CN113385193A - CdZnS ultrafine nanoparticle loaded In2O3Spindle-shaped nanorod composite material and preparation method and application thereof - Google Patents
CdZnS ultrafine nanoparticle loaded In2O3Spindle-shaped nanorod composite material and preparation method and application thereof Download PDFInfo
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- 239000002073 nanorod Substances 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 50
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 7
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 31
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000011941 photocatalyst Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000031700 light absorption Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 27
- 238000001228 spectrum Methods 0.000 description 15
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000004098 selected area electron diffraction Methods 0.000 description 7
- 239000012621 metal-organic framework Substances 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000009210 therapy by ultrasound 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
- 239000013216 MIL-68 Substances 0.000 description 1
- 238000001255 X-ray photoelectron diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000013346 indium-based metal-organic framework Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- B01J35/23—
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- B01J35/39—
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- B01J35/647—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J37/20—Sulfiding
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- 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
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- 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
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Abstract
The invention belongs to the technical field of photocatalyst material preparation, and relates to In loaded with CdZnS ultrafine nanoparticles2O3A fusiform nano rod composite material and a preparation method and application thereof. The invention loads CdZnS superfine nano particles on the fusiform mesoporous In2O3The heterogeneous optical composite material for catalytic hydrogen production prepared on the nanorod can be stably applied to photocatalytic water decomposition hydrogen production, solves the problem of instability of CdZnS under the phenomenon of photo-corrosion in the photocatalytic process, and widens the application rangeThe light absorption range of the photocatalytic material is widened, and the catalytic hydrogen production efficiency is greatly enhanced. The invention has simple integral preparation process, easy control of reaction, good repeatability and high industrial production value.
Description
Technical Field
The invention belongs to the technical field of photocatalyst material preparation, and relates to In loaded with CdZnS ultrafine nanoparticles2O3A fusiform nano rod composite material and a preparation method and application thereof.
Background
With the rapid development of economy, the energy crisis is getting worse, and the development of clean renewable resources is urgent to better achieve the goals of "carbon peak reaching" and "carbon neutralization". Hydrogen energy is used as a pollution-free high-heat energy source, solar energy is an inexhaustible natural resource, and the solar energy is used for decomposing water to generate clean and high-value hydrogen, so that the hydrogen energy is always considered to be one of the most promising strategies for producing renewable clean energy sources in a sustainable mode for a long time. Generally, such photocatalytic water splitting processes require efficient and economical photocatalysts.
Indium oxide (In)2O3) The photocatalyst is an n-type semiconductor photocatalyst with a relatively narrow band gap, and has attracted wide attention in photocatalytic application due to excellent conductivity, thermodynamic stability and visible light responsiveness. However, ordinary In2O3Since the photocatalyst has a small specific surface area, a limited visible light capturing ability, and a high charge recombination efficiency, the photocatalytic efficiency of the photocatalyst is still poor, and many attempts have been made to improve the photocatalytic activity of indium oxide in order to overcome these disadvantages. It is generally accepted that In is derived from Metal Organic Frameworks (MOFs)2O3The high specific surface area and the porous framework structure of the MOFs can be completely reserved, and a large number of reaction sites are provided for photocatalytic reaction, so that the photocatalytic activity is improved.
Porous In derived by MOFs2O3Not only is the In obviously widened by compounding with the narrow-band-gap semiconductor2O3The visible light absorption range also obviously improves the separation and transmission of photo-generated electron hole pairs, thereby obviously improving the photocatalytic activity, but the currently reported MOFs-derived photocatalyst is often fragile in photocatalytic reactionAnd is unstable.
Disclosure of Invention
The invention aims to solve the problems In the prior art and provides the CdZnS ultrafine nanoparticle-loaded In with high efficiency and stability2O3A fusiform nano rod composite material and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
CdZnS ultrafine nanoparticle loaded In2O3The spindle-shaped nanorod composite material is prepared by loading CdZnS In spindle-shaped mesoporous In the form of ultrafine nanoparticles2O3A heterostructure is formed on the nanorod, and the loading capacity of the CdZnS ultrafine nanoparticles is 5-10 wt%.
The CdZnS can be used as one of the most promising metal sulfides in photocatalytic water decomposition due to a wider light absorption range and remarkable photocatalytic activity, but the application of the CdZnS in photocatalysis is limited due to instability of the photocatalyst caused by a photo-corrosion phenomenon in a photocatalytic process. In derived from MOFs2O3The formed holes are taken as objects and are compounded with CdZnS ultrafine nanoparticles In situ, so that trace CdZnS nanoparticles and mesoporous spindle-shaped In are passed2O3The nanorod is compounded to form a heterostructure, so that the photocatalytic activity is greatly improved, and the instability of CdZnS caused by a photo-corrosion phenomenon in the photocatalytic process is solved.
In loaded on the CdZnS ultrafine nano-particles2O3In the spindle-shaped nanorod composite material, the particle size of CdZnS ultrafine nanoparticles is 3-8 nm. When the particle size of the CdZnS ultrafine nano-particles is 3-8nm, the active sites of catalytic reaction can be obviously increased.
In loaded on the CdZnS ultrafine nano-particles2O3In the spindle-shaped nanorod composite material, spindle-shaped mesoporous In2O3The diameter of the nano rod is 0.5-1.5 μm, and the aperture is 8-15 nm. The uniform size of the nano rods and the mesopores can fully increase the active sites and the stability of the catalytic reaction.
The invention also relates toProvides In loaded by CdZnS ultrafine nano particles2O3The preparation method of the fusiform nanorod composite material comprises the following steps:
s1, dissolving indium nitrate and 2-amino terephthalic acid In a reaction bottle to react In an oil bath, taking out the solution, cleaning the solution with ethanol, centrifugally drying the solution, placing the solution In a muffle furnace, and calcining the solution In an air atmosphere to obtain the fusiform mesoporous In2O3A nanorod;
s2 preparation of fusiform mesoporous In2O3Mixing the nano-rods with cadmium acetate and zinc acetate, adding deionized water for soaking, adding sodium sulfide, reacting In an oil bath, taking out, cleaning with ethanol, and centrifugally drying to obtain In2O3CdZnS heterogeneous composite material.
Preferably, the oil bath reaction temperature of the step S1 is 110-130 ℃, and the time is 0.3-0.8 h.
Preferably, the calcination temperature of the step S1 is 480-550 ℃ under the air atmosphere.
Preferably, the oil bath reaction temperature of the step S2 is 70-90 ℃ and the time is 0.3-0.8 h.
In loaded on the CdZnS ultrafine nano-particles2O3In the preparation method of the spindle-shaped nanorod composite material, the mass ratio of indium nitrate to 2-amino terephthalic acid in the step S1 is 1: (1-1.2). By better controlling the proportion, the uniform In-MOF spindle-shaped nanorod structure is favorably formed.
In loaded on the CdZnS ultrafine nano-particles2O3In the preparation method of the fusiform nanorod composite material, the zinc acetate, the cadmium acetate and the fusiform mesoporous In added In the step S22O3The mass ratio of the nano rods is 1: (2-3): (4-6).
Cadmium ions are more than zinc ions, so that the photocatalytic hydrogen production activity of the final heterogeneous composite material is stronger; the addition of sodium sulfide is too little to generate CdZnS, the addition of sodium sulfide is too much to influence the whole reaction, and the redundant addition can be cleaned subsequently, but can cause the waste of raw materials.
In loaded on the CdZnS ultrafine nano-particles2O3In the preparation method of the fusiform nanorod composite material, the sodium sulfide and the fusiform mesoporous In added In the step S22O3The mass ratio of the nano rods is 1: (1.5-2).
The invention also provides In loaded by CdZnS ultrafine nanoparticles2O3The application of the fusiform nanorod composite material specifically comprises the following steps: ultrasonically dispersing the heterogeneous composite material in deionized water, adding a sacrificial agent, and catalyzing to produce hydrogen under the irradiation of a visible light source.
The heterogeneous composite material of the invention is irradiated by visible light due to In2O3And CdZnS, both of which can efficiently generate electron-hole pairs from In2O3The valence band of CdZnS is transferred to the valence band of CdZnS, and electrons are rapidly transferred from the conduction band of CdZnS to In2O3Thereby forming a type II heterojunction. Subsequently, In2O3The electrons at the conduction band reduce water to produce hydrogen, and the holes at the valence band of CdZnS are trapped by the sacrificial agent. Therefore, In2O3The compound with CdZnS can effectively accelerate the space transmission of photoexcited electrons and holes, so that more electrons can participate in the process of photocatalytic hydrogen production.
In loaded on the CdZnS ultrafine nano-particles2O3In the application of the spindle-shaped nanorod composite material, the sacrificial agent is prepared from the following components in a mass ratio of 1: sodium sulfide and sodium sulfite of (2-3). The photogenerated holes are captured by the added sacrificial agent.
In loaded on the CdZnS ultrafine nano-particles2O3In the application of the spindle-shaped nanorod composite material, the wavelength of the visible light source is more than or equal to 420 nm. The invention is characterized in that the light absorption range of the photocatalyst material is widened, and the photocatalytic performance is explored through the visible light wavelength being more than or equal to 420nm, so that the advantages and disadvantages of the widened photocatalytic performance can be clearly known.
Compared with the prior art, the invention has the following beneficial effects: the invention loads CdZnS superfine nano particles on the fusiform mesoporous In2O3Heterogeneous optical composite material prepared on nanorod and used for catalytic hydrogen productionThe method can be stably applied to hydrogen production by water decomposition through photocatalysis, solves the problem of instability of CdZnS under the phenomenon of photo-corrosion in the photocatalysis process, widens the light absorption range of the photocatalysis material, and greatly enhances the catalytic hydrogen production efficiency. The invention has simple integral preparation process, easy control of reaction, good repeatability and high industrial production value.
Drawings
FIG. 1 shows fusiform mesoporous In prepared In example 12O3Scanning Electron Microscope (SEM) image of the nanorods;
FIG. 2 shows the fusiform mesoporous In prepared In example 12O3Nanorod X-ray diffraction (XRD) pattern;
FIG. 3 shows In obtained In example 12O3A low-power Scanning Electron Microscope (SEM) image of the/CdZnS heterogeneous composite material;
FIG. 4 shows In obtained In example 12O3A high-power Scanning Electron Microscope (SEM) image of the/CdZnS heterogeneous composite material;
FIG. 5 shows In obtained In example 12O3X-ray diffraction (XRD) pattern of CdZnS heterocomposite;
FIG. 6 shows In obtained In example 12O3A low-power Transmission Electron Microscope (TEM) image of the/CdZnS heterogeneous composite material;
FIG. 7 shows In obtained In example 12O3A selective electron diffraction (SAED) pattern of/CdZnS heterogeneous composite material;
FIG. 8 shows In obtained In example 12O3a/CdZnS heterogeneous composite material High Resolution Transmission Electron Microscopy (HRTEM) image;
FIG. 9 shows In obtained In example 12O3High Resolution Transmission Electron Microscopy (HRTEM) image of CdZnS hetero-composite material magnification;
FIG. 10 shows In obtained In example 12O3CdZnS heterocomposite material energy spectrum diffraction spectrum (EDS);
FIG. 11 shows In obtained In example 12O3The surface scanning energy spectrum of the/CdZnS heterogeneous composite material;
FIG. 12 shows In obtained In example 12O3CdZnS iso-isomerA nitrogen desorption-adsorption curve and a pore size distribution curve of the composite material;
FIG. 13 shows In obtained In example 12O3CdZnS heterocomposite X-ray diffraction (XPS) spectra;
FIG. 14 shows fusiform mesoporous In prepared In comparative example 12O3Scanning Electron Microscope (SEM) image of nanorods;
FIG. 15 shows fusiform mesoporous In prepared In comparative example 12O3High power Scanning Electron Microscope (SEM) picture of nano-rod;
FIG. 16 shows fusiform mesoporous In prepared In comparative example 12O3Nanorod X-ray diffraction (XRD) pattern;
FIG. 17 shows fusiform mesoporous In prepared In comparative example 12O3Low power Transmission Electron Microscope (TEM) image of nanorods;
FIG. 18 shows fusiform mesoporous In prepared In comparative example 12O3A nanorod Selected Area Electron Diffraction (SAED) pattern;
FIG. 19 shows fusiform mesoporous In prepared In comparative example 12O3Nanorod high-resolution transmission electron microscopy (HRTEM) images;
FIG. 20 shows a fusiform mesoporous In prepared In comparative example 12O3A High Resolution Transmission Electron Microscopy (HRTEM) image of nanorod magnification;
FIG. 21 shows a fusiform mesoporous In prepared In comparative example 12O3Nanorod energy spectrum diffraction pattern (EDS);
FIG. 22 shows fusiform mesoporous In prepared In comparative example 12O3A nanorod nitrogen desorption-adsorption curve and a pore size distribution curve;
FIG. 23 shows fusiform mesoporous In prepared In comparative example 12O3Nanorod X-ray diffraction (XPS) spectra;
FIG. 24 is a graph comparing the photocatalytic hydrogen production of application example 1 and application comparative example 1;
fig. 25 is a graph comparing the photocatalytic hydrogen production rates of application example 1 and application comparative example 1.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example 1:
s1, dissolving 60mg of indium nitrate and 65mg of 2-amino terephthalic acid In a reaction bottle, reacting for 0.5h under the condition of oil bath at 120 ℃, taking out, cleaning once with ethanol, centrifugally drying, then placing In a muffle furnace, and calcining at 500 ℃ In air atmosphere to obtain the fusiform mesoporous In2O3A nanorod;
s2, collecting 20mg of fusiform mesoporous In2O3Mixing the nano-rods with 10mg of cadmium acetate and 4.4mg of zinc acetate, then adding 5ml of deionized water for soaking, then adding 20mg of sodium sulfide, reacting for 2 hours at 80 ℃ In an oil bath, taking out, cleaning with ethanol once, and centrifugally drying to obtain In2O3CdZnS heterogeneous composite material, CdZnS superfine nano particle load is 5 wt%, average particle diameter is 5nm, fusiform mesoporous In2O3The average diameter of the nano-rod is 1 μm, and the average pore diameter is 15 nm.
Example 2:
s1, dissolving 60mg of indium nitrate and 65mg of 2-amino terephthalic acid In a reaction bottle, reacting for 0.5h under the condition of oil bath at 120 ℃, taking out, cleaning once with ethanol, centrifugally drying, then placing In a muffle furnace, and calcining at 500 ℃ In air atmosphere to obtain the fusiform mesoporous In2O3A nanorod;
s2, collecting 20mg of fusiform mesoporous In2O3Mixing the nano-rods with 15mg of cadmium acetate and 8mg of zinc acetate, then adding 5ml of deionized water for soaking, then adding 20mg of sodium sulfide, reacting for 2 hours under 80 ℃ oil bath, taking out, cleaning with ethanol once, and centrifugally drying to obtain In2O3CdZnS heterogeneous composite material, CdZnS ultrafine nanoparticle loading capacity is 8 wt%, average particle size is 5nm, fusiform mesoporous In2O3The average diameter of the nano-rod is 1 μm, and the average pore diameter is 15 nm.
Example 3:
s1, dissolving 60mg of indium nitrate and 65mg of 2-amino terephthalic acid In a reaction bottle, reacting for 0.5h under the condition of oil bath at 120 ℃, taking out, cleaning once with ethanol, centrifugally drying, then placing In a muffle furnace, and calcining at 500 ℃ In air atmosphere to obtain the fusiform mesoporous In2O3A nanorod;
s2, collecting 20mg of fusiform mesoporous In2O3Mixing the nano-rods with 18mg of cadmium acetate and 10mg of zinc acetate, then adding 5ml of deionized water for soaking, then adding 20mg of sodium sulfide, reacting for 2 hours under 80 ℃ oil bath, taking out, cleaning with ethanol once, and centrifugally drying to obtain In2O3CdZnS heterogeneous composite material, the CdZnS ultrafine nanoparticle loading is 10 wt%, the average particle diameter is 5nm, and fusiform mesoporous In2O3The average diameter of the nano-rod is 1 μm, and the average pore diameter is 15 nm.
Application example 1:
0.008g of In obtained In example 1 was weighed2O3the/CdZnS heterogeneous composite material is dispersed in 100mL of deionized water, subjected to ultrasonic treatment for 10min, added with 8.4063g of sodium sulfide and 3.151g of sodium sulfite as sacrificial agents, and then placed in a photocatalytic hydrogen production vacuum system. A300W xenon lamp is used as a simulated solar light source, a cut-off filter (more than or equal to 420nm) is added, and the hydrogen yield of the sample under different illumination time is tested by a gas chromatograph.
Comparative example 1:
the difference from the example 1 is only that the material does not contain CdZnS nano-particles and is only fusiform mesoporous In2O3Nanorod, fusiform mesoporous In2O3The average diameter of the nano-rod is 1 μm, and the average pore diameter is 15 nm.
Application comparative example 1:
0.008g of shuttle-shaped mesoporous In obtained In comparative example 1 was weighed2O3Dispersing the nanorod material in 100mL of deionized water, performing ultrasonic treatment for 10min, adding 8.4063g of sodium sulfide and 3.151g of sodium sulfite as sacrificial agents, and then placing the sacrificial agents in a photocatalytic hydrogen production vacuum system. A300W xenon lamp is used as a simulated solar light source, a cut-off filter (more than or equal to 420nm) is added, and the hydrogen yield of the sample under different illumination time is tested by a gas chromatograph.
FIG. 1 shows fusiform mesoporous In prepared In example 12O3Scanning Electron Microscope (SEM) image of nanorods illustrating In prepared by the invention2O3Has obvious spindle-shaped nanorod structure;
FIG. 2 shows the fusiform mesoporous In prepared In example 12O3The nano-rod X-ray diffraction (XRD) spectrum shows that the fusiform mesoporous In prepared by the invention2O3The nano-rod material is MIL-68 (In);
FIG. 3 is a Scanning Electron Microscope (SEM) image of the material prepared in example 1, which illustrates that the material prepared by the present invention has a uniform spindle-shaped nanorod structure;
FIG. 4 is a high-power Scanning Electron Microscope (SEM) image of the material prepared in example 1, which illustrates that the nanorod prepared in the invention has a diameter of about 1 micron;
FIG. 5 is an X-ray diffraction (XRD) pattern of the material prepared in example 1, illustrating that the material prepared in the present invention does not have significant CdZnS recombination;
FIG. 6 is a low-power Transmission Electron Microscope (TEM) image of the material prepared in example 1, which illustrates that the material prepared by the present invention has a typical spindle-shaped nanorod structure;
FIG. 7 is a Selected Area Electron Diffraction (SAED) diagram of the material prepared In example 1, illustrating that the material prepared In the present invention is mainly In2O3A spindle-shaped nanorod;
FIG. 8 is a High Resolution Transmission Electron Microscope (HRTEM) image of the material prepared in example 1, which shows that the material prepared by the present invention has good crystallinity;
FIG. 9 is a High Resolution Transmission Electron Microscopy (HRTEM) image at magnification of the material prepared In example 1, illustrating that the material prepared In the present invention is In2O3CdZnS composite material;
FIG. 10 is an energy spectrum diffraction (EDS) spectrum of the material prepared In example 1, which is detected to contain In, O, Cd, Zn and S elements, fully illustrating that the material prepared by the present invention is In2O3A composite material with CdZnS, and a CdZnS loading of about 5 wt%;
FIG. 11 is a scanning energy spectrum of the material prepared In example 1, again illustrating In, O, Cd, Zn and S elements prepared In2O3The CdZnS heterojunction material is uniformly distributed;
FIG. 12 is a nitrogen desorption-adsorption curve and a pore size distribution curve of the material prepared in example 1, which illustrate that the material prepared by the present invention is a typical mesoporous material;
FIG. 13 is an X-ray photoelectron diffraction (XPS) spectrum of the material prepared In example 1, which was detected to contain mainly In, O, Cd, Zn and S elements, further illustrating that the material prepared was In2O3CdZnS composite material;
FIG. 14 shows fusiform mesoporous In prepared In comparative example 12O3The low-power Scanning Electron Microscope (SEM) image of the nano-rods shows that the prepared material has a fusiform nano-rod structure with uniform size.
FIG. 15 shows fusiform mesoporous In prepared In comparative example 12O3A high power Scanning Electron Microscope (SEM) image of the nanorods, illustrating that the diameter of the prepared nanorods is about 1 micron;
FIG. 16 shows fusiform mesoporous In prepared In comparative example 12O3The nanorod X-ray diffraction (XRD) spectrum shows that the prepared material is In2O3；
FIG. 17 shows fusiform mesoporous In prepared In comparative example 12O3A nanorod low-power Transmission Electron Microscope (TEM) image, which shows that the prepared material has a typical spindle-shaped nanorod structure;
FIG. 18 shows fusiform mesoporous In prepared In comparative example 12O3Nanorod Selected Area Electron Diffraction (SAED) pattern, which illustrates that the prepared material is In2O3A material;
FIG. 19 shows fusiform mesoporous In prepared In comparative example 12O3A nanorod high-resolution transmission electron microscope (HRTEM) image shows that the prepared material has good crystallinity;
FIG. 20 shows a fusiform mesoporous In prepared In comparative example 12O3High Resolution Transmission Electron Microscopy (HRTEM) image of nanorod magnification, again indicating that the prepared material is In2O3A material;
FIG. 21 shows a fusiform mesoporous In prepared In comparative example 12O3The nanorod energy spectrum diffraction spectrum (EDS) detects that the material mainly contains In and O elements, and the prepared material is In2O3A material;
FIG. 22 shows fusiform mesoporous In prepared In comparative example 12O3Nanorod nitrogen gasA desorption-adsorption curve and a pore size distribution curve, which indicate that the prepared material is a typical mesoporous material;
FIG. 23 shows fusiform mesoporous In prepared In comparative example 12O3The nanorod X-ray diffraction (XPS) spectrum detects that the material mainly contains In and O elements, and further indicates that the prepared material is In2O3A material;
FIG. 24 is a comparison graph of photocatalytic hydrogen production using example 1 and comparative example 1, and the results show that In prepared by the present invention2O3Pure In ratio when/CdZnS heterogeneous composite material is used as photocatalyst2O3The material has obviously improved visible light catalytic hydrogen production performance, and the hydrogen production amount can reach 5550 mu mol g after 5 hours of visible light illumination-1And pure In2O3The material is only 30 mu mol g-1。
FIG. 25 is a graph comparing the photocatalytic hydrogen production rates of application example 1 and application comparative example 1, and the results show that In prepared by the present invention2O3CdZnS hetero-composite material used as photocatalyst is In comparison with pure In2O3The material can obviously improve the photocatalytic hydrogen production rate which can reach 1110 mu mol g-1·h-1And In2O3Material only 6. mu. mol. g-1·h-1。
From the above results, it can be seen that the invention loads CdZnS ultrafine nanoparticles on the fusiform mesoporous In2O3The heterogeneous optical composite material for catalytic hydrogen production prepared on the nano-rods can be effectively applied to photocatalytic water decomposition hydrogen production, and the catalytic hydrogen production has high efficiency and stability. And the preparation process is simple, the reaction is easy to control, the repeatability is good, and the industrial production value is high.
The technical scope of the invention claimed by the embodiments of the present application is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed by the present application; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (10)
1. CdZnS ultrafine nanoparticle loaded In2O3The spindle-shaped nanorod composite material is characterized In that CdZnS is loaded on spindle-shaped mesoporous In the form of ultrafine nanoparticles2O3A heterostructure is formed on the nanorod, and the loading capacity of the CdZnS ultrafine nanoparticles is 5-10 wt%.
2. The CdZnS ultrafine nanoparticle supported In according to claim 12O3The spindle-shaped nanorod composite material is characterized in that the particle size of CdZnS ultrafine nanoparticles is 3-8 nm.
3. The CdZnS ultrafine nanoparticle supported In according to claim 12O3The fusiform nano rod composite material is characterized In that fusiform mesoporous In2O3The diameter of the nano rod is 0.5-1.5 μm, and the aperture is 8-15 nm.
4. The CdZnS ultrafine nanoparticle-supported In according to claim 12O3The preparation method of the fusiform nanorod composite material is characterized by comprising the following steps of:
s1, dissolving indium nitrate and 2-amino terephthalic acid In a reaction bottle to react In an oil bath, taking out the solution, cleaning the solution with ethanol, centrifugally drying the solution, placing the solution In a muffle furnace, and calcining the solution In an air atmosphere to obtain the fusiform mesoporous In2O3A nanorod;
s2 preparation of fusiform mesoporous In2O3Mixing the nano-rods with cadmium acetate and zinc acetate, adding deionized water for soaking, adding sodium sulfide, reacting In an oil bath, taking out, cleaning with ethanol, and centrifugally drying to obtain In2O3CdZnS heterogeneous composite material.
5. The CdZnS ultrafine nanoparticle supported In according to claim 42O3The preparation method of the fusiform nanorod composite material is characterized in that the mass ratio of the indium nitrate added in the step S1 to the 2-amino terephthalic acid is 1: (1-1.2).
6. The CdZnS ultrafine nanoparticle supported In according to claim 42O3The preparation method of the fusiform nanorod composite material is characterized In that zinc acetate, cadmium acetate and fusiform mesoporous In added In the step S22O3The mass ratio of the nano rods is 1: (2-3): (4-6).
7. The CdZnS ultrafine nanoparticle supported In according to claim 42O3The preparation method of the fusiform nanorod composite material is characterized In that the sodium sulfide and the fusiform mesoporous In added In the step S22O3The mass ratio of the nano rods is 1: (1.5-2).
8. The CdZnS ultrafine nanoparticle-supported In according to claim 12O3Spindle-shaped nano rod composite materialThe application of the material is characterized by comprising the following specific steps: ultrasonically dispersing the heterogeneous composite material in deionized water, adding a sacrificial agent, and catalyzing to produce hydrogen under the irradiation of a visible light source.
9. The CdZnS ultrafine nanoparticle supported In according to claim 82O3The application of the fusiform nanorod composite material is characterized in that the sacrificial agent is a mixture of a sacrificial agent and a metal oxide, wherein the sacrificial agent is prepared from the following components in a mass ratio of 1: sodium sulfite and sodium sulfide of (2-3).
10. The CdZnS ultrafine nanoparticle supported In according to claim 82O3The application of the fusiform nanorod composite material is characterized in that the wavelength of a visible light source is more than or equal to 420 nm.
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