CN105688969A - Preparation method of catalyst for photo-catalytically splitting water to produce hydrogen - Google Patents
Preparation method of catalyst for photo-catalytically splitting water to produce hydrogen Download PDFInfo
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000012265 solid product Substances 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 235000013877 carbamide Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 abstract description 4
- 239000002055 nanoplate Substances 0.000 abstract 2
- 239000002861 polymer material Substances 0.000 abstract 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 238000000967 suction filtration Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 238000006303 photolysis reaction Methods 0.000 description 8
- 230000015843 photosynthesis, light reaction Effects 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- -1 Graphene compound Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SODQFLRLAOALCF-UHFFFAOYSA-N 1lambda3-bromacyclohexa-1,3,5-triene Chemical compound Br1=CC=CC=C1 SODQFLRLAOALCF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005932 reductive alkylation reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000000926 separation method Methods 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
- B01J27/24—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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1094—Promotors or activators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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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 preparation method of a catalyst for photo-catalytically splitting water to produce hydrogen and relates to nano materials. The preparation method includes: placing urea into a ceramic crucible with a cover, and calcining in a muffle furnace to obtain yellow g-C3N4 polymer material; under nitrogen protection, ultrasonically dispersing the g-C3N4 polymer material into tetrahydrofuran solution, using lithium metal as the electron donor and naphthalene as the first electron acceptor, performing solution-phase stripping in the presence of halogenated hydrocarbon, adding ethanol into the reaction product after reaction to remove unreacted lithium metal, centrifuging, washing the obtained solid product, and drying to obtain g-C3N4 nano-plates; ultrasonically dispersing the g-C3N4 nano-plates into water, adding graphene oxide, continuing ultrasonic dispersion to obtain a mixed solution, transferring the mixed solution into a reaction kettle, rising temperature to 140-200 DEG C, keeping the temperature for 2-12 hours, then cooling to room temperature, performing suction filtration to obtain solid product, and performing vacuum drying to obtain the catalyst for photo-catalytically splitting water to produce hydrogen.
Description
Technical field
The present invention relates to nano material, the preparation method especially relating to a kind of photolytic hydrogen production catalyst。
Background technology
Hydrogen Energy be a kind of pollution-free, calorific value is high, apply wide desirable secondary energy sources, utilize decomposing water with solar energy hydrogen manufacturing to solve the problem such as energy shortage and environmental pollution have great importance。But existing solar photolysis water hydrogen catalyst is it is generally required to expensive, rare metal material for promoter, and visible light-responded weak, and hydrogen production efficiency is low。How to prepare good stability, visible light-responded photolytic hydrogen production catalyst strong, that hydrogen production efficiency is high and cheap becomes problem demanding prompt solution in hydrogen preparation field。
Graphite phase carbon nitride (g-C3N4) it is a kind of only by the polymer semiconducting material that C, N are two kinds elementary composition, owing to its good chemical stability, unique semiconductor energy band structure, nontoxic and raw material are easy to get, it is taken as a kind of getting more and more people's extensive concerning in photolysis water hydrogen field without metal ingredient novel photocatalyst。But, by g-C3N4There is also some problems as photolytic hydrogen production catalyst, as serious in photo-generate electron-hole compound, visible light-responded weak, electric transmission efficiency is low。For these problems, people are to g-C3N4Photocatalyst carries out physics compound or chemical doping modifiies, thus realizing the adjustment to quasiconductor band structure and optical absorption property。Wherein physics is composite modified is improve g-C3N4A kind of short-cut method of photocatalysis performance。By g-C3N4With other Material cladding form heterojunction structure, it is possible to promote exciton fission, accelerating the separation of photo-generate electron-hole, thus suppressing the compound of photo-generated carrier, improving its photocatalysis performance。With the c-based nanomaterial that Graphene and CNT are representative, there is excellent electron transport ability and relatively low fermi level, it is possible to catch light induced electron and suppress the compound of photo-generated carrier, being effectively increased the photocatalysis performance of catalyst。Such as g-C3N4Can with carbon point (Liu etc., Science2015,347:970-974.), CNT (Chen etc., Phys.Chem.Chem.Phys.2014,16:8106-8113), the Graphene (AcsNano2015 such as Duan, 9 (1): 931-940) compound of c-based nanomaterial such as, is used for the composite obtained the field such as photolysis water hydrogen, photocatalysis degradation organic contaminant and obtains remarkable effect。
Summary of the invention
Present invention aims to existing photolytic hydrogen production catalyst photo-generate electron-hole compound serious, visible light-responded weak, hydrogen production efficiency is low, high in cost of production problem, it is provided that the preparation method of a kind of photolytic hydrogen production catalyst。
The present invention comprises the following steps:
1) carbamide is placed in ceramic crucible with cover, calcines in Muffle furnace, obtain the g-C of yellow3N4Polymeric material；
2) when nitrogen protection, by g-C3N4Polymeric material ultrasonic disperse is in tetrahydrofuran solution, with lithium metal for electron donor, naphthalene is the first electron acceptor, under halogenated alkane exists, carry out solution peel off mutually, in reactant, add ethanol after reaction remove unreacted lithium metal, being centrifuged, gained solid product washs again, dried g-C3N4Nanometer sheet；
3) by g-C3N4Nanometer sheet ultrasonic disperse, in water, adds graphene oxide, continues ultrasonic disperse and obtains mixed solution, mixed solution is transferred in reactor, is warming up to 140～200 DEG C, after maintaining 2～12h, be cooled to room temperature, sucking filtration obtains solid product, namely obtains photolytic hydrogen production catalyst through vacuum drying。
In step 1) in, the condition of described calcining can be calcining 2～4h at 450～550 DEG C。
In step 2) in, the time of described reaction can be 5～24h；Described centrifugal condition can the centrifugal 5min of rotating speed of 8000rpm/min；Described washing can use toluene, ethanol, water washing successively。
In step 1) and 2) in, described carbamide, g-C3N4Polymeric material, tetrahydrofuran solution, lithium metal, naphthalene proportioning can be (5～10) g: (10～500) mg: (50～150) mL: (0.23～3.45) g: (0.42～6.26) g, wherein, carbamide, g-C3N4Polymeric material, lithium metal, naphthalene are calculated in mass, and tetrahydrofuran solution is calculated by volume。
In step 3) in, the addition of described graphene oxide can be g-C by mass percentage3N4The 0～1.0% of nanometer sheet；Described vacuum drying temperature can be 60 DEG C。
First the present invention with carbamide for presoma, obtains g-C by heat polymerization3N4Polymeric material, then carries out stripping by reductive alkylation method and obtains g-C3N4Nanometer sheet, finally under solvent thermal hot conditions with Graphene compound, prepare photolysis water hydrogen g-C3N4/ graphene composite material catalyst。
Compared with prior art, the present invention possesses advantages below:
1) prices of raw materials are cheap, and catalyst preparing efficiency is high, controllability is strong, has the prospect of large-scale application。
2) the photolytic hydrogen production catalyst specific surface area prepared is big, it is seen that photoresponse is strong, and hydrogen production efficiency is high。
Accompanying drawing explanation
Fig. 1 is g-C3N4Polymeric material, g-C3N4Nanometer sheet and g-C3N4The X-ray powder diffraction figure (XRD) that/graphene composite material (adds the mass percent respectively 0.02%, 0.05% and 0.1% of graphene oxide)。
Fig. 2 is the transmission electron microscope picture (TEM) that the embodiment of the present invention 1 prepares photolysis water hydrogen photocatalyst。
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) that the embodiment of the present invention 1 prepares photolysis water hydrogen photocatalyst。
Fig. 4 is the catalyst of the embodiment of the present invention 1 preparation photocatalytic water H2-producing capacity comparison diagram under simulated solar irradiation irradiates。
Detailed description of the invention
Embodiment 1
The ceramic crucible with cover of 50mL adds 10g carbamide, crucible is placed in Muffle furnace, is increased to 550 DEG C with the speed of 2.5 DEG C/min from room temperature, constant temperature 2h。Calcining is cooled to room temperature after terminating, and is ground by sample and obtain yellow powder in agate mortar, i.e. g-C3N4Polymeric material。When nitrogen protection, weigh 108mgg-C3N4Polymeric material adds in the tetrahydrofuran solution that 120mL fresh dried is crossed; ultrasonic 5min; then in this dispersion liquid, add 0.55g lithium metal and 5.08g naphthalene; solution becomes blackish green rear continuously stirred 1h; in above-mentioned solution, add Dodecyl Bromide until solution green disappears with the speed of 10mL/h with automatic injector again, continue reaction 12h under nitrogen protection。After reaction terminates, adding ethanol and remove unreacted lithium metal in above-mentioned reactant, with the centrifugal 5min of the rotating speed of 8000rpm/min, gained solid product uses toluene, ethanol, water washing successively, and final drying obtains g-C3N4Nanometer sheet。By g-C3N4Nanometer sheet ultrasonic disperse is in water, and adding mass percent is the graphene oxide of 0.02%, continues ultrasonic disperse and obtains mixed solution。Being transferred to by mixed solution in pyroreaction still, be warming up to 180 DEG C, and be cooled to room temperature after maintaining 6h, sucking filtration also dry obtains solid product。
Fig. 1 is g-C3N4Polymeric material, g-C3N4Nanometer sheet, and g-C3N4The X-ray powder diffraction figure (XRD) of/graphene composite material, as seen from Figure 1, peels off the g-C obtained3N4Nanometer sheet and g-C3N4/ graphene composite material all keeps good crystal formation。Fig. 2 is the transmission electron microscope picture (TEM) that the present invention prepares photolytic hydrogen production catalyst, as shown in Figure 2, and g-C3N4Nanometer sheet and Graphene can well compound, all there is obvious flake structure。Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) that the present invention prepares photolytic hydrogen production catalyst, as can be known from Fig. 3, and g-C after solvent thermal3N4Nanometer sheet and Graphene compound are uniform。Fig. 4 is the photocatalytic water H2-producing capacity comparison diagram of each catalyst when being simulated solar irradiation irradiation, from fig. 4, it can be seen that the Graphene of compound trace can make hydrogen production efficiency be significantly improved。
Embodiment 2
The ceramic crucible with cover of 50mL adds 10g carbamide, crucible is placed in Muffle furnace, is increased to 550 DEG C with the speed of 2.5 DEG C/min from room temperature, constant temperature 2h。Calcining is cooled to room temperature after terminating, and is ground by sample and obtain yellow powder in agate mortar, i.e. g-C3N4Polymeric material。When nitrogen protection, weigh 108mgg-C3N4Polymeric material adds in the tetrahydrofuran solution that 120mL fresh dried is crossed; ultrasonic 5min; then in this dispersion liquid, add 0.55g lithium metal and 5.08g naphthalene; solution becomes blackish green rear continuously stirred 1h; in above-mentioned solution, add Dodecyl Bromide until solution green disappears with the speed of 10mL/h with automatic injector again, continue reaction 12h under nitrogen protection。After reaction terminates, adding ethanol and remove unreacted lithium metal in above-mentioned reactant, with the centrifugal 5min of the rotating speed of 8000rpm/min, gained solid product uses toluene, ethanol, water washing successively, and final drying obtains g-C3N4Nanometer sheet。By g-C3N4Nanometer sheet ultrasonic disperse is in water, and adding mass percent is the graphene oxide of 0.05%, continues ultrasonic disperse and obtains mixed solution。Being transferred to by mixed solution in pyroreaction still, be warming up to 180 DEG C, and be cooled to room temperature after maintaining 6h, sucking filtration also dry obtains solid product。
Embodiment 3
The ceramic crucible with cover of 50mL adds 10g carbamide, crucible is placed in Muffle furnace, is increased to 550 DEG C with the speed of 2.5 DEG C/min from room temperature, constant temperature 2h。Calcining is cooled to room temperature after terminating, and is ground by sample and obtain yellow powder in agate mortar, i.e. g-C3N4Polymeric material。When nitrogen protection, weigh 368mgg-C3N4Polymeric material adds in the tetrahydrofuran solution that 120mL fresh dried is crossed; ultrasonic 5min; then in this dispersion liquid, add 0.21g lithium metal and 2.56g naphthalene; solution becomes blackish green rear continuously stirred 1h; in above-mentioned solution, add 1-bromine normal hexane until solution green disappears with the speed of 10mL/h with automatic injector again, continue reaction 12h under nitrogen protection。After reaction terminates, adding ethanol and remove unreacted lithium metal in above-mentioned reactant, with the centrifugal 5min of the rotating speed of 8000rpm/min, gained solid product uses toluene, ethanol, water washing successively, and final drying obtains g-C3N4Nanometer sheet。By g-C3N4Nanometer sheet ultrasonic disperse is in water, and adding mass percent is the graphene oxide of 0.1%, continues ultrasonic disperse and obtains mixed solution。Being transferred to by mixed solution in pyroreaction still, be warming up to 180 DEG C, and be cooled to room temperature after maintaining 6h, sucking filtration also dry obtains solid product。
The present invention utilizes Graphene for promoter, prepares graphite phase carbon nitride (g-C3N4)/graphene composite material photocatalyst。In composite photo-catalyst, promoter Graphene has good electronics to be assembled and transmission characteristic, can promote efficiently separating of graphite phase carbon nitride photo-generate electron-hole, improve the photocatalysis efficiency of catalyst and the hydrogen production efficiency of photolysis water。Graphite phase carbon nitride and the grapheme material preparation method that the present invention relates to are simple, with low cost, utilize the compound of the two to prepare photolytic hydrogen production catalyst, provide a kind of new method for improving photolysis water hydrogen efficiency, being reduced by solar hydrogen making cost。
Claims (8)
1. the preparation method of a photolytic hydrogen production catalyst, it is characterised in that comprise the following steps:
1) carbamide is placed in ceramic crucible with cover, calcines in Muffle furnace, obtain the g-C of yellow3N4Polymeric material；
2) when nitrogen protection, by g-C3N4Polymeric material ultrasonic disperse is in tetrahydrofuran solution, with lithium metal for electron donor, naphthalene is the first electron acceptor, under halogenated alkane exists, carry out solution peel off mutually, in reactant, add ethanol after reaction remove unreacted lithium metal, being centrifuged, gained solid product washs again, dried g-C3N4Nanometer sheet；
3) by g-C3N4Nanometer sheet ultrasonic disperse, in water, adds graphene oxide, continues ultrasonic disperse and obtains mixed solution, mixed solution is transferred in reactor, is warming up to 140～200 DEG C, after maintaining 2～12h, be cooled to room temperature, sucking filtration obtains solid product, namely obtains photolytic hydrogen production catalyst through vacuum drying。
2. the preparation method of a kind of photolytic hydrogen production catalyst as claimed in claim 1, it is characterised in that in step 1) in, the condition of described calcining is calcining 2～4h at 450～550 DEG C。
3. the preparation method of a kind of photolytic hydrogen production catalyst as claimed in claim 1, it is characterised in that in step 2) in, the time of described reaction is 5～24h。
4. the preparation method of a kind of photolytic hydrogen production catalyst as claimed in claim 1, it is characterised in that in step 2) in, described centrifugal condition is the centrifugal 5min of the rotating speed with 8000rpm/min。
5. the preparation method of a kind of photolytic hydrogen production catalyst as claimed in claim 1, it is characterised in that in step 2) in, described washing is successively with toluene, ethanol, water washing。
6. the preparation method of a kind of photolytic hydrogen production catalyst as claimed in claim 1, it is characterised in that in step 1) and 2) in, described carbamide, g-C3N4Polymeric material, tetrahydrofuran solution, lithium metal, naphthalene proportioning be (5～10) g: (10～500) mg: (50～150) mL: (0.23～3.45) g: (0.42～6.26) g, wherein, carbamide, g-C3N4Polymeric material, lithium metal, naphthalene are calculated in mass, and tetrahydrofuran solution is calculated by volume。
7. the preparation method of a kind of photolytic hydrogen production catalyst as claimed in claim 1, it is characterised in that in step 3) in, the addition of described graphene oxide is g-C by mass percentage3N4The 0～1.0% of nanometer sheet。
8. the preparation method of a kind of photolytic hydrogen production catalyst as claimed in claim 1, it is characterised in that in step 3) in, described vacuum drying temperature is 60 DEG C。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106115639A (en) * | 2016-06-29 | 2016-11-16 | 南京理工大学 | A kind of crimping blade shape nano lamellar g C3n4preparation method |
| CN106185847A (en) * | 2016-07-01 | 2016-12-07 | 陕西科技大学 | A kind of low-density ultralight carbonitride raw powder's production technology with oriented growth |
| CN107321377A (en) * | 2017-08-03 | 2017-11-07 | 河海大学 | A kind of new visible-light photocatalysis material and its preparation method and application |
| CN107747105A (en) * | 2017-09-12 | 2018-03-02 | 天津理工大学 | A kind of preparation method of non-metal base photocathode |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN110756186A (en) * | 2018-07-25 | 2020-02-07 | 南京理工大学 | Au/CN-H nano composite material with large specific surface area, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107321377A (en) * | 2017-08-03 | 2017-11-07 | 河海大学 | A kind of new visible-light photocatalysis material and its preparation method and application |
| CN107747105A (en) * | 2017-09-12 | 2018-03-02 | 天津理工大学 | A kind of preparation method of non-metal base photocathode |
| CN107747105B (en) * | 2017-09-12 | 2019-08-13 | 天津理工大学 | A kind of preparation method of non-metal base photocathode |
| CN108620133A (en) * | 2018-05-03 | 2018-10-09 | 同济大学 | A kind of preparation method and applications of the visible light-responded catalysis production hydrogen material of two-dimensional transversal polymer hetero-junctions |
| CN108620133B (en) * | 2018-05-03 | 2020-10-30 | 同济大学 | Preparation method and application of two-dimensional transverse polymer heterojunction visible light response catalytic hydrogen production material |
| CN110756186A (en) * | 2018-07-25 | 2020-02-07 | 南京理工大学 | Au/CN-H nano composite material with large specific surface area, and preparation method and application thereof |
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