CN112010352A - Silicon dioxide microsphere surface loaded ferrous sulfide nanocrystalline and preparation method and application thereof - Google Patents
Silicon dioxide microsphere surface loaded ferrous sulfide nanocrystalline and preparation method and application thereof Download PDFInfo
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- CN112010352A CN112010352A CN202010974445.5A CN202010974445A CN112010352A CN 112010352 A CN112010352 A CN 112010352A CN 202010974445 A CN202010974445 A CN 202010974445A CN 112010352 A CN112010352 A CN 112010352A
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- ferrous sulfide
- silicon dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 205
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000004005 microsphere Substances 0.000 title claims abstract description 89
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 85
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 15
- 239000011790 ferrous sulphate Substances 0.000 claims description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 15
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000010287 polarization Effects 0.000 claims description 8
- 230000004580 weight loss Effects 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000012667 polymer degradation Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002159 nanocrystal Substances 0.000 abstract description 28
- 230000009257 reactivity Effects 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 230000005540 biological transmission Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 9
- 210000004027 cell Anatomy 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000011160 research Methods 0.000 description 7
- 230000005476 size effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- -1 mercapto group modified silicon dioxide Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/12—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
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
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- B01J35/23—
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- B01J35/33—
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- B01J35/51—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention provides a ferrous sulfide nanocrystalline composite material loaded on the surface of a silicon dioxide microsphere, which comprises a silicon dioxide microsphere carrier and ferrous sulfide crystals loaded on the silicon dioxide microsphere carrier; the silicon dioxide microsphere carrier is a solid sphere with the particle size of 100 nm-500 nm; ferrous sulfide crystals are uniformly distributed on the surface of the silicon dioxide microsphere carrier, and the particle size is 5 nm-15 nm. The invention provides a preparation method of the composite material, which comprises the following steps: (1) preparing silicon dioxide microspheres; (2) carrying out surface sulfydryl modification on the silicon dioxide microspheres; (3) and loading ferrous sulfide crystals on the surface of the mercapto-modified silica microspheres. The invention also provides the application of the composite material. The composite material has higher reactivity, higher mechanical strength and higher stability. The microscopic sizes of the solid silica spheres and the ferrous sulfide of the carrier are controllable, the dispersion degree of the ferrous sulfide nanocrystals on the surface of the carrier is adjustable, the preparation method is simple, the cost is low, and the method has good application prospects in multiple fields.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a silica microsphere surface-loaded ferrous sulfide nanocrystal and a preparation method and application thereof.
Background
The size and the property of the interaction between the nano metal particles or the microcrystal particles and the oxide carrier are key factors for determining the catalytic activity and the selectivity, so that the research on the fields of heterogeneous catalysis and energy conversion of the metal (crystal) particles on the oxide carrier has important scientific research significance and application value. The dispersion and size effect of metal (crystal) particles on a high specific surface area support will be one of the most critical factors in determining the reactivity and specificity of the supported metal catalyst. Silica spheres have been widely used for supporting metal particles on a support, because they have high thermal stability, large specific surface area, high mechanical strength, and surface modification.
Usually, SiO2The loading of the nano-metal particles is achieved by deposition or impregnation. Most of the SiO is synthesized by a template agent2The carrier, the surface of which is coated with nano particles (mostly metal), forms a yolk type core-shell structure, but the catalytic efficiency is low and the process is complex. In order to improve the catalytic efficiency of the nano material, nano SiO2The surface loading of nano-metal materials becomes a research hotspot.
Ferrous sulfide (especially crystal) has high valence electronic energy level, so that 1s orbital electron of sulfur and 3d orbital electron of iron are easy to provide and receive electron transfer of adjacent elements, and meanwhile, the ferrous sulfide is rich in natural reserves and has the characteristics of low cost and the like, so that the ferrous sulfide nanocrystal is widely applied to the fields of energy conversion, energy storage, molecular catalysis and the like. However, because ferrous sulfide has magnetism, and the nano-scale material is easy to self-agglomerate, the specific surface area and the heterogeneous phase contact probability are reduced, and electron self-interference is formed, so that the electron transmission capability is reduced, and the efficiency of catalytic activity and energy conversion is reduced, therefore, the dispersion degree of ferrous sulfide is improved, the synthesis process is simplified, and the control of the crystal size effect (below 50 nm) is always a bottleneck which is difficult to break through in research hotspots and application popularization in academia.
Ren et al synthesize a Fe/FeS @ SiO with a core-shell structure2Particles (Catalysis Today,2019,327,2-9), tetrabromobisphenol, and the like. Although the silica has a microporous structure as the shell materialThe organic matter, iron and ferrous sulfide can be used for catalytic degradation, but the use of various templates and the synthesis steps are complicated, the size of the ferrous sulfide is large (about 100 nm), and the ferrous sulfide is of an amorphous structure, so that the catalytic efficiency is not high.
The Chinese patent application with the application number of 201910962440.8 discloses a synthetic method of modified three-dimensional mesoporous silica-loaded vulcanized nano zero-valent iron. The method takes three-dimensional mesoporous silicon dioxide as a shell, and vulcanized nano zero-valent iron is dispersed in the shell. Although the method achieves the dispersion of the vulcanized nano zero-valent iron, the raw materials are too complex, the steps of synthesizing a silicon dioxide mesoporous shell by using a polymer template, reducing the valence state of iron by using sodium borohydride and the like are too complicated, the cost is increased, and meanwhile, the defect that the catalytic performance of the vulcanized nano zero-valent iron with an amorphous structure is not improved sufficiently exists.
Therefore, at present, a method which is simple and convenient in preparation process, free of template agent, low in cost, low in ferrous sulfide crystal size smaller than 50nm and high in dispersity is urgently needed to be developed, the electron transfer efficiency and the size effect of the material can be improved, the capabilities of molecular catalysis and energy transfer are improved, the application field of the material can be expanded, and the material has academic research value.
Disclosure of Invention
In order to solve all or part of the problems, the invention aims to provide a silica microsphere surface-supported ferrous sulfide nanocrystal, and a preparation method and application thereof, so as to improve the electron transfer efficiency and size effect of the material, improve the capabilities of molecular catalysis and energy transfer, and expand the application field of the material.
On one hand, the invention provides a ferrous sulfide nanocrystalline composite material loaded on the surface of a silicon dioxide microsphere, which comprises a silicon dioxide microsphere carrier and ferrous sulfide crystals loaded on the silicon dioxide microsphere carrier; the silicon dioxide microsphere carrier is a solid sphere with the particle size of 100 nm-500 nm; the ferrous sulfide crystals are uniformly distributed on the surface of the silicon dioxide microsphere carrier, and the particle size is 5-15 nm.
Alternatively, the ferrous sulfide crystals belong to the orthorhombic system, Pmnn space group,the unit cell parameters are: a is not equal to b is not equal to c,
5.388≤c≤5.407。
optionally, the loading of the ferrous sulfide crystals is 6.8 wt% to 26.6 wt%.
Optionally, the redox polarization potential difference of the ferrous sulfide crystal is 0.2-0.5V, the oxidation weight loss temperature is 650-680 ℃, and CO is catalyzed by molecules2The conversion rate of (A) is 78.1 to 86.5%.
On the other hand, the invention provides a preparation method of a silica microsphere surface-supported ferrous sulfide nanocrystalline composite material, which comprises the following steps:
(1) preparing solid silica microspheres without a template;
(2) carrying out surface sulfydryl modification on the silicon dioxide solid microspheres to obtain sulfydryl modified silicon dioxide microspheres;
(3) and loading ferrous sulfide crystals on the surface of the mercapto-modified silica microspheres.
Alternatively, in step (1), the silica solid microspheres are prepared by the following method:
uniformly mixing 5-20 parts by volume of absolute ethyl alcohol, 3-10 parts by volume of deionized water and 0.5-2 parts by volume of ammonia water at 25-50 ℃ to obtain a mixed solution, and adjusting the pH value of the mixed solution to 8-10;
adding 1 volume part of tetraethoxysilane into the mixed solution, and reacting at 25-50 ℃ to obtain the silicon dioxide microspheres.
Optionally, in step (2), the silica microspheres are surface mercapto-modified with 3- (mercaptopropyl) triethoxysilane.
Optionally, in the step (3), the ferrous sulfide crystals are loaded on the surface of the mercapto-modified silica microspheres by the following method:
dispersing mercapto-modified silicon dioxide microspheres in water, uniformly mixing with a ferrous sulfate solution, dropwise adding thioacetamide into the mixture, and reacting at 15-55 ℃ to obtain a dispersion liquid;
and carrying out centrifugal separation, washing and drying on the dispersion liquid to obtain the silicon dioxide microsphere surface-supported ferrous sulfide nanocrystalline composite material.
Optionally, the mass ratio of the mercapto-modified silica microspheres to water is 1:10 to 1: 30; the mass ratio of the mercapto-modified silica microspheres to the ferrous sulfate is 5:1 to 10: 1; the ratio of the amount of ferrous sulfate to the amount of thioacetamide is 1:1 to 1.5: 1.
On the other hand, the invention provides the application of the composite material of the ferrous sulfide nanocrystalline loaded on the surface of the silicon dioxide microsphere in wastewater treatment, polymer degradation and molecular catalysis.
Compared with the prior art, the silica microsphere surface-loaded ferrous sulfide nanocrystalline and the preparation method thereof have the following beneficial effects:
according to the invention, ferrous sulfide nanocrystalline particles are loaded on the surface of the mercapto-modified silicon dioxide solid microsphere instead of being wrapped in a silicon dioxide shell, so that the reaction activity is higher, the mechanical strength is higher, and the stability is higher. Meanwhile, the microscopic sizes of the solid silica spheres and the ferrous sulfide of the carrier are controllable, the dispersion degree of the ferrous sulfide nanocrystals on the surface of the carrier is adjustable, the preparation method is simple, the cost is low, and the method has good application prospects in the fields of energy transfer and storage, environmental pollution treatment, molecular catalysis and the like.
Drawings
Fig. 1 is a transmission electron microscope image of the silica microspheres prepared in example 1 with ferrous sulfide nanocrystals loaded on the surfaces.
Fig. 2 is a high-resolution transmission electron microscope image of the silica microspheres prepared in example 1 with ferrous sulfide nanocrystals loaded on the surfaces.
Fig. 3 is an energy dispersion X-ray diagram of the surface-supported ferrous sulfide nanocrystal of the silica microsphere prepared in example 1.
Fig. 4 is a graph of the size effect of ferrous sulfide nanocrystals versus the electrochemically active surface area.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to fully understand the objects, features and effects of the invention. The following noun terms have meanings commonly understood by those skilled in the art unless otherwise specified.
Aiming at the problems of low efficiency, complex preparation method and the like of the existing silicon dioxide loaded metal composite material, the inventor of the invention creatively provides a silicon dioxide microsphere surface loaded ferrous sulfide nanocrystalline composite material, and a preparation method and application thereof through research.
In a first aspect, the invention provides a ferrous sulfide nanocrystalline composite material loaded on the surface of a silica microsphere.
The composite material of the silica microsphere surface loaded with ferrous sulfide nanocrystalline comprises a silica microsphere carrier and ferrous sulfide crystals loaded on the silica microsphere carrier. Wherein, the silicon dioxide microsphere carrier is a solid sphere with the grain diameter of 100 nm-500 nm; ferrous sulfide crystals are uniformly distributed on the surface of the silicon dioxide microsphere carrier, and the particle size is 5 nm-15 nm.
Preferably, the ferrous sulfide crystals belong to the orthorhombic system, Pmnn space group, unit cell parameters are: a is not equal to b is not equal to c,
5.388≤c≤5.407。
preferably, the load capacity of the ferrous sulfide crystal is 6.8-26.6 wt%, the oxidation-reduction polarization potential difference is 0.2-0.5V, the oxidation weight loss temperature of the ferrous sulfide crystal is 650-680 ℃, and CO is catalyzed by molecules2The conversion rate of (A) is 78.1% -86.5%.
In a second aspect, the invention provides a preparation method of a silica microsphere surface-supported ferrous sulfide nanocrystalline composite material. The preparation method comprises the following steps: (1) preparing solid silica microspheres; (2) carrying out surface sulfydryl modification on the silicon dioxide solid microspheres to obtain sulfydryl modified silicon dioxide microspheres; (3) and loading ferrous sulfide crystals on the surface of the mercapto-modified silica microspheres.
In one embodiment, the preparation method of the composite material of the silica microsphere surface loaded with ferrous sulfide nanocrystal comprises the following steps:
(1) preparation of silica solid microspheres without template agent
Mixing 5-20 parts by volume of absolute ethyl alcohol, 3-10 parts by volume of deionized water and 0.5-2 parts by volume of ammonia water, stirring in a constant-temperature water bath kettle at 25-50 ℃ until the mixture is uniformly mixed to obtain a mixed solution, and adjusting the pH value of the mixed solution to 8-10.
Adding 1 volume part of tetraethoxysilane into the mixed solution, and stirring and reacting in the constant-temperature water bath kettle at the temperature of 25-50 ℃ for 3-24 hours (preferably 12 hours) to obtain the solid silica microspheres.
In the step, the ethanol and the deionized water are used as solvents, and have the function of regulating and controlling the size of the silicon oxide microspheres, and the particle size of the obtained silicon dioxide microspheres can be controlled to be 100 nm-500 nm by adopting 5-20 parts by volume of absolute ethanol and 3-10 parts by volume of deionized water.
In this step, the ammonia water acts as a catalyst, and can promote the crosslinking of the silicon hydroxyl groups, thereby controlling the density of the silicon spheres.
In the step, the physical factors of the morphology and the surface sulfydryl modification of the synthetic spherical silicon dioxide can be controlled under the condition without a template agent through the combined action of the reaction temperature, the reaction time and the pH value.
(2) Carrying out surface sulfydryl modification on the silicon dioxide solid microspheres to obtain sulfydryl-modified silicon dioxide microspheres
And (2) adding 0.05-0.2 volume part of 3- (mercaptopropyl) triethoxysilane into the system in the step (1), continuing to react for 3-24 hours (preferably 12 hours), and then performing ultrasonic dispersion to obtain the surface mercapto group modified silicon dioxide solid microspheres.
The preparation of the supported FeS nanocrystal is based on that iron ions are combined with-SH on the surface of a silicon dioxide microsphere, and the FeS nanocrystal is further formed by dehydration, namely: the sulfydryl not only provides a sulfur source, but also can induce the iron ions in the solution to be combined and deposited with the sulfydryl on the surface of the silicon dioxide microsphere to form ferrous sulfide seed crystals, and the dispersion degree of the nanocrystals is controlled. No matter the surface of the silica spheres modified by other groups is amino, nitro or other modified groups can only form metal particles, FeS crystals cannot be formed, and the target product cannot be prepared.
In the above steps (1) and (2), the amounts of each of the substances used are preferably: 10 parts by volume of absolute ethyl alcohol, 5 parts by volume of deionized water, 1 part by volume of ammonia water, 1 part by volume of ethyl orthosilicate and 0.1 part by volume of 3- (mercaptopropyl) triethoxysilane.
(3) Ferrous sulfide crystal loaded on surface of sulfydryl modified silicon dioxide microsphere
Dispersing the surface mercapto-modified silica solid microspheres into water under the protection of nitrogen according to the mass ratio of the surface mercapto-modified silica solid microspheres to the water of 1:10 to 1:30, then uniformly mixing the surface mercapto-modified silica solid microspheres and ferrous sulfate solution with the concentration of 1.5 to 15mmol/L (preferably 5mmol/L) according to the mass ratio of the surface mercapto-modified silica solid microspheres to the ferrous sulfate of 5:1 to 10:1 (preferably 8:1) to obtain a solution, then dropwise adding the thioacetamide solution with the concentration of 1.5 to 15mmol/L (preferably 5mmol/L) according to the mass ratio of the ferrous sulfate to the thioacetamide of 1:1 to 1.5:1 (preferably 1.2:1), wherein the dropwise adding speed is 2mL/min for example, stirring and reacting in a water bath at 15 ℃ to 55 ℃ (preferably 35 ℃) for 0.5 to 3 hours (preferably 2 hours), a dispersion was obtained.
And (3) carrying out centrifugal separation on the dispersion liquid at room temperature, washing the obtained solid with water (for example, twice), and drying in a constant-temperature drying oven (for example, 50 ℃) to obtain the silica microsphere surface-supported ferrous sulfide nanocrystalline composite material.
In this step, the amount of the solid silica microspheres with surface mercapto groups modified to ferrous sulfate is limited to 5:1 to 10:1, so that the amount of the ferrous sulfide crystals loaded can be controlled to 6.8 wt% to 26.6 wt%.
In this step, the particle size of the ferrous sulfide nanocrystals can be controlled to 5nm to 15nm by limiting the ratio of the amounts of the ferrous sulfate and thioacetamide to 1:1 to 1.5: 1.
In the step, the physical factors of the loaded ferrous sulfide nanocrystalline can be controlled through the effects of the reaction temperature and the reaction time.
In a third aspect, the invention also provides application of the ferrous sulfide nanocrystalline composite material loaded on the surface of the silica microsphere, such as application in wastewater treatment, polymer degradation and molecular catalysis.
Examples
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
First, the detection method employed in the following examples is explained as follows:
1. taking saturated calomel as a reference electrode, and 0.1-0.5 mol/L H mol of electrolyte solution2SO4And 0.1 to 0.5mol/L of Na2SO4And protecting with nitrogen. And (3) characterizing the anodic polarization potential and the active surface area of the ferrous sulfide nanocrystalline loaded on the surface of the silicon dioxide microsphere by adopting a cyclic voltammetry, wherein the voltage scanning speed range is 1-5 mV/s.
2. And (3) performing thermal stability characterization on the ferrous sulfide nanocrystalline loaded on the surface of the silicon dioxide microsphere by using a thermal analyzer, testing the temperature of oxidative weight loss of the ferrous sulfide nanocrystalline within the range of room temperature to 800 ℃, and controlling the heating rate to be 2-15 ℃/min.
3. Whether the silicon dioxide carrier is a solid sphere or not and the size of the ferrous sulfide nanocrystalline can be determined through a scanning electron microscope or a transmission electron microscope, and space group information such as ferrous sulfide unit cell parameters can be obtained through a high-resolution transmission electron microscope X-ray diffraction mode, or X-ray diffraction characterization is carried out and the space group information is obtained through unit cell fine modification.
Example 1
(1) Mixing 50mL of absolute ethyl alcohol, 15mL of deionized water and 5mL of ammonia water, and stirring for 10min in a constant-temperature water bath kettle at 35 ℃ to uniformly mix all the components; adding 5mL of ethyl orthosilicate into the system, continuously stirring at a constant speed in a constant-temperature water bath kettle at 35 ℃, reacting for 12 hours, adding 0.5mL of 3- (mercaptopropyl) triethoxysilane into the system, and continuously reacting for 12 hours to ultrasonically disperse the surface mercapto-modified silicon dioxide solid microspheres.
(2) Under the protection of nitrogen, dispersing the product obtained in the step (1) into 60mL of water, uniformly mixing with 5mL of 15mmol/L ferrous sulfate solution, dropwise adding 4.2mL of 5mmol/L thioacetamide solution at the speed of 2mL/min, and reacting at 35 ℃ for 2 h.
(3) Centrifuging the obtained dispersion liquid at room temperature at 10000r/min for 5min, washing the separated solid twice, and drying in a constant-temperature drying oven at 50 ℃ to obtain the ferrous sulfide nanocrystalline loaded on the surface of the silicon dioxide microsphere.
The average particle size, unit cell parameters, ferrous sulfide loading capacity, polarization potential difference, oxidation weight loss temperature, CO, of the ferrous sulfide nanocrystal loaded on the surface of the silica microsphere obtained in this example were measured2The results are shown in Table 1.
In addition, a transmission electron microscope image, a high-resolution transmission electron microscope image and an energy dispersion X-ray image of the ferrous sulfide nanocrystal loaded on the surface of the silica microsphere obtained in the present embodiment are taken, and are respectively shown in fig. 1, fig. 2 and fig. 3.
Fig. 1 is a transmission electron microscope picture of ferrous sulfide nanocrystalline loaded on the surface of a silica microsphere, and the result shows that the silica is a solid microsphere and highly dispersed ferrous sulfide is loaded on the surface. Effectively avoids the defect that the nano-grade material is easy to self-agglomerate, and can control the loading capacity and the nano-scale of the ferrous sulfide.
Fig. 2 is a high-resolution transmission electron microscope image of ferrous sulfide nanocrystals loaded on the surface of a silica microsphere, and the result of characterization of the crystal face stripes shows that ferrous sulfide is a nanocrystal, and the crystal material can provide electron transfer efficiency and improve the capabilities of molecular catalysis and energy transfer.
Fig. 3 is an energy dispersion X-ray diagram of the ferrous sulfide nanocrystal loaded on the surface of the silica microsphere, and the result shows that the elemental composition of the synthesized product is consistent with that of the designed ferrous sulfide nanocrystal loaded on the surface of the silica microsphere.
Example 2
(1) Mixing 70mL of absolute ethyl alcohol, 25mL of deionized water and 5mL of ammonia water, and stirring for 10min in a water bath kettle with a constant temperature of 25 ℃ to uniformly mix all the components; adding 5mL of ethyl orthosilicate into the system, continuously stirring at a constant speed in a constant-temperature water bath kettle at 25 ℃, reacting for 24 hours, adding 1mL of 3- (mercaptopropyl) triethoxysilane into the system, and continuously reacting for 24 hours to ultrasonically disperse the surface mercapto-modified silicon dioxide solid microspheres.
(2) Under the protection of nitrogen, dispersing the product obtained in the step (1) into 60mL of water, uniformly mixing with 5mL of 10mmol/L ferrous sulfate solution, dropwise adding 3.3mL of 10mmol/L thioacetamide solution at the speed of 2mL/min, and reacting at 55 ℃ for 0.5 h.
(3) Centrifuging the obtained dispersion liquid at room temperature at 10000r/min for 5min, washing the separated solid twice, and drying in a constant-temperature drying oven at 50 ℃ to obtain the ferrous sulfide nanocrystalline loaded on the surface of the silicon dioxide microsphere.
The average particle size, unit cell parameters, ferrous sulfide loading capacity, polarization potential difference, oxidation weight loss temperature, CO, of the ferrous sulfide nanocrystal loaded on the surface of the silica microsphere obtained in this example were measured2The results are shown in Table 1.
Example 3
(1) Mixing 60mL of absolute ethyl alcohol, 15mL of deionized water and 7mL of ammonia water, and stirring for 10min in a constant-temperature water bath kettle at 40 ℃ to uniformly mix all components; adding 5mL of ethyl orthosilicate into the system, continuously stirring at a constant speed in a constant-temperature water bath kettle at 40 ℃, reacting for 15 hours, adding 0.75mL of 3- (mercaptopropyl) triethoxysilane into the system, continuously reacting for 15 hours, and ultrasonically dispersing the surface mercapto-modified silicon dioxide solid microspheres.
(2) Under the protection of nitrogen, dispersing the product obtained in the step (1) into 60mL of water, uniformly mixing with 5mL of 7mmol/L ferrous sulfate solution, dropwise adding 5mL of 7mmol/L thioacetamide solution at the speed of 2mL/min, and reacting for 3h at 35 ℃.
(3) Centrifuging the obtained dispersion liquid at room temperature at 10000r/min for 5min, washing the separated solid twice, and drying in a constant-temperature drying oven at 50 ℃ to obtain the ferrous sulfide nanocrystalline loaded on the surface of the silicon dioxide microsphere.
The average particle diameter, unit cell parameters and ferrous sulfide of the ferrous sulfide nanocrystal loaded on the surface of the silica microsphere obtained in the example were measuredLoad capacity, polarization potential difference, oxidation weight loss temperature, CO2The results are shown in Table 1.
Example 4
(1) Mixing 90mL of absolute ethyl alcohol, 20mL of deionized water and 3mL of ammonia water, and stirring for 10min in a constant-temperature water bath kettle at 45 ℃ to uniformly mix all components; adding 5mL of ethyl orthosilicate into the system, continuously stirring at a constant speed in a constant-temperature water bath kettle at 45 ℃, reacting for 3 hours, adding 0.25mL of 3- (mercaptopropyl) triethoxysilane into the system, and continuously reacting for 3 hours to ultrasonically disperse the surface mercapto-modified silicon dioxide solid microspheres.
(2) Under the protection of nitrogen, dispersing the product obtained in the step (1) into 60mL of water, uniformly mixing with 5mL of 2.5mmol/L ferrous sulfate solution, dropwise adding 5mL of 2.5mmol/L thioacetamide solution at the speed of 2mL/min, and reacting for 2h at 35 ℃.
(3) Centrifuging the obtained dispersion liquid at room temperature at 10000r/min for 5min, washing the separated solid twice, and drying in a constant-temperature drying oven at 50 ℃ to obtain the ferrous sulfide nanocrystalline loaded on the surface of the silicon dioxide microsphere.
The average particle size, unit cell parameters, ferrous sulfide loading capacity, polarization potential difference, oxidation weight loss temperature, CO, of the ferrous sulfide nanocrystal loaded on the surface of the silica microsphere obtained in this example were measured2The results are shown in Table 1.
TABLE 1
The data in table 1 prove that the controllable synthesis and preparation of the ferrous sulfide nanocrystal loaded on the surface of the silica microsphere can improve the electron transfer efficiency of the material and improve the molecular catalytic ability and thermal stability through the nanocrystal size effect.
In addition, the inventor also researches the rule between the size effect and the electrochemical active surface area of the ferrous sulfide nanocrystal, and the specific result is shown in fig. 4. As can be seen from fig. 4, as the size of the ferrous sulfide nanocrystal is gradually reduced, the active area thereof is gradually increased, and the catalytic efficiency is also gradually increased.
Further, it can be seen from the data in table 1 and fig. 4 that the preparation method of the present invention can obtain ferrous sulfide nanocrystals with a particle size of at least 5nm and an electrochemical active surface area of 120m2Has extremely high reaction activity per gram.
The above examples are intended to be merely illustrative of the preferred embodiments of the present invention and not restrictive thereof. In practice, many modifications and variations are possible in light of the above teaching, but it is not necessary or necessary to exhaustively enumerate all embodiments. All changes and modifications that come within the spirit of the invention are desired to be protected by the following claims.
Claims (10)
1. The composite material is characterized by comprising a silicon dioxide microsphere carrier and ferrous sulfide crystals loaded on the silicon dioxide microsphere carrier; the silicon dioxide microsphere carrier is a solid sphere with the particle size of 100 nm-500 nm; the ferrous sulfide crystals are uniformly distributed on the surface of the silicon dioxide microsphere carrier, and the particle size is 5-15 nm.
2. The silica microsphere surface-supported ferrous sulfide nanocrystalline composite according to claim 1, characterized in that the ferrous sulfide crystals belong to orthorhombic system, Pmnn space group, and the unit cell parameters are: a is not equal to b is not equal to c,
5.388≤c≤5.407。
3. the silica microsphere surface-supported ferrous sulfide nanocrystalline composite according to claim 1, wherein the supported amount of the ferrous sulfide crystals is 6.8 wt% to 26.6 wt%.
4. Silica according to claim 1The composite material with ferrous sulfide nanocrystalline loaded on the surface of the microsphere is characterized in that the redox polarization potential difference of the ferrous sulfide nanocrystalline is 0.2V-0.5V, the oxidation weight loss temperature is 650-680 ℃, and CO is catalyzed by molecules2The conversion rate of (A) is 78.1% -86.5%.
5. The preparation method of the silica microsphere surface-supported ferrous sulfide nanocrystalline composite material according to any one of claims 1 to 4, characterized by comprising the following steps:
(1) preparing solid silica microspheres without a template;
(2) carrying out surface sulfydryl modification on the silicon dioxide solid microspheres to obtain sulfydryl modified silicon dioxide microspheres;
(3) and loading ferrous sulfide crystals on the surface of the mercapto-modified silica microspheres.
6. The method of claim 5, wherein in step (1), the silica solid microspheres are prepared by the following method:
uniformly mixing 5-20 parts by volume of absolute ethyl alcohol, 3-10 parts by volume of deionized water and 0.5-2 parts by volume of ammonia water at 25-50 ℃ to obtain a mixed solution, and adjusting the pH value of the mixed solution to 8-10;
adding 1 volume part of tetraethoxysilane into the mixed solution, and reacting at 25-50 ℃ to obtain the silicon dioxide microspheres.
7. The method of claim 5, wherein in the step (2), the silica microspheres are surface-mercapto-modified with 3- (mercaptopropyl) triethoxysilane.
8. The preparation method according to claim 5, wherein in the step (3), the ferrous sulfide crystals are loaded on the surface of the mercapto-modified silica microspheres by the following method:
dispersing mercapto-modified silicon dioxide microspheres in water, uniformly mixing with a ferrous sulfate solution, dropwise adding thioacetamide into the mixture, and reacting at 15-55 ℃ to obtain a dispersion liquid;
and carrying out centrifugal separation, washing and drying on the dispersion liquid to obtain the silicon dioxide microsphere surface-supported ferrous sulfide nanocrystalline composite material.
9. The production method according to claim 8, wherein the mass ratio of the mercapto-modified silica microspheres to water is 1:10 to 1: 30; the mass ratio of the mercapto-modified silica microspheres to the ferrous sulfate is 5:1 to 10: 1; the ratio of the amount of ferrous sulfate to the amount of thioacetamide is 1:1 to 1.5: 1.
10. Use of the silica microsphere surface-supported ferrous sulfide nanocrystalline composite material according to any one of claims 1 to 4 in wastewater treatment, polymer degradation and molecular catalysis.
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