CN115845894B - Carbon-doped hexagonal porous tubular carbon nitride and preparation method and application thereof - Google Patents
Carbon-doped hexagonal porous tubular carbon nitride and preparation method and application thereof Download PDFInfo
- Publication number
- CN115845894B CN115845894B CN202211302765.1A CN202211302765A CN115845894B CN 115845894 B CN115845894 B CN 115845894B CN 202211302765 A CN202211302765 A CN 202211302765A CN 115845894 B CN115845894 B CN 115845894B
- Authority
- CN
- China
- Prior art keywords
- carbon
- carbon nitride
- porous tubular
- doped hexagonal
- hexagonal porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title abstract description 13
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 34
- 239000001257 hydrogen Substances 0.000 abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 34
- 238000004519 manufacturing process Methods 0.000 abstract description 29
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract 1
- 102100024315 Pericentrin Human genes 0.000 description 26
- 230000001699 photocatalysis Effects 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 101001117010 Homo sapiens Pericentrin Proteins 0.000 description 15
- 239000000463 material Substances 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000004065 semiconductor Substances 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
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical group CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 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
Landscapes
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses carbon-doped hexagonal porous tubular carbon nitride and a preparation method and application thereof, wherein the method comprises the following steps: sequentially adding melamine and isonicotinic acid into deionized water, and magnetically stirring at normal temperature to form mixed dispersion liquid; carrying out hydrothermal reaction on the mixed dispersion liquid, and cooling a product after the hydrothermal reaction to room temperature; carrying out centrifugal separation, washing and drying treatment on the product after the hydrothermal reaction to obtain white solid powder; and calcining the white solid powder, and cooling to obtain the carbon-doped hexagonal porous tubular carbon nitride. The carbon-doped hexagonal porous tubular carbon nitride prepared by the invention can improve pi electron density and optimize electron energy band structure and surface properties; meanwhile, the specific surface area can be obviously increased, more hydrogen production active sites are provided, and the photon utilization rate is fully improved. The method has the advantages of easily available raw materials, low cost, no toxicity or harm, simple operation and high-efficiency hydrogen production performance by decomposing water under the irradiation of visible light.
Description
Technical Field
The invention relates to the technical field of application of semiconductor photocatalytic materials, in particular to carbon-doped hexagonal porous tubular carbon nitride, and a preparation method and application thereof.
Background
The renewable solar photocatalytic water splitting hydrogen production technology can convert low-density solar energy into high-density green hydrogen energy, and has great potential in solving the energy shortage and environmental pollution fields. In a semiconductor photocatalytic water splitting hydrogen production system, the development and preparation of the photocatalyst with high-efficiency visible light response have important scientific and practical significance. Carbon nitride is a nonmetallic polymer semiconductor material, and has the characteristics of simple preparation method, visible light response, high chemical and thermal stability and the like, so that the carbon nitride becomes a research hot spot of the current photocatalytic water splitting hydrogen production material. However, carbon nitride prepared directly by thermally polymerizing precursors such as melamine, urea, dicyandiamide and the like has the disadvantages of limited hydrogen production active sites, low visible light utilization rate, easy recombination of photo-generated carriers and the like of photocatalytic decomposition of water to produce hydrogen. In order to improve the above-mentioned intrinsic defects and enhance photocatalytic performance, various strategies have been reported for defect control, construction of heterojunction, doping of elements, and morphological design. The carbon and nitrogen atoms in the carbon nitride can be asymmetrically distributed by proper element doping, pi electron delocalization of the heptazine ring of the carbon nitride composition unit is expanded, so that the energy band structure can be regulated, the electron performance is improved, and the photocatalytic activity is improved. In addition, the specific surface area of the carbon nitride can be increased, the active site is increased, multiple reflection of incident light in the structure can be increased, light absorption is improved, and separation of photogenerated carriers is promoted through morphology regulation. Therefore, the design and development of the method for realizing the efficient hydrogen production by photocatalytic water splitting through element doping and controlling the pi electron density of the carbon nitride with the special morphology has important practical application value.
Disclosure of Invention
The invention aims to provide carbon-doped hexagonal porous tubular carbon nitride, a preparation method and application thereof. The invention provides the following technical scheme:
the invention provides a preparation method of carbon-doped hexagonal porous tubular carbon nitride, which comprises the following steps:
sequentially adding melamine and isonicotinic acid into deionized water, and magnetically stirring at normal temperature to form mixed dispersion liquid;
carrying out hydrothermal reaction on the mixed dispersion liquid, and cooling a product after the hydrothermal reaction to room temperature;
carrying out centrifugal separation, washing and drying treatment on the product after the hydrothermal reaction to obtain white solid powder;
and calcining the white solid powder, and cooling to obtain the carbon-doped hexagonal porous tubular carbon nitride.
Further, the mass ratio of melamine to isonicotinic acid is 1-10: 1.
further, the hydrothermal reaction temperature is 180-200 ℃ and the reaction time is 20-30h.
Further, the rotational speed of the centrifugal separation is 6000-10000r/min.
Further, the washing method is to wash 3 times with deionized water and absolute ethanol, respectively.
Further, the drying temperature is 60-80 ℃ and the drying time is 6-10h.
Further, the calcining temperature is 450-550 ℃; the calcination time is 1-4h.
The invention also provides carbon-doped hexagonal porous tubular carbon nitride, which is prepared according to the method.
The invention also provides application of the carbon-doped hexagonal porous tubular carbon nitride.
Further, the method is applied to photocatalytic decomposition of water under visible irradiation to produce hydrogen.
The invention has the technical effects and advantages that:
firstly, the invention takes supermolecules formed by melamine and isonicotinic acid as precursors, and adopts a thermal polymerization mode to successfully prepare the carbon-doped hexagonal porous tubular carbon nitride. The carbon doping can not only increase the conductivity of the material, and is beneficial to the transmission of photo-generated charges, but also improve pi electron density, optimize electron energy band structure and surface property, and improve the kinetics of photocatalytic hydrogen production. The hexagonal porous tubular structure can remarkably increase the specific surface area, provide more hydrogen production active sites, and simultaneously, incident light can be reflected and refracted for multiple times in the hexagonal porous tubular structure, so that the photon utilization rate is fully improved. In addition, the transmission distance from the inside of the material to the active surface of the photo-generated charge can be effectively reduced, and the separation and the transportation of the photo-generated charge are accelerated.
Secondly, through a photocatalytic hydrogen production model test, the prepared carbon-doped hexagonal porous tubular carbon nitride material shows high-efficiency hydrogen production performance by decomposing water under visible light irradiation and has good hydrogen production stability.
Thirdly, the raw materials for preparing the carbon-doped hexagonal porous tubular carbon nitride are easy to obtain, low in price, nontoxic and harmless, simple to operate and good in application prospect in hydrogen production by photocatalytic water splitting.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing carbon-doped hexagonal porous tubular carbon nitride according to the present invention;
FIG. 2 is an X-ray diffraction pattern comparing the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention with the bulk carbon nitride prepared in comparative example 1;
FIG. 3 is a graph showing the comparison of the UV-visible absorption spectra of carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention and bulk carbon nitride prepared in comparative example 1;
FIG. 4 is a scanning electron microscope image of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention;
FIG. 5 is a transmission electron micrograph of a carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention;
FIG. 6 is a graph showing comparison of nitrogen adsorption/desorption isotherms of carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention and bulk carbon nitride prepared in comparative example 1;
FIG. 7 is a graph showing the contrast of the X-ray photoelectron spectrum of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention and the bulk carbon nitride prepared in comparative example 1;
FIG. 8 is a graph showing the hydrogen production performance under irradiation of visible light of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention versus the bulk carbon nitride prepared in comparative example 1;
FIG. 9 is a graph showing the band position comparison of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention with the bulk carbon nitride prepared in comparative example 1;
fig. 10 is a graph comparing transient photocurrent response curves of carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention with bulk carbon nitride prepared in comparative example 1.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to solve the defects in the prior art, on one hand, the invention discloses a preparation method of carbon-doped hexagonal porous tubular carbon nitride, and fig. 1 is a schematic flow chart of the preparation method of carbon-doped hexagonal porous tubular carbon nitride, as shown in fig. 1, and the preparation method comprises the following steps:
s1, adding melamine and isonicotinic acid into deionized water, and magnetically stirring at normal temperature to form a mixed dispersion liquid;
s2, carrying out hydrothermal reaction on the mixed dispersion liquid, and cooling a product after the hydrothermal reaction to room temperature;
s3, carrying out centrifugal separation, washing and drying treatment on the product after the hydrothermal reaction to obtain white solid powder;
and S4, calcining the white solid powder, and cooling to obtain the carbon-doped hexagonal porous tubular carbon nitride.
In the step S1 of the invention, melamine is firstly placed in deionized water, magnetically stirred at normal temperature, then isonicotinic acid is added, and stirring is continued at normal temperature to form mixed dispersion liquid; the mass ratio of the melamine to the isonicotinic acid is 1-10: 1, preferably, the amount ratio of melamine to isonicotinic acid is 1:1, 3:1, 10:1, more preferably 3:1; preferably, the magnetic stirring time is 30min at normal temperature for both times.
In step S2 of the invention, transferring the obtained mixed dispersion liquid into a hydrothermal reaction kettle, carrying out a hydrothermal reaction, and cooling to room temperature, wherein the hydrothermal reaction temperature is 180-200 ℃, preferably 190 ℃; the reaction time is 20 to 30 hours, preferably 24 hours.
In the step S3 of the invention, the rotation speed of the centrifugal separation is 6000-10000r/min, preferably 8000r/min; the washing method is to wash 3 times by using ionized water and absolute ethyl alcohol respectively; the drying temperature is 60-80 ℃, preferably 60 ℃, and the drying time is 6-10h, preferably 8h.
In the step S4 of the invention, the obtained white solid powder is placed in a tube furnace, heated and calcined under argon atmosphere, and cooled to obtain carbon-doped hexagonal porous tubular carbon nitride; the heating rate in the calcination process is 2.5 ℃/min; the calcination temperature is 450-550 ℃, preferably 450 ℃, 500 ℃, 550 ℃, more preferably 500 ℃; the calcination time is 1 to 4 hours, preferably 2 hours.
Based on the preparation method, on the other hand, the invention also discloses application of the carbon-doped hexagonal porous tubular carbon nitride material, which takes photocatalytic water decomposition to prepare hydrogen as a model, and inspects the photocatalytic hydrogen preparation performance of the prepared carbon-doped hexagonal porous tubular carbon nitride by detecting hydrogen generated in the photocatalytic water decomposition process.
Example 1
Step one, 1.134g of melamine is placed in 50ml of deionized water, stirred for 30min at normal temperature, then 0.369g of isonicotinic acid is added to dissolve the melamine, and stirring is continued for 30min to form a uniform mixed dispersion, wherein the mass ratio of the melamine to the isonicotinic acid is 3:1.
Transferring the mixed dispersion liquid obtained in the first step into a 100ml hydrothermal reaction kettle, placing the hydrothermal reaction kettle into a constant-temperature oven at 190 ℃ for reaction for 24 hours, naturally cooling to room temperature, centrifugally separating at a rotating speed of 8000r/min, collecting solids, washing the collected solids with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the solid into the constant-temperature oven at 60 ℃ for drying for 8 hours to obtain white solid powder for use.
And thirdly, weighing 1g of the white solid powder in the second step, placing the white solid powder in a magnetic boat with a cover, calcining at a heating rate of 2.5 ℃/min to 500 ℃ under the protection of argon atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the carbon-doped hexagonal porous tubular carbon nitride.
Example 2
Step one, 1.134g of melamine is placed in 50ml of deionized water, stirred for 30min at normal temperature, then 1.107g of isonicotinic acid is added to dissolve the melamine, and stirring is continued for 30min to form a uniform mixed dispersion, wherein the mass ratio of the melamine to the isonicotinic acid is 1:1.
Transferring the mixed dispersion liquid obtained in the step one into a 100ml hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature oven for reaction for 24 hours at 190 ℃, naturally cooling to room temperature, centrifugally separating at a rotating speed of 8000r/min, collecting solids, washing the collected solids with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the solid into a constant-temperature oven for drying at 60 ℃ for 8 hours to obtain white solid powder for use.
And thirdly, weighing 1g of the white solid powder in the second step, placing the white solid powder in a magnetic boat with a cover, calcining at a heating rate of 2.5 ℃/min to 500 ℃ under the protection of argon atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the carbon-doped hexagonal porous tubular carbon nitride.
Example 3
Step one, 1.134g of melamine is placed in 50ml of deionized water, stirred for 30min at normal temperature, then 0.111g of isonicotinic acid is added to dissolve the melamine, and stirring is continued for 30min to form uniform mixed dispersion, wherein the mass ratio of the melamine to the isonicotinic acid is 10:1.
Transferring the mixed dispersion liquid obtained in the step one into a 100ml hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature oven for reaction for 24 hours at 190 ℃, naturally cooling to room temperature, centrifugally separating at a rotating speed of 8000r/min, collecting solids, washing the collected solids with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the solid into a constant-temperature oven for drying at 60 ℃ for 8 hours to obtain white solid powder for use.
And thirdly, weighing 1g of the white solid powder in the second step, placing the white solid powder in a magnetic boat with a cover, calcining at a heating rate of 2.5 ℃/min to 500 ℃ under the protection of argon atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the carbon-doped hexagonal porous tubular carbon nitride.
Example 4
Step one, 1.134g of melamine is placed in 50ml of deionized water, stirred for 30min at normal temperature, then 0.369g of isonicotinic acid is added to dissolve the melamine, and stirring is continued for 30min to form a uniform mixed dispersion, wherein the mass ratio of the melamine to the isonicotinic acid is 3:1.
Transferring the mixed dispersion liquid obtained in the step one into a 100ml hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature oven for reaction for 24 hours at 190 ℃, naturally cooling to room temperature, centrifugally separating at a rotating speed of 8000r/min, collecting solids, washing the collected solids with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the solid into a constant-temperature oven for drying at 60 ℃ for 8 hours to obtain white solid powder for use.
And thirdly, weighing 1g of the white solid powder in the second step, placing the white solid powder in a magnetic boat with a cover, calcining at the heating rate of 2.5 ℃/min to 450 ℃ under the protection of argon atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the carbon-doped hexagonal porous tubular carbon nitride.
Example 5
Step one, 1.134g of melamine is placed in 50ml of deionized water, stirred for 30min at normal temperature, then 0.369g of isonicotinic acid is added to dissolve the melamine, and stirring is continued for 30min to form a uniform mixed dispersion, wherein the mass ratio of the melamine to the isonicotinic acid is 3:1.
Transferring the mixed dispersion liquid obtained in the step one into a 100ml hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a constant-temperature oven for reaction for 24 hours at 190 ℃, naturally cooling to room temperature, centrifugally separating at a rotating speed of 8000r/min, collecting solids, washing the collected solids with deionized water and absolute ethyl alcohol for 3 times respectively, and then placing the solid into a constant-temperature oven for drying at 60 ℃ for 8 hours to obtain white solid powder for use.
And thirdly, weighing 1g of the white solid powder in the second step, placing the white solid powder in a magnetic boat with a cover, calcining at a heating rate of 2.5 ℃/min to 550 ℃ under the protection of argon atmosphere, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the carbon-doped hexagonal porous tubular carbon nitride.
Comparative example 1
Weighing 1g of melamine powder, placing the melamine powder into a magnetic boat with a cover, calcining the melamine powder at a heating rate of 2.5 ℃/min to 500 ℃ under the protection of argon atmosphere, keeping the temperature for 2 hours, and naturally cooling the melamine powder to room temperature to obtain a bulk carbon nitride material named PCN.
Activity effect experiment of photocatalytic Hydrogen production
The carbon nitride materials prepared in the above examples and comparative examples are used for carrying out an activity effect experiment of photocatalytic hydrogen production under the irradiation of visible light (lambda >420 nm), and the method mainly comprises the following operation steps:
step one, 10mg of a photocatalyst, 20ml of a 10% volume fraction aqueous triethanolamine solution as a sacrificial agent, a chloroplatinic acid solution (0.5 wt% pt) as a promoter, and sealing were added to a commercial photocatalytic decomposition water reactor.
And step two, introducing argon for 15min under the condition of continuous magnetic stirring, removing air in the reactor, opening a 300W xenon lamp with a wavelength greater than 420nm filter as a light source, carrying out photolysis water hydrogen production reaction, extracting 500 mu L of gas every 1h, and detecting the hydrogen production amount by using gas chromatography.
Description of the results of the drawings
The carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention and the carbon nitride prepared in comparative example were named PCNTs and PCN, respectively, and the performances of PCNTs and PCN were characterized by an X-ray diffractometer, a scanning electron microscope, a transmission electron microscope, a nitrogen adsorption-desorption instrument, an X-ray electron spectrometer, an ultraviolet-visible absorption spectrometer, and an electrochemical workstation.
Fig. 2 is an X-ray diffraction (XRD) contrast plot of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention and the bulk carbon nitride prepared in comparative example 1, as shown in fig. 2, XRD characteristic peaks of (100) and (002) two crystal planes of PCNTs become weaker and broader as compared with PCN, and the angle of the (002) characteristic peak is slightly reduced, which is a sufficient demonstration that the tubular structure of carbon nitride is formed.
FIG. 3 is a graph of X-ray photoelectron spectroscopy (XPS) for C1s of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention versus bulk carbon nitride prepared in comparative example 1, as shown in FIG. 3, the characteristic peak of PCNTs at 284.8eV is significantly greater than that of PCN, revealing that carbon-doped carbon nitride can be obtained by the technique of thermal polymerization after formation of supramolecules by melamine and isonicotinic acid.
Fig. 4 is a graph showing the comparison of the ultraviolet-visible absorption spectrum (UV-Vis) of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention and the bulk carbon nitride prepared in comparative example 1, and as shown in fig. 4, the PCNTs have significantly enhanced light absorption at 450-700nm compared to PCN, indicating that the PCNTs prepared in the present invention can improve the utilization ratio of visible light.
FIG. 5 is a Scanning Electron Microscope (SEM) of a carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention, as shown in FIG. 5, which illustrates that the carbon nitride prepared in accordance with the present invention is a regular hexagonal tubular structure.
FIG. 6 is a Transmission Electron Micrograph (TEM) of a carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention; as shown in FIG. 6, PCNTs are a hexagonal porous tubular structure, and are completely consistent with SEM results, so that the PCNTs prepared by the invention can improve the utilization rate of visible light.
Fig. 7 is a graph comparing the nitrogen desorption isothermal curves (BET) of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention with the bulk carbon nitride prepared in comparative example 1, and as shown in fig. 7, it is more clearly revealed that PCNTs prepared in the present invention can increase the specific surface area, increase the hydrogen production active site, facilitate multiple reflection of visible light inside thereof, and reduce the transmission distance of photo-generated charges.
FIG. 8 is a graph showing the hydrogen production performance of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention compared with the bulk carbon nitride prepared in comparative example 1 under irradiation of visible light, wherein the hydrogen production performance of PCNTs reaches 20.1. Mu. Mol/h under irradiation of 420nm visible light, and the hydrogen production performance of PCN is significantly improved by only 3.4. Mu. Mol/h, as shown in FIG. 8.
Fig. 9 is a graph comparing the band positions of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention with that of bulk carbon nitride prepared in comparative example 1 under irradiation of visible light, and as shown in fig. 9, comparing the band structures of PCNTs and PCN, it was found that the band gap of PCNTs was reduced from 2.60eV to 2.42eV, which would widen the absorption range for visible light, which is completely consistent with the uv-vis absorption spectrum results. In addition, the conduction band of PCNTs is obviously reduced, which is beneficial to improving the dynamics of photocatalytic hydrogen production.
Fig. 10 is a graph comparing transient photocurrent response curves of the carbon-doped hexagonal porous tubular carbon nitride prepared in example 1 of the present invention with bulk carbon nitride prepared in comparative example 1, and as shown in fig. 10, the photocurrent response of PCNTs is significantly greater than PCN, revealing that the photo-generated charge separation efficiency of PCNTs is higher and the recombination of photo-generated carriers is significantly reduced.
As can be seen from the above figures, the PCN prepared in the comparative example can only absorb visible light below 460nm, has smaller specific surface area and easily combines photo-generated charges, so that the hydrogen production activity is lower and is only 3.4 mu mol/h. The carbon-doped hexagonal porous tubular carbon nitride prepared by the method can optimize the electron energy band structure by regulating and controlling pi electron density on one hand, promote the separation of photo-generated electrons and holes, increase the specific surface area on the other hand, improve the hydrogen production active site and improve the utilization efficiency of visible light on the other hand. Under the synergistic effect of the factors, the photocatalytic hydrogen production rate reaches 20.1 mu mol/h, which is 5.9 times of the hydrogen production performance of PCN. The data of the invention fully prove that the carbon-doped hexagonal porous tubular carbon nitride can improve the electronic structure and the surface physicochemical property of the carbon nitride, and obviously improve the hydrogen production performance of photocatalytic water splitting.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (7)
1. A method for preparing carbon-doped hexagonal porous tubular carbon nitride, which is characterized by comprising the following steps:
sequentially adding melamine and isonicotinic acid into deionized water, and magnetically stirring at normal temperature to form mixed dispersion liquid;
carrying out hydrothermal reaction on the mixed dispersion liquid, and cooling a product after the hydrothermal reaction to room temperature;
carrying out centrifugal separation, washing and drying treatment on the product after the hydrothermal reaction to obtain white solid powder;
and calcining the white solid powder, and cooling to obtain the carbon-doped hexagonal porous tubular carbon nitride.
2. The method for preparing carbon-doped hexagonal porous tubular carbon nitride according to claim 1, wherein the mass ratio of melamine to isonicotinic acid is 1-10: 1.
3. the method for preparing carbon-doped hexagonal porous tubular carbon nitride according to claim 1, wherein the hydrothermal reaction temperature is 180-200 ℃ and the reaction time is 20-30h.
4. The method for preparing carbon-doped hexagonal porous tubular carbon nitride according to claim 1, wherein the centrifugal separation is performed at a rotational speed of 6000-10000r/min.
5. The method for preparing a carbon-doped hexagonal porous tubular carbon nitride according to claim 1, wherein the washing method is to wash 3 times with deionized water and absolute ethanol, respectively.
6. The method for preparing a carbon-doped hexagonal porous tubular carbon nitride according to claim 1, wherein the drying temperature is 60-80 ℃ and the drying time is 6-10h.
7. The method for preparing a carbon-doped hexagonal porous tubular carbon nitride according to claim 1, wherein the calcining temperature is 450 ℃ to 550 ℃; the calcination time is 1-4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211302765.1A CN115845894B (en) | 2022-10-24 | 2022-10-24 | Carbon-doped hexagonal porous tubular carbon nitride and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211302765.1A CN115845894B (en) | 2022-10-24 | 2022-10-24 | Carbon-doped hexagonal porous tubular carbon nitride and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115845894A CN115845894A (en) | 2023-03-28 |
| CN115845894B true CN115845894B (en) | 2024-03-29 |
Family
ID=85661724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211302765.1A Active CN115845894B (en) | 2022-10-24 | 2022-10-24 | Carbon-doped hexagonal porous tubular carbon nitride and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115845894B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486233A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of carbonitride adulterates the preparation method and application of carbon-based cobalt/cobalt oxide nanocatalyst |
| CN107576714A (en) * | 2017-09-05 | 2018-01-12 | 济南大学 | A kind of preparation method and application of graphite phase carbon nitride@MOF nanocrystals |
| CN109261207A (en) * | 2018-09-26 | 2019-01-25 | 合肥国轩高科动力能源有限公司 | Photocatalytic material, preparation method thereof and application of photocatalytic material in treatment of waste lithium battery electrolyte |
| CN109399584A (en) * | 2018-10-17 | 2019-03-01 | 济南大学 | Six rib tubulose carbonitrides of one kind and its preparation method and application |
| MX2017014760A (en) * | 2017-11-17 | 2019-05-20 | Centro De Investigacion En Quim Aplicada | Process for the biomimetic synthesis of polyaniline compounds and use thereof to manufacture supercapacitors. |
| CN111330613A (en) * | 2018-12-19 | 2020-06-26 | 南京理工大学 | Preparation method of hollow porous prismatic graphite phase carbon nitride |
| CN114618546A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of transition metal catalyst and application of transition metal catalyst in preparation of aromatic aldehyde |
| CN114904550A (en) * | 2022-05-18 | 2022-08-16 | 安徽大学 | Method for efficiently preparing melamine self-assembled supramolecular material |
-
2022
- 2022-10-24 CN CN202211302765.1A patent/CN115845894B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486233A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of carbonitride adulterates the preparation method and application of carbon-based cobalt/cobalt oxide nanocatalyst |
| CN107576714A (en) * | 2017-09-05 | 2018-01-12 | 济南大学 | A kind of preparation method and application of graphite phase carbon nitride@MOF nanocrystals |
| MX2017014760A (en) * | 2017-11-17 | 2019-05-20 | Centro De Investigacion En Quim Aplicada | Process for the biomimetic synthesis of polyaniline compounds and use thereof to manufacture supercapacitors. |
| CN109261207A (en) * | 2018-09-26 | 2019-01-25 | 合肥国轩高科动力能源有限公司 | Photocatalytic material, preparation method thereof and application of photocatalytic material in treatment of waste lithium battery electrolyte |
| CN109399584A (en) * | 2018-10-17 | 2019-03-01 | 济南大学 | Six rib tubulose carbonitrides of one kind and its preparation method and application |
| CN111330613A (en) * | 2018-12-19 | 2020-06-26 | 南京理工大学 | Preparation method of hollow porous prismatic graphite phase carbon nitride |
| CN114618546A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Preparation method of transition metal catalyst and application of transition metal catalyst in preparation of aromatic aldehyde |
| CN114904550A (en) * | 2022-05-18 | 2022-08-16 | 安徽大学 | Method for efficiently preparing melamine self-assembled supramolecular material |
Non-Patent Citations (5)
| Title |
|---|
| In situ self-assembly synthesis of carbon self-doped graphite carbon nitride hexagonal tubes with enhanced photocatalytic hydrogen evolution;Yun Yang et al.;《International Journal of Hydrogen Energy》;20190918;第44卷(第50期);摘要和第27357页第1段 * |
| Increasing -electron availability in benzene ring incorporated graphitic carbon nitride for increased photocatalytic hydrogen generation;Xiangang Lin et al.;《Journal of Materials Science & Technology》;20200715;第65卷;第164-170页 * |
| 有机半导体氮化碳的分子结构调控及催化机理研究;李琪;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20210915(第9期);第B014-332页 * |
| 类石墨相氮化碳的制备、改性及其在可见光催化分解水制氢中的催化作用;诸葛桂英;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20200115(第1期);第B014-1050页 * |
| 超分子自组装法制备氮化碳聚合物光催化剂;郑云等;《中国材料进展》;20170131;第36卷(第1期);第25-32页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115845894A (en) | 2023-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112427045A (en) | CdS/g-C synthesized by hydrothermal method and having Z-shaped heterojunction3N4Preparation method of composite photocatalyst material | |
| CN110961133B (en) | Nonmetal BCN/g-C3N4Van der Waals heterojunction photocatalyst and preparation method and application thereof | |
| CN110876953A (en) | P and S co-doped carbon nitride homotype heterojunction composite photocatalyst | |
| CN112023974A (en) | P-CeO2/g-C3N4Heterojunction material, preparation method and application thereof | |
| CN115007194B (en) | Preparation method and application of amorphous boron-doped carbon nitride | |
| CN113262809A (en) | Method for preparing CdS @ CoP @ NC heterojunction photocatalyst based on ZIF-67 precursor | |
| CN112791730A (en) | Z-type nano-copper vanadate-based composite photocatalyst and preparation method and application thereof | |
| CN114534783B (en) | Method for preparing single-atom Pt-embedded covalent organic framework photocatalyst and application thereof | |
| CN111604063A (en) | g-C3N4/In2Se3Composite photocatalyst and preparation method and application thereof | |
| Huang et al. | Cooperative enhancement solar hydrogen generation of reformed g-C3N4/TiO2 mesocrystals composites | |
| CN115845894B (en) | Carbon-doped hexagonal porous tubular carbon nitride and preparation method and application thereof | |
| CN116726973A (en) | Flower-ball-shaped sulfur indium zinc/carbon nitride heterojunction photocatalyst, and preparation method and application thereof | |
| CN108940343B (en) | Fe-TiO2nanotube/g-C3N4Composite material and preparation method and application thereof | |
| CN115254169B (en) | Nonmetal catalyst and preparation method and application thereof | |
| CN108906103B (en) | Preparation method and application of ultrathin nano flaky graphite phase carbon nitride | |
| CN116393155A (en) | Carbocyclic doped g-C 3 N 4 Preparation method of heterojunction in basal plane and application of heterojunction in photo-reforming cellulose | |
| CN113697783B (en) | Porous g-C 3 N 4 Preparation method and application of nano-sheet | |
| CN116689006A (en) | Carbon nitride nano-sheet composite material and preparation method and application thereof | |
| CN115870000A (en) | Porphyrin-based porous organic polymer/indium zinc sulfide direct Z-scheme photocatalyst, preparation method and application | |
| CN111617778B (en) | Preparation method of hydrothermally synthesized flower-rod-shaped sulfur indium zinc photocatalyst | |
| CN111495391A (en) | Composite photocatalyst and preparation method and application thereof | |
| CN115055199B (en) | Sulfur-doped honeycomb nano sheet g-C 3 N 4 Preparation method and application thereof | |
| CN115193466B (en) | Bimetallic hydrogen evolution catalyst and preparation method thereof | |
| CN116272937B (en) | TiO (titanium dioxide)2Preparation method and application of nanosheet material | |
| CN113600242B (en) | S-type T-COF @ CdS core-shell heterojunction composite photocatalytic material, preparation method thereof and application of S-type T-COF @ CdS core-shell heterojunction composite photocatalytic material in photolysis hydrogen production |
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 |