction on the solution for 30 minutes at the power of 750W and the room temperature in a cell grinder, and cleaning and drying to obtain the high-entropy CoCrFeMnNi alloy;
s3, weighing 1.0mmol of nickel chloride hexahydrate, 2.0mmol of indium trichloride and 8.0mmol of thiourea, adding into 70ml of a mixed solvent of N, N-dimethylformamide and ethylene glycol (volume ratio of 1:1), and fully stirring for dissolving to form NiIn 2 S 4 Is a precursor solution of (a);
s4, transferring the solution into a high-pressure reaction kettle, adding 0.1g of high-entropy CoCrFeMnNi alloy, performing hydrothermal reaction at 180 ℃ for 12 hours, cleaning and drying to obtain NiIn 2 S 4 CoCrFeMnNi composite material.
For the NiIn prepared 2 S 4 the/CoCrFeMnNi composite material is subjected to photodegradation performance test.
Photodegradation performance test: the synthesized composite material is added into sewage containing organic dye, the adding amount of the catalyst is 0.1-1g/L, a 300W xenon lamp is used as a light source, an ultraviolet light part is filtered out by a filter, and the used light source is visible light with the wavelength of more than 420 nm. When in use, the catalyst concentration can be adjusted according to specific conditions.
The initial concentration of the organic dye is 5-50mg/L.
After the reaction is finished, the degradation rate is calculated by the following steps:
degradation rate = [ (C) 0 -C t )/C 0 ]*100％
Wherein C is 0 For initial concentration of organic dye, C t The unit is mg/L for the concentration of the organic dye measured after the reaction.
| Methylene blue degradation rate after 1h of illumination | |
| Example 1 | 99.1％ |
| Example 2 | 98.9％ |
| Example 3 | 99.5％ |
| Comparative example 1 (No addition in Sewage) | 56.3％ |
| Comparative example 2 | 43.8％ |
Note that: the photodegradation performance test performed in comparative example 1 was performed, and the synthetic composite material was not added to the sewage, otherwise the photodegradation performance test performed in example 1 was the same.
Photodegradation performance test performed in comparative example 2, the synthetic composite material was not added to the sewage, and the photodegradation performance test was otherwise the same as that performed in example 2.
Claims (4)
1. High-entropy alloy/NiIn 2 S 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps:
s1, weighing a metal source comprising 5 metal ions, a surfactant and a reducing agent, adding the metal source, the surfactant and the reducing agent into a solvent A, fully stirring and dissolving the solvent A which is one or two of water, ethanol, glycol, glycerol and isopropanol to form a high-entropy alloy precursor solution, wherein the metal source is five of hydrochloride, nitrate, sulfate and acetate of Co, fe, ni, cu, mn, cr, au, ag, pt, pd, ir, rh, and the molar ratio of the 5 metal ions is 1:1:1:1:1, the molar concentration of the total metal ions is 1-1000mmol/L;
s2, performing ultrasonic reduction on the high-entropy alloy precursor solution by adopting an ultrasonic auxiliary method under the condition that the ultrasonic power is 300-1500W, wherein the ultrasonic time is 5-60min, and the temperature is 20-60 ℃ to obtain the high-entropy alloy;
s3, weighing nickel salt, indium salt and a sulfur source, wherein the indium salt is one of hydrochloride, nitrate, sulfate and acetate of indium, the sulfur source is one of thiourea, thioacetamide, sodium sulfide, ethylenediamine, thiosemicarbazide, sodium thiosulfate, ammonium thiosulfate, thioacetic acid, dithioacetamide and dithiobiuret, the nickel salt is added into a solvent B, the solvent B is one or two of water, ethanol, glycol, N-dimethylformamide and N, N-dimethylacetamide, and the mass ratio of the nickel salt to the solvent B is 1:50-200, wherein the molar ratio of nickel salt, indium salt and sulfur source is 1:2:4, fully stirring and dissolving to form NiIn 2 S 4 Is a precursor solution of (a);
s4, niIn above 2 S 4 Adding high-entropy alloy into the precursor solution of (1), reacting for 6-48h at 160-220 ℃ in a high-pressure reaction kettle, and cleaning and drying after the reaction is finished to obtain NiIn 2 S 4 High entropy alloy composite.
2. A high entropy alloy/NiIn according to claim 1 2 S 4 The preparation method of the composite photocatalyst is characterized in that in the step S1, the surfactant is one or two of CTAB, PVP, SDS, P, 123 and F127.
3. A high entropy alloy/NiIn according to claim 1 2 S 4 The preparation method of the composite photocatalyst is characterized in that in the step S1, the reducing agent is one of ethylene glycol, ethylenediamine, ascorbic acid, sodium borohydride and triethylamine.
4. A high entropy alloy/NiIn according to claim 1 2 S 4 The preparation method of the composite photocatalyst is characterized in that in the step S4, high-entropy alloy and NiIn are mixed 2 S 4 4 is 10:1 to 1:10.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031799A (en) * | 2005-07-28 | 2007-02-08 | Toda Kogyo Corp | Method for producing metal nanoparticle |
| JP2009066529A (en) * | 2007-09-13 | 2009-04-02 | Tokyo Univ Of Science | Photocatalyst, its manufacturing method, and method for generating hydrogen gas |
| CN102000580A (en) * | 2010-11-05 | 2011-04-06 | 北京化工大学 | Method for preparing spinel-type magnetic nano composite metal oxide visible light catalyst |
| CN108620105A (en) * | 2018-05-04 | 2018-10-09 | 福州大学 | Composite photo-catalyst MxP/ sulfur-indium-zincs and the preparation method and application thereof |
| CN109999830A (en) * | 2019-05-05 | 2019-07-12 | 中国矿业大学 | Load C oCr(Mn/Al) FeNi high-entropy alloy nanoparticle catalyst and its preparation method and application |
| CN110280273A (en) * | 2018-09-30 | 2019-09-27 | 湖北工业大学 | A kind of AuPd/ZnIn2S4The preparation method of composite nano-grade sheet material |
| CN113198489A (en) * | 2021-04-02 | 2021-08-03 | 常熟氢能源研究院有限公司 | Preparation method of platinum-series high-entropy alloy catalyst |
| CN113224334A (en) * | 2021-04-02 | 2021-08-06 | 常熟氢能源研究院有限公司 | Preparation method of platinum-containing high-entropy alloy/MXene composite catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100490970C (en) * | 2005-10-24 | 2009-05-27 | 南开大学 | Expanded graphite supporting NiB amorphous alloy catalyst, its preparation method and application |
| CN106076366B (en) * | 2016-06-20 | 2018-05-01 | 广东工业大学 | A kind of short-bore road ordered mesopore carbon sulfur loaded indium cobalt and sulphur indium nickel Three-element composite photocatalyst and its preparation method and application |
-
2021
- 2021-12-13 CN CN202111519347.3A patent/CN114160165B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007031799A (en) * | 2005-07-28 | 2007-02-08 | Toda Kogyo Corp | Method for producing metal nanoparticle |
| JP2009066529A (en) * | 2007-09-13 | 2009-04-02 | Tokyo Univ Of Science | Photocatalyst, its manufacturing method, and method for generating hydrogen gas |
| CN102000580A (en) * | 2010-11-05 | 2011-04-06 | 北京化工大学 | Method for preparing spinel-type magnetic nano composite metal oxide visible light catalyst |
| CN108620105A (en) * | 2018-05-04 | 2018-10-09 | 福州大学 | Composite photo-catalyst MxP/ sulfur-indium-zincs and the preparation method and application thereof |
| CN110280273A (en) * | 2018-09-30 | 2019-09-27 | 湖北工业大学 | A kind of AuPd/ZnIn2S4The preparation method of composite nano-grade sheet material |
| CN109999830A (en) * | 2019-05-05 | 2019-07-12 | 中国矿业大学 | Load C oCr(Mn/Al) FeNi high-entropy alloy nanoparticle catalyst and its preparation method and application |
| CN113198489A (en) * | 2021-04-02 | 2021-08-03 | 常熟氢能源研究院有限公司 | Preparation method of platinum-series high-entropy alloy catalyst |
| CN113224334A (en) * | 2021-04-02 | 2021-08-06 | 常熟氢能源研究院有限公司 | Preparation method of platinum-containing high-entropy alloy/MXene composite catalyst |
Non-Patent Citations (4)
| Title |
|---|
| "Design of AgxAu1-xalloy/ZnIn2S4 system with tunable spectral response and Schottky barrier height for visible-light-driven hydrogen evolution";Huiqin An et al.;《Chemical Engineering Journal》;第382卷;第2页第2-4段、第2.2节 * |
| "Development of a novel (Ni40Fe30Co20Al10)90Ti10 high-entropy alloy with excellent photocatalytic performance";Tao Wang et al.;《Materials Letters》;第283卷;第1-5页 * |
| "不同表面活性剂对合成NiIn2S4 纳米花的影响及其光催化还原性能";王驭晗等;《辽宁化工》;第49卷(第6期);607-610 * |
| Yue Xin et al.."High-Entropy Alloys as a Platform for Catalysis: Progress,Challenges, and Opportunities".《ACS Catalysis》.2020,第10卷(第19期),第1、2.6、4.3、4.9、4.10节. * |
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