CN115283002B - Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst - Google Patents
Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst Download PDFInfo
- Publication number
- CN115283002B CN115283002B CN202211026337.0A CN202211026337A CN115283002B CN 115283002 B CN115283002 B CN 115283002B CN 202211026337 A CN202211026337 A CN 202211026337A CN 115283002 B CN115283002 B CN 115283002B
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- nickel
- red phosphorus
- composite photocatalyst
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 76
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 45
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 34
- 238000001354 calcination Methods 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 29
- 239000000725 suspension Substances 0.000 claims abstract description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 19
- 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 16
- 238000001035 drying Methods 0.000 claims abstract description 16
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 51
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 27
- 239000004202 carbamide Substances 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 27
- 230000003595 spectral effect Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002272 high-resolution X-ray photoelectron spectroscopy Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- B01J35/19—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention discloses a preparation method and application of a carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst, comprising the following steps: will g-C 3 N 4 Dispersing the powder in ethanol, and carrying out ultrasonic treatment and uniform stirring to obtain a suspension; adding ammonia water, nickel chloride aqueous solution and deionized water into the suspension, uniformly stirring, performing hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, taking out powder obtained by the hydrothermal reaction, washing and drying to obtain nickel-doped carbon nitride; and grinding and mixing the nickel-doped carbon nitride and sodium hypophosphite uniformly, performing a calcination reaction, naturally cooling to room temperature after the reaction is finished, taking out powder obtained by the calcination reaction, washing and drying to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst. The invention provides a preparation scheme of a Z-type composite photocatalyst with simple synthesis method, wide spectral response and strong photo-generated carrier separation and migration capability, and the composite photocatalyst can efficiently decompose pure water by photocatalysis.
Description
Technical Field
The invention relates to the technical field of energy chemistry, in particular to a preparation method and application of a carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Background
In order to build a sustainable society and meet the increasing energy demand, the development and research of renewable energy sources with low cost, high efficiency and stability are urgent. In various new energy sources, the solar energy reserves are rich and widely distributed; the hydrogen energy density is high, and the combustion products are clean and pollution-free. Therefore, the solar photocatalytic water splitting hydrogen production is a new renewable energy conversion mode with research and application prospects.
Graphite carbon nitride (g-C) 3 N 4 ) The two-dimensional lamellar nonmetallic material is simple in synthesis method, good in thermal stability and large in specific surface area. However, the band gap of carbon nitride is wider, the solar energy utilization rate is lower, the photo-induced charge recombination rate is higher, and the photo-catalytic activity is lower. The red phosphorus is a nonmetallic material with narrow forbidden band, low cost and stable chemical property, has wider light absorption performance, can utilize long wavelength photons larger than 700nm, and can expand the spectral response range of the photocatalyst when the red phosphorus and carbon nitride form a heterojunction structure, thereby improving the photocatalytic hydrogen production activity. However, red phosphorus has low charge mobility, is easy to accumulate charges at a solid-liquid interface, and is easy to recombine by photoinduced charges.
The Z-type photocatalytic water splitting system can accelerate charge transfer and reduce the recombination rate of photoinduced charges due to the unique structure, so that the photocatalytic activity is enhanced, and the problem that the photoinduced charges of red phosphorus are easy to recombine can be solved. The Z-type system consists of a hydrogen evolution photocatalyst, an oxygen evolution photocatalyst and a proper electronic medium. When excited by light, both photocatalysts generate electron-hole pairs, wherein the photo-generated holes of the hydrogen evolution photocatalysts and the photo-generated electrons of the oxygen evolution photocatalysts migrate into the electron medium and recombine rapidly, and the rest of the photo-generated electrons and holes respectively undergo oxidation-reduction reactions on the respective semiconductors. The special structure can realize the directional transfer of electrons and holes, enhance the separation and migration capability of photo-generated carriers and inhibit the recombination of photo-induced charges. Meanwhile, the active site separation of the oxidation end and the reduction end inhibits the reverse reaction of the oxidation-reduction reaction to a certain extent, and improves the photocatalytic activity.
Currently, common electronic media mostly include Fe 3+ /Fe 2+ ，IO 3- /I - A liquid redox couple, and a solid-state electron mediator such as noble metal particles (gold, silver). The liquid redox couple is susceptible to reverse reaction and has some absorption of photons, thereby reducing the number of photons available for photocatalysis. However, noble metal particles (gold and silver) have higher cost and are not easy for large-scale production。
Disclosure of Invention
The invention aims to provide a preparation method and application of a carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst, and the invention provides a preparation scheme of a Z-type composite photocatalyst which has the advantages of simple synthesis method, wide spectral response and strong photo-generated carrier separation and migration capability, and can efficiently decompose pure water by photocatalysis, wherein an oxidation product in the photocatalysis process is H in a liquid phase 2 O 2 The separation of reaction products is facilitated.
In order to achieve the above purpose, the preparation method of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
a preparation method of a carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
will g-C 3 N 4 Dispersing the powder in ethanol, and carrying out ultrasonic treatment and uniform stirring to obtain a suspension;
adding ammonia water, nickel chloride aqueous solution and deionized water into the suspension, uniformly stirring, performing hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, taking out powder obtained by the hydrothermal reaction, washing and drying to obtain nickel-doped carbon nitride;
and grinding and mixing the nickel-doped carbon nitride and sodium hypophosphite uniformly, performing a calcination reaction, naturally cooling to room temperature after the reaction is finished, taking out powder obtained by the calcination reaction, washing and drying to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
As a further improvement of the invention, the g-C 3 N 4 The preparation method of the powder comprises the following steps:
heating urea to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature after the calcining is finished to obtain g-C 3 N 4 And (3) powder.
As a further improvement of the invention, the g-C 3 N 4 The solid-liquid ratio of the powder and the ethanol is (300-60) 5mg/ml.
As a further improvement of the invention, the ultrasonic power is 180W, and the ultrasonic time is 60-90 min;
the stirring speed is 600-1000 rpm, and the stirring time is 30-60 min.
As a further improvement of the invention, the concentration of the added ammonia water is 25 percent, and the volume ratio of the ammonia water to the ethanol is 1:40, a step of performing a; the concentration of the added nickel chloride solution is 4mg/mL, and the ratio of the nickel chloride solution to ethanol is 1: (20-40).
As a further improvement of the invention, the hydrothermal reaction is carried out by heating at 120-160 ℃ for 20-30 h.
As a further improvement of the invention, the mass ratio of the nickel-doped carbon nitride to the sodium hypophosphite is 1: (8-12).
As a further improvement of the present invention, the calcination reaction was carried out by raising the temperature to 300℃at a rate of 2℃/mm in an Ar atmosphere, and calcining at that temperature for 2 hours.
As a further improvement of the invention, the specific steps of washing and drying are as follows: centrifugal washing with deionized water for several times, and vacuum drying at 60-70 deg.c for 6-8 hr.
The application of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst prepared by the preparation method in decomposing pure water to produce hydrogen.
Compared with the prior art, the invention has the following advantages:
in the invention, nickel chloride is introduced as a nickel source in the solvothermal process, reacts with ammonium hydroxide to generate nickel hydroxide, and is attached to carbon nitride. In the subsequent high-temperature phosphating process, sodium hypophosphite is decomposed into phosphine gas at high temperature, nickel hydroxide is phosphated into nickel phosphide crystals, and the nickel phosphide crystals are used as nucleation centers to induce the redundant phosphine gas to be converted into crystalline red phosphorus, so that a Z-type photocatalytic water-splitting system which takes carbon nitride as a hydrogen evolution catalyst, nickel phosphide as an electronic medium and crystalline red phosphorus as an oxygen evolution catalyst is successfully prepared. Due to the existence of the electron medium nickel phosphide, the electron and the hole realize directional transfer, and the recombination of photoinduced charges is greatly inhibited. Meanwhile, the effective doping of red phosphorus ensures that the composite photocatalyst still has a broad spectrum effect, improves the photocatalytic performance, achieves the effect of decomposing pure water, and the oxidation product is H in liquid phase 2 O 2 AdvantageouslyAnd separating the reaction product.
The prepared composite photocatalyst is suitable for a Z-type photocatalytic water splitting system, wherein carbon nitride is a hydrogen evolution catalyst, crystalline red phosphorus is an oxygen evolution catalyst, and nickel phosphide is an electronic medium. The unique structure of the Z-type photocatalytic water splitting system can realize the directional transfer of electrons and holes and inhibit the recombination of photoinduced charges. The solid nickel phosphide raw material used as the electronic medium is low in price, and is not easy to cause reverse reaction and does not reduce the number of photons used for photocatalysis. Meanwhile, the prepared carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst retains the broad spectral response of red phosphorus and also shows enhanced spectral absorption in the near infrared region due to the presence of nickel phosphide.
Drawings
FIG. 1 is a transmission electron microscope picture of a composite photocatalyst of carbon nitride-nickel phosphide-crystalline red phosphorus prepared by the present invention; wherein a-e are transmission electron microscope pictures of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst prepared by the method; f to i are element distribution diagrams corresponding to carbon element, nitrogen element, phosphorus element and nickel element in the region d, respectively.
FIG. 2 is an X-ray diffraction image of an untreated carbon nitride and carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst obtained in accordance with the present invention;
FIG. 3 is a high resolution X-ray photoelectron spectroscopy image contrast map; a, b are C1s and N1 s high-resolution X-ray photoelectron spectroscopy images of the untreated carbon nitride and carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst obtained by the invention; and c, d is a P2P and Ni 2P high-resolution X-ray photoelectron spectrum image of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst prepared by the invention.
FIG. 4 is a comparison of UV-visible absorbance spectra images; a and b are respectively ultraviolet-visible absorption spectrum images of untreated carbon nitride, carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst and commercial red phosphorus obtained by the invention.
FIG. 5 is a comparative photo-catalytic hydrogen production activity image; a is a photo-catalytic hydrogen production active image of the obtained carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst at 35 ℃ under the irradiation of different cut-off sheet wavelengths; b is a photo-catalytic hydrogen production active image of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst obtained by the invention under the irradiation of visible light at different temperatures.
FIG. 6 shows the addition of MnO to the supernatant after five hours of photocatalytic decomposition of pure water and removal of the light source by the composite photocatalyst of nickel nitride-phosphorus and crystalline red phosphorus obtained in the present invention 2 And (5) a comparison image of the hydrogen and oxygen produced.
FIG. 7 is a schematic image of photocatalytic decomposition of pure water by the composite photocatalyst of carbon nitride-nickel phosphide-crystalline red phosphorus obtained by the present invention.
Detailed Description
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
The invention relates to a preparation method of a carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst, which comprises the following steps:
s1, placing urea into a muffle furnace for high-temperature calcination to obtain g-C 3 N 4 Powder, g-C to be prepared 3 N 4 Dispersing the powder in ethanol, and carrying out ultrasonic treatment and uniform stirring to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding ammonia water, nickel chloride aqueous solution and deionized water, uniformly stirring, then placing the hydrothermal kettle into an oven, heating at 120-160 ℃ for 24 hours, taking out, washing and drying the obtained powder after naturally cooling to room temperature to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and uniformly mixing the powder B obtained in the step S2 with sodium hypophosphite, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2 hours at the temperature, taking out the obtained powder after naturally cooling to room temperature, washing and drying to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Alternatively, the parameters of each step in the present invention are selected as follows:
in the step S1, the solid-to-liquid ratio of the carbon nitride powder to ethanol is (300-60): 5mg/ml.
In the step S1, the ultrasonic power is 180W, and the ultrasonic time is 60-90 min. In an embodiment, the specific ultrasound time is selected as desired, e.g., 60min,70min,75min,80min,90min, etc.
In the step S1, the stirring rotation speed is 600-1000 rpm, and the stirring time is 30-60 min. In the embodiment, the specific stirring speed and stirring time are selected according to the requirement, for example, the stirring speed is 600rpm, and the stirring time is 60min; the stirring speed is 700rpm, and the stirring time is 40min; the stirring speed is 800rpm, and the stirring time is 30min; the stirring speed is 1000rpm, the stirring time is 30min, and the like.
In the step S2, the concentration of the ammonia water is 25%, and the volume ratio of the ammonia water to the ethanol is as follows: 1:40.
in the step S2, the concentration of nickel chloride is 4mg/mL, and the volume ratio of nickel chloride solution to ethanol is 1: (20-40). In an embodiment, as desired, select, for example, 1:20, a step of; 1:26;1:35;1:40, etc.
In the step S3, the mass ratio of the powder B to the sodium hypophosphite is 1: (8-12). In an embodiment, as desired, select, for example, 1:8, 8;1:9, a step of performing the process; 1:10;1:12, etc.
In the steps S2 and S3, the specific steps of washing and drying are as follows: centrifugal washing with deionized water for several times, and vacuum drying at 60-70 deg.c for 6-8 hr. In the examples, the drying is carried out for 8 hours at 60 ℃ in vacuum, for example, according to the need; vacuum drying at 70 ℃ for 6 hours; vacuum drying at 65 ℃ for 7 hours; vacuum drying at 64 ℃ for 8 hours, etc.
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, reference is made to the following detailed description of the invention, taken in conjunction with the accompanying drawings and examples, which illustrate, but not limit, the invention.
Example 1
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtain light yellow g-C 3 N 4 And (3) powder. 300mg of the prepared g-C is taken 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 60min, and stirring at 800rpm for 30min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 1.5mL of nickel chloride aqueous solution and 7mL of deionized water until the total volume of the solution is 70mL, stirring for 30min, placing the hydrothermal kettle into an oven, heating at 140 ℃ for 24h, taking out the obtained powder after natural cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 70 ℃ for 6 hours to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 1g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and drying the powder in vacuum at 70 ℃ for 6 h to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Example 2
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtain light yellow g-C 3 N 4 And (3) powder. 300mg of the prepared g-C is taken 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 90min, and stirring at 700rpm for 40min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 2mL of nickel chloride aqueous solution and 6.5mL of deionized water until the total volume of the solution is 70mL, stirring for 30min, placing the hydrothermal kettle into an oven, heating at 120 ℃ for 24h, taking out the obtained powder after natural cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 70 ℃ for 6 h to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 1.2g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and vacuum drying the powder at 70 ℃ for 6 h to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Example 3
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtain light yellow g-C 3 N 4 And (3) powder. 300mg of the prepared g-C is taken 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 45min, and stirring at a stirring speed of 1000rpm for 30min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 1.5mL of nickel chloride aqueous solution and 7mL of deionized water until the total volume of the solution is 70mL, stirring for 30min, placing the hydrothermal kettle into an oven, heating at 140 ℃ for 24h, taking out the obtained powder after natural cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 60 ℃ for 8 hours to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 1g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and drying the powder in vacuum at 60 ℃ for 8 hours to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Example 4
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtain light yellow g-C 3 N 4 And (3) powder. 600mg of the prepared g-C is taken 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 60min, and stirring at a stirring speed of 1000rpm for 30min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 3mL of nickel chloride aqueous solution and 5.5mL of deionized water until the total volume of the solution is 70mL, stirring for 30min, placing the hydrothermal kettle into an oven, heating at 150 ℃ for 24h, taking out the obtained powder after natural cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 70 ℃ for 6 h to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 1g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and drying the powder in vacuum at 70 ℃ for 6 h to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Example 5
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtainPale yellow g-C 3 N 4 And (3) powder. Taking 500mg of g-C prepared by S1 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 60min, and stirring at a stirring speed of 600rpm for 60min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 3mL of nickel chloride aqueous solution and 5.5mL of deionized water until the total volume of the solution is 70mL, stirring for 30min, placing the hydrothermal kettle into an oven, heating at 160 ℃ for 24h, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 60 ℃ for 8 hours to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 1g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and drying the powder in vacuum at 60 ℃ for 8 hours to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Example 6
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtain light yellow g-C 3 N 4 And (3) powder. 300mg of the prepared g-C is taken 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 60min, and stirring at a stirring speed of 700rpm for 40min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 1.5mL of nickel chloride aqueous solution and 7mL of deionized water until the total volume of the solution is 70mL, stirring for 60min, placing the hydrothermal kettle into an oven, heating at 140 ℃ for 24h, taking out the obtained powder after natural cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 70 ℃ for 6 hours to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 1.2g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and vacuum drying the powder at 70 ℃ for 6 h to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
FIG. 1 is a transmission electron microscope picture of a composite photocatalyst of carbon nitride-nickel phosphide-crystalline red phosphorus prepared in example 1; wherein a-e are transmission electron microscope pictures of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst prepared in example 1; f to i are element distribution diagrams corresponding to carbon element, nitrogen element, phosphorus element and nickel element in the region d, respectively.
In FIG. 1, the bulk amorphous region of the sample surface shown as a is carbon nitride, while red phosphorus is located in the bulk crystalline region of the sample surface, as shown in b and e, with a lattice spacing of 0.567nm corresponding to the (013) crystal plane of red phosphorus (JCDF: 00-044-0906) and a lattice spacing of 0.539nm corresponding to the (004) crystal plane of red phosphorus. The other small piece crystallization area on the surface of the sample in e is nickel phosphide crystal, and the lattice spacing of 0.314nm corresponds to the (111) crystal face of the nickel phosphide crystal (JCPDF: 01-073-0436). These results show successful loading of red phosphorus with nickel phosphide on carbon nitride. The element distribution diagrams of f-i show that the phosphorus element is widely distributed, and the nickel element is only concentrated in partial areas, and according to the synthesis steps, it can be inferred that the nickel phosphide is positioned between the carbon nitride and the crystalline red phosphorus of the substrate material.
FIG. 2 is an X-ray diffraction pattern of an untreated carbon nitride and carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst obtained in example 1. As can be seen from the graph, compared with untreated carbon nitride, the high-temperature phosphating treatment of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst shows a new stronger diffraction peak at 15.5 degrees and a weaker diffraction peak at 33.9 degrees, which are consistent with the diffraction peak of red phosphorus (JCDF: 00-04-0906), and the generation of crystalline red phosphorus is proved. The generated nickel phosphide has low content, and basically has no influence on the structural change of the composite photocatalyst, so that the lattice structure of the composite photocatalyst cannot be shown in an X-ray diffraction spectrogram.
FIG. 3 is a high resolution X-ray photoelectron spectroscopy image contrast map; a, b are the C1s, N1 s high resolution X-ray photoelectron spectroscopy images of the untreated carbon nitride and carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst obtained in example 1; and c, d is a P2P and Ni 2P high-resolution X-ray photoelectron spectrum image of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst prepared in the example 1.
As can be seen from the figure, the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst shows a signal of 0-valent red phosphorus, and a signal obtained by unavoidable oxidation of red phosphorus in air of a sample. The nickel phosphide has a low content, and the signal is weak, but the signal of nickel element in the nickel phosphide at 852.9eV can be observed, which proves that the formation of the nickel phosphide electron mediator has good electron level contact with carbon nitride and red phosphorus.
FIG. 4 is a comparison of UV-visible absorbance spectra images; a, b are respectively the ultraviolet-visible absorption spectrum images of untreated carbon nitride, carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst and commercial red phosphorus obtained in example 1. The absorption edge of the carbon nitride is positioned at 460nm, the spectral absorption performance of red phosphorus is positioned in the whole visible light section, and the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst retains the broad spectral response of red phosphorus and also shows enhanced spectral absorption above 600nm due to the existence of nickel phosphide.
FIG. 5 is a comparative photo-catalytic hydrogen production activity image; a is a photo-catalytic hydrogen production active image of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst obtained in example 1 at 35 ℃ under irradiation of different cut-off sheet wavelengths; b is a photo-catalytic hydrogen-generating active image of the composite photo-catalyst of carbon nitride-nickel phosphide-crystalline red phosphorus obtained in example 1 under irradiation of visible light at different temperatures. The carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst has good photocatalytic activity under the irradiation of all wave bands and visible light, and the photocatalytic activity is improved along with the temperature rise.
FIG. 6 is a graph showing the comparative results of hydrogen and oxygen production of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst obtained in example 1, obtained by photocatalytic decomposition of pure water for five hours and removal of the light source, after addition of manganese dioxide to the supernatant. After the addition of manganese dioxide, the amount of hydrogen in the reaction system remained unchanged, the amount of oxygen gradually increased, and the molar ratio of oxygen to hydrogen was finally about 1:2. This result demonstrates that the photocatalyst breaks down pure water into two different products, hydrogen and hydrogen peroxide, simultaneously, facilitating the separation of the reaction products.
FIG. 7 is a schematic image of photocatalytic decomposition of pure water by the composite photocatalyst of carbon nitride-nickel phosphide-crystalline red phosphorus obtained in example 1. Under the irradiation of visible light, both carbon nitride and crystalline red phosphorus can realize photoexcitation by absorbing photons, and generate photo-generated electron hole pairs. Because the solid-state electron medium nickel phosphide is connected with carbon nitride and crystalline red phosphorus, holes on the carbon nitride are transferred to the nickel phosphide, and at the same time, electrons on the crystalline red phosphorus are also transferred to the nickel phosphide, so that the two materials are compounded. The rest of the photo-generated electrons on the carbon nitride are transferred to the surface of the photocatalyst and react with hydrogen ions to generate hydrogen. The holes on the crystalline red phosphorus oxidize water and produce hydrogen peroxide.
The invention also provides the following examples to illustrate the method of the invention:
example 7
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtain light yellow g-C 3 N 4 And (3) powder. 300mg of the prepared g-C is taken 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 90min, and stirring at 1000rpm for 30min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 2mL of nickel chloride aqueous solution and 7mL of deionized water until the total volume of the solution is 70mL, stirring for 30min, placing the hydrothermal kettle into an oven, heating at 120 ℃ for 24h, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 60 ℃ for 8 hours to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 1.2g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and drying the powder in vacuum at 60 ℃ for 8 hours to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
Example 8
The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst comprises the following steps:
s1, weighing 5g of urea, placing the urea into a 20mL alumina crucible with a cover, transferring the urea into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature to obtain light yellow g-C 3 N 4 And (3) powder. 300mg of the prepared g-C is taken 3 N 4 Dispersing the powder in 60mL of ethanol, carrying out ultrasonic treatment for 90min, and stirring at 1000rpm for 30min to obtain a suspension A;
s2, transferring the suspension A obtained in the step S1 into a hydrothermal kettle, gradually dropwise adding 1.5mL of ammonia water, 2mL of nickel chloride aqueous solution and 7mL of deionized water until the total volume of the solution is 70mL, stirring for 30min, placing the hydrothermal kettle into an oven, heating at 160 ℃ for 24h, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing with deionized water for 5 times, and vacuum drying at 70 ℃ for 6 h to obtain powder B, wherein the obtained powder B is nickel-doped carbon nitride;
s3, grinding and mixing 100mg of the powder B obtained in the step S2 with 0.8g of sodium hypophosphite for 20min, placing the mixture in a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/mm in Ar atmosphere, calcining for 2h at the temperature, taking out the obtained powder after naturally cooling to room temperature, repeatedly centrifuging and washing the powder with deionized water for 5 times, and vacuum drying the powder at 70 ℃ for 6 h to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst.
The foregoing is illustrative of the present invention only. Various modifications and additions may be made to the described examples by those skilled in the art to which the invention pertains without departing from the spirit of the invention, which is defined by the scope of the appended claims.
Although the embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above embodiments, which are merely illustrative, instructive, and not restrictive. Those skilled in the art, having the benefit of this disclosure, may make numerous forms of the invention without departing from the scope of the invention as defined by the appended claims.
Claims (7)
1. The preparation method of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst is characterized by comprising the following steps of:
will g-C 3 N 4 Dispersing the powder in ethanol, and carrying out ultrasonic treatment and uniform stirring to obtain a suspension;
adding ammonia water, nickel chloride aqueous solution and deionized water into the suspension, uniformly stirring, performing hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, taking out powder obtained by the hydrothermal reaction, washing and drying to obtain nickel-doped carbon nitride;
grinding and mixing nickel-doped carbon nitride and sodium hypophosphite uniformly, performing calcination reaction, naturally cooling to room temperature after the reaction is finished, taking out powder obtained by the calcination reaction, washing and drying to obtain the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst;
the hydrothermal reaction is carried out by heating for 20-30 h at 120-160 ℃;
the mass ratio of the nickel-doped carbon nitride to the sodium hypophosphite is 1: (8-12);
the calcination reaction was carried out by heating to 300℃in an Ar atmosphere at a heating rate of 2℃per mm, and calcining at that temperature for 2 hours.
2. The method for preparing a composite photocatalyst of carbon nitride-nickel phosphide-crystalline red phosphorus according to claim 1, wherein the g-C 3 N 4 The preparation method of the powder comprises the following steps:
heating urea to 550 ℃ at a heating rate of 5 ℃/min, calcining for 2h at the temperature, and naturally cooling to room temperature after the calcining is finished to obtain g-C 3 N 4 And (3) powder.
3. The method for preparing a composite photocatalyst of carbon nitride-nickel phosphide-crystalline red phosphorus according to claim 1, wherein the g-C 3 N 4 The solid-liquid ratio of the powder and the ethanol is (300-60) 5mg/ml.
4. The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst according to claim 1, wherein in the process of ultrasonic and uniform stirring, the ultrasonic power is 180W, and the ultrasonic time is 60-90 min; the stirring speed is 600-1000 rpm, and the stirring time is 30-60 min.
5. The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst according to claim 1, wherein the added ammonia water concentration is 25%, and the volume ratio of ammonia water to ethanol is 1:40, a step of performing a; the concentration of the added nickel chloride solution is 4mg/mL, and the volume ratio of the nickel chloride solution to the ethanol is 1: (20-40).
6. The method for preparing the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst according to claim 1, which is characterized by comprising the following specific steps of: centrifugal washing with deionized water for several times, and vacuum drying at 60-70 deg.c for 6-8 hr.
7. Use of the carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst prepared by the preparation method as defined in any one of claims 1 to 6 in decomposing pure water to produce hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211026337.0A CN115283002B (en) | 2022-08-25 | 2022-08-25 | Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211026337.0A CN115283002B (en) | 2022-08-25 | 2022-08-25 | Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115283002A CN115283002A (en) | 2022-11-04 |
| CN115283002B true CN115283002B (en) | 2023-07-14 |
Family
ID=83831506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211026337.0A Active CN115283002B (en) | 2022-08-25 | 2022-08-25 | Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115283002B (en) |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170120931A (en) * | 2016-04-22 | 2017-11-01 | 영남대학교 산학협력단 | Preparing method of nanopaticle, nanopaticle prepared by thereof and photocatalyst comprising the nanopaticle |
| CN107138173A (en) * | 2017-05-10 | 2017-09-08 | 江南大学 | A kind of simple and convenient process for preparing of unformed nickel phosphide/class graphene carbon nitrogen compound composite catalyst |
| CN108704657B (en) * | 2018-05-31 | 2020-12-11 | 广东工业大学 | Red phosphorus/graphite phase carbon nitride composite nanosheet and preparation method and application thereof |
| CN109277107B (en) * | 2018-09-21 | 2021-09-03 | 西北大学 | Transition metal phosphide/red phosphorus photocatalytic material, preparation method and application |
| CN109746016A (en) * | 2018-12-19 | 2019-05-14 | 江苏大学 | Metallicity nickel oxide/azotized carbon nano piece catalysis material and preparation method and application |
| CN109746017B (en) * | 2018-12-27 | 2021-07-13 | 西安交通大学 | Preparation method of P-doped solvent thermal graphite phase carbon nitride photocatalyst |
| CN109746018A (en) * | 2018-12-28 | 2019-05-14 | 西安交通大学 | A kind of preparation method of the graphite phase carbon nitride photochemical catalyst of the phosphorus doping of metal phosphide modification |
| CN110560105B (en) * | 2019-09-03 | 2022-03-01 | 西北师范大学 | Preparation of nickel phosphide-loaded sulfur indium zinc nano microsphere composite material and application of composite material in photocatalytic hydrogen production |
| CN111774084B (en) * | 2020-07-09 | 2023-02-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of phosphorus-doped carbon nitride-supported nickel efficient catalyst, product and application thereof |
| CN114130411B (en) * | 2020-09-03 | 2023-12-08 | 陕西科技大学 | V-Ni 2 P/g-C 3 N 4 Photocatalyst, preparation method and application thereof |
| CN112588310A (en) * | 2020-12-02 | 2021-04-02 | 江苏大学 | Preparation method of visible light response nickel-phosphorized carbon nitride photocatalyst |
| CN113952971A (en) * | 2021-11-25 | 2022-01-21 | 青岛旭晟东阳新材料有限公司 | Preparation of red phosphorus/transition metal phosphide/SiO with high-efficiency photocatalytic hydrogen evolution activity2Method for preparing photocatalyst |
| CN114588925A (en) * | 2022-03-21 | 2022-06-07 | 福州大学 | Noble-metal-free supported nickel phosphide/carbon nitride visible-light-driven photocatalyst and preparation method thereof |
| CN114618537B (en) * | 2022-04-10 | 2023-05-26 | 贵州大学 | Red phosphorus/strontium titanate heterojunction photocatalyst, and preparation method and application thereof |
-
2022
- 2022-08-25 CN CN202211026337.0A patent/CN115283002B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115283002A (en) | 2022-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108067281B (en) | Porous g-C3N4Photocatalyst and preparation method and application thereof | |
| CN110975886B (en) | Porous two-dimensional zinc cadmium sulfide nanosheet and preparation method and application thereof | |
| CN107983387B (en) | Preparation method and application of carbon nitride/bismuth selenate composite material | |
| CN109806902B (en) | W18O49/NiWO4Preparation method of/NF self-supporting electrocatalytic material | |
| CN111036243B (en) | Oxygen vacancy-containing transition metal-doped BiOBr nanosheet photocatalyst and preparation method and application thereof | |
| CN113145138B (en) | Thermal response type composite photocatalyst and preparation method and application thereof | |
| CN113289653A (en) | g-C of load metal monoatomic3N4Method for preparing photocatalyst | |
| CN105771948A (en) | Double-shell titanium dioxide catalyst with high photocatalytic hydrogen generation performance and preparation method thereof | |
| CN111841530A (en) | Catalyst for promoting water photolysis to produce hydrogen and preparation method thereof | |
| CN112473712A (en) | CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof | |
| CN114632549A (en) | alpha-TiO2@NH2Preparation method of-MIL-125 composite photocatalytic material | |
| CN112047372B (en) | CuO porous nanosheet, preparation method thereof and application thereof in thermal catalysis and photo-thermal catalysis | |
| CN113385210A (en) | Photocatalytic hydrogen production catalyst and preparation method and application thereof | |
| CN113413920A (en) | Single metal In2S3Application of/In-MOF semiconductor material In photolysis of water to produce hydrogen | |
| CN109833893B (en) | Titanium carbide composite phosphorus-doped tungsten oxide photoelectric catalyst and preparation method thereof | |
| CN115283002B (en) | Preparation method and application of carbon nitride-nickel phosphide-crystalline red phosphorus composite photocatalyst | |
| CN115999614A (en) | Ultraviolet-visible-near infrared light responsive carbon dioxide reduction photocatalyst | |
| CN115090318A (en) | Preparation method and application of intermolecular heterojunction carbon nitride photocatalyst with high specific surface area | |
| CN114570385A (en) | Preparation method of semiconductor catalyst for hydrogen production and oxygen production through sunlight catalysis and water decomposition | |
| CN109772419B (en) | Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space | |
| CN111974428A (en) | Bi2O2CO3-Bi2WO6Preparation method of composite photocatalyst | |
| CN112403505A (en) | CoP-g-C3N4Electronic current collector photocatalyst and preparation method and application thereof | |
| CN110876945A (en) | ZnIn grown in limited area in carbon nano hollow sphere2S4Photocatalyst and preparation method thereof | |
| CN111468133A (en) | Preparation method of potassium niobate/α -ferric oxide heterogeneous photocatalyst | |
| CN104959159A (en) | Nitrogen-doped titanium dioxide film, and preparation method and applications thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |