NL2030279B1 - Go@cd1-xznxs polyhedral material with rich sulphur vacancies and high-index facets and preparation method of material - Google Patents
Go@cd1-xznxs polyhedral material with rich sulphur vacancies and high-index facets and preparation method of material Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 38
- 239000005864 Sulphur Substances 0.000 title abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 23
- 239000013535 sea water Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- 238000010168 coupling process Methods 0.000 claims abstract description 11
- 238000005859 coupling reaction Methods 0.000 claims abstract description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 11
- 239000006104 solid solution Substances 0.000 claims abstract description 10
- 230000008878 coupling Effects 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011592 zinc chloride Substances 0.000 claims abstract 2
- 235000005074 zinc chloride Nutrition 0.000 claims abstract 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 58
- 239000011593 sulfur Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 22
- 230000002153 concerted effect Effects 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 abstract 2
- 230000001699 photocatalysis Effects 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052984 zinc sulfide Inorganic materials 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 241001663154 Electron Species 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J27/20—Carbon compounds
-
- B01J35/39—
-
- 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
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a GO@CdLfiZnXS polyhedral material with rich sulphur vacancies and high—index facets and a preparation method thereof. A CdLüZnXS solid solution polyhedron with rich sulphur vacancies exposes high—index facets and the surface of the polyhedron is coated with graphene oxide. The method comprises the steps of mixing CdCl2°2.5H20, ZnCl2 and ethylene glycol, heating and stirring to form uniform and transparent liguid, adding Na2S°9 H20, and uniformly stirring; and transferring the mixture into a porcelain boat, placing in a tube furnace, heating to 300—700 DEG C under a nitrogen atmosphere, and keep the temperature for 1—6 h. Through one—step pyrolysis carbonization—coupling concerted reaction and one—step completion of generation of a CdlfianS polyhedron and growth and interfacial coupling of a graphene oxide shell, the GO@CdlfiZnXS polyhedral composite material has efficient hydrogen production performance by absorbing visible light for catalyzing seawater decomposition.
Description
GOOCD: zZN;S POLYHEDRAL MATERIAL WITH RICH SULPHUR VACANCIES AND
HIGH-INDEX FACETS AND PREPARATION METHOD OF MATERIAL
The invention belongs to the field of new energy and environ- ment materials, relates to a GOECd; .7Zn,S polyhedral material with rich sulphur vacancies and high-index facets and a preparation method of the polyhedral material, in particular to a Cd;.,Zn,S sol- id solution polyhedral composite material which is coated with graphene oxide, rich in sulphur vacancies and exposes high-index facets and a preparation method of the polyhedral composite mate- rial.
Due to the shortage of energy and fresh water, the use of semiconductor absorption of solar energy to decompose seawater so as to produce hydrogen can convert solar energy into clean hydro- gen energy and is recognized as one of the most promising green energy technology. The photocatalyst designed to efficiently and stably decompose seawater for hydrogen evolution under visible light receives more and more attention from people. A Cd;-.Zn,S sol- id solution, with a suitable band gap structure that can be regu- lated and excellent redox capacity of a carrier, is one of the most promising photocatalyst. However, the self-luminous corrosion phenomenon generated during the photocatalytic reaction and the complex chemical environment in the seawater seriously affect the stability of a Cdi,„2n,S catalyst. Graphene oxide (GO) has a unique two-dimensional planar structure, excellent conductivity, large specific surface area and superior mechanical properties, so that the GOECd; .7Zn,S composite material coated with GO becomes an ideal strategy for improving the photocatalytic activity, stability and charge separation performance of the Cd; 2n,S solid solution. Alt- hough synthesis methods for the GORCd: „Zn,S material have been re- ported in large quantities, including a water/solvothermal method, a self-assembly method, a chemical vapor deposition method, etc., the currently prepared GO@Cd: .2n.S material is either low in photo-
catalytic efficiency in seawater or poor in long-term stability of photocatalysis in seawater, thereby limiting its application. For another, photocatalytic materials with high-index facets generally have high catalytic activity, but the preparation of materials with high-index facets is disadvantageous regardless of whether from a thermodynamic angle or a kinetic angle, so a conventional method of synthesizing a GO-coated Cd, ,Zn.S solid solution material with high-index facets is difficult.
In recent years, defect engineering is considered to be an- other effective strategy to improve photocatalytic efficiency. Va- cancy, as a common defect in a crystal structure, can not only be used as an adsorption site to facilitate charge transfer and pre- vent recombination of photogenerated electrons and holes, but also capture free electrons and holes as traps for electron-hole recom- bination. This effect may cause more photogenerated electrons on a semiconductor conduction band to react with water to produce more hydrogen. Therefore, the preparation of the Cd; 2n,S solid solution catalyst with rich sulfur vacancies can help to improve photocata- lytic activity.
Therefore, the design of the GOECd;..Zn,S polyhedral material with rich sulfur vacancies and high-index facets provides a new choice for photocatalyst used for efficient hydrogen production by seawater decomposition, with important practical value and social significance.
The invention provides a GO@Cd; .Zn,S polyhedral material with rich sulphur vacancies and high-index facets and a preparation method of the polyhedral material and aims to overcome the defects that in the prior art, the preparation of a GOGCd;..Zn,S catalyst is complex and tedious and requires multi-step synthesis, the prepa- ration of a GORCd, .Zn,S solid solution polyhedron is difficult, tight two-phase interfacial coupling of GORCd: ,Zn.S is difficult to realize, the photocatalytic efficiency is low, and the long-term stability is poor and the like. The Cd; ,Zn,S solid solution polyhe- dron with rich sulphur vacancies exposes the high-index facets, the surface of the polyhedron is coated with graphene oxide (GO), and the GORCd;:-,Zn,S has efficient hydrogen production performance by absorbing visible light for catalyzing seawater decomposition.
The preparation method comprises a one-step pyrolysis carboniza- tion-coupling concerted reaction, a sulfurization reaction and the growth of a graphene oxide shell and the interface coupling com- plete in one-step, specifically comprising the following steps of, (1) mixing 0.01-2 mmol/L of CdCl:+2.5H;0, 0.01-2 mmol/L of
ZnCl, and 0.3-40 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 30-90 DEG C for heating and stirring for 0.5-4 h to form uniform and transparent liquid; {2) adding 0.02-8 mmol of Na:S+*9H,C into the transparent liq- uid in step 1, and continuing to stir for 0.5-4 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 300-700 DEG C at a speed of 1-10 DEG C/min under a nitrogen at- mosphere, and keeping at this temperature for 1-6 h to obtain the
GORCd;_4Zn,S polyhedral composite material with rich sulphur vacan- cies and high-index facets.
The method has the advantages that the process is simple, the one-step pyrolysis-coupling concerted reaction is adopted, and the
GORCd:«2n.S polyhedral composite material with rich sulphur vacan- cies and high-index facets is prepared. Through the sulfuration reaction and one-step completion of growth and interfacial cou- pling of the graphene oxide shell, a molecular-level coupling in- terface is formed, so that the corrosion resistance, high tempera- ture resistance and acid and alkali resistance of the catalyst are improved, and long-term photocatalytic stability and effective in- terface charge transfer in seawater are facilitated. Meanwhile, a unique two-dimensional planar structure of the graphene oxide shell promotes the rapid migration of electrons to the surface to adsorb H' so as to generate H,, so that the hydrogen evolution per- formance is improved; the Cd; zn,S polyhedron has high catalytic activity; and introduction of sulfur vacancies is beneficial to charge transfer, and photogeneration electrons and hole recombina- tion are prevented.
The GO@Cd; .Z2n,S polyhedral material with rich sulfur vacan- cies prepared by the method is high in photocatalytic efficiency,
and has good photocatalytic activity for photocatalytic decomposi- tion of seawater for hydrogen production and photocatalytic degra- dation of organic pollutants in water.
FIG. 1 shows XRD patterns of the GO@Cd: .Zn,S polyhedral mate- rials with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1, Embodiment 2, Embodiment 3 and Embodiment 4 of the present invention and a GO@CdS and GOEZnS composite material prepared by the method according to Comparative
Example 1 and Comparative Example 2.
FIG. 2 shows Raman spectra of the GORCd;_4Zn.S polyhedral ma- terial with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention and a commodity GO.
FIG. 3 shows SEM photos of different magnification of the
GO@Cd; ZnS polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention.
FIG. 4 shows a TEM photo (a) and a HRTEM photos (kb, c) of the
GO@Cd: ZnS polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention.
FIG. 5 shows a STEM photo (a) of the GOG@Cd; .Zn.,S polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention and the mapping distribution diagrams (b-f) of corresponding com- ponents.
FIG. 6 shows an N; adsorption/desorption isotherm (a) and a pore size distribution curve (b) of the GO@Cd: ‚2n,S polyhedral ma- terial with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention.
FIG. 7 sows an ESR spectrogram of the GO@Cd: ,2n,S polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according te Embodiment 1 of the present invention.
FIG. 8 shows visible light photocatalytic hydrogen production rates of the GOEGCd; ZnS polyhedral material with rich sulfur va- cancies and high-index facets prepared by the method according to
Embodiment 1 of the present invention and the GORCdS composite ma- terial and the GORZnS composite material prepared by the method according to Comparative Example 1 and Comparative Example 2 in water and seawater. 5 FIG. 9 shows quantum efficiency (AQY) of the GO@Cdi2n,S pol- yhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention under different wavelengths of illumination to decompose water and seawater for hydrogen production.
FIG. 10 shows cycling stability of photocatalytic hydrogen production in water and seawater of the GO@Cd: «2n,S polyhedral ma- terial with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention.
The detailed description of the invention is made below by means of specific embodiments.
Embodiment 1: (1) mixing 0.12 mmol/L of CdCl:°2.5H:0, 0.18 mmol/L of ZnCl, and 3 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 80 DEG C for heating and stirring for 0.5 h to form uniform and transparent liquid; (2) adding 0.03 mmol of Na:S+9H:0 into the transparent liquid in step 1, and continuing to stir for 0.5 h, and uniformly mixing; and {3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 550 DEG C at a speed of 5 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 4 h to obtain the
GORCd;.+Zn.5 polyhedral composite material with rich sulphur vacan- cies and high-index facets.
Embodiment 2: (1) mizing 0.18 mmol/L of CdCl;*2.5H,0, 0.12 mmol/L of ZnCl; and 3 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 80 DEG C for heating and stirring for 0.5 h to form uniform and transparent liquid; (2) adding 0.03 mmol of Na,;S+*9H,0 into the transparent liquid in step 1, and continuing to stir for 0.5 h, and uniformly mixing;
and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 550 DEG C at a speed of 5 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 4 h to obtain the
GORCd; (Zn,S polyhedral composite material with rich sulphur vacan- cies and high-index facets.
Embodiment 3: (1) mizing 0.24 mmol/L of CdCl,+2.5H,0, 0.06 mmol/L of ZnCl, and 3 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 80 DEG C for heating and stirring for 0.5 h to form uniform and transparent liquid; (2) adding 0.03 mmol of Na;S+*9H:0 into the transparent liquid in step 1, and continuing to stir for 0.5 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 550 DEG C at a speed of 5 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 4 h to obtain the
GO@Cd:-xZn:S polyhedral composite material with rich sulphur vacan- cies and high-index facets.
Embodiment 4: (1) mixing 0.06 mmol/L of CdCl,*2.5H.0, 0.24 mmol/L of ZnCl, and 3 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 80 DEG C for heating and stirring for 0.5 h to form uniform and transparent liquid; (2) adding 0.03 mmol of Na:S+9H:0 into the transparent liquid in step 1, and continuing to stir for 0.5 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 550 DEG C at a speed of 5 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 4 h to obtain the
GORCd;_,Zn,S polyhedral composite material with rich sulphur vacan- cies and high-index facets.
Embodiment 5: (1) mixing 0.15 mmol/L of CdCl,*2.5H.0, 0.15 mmol/L of ZnCl,
and 6 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 80 DEG C for heating and stirring for 1 h to form uni- form and transparent liquid; (2) adding 0.06 mmol of Na:S+9H:0 into the transparent liquid in step 1, and continuing to stir for 1 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 650 DEG C at a speed of 10 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 2 h to obtain the
GORCd: -Z2n,S polyhedral composite material with rich sulphur vacan- cies and high-index facets.
Embodiment 6: (1) mixing 1 mmol/L of CdC1:+2.5H:0, 1 mmol/L of ZnCl, and 30 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 550 DEG C for heating and stirring for 2 h to form uniform and transparent liquid; (2) adding 4 mmol of Na,S+*9H,0 into the transparent liquid in step 1, and continuing to stir for 2 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 600 DEG C at a speed of 2 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 3 h to obtain the
GORCd; ,Zn,5 polyhedral composite material with rich sulphur vacan- cies and high-index facets.
Embodiment 7: (1) mixing 0.5 mmol/L of CdCl:+2.5H:0, 0.15 mmol/L of ZnCl, and 10 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 60 DEG C for heating and stirring for 1 h to form uni- form and transparent liquid; (2) adding lmmol of Na;S+*9H,0 into the transparent liquid in step 1, and continuing to stir for 0.5 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 550 DEG C at a speed of 10 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 4 h to obtain the
GORCd: ‚zn,S polyhedral composite material with rich sulphur vacan- cies and high-index facets.
Comparative Example 1: (1) mixing 0.3 mmol/L of CdCl:+2.5H;0 and 3 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 80 DEG C for heating and stirring for 0.5 h to form uniform and transparent liquid; (2) adding 0.03mmel of Na:S°9H;0 into the transparent liquid in step 1, and continuing to stir for 0.5 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 550 DEG C at a speed of 5 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 4 h to obtain a GO@cCds composite material.
Comparative Example 2: (1) mizing 0.3 mmol/L of ZnCl, and 3 mmol of ethylene glycol, and placing the mixture in an oil bath pan at 80 DEG C for heating and stirring for 0.5 h to form uniform and transparent liquid; (2) adding 0.03mmol of Na:S+9H:0 into the transparent liquid in step 1, and continuing to stir for 0.5 h, and uniformly mixing; and (3) transferring the mixture obtained in step 2 to a porce- lain boat, putting the porcelain boat into a tube furnace, heating to 550 DEG C at a speed of 5 DEG C/min under a nitrogen atmos- phere, and keeping at this temperature for 4 h to obtain a GORZnS composite material.
FIG. 1 shows XRD patterns of the GOGCd:_Zn,S polyhedral mate- rial with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1, Embodiment 2, Embodiment 3 and Embodiment 4 of the present invention and a GO@CdS composite material and GORZnS composite material prepared by the method ac- cording to Comparative Example 1 and Comparative Example 2. As can be seen from the figure, the XRD spectrogram of the material pre- pared in Comparative Example 1 and Comparative Example 2 is con- sistent with the standard spectrogram of CdS and ZnS, respective- ly. The XRD spectra of all other samples correspond to the dif-
fraction peaks of the Cd; ,Zn,S solid solution. The diffraction peaks of the samples are sharp without other peaks, indicating that the samples are good in crystallinity and pure in product phase. It shall be noted that as the proportion of ZnCl: in a pre- cursor is continuously increased, the value of X in the CdiZzn,S sample is continuously increased, and the diffraction peaks of the samples offset to a high angle and the offset gradually increases.
The continuous shift of the XRD spectrogram shows that since zn“ ions are smaller than Cd“ in radius, the Zn** ions enter a Cds lat- tice or enters an interstitial site of the CdS to obtain the Cdi. z2zn,S solid solution.
FIG. 2 shows Raman spectra of the GORCd«2n.S polyhedral ma- terial with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention and a commodity GO. As can be seen from the figure, there are two typical graphene characteristic peaks at 1340 cm* and 1594 cm’, respectively matching the D peak and the G peak of the GO. The catalyst prepared by the method of the present invention is the
GORCd: ZnS composite material.
FIG. 3 shows SEM photos of different magnification of the
GO@Cd:«2n,S polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention. As can be seen from FIG. 3a, the compo- site material according to Embodiment 1 is particles having a di- ameter of about 500 nm. Upon magnification, it can be clearly ob- served from FIG. 3b that the sample particles are of polyhedral structures.
FIG. 4 shows a TEM photo (a) and a HRTEM photo (b, c) of the
GO@Cd:.2n,S polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention. As can be seen from FIG. 4a, the GO@Cdi „zn,‚S sample particles are of core-shell structures, the outer lay- ers of the Cd; .Z2n,S polyhedral particles are uniformly wrapped with a thin graphene oxide shell, and the graphene oxide shell is of a porous structure, thus promoting proton transmission and gas ex- change, and facilitating the acceleration of photocatalytic reac- tion. From FIG. 4c of the HRTEM photo, a tight heterogeneous in-
terface between Cd, .72n,S and the graphene oxide can be clearly ob- served, and the interplanar crystal spacing of 0.37 nm is measured to match the layer spacing of the graphene oxide, while the inter- planar crystal spacing of 0.32 nm corresponds to a (002) facet (JPCdS, 35-1469) of hexagonal wurtzite Cd;.Zn.S (002) while 0.18 nm corresponds to a (103) facet, and the exposed two high-index fac- ets have higher surface energy, which is beneficial to improving photocatalytic activity. The above results demonstrate that the
Cd: -2n,S polyhedron composed of (002) and (103) facets of the com- posite material according to Embodiment 1 can form the tight cou- pling interface with the GO shell.
FIG. 5 shows a STEM photo (a) of the GOG@Cd; .72n.,S polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention and a Mapping distribution diagram (b-f}) of corresponding compo- nents. From the STEM photo (a), the step features on the surface of the GORCd; .Zn,S polyhedron can be clearly observed; and from the element distribution mapping (b-f), it can be clearly observed that five elements, specifically, C, O0, Cd, Zn and S, are uniform- ly distributed on the sample polyhedron, and the size of the dis- tribution diagram of C and O is slightly larger than the distribu- tion range of Cd, Zn and S, thereby further confirming that the sample is of the core-shell structure with Cd, ZnS being coated with the graphene oxide.
FIG. 6 shows an N; adsorption/desorption isotherm (a) and a pore size distribution curve (b) of the GOECd; ‚2n,S polyhedral ma- terial with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention.
In FIG. 6a, the N; adsorption desorption isotherm has an isotherm of a type IV mesoporous structure, and the specific surface area is 115.76 cm? g' through BET calculation, and the specific surface area is large. FIG. 6b pore size distribution diagram demonstrates that there are abundant pore structures in the sample, mainly pore structures less than 10 nm. The GO@Cd: .Zn,S composite material with the mesoporous structure of large specific surface area is benefi- cial to the performance of catalytic activity.
FIG. 7 shows an ESR spectrum of the GO@Cd: ZnS polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention.
As can be seen from the figure, a pair of strong peaks appears at the place with g equal to 2.003, which is the characteristic peaks of the sulfur vacancies, indicating that there are unpaired elec- trons produced by the sulfur vacancies in the GOQCd, .Zn,S composite material.
FIG. 8 shows visible light photocatalytic hydrogen production rates in water and seawater of the GOQCd, ,Zn,S polyhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention and the
GORCdS composite material and the GORZnS composite material pre- pared by the method according to Comparative Example 1 and Compar- ative Example 2. In the photocatalytic hydrogen production experi- ment, visible light irradiation is provided by a 300 W xenon lamp (China Education Au-light), and a 400 nm cut-off filter is equipped. The optical density is 100 mcm:‘em?. In each test, 30 mg of the catalyst was dispersed by ultrasound in 100 mL of deionized water containing 30% (Vt) methanol or 0.25M of Na;5+9H;0/0.35 M of
Na:S03 as a sacrificial agent or simply filtered natural seawater.
The natural seawater is taken from the Qingdao Coast of Yellow Sea of China. The mixed solution was transferred into a quartz reactor connected to a detection system and evacuated for 15 min to clear dissolved ©, and CO, in the solution. The temperature of the system is maintained at 7 DEG C by circulating cooling water. The gener- ated hydrogen was automatically detected every 30 min with an on- line gas chromatograph (Agilent 7890 A, high purity N; as carrier gas) From FIG. 8, the hydrogen production efficiency of the Cdi <2zn,S solid solution photocatalyst according to Embodiment 1, whether in pure water or seawater, was far higher than that of the single component CdS and ZnS according to Comparative Example 1 and Comparative Example 2, and the photocatalytic hydrogen produc- tion rate in water and seawater could reach 28.4 mmol/h* gt and 23.2 mmol/h't g%, the high photocatalytic hydrogen production rate in water, especially in seawater, has important application value for the development and utilization of hydrogen energy.
FIG. 9 shows quantum efficiency (AQY) of the GO@eCd:i ZnS pol-
yhedral material with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention under different wavelengths (365, 400, 420 and 450 nm) of illumination to decompose water and seawater for hydrogen pro- duction. Through calculation, the quantum efficiency of the photo- catalytic reaction of the GO@Cd: ,Zn,S material in water and sea- water according to Embodiment 1 can reach 37.5% and 30.3% respec- tively under the irradiation of 400 nm monochromatic light, and the quantum efficiency is higher.
FIG. 10 shows a cycling stability of photocatalytic hydrogen production in water and seawater of the GOECd; (Zn,S polyhedral ma- terial with rich sulfur vacancies and high-index facets prepared by the method according to Embodiment 1 of the present invention.
The stability of the prepared catalyst is characterized by using 0.25 M Na,S*9H.0/ 0.35 M Na,30; as sacrificial agents. As can be seen from the figure, after 5 cycles of reaction for 30 h, the hy- drogen production efficiency is basically kept unchanged, indicat- ing that the GORCd; ,Zn,S polyhedron material with high-index facets and promoted by the sulfur vacancies has good stability in photo- catalytic hydrogen production.
The GORCd;..Zn.,S polyhedral material with rich sulphur vacan- cies and high-index facets prepared by the method is used for pho- tocatalytic degradation of organic dyes in an aqueous solution, and the results show that the prepared GORCd: .Zn,S composite mate- rial has good photocatalytic degradation effect on the organic dyes in water, and can be used for the treatment of organic wastewater.
The GOR@Cd;_.Zn.S polyhedral material with rich sulphur vacan- cies and high-index facets prepared by the method is used for se- lective photocatalytic oxidation of organic matters, and also has good photocatalytic oxidation selectivity.
The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present inven- tion are not limited by the above-mentioned embodiments, and any other changes, substitutions, simplification and the like made without departing from the principle and the process of the pre- sent invention are all equivalent permutations and shall all be included in the protection scope of the present invention.
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