CN109174127A - A kind of photocatalytic water prepares the composite photo-catalyst and preparation method of fuel cell hydrogen - Google Patents
A kind of photocatalytic water prepares the composite photo-catalyst and preparation method of fuel cell hydrogen Download PDFInfo
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- CN109174127A CN109174127A CN201811090031.5A CN201811090031A CN109174127A CN 109174127 A CN109174127 A CN 109174127A CN 201811090031 A CN201811090031 A CN 201811090031A CN 109174127 A CN109174127 A CN 109174127A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000001257 hydrogen Substances 0.000 title claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 26
- 239000000446 fuel Substances 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 80
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000004073 vulcanization Methods 0.000 claims abstract description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000006722 reduction reaction Methods 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims description 29
- 239000003638 chemical reducing agent Substances 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 16
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 16
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 16
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 16
- 229960001763 zinc sulfate Drugs 0.000 claims description 16
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 239000004280 Sodium formate Substances 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 6
- 235000019254 sodium formate Nutrition 0.000 claims description 6
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical group [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- 239000005083 Zinc sulfide Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000006303 photolysis reaction Methods 0.000 description 8
- 230000015843 photosynthesis, light reaction Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FQGMPQGXUXIOKI-UHFFFAOYSA-N [S--].[S--].[Cu++].[Zn++] Chemical compound [S--].[S--].[Cu++].[Zn++] FQGMPQGXUXIOKI-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000007144 microwave assisted synthesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000013102 re-test Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing 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
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- 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
-
- 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
-
- 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 belongs to the technical field of catalyzing manufacturing of hydrogen, composite photo-catalyst and preparation method that a kind of photocatalytic water prepares fuel cell hydrogen are provided.This method is using graphene oxide as carrier, pass through hydro-thermal reaction fabricated in situ zinc sulphide bronzing catalyst, then graphene oxide/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made by reduction reaction.It is compared with the traditional method, composite photo-catalyst prepared by the present invention, epigranular, large specific surface area, it is seen that light utilization efficiency is high, and photocatalytic activity is high, and hydrogen-producing speed is high.
Description
Technical field
The invention belongs to the technical field of catalyzing manufacturing of hydrogen, the complex light that a kind of photocatalytic water prepares fuel cell hydrogen is provided
Catalyst and preparation method.
Background technique
Hydrogen is first element in the periodic table of elements, its quality is minimum, and calorific value is high when burning, easily storage, transport and
Regeneration, and any pollution is not generated, be conducive to environmental protection, be counted as the ideal clean energy resource of 21st century.With full generation
The old resource such as the fast development of boundary's modern industry and petroleum is increasingly exhausted, hydrogen fuel cell as it is a kind of cleaning, efficiently, safety
New energy shows wide, tempting market development prospect.
Hydrogen producing technology plays decisive role to the development of hydrogen energy fuel battery.Hydrogen producing technology mainly has fossil fuel at present
Hydrogen manufacturing, water electrolysis hydrogen producing, photolysis water hydrogen etc..Solar energy is a kind of inexhaustible, nexhaustible disposable energy, on the earth
Hydrogen energy source abundant resides in water, and wherein the method for conductor photocatalysis hydrogen manufacturing is to be decomposed by photoelectric process using solar energy
Most economical, the cleaning, practical method of water, the most prospect in hydrogen producing technology, thus by attention.
Currently, mainly thering is photoelectrochemical method, homogeneous light to help complexing using the approach of solar energy photocatalytic water by photoelectric process
Method and conductor photocatalysis method, wherein photochemical catalyst is the key that its development and applies, the most frequently used photochemical catalyst such as titanium dioxide,
Due to its good chemical stability, abrasion resistance, it is inexpensive and nontoxic the features such as, but there is also crystallite dimension is big, compare table
The disadvantages of area is small and low dispersed.In recent years, in novel photocatalyst research, vulcanization zinc-copper composite catalyst is excellent with its
Performance and enter the people visual field.
Chinese invention patent application number 201610321627.6 discloses a kind of solar photolysis water hydrogen and is urged with titanium oxide
Agent, the composition of the titanium oxide catalyst powder body material are as follows: 98.00 ~ 99.88wt% of titanium dioxide, tungstic acid 0.1 ~
1wt%, 0.01 ~ 1wt% of carbon, 0.01 ~ 1wt% of nitrogen.The defect of the invention is titania photocatalyst there are specific surface areas small, powder
Body bad dispersibility in water, it is seen that light utilization efficiency is low, causes hydrogen production rate undesirable.
Chinese invention patent application number 201410181986.7 discloses a kind of vulcanization zinc-copper nanometer of cuprous ion doping
The rapid synthesis method of line visible light catalyst and application, the invention use pressure Microwave-assisted synthesis method, do solvent, divalent with water
Zinc salt is zinc source, and copper nano-wire is substrate, is vulcanized by sulphur source, cleans rapid synthesis with cuprous compared with high visible-light activity
The zinc sulphide copper nano-wire visible light catalyst of ion doping.Can be widely applied to photolysis water hydrogen, solar battery, antibacterial,
The fields such as photocatalysis treatment pollutant.But the visible light utilization efficiency of visible light catalyst made from the invention is still lower, photoproduction
Electronics is easy compound with hole, affects photocatalytic activity, and it is undesirable to be used for effect when photolysis water hydrogen.
In conclusion in the prior art in the catalyst of photolysis water hydrogen, there are photoproduction for zinc sulphide bronzing catalyst
Electronics and hole are easy compound defect, cause photocatalytic activity bad, hydrogen-producing speed is low, therefore develops one kind and can be effectively suppressed
Light induced electron and the high-efficient vulcanization zinc-copper composite photo-catalyst of the compound of hole, photolysis water hydrogen, have great significance.
Summary of the invention
As it can be seen that the zinc sulphide copper catalyst for photolysis water hydrogen of the prior art, there are light induced electrons and hole to be easy
The compound, defects such as photocatalytic activity is bad, hydrogen-producing speed is low.In response to this, the present invention proposes a kind of photocatalytic water preparation combustion
The compound of light induced electron and hole pair can be effectively suppressed in the composite photo-catalyst and preparation method for expecting battery hydrogen, is used for photodissociation
Hydrogen generation efficiency is high when water hydrogen manufacturing.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen, the composite photo-catalyst preparation
Specific step is as follows:
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
30 ~ 40min is mixed, thioacetamide is added, 10 ~ 15min of magnetic agitation is transferred in hydrothermal reaction kettle, and heating pressurization carries out
Reaction, in-situ preparation vulcanization zinc-copper are simultaneously carried on graphene oxide, are filtered, washed, are dried in vacuo, graphite oxide is made
Alkene/vulcanization zinc-copper composite photo-catalyst；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene.
Preferably, the parts by weight of step (1) each raw material are 10 ~ 15 parts by weight of graphene oxide, 1 ~ 2 weight of dispersing agent
Measure part, 4 ~ 8 parts by weight of copper acetate, 4 ~ 8 parts by weight of zinc sulfate, 8 ~ 16 parts by weight of thioacetamide, 51 ~ 73 parts by weight of water.
Preferably, step (1) dispersing agent be sodium methylene bis-naphthalene sulfonate, in dispersing agent MF extremely
Few one kind.
Preferably, the temperature of step (1) described hydro-thermal reaction is 120 ~ 130 DEG C, and pressure is 5 ~ 8MPa, and the time is 2 ~ 3h.
Preferably, the mode of step (1) described washing is first to be washed 2 ~ 4 times using dehydrated alcohol, then use deionized water
Washing to pH value is 7.
Preferably, step (1) the vacuum drying temperature is 40 ~ 60 DEG C, and the time is 15 ~ 20h.
Preferably, the parts by weight of step (2) each raw material are, graphene oxide/vulcanization zinc-copper composite photo-catalyst 20 ~
30 parts by weight, 70 ~ 80 parts by weight of chloroplatinic acid aqueous solution.
Preferably, the mass concentration of step (2) described chloroplatinic acid aqueous solution is 30 ~ 50%.
Preferably, step (2) reducing agent is at least one of sodium borohydride, sodium formate, the temperature of reduction reaction
It is 70 ~ 90 DEG C, the time is 1 ~ 2h.
The present invention also provides a kind of photocatalytic waters that above-mentioned preparation method is prepared to prepare the compound of fuel cell hydrogen
Photochemical catalyst.The composite photo-catalyst is graphene/vulcanization zinc-copper/platinum composite photo-catalyst, is with graphene oxide for load
Body, by hydro-thermal reaction fabricated in situ zinc sulphide bronzing catalyst, then by graphene oxide/vulcanization zinc-copper composite photo-catalyst
It is added in chloroplatinic acid aqueous solution, is made by reduction reaction.
It is and existing the present invention provides composite photo-catalyst and preparation method that a kind of photocatalytic water prepares fuel cell hydrogen
Technology is compared, and the feature and excellent effect protruded is:
1. preparation method of the invention, the carrier using graphene oxide as vulcanization zinc-copper make the grain of vulcanization zinc-copper generated
Degree is uniform, structure-controllable, large specific surface area.
2. zinc sulphide bronzing catalyst produced by the present invention, the crystal structure with ZnS, by Cu2+Introduce the structure of ZnS
In, the absorption to visible light can be enhanced, with the increase of copper zinc molar ratio, the increased activity of photochemical catalyst.
3. in composite photo-catalyst produced by the present invention, graphene has excellent carrier mobility, therefore can be used as
Co-catalyst further in vulcanization zinc-copper surface in situ depositing noble metal platinum, can obviously accelerate the separation speed of photo-generated carrier
Degree inhibits the compound of light induced electron and hole pair, plays synergistic effect with graphene, significantly improves the rate of catalysis production hydrogen.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
34min is mixed, thioacetamide is added, magnetic agitation 13min is transferred in hydrothermal reaction kettle, and heating pressurization is reacted, former
Position generates vulcanization zinc-copper and is carried on graphene oxide, is filtered, washed, is dried in vacuo, and graphene oxide/zinc sulphide is made
Copper composite photo-catalyst；Dispersing agent is sodium methylene bis-naphthalene sulfonate；The temperature of hydro-thermal reaction is 126 DEG C, pressure 7MPa, the time
For 2.5h；The mode of washing is, is first washed 3 times using dehydrated alcohol, then adopts that be washed with deionized to pH value be 7；Vacuum is dry
Dry temperature is 48 DEG C, time 17h；The parts by weight of each raw material are 13 parts by weight of graphene oxide, 1 parts by weight of dispersing agent, second
Sour 5 parts by weight of copper, 6 parts by weight of zinc sulfate, 11 parts by weight of thioacetamide, 64 parts by weight of water；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene；The mass concentration of chloroplatinic acid aqueous solution is 38%；Reducing agent
For sodium borohydride, the temperature of reduction reaction is 78 DEG C, time 1.5h；The parts by weight of each raw material are graphene oxide/zinc sulphide
24 parts by weight of copper composite photo-catalyst, 76 parts by weight of chloroplatinic acid aqueous solution.
Embodiment 2
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
32min is mixed, thioacetamide is added, magnetic agitation 11min is transferred in hydrothermal reaction kettle, and heating pressurization is reacted, former
Position generates vulcanization zinc-copper and is carried on graphene oxide, is filtered, washed, is dried in vacuo, and graphene oxide/zinc sulphide is made
Copper composite photo-catalyst；Dispersing agent is dispersing agent MF；The temperature of hydro-thermal reaction is 122 DEG C, pressure 6MPa,
Time is 3h；The mode of washing is, is first washed 2 times using dehydrated alcohol, then adopts that be washed with deionized to pH value be 7；Vacuum
Dry temperature is 45 DEG C, time 19h；The parts by weight of each raw material are, 11 parts by weight of graphene oxide, 1 parts by weight of dispersing agent,
5 parts by weight of copper acetate, 5 parts by weight of zinc sulfate, 9 parts by weight of thioacetamide, 69 parts by weight of water；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene；The mass concentration of chloroplatinic acid aqueous solution is 35%；Reducing agent
For sodium formate, the temperature of reduction reaction is 75 DEG C, time 2h；The parts by weight of each raw material are that graphene oxide/vulcanization zinc-copper is multiple
22 parts by weight of light combination catalyst, 78 parts by weight of chloroplatinic acid aqueous solution.
Embodiment 3
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
38min is mixed, thioacetamide is added, magnetic agitation 14min is transferred in hydrothermal reaction kettle, and heating pressurization is reacted, former
Position generates vulcanization zinc-copper and is carried on graphene oxide, is filtered, washed, is dried in vacuo, and graphene oxide/zinc sulphide is made
Copper composite photo-catalyst；Dispersing agent is sodium methylene bis-naphthalene sulfonate；The temperature of hydro-thermal reaction is 122 DEG C, pressure 6MPa, the time
For 3h；The mode of washing is, is first washed 4 times using dehydrated alcohol, then adopts that be washed with deionized to pH value be 7；Vacuum drying
Temperature be 55 DEG C, time 16h；The parts by weight of each raw material are 14 parts by weight of graphene oxide, 2 parts by weight of dispersing agent, acetic acid
6 parts by weight of copper, 7 parts by weight of zinc sulfate, 14 parts by weight of thioacetamide, 57 parts by weight of water；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene；The mass concentration of chloroplatinic acid aqueous solution is 45%；Reducing agent
For sodium borohydride, the temperature of reduction reaction is 86 DEG C, time 1h；The parts by weight of each raw material are graphene oxide/vulcanization zinc-copper
27 parts by weight of composite photo-catalyst, 73 parts by weight of chloroplatinic acid aqueous solution.
Embodiment 4
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
30min is mixed, thioacetamide is added, magnetic agitation 10min is transferred in hydrothermal reaction kettle, and heating pressurization is reacted, former
Position generates vulcanization zinc-copper and is carried on graphene oxide, is filtered, washed, is dried in vacuo, and graphene oxide/zinc sulphide is made
Copper composite photo-catalyst；Dispersing agent is dispersing agent MF；The temperature of hydro-thermal reaction is 120 DEG C, pressure 5MPa,
Time is 3h；The mode of washing is, is first washed 2 times using dehydrated alcohol, then adopts that be washed with deionized to pH value be 7；Vacuum
Dry temperature is 40 DEG C, time 20h；The parts by weight of each raw material are, 10 parts by weight of graphene oxide, 1 parts by weight of dispersing agent,
4 parts by weight of copper acetate, 4 parts by weight of zinc sulfate, 8 parts by weight of thioacetamide, 73 parts by weight of water；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene；The mass concentration of chloroplatinic acid aqueous solution is 30%；Reducing agent
For sodium formate, the temperature of reduction reaction is 70 DEG C, time 2h；The parts by weight of each raw material are that graphene oxide/vulcanization zinc-copper is multiple
20 parts by weight of light combination catalyst, 80 parts by weight of chloroplatinic acid aqueous solution.
Embodiment 5
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
40min is mixed, thioacetamide is added, magnetic agitation 15min is transferred in hydrothermal reaction kettle, and heating pressurization is reacted, former
Position generates vulcanization zinc-copper and is carried on graphene oxide, is filtered, washed, is dried in vacuo, and graphene oxide/zinc sulphide is made
Copper composite photo-catalyst；Dispersing agent is sodium methylene bis-naphthalene sulfonate；The temperature of hydro-thermal reaction is 130 DEG C, pressure 8MPa, the time
For 2h；The mode of washing is, is first washed 4 times using dehydrated alcohol, then adopts that be washed with deionized to pH value be 7；Vacuum drying
Temperature be 60 DEG C, time 15h；The parts by weight of each raw material are 15 parts by weight of graphene oxide, 2 parts by weight of dispersing agent, acetic acid
8 parts by weight of copper, 8 parts by weight of zinc sulfate, 16 parts by weight of thioacetamide, 51 parts by weight of water；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene；The mass concentration of chloroplatinic acid aqueous solution is 50%；Reducing agent
For sodium formate, the temperature of reduction reaction is 90 DEG C, time 2h；The parts by weight of each raw material are that graphene oxide/vulcanization zinc-copper is multiple
30 parts by weight of light combination catalyst, 70 parts by weight of chloroplatinic acid aqueous solution.
Embodiment 6
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
35min is mixed, thioacetamide is added, magnetic agitation 12min is transferred in hydrothermal reaction kettle, and heating pressurization is reacted, former
Position generates vulcanization zinc-copper and is carried on graphene oxide, is filtered, washed, is dried in vacuo, and graphene oxide/zinc sulphide is made
Copper composite photo-catalyst；Dispersing agent is dispersing agent MF；The temperature of hydro-thermal reaction is 125 DEG C, pressure 6MPa,
Time is 2.5h；The mode of washing is, is first washed 3 times using dehydrated alcohol, then adopts that be washed with deionized to pH value be 7；Very
The dry temperature of sky is 50 DEG C, time 18h；The parts by weight of each raw material are 12 parts by weight of graphene oxide, 2 weight of dispersing agent
Part, 6 parts by weight of copper acetate, 6 parts by weight of zinc sulfate, 12 parts by weight of thioacetamide, 62 parts by weight of water；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene；The mass concentration of chloroplatinic acid aqueous solution is 40%；Reducing agent
For sodium formate, the temperature of reduction reaction is 80 DEG C, time 1.5h；The parts by weight of each raw material are graphene oxide/vulcanization zinc-copper
25 parts by weight of composite photo-catalyst, 75 parts by weight of chloroplatinic acid aqueous solution.
Comparative example 1
In preparation process, graphene oxide is not used, other preparation conditions and embodiment 6 are consistent.
Comparative example 2
In preparation process, unsupported platinum, other preparation conditions and embodiment 6 are consistent.
Performance test:
(1) composite photocatalyst produced by the present invention specific surface area: is measured using Bei Shide 3H-2000 series specific-surface area detection instrument
The specific surface area of agent, retest 5 calculate average value；
(2) visible light utilization efficiency: any composite photo-catalyst produced by the present invention is taken, is irradiated with visible light, test can phase
It answers visible wavelength range spectrum to account for the ratio of the total wave-length coverage of visible light, indicates visible light utilization efficiency；
(3) hydrogen-producing speed: weighing 0.1g photochemical catalyst in the balance, 20mL water is measured, in the photocatalyst reaction vessel of diameter 9cm
It is sufficiently mixed, after irradiation 1h, accesses homemade vacuum under artificial light source 300W xenon lamp after emptying air and survey hydrogen system, use gas phase
Generated amounts of hydrogen is reacted in chromatograph detection, calculates hydrogen-producing speed；
The data obtained is as shown in table 1.
Table 1:
Claims (10)
1. the preparation method that a kind of photocatalytic water prepares the composite photo-catalyst of fuel cell hydrogen, which is characterized in that described compound
Specific step is as follows for photochemical catalyst preparation:
(1) graphene oxide, dispersing agent are added to the water, ultrasonic disperse is uniform, and copper acetate, zinc sulfate is then added, and magnetic force stirs
30 ~ 40min is mixed, thioacetamide is added, 10 ~ 15min of magnetic agitation is transferred in hydrothermal reaction kettle, and heating pressurization carries out
Reaction, in-situ preparation vulcanization zinc-copper are simultaneously carried on graphene oxide, are filtered, washed, are dried in vacuo, graphite oxide is made
Alkene/vulcanization zinc-copper composite photo-catalyst；
(2) graphene oxide made from step (1)/vulcanization zinc-copper composite photo-catalyst is added in chloroplatinic acid aqueous solution, ultrasound
It is uniformly dispersed, reducing agent is added and heats reaction, generate platinum and be carried on catalyst surface, while graphene oxide being reduced to
Graphene/vulcanization zinc-copper/platinum composite photo-catalyst is made in graphene.
2. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: the parts by weight of step (1) each raw material are 10 ~ 15 parts by weight of graphene oxide, 1 ~ 2 parts by weight of dispersing agent, second
Sour 4 ~ 8 parts by weight of copper, 4 ~ 8 parts by weight of zinc sulfate, 8 ~ 16 parts by weight of thioacetamide, 51 ~ 73 parts by weight of water.
3. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: step (1) dispersing agent is sodium methylene bis-naphthalene sulfonate, at least one in dispersing agent MF
Kind.
4. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: the temperature of step (1) described hydro-thermal reaction is 120 ~ 130 DEG C, and pressure is 5 ~ 8MPa, and the time is 2 ~ 3h.
5. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: the mode of step (1) described washing is, is first washed 2 ~ 4 times using dehydrated alcohol, then adopt be washed with deionized to
PH value is 7.
6. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: step (1) the vacuum drying temperature is 40 ~ 60 DEG C, and the time is 15 ~ 20h.
7. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: the parts by weight of step (2) each raw material are graphene oxide/20 ~ 30 weight of vulcanization zinc-copper composite photo-catalyst
Part, 70 ~ 80 parts by weight of chloroplatinic acid aqueous solution.
8. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: the mass concentration of step (2) described chloroplatinic acid aqueous solution is 30 ~ 50%.
9. a kind of photocatalytic water prepares the preparation method of the composite photo-catalyst of fuel cell hydrogen according to claim 1,
Be characterized in that: step (2) reducing agent is at least one of sodium borohydride, sodium formate, and the temperature of reduction reaction is 70 ~ 90
DEG C, the time is 1 ~ 2h.
10. a kind of photocatalytic water that any one of claim 1 ~ 9 preparation method is prepared prepares answering for fuel cell hydrogen
Light combination catalyst.
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