CN109692691A - Counter opal structure MIn2S4Catalysis material and its preparation method and application - Google Patents
Counter opal structure MIn2S4Catalysis material and its preparation method and application Download PDFInfo
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- CN109692691A CN109692691A CN201811454394.2A CN201811454394A CN109692691A CN 109692691 A CN109692691 A CN 109692691A CN 201811454394 A CN201811454394 A CN 201811454394A CN 109692691 A CN109692691 A CN 109692691A
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- polymer microsphere
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- 239000000463 material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000004005 microsphere Substances 0.000 claims abstract description 79
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 47
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 229910052738 indium Inorganic materials 0.000 claims abstract description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- 239000004626 polylactic acid Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 238000005253 cladding Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- -1 caddy Chemical compound 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 239000011521 glass Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 13
- 230000008901 benefit Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000006303 photolysis reaction Methods 0.000 description 5
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 4
- 239000011022 opal Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000000877 morphologic effect Effects 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000006193 liquid solution Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 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
-
- 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—
-
- B01J35/39—
-
- B01J35/61—
-
- B01J35/651—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of counter opal structure MIn2S4Catalysis material and its preparation method and application.Wherein, the counter opal structure MIn2S4Catalysis material is impregnated in polymer microsphere template dispersion liquid by substrate, obtains the substrate that load has polymer microsphere template；The substrate is impregnated in the precursor solution containing the source M, indium source and sulphur source again, and carries out heating reaction and generates the MIn for coating the polymer microsphere template2S4；Wherein, the source M is one or both of zinc source and cadmium source；The MIn2S4For ZnIn2S4Or CdIn2S4；The polymer microsphere template is removed later to be prepared.The MIn2S4Catalysis material has counter opal structure, and dispersibility is strong, and neat rule of arranging improves photocatalysis efficiency in light-catalyzed reaction.Furthermore the invention also includes counter opal structure MIn2S4The preparation method and counter opal structure MIn of catalysis material2S4Application of the catalysis material in terms of photocatalysis.
Description
Technical field
The present invention relates to semiconductor light-catalyst field more particularly to a kind of counter opal structure MIn2S4Catalysis material
And its preparation method and application.
Background technique
Energy shortage and environmental pollution are the significant problems that current mankind faces.Photocatalysis technology has at low cost, high
The advantages that imitating, be green, is environmentally friendly, without secondary pollution, in environmental pollution improvement, photolysis water hydrogen, carbon dioxide reduction, fixed nitrogen etc.
Aspect shows huge potential advantages.Although photocatalysis technology is rapidly developed in recent decades, and is controlled in environmental pollution
Reason field obtains practical application.But due to catalysis material be primarily limited to low the efficiency of solar energy utilization, light induced electron and
Hole is easy to the problems such as compound, so that there is also obvious gaps for benefit and actual demand brought by photocatalysis technology.
Currently, the semiconductor material with visible light photocatalysis active has been widely studied and has reported.Wherein ternary gold
Belong to sulfide M In2S4(M be Zn and/or Cd) catalysis material is because of its unique lamellar structure, suitable position of energy band, significant
Visible light-responded and preferable chemical stability, in recent years in organic pollutant degradation, photodissociation aquatic products hydrogen, CO2It restores, is solid
The fields such as nitrogen reaction and solar battery are widely studied and report.Based on existing document report, although MIn2S4(M is
Zn and/or Cd) catalysis material has unique advantage, but the separation of its photo-generated carrier and transfer ability are lower, drop significantly
Low visible light photocatalysis effect.At this stage be directed to this problem, scholars mainly use Morphological control, hetero-junctions construction and
The strategies such as element doping, further promote MIn2S4(M is Zn and/or Cd) material entirety photocatalysis performance.Wherein, Morphological control
Technology is present modification MIn2S4(M is Zn and/or Cd) common technological means of material.The strategy is main to be tieed up by controlled material
The parameters such as degree, thickness and microscopic appearance, the light-receiving area of Lai Zeng great material, increases reactivity site or shortening body mutually carries
Sub- average mobility free path is flowed, to effectively improve MIn2S4(M is Zn and/or Cd) reduces carrier to visible light utilization efficiency
Combined efficiency improves photocatalysis efficiency.But the MIn reported at present2S4(M is Zn and/or Cd) material still remains stacking group
The problems such as poly-, bad dispersibility.These problems will lead to the reduction of material light-receiving area, carrier separation efficiency drop to a certain extent
Low, reaction mass transfer process is obstructed, and amount of activated site is shielded, to influence Morphological control modified effect.Overcome these not
Foot, key are to design and prepare the MIn with specific morphology and structure2S4(M is Zn and/or Cd) catalysis material, utilizes
Its pattern or design feature improve material scatter, increase reactivity number of sites amount, enhance light Utilization ability, improve current-carrying
Sub- separative efficiency accelerates reaction mass transfer process, and then improves photocatalysis efficiency.
Summary of the invention
The technical problems to be solved by the present invention are: MIn2S4Stack reunion, bad dispersibility.
In order to solve the above technical problems, the invention proposes a kind of counter opal structure MIn2S4Catalysis material and its system
Preparation Method and application.
The present invention proposes a kind of counter opal structure MIn2S4Catalysis material is impregnated in polymer microsphere template by substrate
In dispersion liquid, the substrate that load has polymer microsphere template is obtained；The substrate is impregnated in containing the source M, indium source and sulphur source again
Precursor solution in, and carry out heating reaction and generate the MIn for coating the polymer microsphere template2S4；Wherein, the source M
For one or both of zinc source and cadmium source；The MIn2S4For ZnIn2S4And/or CdIn2S4；The macromolecule is removed later
Microsphere template is prepared.
Preferably, the polymer microsphere in the polymer microsphere template dispersion liquid is polystyrene microsphere, poly- methyl-prop
One of e pioic acid methyl ester microballoon, polylactic acid microsphere and polycaprolactone microballoon sphere are a variety of；
And/or the source M be one of zinc chloride, zinc nitrate, zinc sulfate, caddy, cadmium nitrate and cadmium sulfate or
It is a variety of；
And/or the sulphur source is one of vulcanized sodium, thiocarbamide and thioacetamide or a variety of；
And/or the solvent in the precursor solution is one of water, ethyl alcohol and methanol or a variety of.
Preferably, polymer microsphere the polymer microsphere template dispersion liquid mass percent be 0.01%~
0.25%.
Preferably, the molar ratio in the source M, the indium source and the sulphur source is 1:2:5~8.Excessive sulphur source is conducive to
MIn2S4It generates.
Preferably, the organic solvent is one of n,N-Dimethylformamide, dimethyl sulfoxide and acetonitrile or more
Kind.
The invention also provides a kind of counter opal structure MIn described above2S4The preparation method of catalysis material, packet
Include following steps:
1) substrate is impregnated in polymer microsphere template dispersion liquid, obtains the substrate that load has polymer microsphere template；
2) by obtained in step 1) it is described load have polymer microsphere template substrate be impregnated in containing the source M, indium source and
In the precursor solution of sulphur source, and carries out heating reaction and generate the MIn for coating the polymer microsphere template2S4Substrate；Wherein,
The source M is one or both of zinc source and cadmium source；The MIn2S4For ZnIn2S4And/or CdIn2S4；
3) MIn of the cladding obtained step 2) the polymer microsphere template2S4Substrate is placed in organic solution,
For 24 hours~48h is stood, the polymer microsphere template is removed, obtains counter opal structure MIn2S4。
Preferably, in step 2), the heating reaction of progress is that oil bath is reacted, wherein the temperature of the oil bath reaction
Degree is 80~100 DEG C, and the time is 4~12h.Be conducive to MIn under the conditions of the temperature2S4Generation.
Preferably, in step 3), the MIn of the cladding that step 2) the is obtained polymer microsphere template2S4Base
Bottom is placed in organic solution, is impregnated for 24 hours~48h, is removed the polymer microsphere template.
Preferably, in step 1), substrate is impregnated in polymer microsphere template dispersion liquid, later 40 DEG C~80
Vacuum drying obtains the substrate that load has polymer microsphere template at DEG C.
Preferably, it in step 3), removes the polymer microsphere template and is dried in vacuo at 80~100 DEG C later
To counter opal structure MIn2S4。
Preferably, the substrate is substrate of glass.
In addition, the present invention also proposes counter opal structure MIn described above2S4Catalysis material or the preparation
The counter opal structure MIn of method preparation2S4Catalysis material is in photocatalytic degradation, production hydrogen, CO2In terms of reduction or fixed nitrogen
Using.
The beneficial effect of the present invention compared with the prior art includes: to be impregnated in polymer microsphere template point by substrate first
In dispersion liquid, the substrate that load has polymer microsphere template is obtained, then the substrate of glass is impregnated in containing the source M, indium source and sulphur
In the precursor solution in source, the MIn that heating reaction generates is carried out2S4Coat the polymer microsphere template, polymer microsphere mould
The shape of plate determines MIn2S4Shape, the shape of polymer microsphere template is counter opal structure, wherein the source M is
One or both of zinc source and cadmium source, i.e., the described MIn2S4For ZnIn2S4And/or CdIn2S4, the macromolecule is coated later
The MIn of microsphere template2S4It is placed in organic solvent, polymer microsphere template can be dissolved in organic solvent, MIn2S4It cannot
It is dissolved in organic solvent, so that removing the polymer microsphere template can be obtained the MIn with counter opal structure2S4
Catalysis material, counter opal structure MIn2S4Catalysis material dispersibility is strong, neat rule of arranging, to increase MIn2S4
Reactivity number of sites amount, enhance light Utilization ability, improve carrier separation efficiency, accelerate reaction mass transfer process,
And then photocatalysis efficiency is improved in light-catalyzed reaction.
Detailed description of the invention
The features and advantages of the present invention will be more clearly understood by referring to the accompanying drawings, and attached drawing is schematically without answering
It is interpreted as carrying out any restrictions to the present invention, in the accompanying drawings:
Fig. 1 is counter opal structure ZnIn prepared by the embodiment of the present invention 12S4XRD diagram.
Fig. 2 is counter opal structure ZnIn prepared by the embodiment of the present invention 12S4SEM figure.
Fig. 3 is counter opal structure ZnIn prepared by the embodiment of the present invention 12S4SEM figure.
Fig. 4 is counter opal structure ZnIn prepared by the embodiment of the present invention 12S4H2-producing capacity.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this
Invention.But the invention can be embodied in many other ways as described herein, those skilled in the art can be
Without prejudice to doing similar improvement in the case where intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Embodiment 1
Counter opal structure ZnIn in the present embodiment2S4Catalysis material is prepared by following step:
1) substrate of glass is vertically impregnated in 0.05% polystyrene microsphere aqueous solution, 50 DEG C of vacuum drying obtain
Load has the substrate of glass of polystyrene microsphere template；Wherein, polystyrene microsphere is opal structural；
2) precursor solution configures: weighing 1mmol ZnCl2, 2mmol InCl3·4H2O and 6mmol thioacetamide is set
In 80ml deionized water, stir evenly；
3) will described in step 1) load have polystyrene microsphere template substrate of glass be impregnated in step 2) preparation before
It drives in liquid solution, oil bath reaction 6h dries to obtain the glass base for coating the polystyrene microsphere template to solution at 80 DEG C
The MIn at bottom2S4Substrate of glass；
4) MIn for the cladding polystyrene microsphere template for obtaining step 3)2S4Substrate of glass is placed in N, N- diformazan
In base formamide, room temperature immersion 12h removes the polystyrene microsphere template；
5) step 4) is removed to the MIn after the polystyrene microsphere template2S4Substrate of glass is washed with deionized, and 80
DEG C vacuum drying, obtain counter opal structure ZnIn2S4。
As shown in Figure 1, counter opal structure ZnIn obtained by the embodiment of the present invention2S4XRD diffraction maximum and standard card
(PDF#65-2023) unanimously, illustrate gained ZnIn2S4For pure phase, polymer microsphere template is not remained.
It as shown in Figures 2 and 3, can the present invention visible in detail under 30000 times and 80000 times of scanning electron microscope
ZnIn obtained by embodiment2S4Pattern be counter opal structure, aperture size 100nm, ZnIn2S4It is dispersed strong, it arranges whole
Neat rule.
Counter opal structure ZnIn is prepared in order to illustrate the present invention2S4H2-producing capacity, the present embodiment is by photodissociation aquatic products hydrogen
It is carried out in efficiency rating experiment luxuriant and rich with fragrance Lay photodissociation water installations on the berth, using day U.S. gas chromatographic detection H2Yield.Experimentation
Are as follows: by ZnIn obtained by 30mg2S4Catalysis material is added in 70mL deionized water, and 30mL triethanolamine is added as hole
Sacrifice agent carries out photocatalytic water reaction using LED light as light source in photodissociation water installations.System vacuumizes, and 25 DEG C of reaction temperature, so
Illumination is carried out to system with LED lamplight afterwards, every H in 1h detection system2Content, reaction was completed after 5h.It is prepared by embodiment 1
ZnIn2S4With the ZnIn of no addition microsphere template preparation2S4It compares, in conjunction with Fig. 4 it is found that hydrogen-producing speed is respectively 100 μ
mol/g-1·h-1With 39.8 μm of ol/g-1·h-1, the ZnIn of the preparation of embodiment 12S4Hydrogen-producing speed be far longer than common oil bath
The ZnIn of preparation2S4Hydrogen-producing speed, counter opal structure ZnIn2S4With excellent H2-producing capacity.
Embodiment 2
Counter opal structure CdIn in the present embodiment2S4Catalysis material is prepared by following step:
1) substrate of glass is vertically impregnated in 0.1% polylactic acid microsphere aqueous solution, 50 DEG C of vacuum drying are loaded
There is the substrate of glass of polylactic acid microsphere template；Wherein, the polylactic acid microsphere is opal structural；
2) precursor solution configures: weighing 1mmol CdSO4, 2mmol In (NO3)3·4H2O and 6mmol thioacetyl
Amine is placed in 80ml deionized water, is stirred evenly.
3) substrate of glass that the load for obtaining step 1) has polylactic acid microsphere template is impregnated in the forerunner of step 2) preparation
In liquid solution, oil bath is reacted 6h and is dried to solution at 90 DEG C, obtains the CdIn for coating the polylactic acid microsphere template2S4Glass
Substrate；
4) CdIn for the cladding polylactic acid microsphere template for obtaining step 3)2S4Substrate of glass is placed in N, N- dimethyl
In formamide, room temperature immersion 12h removes the polylactic acid microsphere template；
5) CdIn of the polylactic acid microsphere template will be removed2S4Substrate of glass is washed with deionized, and 80 DEG C of vacuum are dry
It is dry, obtain counter opal structure CdIn2S4。
Embodiment 3
Counter opal structure ZnIn in the present embodiment2S4Catalysis material is prepared by following step:
1) substrate of glass is vertically impregnated in 0.05% poly (methyl methacrylate) micro-sphere aqueous solution, 50 DEG C of vacuum are dry
It is dry, obtain the substrate of glass that load has poly (methyl methacrylate) micro-sphere template；Wherein, poly (methyl methacrylate) micro-sphere is
Opal structural；
2) precursor solution configures: weighing 1mmol Zn (NO3)2, 2mmol InCl3·4H2O and 6mmol Na2S is placed in
In 80ml deionized water, stir evenly；
3) substrate of glass of poly (methyl methacrylate) micro-sphere template is impregnated in step load obtained in step 1)
2) in the precursor solution prepared, oil bath is reacted 6h and is dried to solution at 80 DEG C, and it is micro- to obtain cladding polymethyl methacrylate
The ZnIn of ball template2S4Substrate of glass；
4) MIn for the cladding poly (methyl methacrylate) micro-sphere template for obtaining step 3)2S4Substrate of glass is placed in N, N- bis-
In methylformamide, room temperature immersion 12h removes poly (methyl methacrylate) micro-sphere template；
5) ZnIn of the methyl methacrylate microsphere template will be removed2S4Substrate of glass is washed with deionized, and 80
DEG C vacuum drying, obtain counter opal structure ZnIn2S4。
The present invention uses low temperature oil bath-self assembly counter opal structure MIn2S4(M is Zn and/or Cd) semiconductor light
Catalyst also has the following advantages and effect:
1) present invention is combined using self assembly with low temperature oil bath, and process is simple, easy to operate, repetitive operation is strong；
2) the counter opal structure MIn that the present invention obtains2S4It can be controlled by controlling the size of polymer microsphere template
The pore size of counter opal structure processed；
3) the counter opal structure MIn that the present invention obtains2S4With biggish specific surface area, excellent photocatalytic degradation,
Produce hydrogen, CO2Reduction, fixed nitrogen performance and cycle performance；
Preparation method of the present invention is simple, low in cost.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff it is identical.Term as used herein in the specification of the present invention is intended merely to retouch
State the purpose of specific embodiment, it is not intended that in the limitation present invention.Each technical characteristic of embodiment described above can carry out
Arbitrary combination, for simplicity of description, combination not all possible to each technical characteristic in above-described embodiment all carry out
Description, as long as all should be considered as described in this specification however, there is no contradiction in the combination of these technical features.
Claims (10)
1. a kind of counter opal structure MIn2S4Catalysis material, which is characterized in that polymer microsphere template point is impregnated in by substrate
In dispersion liquid, the substrate that load has polymer microsphere template is obtained；The substrate is impregnated in containing the source M, indium source and sulphur source again
In precursor solution, and carries out heating reaction and generate the MIn for coating the polymer microsphere template2S4；Wherein, the source M is zinc
One or both of source and cadmium source；The MIn2S4For ZnIn2S4And/or CdIn2S4；The polymer microsphere will be coated later
The MIn of template2S4It is placed in organic solvent and removes the polymer microsphere template and be prepared.
2. counter opal structure Maccording to claim 12S4Catalysis material, which is characterized in that the macromolecule is micro-
Polymer microsphere in ball template dispersion liquid is polystyrene microsphere, poly (methyl methacrylate) micro-sphere, polylactic acid microsphere and gathers
One of caprolactone microballoon is a variety of；
And/or the source M is one of zinc chloride, zinc nitrate, zinc sulfate, caddy, cadmium nitrate and cadmium sulfate or a variety of；
And/or the sulphur source is one of vulcanized sodium, thiocarbamide and thioacetamide or a variety of；
And/or the solvent in the precursor solution is one of water, ethyl alcohol and methanol or a variety of.
3. counter opal structure Maccording to claim 12S4Catalysis material, which is characterized in that polymer microsphere exists
The mass percent of the polymer microsphere template dispersion liquid is 0.01%~0.25%.
4. counter opal structure Maccording to claim 12S4Catalysis material, which is characterized in that the source M, described
The molar ratio of indium source and the sulphur source is 1:2:5~8.
5. counter opal structure Maccording to claim 12S4Catalysis material, which is characterized in that the organic solvent
For one of N,N-dimethylformamide, dimethyl sulfoxide and acetonitrile or a variety of.
6. a kind of counter opal structure MIn as described in any one in claim 1-52S4The preparation method of catalysis material, it is special
Sign is, comprising the following steps:
1) substrate is impregnated in polymer microsphere template dispersion liquid, obtains the substrate that load has polymer microsphere template；
2) substrate for having polymer microsphere template that loads obtained in step 1) is impregnated in containing the source M, indium source and sulphur source
Precursor solution in, and carry out heating reaction and generate the MIn for coating the polymer microsphere template2S4Substrate；Wherein, the M
Source is one or both of zinc source and cadmium source；The MIn2S4For ZnIn2S4And/or CdIn2S4；
3) MIn of the cladding obtained step 2) the polymer microsphere template2S4Substrate is placed in organic solution, removal
The polymer microsphere template, obtains counter opal structure MIn2S4。
7. preparation method according to claim 6, which is characterized in that in step 2), the heating reaction of progress is
Oil bath reaction, wherein the temperature of the oil bath reaction is 80~100 DEG C, and the time is 4~12h.
8. preparation method according to claim 6, which is characterized in that in step 3), the packet that step 2) is obtained
Cover the MIn of the polymer microsphere template2S4Substrate is placed in organic solution, is impregnated for 24 hours~48h, is removed the polymer microsphere
Template.
9. preparation method according to claim 6, which is characterized in that in step 1), it is micro- that substrate is impregnated in macromolecule
In ball template dispersion liquid, vacuum drying obtains the substrate that load has polymer microsphere template at 40 DEG C~80 DEG C later.
10. the described in any item counter opal structure MIn of Claims 1 to 52S4Catalysis material or claim 6~9 times
The counter opal structure MIn of the preparation of preparation method described in one2S4Catalysis material is in photocatalytic degradation, production hydrogen, CO2Reduction
Or the application in terms of fixed nitrogen.
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