CN115837285A - CoP/coralliform carbon nitride heterogeneous composite material and preparation method and application thereof - Google Patents
CoP/coralliform carbon nitride heterogeneous composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115837285A CN115837285A CN202211494293.4A CN202211494293A CN115837285A CN 115837285 A CN115837285 A CN 115837285A CN 202211494293 A CN202211494293 A CN 202211494293A CN 115837285 A CN115837285 A CN 115837285A
- Authority
- CN
- China
- Prior art keywords
- cop
- carbon nitride
- composite material
- heterogeneous composite
- coralline
- 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.)
- Granted
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 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 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 238000007146 photocatalysis Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 4
- 238000013032 photocatalytic reaction Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000272186 Falco columbarius Species 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method of a CoP/coralliform carbon nitride heterogeneous composite material with a photocatalytic anisyl alcohol oxidation synergistic hydrogen production effect. Firstly, melamine and cyanuric acid are used as raw materials, and coralline carbon nitride is synthesized through improved solution assembly and a subsequent pyrolysis process; then Co (NO) is added 3 ) 3 ·6H 2 Co prepared by taking O and NaOH as raw materials 3 O 4 Mixed with sodium hypophosphite in N 2 Calcining to obtain CoP; and finally stirring and evaporating the coralline carbon nitride and the CoP in the solution to dryness to obtain the CoP/coralline carbon nitride heterogeneous composite material. The method optimizes the obtained CoP/coralline nitrogenationThe carbon heterogeneous composite material has strong light absorption capacity, can increase the photocatalytic oxidation value of the anisyl alcohol into anisaldehyde on the premise of not needing a sacrificial agent and a noble metal cocatalyst, and simultaneously obtains clean energy H 2 The material is a photocatalytic organic matter oxidation value-rising synergetic hydrogen evolution material with a good application prospect.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method of a CoP/coralliform carbon nitride heterogeneous composite material with a photocatalytic anisyl alcohol oxidation synergistic hydrogen production effect.
Background
The solar energy is converted into hydrogen energy through the photocatalytic water cracking process, no additional energy supply is needed, and green fuel H is obtained 2 The most promising mode. However, to improve hydrogen evolution efficiency, there are two general operations in most studies today: (1) Use of a sacrificial agent, methanol, triethanolamine, etc., as sacrificial agent (completely oxidized to CO by photogenerated holes) 2 And H 2 O) promoting a reduction half reaction of photocatalytic water decomposition for hydrogen analysis; (2) The addition of noble metals, such as Pt and Au, is commonly used to support the catalyst to accelerate the extraction of photo-generated electrons. The use of a sacrificial agent wastes resources, the generated hydrogen energy is sometimes insufficient to offset the consumption of the sacrificial agent, and the addition of noble metals greatly increases the preparation cost of the catalyst. If the oxidation effect of the photo-generated holes is effectively utilized, the organic matters with low cost are oxidized into high-value organic chemicals, meanwhile, the hydrogen production by photolysis of water is promoted, and the economic value of photocatalysis is remarkably improved. Therefore, it is important to develop a noble metal-free, efficient and economical photocatalyst and use it in a photocatalytic co-technology without a sacrificial agent.
In addition, since graphitic carbon nitride (g-C) 3 N 4 ) Surface functional groups with appropriate band structure and high controllability and excellent organic oxidation and water decomposition activities are one of the most potential candidates for the concerted catalytic reaction. Pt/C 3 N 4 、C 3 N 4 the/BP @ Ni et al have been found to have excellent activity for both oxidizing benzyl alcohol and hydrogen evolution in water/benzyl alcohol solutions. g-C obtained by conventional pyrolysis of melamine 3 N 4 Is a bulk material formed by sheet aggregation, has high carrier recombination rate and poor adsorption capacity to a substrate. The construction of ultrathin, porous, hollow, highly exposed surface and regular carbon nitride will certainly improve the adsorption capacity of the carbon nitride to a substrate, and simultaneously can reduce the carrier recombination efficiency by shortening the carrier transmission distance. The other partyIn order to reduce the cost of the catalyst, it is necessary to find a substitute for noble metals. Transition metals and their phosphides have been shown to have work functions similar to Pt, extracting photogenerated electrons and promoting carrier separation. In addition, the transition metal phosphide has certain semiconductor performance and can catalyze the hydrogen desorption reaction of water decomposition, which shows that the transition metal phosphide can be an excellent substitute of noble metal. Therefore, the CoP/ultrathin porous coralliform carbon nitride heterogeneous composite material is prepared and used in the photocatalytic organic matter oxidation and hydrogen production technology, and the method has important significance for improving the economic value of the photocatalytic hydrogen production technology.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a CoP/coralliform carbon nitride heterogeneous composite material with low cost and high-efficiency photocatalytic synergistic effect and application of the CoP/coralliform carbon nitride heterogeneous composite material in photocatalytic anisyl alcohol oxidation-synergistic hydrogen production, aiming at the defects of the prior art.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a CoP/coralline carbon nitride heterogeneous composite material comprises the following steps:
1) Melamine and cyanuric acid are used as raw materials, and coral-shaped carbon nitride is obtained through stirring reaction and pyrolysis;
2) Mixing Co 3 O 4 Mixing with sodium hypophosphite and calcining to obtain CoP;
3) Stirring and evaporating the coralline carbon nitride obtained in the step 1) and the CoP obtained in the step 2) in a solution to dryness to obtain the CoP/coralline carbon nitride heterogeneous composite material.
Optionally, in the step 1), the mass ratio of melamine to cyanuric acid is 0.5-2: 1, stirring and reacting for 18 hours; the pyrolysis conditions are as follows: heating to 500-600 ℃ at the speed of 2-10K/min in the air atmosphere, and calcining for 3-5 hours.
Alternatively, the calcination conditions in step 2) are: at N 2 Heating to 250-350 ℃ at the rate of 10K/min under the atmosphere, and calcining for 1-3 hours.
Optionally, in the step 3), the mass ratio of the CoP to the coralline carbon nitride is (1-100): 100, and the stirring and evaporating temperature is 60 ℃.
Specifically, the mass ratio of the CoP to the coral-shaped carbon nitride is 1%, 5%, 20%, 50%, 70%, 100%.
The invention also requests the CoP/coralliform carbon nitride heterogeneous composite material prepared by the method.
The composite material takes coral-shaped carbon nitride with porous, ultrathin-layer and curled appearance as a carrier, coP is loaded on the coral-shaped carbon nitride, and the CoP and the coral-shaped carbon nitride form a heterojunction.
The CoP is uniformly adhered to the coral-shaped carbon nitride, and the mass ratio of the CoP to the coral-shaped carbon nitride is (1-100): 100.
In addition, the invention also claims the application of the CoP/coralliform carbon nitride heterogeneous composite material in the field of photocatalysis.
Specifically, the application is the application of the CoP/coralliform carbon nitride heterogeneous composite material in photocatalytic anisyl alcohol oxidation value increase and hydrogen production at the same time.
And, the application comprises the steps of: adding the CoP/coralline carbon nitride heterogeneous composite material into an aqueous solution containing anisyl alcohol, performing ultrasonic dispersion, and then replacing gas in a reactor with N 2 And then sealing, and finally stirring under the irradiation of a xenon lamp to carry out a photocatalytic reaction to complete the oxidation of organic matters and the hydrogen evolution reaction.
Optionally, the concentration of the anisyl alcohol in the anisyl alcohol aqueous solution is 1 g/L-20 g/L, the ratio of the CoP/coral-shaped carbon nitride heterogeneous composite material to the anisyl alcohol aqueous solution is 0.5 g-1 g: 1L, and the temperature of the photocatalytic reaction is 20-35 DEG C
According to the technical scheme, compared with the prior art, the CoP/coralliform carbon nitride heterogeneous composite material and the preparation method and application thereof provided by the invention have the following excellent effects:
1) Compared with the traditional bulk carbon nitride (bulk-CN), the provided coralline carbon nitride (CorCN) has larger specific surface area, thinner lamella thickness, wider interlayer distance and more nitrogen vacancies, which are beneficial to the diffusion and adsorption of substrate molecules in the catalyst, the transfer of excited photo-generated carriers and the higher visible light absorption capacity of the coralline carbon nitride. CoP is uniformly distributed on the coralline carbon nitride, and the CoP and the coralline carbon nitride form a tightly combined heterojunction, so that the separation of photo-generated electrons and holes can be accelerated, and the visible light absorption capacity can be improved.
2) The invention respectively uses CoP and anisyl alcohol to replace noble metal platinum and a traditional sacrificial agent, and realizes the oxidation value increase of alcohol while ensuring high-efficiency hydrogen evolution, so the CoP/coralliform carbon nitride heterogeneous composite material (CoP/CorCN) provided by the invention can efficiently obtain H without adding the sacrificial agent and the noble metal cocatalyst 2 Meanwhile, the anisic alcohol is oxidized into anisaldehyde, so that the method has the characteristics of high economic value, simple process, greenness, no pollution and the like, and has good practical application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of CorCN, bulk-CN, coP and CoP/CorCN.
FIG. 2 is an X-ray photoelectron spectrum of CorCN, bulk-CN and CoP/CorCN.
FIG. 3 is N for CorCN and bulk-CN 2 Adsorption and desorption curve chart.
FIG. 4 is a scanning electron micrograph of (a) bulk-CN and (b) CorCN.
FIG. 5 shows (a) TEM image, (b) TEM image of high resolution, and (c) TEM image of dark field and related EDS-mapping image of CoP/CorCN.
FIG. 6 is a UV-visible diffuse reflectance chart of bulk-CN, corCN, and CoP/CorCN.
FIG. 7 is a photoluminescence spectrum of CorCN and CoP/CorCN.
FIG. 8 is a graph of the photocurrent of CoP, corCN, and CoP/CorCN.
FIG. 9 is a graph showing the photocatalytic hydrogen evolution activity of CoP/CorCN with different combination ratios.
FIG. 10 is a gas chromatogram of the photocatalytic anisyl alcohol oxidation product of CoP/CorCN.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely in the following description with reference to the embodiments of the present invention and the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a preparation method of a CoP/coralliform carbon nitride heterogeneous composite material with photocatalysis and anisyl alcohol oxidation synergistic hydrogen production.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
And, unless otherwise specified, the reagents used in the examples were all purchased commercially and used without treatment; the test conditions recommended by the manufacturer of the test selection instrument are analyzed.
In the examples, the X-ray pattern of the samples was tested on a SHIMADZU XRD-7000X-ray powder diffractometer, range tested: 10-70 degrees, and the scanning speed is 6 degrees/min.
Elemental and nitrogen vacancy analysis of the samples was analyzed by Thermo ESCALAB 250X-ray photoelectron spectroscopy.
The specific surface area of the sample is analyzed by using a BSD/3H-2000 gas adsorption instrument.
The morphology of the samples was analyzed using a Zeiss MERLIN scanning electron microscope.
The element distribution and the pore structure of the sample are analyzed by using a FEI Tecnai G2F 20S-Twin transmission electron microscope.
The absorption range of the sample adopts an Agilent Cary5000 ultraviolet-visible-near infrared spectrometer, and the collection wavelength range is 200-800nm.
Photoluminescence spectroscopy of the samples was analyzed using a prism Technology F97pro fluorescence spectrometer.
The photocurrent response of the sample was analyzed using Chenghua CHI660E electrochemical workstation.
The photocatalytic hydrogen evolution activity and organic oxidation products of the sample are analyzed by a FuliGC-9790 gas chromatograph.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1: preparation of coral-like carbon nitride
Preparation of CorCN
The coral compound CorCN is prepared by adopting a solution method combined with a calcination method. Firstly, respectively dispersing 2g of melamine and 2g of cyanuric acid in 60mL of deionized water, stirring for 1 hour, and mixing the two suspensions together; continuously stirring the mixed solution for 18 hours, and then stirring and evaporating the mixed solution to dryness at 90 ℃ to obtain a powdery precursor; finally, the prepared precursor was calcined at 500 ℃ for 4 hours to obtain a CorCN material.
Example 2: preparation of CoP/coralliform carbon nitride heterogeneous composite material
Preparation of CoP/CorCN
Adding 0.05mol/L Co (NO) into a beaker 3 ) 2 ·6H 2 50mL of O solution is slowly added into 25mL of 0.25mol/L NaOH solution and stirred for about 2 hours; centrifuging, washing and drying the obtained suspension to obtain Co 3 O 4 (ii) a 0.05g of Co 3 O 4 And 0.25g NaH 2 PO 2 Are mixed homogeneously in N 2 Calcining for 1 hour at 300 ℃ under the atmosphere; cooling the powder to room temperature by a heating furnace, and filtering, washing and drying the powder to obtain the final CoP; weighing CoP and CorCN in a certain mass ratio, and dispersing in deionized water to form a suspension; the suspension was stirred at 60 ℃ until the water was completely evaporatedForming a CoP/CorCN heterogeneous composite material, and obtaining the heterogeneous composite material with the mass ratio of the CoP to the CorCN of 1%, 5%, 20%, 50%, 70% and 100% according to the charging ratio of the CoP to the CorCN.
Example 3: XRD characterization of CoP/coralliform carbon nitride heterogeneous composite material
X-ray diffraction (XRD) analysis is carried out on CorCN, bulk-CN, coP and CoP/CorCN obtained in example 2, as shown in figure 1, XRD spectrums of the obtained CorCN and bulk-CN are consistent with the literature reports, XRD spectrums of the obtained CoP are consistent with standard PDF card (PDF # 89-2747), and characteristic peaks of CorCN and CoP are obvious on the XRD spectrums of the CoP/CorCN and are indicated as composite samples of the CoP and the CorCN.
Example 4: characterization of surface vacancies of CoP/coral-like carbon nitride heterogeneous composite materials
X-ray photoelectron Spectroscopy (XPS) analysis of CorCN and bulk-CN was performed, and N1s spectra of the obtained CorCN and CoP/CorCN were obtained as shown in FIG. 2 3C The peak area is obviously smaller than N of the N1s spectrogram of bulk-CN 3C Peak area.
Example 5: characterization of specific surface area of coral-like carbon nitride and conventional bulk carbon nitride
N is carried out on CorCN and bulk-CN 2 The adsorption and desorption measurements, as shown in FIG. 3, revealed that the specific surface areas of CorCN and bulk-CN were 68.5m, respectively 2 G and 30.1m 2 /g。
Example 6: morphology characterization of coral-like carbon nitride
The morphology of the coralline carbon nitride was analyzed by scanning electron microscopy, and as shown in fig. 4b, the obtained CorCN sample was coralline and had a large number of holes. In contrast, the morphology of the bulk-CN sample was bulk as shown in FIG. 4 a. This demonstrates that the improved pyrolysis process of the present invention is capable of obtaining porous, curly coral-like carbon nitride.
Example 7: characterization of element distribution of CoP/coralliform carbon nitride heterogeneous composite material
EDS-mapping is adopted to characterize the distribution characteristics of C, N, co, P and O elements in the CoP/coralliform carbon nitride heterogeneous composite material, as shown in a transmission electron microscope image of FIG. 5a, according to the characteristics of the transmission electron microscope, the contrast of the image is related to the weight of the elements, so that the small particles with darker colors are CoP, and the lighter particles are CorCN consisting of lighter elements, and the CoP can be seen to be attached to the CorCN; FIG. 5b is a high-resolution transmission electron micrograph showing that CoP is small nanoparticles, the lattice fringes are 0.248nm and are consistent with the (111) interplanar spacing of CoP, and the small particles are proved to be CoP; fig. 5c and the corresponding elemental maps show that the Co and P elements are well dispersed on the carbon nitride particles, indicating that the CoP is uniformly supported on the coral-like carbon nitride support.
Example 8: characterization of light absorption range of CoP/coralliform carbon nitride heterogeneous composite material
Ultraviolet-visible diffuse reflection absorption spectra are adopted to characterize the light absorption ranges of the CoP, bulk-CN, corCN and CoP/coralliform carbon nitride heterogeneous composite materials, as shown in figure 6, the result shows that the bulk-CN can only absorb a small part of visible light, and the CorCN widens the light absorption range to a certain extent, because CoP has good visible light absorption capacity, and CoP/coralliform carbon nitride composite samples can absorb light in all visible light regions.
Example 9: photoluminescence spectrum characterization of CoP/coralliform carbon nitride heterogeneous composite material
The photoluminescence spectrum is used for characterizing the luminescence property of the CoP/coralliform carbon nitride heterogeneous composite material, and as shown in FIG. 7, the result shows that the coralliform carbon nitride alone shows a strong emission spectrum, which indicates that the photogenerated electrons generated under illumination are easy to recombine with holes in a luminescence form. The CoP/coralline carbon nitride has almost no luminous activity, which shows that the photon-generated carrier of the CoP/coralline carbon nitride composite material is not easy to be compounded with the hole in a luminous form, the carrier separation efficiency is improved, and more electrons are used for reducing H 2 O/H + Hydrogen is produced, more cavities are used for oxidizing anisyl alcohol to generate anisaldehyde, and the catalytic efficiency is improved.
Example 10: photocurrent response characterization of CoP/coralliform carbon nitride heterogeneous composite material
The photocurrent response of the CoP/coralliform carbon nitride heterogeneous composite material is characterized by adopting photocurrent detection, and as shown in fig. 8, the result shows that the photocurrent response strength of the CoP/coralliform carbon nitride heterogeneous composite material is greatly improved compared with that of coralliform carbon nitride, which indicates that the separation efficiency of a photon-generated carrier of the CoP/coralliform carbon nitride heterogeneous composite material obtained after the CoP and the coralliform carbon nitride are compounded is greatly improved, and the photocatalysis hydrogen evolution is promoted to cooperate with the oxidation activity of anisyl alcohol.
Example 11: photocatalytic performance characterization of CoP/coralliform carbon nitride heterogeneous composite material
The photocatalytic performance of the sample CoP/coralline carbon nitride was measured. The hydrogen evolution activity of the CoP/coralline carbon nitride, the CoP and coralline carbon nitride in the process of photolytic water hydrogen evolution and anisyl alcohol oxidation is shown in figure 9, and the gas chromatogram of the anisyl alcohol oxidation product is shown in figure 10;
it can be seen from FIG. 9 that the hydrogen evolution activity of the aqueous solution of cumyl alcohol photolyzed by the CoP/CorCN catalyst at the optimum ratio under the xenon lamp irradiation is 353. Mu. Mol. H -1 ·g -1 Is (16 mol. G) of CoP -1 ·h -1 ) 22 times, and H cannot be detected by the coral-shaped carbon nitride alone due to high carrier recombination efficiency 2 . By comparing the photocatalytic activities of different CoP-to-CorCN mass ratios (1%, 5%, 20%, 50%, 70%, 100%), it was found that the catalytic activity exhibited a tendency to increase and then decrease as the CoP-to-CorCN ratio increased, with the CoP-to-CorCN mass ratio of 50% being the most active, probably because too little CoP was detrimental to carrier separation, while too much CoP masked the photoabsorption and active sites of CorCN.
And from FIG. 10 it can be seen that the oxidation product of anisyl alcohol is anisaldehyde.
By combining the above analysis, compared with the existing traditional photocatalytic hydrogen evolution technology, the method effectively utilizes the photogenerated hole oxidation to realize the oxidation upgrading of the organic matters (the oxidation of the anisyl alcohol to the anisaldehyde), avoids the use of a sacrificial agent, reduces the hydrogen evolution cost, and additionally obtains an organic upgrading product. In addition, the catalyst does not contain noble metal, and CoP is used for replacing the noble metal, so that the cost of the catalyst is reduced.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the CoP/coralliform carbon nitride heterogeneous composite material is characterized by comprising the following steps:
1) Melamine and cyanuric acid are used as raw materials, and coral-shaped carbon nitride is obtained by stirring, assembling and pyrolyzing;
2) Mixing Co 3 O 4 Mixing with sodium hypophosphite and calcining to obtain CoP;
3) Stirring and evaporating the coralline carbon nitride obtained in the step 1) and the CoP obtained in the step 2) in a solution to dryness to obtain the CoP/coralline carbon nitride heterogeneous composite material.
2. The method for preparing the CoP/coralline carbon nitride heterogeneous composite material according to claim 1, wherein in the step 1), the mass ratio of the melamine to the cyanuric acid is 0.5-2: 1, stirring and reacting for 18 hours; the pyrolysis conditions are as follows: heating to 500-600 ℃ at the speed of 2-10K/min in the air atmosphere, and calcining for 3-5 hours.
3. The method for preparing a CoP/coralline carbon nitride heterogeneous composite material according to claim 1, wherein the calcining conditions in the step 2) are as follows: in N 2 Heating to 250-350 ℃ at the speed of 10K/min under the atmosphere, and calcining for 1-3 hours.
4. The method for preparing the CoP/coralline carbon nitride heterogeneous composite material according to claim 1, wherein in the step 3), the mass ratio of the CoP to the coralline carbon nitride is (1-100): 100, and the stirring and evaporating temperature is 60 ℃.
5. A CoP/coral-shaped carbon nitride heterogeneous composite material prepared by the method as claimed in any one of claims 1 to 4, wherein said composite material is prepared by using coral-shaped carbon nitride having a porous, ultrathin-layer, curled morphology as a carrier, loading CoP on said coral-shaped carbon nitride, and said CoP and coral-shaped carbon nitride forming a heterojunction.
6. The CoP/coral-shaped carbon nitride heterogeneous composite material according to claim 5, wherein the CoP is uniformly attached to the coral-shaped carbon nitride, and the mass ratio of the CoP to the coral-shaped carbon nitride is (1-100): 100.
7. The use of the CoP/coralline carbon nitride heterogeneous composite material prepared by the method as claimed in claim 1 or the CoP/coralline carbon nitride heterogeneous composite material as claimed in claim 5 in the field of photocatalysis.
8. The use of claim 7, further comprising: the CoP/coralliform carbon nitride heterogeneous composite material is applied to photocatalysis of anisyl alcohol oxidation in cooperation with hydrogen production.
9. The application according to claim 8, characterized in that it comprises the following steps: adding the CoP/coralliform carbon nitride heterogeneous composite material into an anisyl alcohol aqueous solution, performing ultrasonic dispersion, and then replacing gas in a reactor with N 2 And then sealing, and finally stirring under the irradiation of a xenon lamp for carrying out photocatalytic reaction to complete the oxidation of organic matters and the hydrogen evolution reaction.
10. The use according to claim 8 or 9, wherein the concentration of anisyl alcohol in the anisyl alcohol aqueous solution is 1 g/L-20 g/L, the mass/volume ratio of the CoP/coralline carbon nitride heterogeneous composite material to the anisyl alcohol aqueous solution is 0.5 g-1 g: 1L, and the temperature of the photocatalytic reaction is 20 ℃ to 35 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211494293.4A CN115837285B (en) | 2022-11-25 | 2022-11-25 | CoP/coralloid carbon nitride heterogeneous composite material, and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211494293.4A CN115837285B (en) | 2022-11-25 | 2022-11-25 | CoP/coralloid carbon nitride heterogeneous composite material, and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115837285A true CN115837285A (en) | 2023-03-24 |
CN115837285B CN115837285B (en) | 2024-04-19 |
Family
ID=85577300
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211494293.4A Active CN115837285B (en) | 2022-11-25 | 2022-11-25 | CoP/coralloid carbon nitride heterogeneous composite material, and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115837285B (en) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107126971A (en) * | 2017-07-09 | 2017-09-05 | 华东理工大学 | A kind of preparation and application of compound CoP/g C3N4 photochemical catalysts |
CN109107597A (en) * | 2018-08-31 | 2019-01-01 | 华南农业大学 | A kind of transition metal phosphide/g-C3N4Composite material and preparation method and application |
CN110756215A (en) * | 2019-11-08 | 2020-02-07 | 江苏科技大学 | CoP-HCCN composite photocatalyst and preparation method and application thereof |
CN112871195A (en) * | 2020-09-27 | 2021-06-01 | 江南大学 | Multi-morphology carbon nitride synthesized by salt assistance, and preparation method and application thereof |
EP3943598A1 (en) * | 2020-07-21 | 2022-01-26 | Institut national de recherche pour l'agriculture l'alimentation et l'environnement | Use of uv-activated enzymes to implement oxidation reactions and the corresponding processes |
CN114570368A (en) * | 2022-02-28 | 2022-06-03 | 湖南大学 | Preparation of cobalt-phosphorus-based catalyst and application of cobalt-phosphorus-based catalyst in activation of persulfate to degradation of antibiotics in wastewater |
CN114768846A (en) * | 2022-03-25 | 2022-07-22 | 东莞理工学院 | Preparation method and application of visible light catalytic material for efficiently degrading enoxacin |
CN114797940A (en) * | 2022-05-13 | 2022-07-29 | 常州工程职业技术学院 | M with interface synergistic interaction X P/P-PCN composite catalyst and preparation method and application thereof |
CN114950524A (en) * | 2022-05-25 | 2022-08-30 | 华南理工大学 | Porous carbon nitride-tungsten trioxide composite material and preparation method and application thereof |
-
2022
- 2022-11-25 CN CN202211494293.4A patent/CN115837285B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107126971A (en) * | 2017-07-09 | 2017-09-05 | 华东理工大学 | A kind of preparation and application of compound CoP/g C3N4 photochemical catalysts |
CN109107597A (en) * | 2018-08-31 | 2019-01-01 | 华南农业大学 | A kind of transition metal phosphide/g-C3N4Composite material and preparation method and application |
CN110756215A (en) * | 2019-11-08 | 2020-02-07 | 江苏科技大学 | CoP-HCCN composite photocatalyst and preparation method and application thereof |
EP3943598A1 (en) * | 2020-07-21 | 2022-01-26 | Institut national de recherche pour l'agriculture l'alimentation et l'environnement | Use of uv-activated enzymes to implement oxidation reactions and the corresponding processes |
CN112871195A (en) * | 2020-09-27 | 2021-06-01 | 江南大学 | Multi-morphology carbon nitride synthesized by salt assistance, and preparation method and application thereof |
CN114570368A (en) * | 2022-02-28 | 2022-06-03 | 湖南大学 | Preparation of cobalt-phosphorus-based catalyst and application of cobalt-phosphorus-based catalyst in activation of persulfate to degradation of antibiotics in wastewater |
CN114768846A (en) * | 2022-03-25 | 2022-07-22 | 东莞理工学院 | Preparation method and application of visible light catalytic material for efficiently degrading enoxacin |
CN114797940A (en) * | 2022-05-13 | 2022-07-29 | 常州工程职业技术学院 | M with interface synergistic interaction X P/P-PCN composite catalyst and preparation method and application thereof |
CN114950524A (en) * | 2022-05-25 | 2022-08-30 | 华南理工大学 | Porous carbon nitride-tungsten trioxide composite material and preparation method and application thereof |
Non-Patent Citations (3)
Title |
---|
YAZI LIU等: "CoP imbedded g-C3N4 heterojunctions for highly efficient photo, electro and photoelectrochemical water splitting", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 599, pages 1 - 2 * |
YAZI LIU等: "Graphitic Carbon Nitride Decorated with CoP Nanocrystals for Enhanced Photocatalytic and Photoelectrochemical H2 Evolution", 《ENERGY FUELS》, no. 33, pages 11663 * |
YUELAN ZHANG等: "Bifunctional synergistic CoP/Coral-like g-C3N4 catalyst: Boosting the photocatalytic water splitting hydrogen evolution and appreciation of anisalcohol at same time", 《APPLIED SURFACE SCIENCE》, pages 156187 * |
Also Published As
Publication number | Publication date |
---|---|
CN115837285B (en) | 2024-04-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Jiang et al. | Nature-based catalyst for visible-light-driven photocatalytic CO 2 reduction | |
Ye et al. | A highly stable non-noble metal Ni 2 P co-catalyst for increased H 2 generation by gC 3 N 4 under visible light irradiation | |
CN110947376B (en) | Monoatomic noble metal anchoring defect type WO3/TiO2Nanotubes, their preparation and use | |
Liu et al. | Water reduction and oxidation on Pt–Ru/Y 2 Ta 2 O 5 N 2 catalyst under visible light irradiation | |
Hsu et al. | Au-decorated GaOOH nanorods enhanced the performance of direct methanol fuel cells under light illumination | |
CN109908959B (en) | Core-shell ZnO/precious metal @ ZIF-8 photocatalytic material and preparation method and application thereof | |
Pan et al. | Photocatalytic overall water splitting by spatially-separated Rh and RhOx cocatalysts on polymeric carbon nitride nanosheets | |
Yu et al. | TiO2/TiN core/shell nanobelts for efficient solar hydrogen generation | |
Xing et al. | Interfacial microenvironment-regulated cascade charge transport in Co6Mo6C2-MoO2-CoNC@ ZnIn2S4 photocatalyst for efficient hydrogen evolution | |
Flores-Flores et al. | CO2 adsorption and photocatalytic reduction over Mg (OH) 2/CuO/Cu2O under UV-Visible light to solar fuels | |
CN109225222B (en) | Composite photocatalyst and application thereof | |
CN112473717B (en) | Nickel monoatomic/functionalized graphite-phase carbon nitride composite catalyst | |
CN110586166A (en) | Preparation of molybdenum oxide nanosheet and application of molybdenum oxide nanosheet in photocatalytic nitrogen fixation | |
CN110882714A (en) | Curled carbon nitride thin sheet, preparation method and application thereof in hydrogen production through photocatalytic water decomposition | |
CN110116015B (en) | Photocatalyst for completely decomposing water, preparation method and application thereof, reaction method for completely decomposing water through photocatalysis and catalytic mixed solution | |
Wang et al. | Hexagonal SiC with spatially separated active sites on polar and nonpolar facets achieving enhanced hydrogen production from photocatalytic water reduction | |
CN114632513B (en) | Preparation method and application of monoatomic Au-loaded strontium titanate/titanium dioxide composite photocatalyst | |
An et al. | 0D ultrafine ruthenium quantum dot decorated 3D porous graphitic carbon nitride with efficient charge separation and appropriate hydrogen adsorption capacity for superior photocatalytic hydrogen evolution | |
Gan et al. | An amorphous NiS x film as a robust cocatalyst for boosting photocatalytic hydrogen generation over ultrafine ZnCdS nanoparticles | |
Chen et al. | A novel strategy for loading metal cocatalysts onto hollow nano-TiO2 inner surface with highly enhanced H2 production activity | |
CN113600221B (en) | Au/g-C 3 N 4 Monoatomic photocatalyst, and preparation method and application thereof | |
Huang et al. | The heterojunction construction of hybrid B-doped g-C3N4 nanosheets and ZIF67 by simple mechanical grinding for improved photocatalytic hydrogen evolution | |
CN110386626B (en) | Cobaltous oxide sheet, preparation method thereof and application thereof in visible light catalytic total decomposition of water | |
CN112916000B (en) | Photocatalytic material for reducing nitrogen to produce ammonia and preparation method and application thereof | |
CN113617367B (en) | Noble metal ruthenium monoatomic supported catalyst and preparation method and application 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 |