CN112275305A - High-efficiency hydrogen evolution catalyst and preparation method thereof - Google Patents
High-efficiency hydrogen evolution catalyst and preparation method thereof Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 74
- 239000007788 liquid Substances 0.000 claims description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- -1 polytetrafluoroethylene Polymers 0.000 claims description 28
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 28
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 6
- 238000013329 compounding Methods 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
-
- B01J35/39—
-
- 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
Abstract
The invention discloses a high-efficiency hydrogen evolution catalyst, which mainly comprises Ni25-10% of P; 10-30% of cocatalyst or g-C3N460-85% of the composition. The invention also discloses a preparation method of the high-efficiency hydrogen evolution catalyst. The invention has the beneficial effects that: low production cost and simple process, the obtained catalyst has the characteristics of high efficiency, low cost, long service life and the like, and the hydrogen evolution effect can be comparable to that of noble metal modified g-C3N4(C3N4/Pt)。
Description
Technical Field
The invention relates to the technical field of photolysis water hydrogen evolution, in particular to a high-efficiency hydrogen evolution catalyst and a preparation method thereof.
Background
With the rapid development of economic society, the energy demand is remarkably improved, and the occurrence of energy crisis is inevitable. Meanwhile, excessive use of traditional fossil energy causes a series of ecological, environmental and climatic problems. The hydrogen energy has incomparable advantages as the substitute of the traditional fossil energy, and is idealGreen energy source. The semiconductor photocatalyst is used for decomposing water, which is a hydrogen production method with great prospect, but the efficiency of the hydrogen production method is greatly related to the catalyst. Graphite phase carbon nitride (g-C)3N4) The practical application of the photo-catalytic hydrogen production is limited due to the low photoresponse range and the recombination of photo-generated electrons and holes. Therefore, the design and preparation of the photocatalyst with excellent hydrogen production performance have very important practical significance
Disclosure of Invention
The invention aims to provide a high-efficiency hydrogen evolution catalyst aiming at the defects of the semiconductor photocatalyst. By the pair g-C3N4The heterojunction is constructed by compounding other semiconductor materials with narrow forbidden bands, and the g-C is widened3N4The photoresponse range of the material is reduced, the probability of recombination of photoproduction electrons and holes is reduced, the integral catalytic efficiency is improved, and then metal phosphide is compounded, and the hydrogen evolution sites of the material are increased; the catalyst has the characteristics of high efficiency, low cost, long service life and the like.
The invention also aims to provide a preparation method of the high-efficiency hydrogen evolution catalyst, which has low requirements on production equipment, low production cost and simple process and has a certain guiding function on the preparation of other photocatalysts.
In order to achieve the purpose, the invention adopts the technical scheme that: a high-efficiency hydrogen evolution catalyst is prepared from the following components in percentage by mass:
Ni2P 5～10％
10-30% of cocatalyst
g-C3N4 60～85％。
The catalyst promoter is a black phosphorus superlattice material and/or a nano red phosphorus material.
The black phosphorus superlattice material is prepared from the following ultrapure water, yellow phosphorus, phosphorus pentoxide and ethylenediamine in percentage by mass:
the preparation method of the black phosphorus superlattice material comprises the following steps:
(1) uniformly mixing and dispersing the components to prepare a mixed sample, wherein the stirring speed is 400-;
(2) placing the mixed sample in a polytetrafluoroethylene lining;
(3) screwing down a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a high-temperature oven, preserving heat for 1-5h at 100-120 ℃, and then reacting for 10-15h at 180-220 ℃;
(4) after the reaction is finished, washing the sample to be neutral by water, washing the sample by ethanol once, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain the black phosphorus superlattice material;
the nano red phosphorus material is prepared from the following ultra-pure water and red phosphorus in percentage by mass:
the preparation method of the nano red phosphorus material comprises the steps of grinding red phosphorus, mixing the ground red phosphorus with ultrapure water, then placing the mixture into a high-temperature oven, keeping the temperature of 180-200 ℃ for 1-5h,
Preferably, the preparation method of the nano red phosphorus material comprises the following steps:
(1) grinding red phosphorus into powder according to the component proportion and then mixing;
(2) adding 30ml of the mixed sample into a 50ml of polytetrafluoroethylene lining;
(3) and screwing down the polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a high-temperature oven, preserving heat for 3 hours at 180-200 ℃, and then drying and filtering to obtain the nano red phosphorus.
A preparation method of a high-efficiency hydrogen evolution catalyst comprises the following steps: mixing the above-mentioned g-C3N4Cocatalyst and Ni2And respectively dispersing the P in deionized water to form dispersion liquid, and then mixing and dispersing.
A preparation method of a high-efficiency hydrogen evolution catalyst comprises the following steps:
(1) g to C3N4Dispersing in water to obtain a first dispersion;
(2) dispersing part of the cocatalyst in deionized water to obtain a second dispersion liquid;
(3) another part of the cocatalyst and NiCl2According to the mass ratio of 1: 1-1: 3 is dispersed into dimethyl formamide (DMF), and then is transferred into a polytetrafluoroethylene lining to react for 2 to 5 hours at the temperature of 160-220 ℃;
(4) washing the sample obtained by the reaction for three times to obtain Ni2A third dispersion of P;
(5) the first dispersion and the second dispersion are mixed according to the above proportion and are stirred overnight and then are mixed with the third dispersion.
A preparation method of a high-efficiency hydrogen evolution catalyst comprises the following steps:
(1) g-C of 0.6 to 0.85g3N4Taking g-C according to the proportion of dispersing in 100g of deionized water3N4Adding into deionized water to obtain a first dispersion;
(2) ni in an amount of 0.01 to 0.05g2Dispersing P in 100g of deionized water to prepare a second dispersion liquid;
(3) preparing a third dispersion liquid according to the proportion that 0.1-0.3 g of cocatalyst is dispersed in 100g of deionized water;
(4) mixing the first dispersion liquid and the third dispersion liquid with equal volumes, and stirring overnight to obtain a fourth dispersion liquid;
(5) adding the second dispersion liquid with the same volume as the first dispersion liquid into the fourth dispersion liquid for dispersion treatment.
A preparation method of a high-efficiency hydrogen evolution catalyst comprises the following steps:
(1) g-C of 0.6 to 0.85g3N4Taking g-C according to the proportion of dispersing in 100g of deionized water3N4Adding into deionized water to obtain a first dispersion;
(2) the cocatalyst is taken as 0.1g and NiCl2According to the mass ratio of 1: 1-1: 3 is dispersed in 40ml DMF and transferred to a lining of 50ml polytetrafluoroethylene for reaction at the temperature of 160-220 ℃ for 2-5h to obtain Ni2P in the range of 0.01 to 0.05Ni2P is dispersed in 100g to removeTaking Ni as the proportion of the seed water2Adding deionized water into the solution P to obtain a second dispersion liquid;
(3) dispersing 0.1-0.3 g of cocatalyst in 100g of deionized water to prepare a third dispersion liquid;
(4) weighing 10g of the first dispersion liquid and 10g of the third dispersion liquid respectively, mixing for 2h, and stirring overnight to obtain a fourth dispersion liquid;
(5) and weighing 10g of the second dispersion liquid, adding the second dispersion liquid into the fourth dispersion liquid, and performing dispersion treatment for 3 hours to obtain the high-efficiency hydrogen evolution catalyst.
The g to C3N4The preparation method comprises the following steps:
(1) dissolving 20g of urea in 20ml of deionized water, adjusting the pH value of the solution to 4-5 by using 0.1mol/L HCl, and drying the solution overnight at 60 ℃ in an oven;
(2) transferring the dried urea to an alumina crucible with a cover, and placing the alumina crucible into a muffle furnace to preserve heat for 2 hours at 550 ℃ to obtain g-C3N4。
All the dispersing means are ultrasonic treatment with the frequency of 600W for 3 h.
The passing pair of the present invention g-C3N4The heterojunction is constructed by compounding other semiconductor materials with narrow forbidden bands, so that the photoresponse range of g-C3N4 is widened, the probability of compounding photo-generated electrons and holes is reduced, the overall catalytic efficiency is improved, and the hydrogen evolution sites of the materials are increased by compounding metal phosphide. The method has low requirements on production equipment, low production cost and simple process, and the obtained catalyst has the characteristics of high efficiency, low cost, long service life and the like, and the hydrogen evolution effect can be comparable to that of noble metal modified g-C3N4(C3N4Pt) has a certain guiding function on the preparation of the photocatalyst.
Compared with the prior art, the invention has the following outstanding effects:
1) the catalyst obtained by the invention has high reaction activity and long service life, and the hydrogen evolution amount is still kept at 2000ml/h after 12 times of cyclic hydrogen evolution tests;
2) the reaction has low requirements on production equipment, low production cost and simple process; compared with the current g-C3N4Solvothermal compounding of metalsThe phosphide technology only needs simple mixing, and has relatively low energy consumption and simple operation;
3) the preparation of the catalyst of the invention does not need gas assistance, the material property is stable, and the catalyst can not be oxidized and inactivated when exposed to air.
Drawings
FIG. 1 is a scanning electron micrograph of a high efficiency hydrogen evolution catalyst of the present invention;
FIG. 2 is a graph of the hydrogen evolution effect of the high efficiency hydrogen evolution catalyst of the present invention tested with a CEL-SPEH2 photoelectrocatalytic hydrogen production system.
Detailed Description
The present invention is further described with reference to the following specific examples, which should be construed as limiting the scope of the invention as claimed.
Example 1
A high-efficiency hydrogen evolution catalyst mainly comprises Ni with the following mass percentage2P, black phosphorus superlattice materials and g-C3N4Preparing red phosphorus:
the preparation method of the high-efficiency hydrogen evolution catalyst comprises the following steps:
a. mixing 1g of ultrapure water, 30g of yellow phosphorus, 20g of phosphorus pentoxide and 49g of ethylenediamine, mechanically stirring and uniformly dispersing at the stirring speed of 600rpm for 2 hours to form a mixed sample;
b. adding 30ml of the mixed sample into a 50ml of polytetrafluoroethylene lining;
c. screwing down a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a high-temperature oven, preserving heat for 3 hours at 100 ℃, and then reacting for 12 hours at 180 ℃;
d. after the reaction is finished, washing the sample to be neutral by water, washing the sample by ethanol once, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain the black phosphorus superlattice material;
e. dissolving 20g of urea in 20ml of deionized water, adjusting the pH value of the solution to 4 by using 0.1mol/L HCl, and placing the solution in an oven to dry at 60 ℃ overnight;
f. transferring the dried urea to an alumina crucible with a cover, and placing the alumina crucible into a muffle furnace to preserve heat for 2 hours at 550 ℃ to obtain g-C3N4。
g. G to C to be prepared3N4Dispersing 0.7g of the dispersion in 100g of deionized water to obtain a first dispersion;
h. taking 0.05g and 0.05g NiCl of the black phosphorus superlattice material2Dispersing in 40ml DMF, transferring into 50ml polytetrafluoroethylene lining, reacting at 160 deg.C for 3h to obtain Ni2After washing P for three times, 0.05g of P is taken and dispersed in 100g of deionized water to obtain a second dispersion liquid;
i. dispersing 0.25g of the black phosphorus superlattice material in 100g of deionized water to obtain a third dispersion liquid;
j. weighing 10g of the first dispersion liquid and 10g of the third dispersion liquid respectively, mixing for 2h, and stirring overnight to obtain a fourth dispersion liquid;
k. and weighing 10g of the second dispersion liquid, adding the second dispersion liquid into the fourth dispersion liquid, and carrying out ultrasonic treatment at 600W for 3h to obtain the high-efficiency hydrogen evolution catalyst.
Example 2
A high-efficiency hydrogen evolution catalyst mainly comprises Ni with the following mass percentage2P, nano red phosphorus and g-C3N4Preparing red phosphorus:
the preparation method of the high-efficiency hydrogen evolution catalyst comprises the following steps:
a. grinding 30g of red phosphorus into powder and mixing with 70g of deionized water;
b. adding 30ml of the mixed sample into a 50ml of polytetrafluoroethylene lining;
c. screwing down a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a high-temperature oven, keeping the temperature of 180 ℃ for 3 hours, and then drying and filtering to obtain nano red phosphorus;
d. dissolving 20g of urea in 20ml of deionized water, adjusting the pH value of the solution to 5 by using 0.1mol/L HCl, and placing the solution in an oven to dry at 60 ℃ overnight;
e. taking out dried urineTransferring the elements to an alumina crucible with a cover, and putting the alumina crucible into a muffle furnace to preserve heat for 2 hours at 550 ℃ to obtain g-C3N4。
f. G to C to be prepared3N4Dispersing 0.65g of the dispersion in 100g of deionized water to obtain a first dispersion liquid;
g. taking 0.1g and 0.1g NiCl of the prepared black phosphorus superlattice material2Dispersing in 40ml DMF, transferring into 50ml polytetrafluoroethylene lining, reacting at 180 deg.C for 3h to obtain Ni2After washing P with water for three times, 0.1g of P is taken and dispersed in 100g of deionized water to obtain a second dispersion liquid;
h. dispersing 0.25g of nano red phosphorus in 100g of deionized water to obtain a third dispersion liquid;
i. weighing 10g of the first dispersion liquid and 10g of the third dispersion liquid respectively, mixing for 2h, and stirring overnight to obtain a fourth dispersion liquid;
j. and weighing 10g of the second dispersion liquid, adding the second dispersion liquid into the fourth dispersion liquid, and carrying out ultrasonic treatment at 600W for 3h to obtain the high-efficiency hydrogen evolution catalyst.
Example 3
A high-efficiency hydrogen evolution catalyst mainly comprises Ni with the following mass percentage2P, nano red phosphorus and g-C3N4Preparing red phosphorus:
the preparation method of the high-efficiency hydrogen evolution catalyst comprises the following steps:
a. grinding 30g of red phosphorus into powder and mixing with 70g of deionized water;
b. adding 30ml of the mixed sample into a 50ml of polytetrafluoroethylene lining;
c. screwing down a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a high-temperature oven, keeping the temperature for 3 hours at 200 ℃, and then drying and filtering to obtain nano red phosphorus;
d. dissolving 20g of urea in 20ml of deionized water, adjusting the pH value of the solution to 4.5 by using 0.1mol/L HCl, and placing the solution in an oven to dry at 60 ℃ overnight;
e. transferring the dried urea to an alumina crucible with a coverPlacing the crucible in a muffle furnace, and keeping the temperature at 550 ℃ for 2h to obtain g-C3N4。
f. G to C to be prepared3N4Dispersing 0.7g of the dispersion in 100g of deionized water to obtain a first dispersion;
g. taking 0.05g and 0.1g NiCl of the prepared nano red phosphorus2Dispersing in 40ml DMF, transferring into 50ml polytetrafluoroethylene lining, reacting at 160 deg.C for 3h to obtain Ni2After washing P for three times, 0.05g of P is taken and dispersed in 100g of deionized water to obtain a second dispersion liquid;
h. dispersing 0.25g of nano red phosphorus in 100g of deionized water to obtain a third dispersion liquid;
i. weighing 10g of the first dispersion liquid and 10g of the third dispersion liquid respectively, mixing for 2h, and stirring overnight to obtain a fourth dispersion liquid;
j. and weighing 10g of the second dispersion liquid, adding the second dispersion liquid into the fourth dispersion liquid, and carrying out ultrasonic treatment at 600W for 3h to obtain the high-efficiency hydrogen evolution catalyst.
Example 4
A high-efficiency hydrogen evolution catalyst mainly comprises Ni with the following mass percentage2P, black phosphorus superlattice materials and g-C3N4Preparing red phosphorus:
the preparation method of the high-efficiency hydrogen evolution catalyst comprises the following steps:
a. 5g of ultrapure water, 35g of yellow phosphorus, 15g of phosphorus pentoxide and 45g of ethylenediamine are mixed, mechanically stirred and uniformly dispersed, the stirring speed is 600rpm, and the stirring time is 2 hours;
b. adding 30ml of the mixed sample into a 50ml of polytetrafluoroethylene lining;
c. screwing down a polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a high-temperature oven, preserving heat for 3 hours at 120 ℃, and then reacting for 12 hours at 220 ℃;
d. after the reaction is finished, washing the sample to be neutral by water, washing the sample by ethanol once, and drying the sample for 12 hours at the temperature of 60 ℃ to obtain the black phosphorus superlattice material;
e. dissolving 20g of urea in 20ml of deionized water, adjusting the pH value of the solution to 4 by using 0.1mol/L HCl, and placing the solution in an oven to dry at 60 ℃ overnight;
f. transferring the dried urea to an alumina crucible with a cover, and placing the alumina crucible into a muffle furnace to preserve heat for 2 hours at 550 ℃ to obtain g-C3N4。
g. G to C to be prepared3N4Dispersing 0.8g of the dispersion in 100g of deionized water to obtain a first dispersion liquid;
h. taking 0.05g and 0.05g NiCl of the prepared black phosphorus superlattice material2Dispersing in 40ml DMF, transferring into 50ml polytetrafluoroethylene lining, reacting at 160 deg.C for 3h to obtain Ni2After washing P for three times, 0.05g of P is taken and dispersed in 100g of deionized water to obtain a second dispersion liquid;
i. dispersing 0.15g of the black phosphorus superlattice material in 100g of deionized water to obtain a third dispersion liquid;
j. weighing 10g of the first dispersion liquid and 10g of the third dispersion liquid respectively, mixing for 2h, and stirring overnight to obtain a fourth dispersion liquid;
k. and weighing 10g of the second dispersion liquid, adding the second dispersion liquid into the fourth dispersion liquid, and carrying out ultrasonic treatment at 600W for 3h to obtain the high-efficiency hydrogen evolution catalyst.
By detecting the high-efficiency hydrogen evolution catalyst obtained in the above embodiment through a scanning electron microscope, as can be seen from the morphology shown in fig. 1, the rod-shaped carbon nitride and the cocatalyst are compounded together. The photoresponse range is widened by a cocatalyst with narrow forbidden band width, and Ni is used2P is used as a hydrogen evolution site to improve the hydrogen evolution activity of CN.
The hydrogen evolution effect of the high-efficiency hydrogen evolution catalyst obtained in the above embodiment is characterized by using a CEL-SPEH2 photoelectrocatalytic hydrogen production system, as shown in FIG. 2, the hydrogen evolution activity of several materials is shown, and CN/X/Ni can be seen from the figure2The hydrogen evolution activity of the P composite material is far higher than that of any one or two composite materials, and can be comparable to that of a noble CN loaded metal platinum (pt) material.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention should not be limited thereby, and all the simple equivalent changes and modifications made in the claims and the description of the present invention are within the scope of the present invention.
Claims (7)
1. The efficient hydrogen evolution catalyst is characterized by being prepared from the following components in percentage by mass:
Ni2P 5～10％
10-30% of cocatalyst
g-C3N4 60～85％。
2. The high-efficiency hydrogen evolution catalyst according to claim 1, wherein the promoter is a black phosphorus superlattice material and/or a nano red phosphorus material.
3. The efficient hydrogen evolution catalyst as claimed in claim 1, wherein the black phosphorus superlattice material is prepared from the following components in percentage by mass:
the preparation method of the black phosphorus superlattice material comprises the following steps:
(1) uniformly mixing and dispersing the components to prepare a mixed sample, wherein the stirring speed is 400-;
(2) placing the mixed sample in a polytetrafluoroethylene lining;
(3) screwing down the polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining in a high-temperature oven for heat preservation for 1-5h at 100-120 ℃, and then reacting for 10-15h at 180-220 ℃.
4. The efficient hydrogen evolution catalyst as claimed in claim 1, wherein the nano red phosphorus material is prepared from the following components in percentage by mass:
the preparation method of the nano red phosphorus material comprises the steps of grinding red phosphorus, mixing the ground red phosphorus with ultrapure water, and then placing the mixture in a high-temperature oven to keep the temperature of 180-200 ℃ for 1-5 hours.
5. The method for preparing a high efficiency hydrogen evolution catalyst according to claim 1, characterized by comprising the steps of: mixing the above-mentioned g-C3N4Cocatalyst and Ni2And respectively dispersing the P in deionized water to form dispersion liquid, and then mixing and dispersing.
6. The method for preparing the high-efficiency hydrogen evolution catalyst according to claim 5, characterized by comprising the steps of:
(1) g to C3N4Dispersing in water to obtain a first dispersion;
(2) dispersing part of the cocatalyst in deionized water to obtain a second dispersion liquid;
(3) another part of the cocatalyst and NiCl2According to the mass ratio of 1: 1-1: 3 is dispersed into dimethyl formamide (DMF), and then is transferred into a polytetrafluoroethylene lining to react for 2 to 5 hours at the temperature of 160-220 ℃;
(4) washing the sample obtained by the reaction for three times to obtain Ni2A third dispersion of P;
(5) the first dispersion and the second dispersion are mixed according to the above proportion and are stirred overnight and then are mixed with the third dispersion.
7. The method for preparing a high efficiency hydrogen evolution catalyst according to claim 7, wherein the g-C is3N4The preparation method comprises the following steps:
(1) dissolving 20g of urea in 20ml of deionized water, adjusting the pH value of the solution to 4-5 by using 0.1mol/L HCl, and drying the solution overnight at 60 ℃ in an oven;
(2) and transferring the dried urea to an alumina crucible with a cover, and placing the alumina crucible into a muffle furnace for heat preservation at 550 ℃ for 2 hours.
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