CN116273124B - Ni-Ni2P-Ni5P4/g-C3N4Photocatalyst, preparation method and application thereof - Google Patents
Ni-Ni2P-Ni5P4/g-C3N4Photocatalyst, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910003298 Ni-Ni Inorganic materials 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 15
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011812 mixed powder Substances 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 18
- 239000004570 mortar (masonry) Substances 0.000 claims description 16
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 12
- 239000012498 ultrapure water Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 208000016253 exhaustion Diseases 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
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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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- 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
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Abstract
The invention discloses a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst, a preparation method and application thereof, wherein the method comprises the following steps: preparing g-C 3N4 by a muffle furnace one-step calcination method; mixing cetyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and g-C 3N4 prepared in the first step in a mass ratio of (0.1-2) to (3-20) to (1-5) to (8-30) to obtain mixed powder; placing 0.1-2g of mixed powder into deionized water, adding 0.005-0.02g of PVP (polyvinyl and pyrrolidone), fully stirring until the mixture is uniformly mixed, pouring the mixture into a liner of a reaction kettle, placing the liner into a baking oven at 100-200 ℃, preserving heat for 12-24h, centrifuging the solution after cooling, cleaning and drying to obtain a Ni/g-C 3N4 precursor; mixing Ni/g-C 3N4 precursor and sodium hypophosphite according to a mass ratio of 1: (1-10) placing the mixture in a white porcelain boat, placing the white porcelain boat in a tube furnace, and heating to 300-500 ℃ at a heating rate of 2-10 ℃/min under argon atmosphere, and preserving heat for 1-5h to obtain the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst; the composite catalytic material with more active sites and good conductivity, strong adsorption energy and reaction kinetics is prepared, and the photocatalytic hydrogen production efficiency is high.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a composite photocatalytic material, and in particular relates to a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst, a preparation method and application thereof.
Background
The energy source is a foundation stone for the civilization development of the whole human being, and the energy source permeates into the aspects of life of people, is small to the eating and holding of common people, and is large to the aerospace of national construction and the like. In order to seek faster progress, we pay more and more attention to the development and efficient utilization of new energy. Currently, the main energy sources of human beings are fossil energy sources, but the reserves are certain, and the exhaustion risk exists, and most importantly, the fossil energy sources cause environmental pollution after being burnt. Exploring new energy sources and applying them is the most direct and effective way to solve the problems of energy exhaustion and environmental pollution. Among them, the use of photocatalysis technology to convert solar energy into clean hydrogen energy is a means with long-term development, while the development of low-cost photocatalysts is a long-term work goal of large researchers.
G-C 3N4 is used as a non-noble metal catalyst, and in theoretical research, the structural analysis of the catalyst mainly comprises a heptazine ring structure. g-C 3N4 has a valence band and conduction band structure, and the valence band is hybridized by N2 p orbit, so that the chemical property is stable, the cost is low, the preparation is easy, and the wide attention is rapidly drawn. But its application is greatly limited due to the low specific surface area and high photo-generated electron recombination rate of g-C 3N4. [ dream. Preparation of TiO 2/rod g-C 3N4 composite material and study of photocatalytic Property [ D ] university of Yanshan ]. Therefore, how to improve the photocatalytic activity of g-C 3N4, a photocatalyst with excellent luminescence performance and low cost is a goal which scientists have been struggling with.
Transition Metal Phosphides (TMPs) are a class of compounds that have desirable electron arrangements and are varied in composition and structure, and have potential advantages in becoming photocatalytic cocatalysts. However, there is a certain gap between the phosphide type cocatalyst and the noble metal catalyst commonly used in the current electrolysis of water, and the gap is reflected in aspects. Therefore, the phosphide is intended to be used as a catalyst capable of replacing noble metals and being used in a large scale, and a certain optimization is required for the phosphide itself. The chemistry of phosphides is relatively complex, since it is also possible to produce different structures at stoichiometric ratios for the same constituent elements. In the case of nickel-based phosphides, there are more than 9 types of nickel phosphide with different stoichiometric ratios. Ni 2 P, a common nickel phosphide material, was predicted by Density Functional Theory (DFT) as early as 2005 to be a highly active HER catalyst [Zhou G Y,Li M,Li Y L,et al.Regulating the Electronic Structure of CoP Nanosheets by O Incorporation for High-efficiency Electrochemical Overall Water Splitting[J].Advanced Functional Materials,2020,30(7):1905252.]. and was also demonstrated in later experiments. Ni 5P4 as a metal-rich species, each Ni atom is linked to 2P atoms in the environment of Ni-Ni bonds. Under such conditions, the generated P vacancies would greatly enhance HER activity and stability. The presence of a plurality of different stoichiometric ratios of nickel phosphide also makes it possible to construct a nickel phosphide heterojunction catalyst.
At present, a nickel phosphide/carbon nitride composite material has been used as a photocatalyst, but the prior art still has some defects. In the prior art, nickel phosphide and carbon nitride are respectively prepared and then compounded, but the method has the defects of complex compounding steps, uneven compounding, non-compactness and the like; or, nickel phosphide and carbon nitride are mixed and then calcined in one step, and although the method reduces the process steps to a certain extent, the prepared sample has single appearance, is mostly granular and is easy to agglomerate, and the exposure of active sites of the catalytic material is not facilitated.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims at preparing a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst, a preparation method and application thereof, and preparing a composite catalytic material with the advantages of a large number of active sites, high conductivity, high adsorption energy, good reaction kinetics and high hydrogen production efficiency.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
A preparation method of a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst comprises the following steps:
Step one, preparing g-C 3N4 by adopting a muffle furnace one-step calcination method;
Step two, mixing hexadecyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and g-C 3N4 prepared in the step one according to the mass ratio of (0.1-2), (3-20), (1-5) and (8-30), so as to obtain mixed powder;
Placing 0.1-2g of the mixed powder prepared in the step two into 50-150mL of deionized water, performing ultrasonic treatment for 40-120min, adding 0.005-0.02g of polyvinylpyrrolidone, fully stirring until the mixture is uniformly mixed, rapidly pouring the mixed solution into a 50mL of reaction kettle lining, placing the reaction kettle into a 100-200 ℃ oven, preserving heat for 10-24h, taking out the reaction kettle after the temperature in the oven is reduced to room temperature, cooling, pouring out the cooled reaction solution, centrifuging, cleaning and drying to obtain a Ni/g-C 3N4 precursor;
And fourthly, respectively placing the Ni/g-C 3N4 precursor prepared in the third step and sodium hypophosphite at two ends of a white porcelain boat according to the mass ratio of 1 (1-10), placing the white porcelain boat into a tubular furnace, heating to 300-500 ℃ at the heating rate of 2-10 ℃/min under argon atmosphere, preserving heat for 1-5 hours, taking out and grinding after the product is cooled, and obtaining the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst.
Preferably, the preparation method of g-C 3N4 in the first step comprises the following steps:
Placing 6-16 urea and 4-16g melamine into a mortar, fully mixing, transferring to a white porcelain boat, placing into a muffle furnace, setting the calcining temperature to 450-650 ℃, keeping the temperature for 2-6h, and heating at a speed of 2-15 ℃/min; and naturally cooling the calcined sample along with a furnace, and grinding the sample in a mortar for 30-90min to obtain yellow powder, namely flaky g-C 3N4.
Preferably, the full stirring in the third step is stirring for 120-360min by using a stirrer.
Preferably, the washing agent in the third step is washed 3-5 times with ultrapure water and absolute ethanol respectively.
Preferably, the drying in the step three is performed in a vacuum drying oven at 80 ℃ for 8-26 hours.
Preferably, the grinding in the fourth step is grinding for 30-100min by using a mortar.
The invention also protects the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst prepared by the method and the application of the photocatalyst in photocatalytic water electrolysis hydrogen production.
Compared with the prior art, the invention has the following technical effects:
The Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst is prepared by a simple hydrothermal method and a calcination method, and the photocatalyst prepared by the technology is flaky, has more active sites, excellent conductivity, stronger adsorption energy and good reaction kinetics, and is an excellent composite catalytic material with good hydrogen production efficiency;
According to the heterojunction structure composite material synthesized by Ni-Ni 2P-Ni5P4 and g-C 3N4, in the heterojunction structure, the strong electronic interaction of the two-phase heterogeneous interface can improve the overall conductivity, adsorption energy and reaction dynamics, the existence of promoter metal nickel also greatly improves the conductivity of the catalyst, the rapid transmission of photo-generated electron-hole pairs in the catalyst is just facilitated, ni 5P4 is used as a metal-rich substance, each Ni atom is connected with 2P atoms in the environment of Ni-Ni bonds, and under the condition, the generated P vacancy can greatly improve the activity and stability of HER;
The invention adopts the solid phase sintering method Ni-Ni 2P-Ni5P4 material, avoids introducing other hetero-phase atoms, has simple process, easy control of conditions, lower production cost and easy industrialized production;
the g-C 3N4 nano sheet formed by the preparation method provided by the invention has holes on the surface, so that the number of active sites of the composite photocatalyst can be effectively increased, and the hydrogen production efficiency of the composite photocatalyst is improved.
Drawings
FIG. 1 is an X-ray diffraction analysis chart of Ni-Ni 2P-Ni5P4 prepared in example 2;
FIG. 2 is a scan of Ni-Ni 2P-Ni5P4/g-C3N4 prepared in example 2;
FIG. 3 is a graph showing hydrogen production energy of Ni-Ni 2P-Ni5P4/g-C3N4 prepared in example 2 under visible light for 4 hours.
Detailed Description
The following examples illustrate the invention in further detail.
The average molecular weight of polyvinylpyrrolidone is 58000, K29-32.
Example 1:
Step one, g-C 3N4 can be obtained by one-step calcination in a muffle furnace: firstly, placing 6 urea and 10g melamine into a mortar, fully mixing, transferring to a white porcelain boat, placing into a muffle furnace, setting the calcining temperature to 500 ℃, keeping the temperature for 4 hours, and heating at a speed of 10 ℃/min;
Naturally cooling the calcined sample along with a furnace, and grinding the sample in a mortar for 60min to obtain yellow powder A, namely flaky g-C 3N4;
step two, mixing cetyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and powder A according to the mass ratio of 0.6:5:2:10 to obtain mixed powder B;
Step three, placing 0.2g of powder B into 100mL of deionized water, firstly performing ultrasonic treatment for 90min, then adding 0.015g of PVP (polyvinylpyrrolidone), then placing on a magnetic stirrer for stirring for 120min, and then rapidly pouring the mixed solution into a 50mL reaction kettle liner;
Setting the working temperature of an oven to 160 ℃, placing a reaction kettle into the oven after the temperature in the oven rises to the set temperature, preserving heat for 10 hours, taking out the reaction kettle for cooling after the temperature in the oven is reduced to room temperature, pouring out the cooled reaction solution for centrifugation, respectively washing three times by using ultrapure water and absolute ethyl alcohol to obtain a precipitate, and placing the precipitate into a vacuum drying oven for drying at 80 ℃ for 10 hours to obtain a solid D, namely a Ni/g-C 3N4 precursor;
Placing the powder D at the air inlet end of a white porcelain boat, placing sodium hypophosphite at the air outlet end of the white porcelain boat according to the mass ratio of Ni/g-C 3N4 precursor to sodium hypophosphite of 1:1, pumping the tubular furnace to a vacuum state, slowly introducing argon, repeatedly operating for three times until the air in the tubular furnace is completely discharged, heating the tubular furnace to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 2h, taking out and grinding for 60min after the product is cooled, and obtaining the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst;
The photocatalytic effect test was performed on Ni-Ni 2P-Ni5P4/g-C3N4 using Lab Solar 6A model equipment. The specific test process comprises weighing 50mg of photocatalyst and 15mL of silver nitrate, sequentially placing into a glass reaction vessel filled with 85mL of ultrapure water, and illuminating for 5h.
Example 2:
step one, g-C 3N4, may be obtained by one-step calcination in a muffle furnace. Firstly, placing 12 urea and 4g melamine into a mortar, fully mixing, transferring to a white porcelain boat, placing into a muffle furnace, setting the calcining temperature to be 600 ℃, keeping the temperature for 4 hours, and heating at the speed of 10 ℃/min;
Naturally cooling the calcined sample along with a furnace, and grinding the sample in a mortar for 60min to obtain yellow powder A, namely flaky g-C 3N4;
step two, mixing cetyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and powder A according to the mass ratio of 1:6:2:9 to obtain mixed powder B;
step three, placing 0.1g of powder B into 150mL of deionized water, firstly performing ultrasonic treatment for 100min, then adding 0.005g of PVP (polyvinylpyrrolidone), then placing on a magnetic stirrer to stir for 360min, and then rapidly pouring the mixed solution into a 50mL reaction kettle liner;
Setting the working temperature of the oven to 160 ℃, placing the reaction kettle into the oven after the temperature in the oven rises to the set temperature, preserving the heat for 12 hours, and taking out the reaction kettle for cooling after the temperature in the oven is reduced to the room temperature. Pouring out the cooled reaction solution, centrifuging, washing with ultrapure water and absolute ethyl alcohol for 4 times respectively to obtain a precipitate, and drying in a vacuum drying oven at 80 ℃ for 16 hours to obtain a solid D, namely a Ni/g-C 3N4 precursor;
And fourthly, placing the powder D at the air inlet end of a white porcelain boat, placing sodium hypophosphite at the air outlet end of the white porcelain boat according to the mass ratio of the Ni/g-C 3N4 precursor to the sodium hypophosphite of 1:3, pumping the tubular furnace to a vacuum state, slowly introducing argon, repeatedly operating for three times until the air in the tubular furnace is completely discharged, heating the tubular furnace to 400 ℃ at the heating rate of 10 ℃/min, preserving heat for 2h, taking out and grinding for 60min after the product is cooled, and obtaining the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst.
The photocatalytic effect test was performed on Ni-Ni 2P-Ni5P4/g-C3N4 using Lab Solar 6A model equipment. The specific test process comprises weighing 40mg of photocatalyst and 15mL of triethanolamine, sequentially placing into a glass reaction vessel filled with 85mL of ultrapure water, and irradiating for 6h.
FIG. 1 is an X-ray diffraction analysis chart of Ni-Ni 2P-Ni5P4 prepared in this example 2, wherein the abscissa is 2 theta angle and the ordinate is diffraction peak intensity, and PDF#04-0850 of Ni, PDF#03-0953 of Ni 2 P and PDF#18-0883 of Ni 5P4 can be accurately corresponded, which shows that Ni-Ni 2P-Ni5P4 photocatalyst promoter is successfully prepared.
FIG. 2 is a scan of Ni-Ni 2P-Ni5P4/g-C3N4 prepared in this example 2, as evident from FIG. 2, g-C 3N4 has a smaller nanoplatelet structure, and Ni-Ni 2P-Ni5P4 nanoplatelets are uniformly dispersed over g-C 3N4 nanoplatelets.
FIG. 3 is a graph showing the hydrogen production capacity of Ni-Ni 2P-Ni5P4/g-C3N4 prepared in example 2 for 4 hours under visible light, and it is obvious from the graph that the photocatalyst prepared in the invention has better visible light hydrogen production performance, and opens up a new way for nickel-based phosphide as a cocatalyst of carbon nitride.
Example 3:
Step one, g-C 3N4, may be obtained by one-step calcination in a muffle furnace. Firstly, placing 6 urea and 10g melamine into a mortar, fully mixing, transferring to a white porcelain boat, placing into a muffle furnace, setting the calcining temperature to 550 ℃, keeping the temperature for 5 hours, and heating the mixture at a speed of 15 ℃/min;
Naturally cooling the calcined sample along with a furnace, and grinding the sample in a mortar for 40min to obtain yellow powder A, namely flaky g-C 3N4;
Step two, mixing cetyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and powder A according to the mass ratio of 1:5:2:10 to obtain mixed powder B;
Step three, placing 0.5g of powder B into 100mL of deionized water, firstly performing ultrasonic treatment for 120min, then adding 0.01g of PVP (polyvinylpyrrolidone), then placing on a magnetic stirrer for stirring for 120min, and then rapidly pouring the mixed solution into a 50mL reaction kettle liner;
setting the working temperature of an oven to 180 ℃, placing a reaction kettle into the oven after the temperature in the oven rises to the set temperature, preserving heat for 14 hours, taking out the reaction kettle for cooling after the temperature in the oven is reduced to room temperature, pouring out the cooled reaction solution for centrifugation, respectively washing with ultrapure water and absolute ethyl alcohol for five times to obtain a precipitate, and then placing the precipitate into a vacuum drying oven for drying for 16 hours to obtain a solid D, namely a Ni/g-C 3N4 precursor;
and fourthly, placing the powder D at the air inlet end of a white porcelain boat, placing sodium hypophosphite at the air outlet end of the white porcelain boat according to the mass ratio of 1:10 of the Ni/g-C 3N4 precursor to the sodium hypophosphite, pumping the tubular furnace to a vacuum state, slowly introducing argon, repeatedly operating for three times until the air in the tubular furnace is completely discharged, heating the tubular furnace to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 2h, taking out and grinding for 80min after the product is cooled, and obtaining the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst.
The photocatalytic effect test was performed on Ni-Ni 2P-Ni5P4/g-C3N4 using Lab Solar 6A model equipment. The specific test process comprises weighing 50mg of photocatalyst and 20mL of triethanolamine, sequentially placing into a glass reaction vessel filled with 80mL of ultrapure water, and irradiating for 6h.
Example 4:
Step one, g-C 3N4, may be obtained by one-step calcination in a muffle furnace. Firstly, placing 16 urea and 16g melamine into a mortar, fully mixing, transferring to a white porcelain boat, placing into a muffle furnace, setting the calcining temperature to 450 ℃, keeping the temperature for 6 hours, and heating the mixture at a speed of 2 ℃/min;
Naturally cooling the calcined sample along with a furnace, and grinding the sample in a mortar for 30min to obtain yellow powder A, namely flaky g-C 3N4;
step two, mixing cetyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and powder A according to the mass ratio of 0.1:3:1:8 to obtain mixed powder B;
thirdly, placing 2g of powder B in 150mL of deionized water, firstly performing ultrasonic treatment for 60min, then adding 0.02g of PVP (polyvinylpyrrolidone), then placing on a magnetic stirrer to stir for 240min, and then rapidly pouring the mixed solution into a 50mL reaction kettle liner;
Setting the working temperature of an oven to be 200 ℃, placing a reaction kettle into the oven after the temperature in the oven rises to the set temperature, preserving heat for 16 hours, taking out the reaction kettle for cooling after the temperature in the oven is reduced to room temperature, pouring out the cooled reaction solution for centrifugation, respectively washing with ultrapure water and absolute ethyl alcohol for five times to obtain a precipitate, and then placing the precipitate into a vacuum drying oven for drying for 26 hours to obtain a solid D, namely a Ni/g-C 3N4 precursor;
And fourthly, placing the powder D at the air inlet end of a white porcelain boat, placing sodium hypophosphite at the air outlet end of the white porcelain boat according to the mass ratio of the Ni/g-C 3N4 precursor to the sodium hypophosphite of 1:5, pumping the tubular furnace to a vacuum state, slowly introducing argon, repeatedly operating for three times until the air in the tubular furnace is completely discharged, heating the tubular furnace to 350 ℃ at the heating rate of 3 ℃/min, preserving heat for 5h, taking out and grinding for 100min after the product is cooled, and obtaining the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst.
The photocatalytic effect test was performed on Ni-Ni 2P-Ni5P4/g-C3N4 using Lab Solar 6A model equipment. The specific test process comprises weighing 50mg of photocatalyst and 20mL of triethanolamine, sequentially placing into a glass reaction vessel filled with 80mL of ultrapure water, and irradiating for 6h.
Example 5:
Step one, g-C 3N4, may be obtained by one-step calcination in a muffle furnace. Firstly, placing 6 urea and 10g melamine into a mortar, fully mixing, transferring to a white porcelain boat, placing into a muffle furnace, setting the calcining temperature to 650 ℃, keeping the temperature for 2 hours, and heating the mixture at a speed of 2 ℃/min;
Naturally cooling the calcined sample along with a furnace, and grinding the sample in a mortar for 90min to obtain yellow powder A, namely flaky g-C 3N4;
step two, mixing cetyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and powder A according to the mass ratio of 2:20:5:30 to obtain mixed powder B;
Thirdly, placing 1g of powder B in 50mL of deionized water, firstly performing ultrasonic treatment for 40min, then adding 0.015g of PVP (polyvinylpyrrolidone), then placing on a magnetic stirrer to stir for 240min, and then rapidly pouring the mixed solution into a 50mL reaction kettle liner;
Setting the working temperature of an oven to be 100 ℃, placing a reaction kettle into the oven after the temperature in the oven rises to the set temperature, preserving heat for 24 hours, taking out the reaction kettle for cooling after the temperature in the oven is reduced to room temperature, pouring out the cooled reaction solution for centrifugation, respectively washing with ultrapure water and absolute ethyl alcohol for five times to obtain a precipitate, and then placing the precipitate into a vacuum drying oven for drying for 8 hours to obtain a solid D, namely a Ni/g-C 3N4 precursor;
And fourthly, placing the powder D at the air inlet end of a white porcelain boat, placing sodium hypophosphite at the air outlet end of the white porcelain boat according to the mass ratio of the Ni/g-C 3N4 precursor to the sodium hypophosphite of 1:8, pumping the tubular furnace to a vacuum state, slowly introducing argon, repeatedly operating for three times until the air in the tubular furnace is completely discharged, heating the tubular furnace to 450 ℃ at the heating rate of 6 ℃/min, preserving heat for 1h, taking out and grinding for 30min after the product is cooled, and obtaining the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst.
The photocatalytic effect test was performed on Ni-Ni 2P-Ni5P4/g-C3N4 using Lab Solar 6A model equipment. The specific test process comprises weighing 50mg of photocatalyst and 20mL of triethanolamine, sequentially placing into a glass reaction vessel filled with 80mL of ultrapure water, and irradiating for 6h.
It should be noted that while the embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention.
Claims (8)
1. The preparation method of the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst is characterized by comprising the following steps of:
Step one, preparing g-C 3N4 by adopting a muffle furnace one-step calcination method;
Step two, mixing hexadecyl trimethyl ammonium bromide, urea, nickel nitrate hexahydrate and g-C 3N4 prepared in the step one according to the mass ratio of (0.1-2), (3-20), (1-5) and (8-30), so as to obtain mixed powder;
Placing 0.1-2g of the mixed powder prepared in the step two into 50-150mL of deionized water, performing ultrasonic treatment for 40-120min, adding 0.005-0.02g of polyvinylpyrrolidone, fully stirring until the mixture is uniformly mixed, rapidly pouring the mixed solution into a 50mL of reaction kettle lining, placing the reaction kettle into a 100-200 ℃ oven, preserving heat for 10-24h, taking out the reaction kettle after the temperature in the oven is reduced to room temperature, cooling, pouring out the cooled reaction solution, centrifuging, cleaning and drying to obtain a Ni/g-C 3N4 precursor;
And fourthly, respectively placing the Ni/g-C 3N4 precursor prepared in the third step and sodium hypophosphite at two ends of a white porcelain boat according to the mass ratio of 1 (1-10), placing the white porcelain boat into a tubular furnace, heating to 300-500 ℃ at the heating rate of 2-10 ℃/min under argon atmosphere, preserving heat for 1-5 hours, taking out and grinding after the product is cooled, and obtaining the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst.
2. The method for preparing a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst according to claim 1, wherein the method for preparing g-C 3N4 in the first step comprises:
Placing 6-16 urea and 4-16g melamine into a mortar, fully mixing, transferring to a white porcelain boat, placing into a muffle furnace, setting the calcining temperature to 450-650 ℃, keeping the temperature for 2-6h, and heating at a speed of 2-15 ℃/min; and naturally cooling the calcined sample along with a furnace, and grinding the sample in a mortar for 30-90min to obtain yellow powder, namely flaky g-C 3N4.
3. The method for preparing a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst according to claim 1, wherein the sufficient stirring in the third step is stirring for 120-360min by using a stirrer.
4. The method for preparing a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst according to claim 1, wherein the washing agent in the third step is washed with ultrapure water and absolute ethanol for 3 to 5 times, respectively.
5. The method for preparing a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst according to claim 1, wherein the drying in the third step is performed in a vacuum drying oven at 80 ℃ for 8-26 hours.
6. The method for preparing a Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst according to claim 1, wherein the grinding in the fourth step is grinding for 30-100min by using a mortar.
7. A Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst prepared by the method of any one of claims 1 to 6.
8. Use of the Ni-Ni 2P-Ni5P4/g-C3N4 photocatalyst of claim 7 in photocatalytic electrolysis of water to produce hydrogen.
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