CN113145138B - Thermal response type composite photocatalyst and preparation method and application thereof - Google Patents
Thermal response type composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- 230000004044 response Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 28
- 239000002073 nanorod Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 239000011572 manganese Substances 0.000 claims description 87
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 238000004729 solvothermal method Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 9
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 6
- 229960001471 sodium selenite Drugs 0.000 claims description 6
- 235000015921 sodium selenite Nutrition 0.000 claims description 6
- 239000011781 sodium selenite Substances 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 33
- 239000001257 hydrogen Substances 0.000 abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 32
- 238000004519 manufacturing process Methods 0.000 abstract description 26
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000006698 induction Effects 0.000 abstract description 5
- 238000003421 catalytic decomposition reaction Methods 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000011669 selenium Substances 0.000 description 56
- 230000000694 effects Effects 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229910052711 selenium Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 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
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940091258 selenium supplement Drugs 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001308 synthesis method Methods 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
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- B01J35/39—
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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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- 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 Co rich in sulfur vacancy 0.85 Se/Mn 0.3 Cd 0.7 S thermal response type composite photocatalysisThe preparation method of the agent and the application of the agent in hydrogen production by catalytic decomposition of water under the induction of visible light. The composite photocatalyst is rich in Mn of sulfur vacancy 0.3 Cd 0.7 S nano rod as main body, in-situ growing Co on its surface 0.85 Se nanoparticles. The invention constructs Co 0.85 Se nanoparticles and Mn 0.3 Cd 0.7 The close interface contact among the S nano rods fully exposes reaction sites, and is beneficial to accelerating the effective separation/transmission of the photo-generated electron-hole pairs and inhibiting the recombination of the photo-generated electron-hole pairs. The obtained composite material and pure Mn 0.3 Cd 0.7 Compared with S, the photocatalytic water splitting hydrogen production performance is remarkably improved, and the photocatalytic water splitting hydrogen production system is different from the traditional photocatalytic reaction, and the reaction temperature can remarkably regulate and control the hydrogen production rate. The invention has the advantages of low cost of raw materials, wide sources, simple preparation method, mild conditions, no need of noble metals, less pollution and industrial popularization.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to Co rich in sulfur vacancy 0.85 Se/Mn 0.3 Cd 0.7 A preparation method of an S thermal response type composite photocatalyst and application of the S thermal response type composite photocatalyst in hydrogen production through visible light induced catalytic decomposition.
Background
Hydrogen energy is widely considered as an ideal choice of a new generation of energy due to environmental friendliness, cleanness and reproducibility, so that the absorption of continuous sunlight to directly decompose water on a semiconductor material to produce hydrogen and the conversion of solar energy into hydrogen energy has important significance for solving energy crisis and treating environmental pollution.
Sulfide solid solutions have received much attention because of their adjustable band gap width and catalytic activity under visible light. But their rapid recombination of photogenerated carriers limits their practical applications and modification thereof is necessary. The intrinsic properties (e.g., vacancies) of semiconductor photocatalysts and the construction of semiconductor heterojunctions can adjust their band structures, change carrier concentrations and charge transfer efficiencies, and thus can affect photocatalytic activity. In addition, compared with single photocatalysis, the efficiency of photocatalysis can be further improved by the synergistic utilization of multiple energy sources.
Disclosure of Invention
The purpose of the present invention is to provide a Co with more efficiency and optical response 0.85 Se/Mn 0.3 Cd 0.7 A preparation method of the S composite photocatalyst and application thereof in hydrogen production by catalytic decomposition of water under the induction of visible light. The invention constructs Co 0.85 Se nanoparticles and Mn rich in sulfur vacancies 0.3 Cd 0.7 The S nanorods are in close interface contact, reaction sites are fully exposed, effective separation/transmission of photon-generated carriers is realized, recombination of photon-generated carriers is inhibited, excellent activity and stability are shown in hydrogen production through visible light catalytic decomposition of water, and regulation and control of the photocatalytic hydrogen production rate through temperature can be realized.
In order to achieve the purpose, the invention adopts the following technical scheme:
co rich in sulfur vacancy 0.85 Se/Mn 0.3 Cd 0.7 The S composite photocatalyst is prepared from Mn rich in sulfur vacancy 0.3 Cd 0.7 S nano-rod is used as a carrier, and Co grows in situ on the surface of the S nano-rod 0.85 Se nanoparticles; wherein, co 0.85 Se nanoparticles and Mn 0.3 Cd 0.7 The mass ratio of the S nano rod is 3-20%.
The Mn is 0.3 Cd 0.7 The length of the S nanorod is 150-700 nm, and the diameter of the S nanorod is 50 nm; the Co 0.85 The diameter of the Se nano-particles is 5-10 nm.
Said sulfur vacancy-rich Co 0.85 Se/Mn 0.3 Cd 0.7 The preparation method of the S thermal response type composite photocatalyst comprises the following steps:
(1) Solvothermal method for preparing Mn rich in sulfur vacancy 0.3 Cd 0.7 S nanorod:
dissolving cadmium acetate and manganese acetate in a mixed solvent of ethylenediamine and deionized water, adding thioacetamide, continuously stirring and uniformly mixing, then transferring the obtained mixed solution into a high-pressure reaction kettle, reacting at a constant temperature of 200 ℃ for 24 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water and ethanol for three times respectively in sequence, and then drying at 60 ℃ in vacuum overnight to obtain Mn 0.3 Cd 0.7 And (4) S powder.
(2) Solvothermal method for preparing Co 0.85 Se/Mn 0.3 Cd 0.7 S thermal response type composite photocatalyst:
weighing the Mn obtained in the step (1) 0.3 Cd 0.7 S powder 0.1 g is dispersed in 30 ml ethylene glycol solution and stirred for 30 min, then 10 ml cobalt chloride and sodium selenite (molar ratio is 0.85 0.85 Se/Mn 0.3 Cd 0.7 And (S) a composite photocatalyst.
The molar ratio of manganese acetate, cadmium acetate and thioacetamide used in the step (1) is 6; the volume ratio of the ethylenediamine to the deionized water in the mixed solvent is 1:1.
Co in step (2) 0.85 Se nanoparticles and Mn 0.3 Cd 0.7 The theoretical mass ratio of the S nano rod is 3-20%.
Mn during hydrothermal treatment 0.3 Cd 0.7 S is taken as a carrier, and Co grows in situ on the surface of the S 0.85 Nanoparticles of Se to ultimately form Co 0.85 Se/Mn 0.3 Cd 0.7 And (5) an S composite structure.
The resulting sulfur vacancy-rich Co 0.85 Se/Mn 0.3 Cd 0.7 The S composite photocatalyst can be used for photocatalytic decomposition of water to produce hydrogen.
The invention has the following remarkable advantages:
（1）Co 0.85 se has better conductivity and chemical bonds which are easier to break, is favorable for promoting the catalytic reaction, and is applied to the field of electrocatalytic water decomposition. The invention firstly prepares Co by solvothermal method 0.85 Se nanoparticles and Mn rich in sulfur vacancies 0.3 Cd 0.7 And compounding the S nano-rods to construct a composite photocatalytic system with close interface contact. Co relative to other cobalt-based, selenium-based promoters 0.85 Se as a promoter exhibits more efficient photocatalytic activity.
(2) Co rich in sulfur vacancy prepared by the invention 0.85 Se/Mn 0.3 Cd 0.7 The S heterojunction is beneficial to accelerating the effective separation/transmission of the photoproduction electron-hole pair and inhibiting the recombination of the photoproduction electron-hole pair, has higher activity and stability, can effectively convert solar energy into chemical energy, and has high practical application value in industry. The method has the advantages of low cost of required raw materials, easiness in obtaining, simple and easily repeated operation steps, mild and safe conditions, easiness in operation and control, no need of using noble metals, great reduction of production cost and contribution to industrial popularization and application.
(3) Co rich in sulfur vacancy prepared by the invention 0.85 Se/Mn 0.3 Cd 0.7 The S composite photocatalyst has the characteristic of thermal response, and the heat energy and the light energy can generate a synergistic effect, so that the photocatalytic reaction efficiency is further improved, and more efficient and stable hydrogen energy is provided in the practical industrial application.
Drawings
FIG. 1 (a) shows Mn 0.3 Cd 0.7 X-ray diffraction pattern of S composite photocatalyst and CdS and MnS standard XRD card, and (b) is Mn 0.3 Cd 0.7 S、Co 0.85 Se and Co obtained in examples 1 to 4 0.85 Se/Mn 0.3 Cd 0.7 An X-ray diffraction pattern of the S composite photocatalyst;
FIG. 2 at Co 0.85 Se/Mn 0.3 Cd 0.7 During S synthesis, mn is not added 0.3 Cd 0.7 S pure Co 0.85 An X-ray diffraction pattern of the Se sample and a standard XRD card;
FIG. 3 is 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (example 2) scanning electron micrographs and (b-d) transmission electron micrographs of the composite photocatalyst;
FIG. 4 shows 7 wt% Co in the present invention 0.85 Se/Mn 0.3 Cd 0.7 S (embodiment 2) a transmission electron microscope selected area element distribution diagram of the composite photocatalyst;
FIG. 5 Mn deficiency of Sulfur vacancies 0.3 Cd 0.7 S-p and Mn rich in sulfur vacancy 0.3 Cd 0.7 Electron paramagnetic resonance intensity of S and
FIG. 6 is a graph showing a comparison of (a) hydrogen production activity by photocatalytic decomposition of water induced by visible light for different catalyst samples; (b) Different Co 0.85 Se loading hydrogen production rate diagram and (c) different reaction temperatures of 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (example 2) hydrogen production rate of the composite photocatalyst; (d) 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 And S (example 2) a long-time hydrogen production cycle experimental diagram of the composite photocatalyst.
Detailed Description
In order to make the content of the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Solvothermal method for preparing Mn rich in sulfur vacancy 0.3 Cd 0.7 S nano rod
Dissolving 14 mmol of cadmium acetate and 6 mmol of manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stirring for 20 min, adding 25 mmol of thioacetamide, continuing stirring for 30 min, transferring the obtained mixed solution into a 100 mL high-pressure reaction kettle, reacting at 200 ℃ at 24 h under constant temperature, naturally cooling to room temperature, washing the obtained precipitate with deionized water and ethanol for three times respectively, and vacuum drying at 60 ℃ overnight to obtain Mn 0.3 Cd 0.7 And (4) S powder.
(2) Solvothermal method for preparing Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst
Weighing the Mn obtained in the step (1) 0.3 Cd 0.7 Dispersing S powder 0.1 g in 30 ml glycol solution, stirring for 30 min, adding 10 ml glycol mixed solution containing 19.53 mu mol of cobalt chloride hexahydrate and 23.05 mu mol of sodium selenite, stirring for 30 min, transferring to a high-pressure reaction kettle, keeping the temperature at 180 ℃ at 24 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, drying, washing the obtained precipitate with deionized water and ethanol for three times respectively, and vacuum drying at 60 ℃ for overnight to obtain the Co powder 0.85 Se/Mn 0.3 Cd 0.7 S-shaped thermal soundA composite photocatalyst is provided.
Example 2
(1) Solvothermal method for preparing Mn rich in sulfur vacancy 0.3 Cd 0.7 S nano rod
Dissolving 14 mmol of cadmium acetate and 6 mmol of manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stirring for 20 min, adding 25 mmol of thioacetamide, continuing stirring for 30 min, transferring the obtained mixed solution into a 100 mL high-pressure reaction kettle, reacting at the constant temperature of 200 ℃ for 24 h, naturally cooling to the room temperature, washing the obtained precipitate with deionized water and ethanol for three times respectively, and then carrying out vacuum drying at the temperature of 60 ℃ overnight to obtain Mn 0.3 Cd 0.7 And (4) S powder.
(2) Solvothermal method for preparing Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst
Weighing the Mn obtained in the step (1) 0.3 Cd 0.7 Dispersing S powder 0.1 g in 30 ml glycol solution and stirring for 30 min, then adding 10 ml glycol mixed solution containing 45.71 mu mol cobalt chloride hexahydrate and 53.78 mu mol sodium selenite, continuously stirring for 30 min, transferring to a high-pressure reaction kettle, keeping the temperature of 180 ℃ for 24 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, drying, washing the obtained precipitate with deionized water and ethanol for three times respectively, and vacuum drying at 60 ℃ for overnight to obtain the Co powder 0.85 Se/Mn 0.3 Cd 0.7 And S, a thermal response composite photocatalyst.
Example 3
(1) Solvothermal method for preparing Mn rich in sulfur vacancy 0.3 Cd 0.7 S nano rod
Dissolving 14 mmol of cadmium acetate and 6 mmol of manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stirring for 20 min, adding 25 mmol of thioacetamide, continuing stirring for 30 min, transferring the obtained mixed solution into a 100 mL high-pressure reaction kettle, reacting at 200 ℃ at 24 h under constant temperature, naturally cooling to room temperature, washing the obtained precipitate with deionized water and ethanol for three times respectively, and vacuum drying at 60 ℃ overnight to obtain Mn 0.3 Cd 0.7 And (4) S powder.
(2) Solvothermal method for preparing Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst
Weighing the Mn obtained in the step (1) 0.3 Cd 0.7 Dispersing S powder 0.1 g in 30 ml glycol solution, stirring for 30 min, adding 10 ml glycol mixed solution containing 65.30 mu mol cobalt chloride hexahydrate and 76.83 mu mol sodium selenite, continuously stirring for 30 min, transferring to a high-pressure reaction kettle, keeping the temperature at 180 ℃ for 24 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, drying, washing the obtained precipitate with deionized water and ethanol for three times, and vacuum drying at 60 ℃ for overnight to obtain the Co powder Co 0.85 Se/Mn 0.3 Cd 0.7 And S, preparing the thermal response composite photocatalyst.
Example 4
(1) Solvothermal method for preparing Mn rich in sulfur vacancy 0.3 Cd 0.7 S nano-rod
Dissolving 14 mmol of cadmium acetate and 6 mmol of manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stirring for 20 min, adding 25 mmol of thioacetamide, continuing stirring for 30 min, transferring the obtained mixed solution into a 100 mL high-pressure reaction kettle, reacting at 200 ℃ at 24 h under constant temperature, naturally cooling to room temperature, washing the obtained precipitate with deionized water and ethanol for three times respectively, and vacuum drying at 60 ℃ overnight to obtain Mn 0.3 Cd 0.7 And (4) S powder.
(2) Solvothermal method for preparing Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst
Weighing the Mn obtained in the step (1) 0.3 Cd 0.7 Dispersing S powder 0.1 g in 30 ml glycol solution, stirring for 30 min, adding 10 ml glycol mixed solution containing 130.60 mu mol cobalt chloride hexahydrate and 153.66 mu mol sodium selenite, stirring for 30 min, transferring to a high-pressure reaction kettle, keeping the temperature at 180 ℃ for 24 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, drying, washing the obtained precipitate with deionized water for three times, and drying at 60 ℃ in vacuum for overnight to obtain the Co powder 0.85 Se/Mn 0.3 Cd 0.7 S HeatResponding to the composite photocatalyst.
FIG. 1 (a) shows Mn 0.3 Cd 0.7 X-ray diffraction pattern of S composite photocatalyst and CdS and MnS standard XRD card, and (b) is Mn 0.3 Cd 0.7 S、Co 0.85 Se and Co obtained in examples 1 to 4 0.85 Se/Mn 0.3 Cd 0.7 And an X-ray diffraction pattern of the S composite photocatalyst. As can be seen from FIG. 1, mn was obtained 0.3 Cd 0.7 S and Co 0.85 Se/Mn 0.3 Cd 0.7 The X-ray diffraction peak of the S composite material is matched with a corresponding standard XRD card, which indicates the successful preparation of the catalyst.
FIG. 2 is a graph showing the formation of a precipitate in Co 0.85 Se/Mn 0.3 Cd 0.7 During S synthesis, mn is not added 0.3 Cd 0.7 S pure Co 0.85 X-ray diffraction pattern of Se sample, diffraction peak and Co 0.85 Se standard card matching, proving Co 0.85 The successful preparation of Se.
FIG. 3 is 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (example 2) scanning electron micrographs and (b-d) transmission electron micrographs of the composite photocatalyst. As can be seen from the figure, mn 0.3 Cd 0.7 S has a smooth nanorod structure with a diameter of about 50nm and a length of 150-700 nm; co 0.85 Se nanoparticles about 10nm are successfully loaded in Mn 0.3 Cd 0.7 On the surface of the S nano-rod. The lattice fringes of 0.34 and 0.25 nm are attributed to Mn, respectively 0.3 Cd 0.7 (002) face of S and Co 0.85 The (101) crystal plane of Se, further proving that Co 0.85 Se and Mn 0.3 Cd 0.7 And (4) successfully preparing S.
FIG. 4 is 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 And S (embodiment 2) a transmission electron microscope selected element distribution diagram of the composite photocatalyst. As can be seen from the figure, co produced 0.85 Se nanoparticles are uniformly dispersed and attached to Mn 0.3 Cd 0.7 And the S nano rod is arranged on the surface and is in close contact with the surface.
FIG. 5 shows Mn with a deficiency of sulfur vacancies 0.3 Cd 0.7 S-p and S-rich vacancy Mn 0.3 Cd 0.7 Electron paramagnetic resonance of SIn contrast, it could be confirmed that a sulfur vacancy is present in Mn 0.3 Cd 0.7 In the S structure. Mn 0.3 Cd 0.7 The S-p synthesis method comprises the following steps: the same procedure as in example was repeated except that the amount of thioacetamide used in step (1) of example was changed to 20 mmol, to obtain Mn lacking sulfur vacancies 0.3 Cd 0.7 S（S vacancies-poor Mn 0.3 Cd 0.7 S) and named Mn 0.3 Cd 0.7 S-p。
Application example
1. Co obtained in examples 1 to 4 0.85 Se/Mn 0.3 Cd 0.7 The S composite photocatalysts are respectively used for hydrogen production by water decomposition under the induction of visible light, and the method comprises the following specific steps: a sample of 5 mg catalyst was weighed into 50 mL containing 0.25M Na 2 S and 0.35M Na 2 SO 3 The solution is placed in a photocatalytic hydrogen production system, the reaction temperature is controlled by constant-temperature circulating condensed water, after the system is vacuumized, a xenon lamp light source is started to carry out photocatalytic decomposition on water to produce hydrogen, and the amount of the produced hydrogen is detected by gas chromatography.
FIG. 6 (a) is a comparison of hydrogen production activity of different catalyst samples photocatalytic decomposed water under visible light induction, with catalysts with sulfur defects having higher hydrogen production activity than samples with sulfur vacancies lacking; dark treatment experiments show that the hydrogen production by thermal catalysis is not performed at 25 ℃, and the introduction of heat is proved not to initiate the hydrogen production by thermal catalysis.
FIG. 6 (b) shows Mn 0.3 Cd 0.7 S、Co 0.85 Se and Co obtained in examples 1 to 4 0.85 Se/Mn 0.3 Cd 0.7 And (3) a comparison graph of hydrogen activity of the S composite photocatalyst in photocatalytic decomposition of water under the induction of visible light. As can be seen from the figure, co 0.85 Se/Mn 0.3 Cd 0.7 The activity of the S composite photocatalyst is higher than that of simple Mn 0.3 Cd 0.7 The activity of the S catalyst is obviously improved, and the highest hydrogen production rate is improved by about 4 times, which proves that the Co prepared by the invention 0.85 Se/Mn 0.3 Cd 0.7 The S composite photocatalyst has high-efficiency photocatalytic hydrogen production activity.
FIG. 6 (c) shows 7 wt% Co at different temperatures 0.85 Se/Mn 0.3 Cd 0.7 And S (example 2) the hydrogen production rate of the composite photocatalyst. As can be seen from the figure, the photocatalytic hydrogen production rate can be remarkably improved by increasing the temperature, which shows that the composite catalyst prepared by the invention has obvious response to the temperature, and the photocatalytic hydrogen production rate can be controlled by adjusting the temperature.
FIG. 6 (d) is 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S long-time hydrogen production circulation experiment chart of the composite photocatalyst. As can be seen in the figure, after four light reaction cycles (total 16 h), the activity of the composite catalyst is only slightly reduced, which indicates that the catalyst has better stability.
TABLE 1
Table 1 shows that the photocatalyst of the present invention has significantly higher hydrogen production activity compared with the related photocatalyst reported recently.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. Co rich in sulfur vacancy 0.85 Se/Mn 0.3 Cd 0.7 The S thermal response type composite photocatalyst is characterized in that: the composite photocatalyst is prepared from Mn rich in sulfur vacancy 0.3 Cd 0.7 S nanorod loaded Co 0.85 A composite material of Se nanoparticles;
the Mn is 0.3 Cd 0.7 The length of the S nanorod is 150-700 nm, and the diameter of the S nanorod is 50 nm; the Co 0.85 The diameter of the Se nano-particles is 5-10 nm;
the Co rich in sulfur vacancy 0.85 Se/Mn 0.3 Cd 0.7 The preparation method of the S thermal response type composite photocatalyst comprises the following steps:
(1) Solvothermal method for preparing Mn rich in sulfur vacancy 0.3 Cd 0.7 S nano-rod:
dissolving cadmium acetate and manganese acetate in a mixed solvent of ethylenediamine and deionized water, adding thioacetamide, continuously stirring and uniformly mixing, transferring the obtained mixed solution into a high-pressure reaction kettle, reacting at a constant temperature of 200 ℃ for 24 h, naturally cooling to room temperature, sequentially washing the obtained precipitate with deionized water and ethanol for three times respectively, and then drying at 60 ℃ in vacuum overnight to obtain Mn 0.3 Cd 0.7 S powder;
(2) Solvothermal method for preparing Co 0.85 Se/Mn 0.3 Cd 0.7 S thermal response type composite photocatalyst:
the obtained Mn 0.3 Cd 0.7 Dispersing S powder in 30 ml glycol solution, stirring for 30 min, adding a glycol mixed solution containing cobalt chloride and sodium selenite, continuously stirring for 30 min, transferring to a high-pressure reaction kettle, keeping the temperature of the high-pressure reaction kettle at 180 ℃ at 24 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, drying, washing the obtained precipitate with deionized water and ethanol for three times respectively, and vacuum-drying at 60 ℃ overnight to obtain the Co powder 0.85 Se/Mn 0.3 Cd 0.7 S thermal response type composite photocatalyst.
2. Sulfur vacancy rich Co of claim 1 0.85 Se/Mn 0.3 Cd 0.7 The S thermal response type composite photocatalyst is characterized in that: the molar ratio of manganese acetate, cadmium acetate and thioacetamide used in step (1) is 6.
3. Co of claim 1 0.85 Se/Mn 0.3 Cd 0.7 The S thermal response type composite photocatalyst is characterized in that: the volume ratio of the ethylenediamine to the deionized water in the mixed solvent in the step (1) is 1:1.
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