CN116474801A - Core-shell structure Co 2 P/Cd x Zn 1-x Synthesis method of S-micron sphere and photocatalytic hydrogen production application thereof - Google Patents
Core-shell structure Co 2 P/Cd x Zn 1-x Synthesis method of S-micron sphere and photocatalytic hydrogen production application thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 25
- 239000001257 hydrogen Substances 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000011258 core-shell material Substances 0.000 title claims description 9
- 230000001699 photocatalysis Effects 0.000 title abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004005 microsphere Substances 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 239000013256 coordination polymer Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002086 nanomaterial Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 7
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract description 3
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- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 235000019445 benzyl alcohol Nutrition 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
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- 238000012512 characterization method Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 210000004690 animal fin Anatomy 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
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- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1252—Cyclic or aromatic hydrocarbons
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a shell-core structure Co 2 P/Cd x Zn 1‑x Synthesis method of S-micron sphere and application thereof in photocatalytic hydrogen production by Cd x Zn 1‑x S is a core, and Co is prepared by adopting a self-assembly method 2 P load to Cd x Zn 1‑x S surface. The invention is in Cd x Zn 1‑x S catalyst surface builds Co 2 P protective layer by Co 2 Co-catalysis of P layer and Co 2 P and Cd x Zn 1‑x Electrostatic action of S, co 2 P/Cd x Zn 1‑x S microspheres exhibit a higher Pt/Cd ratio x Zn 1‑x S has better photocatalytic water splitting activity and anti-corrosion performance, and the charge separation efficiency of the catalyst is also enhanced.
Description
Technical Field
The invention relates to the technical field of surface regulation and photocatalysis of nano materials, in particular to a shape-controllable Co with a shell-core structure 2 P/Cd x Zn 1-x Preparation method of S-micron spheres and application of S-micron spheres in field of energy photocatalysis。
Background
In recent decades, research for finding new energy has been receiving more and more attention as global energy demand continues to increase. The hydrogen energy, which is a secondary energy source, has the advantages of cleanness, high efficiency, safety, storability, transportation and the like, is widely regarded as an ideal pollution-free green energy source in the new century, and is therefore highly valued in various countries. The photolytic hydrogen production is the best way for solar photochemical conversion and storage. Early studies showed that Cd x Zn 1-x The S photocatalyst has good visible light absorption characteristic and excellent photocatalytic hydrogen production activity, and the performance of the S photocatalyst can be even comparable to that of a catalyst carrying noble metals. However, this catalyst may undergo some photo-corrosion phenomenon during the reaction, resulting in the destruction of the catalyst structure itself. The cocatalyst itself has little or no activity, but can change part of the properties of the catalyst, and is an effective way to improve the activity, selectivity, stability and other properties of the catalyst. Commonly used hydrogen evolution promoters are Co-based, ni-based, mo-based, and the like. The P is added into the Co-based catalyst to form a doped Co-P catalyst, and the surface of the catalyst has more coordination unsaturated bonds due to the phosphating effect, so that reactant molecules are easy to adsorb, and the catalyst has a very high catalytic effect when used as a catalyst. Therefore, the transition metal phosphide is introduced to be used as a catalyst promoter for preparing hydrogen by photocatalytic water splitting, a hydrogen preparation system capable of replacing noble metal catalyst promoter is expected to be obtained, and the cost of large-scale photocatalytic water splitting hydrogen preparation is reduced.
Disclosure of Invention
Aiming at the corrosion phenomenon of the existing metal sulfide, the invention provides a Co with a shell-core structure 2 P/Cd x Zn 1-x The synthesis method of S micrometer sphere and the application of the S micrometer sphere in the photocatalysis hydrogen production, the technical problem to be solved is that the method is characterized in that the method comprises the following steps of x Zn 1-x And growing a thin oxide layer on the surface of the S material to protect the S material so as to construct the efficient and stable composite material.
In order to solve the problems in the prior art, the invention adopts the following technical scheme:
core-shell structure Co 2 P/Cd x Zn 1-x The synthesis method of the S-micrometer sphere is characterized in that: co is self-assembled 2 P load to Cd x Zn 1-x The surface of the S microsphere. The method specifically comprises the following steps:
step 1, cd x Zn 1-x Preparation of S-microspheres
Cd (NO) 3 ) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 O is dissolved in deionized water, and then deionized water solution containing thioacetamide is added dropwise, and the mixture is stirred for 30min; the resulting mixed solution was transferred to a 100mL polytetrafluoroethylene-lined stainless steel autoclave and heated at 160 ℃ for 12 hours; naturally cooling the autoclave to room temperature, centrifugally collecting precipitate, washing with distilled water and ethanol in sequence, and vacuum drying to obtain Cd x Zn 1-x S-microspheres.
Step 2, co 2 Preparation of P nanomaterial
NaBH is carried out 4 Slowly add to dissolve CoCl 2 ·6H 2 O and NaH 2 PO 2 Stirring for 20min, transferring the resulting purple mixed solution into a 100mL stainless steel autoclave lined with polytetrafluoroethylene, and heating at 160 ℃ for 24 hours; naturally cooling the autoclave to room temperature, centrifugally collecting black precipitate, washing with distilled water and ethanol in sequence to obtain Co 2 P nanomaterial.
Step 3, shell-core structure Co 2 P/Cd x Zn 1-x Preparation of S-microspheres
Adding Co obtained in the step 2 into absolute ethyl alcohol 2 Performing ultrasonic treatment on the P nano material for 30min, and adding the Cd obtained in the step 1 x Zn 1-x S, continuously carrying out ultrasonic treatment on the S micrometer spheres for 30min; directly drying the obtained mixed solution in a vacuum oven at 60 ℃ for 12 hours to remove ethanol, thus obtaining the Co with the shell-core structure 2 P/Cd x Zn 1-x S, denoted as y% CP/CZS, where y represents Co in the core-shell structure 2 Weight percent (wt.%) of P.
Further, in step 1, cd (NO 3 ) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 The molar ratio of O is x, 1-x, the molar amount of thioacetamide is Cd (NO 3 ) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 The sum of the molar amounts of O.
Further, the dosage ratio of thioacetamide to deionized water in the mixed solution in the step 1 is 10.00mmol:80mL.
Further, in step 1, the drying is performed in a vacuum oven at 60 ℃ for 12 hours.
Further, in step 2, coCl 2 ·6H 2 O、NaBH 4 、NaH 2 PO 2 The dosage ratio of the catalyst to the ethylenediamine is 0.952g:0.228 to 0.456g:1.76 to 2.82g:70mL.
Co with shell-core structure is designed and prepared by the invention 2 P/Cd x Zn 1-x S-microspheres. Under visible light, co 2 P/Cd x Zn 1-x S shows good potential application in the field of energy photocatalysis.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes the self-assembly method in Cd x Zn 1-x S catalyst surface builds Co 2 P protective layer by Co 2 Co-catalysis of P layer and Co 2 P and Cd x Zn 1-x Electrostatic action of S, co 2 P/Cd x Zn 1-x S microspheres exhibit a higher Pt/Cd ratio x Zn 1-x S has better photocatalytic water splitting activity and anti-corrosion performance, and the charge separation efficiency of the catalyst is also enhanced.
2. Under visible light, co obtained by the invention 2 P/Cd x Zn 1-x S shows excellent hydrogen-producing activity up to 16.05mmol g -1 h -1 . In particular, under the condition of 450nm visible light, the quantum efficiency of decomposing benzyl alcohol to produce hydrogen can reach 34.27 percent, and no obvious catalyst photo-corrosion is found in the reaction for 12 hours.
3. The preparation method has simple steps, and can realize Co by a self-assembly method 2 P is Cd x Zn 1-x S provides a distribution for the surface regulation of other nano materialsA simple new strategy for reference;
4. the invention aims at Cd x Zn 1-x The S surface is regulated and controlled, and under visible light, CP/CZS shows excellent photocatalytic aromatic alcohol hydrogen production activity.
Drawings
FIG. 1 is a schematic diagram of Cd synthesized in example 1 x Zn 1-x XRD pattern of S;
FIG. 2 is a Co synthesized in example 2 2 XRD pattern of P;
FIG. 3 is Co synthesized in example 2 2 SEM, EDS, and TEM images of P;
FIG. 4 is an XRD pattern for y% CP/CZS synthesized in example 3;
FIG. 5 is a SEM, EDS, TEM and Zeta plot of 3% CP/CZS synthesized in example 3;
FIG. 6 is a graph of the activity of the synthesized y% CP/CZS benzyl alcohol of example 3 in hydrogen production;
FIG. 7 is a graph of hydrogen production activity of 3% CP/CZS in various aromatic alcohols synthesized in example 3;
FIG. 8 is a graph of hydrogen production activity of 3% CP/CZS in various solvents synthesized in example 3;
FIG. 9 is a graph of hydrogen production activity at various wavelengths of 3% CP/CZS synthesized in example 3;
FIG. 10 is a graph of cyclic activity of 3% CP/CZS synthesized in example 3;
FIG. 11 is a plot of Cd after reaction of 3% CP/CZS synthesized in example 3 2+ Concentration.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are merely examples in nature, and on the basis of the technical solutions of the present invention, the following examples are given in detail, and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
Example 1
This example prepares Cd as follows x Zn 1-x S microspheres (x=0.1 to 0.9):
10x mmol Cd (NO) 3 ) 2 ·4H 2 O and 10 (1-x) mmol Zn (Ac) 2 ·2H 2 After O was dissolved in 60mL of deionized water, 10.00mmol of an aqueous solution of thioacetamide (20 mL) was added dropwise and stirred for 30min. The resulting mixed solution was transferred to a 100mL polytetrafluoroethylene-lined stainless steel autoclave and heated at 160 ℃ for 12 hours. Naturally cooling the autoclave to room temperature, centrifugally collecting precipitate, washing with distilled water and ethanol in sequence, and drying in a vacuum oven at 60 ℃ for 12 hours to obtain Cd x Zn 1-x S microspheres, denoted CZS.
Example 2
This example prepares Co as follows 2 P nano material:
first, 0.952g of CoCl 2 ·6H 2 O and 1.760g NaH 2 PO 2 After adding to and dissolving 70mL of ethylenediamine solution, 0.456g of NaBH was added 4 Slowly add to the above solution and stir for another 20min to form a purple mixed solution. The purple mixed solution was transferred to a 100mL teflon lined stainless steel autoclave and heated at 160 ℃ for 24 hours. Naturally cooling the autoclave to room temperature, centrifugally collecting black precipitate, washing with distilled water and ethanol to obtain Co 2 P nanomaterial, denoted CP.
Example 3
The embodiment synthesizes the shell-core structure Co according to the following steps 2 P/Cd x Zn 1-x S micrometer spheres:
a certain amount of CP obtained in example 2 was added to absolute ethanol (2.0 mL) and sonicated for 30min. Subsequently, cd obtained in example 1 was added to the above solution x Zn 1-x S (x=0.9) and further ultrasonic treatment was continued for 30min. To remove the ethanol, the solution was directly dried in a vacuum oven at 60 ℃ for 12 hours. The resulting sample was noted as y% CP/CZS (y=1-10), where y represents the weight percent (wt.%) of CP.
Example 4
The performance of the y% CP/CZS visible light photocatalytic oxidation of benzyl alcohol to hydrogen was tested as follows: the photocatalytic oxidation of benzyl alcohol to produce hydrogen is carried out in a top heat-resistant irradiation reactor. Firstly, 100mg of catalyst, 10mL of benzyl alcohol and 90mL of water are added into a reactor and stirred uniformly, thenThe reactor was then connected to a photocatalytic reaction system and evacuated (mechanical pump). After stirring in the dark for 30 minutes to reach adsorption-desorption equilibrium, a filter equipped with a UV-CUT (lambda) was used>420 nm) was used as a visible light source to irradiate the reaction carried out in the sealed reactor. During the whole photocatalytic reaction, the temperature of the reactor is controlled by a circulating condensing device, and the temperature is kept at 5 ℃. During the reaction, H 2 On-line detection by gas chromatography (GC 9790 II, FULI). After the reaction, H is calculated and generated 2 Is a mixture of the above substances. The collected reaction solution was then quantitatively analyzed by a high performance liquid chromatograph equipped with a separation unit (e 2695, waters, usa) and a photodiode array detector (PDA-e 2998, waters, usa).
Nanomaterial Cd x Zn 1-x Characterization of S: solid solution photocatalysts are composed of two or more crystals of similar structure and size, wherein the ionic radii of different metal ions are relatively close. Therefore, by adjusting the composition ratio of Cd/Zn, the band gap adjustable Cd can be formed x Zn 1-x S solid solution. To study Cd 2+ And Zn 2+ Cd was compared with the amount of the catalyst x Zn 1-x The XRD analysis was performed on the sample under the influence of the S catalyst phase structure. Cd was found by comparison with CdS (PDF # 77-2306) and cubic ZnS (PDF # 77-2100) in fig. 1 x Zn 1-x The XRD pattern of S solid solution (x=0.1 to 0.9) samples did not fully meet the standard spectra of CdS and ZnS. In addition, as the Cd/Zn ratio increases, the diffraction peak position of the sample gradually moves toward a low angle. The continuous shift of the diffraction peaks further confirmed that the catalyst prepared was Cd x Zn 1-x Solid solutions of S, rather than a mixture of CdS and ZnS. Thus, the phase structure of solid solutions depends largely on the Cd/Zn ratio. The x values of the CZS used in the following tests were all 0.9.
Nanomaterial Co 2 Characterization of P: when CoCl 2 ·6H 2 O has a mass of 0.952g and NaH 2 PO 2 In an amount of 1.760g, i.e. n (H) 2 PO 2 - ):n(Co 2+ ) At 5:1, a Co to Co separation can be achieved 2 Complete phosphating of P. The product isThe diffraction peaks of (2) may be attributed to Co 2 P (JCPDS No. 54-0413). With NaBH 4 Further increase to 0.456g or NaH 2 PO 2 Further increase to 2.820g, co 2 P may also be formed (fig. 2).
Since the CP/CZS synthesized in example 3 had the best hydrogen generating activity, CP was selected as the optimized Co 2 P samples were probed. The microstructure and morphology of the CP obtained in example 2 can be observed by SEM and TEM (fig. 3). Many spheres are formed by aggregation of nanoparticles, approximately 1.0 micron in size (fig. 3 (a) and 3 (b)). The energy dispersive X-ray spectrometer (EDX) element map image shows that cobalt and phosphorus elements are present and uniformly distributed throughout the sample (fig. 3 (c) and fig. 3 (d)). However, this spherical structure is unstable and easily dispersed after ultrasound (fig. 3 (e) and fig. 3 (f)). In addition to nanoparticles, some special shapes were observed, similar to a fish fin (fig. 3 (g)). The lattice spacing was measured to be 0.220nm (FIG. 3 (h)), which is Co 2 The (111) plane of P. These results indicate that Co consisting of nanoparticles and fin structures was prepared 2 P greatly improves the photocatalytic activity of CZS.
Characterization of nanomaterial CP/CZS: the CP/CZS obtained in example 3 was characterized by a series of physicochemical properties, such as XRD, SEM, TEM and Zeta potential and photocatalytic properties. Figure 4 shows XRD patterns of CZS, CP and y% CP/CZS samples. Diffraction peaks of CZS and CP are respectively matched with CdS (JCPDS No. 77-2306) and Co 2 P (JCPDS No. 54-0413) conforms to the standard. The addition of CP did not change the crystal phase and crystallinity of the CZS solid solution, indicating that the incorporation of CP and CZS was by surface deposition and did not enter the CZS interior. The absence of CP peaks in CP/CZS may be due to their high dispersity, low crystallinity and low loading. Changes in morphology and microstructure after CP addition to CZS can be observed using SEM and TEM images (fig. 5). CZS is spherical in shape, approximately 1-2 μm in size, rough in surface, and aggregated by nanoparticles (FIGS. 5 (a) and 5 (b)). After CP modification, the surface particles became smaller and more fluffy (fig. 5 (c) and 5 (d)), and both Co, P, cd, zn and S elements can be seen from the EDX element diagrams (fig. 5 (e 1) - (e 5)). From the TEM image, it is known that CP and CZS form a core-shell structure. Microsphere-shaped CZSAs a core (fig. 5 (f) - (k)), and many burr-like CPs are decorated at the CZS surface as shells. The rays around the raised area are CP (represented by the small red rectangle, fig. 5 (j)), because the grid fringes of the CP (110) plane are observed, with a d value of about 0.28nm (fig. 5 (k)). In addition, lattice fringes of the CZS (101) plane having a d value of about 0.32nm were found (fig. 5 (h)). This phenomenon is due to the electrostatic attraction that occurs between CP-4 and CZS microspheres, because CZS is positively charged and Co 2 P is negatively charged and is obtained from the Zeta potential (FIG. 5 (1)). The core-shell structure is beneficial to the improvement of charge transfer and photocatalytic performance.
Test of catalytic Activity of nanomaterial CP/CZS to investigate the production of H by photocatalytic benzyl alcohol 2 The catalytic activity of CP, CZS and y% CP/CZS composites was tested as in example 4 under the same mass of catalyst and the same conditions. When CP is added into the reaction system, H is not generated 2 . As shown in FIG. 6, both pure CZS and CP/CZS composites produce H under visible light illumination 2 . CZS, 1% CP/CZS, 2% CP/CZS, 3% CP/CZS, 4% CP/CZS, 5% CP/CZS and 10% CP/CZS H 2 Yields were 5.77, 13.42, 14.47, 16.05, 13.24 and 12.84mmol g, respectively -1 h -1 . It can be seen that the optimal loading of CP is 3wt.%, which is about 3 times the hydrogen production rate of CZS. The enhancement of activity may result from a synergistic effect between CZS and CP. As the CP content increases, the photocatalytic activity of the composite material increases and then decreases. The reason for the decrease may be that the CP itself does not have photocatalytic H production 2 Active and shielding against CZS. CP shields some of the visible light to reduce photons that may reach the CZS surface.
In order to optimize the photocatalytic activity, a reaction substrate (PhCH 2 OH) with activity lower than PhCH 2 OH。PhCH 2 The p-substitution of OH includes Cl-PhCH 2 OH、Br-PhCH 2 OH、F-PhCH 2 OH、CH 3 -PHPhCH 2 OH and CH 3 O-PhCH 2 OH (FIG. 7), others for h + The sacrificial agent of (2) is formic acid, na 2 S/Na 2 SO 3 And lactic acid (fig. 8). Especially without adding PhCH 2 In the case of OH, the activity is very low, only 0.22mmol g -1 h -1 Ratio PhCH 2 OH was 73 times lower. Thus, phCh 2 OH oxidation favors H 2 CP/CZS is PhCh 2 A hydrogen-producing catalyst excellent in OH. At the same time, the photocatalytic production of H was also tested 2 Apparent quantum yield in the process (AQE, fig. 9). The AQEs of 3% CP/CZS at 400nm, 420nm, 450nm, 500nm and 550nm were 20.02%, 20.33%, 34.27%, 23.27% and 0.13%, respectively, with the highest AQEs at 450 nm. In addition, to test the stability of the catalyst, 3% cp/CZS and CZS were subjected to 3 cyclic reactions, each reaction period being 4h (fig. 10). Photocatalytic H of these two samples 2 The yields were relatively stable, indicating that the samples did not exhibit photo-corrosion, indicating that the catalyst was suitable for practical use. In addition, after 4 hours of reaction, cd in the solution 2+ The concentration is greatly reduced, and CdS is 1.87mg L -1 3% CP/CZS is only 0.12mg L -1 (FIG. 11).
From the above results, it is clear that the CP/CZS complex with core-shell structure has excellent hydrogen production activity, showing Co 2 P/Cd x Zn 1-x Potential application of S in the energy field.
Claims (7)
1. Core-shell structure Co 2 P/Cd x Zn 1-x The synthesis method of the S microsphere is characterized by comprising the following steps:
step 1, cd x Zn 1-x Preparation of S-microspheres
Cd (NO) 3 ) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 O is dissolved in deionized water, and then deionized water solution containing thioacetamide is added dropwise, and the mixture is stirred for 30min; the resulting mixed solution was transferred to a 100mL polytetrafluoroethylene-lined stainless steel autoclave and heated at 160 ℃ for 12 hours; naturally cooling the autoclave to room temperature, centrifugally collecting precipitate, washing with distilled water and ethanol in sequence, and vacuum drying to obtain Cd x Zn 1-x S micrometer spheres;
step 2, co 2 Preparation of P nanomaterial
NaBH is carried out 4 Slowly add to dissolve CoCl 2 ·6H 2 O and NaH 2 PO 2 Stirring for 20min, transferring the obtained mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining of 100mL, and heating at 160 ℃ for 24 hours; naturally cooling the autoclave to room temperature, centrifugally collecting black precipitate, washing with distilled water and ethanol in sequence to obtain Co 2 P nano material;
step 3, shell-core structure Co 2 P/Cd x Zn 1-x Preparation of S-microspheres
Adding Co obtained in the step 2 into absolute ethyl alcohol 2 Performing ultrasonic treatment on the P nano material for 30min, and adding the Cd obtained in the step 1 x Zn 1- x S, continuously carrying out ultrasonic treatment on the S micrometer spheres for 30min; directly drying the obtained mixed solution in a vacuum oven at 60 ℃ for 12 hours to remove ethanol, thus obtaining the Co with the shell-core structure 2 P/Cd x Zn 1-x S microspheres, denoted y% CP/CZS, where y represents Co in the core-shell structure 2 Weight percent of P.
2. The synthesis method according to claim 1, wherein: in step 1, cd (NO 3 ) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 The molar ratio of O is x, 1-x, the molar amount of thioacetamide is Cd (NO 3 ) 2 ·4H 2 O and Zn (Ac) 2 ·2H 2 The sum of the molar amounts of O.
3. The synthesis method according to claim 2, characterized in that: the dosage ratio of thioacetamide to deionized water in the mixed solution in the step 1 is 10.00mmol:80mL.
4. The synthesis method according to claim 1, wherein: in step 1, the drying is performed in a vacuum oven at 60 ℃ for 12 hours.
5. The synthesis method according to claim 1, wherein: in step 2, coCl 2 ·6H 2 O、NaBH 4 、NaH 2 PO 2 The dosage ratio of the catalyst to the ethylenediamine is 0.952g:0.228 to 0.456g:1.76 to 2.82g:70mL.
6. A shell-core structure Co prepared by the synthesis method of any one of claims 1 to 5 2 P/Cd x Zn 1-x S-microspheres.
7. A shell-core structure Co as claimed in claim 6 2 P/Cd x Zn 1-x The application of the S-micrometer spheres is characterized in that: when y% is 1% -10%, hydrogen can be produced when used as a photocatalyst.
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