CN108421555A - A kind of preparation method of cobalt/carboritride hydridization photochemical catalyst - Google Patents
A kind of preparation method of cobalt/carboritride hydridization photochemical catalyst Download PDFInfo
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- CN108421555A CN108421555A CN201810156949.9A CN201810156949A CN108421555A CN 108421555 A CN108421555 A CN 108421555A CN 201810156949 A CN201810156949 A CN 201810156949A CN 108421555 A CN108421555 A CN 108421555A
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- carboritride
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- water
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 63
- 239000010941 cobalt Substances 0.000 title claims abstract description 63
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052724 xenon Inorganic materials 0.000 claims description 12
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005286 illumination Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- -1 sodium hypophosphites Chemical class 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling 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
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of cobalt/carboritride hydridization photochemical catalyst, belong to materials science field and photocatalysis field.It foundes short-cut method and prepares a kind of cobalt/carboritride hydridization photochemical catalyst, to reduce photochemical catalyst cost, improve photochemical catalyzing hydrogen-producing speed.The preparation method of the composite catalyst is environmentally protective, and the composite catalyst prepared has longer life, still has higher catalytic activity after 54h.Cobalt/carboritride hydridization photochemical catalyst simple synthetic method, Photocatalyzed Hydrogen Production rate height, stability prepared by the present invention is good, cheap, it is a kind of catalysis material with industrial Photocatalyzed Hydrogen Production foreground applied to can be significantly cost-effective in industrial production.
Description
Technical field
The present invention relates to a kind of preparation methods of cobalt/carboritride hydridization photochemical catalyst, belong to material science and technology neck
Domain and photocatalytic hydrogen production by water decomposition field.
Background technology
Scientific and technological with the mankind is constantly progressive, and fossil energy largely uses so that global environmental pollution and energy crisis day
It is beneficial serious, develop a kind of highest attention for the countries in the world that novel sustainable energy obtains.Hydrogen is as a kind of novel renewable
The extensive concern that clean energy resource obtains, it is considered to be the optimal energy.Water as vast resources on the earth and hydrogen content it is higher,
Therefore hydrogen production by water decomposition is possible to one of the important method of experiment large-scale production hydrogen.And utilize decomposing water with solar energy system
Hydrogen is to convert the solar into the chemical energy being stored in hydrogen energy source, and the cheap, easily of hydrogen is obtained which provides a kind of
Method.Efficient photochemical catalyst is the key that photocatalytic hydrogen production by water decomposition during photocatalytic hydrogen production by water decomposition.
Carboritride is as a kind of novel no metallic compound, and raw material is cheap, preparation method is easy, and with preferable
Thermal stability, chemical stability and its visible absorption, there is extensive research and application prospect.Metal and its compound with
Carboritride is compound to help to improve its catalytic effect, however its synthesis mode and the mode of action are varied, existing gold
It is not clear regularity to belong to the composite photo-catalyst prepared with carboritride.In conjunction with nickel simple substance and its compound
For carboritride since nickel raw material is more expensive, overall cost is high, is unfavorable for industrialization promotion and application, therefore, it is necessary to a kind of synthesis
The lower photochemical catalyst of cost.Cobalt element is widely present in nature, cheap.By metallic cobalt simple substance and carboritride
The photochemical catalyst that hydridization is prepared can significantly inhibit the compound of carboritride photo-generated carrier, to improve carbon nitrification
The performance of object photocatalytic hydrogen production by water decomposition.However existing synthetic method is faced with complicated preparation process, period length, energy consumption at present
The problems such as high, therefore, this invention address that probe into it is a kind of preparing simplicity, low energy consumption, and the method for the high light assistant depositing of product is closed
At cobalt/carboritride hydridization photochemical catalyst and it is used for Photocatalyzed Hydrogen Production.
Invention content
The purpose of the present invention is being directed to current environment and its energy, it is miscellaneous that exploitation simplicity prepares cobalt/carboritride
The method of photocatalysis agent decomposes water H2-producing capacity to improve photochemical catalyst, reduces photochemical catalyst cost.The hydridization photocatalysis
The preparation method of agent is environmentally protective, and the hydridization photochemical catalyst prepared has longer life, and still higher light is urged after reacting 54h
Change and decomposes water activity.
Technical scheme of the present invention includes mainly following content：
The first purpose of the invention is to provide a kind of cobalt/carboritride hydridization photochemical catalyst, the cobalts/carbon nitrification
Object hydridization photochemical catalyst is that simple substance cobalt is incorporated in carboritride surface.
In one embodiment of the invention, the cobalt simple substance is to be incorporated in carboritride table by photochemical method
Face.
In one embodiment of the invention, the carboritride be with thiocarbamide, in urea, melamine extremely
Few one kind is raw material, is obtained after being placed in 500~550 DEG C of 2~5h of calcining.
In one embodiment of the invention, the cobalt/carboritride hydridization photochemical catalyst is to make as follows
Standby：(1) thiocarbamide is calcined into 1.5~3h in 540~560 DEG C, will be calcined in 480~520 DEG C after the solid abrasive after calcining
Carboritride is made in 1.5~3h；(2) by the mixed aqueous solution of carboritride and sodium hypophosphite and cobalt chloride according to 1g：
The ratio of 100~150mL mixes, and 450mL water and 100~150mL triethanolamines is added, and is uniformly mixed；Lead to after 5~8min of ultrasound
Enter 50~70 min of nitrogen to remove oxygen in reaction system, then mixture is placed under xenon lamp and is irradiated, when illumination persistently stirs
It mixes；(3) it centrifuges, collects solid, successively washed with water, ethyl alcohol, dry obtained cobalt/carboritride hydridization photochemical catalyst.
Second object of the present invention is to provide a kind of preparation method of cobalt/carboritride hydridization photochemical catalyst, including
Following steps：(1) carboritride is prepared：Thiocarbamide is calcined into 2~5h at 500~550 DEG C, carboritride is made；(2) illumination
Obtain cobalt/carboritride：By carboritride and the compound containing cobalt with 1g：The ratio of 100~150ml (0.1M) mixes,
40~80min of illumination under xenon lamp；(3) post-processing of photochemical catalyst：Solid, washing, drying is collected by centrifugation.
In one embodiment of the invention, the step of the method specifically includes：
(1) it takes appropriate thiocarbamide to be placed in crucible, crucible is placed in 550 DEG C of calcining 2h in Muffle furnace, will be taken after reaction
Go out crucible, be replaced in crucible after obtained solid is fully ground, and crucible is placed in 500 DEG C of calcining 2h in Muffle furnace, waits for
Gained yellow-white powder is carboritride after reaction；
(2) it takes suitable carboritride to be placed in 50mL single necked round bottom flask, the sodium hypophosphite and chlorine of certain volume is added
Change the mixed aqueous solution of cobalt, suitable quantity of water and triethanolamine is then added, is uniformly mixed.Nitrogen 60min is passed through after ultrasonic 5min
To remove oxygen in reaction system, then mixture is placed under xenon lamp and is irradiated, when illumination keeps uniform stirring；
(3) after irradiating, gained is detached into solid using centrifugal separation, using deionized water centrifuge washing 3-4 times,
Ethyl alcohol washs 1-2 times, gained black solid material is dried, gained black solid material is that product cobalt/carboritride is miscellaneous
Photocatalysis agent.
Third object of the present invention is to provide application of the method in terms of decomposing water and preparing hydrogen.
In one embodiment of the invention, the method is to decompose water with the catalyst to prepare hydrogen.
In one embodiment of the invention, the method is that catalyst is added with the ratio of 5mg/8~10mL water
Into water, the illumination under oxygen-free environment.
Beneficial effects of the present invention：Metallic cobalt/carbon nitrification is quickly made using simple light assisted deposition in the present invention
The photochemical catalyst of object hydridization, gained cobalt nanometer particle are dispersed in carbon nitrification surface, preparation method low using cost of material
Simplicity, cost prepared by the photochemical catalyst being greatly lowered；It is magnetic material to prepare gained photochemical catalyst, for liquid-solid opposite
It answers, convenient for being separated and recovered after reaction, reduces catalyst cost recovery；Using cobalt as the co-catalyst of light-catalyzed reaction, greatly
Photochemical catalyzing hydrogen generation efficiency is improved greatly, there is higher photocatalytic activity compared to other types transition metal, after 7h
Its average hydrogen-producing speed is about 2296 μm of ol g-1h-1, about 75 times are improved than simple carboritride hydrogen-producing speed.The present invention
Gained cobalt/carboritride hydridization photochemical catalyst can be used for the reaction of sunlight hydrogen production by water decomposition, price is low and hydrogen-producing speed compared with
It is high.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of cobalt/carboritride hydridization photochemical catalyst；
Fig. 2 is cobalt/carboritride hydridization photochemical catalyst scanning electron microscope energy dispersion X-ray spectrum；
Fig. 3 is cobalt/carboritride hydridization photochemical catalyst Photocatalyzed Hydrogen Production test chart.
Specific implementation mode
The detection method of cobalt quality：The quality of cobalt in catalyst is detected using atomic absorption spectrophotometer.
Embodiment 1
(1) it takes 20g thiocarbamides to be placed in crucible, crucible is placed in 550 DEG C of Muffle furnaces and calcines two hours, after reaction,
It by blocks of solid grind into powder and is transferred in crucible using mortar, the crucible for filling powder is then placed in 500 DEG C of Muffles
It is calcined two hours in stove, waits for that drop takes out white-yellowish solid powder and obtains carboritride after reaction；
(2) it takes the above-mentioned carboritride powder of 10mg to be placed in single-necked flask, (the complexing of 2mL triethanolamines is then added
Agent), 0.7mL cobalt chloride solutions (0.1M), 2.335mL sodium hypophosphites aqueous solution (0.15M) (sacrifice agent), 4.965mL water,
Ultrasonic disperse handles 1min, and then nitrogen degassing 30min removes oxygen in reaction system；
(3) after the completion of to be de-gassed, round-bottomed flask is placed under 300W xenon lamps after irradiating 2h, is consolidated gained using centrifuge
Body centrifuges, and deionized water is washed 3 times, and ethyl alcohol washs 1 time, the whole night in 60 DEG C of vacuum drying one by solid, gained black object
Matter is cobalt/carboritride hydridization photochemical catalyst.
The present embodiment preparation gained cobalt/carboritride hydridization photochemical catalyst photochemical catalyzing H2-producing capacity is preferable, production
Hydrogen amount reaches 2296 μm of ol g-1h-1.Its cobalt mass percentage is 6.5%.
The photochemical catalyst of preparation is subjected to X-ray diffraction spectra, it can be seen that there is no bright for the characteristic peak of carboritride
It is aobvious to change, when the load capacity of cobalt is 6.5wt%, it can obviously observe the characteristic peak of cobalt simple substance, illustrate that cobalt simple substance is successfully born
It is downloaded on carboritride and does not change its lattice structure.Transmission electron microscope further demonstrates cobalt/carboritride (shown in Fig. 1)
The pattern and structure of hydridization photochemical catalyst, size have successfully loaded to the carbon nitridation of sheet in the cobalt granule of 50-200nm or so
It closes on object.Energy dispersion X-ray spectrum (EDX) (shown in Fig. 2), it was demonstrated that cobalt in cobalt/carboritride hydridization photochemical catalyst,
Carbon, the presence of the elements such as nitrogen, and other impurities element is not found, illustrate successfully to prepare cobalt/carbon nitrification by light assistant depositing
Object hydridization photochemical catalyst.
Embodiment 2
(1) it is placed in round bottom single-necked flask using carboritride 10mg in embodiment 1,2mL triethanolamines is then added,
0.6mL cobalt chloride solutions (0.1M), 2mL sodium hypophosphites aqueous solution (0.15M), 5.4mL water, ultrasonic disperse handle 1min, so
Nitrogen degassing 30min removes oxygen in reaction system afterwards；
(2) after the completion of to be de-gassed, round-bottomed flask is placed under 300W xenon lamps after irradiating 2h, is consolidated gained using centrifuge
Body centrifuges, and deionized water is washed 3 times, and ethyl alcohol washs 1 time, the whole night by 60 DEG C of vacuum drying one of solid, gained atrament
As cobalt/carboritride hydridization photochemical catalyst.
After measured, the present embodiment preparation gained cobalt/carboritride hydridization photochemical catalyst cobalt mass percentage is
5.1%.
Embodiment 3
(1) it is placed in round bottom single-necked flask using carboritride 10mg in embodiment 1,2mL triethanolamines is then added,
0.8mL cobalt chloride solutions (0.1M), 2.670mL sodium hypophosphites aqueous solution (0.15M), 4.530mL water, ultrasonic disperse processing
1min, then nitrogen degassing 30min remove reaction system in oxygen；
(2) after the completion of to be de-gassed, round-bottomed flask is placed under 300W xenon lamps after irradiating 2h, is consolidated gained using centrifuge
Body centrifuges, and deionized water is washed 3 times, and ethyl alcohol washs 1 time, the whole night by 60 DEG C of vacuum drying one of solid, gained atrament
As cobalt/carboritride hydridization photochemical catalyst.
After measured, it is 8.4% to prepare gained cobalt/carboritride hydridization photochemical catalyst cobalt mass percentage.
Embodiment 4
It takes 10mg to be placed in round bottom single-necked flask class graphene carbon nitrogen compound in embodiment 1, tri- second of 2mL is then added
Hydramine, 8mL water.Be ultrasonically treated 1min, nitrogen deaerate 30min exclusion systems in oxygen, round-bottomed flask is placed in 300W xenon lamps
Lower irradiation with the hydrogen generated in thermal conductivity-gas chromatographic detection reaction, reacts its average hydrogen-producing speed after 2h after reaction
For 27.3 μm of ol g-1h-1。
Embodiment 5
It takes 10mg to be placed in round bottom single-necked flask cobalt in embodiment 1/carboritride hydridization photochemical catalyst, is then added
2mL triethanolamines, 8mL water.Be ultrasonically treated 1min, nitrogen deaerate 30min exclusion systems in oxygen, round-bottomed flask is placed in 300
It is irradiated under W xenon lamps, after reaction, with the hydrogen generated in thermal conductivity-gas chromatographic detection reaction, reacts its average production after 7h
Hydrogen rate is about 4430 μm of ol g-1h-1, about 160 times are improved than simple carboritride hydrogen-producing speed.
Embodiment 6
It takes 10mg to be placed in round bottom single-necked flask cobalt in embodiment 1/carboritride hydridization photochemical catalyst, is then added
2mL triethanolamines and 8mL water.Be ultrasonically treated 1min, nitrogen deaerate 30min exclusion systems in oxygen, round-bottomed flask is placed in too
Illumination under sunlight simulator.Every the 6h hydrogen generated in thermal conductivity-gas chromatographic detection reaction, and the 30min that deaerates excludes body
Hydrogen in system continues round-bottomed flask being placed in illumination under solar simulator, and 54h rear catalysts activity to be reacted is still without apparent drop
Low (shown in Fig. 3).
Although the present invention has been described by way of example and in terms of the preferred embodiments, it is not limited to the present invention, any to be familiar with this skill
The people of art can do various change and modification, therefore the protection model of the present invention without departing from the spirit and scope of the present invention
Enclosing be subject to what claims were defined.
Claims (9)
1. a kind of cobalt/carboritride hydridization photochemical catalyst, which is characterized in that the cobalt/carboritride hydridization photochemical catalyst
It is that simple substance cobalt is incorporated in carboritride surface by photochemical method.
2. cobalt according to claim 1/carboritride hydridization photochemical catalyst, which is characterized in that the carboritride
It is to be obtained after being placed in 500~550 DEG C of 2~5h of calcining for raw material at least one of thiocarbamide, urea, melamine.
3. cobalt according to claim 1/carboritride hydridization photochemical catalyst, which is characterized in that the photochemical method
It is by carboritride and the compound containing cobalt as being reacted under xenon lamp.
4. according to any cobalt/carboritride hydridization photochemical catalyst of claims 1 to 3, which is characterized in that the cobalt/
Carboritride hydridization photochemical catalyst is prepared as follows：(1) thiocarbamide is calcined into 1.5~3h in 540~560 DEG C, it will
1.5~3h is calcined in 480~520 DEG C after solid abrasive after calcining, carboritride is made；(2) by carboritride with it is dense
The mixed aqueous solution of sodium hypophosphite and cobalt chloride that degree is 0.05~0.2mol/L is according to 1g：The ratio of 100~150mL mixes,
450mL water and 100~150mL triethanolamines is added, is uniformly mixed；It is passed through 50~70min of nitrogen after 5~8min of ultrasound, then
Mixture is placed under xenon lamp and is irradiated, when illumination persistently stirs；(3) it centrifuges, collects solid, successively washed with water, ethyl alcohol, it is dry
Cobalt/carboritride hydridization photochemical catalyst is made.
5. a kind of preparation method of cobalt/carboritride hydridization photochemical catalyst, which is characterized in that include the following steps：(1) it prepares
Carboritride：Thiocarbamide is calcined into 2~5h at 500~550 DEG C, carboritride is made；(2) illumination obtains cobalt/carbon nitrification
Object：By the compound solution of carboritride and 0.05~0.2M containing cobalt with 1g：The ratio of 100~150ml mixes, light under xenon lamp
According to 40~80min；(3) post-processing of photochemical catalyst：Solid, washing, drying is collected by centrifugation.
6. according to the method described in claim 5, it is characterized in that, specifically comprising the following steps：
(1) thiocarbamide is placed in 530~550 DEG C of 1~2h of calcining, again in 500~520 DEG C of calcinings after obtained solid is fully ground
1~2h；
(2) take carboritride made from step (1), the mixed solution of sodium hypophosphite and cobalt chloride be added, be then added water and
Triethanolamine, mixing are passed through nitrogen after 3~5min of ultrasound, then mixture are placed under xenon lamp and is irradiated, and when illumination keeps uniformly
Stirring；
(3) after irradiating, gained is detached into solid using centrifugal separation, uses deionized water centrifuge washing 3-4 times, ethyl alcohol
The solid matter of gained is dried in washing 1-2 times, and the solid matter of gained is product cobalt/carboritride hydridization photocatalysis
Agent.
7. any cobalt/application of the carboritride hydridization photochemical catalyst in terms of preparing hydrogen of Claims 1 to 4.
8. a kind of method preparing hydrogen, which is characterized in that miscellaneous using any cobalt/carboritride of Claims 1 to 4
Water is decomposed in photocatalysis agent.
9. according to the method described in claim 9, it is characterized in that, by catalyst with the ratio of 5mg/8~10mL water be added to
In water, the illumination under oxygen-free environment.
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