CN112473717B - Nickel monoatomic/functionalized graphite-phase carbon nitride composite catalyst - Google Patents
Nickel monoatomic/functionalized graphite-phase carbon nitride composite catalyst Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 93
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 claims abstract description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 13
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007872 degassing Methods 0.000 claims abstract description 12
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000005286 illumination Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- FSDSKERRNURGGO-UHFFFAOYSA-N cyclohexane-1,3,5-triol Chemical compound OC1CC(O)CC(O)C1 FSDSKERRNURGGO-UHFFFAOYSA-N 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 44
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000002135 nanosheet Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 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 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000002256 photodeposition Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- -1 phosphides Chemical class 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/39—
-
- B01J35/394—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
- 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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a nickel monoatomic/functional graphite-phase carbon nitride composite catalyst, belonging to the field of material science and technology and chemistry. The preparation method of the composite catalyst comprises the following steps: adding a mixed solution of nickel acetate, methanol and ethanol into the functional graphite-phase carbon nitride, performing ultrasonic dispersion, and degassing with nitrogen; after degassing is finished, placing the tube under a xenon lamp for illumination; centrifuging, washing and drying after illumination to obtain the nickel monoatomic/surface functionalized carbonized nitrogen nanosheet composite catalyst with wide spectral response; wherein the volume ratio of methanol to ethanol in the mixed solution is 4-6: 4-6. The nickel monatomic/surface functionalized carbonized nitrogen nanosheet composite catalyst with wide spectral response can be used for hydrogen production reaction of photocatalytic decomposition water, is low in price and high in hydrogen production rate, and the hydrogen production rate reaches 24557.78 mu mol g‑1·h‑1Compared with the pure nitrogen carbide nanosheet, the hydrogen production rate is improved by about 790 times.
Description
Technical Field
The invention relates to a nickel monoatomic/functional graphite-phase carbon nitride composite catalyst, belonging to the field of material science and technology and chemistry.
Background
With the increasing severity of environmental pollution and energy crisis, the efficient implementation of chemical reactions at normal temperature and pressure by using inexhaustible sunlight is one of the ideal schemes for solving the energy and environmental problems and realizing green chemistry. Among them, since hydrogen energy is a clean energy with high combustion value, high efficiency and reproducibility, solar drive photocatalysis water decomposition hydrogen production is attracting much attention. The solar energy is utilized to decompose water to produce hydrogen, and is converted into chemical energy stored in hydrogen energy, so that a cheap and convenient method for obtaining hydrogen is provided, and the development of a cheap and efficient photocatalyst is the key for preparing hydrogen by decomposing water through photocatalysis.
It is well known that noble metal catalysts have high and stable photocatalytic and electrocatalyst properties, but their high price and low content limit their large-scale application. Therefore, there is a need to develop non-noble metal catalysts with high activity, abundance and stability. Over the past few years, many studies have shown that elemental transition metals and their compounds (sulfides, phosphides, hydroxides, etc.) can be used as efficient promoters for photolytic hydrogen production from water. The preparation method of the transition metal-based cocatalyst mainly comprises the following steps: the solvent heating method, the calcining method, the dipping method and the like have complex processes and complicated operation.
Most of the currently prepared hydrogen production promoters exist in the form of nanoparticles, so that the low atom utilization rate is greatly reduced, and the hydrogen production rate is low.
Disclosure of Invention
In order to solve at least one problem, the invention provides a nickel monatomic/functional graphite-phase carbon nitride composite catalyst which is prepared by a simple, mild and low-cost photochemical method, has high hydrogen production efficiency and higher stability and use value.
A first object of the present invention is to provide a method for preparing a nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst, comprising the steps of:
adding a nickel acetate aqueous solution, anhydrous methanol and anhydrous ethanol mixed solution into the functional graphite-phase carbon nitride, and uniformly dispersing; then nitrogen is degassed; after degassing is finished, placing the tube under a xenon lamp for illumination; centrifuging, washing and drying after illumination to obtain the nickel monoatomic/functional graphite-phase carbon nitride composite catalyst; wherein the volume ratio of the absolute methanol to the absolute ethanol in the mixed solution is 4-6: 4-6; the preparation method of the functionalized graphite phase carbon nitride comprises the following steps: uniformly mixing urea and 1,3, 5-cyclohexanetriol to obtain a mixture; then placing the mixture in a crucible, covering the crucible, and heating to 500-600 ℃ for 1-3 h; then placing the obtained product in a crucible without a cover, and heating the product to the temperature of 450-500 ℃ for 1-3 h; the obtained functional graphite-phase carbon nitride.
In an embodiment of the present invention, in the preparation method of the functionalized graphite-phase carbon nitride, the mass ratio of urea to 1,3, 5-cyclohexanetriol is 10: 0.01 to 0.05, more preferably 10: 0.03.
in one embodiment of the present invention, the volume ratio of the absolute methanol to the absolute ethanol in the mixed solution is 1: 1.
in one embodiment of the present invention, the concentration of the nickel acetate aqueous solution is 12 to 14mg/mL, and more preferably 12.5 mg/mL.
In one embodiment of the invention, the functional graphite phase carbon nitride and nickel acetate aqueous solution are used in a ratio of 30 mg/mL: 0.05 to 0.2, more preferably 30: 0.1.
in one embodiment of the present invention, the amount ratio of the mixed solution of the functionalized graphite-phase carbon nitride and the absolute methanol and absolute ethanol is 30: 8 to 12, more preferably 30: 10.
in one embodiment of the invention, the uniform dispersion is ultrasonic dispersion treatment for 3-10 min.
In one embodiment of the present invention, the nitrogen degassing time is 30-60min, and the function is to remove oxygen in the reaction system.
In one embodiment of the invention, the xenon lamp irradiation is specifically 300W xenon lamp irradiation for 0.5-3 h.
In one embodiment of the invention, the washing is deionized water washing 3-5 times, and absolute ethyl alcohol washing 1-3 times.
In one embodiment of the invention, the drying is performed by blowing with nitrogen.
In one embodiment of the present invention, the preparation method of the functionalized graphite-phase carbon nitride comprises:
weighing 10g of urea and 30mg of 1,3, 5-cyclohexanetriol, and uniformly mixing to obtain a mixture; then the mixture was placed in a crucible, capped, and then heated to 550 ℃ for 2 hours; grinding the obtained yellow solid into powder, placing the powder in a crucible without covering, and then heating the powder to 500 ℃ for 2 hours; the obtained lower brown yellow solid is the functional graphite phase carbon nitride.
In one embodiment of the present invention, the preparation method of the functionalized graphite-phase carbon nitride specifically comprises:
weighing 10g of urea and 30mg of 1,3, 5-cyclohexanetriol, placing in a mortar, and grinding to fully mix the urea and the 3, 5-cyclohexanetriol; placing the ground solid in a crucible, covering, then placing in a muffle furnace, heating to 550 ℃ and keeping for 2 hours, wherein the heating rate is 2 ℃/min; grinding the obtained yellow solid in a mortar to powder, putting the powder in a crucible without a cover, then putting the crucible in a muffle furnace, heating to 500 ℃ and keeping for 2 hours, wherein the heating rate is 2 ℃/min; the obtained brown yellow solid is the functional graphite-phase carbon nitride.
The second purpose of the invention is the nickel monoatomic/functional graphite-phase carbon nitride composite catalyst prepared by the method.
The third purpose of the invention is the application of the nickel monoatomic/functional graphite-phase carbon nitride composite catalyst in catalytic hydrogen production, catalytic reduction, catalytic hydrogen release, catalytic oxygen reduction, catalytic oxygen production and catalytic oxidation reactions.
The fourth purpose of the invention is the application of the nickel monoatomic/functionalized graphite phase carbon nitride composite catalyst in the preparation of fuel electrodes.
The invention has the beneficial effects that:
(1) the nickel monoatomic/functional graphite-phase carbon nitride composite catalyst uniformly disperses divalent nickel monoatomic on the surface of functional graphite-phase carbon nitride; the divalent nickel monoatomic catalyst is used as a cocatalyst for photocatalytic reaction, so that the catalytic efficiency is greatly improved, and the photocatalyst has higher photocatalytic activity compared with other non-noble metal modified composite photocatalysts.
(2) The nickel monoatomic/functionalized graphite-phase carbon nitride composite catalyst can be used for hydrogen production reaction of photocatalytic decomposition water, and has the advantages of low cost, high hydrogen production rate reaching 24557.78 mu mol/g-1·h-1Compared with the pure nitrogen carbide nanosheet, the hydrogen production rate is improved by about 790 times.
Drawings
Figure 1 is an XRD pattern of the functionalized graphitic carbon nitride and nickel monoatomic/functionalized graphitic carbon nitride composite catalyst of example 1.
Fig. 2 is a transmission electron microscope image of the nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst of example 1.
Fig. 3 is a fourier transform infrared spectrum of the nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst of example 1.
Fig. 4 is a graph of the uv-vis absorption spectrum of the nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst of example 1.
Fig. 5 is a photoluminescence spectrum of the nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst of example 1.
Fig. 6 is a fluorescence lifetime map of the nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst of example 1.
Fig. 7 is an XPS spectrum of nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst nickel of example 1.
Fig. 8 is a photocatalytic hydrogen production test chart of the nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst in example 2.
FIG. 9 is a graph comparing the production of different promoters in example 3 with the production of hydrogen using a monatomic nickel promoter.
FIG. 10 is a graph of hydrogen production rates for different photo-deposited nickel monatomic times in example 4.
FIG. 11 is a graph showing the hydrogen production rates of catalysts corresponding to the mixed solutions of different ethanol and methanol ratios in example 5.
FIG. 12 is a graph of hydrogen production rates of catalysts prepared from different carbon nitride nanomaterials under different mixed solvents in example 1 and comparative examples 2 and 3.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
Example 1
A method for preparing a nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst, comprising the steps of:
(1) weighing 10g of urea and 30mg of 1,3, 5-cyclohexanetriol, placing in a mortar, and grinding to fully mix the urea and the 3, 5-cyclohexanetriol; then putting the ground solid into a crucible, covering the crucible, then putting the crucible into a muffle furnace, heating the crucible to 550 ℃, and keeping the crucible for 2 hours at the heating rate of 2 ℃/min; then placing the obtained yellow solid in a mortar to be ground into powder, placing the powder in a crucible without a cover, then placing the crucible in a muffle furnace, heating to 500 ℃ and keeping for 2 hours, wherein the heating rate is 2 ℃/min; the obtained brown yellow solid is functional graphite phase carbon nitride (GD-C)3N4)；
(2) Placing 30mg of functionalized graphite-phase carbon nitride in a 25mL single-neck flask, then adding 0.1mL of nickel acetate aqueous solution (12.5mg/mL), 5mL of anhydrous methanol and 5mL of anhydrous ethanol, performing ultrasonic dispersion treatment for 5min, and then degassing for 60min by using nitrogen to remove oxygen in the reaction system;
(3) after degassing is finished, placing the round-bottom single-mouth flask under a 300W xenon lamp for irradiation for 1 h; then, centrifugally separating the obtained solid, washing with deionized water for 4 times, and washing with ethanol for 2 times; drying the obtained solid by using nitrogen to obtain the solid, namely the nickel monoatomic/functional graphite-phase carbon nitride composite catalyst, which is marked as Ni1/GD-C3N4。
Obtained Ni1/GD-C3N4The X-ray diffraction spectrum (XRD) of (a) is shown in fig. 1, and it can be seen from fig. 1 that: ni1/GD-C3N4The structure of the functionalized graphite phase carbon nitride is provided, and no peak corresponding to a nickel-responsive compound appears after the light deposition of Ni single atoms. A Transmission Electron Microscope (TEM) is shown in FIG. 2, and it can be seen from FIG. 2 that: ni1/GD-C3N4A nanosheet being a thin layer of crimp; fourier transform Infrared Spectroscopy (FT-IR) as shown in FIG. 3, it can be seen from FIG. 3 that: the basic structure of the material is not changed after photo-deposition of the Ni monoatomic. The ultraviolet-visible absorption spectrum (UV-Vis) is shown in fig. 4, and it can be seen from fig. 4 that: relative to ordinary g-C3N4，GD-C3N4Has wider spectral response, and the absorbance of the photo-deposited Ni monoatomic layer is not changed, which indicates that the Ni monoatomic layer only serves as a promoter. The photoluminescence spectrum (PL) is shown in fig. 5, from which fig. 5 it can be seen that: after the Ni monoatomic layer is subjected to photo-deposition, stable fluorescence is stronger, which shows that the recombination probability of photo-generated carriers is reduced, and photo-generated electrons are transferred to the surface more quickly. The fluorescence lifetime spectrum is shown in FIG. 6, and it can be seen from FIG. 6 that: the recombination probability of the photo-generated carriers is reduced and the photo-generated electrons are transferred to the surface more quickly. The Ni 2p high resolution XPS spectra are shown in fig. 7, and it can be seen from fig. 7 that: the nickel is present in the form of nickel hydroxide, i.e. divalent nickel.
Example 2: catalytic activity of nickel monoatomic/functionalized graphite-phase carbon nitride
Weighing 5mg of the functionalized graphite-phase carbon nitride obtained in the step (1) in example 1, placing the weighed 5mg in a 25mL round-bottom flask, then adding 2mL of triethanolamine and 8mL of water, carrying out ultrasonic treatment for 2min, degassing by using nitrogen for 1h, removing oxygen in the system, placing the round-bottom flask under 300W xenon light (provided with an AM 1.5 optical filter), and irradiating for 1h to carry out hydrogen production reaction.
After the reaction is finished, detecting the hydrogen generated in the reaction by using a thermal conductivity-gas chromatography, wherein the hydrogen production rate is 31.10 mu mol g-1·h-1。
Taking Ni obtained in example 11/GD-C3N4Weighing 5mg, placing in a 25mL round-bottom flask, and then adding 2mL triethanolamine and 8mL water; ultrasonic treating for 2min, degassing with nitrogen gas for 1 hrIn the system, a round-bottom flask is placed under 300W xenon light (provided with an AM 1.5 optical filter) and irradiated for 1h to carry out hydrogen production reaction.
After the reaction is finished, detecting hydrogen generated in the reaction by using a thermal conductivity-gas chromatography, wherein the hydrogen production rate is 24557.78 mu mol g-1·h-1And the hydrogen production rate is improved by about 790 times compared with the pure nitrogen carbide nanosheet.
As can be seen from example 2 and FIG. 8, Ni prepared in this example1/GD-C3N4The composite catalyst has simple synthesis method, high photocatalytic hydrogen production rate and low price, can greatly save the cost when being applied to industrial production, and is a novel catalytic material with larger industrial photocatalytic hydrogen production prospect.
EXAMPLE 3 optimization of the type of cocatalyst
The procedure (2) in example 1 was adjusted to:
30mg of functionalized graphite-phase carbon nitride was placed in a 25mL single-neck flask, followed by addition of 5mL of anhydrous methanol, 5mL of anhydrous ethanol, 0.1mL of aqueous nickel acetate (12.5mg/mL), 0.1mL of thiourea (5.38mg/mL), otherwise identical to example 1, to prepare NiS/GD-C3N4。
30mg of functionalized graphite-phase carbon nitride is put into a 25mL single-neck flask, then 5mL of anhydrous methanol, 5mL of anhydrous ethanol, 0.1mL of nickel acetate aqueous solution (12.5mg/mL), 0.1mL of sodium hypophosphite (6.22mg/mL) are added, and the rest is consistent with that of the embodiment 1, and Ni is preparedxP/GD-C3N4。
30mg of functionalized graphite-phase carbon nitride was placed in a 25mL single-neck flask, followed by addition of 5mL of anhydrous methanol, 5mL of anhydrous ethanol, 0.01mL of an aqueous solution of cobalt acetate (0.1M), 0.1mL of a thiourea solution (5.38mg/mL), otherwise identical to example 1, to prepare CoS/GD-C3N4。
30mg of functionalized graphite-phase carbon nitride was placed in a 25mL single-neck flask, followed by addition of 5mL of anhydrous methanol, 5mL of anhydrous ethanol, 0.01mL of an aqueous solution of cobalt acetate (0.1M), 0.1mL of a solution of sodium hypophosphite (6.22mg/mL), and others in accordance with example 1, to prepare CoxP/GD-C3N4。
Co/GD-C was prepared by placing 30mg of functionalized graphite-phase carbon nitride in a 25mL single-neck flask, followed by addition of 5mL of anhydrous methanol, 5mL of anhydrous ethanol, and 0.01mL of an aqueous solution of cobalt acetate (0.1M), otherwise identical to example 13N4。
The prepared composite catalyst is subjected to hydrogen production reaction, and the method specifically comprises the following steps:
weighing 5mg of the composite catalyst, placing the composite catalyst in a 25mL round-bottom flask, and then adding 2mL of triethanolamine and 8mL of water; performing ultrasonic treatment for 2min, degassing with nitrogen for 1h, removing oxygen in the system, placing the round bottom flask under 300W xenon light (equipped with AM 1.5 filter), and irradiating for 1h to perform hydrogen production reaction.
The test results are shown in fig. 9, from which it can be seen that: ni1/GD-C3N4Shows the best photocatalytic hydrogen production activity.
Example 4 optimization of illumination time
The light irradiation time in the step (3) in the example 1 was adjusted to 0 hour, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours, and 3 hours, and the others were kept the same as in the example 1, thereby obtaining a nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst.
The prepared composite catalyst is subjected to hydrogen production reaction, and the method specifically comprises the following steps:
weighing 5mg of the composite catalyst, placing the composite catalyst in a 25mL round-bottom flask, and then adding 2mL of triethanolamine and 8mL of water; performing ultrasonic treatment for 2min, degassing with nitrogen for 1h, removing oxygen in the system, placing the round bottom flask under 300W xenon light (equipped with AM 1.5 filter), and irradiating for 1h to perform hydrogen production reaction.
The test results are shown in fig. 10, and it can be seen that the photocatalytic hydrogen production activity of the composite catalyst is the best when the light deposition time is 1 h.
Example 5 optimization of the ratio of anhydrous methanol and ethanol
The ratio of absolute methanol to ethanol in example 1 was adjusted to 0: 10. 1: 9. 2: 8. 3: 7. 4: 6. 6: 4, otherwise, in keeping with example 1, a nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst was obtained.
The prepared composite catalyst is subjected to hydrogen production reaction, and the method specifically comprises the following steps:
weighing 5mg of the composite catalyst, placing the composite catalyst in a 25mL round-bottom flask, and then adding 2mL of triethanolamine and 8mL of water; performing ultrasonic treatment for 2min, degassing with nitrogen for 1h, removing oxygen in the system, placing the round bottom flask under 300W xenon light (equipped with AM 1.5 filter), and irradiating for 1h to perform hydrogen production reaction.
The test results are shown in fig. 11, and it can be seen that the ratio of absolute methanol to absolute ethanol is 1: when 1, the photocatalytic hydrogen production activity of the composite catalyst is best.
Comparative example 1 Using Nitrogen carbide nanosheets
The procedure (1) in example 1 was adjusted to:
1 g of dicyandiamide and 5 g of ammonium chloride are weighed into a mortar and ground to mix them thoroughly. The ground solid was placed in a crucible, covered, and then placed in a muffle furnace, heated at 550 ℃ for 4 hours at a rate of 3 ℃ min-1. The obtained light yellow solid is the nitrogen carbide nanosheet;
otherwise, a composite catalyst was obtained in accordance with example 1.
The obtained composite catalyst was subjected to a hydrogen production reaction (same as example 2), and the results were: the hydrogen production rate is 16500 mu mol g-1·h-1(ii) a Only 67% of the catalyst of example 1.
Comparative example 2A common graphite-phase nitrogen carbide nanosheet was used
The procedure (1) in example 1 was adjusted to:
weighing 10g of urea, placing the urea in a crucible, covering the crucible, heating the urea to 550 ℃, and keeping the urea for 2 hours at the heating rate of 2 ℃/min; grinding the obtained yellow solid into powder, placing the powder in a crucible without covering, and then heating to 500 ℃ for 2 hours at the heating rate of 2 ℃/min; the obtained lower brown yellow solid is the common carbonized nitrogen nanosheet.
The rest of the catalyst was compounded in keeping with example 1.
The resulting composite catalyst was subjected to hydrogen production reaction (same as example 2), and as a result, as shown in fig. 12, it was found that the surface-functionalized carbon nitride nanosheet had the best activity.
Comparative example 3
The procedure (2) in example 1 was adjusted to:
a composite catalyst was prepared by placing 30mg of the functionalized graphite-phase carbon nitride in a 25mL single-neck flask, followed by addition of 5mL of anhydrous methanol, 5mL of water, and 0.1mL of an aqueous nickel acetate solution (12.5mg/mL), all as in example 1.
A composite catalyst was prepared by placing 30mg of functionalized graphite-phase carbon nitride in a 25mL single-neck flask, followed by addition of 5mL of water, 5mL of absolute ethanol, and 0.1mL of an aqueous nickel acetate solution (12.5mg/mL), all as in example 1.
The test results are shown in fig. 12, and it can be seen that the activity of the nickel monatomic/functional graphite-phase carbon nitride composite catalyst prepared in the methanol-ethanol mixed solvent is the best.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A method for preparing a nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst, characterized by comprising the steps of:
adding a mixed solution of absolute methanol and absolute ethanol and a nickel acetate aqueous solution into the functional graphite-phase carbon nitride, and uniformly dispersing; then nitrogen is degassed; after degassing is finished, placing the tube under a xenon lamp for illumination; centrifuging, washing and drying after illumination to obtain the nickel monoatomic/functional graphite-phase carbon nitride composite catalyst;
wherein the volume ratio of the absolute methanol to the absolute ethanol in the mixed solution is 1: 1;
the concentration of the nickel acetate aqueous solution is 12-14 mg/mL;
the dosage ratio of the functional graphite-phase carbon nitride to the nickel acetate aqueous solution is 30 in mg/mL: 0.05-0.2;
the dosage ratio of the mixed solution of the absolute methanol and the absolute ethanol to the functional graphite-phase carbon nitride is 8-12 in terms of mL/mg: 30, of a nitrogen-containing gas;
the xenon lamp irradiation is specifically 300W xenon lamp irradiation for 1 h;
the preparation method of the functionalized graphite phase carbon nitride comprises the following steps: uniformly mixing urea and 1,3, 5-cyclohexanetriol to obtain a mixture; then placing the mixture in a crucible, covering the crucible, and heating to 500-600 ℃ for 1-3 h; then placing the obtained solid in a crucible without a cover, and heating to the temperature of 450-500 ℃ for 1-3h to obtain the functional graphite-phase carbon nitride; in the preparation method of the functionalized graphite-phase carbon nitride, the mass ratio of urea to 1,3, 5-cyclohexanetriol is 10: 0.01-0.05.
2. A nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst produced by the method of claim 1.
3. Use of the nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst according to claim 2, wherein the use is for a catalytic reduction reaction or a catalytic oxidation reaction.
4. Use according to claim 3 for the catalytic production of hydrogen, catalytic reduction of oxygen, catalytic production of oxygen.
5. Use of a nickel monatomic/functionalized graphite-phase carbon nitride composite catalyst according to claim 2, wherein said use is in the production of fuel electrodes.
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