CN109126824A - A kind of the zinc sulphide bronzing catalyst and preparation method of metal/non-metal doping - Google Patents
A kind of the zinc sulphide bronzing catalyst and preparation method of metal/non-metal doping Download PDFInfo
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- CN109126824A CN109126824A CN201811090029.8A CN201811090029A CN109126824A CN 109126824 A CN109126824 A CN 109126824A CN 201811090029 A CN201811090029 A CN 201811090029A CN 109126824 A CN109126824 A CN 109126824A
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- zinc
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- zinc sulphide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 29
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000012545 processing Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 20
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 19
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004073 vulcanization Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 52
- 239000007789 gas Substances 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- FQGMPQGXUXIOKI-UHFFFAOYSA-N [S--].[S--].[Cu++].[Zn++] Chemical compound [S--].[S--].[Cu++].[Zn++] FQGMPQGXUXIOKI-UHFFFAOYSA-N 0.000 claims description 26
- 239000005864 Sulphur Substances 0.000 claims description 25
- 150000003751 zinc Chemical class 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 18
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 17
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 238000006303 photolysis reaction Methods 0.000 abstract description 4
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract 2
- 229910052747 lanthanoid Inorganic materials 0.000 abstract 1
- 150000002602 lanthanoids Chemical class 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 8
- 125000003158 alcohol group Chemical group 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 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 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 sulfide Compound Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical fields of photochemical catalyst, provide the zinc sulphide bronzing catalyst and preparation method of a kind of metal/non-metal doping.This method is prepared for zinc sulphide bronzing catalyst, and doping metals lanthanum in situ, cerium at a lower temperature, further adulterates nonmetallic nitrogen by magnetron sputtering, the zinc sulphide bronzing catalyst of metal/non-metal doping is made.It is compared with the traditional method, the present invention is doped processing to vulcanization zinc-copper using lanthanoid metal, cerium and nonmetallic nitrogen, photochemical catalyst forbidden bandwidth obtained is relatively narrow, it can be seen that light utilization efficiency is higher, and light induced electron be not easy with hole it is compound, photocatalysis efficiency is high, can be widely used for photolysis water hydrogen and treatment of Organic Wastewater field.
Description
Technical field
The invention belongs to the technical field of photochemical catalyst, the zinc sulphide bronzing for providing a kind of metal/non-metal doping is urged
Agent and preparation method.
Background technique
The Major research field of semiconductor light-catalyst includes: (1) using solar energy as the energy, is with the oxygen in air
Oxidant promotes the organic pollutant in water and air to be completely decomposed into CO2、H2O and other inorganic salts are a kind of ideal pollutions
Object control technology；(2) it is the chemical energy such as hydrogen and oxygen by water decomposition using solar energy, is the important composition portion of hydrogen economy
Point；(3) solar energy is directly translated into electric energy.Photocatalitic Technique of Semiconductor has room temperature deep reaction and can be directly using too
The special performances such as positive energy drive response, before wide development is shown in terms of environmental pollution improvement and clear energy sources
Scape.
When the basic catalytic process of semiconductor light-catalyst is that the energy of incident light is greater than the band-gap energy of semiconductor, it will excite
The electron transition of valence band is to higher energy conduction band in semiconductor, to leave hole in valence band.Resulting a part of light induced electron
It will diffuse into the surface of catalyst with hole, finally aoxidized with the electron acceptor or electron donor for being adsorbed on catalyst surface
Reduction reaction, the active group for forming light-catalyzed reaction cause sequence of chemical reaction.In addition, the light induced electron generated and hole are also
Can itself direct combination, energy is discharged in the form of light and heat, and is consumed by self compounding.Therefore, light induced electron
Compound with hole can reduce light-catalyzed reaction efficiency.
The raising of the photocatalysis efficiency of semiconductor light-catalyst mainly reduces the probability of recombination of light induced electron and hole,
Researcher has carried out extensive trial, such as noble-metal-supported, metal ion, nonmetallic ion-doped, dye-sensitized semiconductor with
And semiconductor coupling etc..Currently used photochemical catalyst mainly has metal oxide, sulfide etc., wherein the ternary in sulfide
Compound vulcanization zinc-copper becomes the rising star being concerned, and the research improved to its catalytic efficiency is more and more.
Chinese invention patent application number 201410181986.7 discloses a kind of vulcanization zinc-copper nanometer of cuprous ion doping
The rapid synthesis method of line visible light catalyst and application, the present invention use pressure Microwave-assisted synthesis method, do solvent, divalent with water
Zinc salt is zinc source, and copper nano-wire is substrate, is vulcanized by sulphur source, cleans rapid synthesis with cuprous compared with high visible-light activity
The zinc sulphide copper nano-wire visible light catalyst of ion doping.Can be widely used in photolysis water hydrogen, solar battery, antibacterial,
The fields such as photocatalysis treatment pollutant.The shortcomings that invention is that light induced electron and hole are compound to being easy, and causes catalytic efficiency low,
Using being restricted.
In conclusion in the prior art for vulcanizing in the catalyst in fields such as photocatalysis sewage processing, photolysis water hydrogen
Zinc-copper photochemical catalyst causes visible light utilization efficiency low there are forbidden bandwidth is wider, and light induced electron and hole are to being easy compound to cause to urge
The defects of changing low efficiency, therefore develop that a kind of visible light utilization efficiency is high, zinc sulphide bronzing catalyst of high catalytic efficiency, have emphatically
The meaning wanted.
Summary of the invention
As it can be seen that the zinc sulphide bronzing catalyst of the prior art causes visible light utilization efficiency low there are forbidden bandwidth is wider, light
Give birth to electronics and the hole easily compound defect for causing catalytic efficiency low.In response to this, the present invention proposes a kind of metal/non-metal
The zinc sulphide bronzing catalyst and preparation method of doping, effectively increase the visible light utilization efficiency of photochemical catalyst, and inhibit
Compound, the high catalytic efficiency of photochemical catalyst obtained of light induced electron and hole.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping, the zinc sulphide bronzing catalyst preparation
Specific step is as follows:
(1) mantoquita, zinc salt are added in alcohol/aqueous solution, lanthanum nitrate, cerous nitrate is then added, stirs evenly, adjusting pH value to 4 ~
5, mixed solution A is made；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 120 ~ 150min, be filtered, washed, very
Sky is dry, and the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst.
Preferably, step (1) mantoquita is one of copper chloride, copper sulphate, copper acetate, copper nitrate.
Preferably, step (1) zinc salt is one of zinc chloride, zinc sulfate, zinc acetate, zinc nitrate.
Preferably, step (1) sulphur source is one of vulcanized sodium, thioacetamide, thiocarbamide.
Preferably, step (1) alcohol is one of ethylene glycol, glycerine, isopropanol, n-butanol, isobutanol.
Preferably, in step (1) described mixed solution A, 10 ~ 15 parts by weight of mantoquita, 10 ~ 15 parts by weight of zinc salt, alcohol 20 ~ 30
Parts by weight, 30 ~ 56 parts by weight of water, 2 ~ 5 parts by weight of lanthanum nitrate, 2 ~ 5 parts by weight of cerous nitrate.
Preferably, in step (2) described solution B, 20 ~ 30 parts by weight of sulphur source, 30 ~ 40 parts by weight of alcohol, 30 ~ 50 weight of water
Part.
Preferably, in step (3) described reaction system, 40 ~ 60 parts by weight of solution A, 40 ~ 60 parts by weight of solution B.
Preferably, the temperature of step (3) described reaction is 30 ~ 40 DEG C, and mixing speed is 100 ~ 150r/min.
Preferably, step (3) the vacuum drying temperature is 50 ~ 60 DEG C, and the time is 6 ~ 10h.
Preferably, in step (4) described mixed gas, 30 ~ 40 parts by volume of nitrogen, 60 ~ 70 parts by volume of argon gas.
Preferably, the gas flow of step (4) the magnetron sputtering processing is 15 ~ 20cm3/ min, sputtering power be 80 ~
120W, processing time are 3 ~ 5min.
The present invention also provides a kind of zinc sulphide bronzings of metal/non-metal that above-mentioned preparation method is prepared doping to urge
Agent.The zinc sulphide bronzing catalyst is to be prepared for zinc sulphide bronzing catalyst at a lower temperature, and doping is golden in situ
Belong to lanthanum, cerium, nonmetallic nitrogen is further adulterated by magnetron sputtering and is made.
The present invention provides the zinc sulphide bronzing catalyst and preparation method of a kind of doping of metal/non-metal, with existing skill
Art is compared, and the feature and excellent effect protruded is:
1. zinc sulphide bronzing catalyst prepared by the present invention, doping metals lanthanum, cerium in vulcanization zinc-copper synthesis process, lanthanum ion and
Cerium ion, which enters, can be changed crystallinity in structure, cause lattice defect, regulates and controls electronic structure by changing chemical composition, is conducive to
The separation for promoting light induced electron and hole, significantly improves photocatalysis efficiency.
2. zinc sulphide bronzing catalyst prepared by the present invention adulterates nonmetalloid N by magnetron sputtering, takes N section
For the S in zinc sulphide copper crystal lattice, the 2p energy level of N and the 2p energy level of S overlap, and the forbidden bandwidth for vulcanizing zinc-copper is made to narrow, right
The ability that is absorbed and utilized of visible light significantly improves.
3. preparation method of the invention, the preparation for vulcanizing zinc-copper carries out at a lower temperature, can reduce energy consumption, is made simultaneously
Vulcanization zinc-copper partial size it is smaller, dimensional stability is preferable, can be widely used for photolysis water hydrogen and treatment of Organic Wastewater field.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) by mantoquita, zinc salt be added alcohol/aqueous solution in, then be added lanthanum nitrate, cerous nitrate, stir evenly, adjust pH value to
4.5, mixed solution A is made；Mantoquita is copper chloride；Zinc salt is zinc chloride；Sulphur source is vulcanized sodium；Alcohol is ethylene glycol；Mixed solution A
In, 13 parts by weight of mantoquita, 13 parts by weight of zinc salt, 24 parts by weight of alcohol, 44 parts by weight of water, 3 parts by weight of lanthanum nitrate, 3 weight of cerous nitrate
Part；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；In solution B, 24 parts by weight of sulphur source, 34 weight of alcohol
Part, 42 parts by weight of water；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 130min, be filtered, washed, vacuum is done
It is dry, the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；The temperature of reaction is 32 DEG C, mixing speed 110r/min；Vacuum is dry
Dry temperature is 56 DEG C, time 9h；In reaction system, 48 parts by weight of solution A, 52 parts by weight of solution B；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst；In mixed gas, 34 parts by volume of nitrogen, 66 parts by volume of argon gas；Magnetron sputtering processing gas flow be
17cm3/ min, sputtering power 90W, processing time are 4min.
Embodiment 2
(1) mantoquita, zinc salt are added in alcohol/aqueous solution, lanthanum nitrate, cerous nitrate is then added, stirs evenly, adjusting pH value to 5,
Mixed solution A is made；Mantoquita is copper sulphate；Zinc salt is zinc sulfate；Sulphur source is thioacetamide；Alcohol is glycerine；Mixed solution A
In, 11 parts by weight of mantoquita, 12 parts by weight of zinc salt, 23 parts by weight of alcohol, 48 parts by weight of water, 3 parts by weight of lanthanum nitrate, 3 weight of cerous nitrate
Part；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；In solution B, 23 parts by weight of sulphur source, 33 weight of alcohol
Part, 44 parts by weight of water；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 130min, be filtered, washed, vacuum is done
It is dry, the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；The temperature of reaction is 32 DEG C, mixing speed 110r/min；Vacuum is dry
Dry temperature is 52 DEG C, time 9h；In reaction system, 45 parts by weight of solution A, 55 parts by weight of solution B；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst；In mixed gas, 32 parts by volume of nitrogen, 68 parts by volume of argon gas；Magnetron sputtering processing gas flow be
16cm3/ min, sputtering power 90W, processing time are 5min.
Embodiment 3
(1) mantoquita, zinc salt are added in alcohol/aqueous solution, lanthanum nitrate, cerous nitrate is then added, stirs evenly, adjusting pH value to 5,
Mixed solution A is made；Mantoquita is copper acetate；Zinc salt is zinc acetate；Sulphur source is thiocarbamide；Alcohol is n-butanol；In mixed solution A, copper
14 parts by weight of salt, 14 parts by weight of zinc salt, 27 parts by weight of alcohol, 37 parts by weight of water, 4 parts by weight of lanthanum nitrate, 4 parts by weight of cerous nitrate；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；In solution B, 28 parts by weight of sulphur source, 38 weight of alcohol
Part, 34 parts by weight of water；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 140min, be filtered, washed, vacuum is done
It is dry, the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；The temperature of reaction is 38 DEG C, mixing speed 140r/min；Vacuum is dry
Dry temperature is 58 DEG C, time 7h；In reaction system, 55 parts by weight of solution A, 45 parts by weight of solution B；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst；In mixed gas, 38 parts by volume of nitrogen, 62 parts by volume of argon gas；Magnetron sputtering processing gas flow be
19cm3/ min, sputtering power 115W, processing time are 3min.
Embodiment 4
(1) mantoquita, zinc salt are added in alcohol/aqueous solution, lanthanum nitrate, cerous nitrate is then added, stirs evenly, adjusting pH value to 4,
Mixed solution A is made；Mantoquita is copper nitrate；Zinc salt is zinc nitrate；Sulphur source is vulcanized sodium；Alcohol is n-butanol；In mixed solution A,
10 parts by weight of mantoquita, 10 parts by weight of zinc salt, 20 parts by weight of alcohol, 56 parts by weight of water, 2 parts by weight of lanthanum nitrate, 2 parts by weight of cerous nitrate；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；In solution B, 20 parts by weight of sulphur source, 30 weight of alcohol
Part, 50 parts by weight of water；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 120min, be filtered, washed, vacuum is done
It is dry, the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；The temperature of reaction is 30 DEG C, mixing speed 100r/min；Vacuum is dry
Dry temperature is 50 DEG C, time 10h；In reaction system, 40 parts by weight of solution A, 60 parts by weight of solution B；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst；In mixed gas, 30 parts by volume of nitrogen, 70 parts by volume of argon gas；Magnetron sputtering processing gas flow be
15cm3/ min, sputtering power 80W, processing time are 5min.
Embodiment 5
(1) mantoquita, zinc salt are added in alcohol/aqueous solution, lanthanum nitrate, cerous nitrate is then added, stirs evenly, adjusting pH value to 5,
Mixed solution A is made；Mantoquita is copper chloride；Zinc salt is zinc chloride；Sulphur source is thioacetamide；Alcohol is isobutanol；Mixed solution A
In, 15 parts by weight of mantoquita, 15 parts by weight of zinc salt, 30 parts by weight of alcohol, 30 parts by weight of water, 5 parts by weight of lanthanum nitrate, 5 weight of cerous nitrate
Part；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；In solution B, 30 parts by weight of sulphur source, 40 weight of alcohol
Part, 30 parts by weight of water；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 150min, be filtered, washed, vacuum is done
It is dry, the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；The temperature of reaction is 40 DEG C, mixing speed 150r/min；Vacuum is dry
Dry temperature is 60 DEG C, time 6h；In reaction system, 60 parts by weight of solution A, 40 parts by weight of solution B；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst；In mixed gas, 40 parts by volume of nitrogen, 60 parts by volume of argon gas；Magnetron sputtering processing gas flow be
20cm3/ min, sputtering power 120W, processing time are 3min.
Embodiment 6
(1) by mantoquita, zinc salt be added alcohol/aqueous solution in, then be added lanthanum nitrate, cerous nitrate, stir evenly, adjust pH value to
4.5, mixed solution A is made；Mantoquita is copper sulphate；Zinc salt is zinc nitrate；Sulphur source is thiocarbamide；Alcohol is ethylene glycol；Mixed solution A
In, 13 parts by weight of mantoquita, 12 parts by weight of zinc salt, 25 parts by weight of alcohol, 43 parts by weight of water, 4 parts by weight of lanthanum nitrate, 3 weight of cerous nitrate
Part；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；In solution B, 25 parts by weight of sulphur source, 35 weight of alcohol
Part, 40 parts by weight of water；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 135min, be filtered, washed, vacuum is done
It is dry, the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；The temperature of reaction is 35 DEG C, mixing speed 125r/min；Vacuum is dry
Dry temperature is 55 DEG C, time 8h；In reaction system, 50 parts by weight of solution A, 50 parts by weight of solution B；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst；In mixed gas, 35 parts by volume of nitrogen, 65 parts by volume of argon gas；Magnetron sputtering processing gas flow be
18cm3/ min, sputtering power 100W, processing time are 4min.
Comparative example 1
In preparation process, it is not added with lanthanum nitrate, cerous nitrate, other preparation conditions and embodiment 6 are consistent.
Comparative example 2
In preparation process, magnetron sputtering processing is not carried out, other preparation conditions and embodiment 6 are consistent.
Performance test:
(1) visible light utilization efficiency: any zinc sulphide bronzing catalyst produced by the present invention is taken, is irradiated with visible light, is tested
Can corresponding visible wavelength range spectrum account for the ratio of the total wave-length coverage of visible light, indicate visible light utilization efficiency；
(2) rhodamine B photocatalytic activity: configuring the rhodamine B solution of 100mg/L, takes 500mL as experimental liquid, is put into 1g
Added with the photo catalysis reactor of zinc sulphide bronzing catalyst produced by the present invention, reactor is fixed on magnetic stirring apparatus, and light is urged
Change in reaction, magneton is stirred continuously, to guarantee that photochemical catalyst is dispersed evenly in reaction solution, with 300W xenon lamp as light source, illumination
After beginning, a sample is taken every 20min, is centrifugated immediately after, taken supernatant liquor in the maximum absorption wave strong point of dyestuff, survey
Its absorbance, photocatalytic degradation effect are measured with degradation rate D, D=(A0- A)/A0× 100%, A0, A be respectively Luo Dan before and after illumination
The absorbance of bright B solution, rhodamine B degradation rate when testing respectively and being calculated 20min, 40min, 60min；
(3) hydrogen-producing speed: weighing 0.1g photochemical catalyst in the balance, 20mL water is measured, in the photocatalyst reaction vessel of diameter 9cm
It is sufficiently mixed, after irradiation 1h, accesses homemade vacuum under artificial light source 300W xenon lamp after emptying air and survey hydrogen system, use gas phase
Generated amounts of hydrogen is reacted in chromatograph detection, calculates hydrogen-producing speed；
The data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping, which is characterized in that the vulcanization zinc-copper
Specific step is as follows for photochemical catalyst preparation:
(1) mantoquita, zinc salt are added in alcohol/aqueous solution, lanthanum nitrate, cerous nitrate is then added, stirs evenly, adjusting pH value to 4 ~
5, mixed solution A is made；
(2) sulphur source is added in alcohol/aqueous solution, is stirred evenly, obtained solution B；
(3) solution A is slowly dropped into solution B under stirring, continues to be stirred to react 120 ~ 150min, be filtered, washed, very
Sky is dry, and the zinc sulphide copper nano-particle of lanthanum, cerium dopping is made；
(4) the zinc sulphide copper nano-particle of lanthanum made from step (3), cerium dopping is carried out in the mixed gas of nitrogen and argon gas
Magnetron sputtering processing, makes nitrogen-atoms replace the part sulphur atom in zinc sulphide copper crystal lattice, and the vulcanization of metal/non-metal doping is made
Zinc-copper photochemical catalyst.
2. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
It is:
The mantoquita is one of copper chloride, copper sulphate, copper acetate, copper nitrate；
The zinc salt is one of zinc chloride, zinc sulfate, zinc acetate, zinc nitrate；
The sulphur source is one of vulcanized sodium, thioacetamide, thiocarbamide；
The alcohol is one of ethylene glycol, glycerine, isopropanol, n-butanol, isobutanol.
3. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
It is: in step (1) described mixed solution A, 10 ~ 15 parts by weight of mantoquita, 10 ~ 15 parts by weight of zinc salt, 20 ~ 30 parts by weight of alcohol, water
30 ~ 56 parts by weight, 2 ~ 5 parts by weight of lanthanum nitrate, 2 ~ 5 parts by weight of cerous nitrate.
4. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
It is: in step (2) described solution B, 20 ~ 30 parts by weight of sulphur source, 30 ~ 40 parts by weight of alcohol, 30 ~ 50 parts by weight of water.
5. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
It is: in step (3) described reaction system, 40 ~ 60 parts by weight of solution A, 40 ~ 60 parts by weight of solution B.
6. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
Be: the temperature of step (3) described reaction is 30 ~ 40 DEG C, and mixing speed is 100 ~ 150r/min.
7. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
Be: step (3) the vacuum drying temperature is 50 ~ 60 DEG C, and the time is 6 ~ 10h.
8. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
It is: in step (4) described mixed gas, 30 ~ 40 parts by volume of nitrogen, 60 ~ 70 parts by volume of argon gas.
9. a kind of preparation method of the zinc sulphide bronzing catalyst of metal/non-metal doping according to claim 1, feature
Be: the gas flow of step (4) the magnetron sputtering processing is 15 ~ 20cm3/ min, sputtering power is 80 ~ 120W, when processing
Between be 3 ~ 5min.
10. a kind of zinc sulphide bronzing for metal/non-metal doping that any one of claim 1 ~ 9 preparation method is prepared
Catalyst.
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