CN111215118A - Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof - Google Patents
Sodium-boron double-doped nano-layered graphite-like phase carbon nitride and preparation method and application thereof Download PDFInfo
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- MOOAHMCRPCTRLV-UHFFFAOYSA-N boron sodium Chemical compound [B].[Na] MOOAHMCRPCTRLV-UHFFFAOYSA-N 0.000 title claims abstract description 35
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 58
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 58
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 30
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 30
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 239000012265 solid product Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011941 photocatalyst Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000008247 solid mixture Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- -1 melamine ammonium dinitrate Chemical compound 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 32
- 239000000463 material Substances 0.000 abstract description 14
- 230000000052 comparative effect Effects 0.000 description 32
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- 239000011734 sodium Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
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- 235000019270 ammonium chloride Nutrition 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
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- 238000002189 fluorescence spectrum Methods 0.000 description 2
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- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 238000004904 shortening Methods 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum 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
-
- 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
- C01B2203/1088—Non-supported catalysts
-
- 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 belongs to the technical field of inorganic photocatalyst materials, and particularly relates to a preparation method of sodium boron double-doped nano-layered graphite-like carbon nitride, which comprises the following steps: s1, dissolving melamine in water to obtain a melamine solution, adding ammonium nitrate into the melamine solution, and after the reaction is finished, calcining the obtained solid product to obtain the nano-layered structure g-C3N4(ii) a S2, mixing the nano-layered structure g-C3N4With NaBH4Mixing, calcining and cooling to obtain the sodium boron double-doped nano-layered structure g-C3N4. The sodium boron double-doped nano-layered graphite-like carbon nitride obtained by the preparation method has good photocatalytic performance and better application prospect.
Description
Technical Field
The invention belongs to the technical field of inorganic photocatalyst materials, and particularly relates to sodium boron double-doped nano-layered graphite-like carbon nitride and a preparation method and application thereof.
Background
With the over consumption of fossil fuel and the increasingly prominent problem of environmental pollution, the technology of hydrogen production by solar photocatalytic water splitting gradually becomes a new path for researching extensive solar energy conversion. At present, semiconductors are generally used as photocatalysts, but the ultra-low activity thereof limits industrialization. Therefore, development of a cocatalyst having a low cost and a high efficiency is essential. Noble metal is the acknowledged cocatalyst of high-efficient hydrogen production, but with high costs, and non-noble metal cocatalyst can effectively reduce cost, through assembling noble metal and non-noble metal cocatalyst together, is expected to develop a novel, efficient compound cocatalyst, compromises the advantage of noble metal and non-noble metal cocatalyst.
Graphite-like carbon nitride (g-C)3N4) The polymer semiconductor used as a non-metal photocatalyst has the advantages of excellent thermal stability, chemical stability, easy modification, good visible light responsiveness under visible light radiation and the like, and the g-C is prepared3N4The raw materials have low cost, high stability and rich reserves. g-C3N4Narrow band gap (E)g2.70eV), has a proper energy band structure, the conduction band position is 1.1eV, the valence band position is 1.6eV, and the photocatalyst is particularly suitable for photocatalytic organic pollutant degradation, water decomposition and CO decomposition2Reduction and photocatalytic hydrolysis to produce hydrogen, etc. However, g-C3N4Has the defects of smaller specific surface area, high recombination rate of photo-generated electron-hole pairs, lower photocatalysis efficiency and the like. To solve these problems, various methods have been developed, mainly for g-C from the following three aspects3N4Modification is carried out: increase of g-C3N4Specific surface area of (a); by doping or the likeMethod for regulating g-C3N4The band gap of (a) improves its response to visible light; g to C3N4The photocatalyst is compounded with other semiconductor photocatalysts to prepare the heterojunction composite photocatalyst, so that the response range of the photocatalyst to light and the separation efficiency of photon-generated carriers are improved. Wherein g-C of the nanostructure3N4Has a large specific surface area, is considered to be a very effective method for improving the photocatalytic activity, and the nano structure is beneficial to accelerating the transport of electrons and shortening the diffusion path of photo-excited electron-hole pairs from the bulk to the surface of the catalyst. In addition, the higher specific surface area of the nanostructured material provides more active sites for photocatalytic reactions, increasing the initial adsorption rate of reactants, e.g., NH4Cl is mixed into melamine as a gaseous template to realize one-step synthesis of g-C3N4Nanosheets. g-C prepared by the method3N4The nano-sheet has the characteristics of increased specific surface area, enhanced electron transfer capacity, long life of photo-excited carriers and the like, and the photocatalytic hydrogen production capacity of the nano-sheet is better than that of bulk phase g-C3N4Much enhanced, however, this method has the disadvantage that NH4Cl as a gaseous template cannot be combined with melamine on a microscopic level, but is only macroscopically uniformly mixed, and cannot effectively combine g-C3N3Peeling off, g-C3N3The nanoplatelets are also bonded together in multiple layers at the two-dimensional level.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of sodium boron double-doped nano-layered graphite-like phase carbon nitride. The sodium boron double-doped nano-layered graphite-like phase carbon nitride prepared by the method overcomes the defects of g-C in the prior art3N4The specific surface area is small, the recombination rate of the photoproduction electron-hole pairs is high, and the photocatalysis efficiency is low, so that the photocatalysis material with excellent properties is obtained.
In order to achieve the technical effect, the technical scheme is as follows:
a preparation method of sodium boron double-doped nano-layered graphite-like phase carbon nitride comprises the following steps:
s1, dissolving melamine in water to obtain a melamine solution, adding ammonium nitrate into the melamine solution, and after the reaction is finished, calcining the obtained solid product to obtain the nano-layered structure g-C3N4；
S2, mixing the nano-layered structure g-C3N4With NaBH4Mixing, calcining and cooling to obtain the sodium boron double-doped nano-layered structure g-C3N4。
The preparation method of the invention firstly adopts ammonium nitrate to treat melamine to prepare g-C with a laminated structure3N4Then on the basis of the above-mentioned formula, using high-temp. reduction method to obtain g-C of laminated structure3N4B and Na elements are doped, the B is combined with an N bond to form an N-B-N bond, and the Na is also combined with the N bond to form an N-Na-N bond, so that the recombination rate of photo-generated electrons and holes is effectively reduced, and the g-C is further improved3N4Photocatalytic activity of photocatalytic materials, e.g., when g-C is described in the present invention3N4When the photocatalytic material is used for photocatalytic hydrogen production, the hydrogen production efficiency is obviously improved.
In addition, when the invention adopts ammonium nitrate to treat melamine, nitrate radical and ammonium radical can be combined with melamine on the molecular layer surface at the same time, and the nitrate radical and the ammonium radical are simultaneously used as gaseous templates to prepare g-C with a layered structure3N4And is thinner.
In one embodiment, in step S1, the molar ratio of ammonium nitrate to melamine is 2 to 5.
In one embodiment, in step S1, the concentration of the melamine solution is 0.2 to 0.6 mol/L.
In one embodiment, in step S1, the temperature of the melamine solution is 90 to 100 ℃, preferably 95 ℃.
In one embodiment, in step S1, ammonium nitrate is prepared into an ammonium nitrate solution, and added to the melamine solution at a dropping speed of 1-3S/drop.
In one embodiment, in step S1, the obtained solid product is dried in advance and then calcined.
In a preferred embodiment, in step S1, the obtained solid product is dried at 50 to 65 ℃ for 10 to 12 hours and then calcined.
As a more preferable embodiment, in step S1, the solid product obtained is dried at 60 ℃ for 12 hours and then calcined.
In an embodiment, in step S1, after the reaction is completed, a white floccule is obtained, the white floccule is filtered and precipitated, the obtained solid product melamine ammonium dinitrate is dried in advance and then placed in a crucible, the crucible is placed in a muffle furnace, and the solid product melamine ammonium dinitrate is calcined at 300-350 ℃ for 2-4 h, wherein the heating rate is 1-3 ℃/min; then, calcining for 2-4 h at 500-550 ℃, wherein the heating rate is 1-3 ℃/min.
Further, as a preferred embodiment, in step S1, the obtained solid product, melamine ammonium dinitrate, is dried in advance and then placed in a crucible, the crucible is placed in a muffle furnace, and the solid product is calcined at 350 ℃ for 2h, wherein the heating rate is 1 ℃/min; then, the mixture was calcined at 550 ℃ for 4 hours, wherein the temperature increase rate was 3 ℃/min.
In the step S1, the temperature rise rate is faster than 3 ℃/min or lower than 1 ℃/min, which leads to the gaseous template not well stripping melamine in bulk phase, and causes the prepared g-C3N4A good sheet structure cannot be formed.
In one embodiment, in step S2, NaBH is added4In an amount of said nano-layered structure g-C3N41 to 20% of the mass of (A).
In one embodiment, in step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in anhydrous ethanol, and mixing.
In one embodiment, in step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in anhydrous ethanol, stirring, mixing, and mixingAnd placing the mixed solution in a drying oven at 50-70 ℃, drying for 30-120 min to obtain a solid mixture, and calcining the solid mixture.
Further, as a preferred embodiment, in the step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in absolute ethyl alcohol, stirring and mixing, placing the obtained mixed solution in a drying oven at 60 ℃, drying for 30-60 min to obtain a solid mixture, and calcining the solid mixture.
In one embodiment, in step S2, the obtained solid mixture is calcined at 500 to 550 ℃ for 2 to 4 hours in a nitrogen atmosphere, wherein the temperature rise rate is 1 to 3 ℃/min.
Further, as a preferred embodiment, in the step S2, the obtained solid mixture is calcined at 550 ℃ for 2h under nitrogen atmosphere, wherein the temperature rising rate is 3 ℃/min.
The invention also relates to the sodium boron double-doped nano-layered graphite-like phase carbon nitride, which is prepared by any preparation method.
The invention also relates to application of the sodium boron double-doped nano-layered graphite-like phase carbon nitride as a photocatalyst.
Further, as a preferred embodiment, the sodium boron double-doped nano-layered graphite-like phase carbon nitride is used as a photocatalyst for preparing hydrogen by decomposing water.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
(1) the invention adopts ammonium nitrate to treat melamine to prepare g-C with a laminated structure3N4And on this basis, the layered structure g-C is reduced by a high-temperature reduction method3N4The boron-sodium element is doped, B is combined with an N bond to form an N-B-N bond, Na is also combined with the N bond to form an N-Na-N bond, the recombination rate of photo-generated electrons and holes is effectively reduced, and the g-C is further improved3N4The photocatalytic activity and hydrogen production efficiency of the photocatalytic material.
(2) The inventionB-Na-g-C prepared in (1)3N4The valence band position of the obtained photocatalytic material is reduced by the double doping of the sodium borate, the photocatalytic oxidation performance is enhanced, and the photocatalytic material and the bulk phase g-C3N4In contrast, light absorption is enhanced.
(3) The invention adopts NaBH4As B source and Na source, boron and sodium are doped in g-C of the layered structure3N4The amount of sodium borohydride is g-C3N41 to 20 percent of the mass, boron and sodium substitute C in N-C-N to form N-B-N, N-Na-N, and small part of sodium C-N is coordinated with C-N ring to prepare B-Na-g-C3N4Wherein, NaBH4Can react with absolute ethyl alcohol to generate B (OC)2H5)3And NaOC2H5，B(OC2H5)3And NaOC2H5More easily react with g-C3N4Bonding, NaBH4As a boron source with boric acid (H)3BO3) Or boron oxide (B)2O3) The boron source has obvious advantages compared with the boron source: NaBH4Is not easy to decompose at high temperature to form B2O3Is easier to react with g-C3N4Is bonded to H3BO3Is preferentially decomposed at high temperature to form B2O3，B2O3Stable in nature and not easy to react with g-C3N4Bonding occurs.
(4) B-Na-g-C prepared by the invention3N4Photocatalytic material and nano-layered g-C3N4Compared with the light absorption material, the light absorption material has smaller band gap and wider absorption spectrum band, and the light absorption efficiency and the separation efficiency of hole-electron pairs are greatly improved. More defects exist in the structure, the electric conductivity is improved, the number of photocatalytic active sites is increased, and the structural characteristics can effectively improve the g-C3N4The photocatalytic performance of (a).
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a comparison graph of fluorescence spectrum tests of products obtained in example 1 of the present invention, comparative example 1 and comparative example 2, respectively;
FIG. 2 is a comparative graph of UV-VIS absorption spectrum tests of products obtained in example 1 of the present invention, comparative example 1 and comparative example 2, respectively;
FIG. 3 is a graph showing hydrogen production by photocatalysis of products obtained in example 1, comparative example 2 and example 4 of the present invention, respectively;
FIG. 4 is a graph showing comparison of energy band gaps of products obtained in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of the product obtained in comparative examples 1 and 2 (wherein a is a scanning electron micrograph of the product obtained in comparative example 2, and b is a scanning electron micrograph of the product obtained in comparative example 1);
FIG. 6 is XRD test patterns of products obtained in example 1 of the present invention, comparative example 1 and comparative example 2, respectively;
FIG. 7 is a graph showing the hydrogen production by photocatalysis for the products of examples 1, 2 and 3 of the present invention and comparative examples 1 and 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The invention provides a preparation method of sodium boron double-doped nano-layered graphite-like phase carbon nitride, which comprises the following steps:
s1, dissolving melamine in water to obtain a melamine solution, adding ammonium nitrate into the melamine solution, and after the reaction is finished, calcining the obtained solid product to obtain the nano-layered structure g-C3N4；
S2, mixing the nano-layered structure g-C3N4With NaBH4Mixing and reacting and calcining the reaction productCooling to obtain the sodium boron double-doped nano-layered structure g-C3N4。
In one embodiment, in step S1, the molar ratio of ammonium nitrate to melamine is 2 to 5 (for example, the molar ratio of ammonium nitrate to melamine may be 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 or 5).
When the molar ratio of ammonium nitrate to melamine is less than 2, some melamine cannot be effectively combined with nitrate and ammonium radicals, and the product performance is reduced. When the molar ratio of ammonium nitrate to melamine is more than 5, the improvement of the product performance is not significant.
In one embodiment, in step S1, the concentration of the melamine solution is 0.2 to 0.6mol/L (e.g., 0.2mol/L, 0.22mol/L, 0.24mol/L, 0.25mol/L, 0.27mol/L, 0.29mol/L, 0.30mol/L, 0.32mol/L, 0.34mol/L, 0.35mol/L, 0.37mol/L, 0.39mol/L, 0.4mol/L, 0.42mol/L, 0.44mol/L, 0.45mol/L, 0.47mol/L, 0.49mol/L, 0.50mol/L, 0.52mol/L, 0.54mol/L, 0.56mol/L, 0.58mol/L, or 0.6 mol/L).
When the concentration of the melamine solution is more than 0.6mol/L, a part of the melamine cannot be dissolved, the part of the undissolved melamine cannot react with nitrate and ammonium, and g-C mixed with a bulk phase in the final product is caused3N4. When the concentration of the melamine solution is less than 0.2mol/L, the reaction rate is slow, which is not favorable for improving the production efficiency.
In one embodiment, in the step S1, the temperature of the melamine solution is 90 to 100 ℃ (e.g., 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃ or 100 ℃), preferably 95 ℃.
When the temperature of the melamine solution is lower than 90 ℃, ammonium nitrate is not easy to react with melamine, and when the temperature is higher than 100 ℃, ammonium nitrate is volatilized too fast, so that the yield of the generated product is low.
In one embodiment, in step S1, ammonium nitrate is prepared into an ammonium nitrate solution, and added to the melamine solution at a dropping rate of 1-3S/drop (e.g., 1S/drop, 1.5S/drop, 2S/drop, 2.5S/drop, 3S/drop).
When the dropping speed of the ammonium nitrate solution is higher than 1 s/drop, part of ammonium nitrate can volatilize and consume when not reacting with melamine in time, the dropping speed is lower than 3 s/drop, water can volatilize more, and part of melamine can be separated out when not reacting in time.
In one embodiment, in step S1, the obtained solid product is dried in advance and then calcined.
In a preferred embodiment, in step S1, the solid product obtained is dried at 50 to 65 ℃ (e.g., 50 ℃, 52 ℃, 54 ℃, 55 ℃, 57 ℃, 58 ℃ and 60 ℃) for 10 to 12 hours (e.g., 10 hours, 10.5 hours, 11 hours, 11.5 hours and 12 hours), and then calcined.
As a more preferable embodiment, in step S1, the solid product obtained is dried at 60 ℃ for 12 hours and then calcined.
The purpose of the above drying is to prevent excessive moisture content and to avoid a reverse reaction when heated to high temperatures, whereby nitrate and ammonium radicals are separated from the melamine and are volatilized together with water.
In an embodiment, in step S1, after the reaction is completed, a white floccule is obtained, the white floccule is filtered and precipitated, the obtained solid product melamine ammonium dinitrate is dried in advance and then placed in a crucible, the crucible is placed in a muffle furnace, and the solid product melamine ammonium dinitrate is calcined at 300-350 ℃ for 2-4 h, wherein the heating rate is 1-3 ℃/min; then, calcining for 2-4 h at 500-550 ℃, wherein the heating rate is 1-3 ℃/min.
If the direct heating to 500-550 ℃ without the muffle furnace process is adopted, nitrate radicals and ammonium radicals are decomposed too fast and cannot be effectively used as a gaseous template to strip the bulk melamine, and the bulk melamine can be fully stripped by adopting a temperature gradient method.
Preferably, in the step S1, the obtained solid product, melamine ammonium dinitrate, is dried in advance and then placed in a crucible, the crucible is placed in a muffle furnace, and the solid product is calcined at 350 ℃ for 2h, wherein the heating rate is 1 ℃/min; then, the mixture was calcined at 550 ℃ for 4 hours, wherein the temperature increase rate was 3 ℃/min.
The temperature increase rate in the above step S1 of the present invention refers to the temperature increase rate of the muffle furnace.
In one embodiment, in step S2, NaBH is added4In an amount of said nano-layered structure g-C3N41% to 20% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%) of the mass of (a).
NaBH4If the amount of the compound (B) is more than 20%, excess amounts of boron and sodium will destroy g-C3N4The structure of (2) reduces the overall photocatalytic performance of the composition, NaBH4If the amount of (A) is less than 1%, g-C is caused3N4The lattice distortion of (a) is not sufficient and the recombination rate of electron holes thereof cannot be effectively reduced.
In one embodiment, in step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in absolute ethyl alcohol, stirring and mixing, placing the obtained mixed solution in a drying oven at 50-70 ℃, drying for 30-120 min to obtain a solid mixture, and calcining the solid mixture.
Further, as a preferred embodiment, in the step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in absolute ethyl alcohol, stirring and mixing, placing the obtained mixed solution in a drying oven at 60 ℃, drying for 30-60 min to obtain a solid mixture, and calcining the solid mixture.
In one embodiment, in step S2, the obtained solid mixture is calcined at 500 to 550 ℃ (e.g., 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃) for 2 to 4 hours (e.g., 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours) in a nitrogen atmosphere, wherein the temperature increase rate is 1 to 3 ℃/min (e.g., 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min).
In the step S2, the calcination temperature of the solid mixture is higher than 550 ℃, which results in the complete decomposition of the carbon nitride, and the calcination temperature is lower than 500 ℃, so that the C — N bond in the carbon nitride cannot be broken and cannot form a bond with B or Na atoms.
Further, as a preferred embodiment, in the step S2, the obtained solid mixture is calcined at 550 ℃ for 2h under nitrogen atmosphere, wherein the temperature rising rate is 3 ℃/min.
The temperature increase rate described in the above step S2 of the present invention refers to the temperature increase rate of the temperature increasing heating equipment, for example, the temperature increase rate of the tube furnace.
The invention also relates to the sodium boron double-doped nano-layered graphite-like phase carbon nitride, which is prepared by any preparation method.
The invention also relates to the application of the sodium boron double-doped nano-layered graphite-like phase carbon nitride as a photocatalyst.
Further, as a preferred embodiment, the sodium boron double-doped nano-layered graphite-like phase carbon nitride is used as a photocatalyst for preparing hydrogen by decomposing water.
Example 1
A preparation method of sodium boron double-doped nano-layered graphite-like phase carbon nitride comprises the following steps:
s1: nano-layered structure g-C3N4Preparation of
S11, 7.5672g (60mmol) of melamine is dissolved in 300mL of water and heated to 95 ℃ to obtain a melamine solution.
S12, under the stirring condition, dissolving 9.6g (120mmol) of ammonium nitrate in 20ml of water, dropwise adding into the melamine solution at a dropwise adding speed of 1-3 seconds per drop, and reacting for 1 hour after the dropwise adding is completed.
S13, cooling to room temperature after the reaction is finished to obtain white floccule, filtering and precipitating to obtain melamine ammonium dinitrate, and drying the melamine ammonium dinitrate in a drying oven at 60 ℃ for 12 hours.
S14, drying melamine dinitratePutting ammonium into a 50mL crucible, covering the crucible with a cover, and calcining the ammonium in a muffle furnace at 350 ℃ for 2 hours at the heating rate of 1 ℃/min; then calcining for 4 hours at 550 ℃ with the heating rate of 3 ℃/min to obtain light yellow fluffy and soft nano-layered g-C3N4(labeled NL-CN).
S2: sodium boron doped nano-layered structure g-C3N4
S21, weighing 200mg g-C of nano-layered3N4(NL-CN) and 2mg of NaBH4Placing the mixture into a beaker, adding 0.5ml of absolute ethyl alcohol, and stirring for 6 hours to obtain a reaction mixed solution.
S22, placing the reaction mixed solution in a drying oven at 60 ℃, and drying for 2h to obtain a mixture;
s23, calcining the mixture in a tube furnace at 550 ℃ for 2h under nitrogen atmosphere, wherein the heating rate is 3 ℃/min.
S24, cooling to room temperature to obtain B, Na double-doped g-C3N4(labeled B-Na-NL-CN).
Example 2
This example differs from example 1 in that: the amount of sodium borohydride in step S21 was 5mg, and the other steps and process parameters were consistent with those of example 1.
Example 3
This example differs from example 1 in that: the amount of sodium borohydride in step S21 was 18mg, and the other steps and process parameters were consistent with those of example 1.
Example 4
This example differs from example 1 in that: s21, weighing 200mg g-C of nano-layered3N4(NL-CN) and 2mg of NaBH4The mixture was placed in a beaker, 0.5ml of water was added thereto, and stirred for 6 hours to obtain a reaction mixture. The other steps and parameters were kept consistent with example 1.
Example 5
This example differs from example 1 in that: in step S1, the molar ratio of ammonium nitrate to melamine was 3, and the other steps and process parameters were all in accordance with example 1.
Example 6
This example differs from example 1 in that: in step S1, the molar ratio of ammonium nitrate to melamine was 4, and the other steps and process parameters were all in accordance with example 1.
Example 7
This example differs from example 1 in that: in the step S2, NaBH4In an amount of said nano-layered structure g-C3N45% of the mass of (b), the other steps and process parameters were in accordance with example 1.
Example 8
This example differs from example 1 in that: in the step S2, NaBH4In an amount of said nano-layered structure g-C3N410% of the mass, the other steps and process parameters were in accordance with example 1.
Example 9
This example differs from example 1 in that: in the step S2, NaBH4In an amount of said nano-layered structure g-C3N415% of the mass, the other steps and process parameters were in accordance with example 1.
Example 10
This example differs from example 1 in that: in the step S2, NaBH4In an amount of said nano-layered structure g-C3N420% of the mass of (a), the other steps and process parameters were in accordance with example 1.
Comparative example 1
To examine B, Na double-doped g-C prepared according to the invention as a control3N4With reference to the procedure in S1, g-C of bulk phase was prepared3N4The preparation method is different from the preparation method of S1 in that: the method does not use gas template ammonium nitrate, and specifically comprises the following steps:
placing 7.5672g of melamine into a 50mL crucible, covering the crucible with a cover, placing the crucible into a muffle furnace, and calcining the melamine for 2 hours at 350 ℃ at the heating rate of 1 ℃/min; then calcining for 4 hours at 550 ℃ at a heating rateThe rate was 3 ℃/min, yielding light yellow g-C3N4(labeled BK-CN).
Comparative example 2
S11, 7.5672g of melamine was dissolved in 300mL of water and heated to 95 ℃ to give a melamine solution.
S12, dissolving 9.6g of ammonium nitrate in 20ml of water under the stirring condition, dropwise adding the ammonium nitrate into the melamine solution at a dropwise adding speed of 1-3 seconds per drop, and reacting for 1 hour after the dropwise adding is completed.
S13, cooling to room temperature after the reaction is finished to obtain white floccule, filtering and precipitating to obtain melamine ammonium dinitrate, and drying the melamine ammonium dinitrate in a drying oven at 60 ℃ for 12 hours.
S14, placing the dried melamine ammonium dinitrate into a 50mL crucible, covering the crucible with a cover, and placing the crucible in a muffle furnace to calcine for 2 hours at 350 ℃, wherein the heating rate is 10 ℃/min; then calcining for 4 hours at 550 ℃ with the heating rate of 3 ℃/min to obtain light yellow fluffy and soft nano-layered g-C3N4(labeled NL-CN).
As shown in fig. 5, the scanning electron micrographs of the products obtained in comparative example 1 and comparative example 2 are shown, wherein a is the scanning electron micrograph of the product obtained in comparative example 2, b is the scanning electron micrograph of the product obtained in comparative example 1, a shows a distinct layered structure, and b shows a bulk structure.
Comparative example 3
The comparative example differs from example 1 in that: ammonium nitrate was replaced by ammonium chloride in the same molar ratio of ammonium chloride to melamine as in example 1, with the other parameters being in agreement.
The photocatalyst prepared in this comparative example was then tested for the amount of hydrogen evolution with reference to the test method in example 1, and tested for H under the same test conditions2The yield of (a) was 850.31. mu. mol. h-1·g-1Significantly lower than H of inventive example 12The yield of (a).
Test example 1
In the test example, the products obtained in example 1 and comparative examples 1 to 2 were used as test samples, and the fluorescence spectra of the respective products were measured by the following specific test methods: using a Cary Eclipse fluorescence spectrometer, the excitation wavelength was 320nm, the emission wavelength was 350 nm-700 nm, the slit width was 5, and the scan number was high, as shown in fig. 1.
As shown in FIG. 1, it can be seen that BK-CN has the strongest peak in the PL spectrum, followed by NL-CN and the weakest peak in B-Na-NL-CN, indicating that the nanolaminate structure and doped Na, B promote the separation of electron-hole pairs.
Test example 2
In the test example, the products obtained in example 1 and comparative examples 1 to 2 were used as test samples, and the ultraviolet-visible absorption spectra of the products were measured by the following specific test methods: the UV-visible absorption spectrum was measured using UV-visible spectrophotometer uv-2600, with a slit width of 5 and a high scanning speed, and the specific results are shown in FIG. 2.
From FIG. 2 it can be seen that B-Na-NL-CN has a stronger light absorption in the visible region than BK-CN and NL-CN, and that B, Na doping increases the absorption of visible light by graphite phase carbon nitride.
Test example 3
In the test example, the products obtained in example 1 and comparative examples 1 to 2 were used as test samples, and the energy band gaps of the respective products were tested, and the test method specifically included: the band gap diagram is obtained by an ultraviolet-visible absorption spectrum and a Tauc plot method, and the specific result is shown in fig. 4.
As can be seen from fig. 4: B-Na-g-C prepared in inventive example 13N4Photocatalytic material and nano-layered g-C3N4Compared with the light absorption material, the light absorption material has smaller band gap and wider absorption spectrum band, and the light absorption efficiency and the separation efficiency of hole-electron pairs are greatly improved. More defects exist in the structure, the electric conductivity is improved, the number of photocatalytic active sites is increased, and the structural characteristics can effectively improve the g-C3N4The photocatalytic performance of (a).
Test example 4
This experiment boron prepared in examples 1-10 was doped with B-Na-g-C3N4Comparative examples 1 to 3, respectively as photocatalystsThe method is used for hydrogen production by visible light, and the respective hydrogen production efficiency is tested under the same condition to investigate the photocatalytic activity.
The test method is as follows:
the H of the prepared sample is measured by a photocatalysis parallel reaction instrument WP-TEC-1020HPLC by using a white light LED with the power of 10W as a light source2And (4) precipitation performance. 10mg of photocatalyst was dispersed in 16mL of an aqueous solution containing 10 Vol% triethanolamine and 32. mu.L of chloroplatinic acid was added. Measurement of the H evolved by means of a Gas Chromatograph (GC) equipped with a Thermal Conductivity Detector (TCD)2The amount of (c).
H of the products obtained in examples 1 to 10 and comparative examples 1 to 3 described above2The yields of (a) are specifically shown in table 1 below.
TABLE 1
| Examples | H2Yield (. mu. mol. h)-1·g-1) |
| Example 1 | 2404.26 |
| Example 2 | 1496.98 |
| Example 3 | 1000.31 |
| Example 4 | 1087.14 |
| Example 5 | 2331.31 |
| Example 6 | 2382.23 |
| Example 7 | 1496.99 |
| Example 8 | 1099.78 |
| Example 9 | 831.21 |
| Example 10 | 525.56 |
| Comparative example 1 | 194.96 |
| Comparative example 2 | 384.11 |
| Comparative example 3 | 850.31 |
In which B-Na-g-C was doped with boron prepared in examples 1 to 43N4And comparative examples 1 to 2, see fig. 3 and fig. 7 for specific test results of hydrogen generation rate.
The results of the tests according to fig. 3 and 7 can be concluded as follows:
h of B-Na-NL-CN prepared in example 1 of the invention2The yield is highest, and the photocatalytic performance is best. Examples 2, 3 differ from example 1 only in the amount of sodium borohydride in step S21, but the H of B-Na-NL-CN that is finally obtained2The yield of the product is far lower than that of example 1, and the amount of sodium borohydride has a great influence on the photocatalytic performance of the final product.
Comparative example 1 preparation of a precursorg-C of phase3N4Comparative example 2 preparation of nano-layered g-C without sodium boron double doping3N4The photocatalytic performance of both was significantly lower than that of the products prepared in examples 1-4.
Example 4 differs from example 1 only in that the solvent used in step S21 is water instead of absolute ethanol, and the photocatalytic performance of the product prepared therefrom is also significantly lower than that of example 1, and it can be seen that the use of absolute ethanol also has an important effect on the photocatalytic performance of the final product prepared therefrom. If the solvent is water, NaBH4Reacting with water to form NaBO2，NaBO2Is not easy to react with g-C3N4Bonding, more so as to form B2O3To prepare B-Na-g-C3N4The doping effect is not good, and the photocatalysis effect is not good.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (10)
1. A preparation method of sodium boron double-doped nano-layered graphite-like carbon nitride is characterized by comprising the following steps:
s1, dissolving melamine in water to obtain a melamine solution, adding ammonium nitrate into the melamine solution, and after the reaction is finished, calcining the obtained solid product to obtain the nano-layered structure g-C3N4；
S2, mixing the nano-layered structure g-C3N4With NaBH4Mixing, calcining and cooling to obtain the sodium boron double-doped nano-layered structure g-C3N4。
2. The method for preparing boron-sodium double-doped nano-layered graphite-like phase carbon nitride according to claim 1, wherein in the step S1, the molar ratio of ammonium nitrate to melamine is 2-5;
preferably, in the step S1, the concentration of the melamine solution is 0.2-0.6 mol/L;
preferably, in the step S1, the temperature of the melamine solution is 90 to 100 ℃, and more preferably 95 ℃;
preferably, in the step S1, ammonium nitrate is prepared into an ammonium nitrate solution, and added into the melamine solution at a dropping speed of 1-3S/drop.
3. The method for preparing boron-sodium double-doped nano-layered graphite-like phase carbon nitride according to claim 1, wherein in step S1, the obtained solid product is dried in advance and then calcined;
preferably, in the step S1, the obtained solid product is dried at 50-65 ℃ for 10-12 hours and then calcined;
more preferably, in step S1, the solid product obtained is dried at 60 ℃ for 12h and then calcined.
4. The method for preparing boron-sodium double-doped nano laminar graphite-like carbon nitride according to claim 1 or 3, wherein in step S1, after the reaction is completed, white floccule is obtained, the precipitate is filtered, the obtained solid product melamine ammonium dinitrate is dried in advance and then placed in a crucible, the crucible is placed in a muffle furnace, and the crucible is calcined at 300-350 ℃ for 2-4 h, wherein the heating rate is 1-3 ℃/min; then, calcining for 2-4 h at 500-550 ℃, wherein the heating rate is 1-3 ℃/min;
preferably, in the step S1, the obtained solid product, melamine ammonium dinitrate, is dried in advance and then placed in a crucible, the crucible is placed in a muffle furnace, and the solid product is calcined at 350 ℃ for 2h, wherein the heating rate is 1 ℃/min; then, the mixture was calcined at 550 ℃ for 4 hours, wherein the temperature increase rate was 3 ℃/min.
5. The method for preparing boron-sodium double-doped nano-layered graphite-like phase carbon nitride according to claim 1, wherein in the step S2, NaBH is added4In an amount of said nano-layered structure g-C3N41 to 20% of the mass of (A).
6. The method for preparing boron-sodium double-doped nano-layered graphite-like phase carbon nitride according to claim 1, wherein in the step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in anhydrous ethanol, and mixing;
preferably, in the step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in absolute ethyl alcohol, stirring and mixing, placing the obtained mixed solution in a drying oven at 50-70 ℃, drying for 30-120 min to obtain a solid mixture, and calcining the solid mixture;
more preferably, in the step S2, the nano-layered structure g-C3N4With NaBH4Dissolving in absolute ethyl alcohol, stirring and mixing, placing the obtained mixed solution in a drying oven at 60 ℃, drying for 30-60 min to obtain a solid mixture, and calcining the solid mixture.
7. The method for preparing boron-sodium double-doped nano laminar graphite-like carbon nitride according to claim 6, wherein in the step S2, the obtained solid mixture is calcined at 500-550 ℃ for 2-4 h under nitrogen atmosphere, wherein the heating rate is 1-3 ℃/min; preferably, in the step S2, the obtained solid mixture is calcined at 550 ℃ for 2h under nitrogen atmosphere, wherein the temperature rising rate is 3 ℃/min.
8. The boron-sodium double-doped nano-layered graphite-like phase carbon nitride is characterized by being obtained by the preparation method according to any one of claims 1 to 7.
9. The use of the boron-sodium double-doped nano-layered graphite-like phase carbon nitride according to claim 8, wherein the boron-sodium double-doped nano-layered graphite-like phase carbon nitride is used as a photocatalyst.
10. The use of the boron-sodium double-doped nano-layered graphite-like phase carbon nitride according to claim 9, wherein the boron-sodium double-doped nano-layered graphite-like phase carbon nitride is used as a photocatalyst for decomposing water to prepare hydrogen.
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