CN109663599A - A kind of preparation and its application of the octahedra Cd-Co binary sulfide of pattern size tunable - Google Patents
A kind of preparation and its application of the octahedra Cd-Co binary sulfide of pattern size tunable Download PDFInfo
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- CN109663599A CN109663599A CN201811640466.2A CN201811640466A CN109663599A CN 109663599 A CN109663599 A CN 109663599A CN 201811640466 A CN201811640466 A CN 201811640466A CN 109663599 A CN109663599 A CN 109663599A
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000012266 salt solution Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 18
- SOBHUZYZLFQYFK-UHFFFAOYSA-K trisodium;hydroxy-[[phosphonatomethyl(phosphonomethyl)amino]methyl]phosphinate Chemical compound [Na+].[Na+].[Na+].OP(O)(=O)CN(CP(O)([O-])=O)CP([O-])([O-])=O SOBHUZYZLFQYFK-UHFFFAOYSA-K 0.000 claims description 18
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 238000006303 photolysis reaction Methods 0.000 abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 abstract description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract 1
- 239000010941 cobalt Substances 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 238000000354 decomposition reaction Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- -1 hydrogen Chemical class 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- 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
-
- 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
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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
- C01B2203/02—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
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- 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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- General Health & Medical Sciences (AREA)
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Abstract
A kind of preparation method of the octahedra Cd-Co binary sulfide of pattern size tunable: three sodium water solution of trithiocyanuric acid is added drop-wise to dropwise in the metal salt solution of cadmium and cobalt, is stirred, and is centrifuged, and is washed, dry, obtains solid powder；Octahedra Cd-Co binary sulfide powder is obtained through pyrolytic, is used for photodissociation aquatic products hydrogen.Stable appearance is obtained by the method for chemical coprecipitation, size is uniform, and the high presoma of crystallinity obtains binary sulfur product through pyrolytic.By the ratio for regulating and controlling metal salt, the change that the presoma shape of octahedron partial size of acquisition may be significantly, original pattern can be still kept after pyrolytic, improve its photocatalytic water hydrogen production potential, and the present invention can remove the heavy metal ion in solution, easy to operate, repeatability is high, lower to equipment and environmental requirement；The features such as the pattern partial size of final sulfide can also be regulated and controled by regulating and controlling the ratio of metal ion, optimize it and produce hydrogen activity.
Description
Technical field
The invention belongs to semiconductor nano material and photocatalysis technology field, in particular to the eight of a kind of pattern size tunable
The preparation and its application of face body Cd-Co binary sulfide.
Background technique
With the continuous aggravation of the increasingly depleted and environmental pollution of fossil fuel, clean energy resource is developed to replace conventional fossil
Fuel becomes especially urgent.Because of many advantages, such as higher efficiency of combustion, clean combustion product, hydrogen in the world by
More and more concerns, while the fields such as chemical material and environmental energy are also by the preparation of hydrogen as important technical research side
To.If hydrogen can be used as conventional energy resource, energy problem brought by fossil fuel shortages, Jin Erbao on the one hand can be alleviated
Hinder the normal production and living of the mankind；On the other hand, the combustion product H of hydrogen2O no pollution to the environment will not bring acid rain, greenhouse
The ecological problems such as effect.However currently, industrial production hydrogen mode that there is energy consumptions is excessive, hydrogen generation efficiency is excessively low to ask
Topic, new hydrogen manufacturing mode are urgently developed.In face of inexhaustible, nexhaustible solar energy, using semiconductor material come photocatalytic water
Generating hydrogen and also taking advantage of a situation has the project for exploring meaning as one.
By carefully studying, a large amount of semiconductor material can be applied to photodissociation aquatic products hydrogen field.Wherein, because it is suitable
Band structure, vulcanization cadmium material be widely used.However the vulcanization cadmium material prepared by conventional means, although can be real
Now to the absorption of visible light, photo-generated carrier is generated, but its irregular material morphology is difficult to provide biggish surface area, in turn
Active site needed for producing hydrogen is influenced, therefore also seriously limits its photo-catalysis capability.In recent years, it explores and changes vulcanization cadmium material
Topographical property also seem particularly important come the method for improving its performance.Based on previous report, such as Zhuang etc.
(H.Zhuang, et al., Sci.Rep.2015,5,16947) synthesizes regular octahedron Cd for the first time3(C3N3S3)2Material, after by Yin Shuan
Phoenix etc. (Chinese patent 201711158679.7, publication number CN107827166A, publication date 2017.09.05, examine in-substantive examination)
Octahedra cadmium sulfide is generated by the way that water-soluble sulfide is added, to realize its photocatalytic applications.However, poly- to octahedral coordination
The control of object pattern is closed, the research of the pattern size control of the generating process and octahedron sulfide of final sulfide is relatively
It is few.Therefore, by being further simplified preparation process, improve three-dimensional cadmium sulfide material morphology, for enhancing it in photocatalysis field
Application have far reaching significance.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of octahedrals of pattern size tunable
The preparation and its application of body Cd-Co binary sulfide, the pattern size tunable of octahedron Cd-Co binary sulfide, crystallinity
Height, large specific surface area, phase is stablized, green non-poisonous, and synthesis is convenient, has excellent photocatalytic hydrogen production by water decomposition performance.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of preparation method of the octahedra Cd-Co binary sulfide of pattern size tunable, at room temperature, by caddy and six
Hydrated cobalt chloride, which is dissolved completely in deionized water, obtains metal salt solution, while trithiocyanuric acid trisodium is dissolved in deionized water
Obtain three sodium solution of trithiocyanuric acid；Then under constant stirring, three sodium solution of trithiocyanuric acid is added drop-wise to metal salt dropwise
In solution, precipitating is gradually generated, after completion of dropwise addition, stirs, is centrifuged, clean, it is dry, solid precipitating is obtained, then pyrolytic
Obtain octahedra Cd-Co binary sulfide.
Preferably, the ratio between amount of substance of the caddy and cobalt chloride hexahydrate be 10:0~0:10, as 10:0,8:2,
7:3,6:4,5:5,4:6 or 0:10；The object of metal salt (i.e. the sum of caddy and cobalt chloride hexahydrate) and trithiocyanuric acid trisodium
The ratio between amount of matter is 3:2.
Preferably, after the solution completion of dropwise addition, the time of stirring is 15min, and centrifugation is centrifuged at 10000rpm
15min, cleaning are cleaned twice with deionized water, and drying is to dry 12h at 70 DEG C in air, and pyrolytic is at 400 DEG C
Pyrolytic in air.
Preferably, as Cd in initial metal salt solution2+/Co2+When < 1, with Co2+The increase of content, finally obtains TMT-
The partial size of ligand polymer is gradually increased and there is cotton-shaped particles generation on surface, works as Cd2+/Co2+When > 1, with Co2+Content is further
Increase, partial size is gradually reduced, and pattern also becomes irregular flocculent structure from the octahedron of rule.
The octahedra Cd-Co binary sulfide that the present invention prepares gained pattern size tunable can be used as photocatalytic water catalyst,
In CEL-SPH2N Photocatalyzed Hydrogen Production system, 50mL is dispersed by octahedron Cd-Co binary sulfide powder ultrasonic described in 50mg
Containing 10% triethanolamine aqueous solution, separated in time acquisition generates gas and is analyzed, and calculates hydrogen output.
Compared with prior art, the present invention can efficiently prepare the vulcanization cadmium material of function admirable for photodissociation aquatic products
Hydrogen application.Preparation process specifically include that (1) by the method for chemical coprecipitation obtain pattern size tunable and crystallinity it is high eight
Face body (Cd1-xCox)3TMT2As presoma, (2) are obtained by suitable high-temperature sintering process retains its former shape of octahedron
Cd-Co binary sulfide.Wherein pass through regulation Metal Ions Cd2+/Co2+Ratio, intuitively see, the presoma octahedral of acquisition
Bodily form looks partial size is significantly changed, while original pattern can be still kept after pyrolytic, finally improves it
Splitting water hydrogen production potential.Further the invention has the advantages that on the one hand can be removed in solution using chemical coprecipitation method
Heavy metal ion, easy to operate, repeatability is high, lower to equipment and environmental requirement, while used drug and solvent
It is conventional dose, further decreases cost；It on the other hand can also be by regulating and controlling Metal Ions Cd2+/Co2+Ratio to most
The features such as whole cadmium sulfide pattern partial size are regulated and controled, its photodissociation aquatic products hydrogen activity is optimized, while may be subsequent related real
It tests and the base material of function admirable is provided.
Detailed description of the invention
Fig. 1 is the preparation-obtained difference Cd of 1-7 of the embodiment of the present invention2+/Co2+(the Cd of ratio1-xCox)3TMT2Presoma
And its 400 DEG C of decomposition products stereoscan photograph and high-temperature decomposition product pictorial diagram.
Fig. 2 is the embodiment of the present invention 1,8,9 preparation-obtained (Cd0.6Co0.4)3TMT2Presoma and its in different temperatures
The stereoscan photograph of decomposition product under (300 DEG C, 400 DEG C and 500 DEG C).
Fig. 3 is the preparation-obtained difference Cd of 1-9 of the embodiment of the present invention2+/Co2+(the Cd of ratio1-xCox)3TMT2Presoma
X ray diffracting spectrum.
Fig. 4 is the preparation-obtained difference Cd of 1-9 of the embodiment of the present invention2+/Co2+(the Cd of ratio1-xCox)3TMT2Presoma
The X ray diffracting spectrum of decomposition product at 400 DEG C.
Fig. 5 is that (Cd is prepared in the embodiment of the present invention0.6Co0.4)3TMT2Presoma is at 300 DEG C, 400 DEG C and 500 DEG C
The X ray diffracting spectrum of decomposition product.
Fig. 6 is the preparation-obtained (Cd of 1-9 of the embodiment of the present invention1-xCox)3TMT2400 DEG C of high-temperature decomposition products complete
The Yield mapping of photolysis water hydrogen under spectral illumination.
Fig. 7 is that (Cd is prepared in the embodiment of the present invention0.6Co0.4)3TMT2It decomposes and produces at 300 DEG C, 400 DEG C and 500 DEG C
The Yield mapping of object photolysis water hydrogen under full spectral illumination.
Specific embodiment
The present invention is described in further details below by examples and drawings.
Embodiment 1:
At room temperature, 18mmol caddy and 12mmol cobalt chloride hexahydrate are dissolved completely in 120ml deionized water, together
When 20mmol trithiocyanuric acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, trithiocyanuric acid trisodium is molten
Liquid is added drop-wise in metal salt solution dropwise, gradually generates precipitating, after completion of dropwise addition, is stirred 15min, is centrifuged under 10000rpm
15min, deionized water clean twice, dry 12h at 70 DEG C in air, obtain shallow green powder, and then in air 400 DEG C
Lower pyrolytic obtains brown ceramic powder.
Embodiment 2:
At room temperature, 30mmol caddy is dissolved completely in 120ml deionized water, while by 20mmol trithiocyanuric acid
Trisodium is dissolved in 60ml deionized water；Then under constant stirring, that three sodium solution of trithiocyanuric acid is added drop-wise to metal salt dropwise is molten
In liquid, precipitating is gradually generated, after completion of dropwise addition, stirs 15min, 15min is centrifuged under 10000rpm, deionized water is cleaned twice,
12h is dried at 70 DEG C in air, obtains off-white powder, is then passed through in air that pyrolysis process obtains at 400 DEG C
Yellow powder.
Embodiment 3:
At room temperature, 24mmol caddy and 6mmol cobalt chloride hexahydrate are dissolved completely in 120ml deionized water, together
When 20mmol trithiocyanuric acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, trithiocyanuric acid trisodium is molten
Liquid is added drop-wise in metal salt solution dropwise, gradually generates precipitating, after completion of dropwise addition, is stirred 15min, is centrifuged under 10000rpm
15min, deionized water clean twice, dry 12h at 70 DEG C in air, obtain pale green powder, be then passed through in air
Pyrolysis process obtains dark brown powder at 400 DEG C.
Embodiment 4:
At room temperature, 21mmol caddy and 9mmol cobalt chloride hexahydrate are dissolved completely in 120ml ionized water, simultaneously
20mmol trithiocyanuric acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, by three sodium solution of trithiocyanuric acid
It is added drop-wise in metal salt solution dropwise, gradually generates precipitating, after completion of dropwise addition, stir 15min, be centrifuged 15min under 10000rpm,
Deionized water is cleaned twice, is dried 12h at 70 DEG C in air, is obtained shallow green powder, is then passed through in air at 400 DEG C
Pyrolysis process obtains brown ceramic powder.
Embodiment 5:
At room temperature, 15mmol caddy and 15mmol cobalt chloride hexahydrate are dissolved completely in 120ml deionized water, together
When 20mmol trithiocyanuric acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, trithiocyanuric acid trisodium is molten
Liquid is added drop-wise in metal salt solution dropwise, gradually generates precipitating, after completion of dropwise addition, is stirred 15min, is centrifuged under 10000rpm
15min, deionized water clean twice, dry 12h at 70 DEG C in air, obtain shallow green powder, be then passed through in air
Pyrolysis process obtains dark brown powder at 400 DEG C.
Embodiment 6:
At room temperature, 12mmol caddy and 18mmol cobalt chloride hexahydrate are dissolved completely in 120ml deionized water, together
When 20mmol trithiocyanuric acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, trithiocyanuric acid trisodium is molten
Liquid is added drop-wise in metal salt solution dropwise, gradually generates precipitating, after completion of dropwise addition, is stirred 15min, is centrifuged under 10000rpm
15min, deionized water clean twice, dry 12h at 70 DEG C in air, obtain shallow green powder, be then passed through in air
Pyrolysis process obtains blackish green powder at 400 DEG C.
Embodiment 7:
At room temperature, 30mmol cobalt chloride hexahydrate is dissolved completely in 120ml deionized water, while by 20mmol trimerization
Thiocyanic acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, three sodium solution of trithiocyanuric acid is added drop-wise to gold dropwise
Belong in salting liquid, gradually generate precipitating, after completion of dropwise addition, stir 15min, 15min, deionized water cleaning are centrifuged under 10000rpm
Twice, 12h is dried at 70 DEG C in air, obtains dark brown powder, is then passed through pyrolysis process at 400 DEG C in air
Obtain black powder.
Embodiment 8:
At room temperature, 18mmol caddy and 12mmol cobalt chloride hexahydrate are dissolved completely in 120ml deionized water, together
When 20mmol trithiocyanuric acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, trithiocyanuric acid trisodium is molten
Liquid is added drop-wise in metal salt solution dropwise, gradually generates precipitating, after completion of dropwise addition, is stirred 15min, is centrifuged under 10000rpm
15min, deionized water clean twice, dry 12h at 70 DEG C in air, obtain shallow green powder, be then passed through in air
Pyrolysis process obtains shallow green powder at 300 DEG C.
Embodiment 9:
At room temperature, 18mmol caddy and 12mmol cobalt chloride hexahydrate are dissolved completely in 120ml deionized water, together
When 20mmol trithiocyanuric acid trisodium is dissolved in 60ml deionized water；Then under constant stirring, trithiocyanuric acid trisodium is molten
Liquid is added drop-wise in metal salt solution dropwise, gradually generates precipitating, after completion of dropwise addition, is stirred 15min, is centrifuged under 10000rpm
15min, deionized water clean twice, dry 12h at 70 DEG C in air, obtain shallow green powder, be then passed through in air
Pyrolysis process obtains black powder at 500 DEG C.
It will be seen from figure 1 that as Cd in initial metal salt solution2+/Co2+When < 1, with Co2+The increase of content, is finally obtained
The partial size for obtaining ligand polymer is gradually increased and there is cotton-shaped particles generation on surface, works as Cd2+/Co2+When > 1, with Co2+Further
Increase, partial size is gradually reduced, and pattern is also become the cotton-shaped grain structure of irregular shape from the octahedron of rule.
Figure it is seen that obtained sulfur product is still able to maintain under 300 DEG C and 400 DEG C of hot conditions
(Cd0.6Co0.4)3TMT2Original shape of octahedron, but when temperature is increased to 500 DEG C, shape of octahedron is damaged.
The ligand polymer that can be seen that from Fig. 3, Fig. 4 and Fig. 5 has good crystallinity, but with Co2+Content
Increase, the crystallinity deterioration of powder.Available, (Cd simultaneously0.6Co0.4)3TMT2It is available under 400 DEG C of decomposition conditions
Pure cadmium sulfide crystal phase.
As can be seen from Figures 6 and 7, (Cd0.6Co0.4)3TMT2Decomposition product at 400 DEG C has optimal basic shape
Maximum hydrogen output may be implemented in looks.
In short, appropriate ratio Co2+Addition can accurately regulate and control Cd3TMT2Octahedral pattern partial size generates pattern
(the Cd that partial size has differences1-xCox)3TMT2Presoma, and final pyrolytic sulfur product is influenced, so that it is obtained most ratio of greater inequality
Surface area, sufficient active site, purer sulfide crystal phase realize higher production hydrogen purpose.
Claims (7)
1. a kind of preparation method of the octahedra Cd-Co binary sulfide of pattern size tunable, which is characterized in that at room temperature, will
Caddy and cobalt chloride hexahydrate, which are dissolved completely in deionized water, obtains metal salt solution, while trithiocyanuric acid trisodium is molten
Three sodium solution of trithiocyanuric acid is obtained in deionized water；Then under constant stirring, three sodium solution of trithiocyanuric acid is dripped dropwise
It is added in metal salt solution, gradually generates precipitating, after completion of dropwise addition, stir, be centrifuged, clean, it is dry, solid precipitating is obtained, so
Octahedra Cd-Co binary sulfide is obtained by pyrolytic.
2. the preparation method of the octahedra Cd-Co binary sulfide of pattern size tunable, feature exist according to claim 1
In the ratio between amount of substance of the caddy and cobalt chloride hexahydrate is 10:0~0:10, metal salt and trithiocyanuric acid trisodium
The ratio between the amount of substance be 3:2.
3. the preparation method of the octahedra Cd-Co binary sulfide of pattern size tunable, feature exist according to claim 1
In the ratio between amount of substance of the caddy and cobalt chloride hexahydrate is 10:0,8:2,7:3,6:4,5:5,4:6 or 0:10.
4. the preparation method of the octahedra Cd-Co binary sulfide of pattern size tunable, feature exist according to claim 1
In, after the completion of dropwise addition, time of stirring is 15min, and centrifugation is that 15min is centrifuged at 10000rpm, cleaning be spend from
Twice, drying is to dry 12h at 70 DEG C in air to the cleaning of sub- water, and pyrolytic is pyrolytic in air at 400 DEG C.
5. the preparation method of the octahedra Cd-Co binary sulfide of pattern size tunable, feature exist according to claim 1
In as Cd in initial metal salt solution2+/Co2+When < 1, with Co2+The increase of content, final acquisition TMT- ligand polymer
Partial size is gradually increased and there is cotton-shaped particles generation on octahedra surface；Work as Cd2+/Co2+When > 1, with Co2+Content further increases,
Partial size is gradually reduced, and pattern is also become the cotton-shaped grain structure of irregular shape from the octahedron of rule.
6. the octahedra Cd-Co binary sulfide of claim 1 preparation gained pattern size tunable is as photocatalytic water catalyst
Using.
7. applying according to claim 5, which is characterized in that, will be described in 50mg in CEL-SPH2N Photocatalyzed Hydrogen Production system
Octahedra Cd-Co binary sulfide powder ultrasonic is scattered in 50mL containing 10% triethanolamine aqueous solution, separated in time acquisition
It generates gas to be analyzed, and calculates hydrogen output.
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