CN115025803B - Cyano modified carbon nitride and preparation method and application thereof - Google Patents
Cyano modified carbon nitride and preparation method and application thereof Download PDFInfo
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- CN115025803B CN115025803B CN202210746800.2A CN202210746800A CN115025803B CN 115025803 B CN115025803 B CN 115025803B CN 202210746800 A CN202210746800 A CN 202210746800A CN 115025803 B CN115025803 B CN 115025803B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- -1 Cyano modified carbon nitride Chemical class 0.000 title abstract description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract description 14
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 8
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000002835 absorbance Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 39
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 125000004093 cyano group Chemical group *C#N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
-
- B01J35/39—
-
- 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
- B01J37/344—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 of electromagnetic wave energy
-
- 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 cyano-modified carbon nitride, a preparation method and application thereof, wherein the cyano-modified carbon nitride is obtained by infrared heating treatment of carbon nitride and thiocyanate. In the preparation process of the cyano modified carbon nitride, infrared rays are selected as heating sources, and the carbon nitride and thiocyanate are subjected to branch-connection reaction under the condition of infrared irradiation, so that the obtained cyano modified carbon nitride has the characteristics of high yield, high absorbance, large specific surface area and the like, and finally shows excellent photocatalytic hydrogen production performance.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to cyano-modified carbon nitride, and a preparation method and application thereof.
Background
Photocatalytic hydrogen production is considered as a promising solar energy utilization technology because solar energy stored in hydrogen molecules can be easily extracted, and water molecules generated in the combustion process are environmentally friendly. Since titanium dioxide was used to photolyze water to produce hydrogen, various semiconductor materials have been investigated for use in photocatalysts. However, metal oxides or metal sulfides have disadvantages of high cost, low photocatalytic activity, poor stability, and the like under irradiation of visible light as a semiconductor photocatalyst.
In recent years, graphite-phase carbon nitride photocatalysts have been widely studied in the photocatalytic hydrogen production process due to their excellent characteristics of low cost, no toxicity, good stability and easy synthesis and modification. However, the graphite phase carbon nitride obtained by direct high-temperature roasting at present has poor conductivity and serious charge recombination, so that the photocatalytic performance of the graphite phase carbon nitride is poor.
Disclosure of Invention
Based on the technical problems, the invention provides cyano-modified carbon nitride, a preparation method and application thereof, wherein infrared rays are selected as heating sources, and the carbon nitride and thiocyanate are subjected to branch-connection reaction under the condition of infrared irradiation, so that the obtained cyano-modified carbon nitride has the characteristics of high yield, high absorbance, large specific surface area and the like, and therefore, excellent photocatalytic hydrogen production performance is shown.
The invention provides a preparation method of cyano-modified carbon nitride, which comprises the following steps: and carrying out infrared heating treatment on the carbon nitride and thiocyanate to obtain the cyano-modified carbon nitride.
Compared with the prior art that the branch-connection reaction of the carbon nitride and the thiocyanate is realized by direct calcination, the grafting reaction of the carbon nitride and the thiocyanate is realized under the condition of infrared irradiation by infrared heating treatment; due to the characteristics of rapid temperature rise and uniformity of infrared irradiation, on one hand, cyano groups can effectively branch to heptazine frameworks to form a carbon nitride material with cyano group defects, and on the other hand, the charge transmission structure and the microscopic morphology of the obtained carbon nitride can be further optimized, so that the photoresponse characteristic of the carbon nitride is changed, and finally, the carbon nitride has more excellent photocatalytic hydrogen production activity.
Preferably, the carbon nitride is obtained by calcining nitrogen-rich organic matters at a high temperature;
preferably, the high temperature calcination is carried out at a temperature of 500-600 ℃ for a time of 3-5 hours.
Preferably, the nitrogen-rich organic matter is at least one of melamine, dicyandiamide or urea.
Preferably, the thiocyanate is at least one of potassium thiocyanate, sodium thiocyanate or ammonium thiocyanate.
Preferably, the mass ratio of the carbon nitride to the thiocyanate is 1-3:1-3.
Preferably, the method further comprises grinding and mixing the carbon nitride and the thiocyanate uniformly before carrying out infrared heating treatment on the carbon nitride and the thiocyanate.
Preferably, the temperature of the infrared heating treatment is 400-500 ℃ and the time is 10-60min.
Preferably, the infrared heating treatment has a wavelength of 2.4-4 μm.
The invention provides cyano-modified carbon nitride, which is prepared by the method.
The invention also provides application of the cyano modified carbon nitride in photocatalytic hydrogen production.
The beneficial effects of the invention are as follows:
(1) The invention uses infrared rays as a heating source, the cyano branch connection reaction process can realize the efficient and rapid preparation of the carbon nitride material with cyano defects only in less than 1 hour, and the production efficiency is high.
(2) The invention creatively finds that the infrared heat energy more effectively connects cyano groups to the heptazine skeleton of the carbon nitride material, and has universality in the aspect that cyano groups enter the heptazine skeleton of the carbon nitride material.
(3) Compared with common carbon nitride, the cyano-modified carbon nitride is more suitable for industrial large-scale application in the field of photocatalysis; the model test of photolysis of water to produce hydrogen proves that the photocatalytic hydrogen production effect of the carbon nitride with cyano defects obtained by the invention is tens of times that of carbon nitride prepared by the traditional method.
Drawings
FIG. 1 is a scanning electron microscope image of cyano-modified carbon nitride obtained in example 1;
FIG. 2 is a transmission electron microscopic view of cyano-modified carbon nitride obtained in example 1;
FIG. 3 is an XRD contrast pattern of cyano-modified carbon nitride obtained in example 1 and carbon nitride obtained in comparative example 1;
FIG. 4 is a FT-IR contrast chart of cyano-modified carbon nitride obtained in example 1 and carbon nitride obtained in comparative example 1;
FIG. 5 is a graph showing comparison of ultraviolet absorption of cyano-modified carbon nitride obtained in example 1 and carbon nitride obtained in comparative example 1;
FIG. 6 is a graph showing comparison of the visible photocurrents of the cyano-modified carbon nitride obtained in example 1 and the carbon nitride obtained in comparative example 1;
FIG. 7 is a graph showing the physical adsorption comparison between cyano-modified carbon nitride obtained in example 1 and carbon nitride obtained in comparative example 1;
FIG. 8 is an XRD contrast pattern of cyano-modified carbon nitride obtained in example 1 and cyano-modified carbon nitride obtained in comparative example 4;
FIG. 9 is a FT-IR contrast chart of cyano-modified carbon nitride obtained in example 1 and cyano-modified carbon nitride obtained in comparative example 4;
Detailed Description
The present invention will be described in detail by way of specific examples, which should be clearly set forth for the purpose of illustration and are not to be construed as limiting the scope of the present invention.
Example 1
The embodiment provides cyano-modified carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of carbon nitride and 2g of potassium thiocyanate into a mortar, fully and uniformly grinding, adding the obtained grinding material into a small aluminum oxide boat with a cover and a volume of 20mL, placing into an infrared furnace, performing infrared heating treatment at 450 ℃ for 30min, closing the infrared furnace, naturally cooling to room temperature to obtain cyano-modified carbon nitride, and naming the cyano-modified carbon nitride as BCN qih450 。
FIG. 1 is a scanning electron microscope image of cyano-modified carbon nitride obtained in example 1. As can be seen from FIG. 1, the cyano-modified carbon nitride obtained in example 1 has a rough surface, shows many coral shapes, and has a rich pore structure. FIG. 2 is a transmission electron micrograph of the cyano-modified carbon nitride obtained in example 1. As can be seen from FIG. 2, the overlapping shadows shown in the transmission electron micrograph support the formation of a coral-shaped roughened surface containing holes.
Example 2
The embodiment provides cyano-modified carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of the carbon nitride and 2g of potassium thiocyanate into a mortar, and sufficiently and uniformly grinding to obtainAdding the ground material into a small aluminum oxide boat with a cover and a volume of 20mL, placing into an infrared furnace, performing infrared heating treatment at 400 ℃ for 30min, closing the infrared furnace, naturally cooling to room temperature to obtain cyano-modified carbon nitride, which is named as BCN qih400 。
Example 3
The embodiment provides cyano-modified carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of carbon nitride and 2g of potassium thiocyanate into a mortar, fully and uniformly grinding, adding the obtained grinding material into a small aluminum oxide boat with a cover and a volume of 20mL, placing into an infrared furnace, performing infrared heating treatment at 500 ℃ for 30min, closing the infrared furnace, naturally cooling to room temperature to obtain cyano-modified carbon nitride, and naming the cyano-modified carbon nitride as BCN qih500 。
Example 4
The embodiment provides cyano-modified carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of carbon nitride and 2g of potassium thiocyanate into a mortar, fully and uniformly grinding, adding the obtained grinding material into a small aluminum oxide boat with a cover and a volume of 20mL, placing into an infrared furnace, performing infrared heating treatment at 450 ℃ for 10min, closing the infrared furnace, naturally cooling to room temperature to obtain cyano-modified carbon nitride, and naming the cyano-modified carbon nitride as BCN qih450-10 。
Example 5
The embodiment provides cyano-modified carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of the carbon nitride and 2g of potassium thiocyanate into a mortar, sufficiently and uniformly grinding to obtain a ground productAdding into a small aluminum oxide boat with a cover and a volume of 20mL, placing into an infrared furnace, performing infrared heating treatment at 450 ℃ for 60min, closing the infrared furnace, naturally cooling to room temperature to obtain cyano-modified carbon nitride, which is named as BCN qih450-60 。
Comparative example 1
The comparative example proposes a carbon nitride, which is prepared by the following method:
10g of melamine was charged into a covered alumina crucible having a volume of 25mL, placed in a muffle furnace, and baked at 550℃for 4 hours to give carbon nitride, designated CN.
FIG. 3 is an XRD comparison of cyano-modified carbon nitride obtained in example 1 and carbon nitride obtained in comparative example 1. As can be seen from FIG. 3, BCN of example 1 qih450 The XRD pattern of CN was essentially the same as that of comparative example 1, indicating BCN qih450 Has the same structure as CN, indicating that when-C.ident.N is introduced, BCN qih450 The carbon nitride crystal structure was unchanged, and the two diffraction peaks at 12.8 ° and 27.7 ° correspond to the (100) in-plane alignment distance and interlayer periodic packing (002) of the heptazine units, respectively, however, BCN qih450 The decrease in (100) plane peak intensity may be due to a sequential decrease in structure at the long-range surface.
FIG. 4 is a FT-IR contrast chart of cyano-modified carbon nitride obtained in example 1 and carbon nitride obtained in comparative example 1, as can be seen from FIG. 4, BCN of example 1 qih450 CN at 2176cm relative to comparative example 1 -1 There is a new vibration band indicating successful branching of the cyano group.
FIG. 5 is a graph showing the comparison of the ultraviolet absorption of cyano-modified carbon nitride obtained in example 1 and carbon nitride obtained in comparative example 1. As can be seen from FIG. 5, BCN of example 1 qih450 The absorbance in the visible light band was higher for CN relative to comparative example 1.
FIG. 6 is a graph showing comparison of the visible photocurrents of the cyano-modified carbon nitride obtained in example 1 and the carbon nitride obtained in comparative example 1. As can be seen from FIG. 6, the BCN of example 1 qih450 The CN photocurrent of comparative example 1 has a greater relative intensity and carriers are more easily separated and transported.
FIG. 7 shows cyano-modified carbon nitride obtained in example 1 and a comparative exampleAs can be seen from FIG. 7, the physical adsorption comparison chart of carbon nitride obtained in example 1 shows that BCN of example 1 qih450 The CN specific surface area is increased and the reactive sites are increased relative to comparative example 1.
Comparative example 2
The comparative example proposes a carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of the carbon nitride into a small aluminum oxide boat with a cover and a volume of 20mL, placing in an infrared furnace, performing infrared heating treatment at 450 ℃ for 30min, closing the infrared furnace, naturally cooling to room temperature to obtain infrared treated carbon nitride, which is named CN qih450 。
Comparative example 3
The comparative example proposes a carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of the carbon nitride into a small aluminum oxide boat with a cover and a volume of 20mL, placing in a muffle furnace, roasting for 30min at 450 ℃, naturally cooling to room temperature to obtain roasted carbon nitride, which is named CN mfh450 。
Comparative example 4
The comparative example proposes a cyano-modified carbon nitride, which is prepared by the following method:
(1) Adding 10g of melamine into an alumina crucible with a cover and a volume of 25mL, placing the crucible into a muffle furnace, and roasting for 4 hours at 550 ℃ to obtain carbon nitride;
(2) Adding 2g of carbon nitride and 2g of potassium thiocyanate into a mortar, fully and uniformly grinding, adding the obtained grinding material into a small aluminum oxide boat with a cover and a volume of 20mL, placing into a muffle furnace, roasting at 450 ℃ for 30min, naturally cooling to room temperature, and obtaining cyano-modified carbon nitride which is named as BCN mfh450 。
FIG. 8 shows the result of example 1As can be seen from FIG. 8, the XRD patterns of cyano-modified carbon nitride and the cyano-modified carbon nitride obtained in comparative example 4 show the BCN of example 1 qih450 And BCN of comparative example 4 mfh450 The XRD patterns are essentially identical, indicating that the frames are identical; the two diffraction peaks at 12.8 ° and 27.7 ° are reflections of the (100) and (002) planes, corresponding to the in-plane structural arrangement and interlayer packing of the heptazine units, respectively. Notably, the BCN of comparative example 4 mfh450 There is a distinct amorphous peak around 21.6 °, indicating incomplete polymerization of melamine to form a triazine ring based intermediate, indicating that the BCN obtained by calcination in a muffle furnace mfh450 Slow polymerization kinetics of melamine; in addition, the BCN of comparative example 4 mfh450 The XRD peak at 27.7℃had a weaker peak intensity, indicating BCN mfh450 Lower crystallinity of (3); in sharp contrast, in example 1, BCN qih450 The diffraction peak height at 27.7 degrees is sharp, indicating that infrared assisted heating can produce highly crystalline BCN; notably, in BCN mfh450 Amorphous hump observed in (a) in BCN qih450 The disappearance of the melamine clearly demonstrated by the infrared heating source to accelerate the polymerization of melamine to increase the crystallinity, which is favorable for charge transport, thus showing the more excellent photocatalytic hydrogen production activity of the cyano-modified carbon nitride obtained in example 1
FIG. 9 is a FT-IR contrast chart of cyano-modified carbon nitride obtained in example 1 and cyano-modified carbon nitride obtained in comparative example 4, as seen from FIG. 9, at 1000-1750cm -1 The peak between is due to C-N stretching vibration in C-N heterocycle, BCN of example 1 qih450 BCN of comparative example 4 mfh450 Has a relatively sharp peak in FT-IR, indicating BCN qih450 The arrangement of the heptazine units is more orderly.
Photolytic water hydrogen production performance test
10mg of the carbon nitride materials obtained in the examples and the comparative examples are respectively placed in a photocatalytic water splitting reactor, 20mL of triethanolamine aqueous solution with the mass fraction of 10% is added into the photocatalytic water splitting reactor as a sacrificial agent, 106 mu L of chloroplatinic acid with the concentration of 0.98g/L is added into the photocatalytic water splitting reactor as a cocatalyst, argon is introduced into the photocatalytic water splitting reactor for 15min after sealing, a magnetic stirrer and a light source are turned on after air is exhausted, and the photocatalytic water splitting reaction is carried out for 3h, wherein the light source is a 580W xenon lamp with a filter with the wavelength of 420nm or more.
The amounts of hydrogen produced when the carbon nitride materials obtained in examples and comparative examples were subjected to photolytic hydrogen production are shown in table 1 below:
table 1 list of hydrogen production amounts of carbon nitride materials obtained in examples and comparative examples for hydrogen production by photolysis of water
| Sample of | Rate of hydrogen production (mu mol/h) |
| CN (comparative example 1) | 2.36 |
| CN qih450 Comparative example 2 | 2.32 |
| CN mfh450 Comparative example 3 | 2.18 |
| BCN qih400 Example 2 | 7.23 |
| BCN qih450 Example 1 | 31.21 |
| BCN qih500 Example 3 | 2.87 |
| BCN qih450-10 Example 4 | 5.1 |
| BCN qih450-60 Example 5 | 16.83 |
| BCN mfh450 Comparative example 4 | 22.23 |
As can be seen from Table 1 above, the cyano-modified carbon nitride of example 1 has significantly improved photocatalytic hydrogen production performance relative to the comparative example, and the cyano-defective carbon nitride BCN prepared by infrared heating at 450℃for 30min qih450 The photocatalytic decomposition of water produces hydrogen with the best performance.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (7)
1. The application of cyano-modified carbon nitride in photocatalytic hydrogen production is characterized in that the preparation method of the cyano-modified carbon nitride comprises the following steps: carrying out infrared heating treatment on carbon nitride and thiocyanate to obtain the cyano-modified carbon nitride;
the temperature of the infrared heating treatment is 400-500 ℃, the time is 10-60min, and the wavelength of the infrared heating treatment is 2.4-4 mu m.
2. The use of cyano-modified carbon nitride in photocatalytic hydrogen production according to claim 1, wherein the carbon nitride is obtained by high temperature calcination of nitrogen-rich organics.
3. The use of cyano-modified carbon nitride in photocatalytic hydrogen production according to claim 2, wherein the high temperature calcination is carried out at a temperature of 500-600 ℃ for a time of 3-5 hours.
4. The use of cyano-modified carbon nitride in photocatalytic hydrogen production according to claim 2, wherein the nitrogen-rich organic matter is at least one of melamine, dicyandiamide or urea.
5. The use of cyano-modified carbon nitride in photocatalytic hydrogen production as claimed in any one of claims 1 to 4 wherein the thiocyanate is at least one of potassium thiocyanate, sodium thiocyanate or ammonium thiocyanate.
6. Use of cyano-modified carbon nitride in photocatalytic hydrogen production according to any of claims 1 to 4, characterized in that the mass ratio of carbon nitride to thiocyanate is 1-3:1-3.
7. The use of cyano-modified carbon nitride in photocatalytic hydrogen production as claimed in any one of claims 1 to 4, further comprising grinding and mixing the carbon nitride with thiocyanate uniformly prior to subjecting the carbon nitride to infrared heating treatment.
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