CN115888788A - Preparation method of three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst, product and application thereof - Google Patents
Preparation method of three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst, product and application thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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Abstract
The invention discloses a preparation method of a three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst, a product and application thereof 3‑x Uniformly loaded in honeycomb g-C 3 N 4 In the pore canal, the partial plasma effect is utilized to convert the light energy into heat energy, so that the heat energy is used as a 'nano heater' to provide heat for a photocatalysis system and accelerate the photocatalysis of CO 2 And (4) carrying out reduction reaction. The invention can effectively solve the energy waste of near infrared light in the photocatalytic reaction, broaden the spectrum absorption range and accelerate the dynamic reaction process. The method is novel, the preparation method is simple, the repeatability is good, the operability is strong, and the photo-thermal catalysis CO is performed 2 Good reduction performance and application prospect.
Description
Technical Field
The invention belongs to the field of photocatalytic nano materials, and particularly relates to a preparation method of a three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst, a product and application of the three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst.
Background
Combustion of large quantities of fossil fuels results in carbon dioxide (CO) 2 ) The rising emission level has caused the widespread concern of people about energy shortage and problems of global warming, ocean acidification, etc. Catalytic reduction of CO using renewable solar energy 2 Conversion into other products having high added values is one of effective methods for solving the problems of energy shortage and environment. Due to CO 2 The high chemical stability of (2) leads to lower photocatalytic yield, and the reaction efficiency can be improved by utilizing thermal catalysis.
Photothermal catalysis is based on the synergistic effect of light excitation and thermal activation, and has higher reaction activity compared with single catalysis. After the material absorbs ultraviolet-visible-infrared (UV-Vis-IR) wave band light, electrons on a valence band are excited and migrate to a conduction band in a very fast time, holes are left, and electron-hole pairs are formed. The photoelectrons captured by the holes can perform secondary transition on the conducting band in a thermally activated thermal state, sufficient heat can also accelerate the migration of carriers on a catalyst, the recombination of the carriers is inhibited from two aspects, and the hole-captured photoelectrons play an important role in catalytic reaction; and secondly, the temperature rise is beneficial to the diffusion of reactant and product molecules, the thermal motion of the molecules is enhanced, and the mass transfer process is improved.
Among various photocatalysts that have been reported, graphite-phase carbon nitride (g-C) 3 N 4 ) Has the advantages of easily available raw materials, low price, proper energy band structure, adjustable molecular structure and the like. The forbidden band width is about 2.7eV, the visible light absorption characteristic is good, and the photocatalytic material can be used for photocatalytic degradation of pollutants, photocatalytic water splitting oxygen production and hydrogen production, photocatalytic organic synthesis and photocatalytic CO production 2 Has good application prospect in the aspects of reduction and the like. However, pure g-C is limited by low surface area, energy bandwidth and high recombination rate of electron-hole pairs 3 N 4 Photocatalytic reduction of CO 2 The performance of (c).
To effectively improve g-C 3 N 4 The research personnel develop various schemes to solve the problemThe problems are, for example, to achieve the purposes of increasing the specific surface area, increasing the reactive sites, adjusting the band gap by means of morphological control, defect engineering, doping elements, and the like. However, like most other polymeric semiconductors, covalent g-C 3 N 4 Generally presents higher exciton binding energy, easy carrier recombination and other problems; in addition, C prepared by conventional preparation method 3 N 4 Small specific surface area and only a small amount of visible light can be utilized: (<460 nm), the photogenerated carriers are prone to recombination, resulting in low photocatalytic efficiency. In consideration of the effective progress of the oxidation-reduction reaction, the utilization rate of the full solar spectrum does not exceed 50 percent even under the premise of fully utilizing visible light. Most of the energy in the infrared region (53% of the full solar spectrum) is dissipated mainly as heat dissipation and is wasted during the photoreaction. Furthermore, limited by CO 2 The chemical and thermodynamic stability of the molecule is good, the chemical inertness is strong, and the conversion efficiency of the photocatalytic reaction is not high. Most of the products still have a production rate of mu mol gcat -1 ·h -1 The level of (A) is difficult to meet the requirement index of industrial production.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made keeping in mind the above and/or other problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of the three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst comprises the following steps,
weighing dicyandiamide and sodium chloride, dissolving in water, stirring, adding molybdate solution under the stirring condition, and stirring to obtain a mixed solution;
freezing the mixed solution, freezing and drying after the mixed solution is frozen into solid, putting the dried product into a tubular furnace for calcining and cooling to obtain a calcined sample;
grinding, washing, suction filtering and drying the calcined sample to obtain MoO 3-x Modified honeycombs g-C 3 N 4 And (4) compounding the samples.
As a preferable embodiment of the production method of the present invention, wherein: the molar ratio of dicyandiamide to sodium chloride is 1.
As a preferable embodiment of the production method of the present invention, wherein: the molybdate is one or two of ammonium molybdate and sodium molybdate.
As a preferable embodiment of the production method of the present invention, wherein: the molybdate solution is 1% by mass.
As a preferable embodiment of the production method of the present invention, wherein: the freeze drying is carried out at the drying temperature of-10 to 0 ℃ for 24 to 48 hours.
As a preferable embodiment of the production method of the present invention, wherein: the calcination is carried out at the temperature of 1-4 ℃/min from room temperature to 550-600 ℃, the temperature is kept for 4-8 h, and the calcination atmosphere range is 99% nitrogen.
As a preferable embodiment of the production method of the present invention, wherein: and the temperature is reduced, wherein the temperature reduction rate is 10 ℃/h.
As a preferable embodiment of the production method of the present invention, wherein: the MoO 3-x Modified honeycombs g-C 3 N 4 Composite sample of molybdenum with g-C 3 N 4 The mass ratio of (A) to (B) is 0.1-5%: 1.
it is a further object of the present invention to overcome the deficiencies of the prior art and to provide a product prepared by the method for preparing a three-dimensional cellular graphite phase carbon nitride composite photo-thermal catalyst.
The invention also aims to overcome the defects in the prior art and provide the three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst for photo-thermal catalytic reduction of CO 2 The use of (1).
The invention has the beneficial effects that:
the invention provides a preparation method of a three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst, which is simple and feasible, the preparation conditions are easy to control, and the prepared oxygen defect MoO 3-x Modified honeycomb g-C 3 N 4 The composite photocatalyst has better photo-thermal catalysis CO 2 And (4) performing active reduction.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows the blocks g-C obtained in examples 2 to 3 of the present invention 3 N 4 Honeycomb g-C 3 N 4 And oxygen deficient MoO 3-x Modified honeycombs g-C 3 N 4 An X-ray diffraction pattern of the composite catalyst;
FIG. 2 shows the oxygen deficient MoO prepared in example 3 of the present invention 3-x Modified honeycombs g-C 3 N 4 Scanning electron microscope images of the composite catalyst;
FIG. 3 oxygen deficient MoO prepared according to example 3 of the invention 3-x Modified honeycombs g-C 3 N 4 Transmission electron micrographs of the composite catalyst;
FIG. 4 shows the blocks g-C obtained in examples 1 to 3 of the present invention 3 N 4 Honeycomb g-C 3 N 4 And oxygen deficient MoO 3-x Modified honeycombs g-C 3 N 4 Photo-thermal catalysis of CO by composite catalyst 2 And (5) reducing the effect graph.
FIG. 5 shows the blocks g-C obtained in examples 1 to 3 of the present invention 3 N 4 Honeycomb g-C 3 N 4 And oxygen deficient MoO 3-x Modified honeycombs g-C 3 N 4 Surface temperature of photo-thermal catalystFigure (a).
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Synthesis of Block g-C 3 N 4 (DCN)：
Block shape g-C 3 N 4 Preparation of (DCN): weighing 5g of dicyandiamide and placing the dicyandiamide in a crucible with a cover, then placing the crucible with the cover in the middle of a muffle furnace, heating to 550 ℃ at a heating rate of 2 ℃/min, keeping the temperature of 550 ℃ for 4 hours, taking out a yellow sample in the crucible after calcining, and grinding the yellow sample until the yellow sample has no granular sensation.
Example 2
Synthesis of cellular g-C 3 N 4 (NCN)：
Honeycomb g-C modified by template method 3 N 4 Preparation of (NCN):
dicyandiamide (1.26 g) and sodium chloride (8.77 g) are weighed and dissolved in 100mL of deionized water, the mixture is stirred in a 150mL beaker for 12 hours, then the mixed solution is poured into a glass culture dish and is put into a refrigerator for freezing for 12 hours, and liquid nitrogen is poured for freeze drying for 48 hours after the mixed solution is frozen into a solid.
After freeze drying, lightly grinding, loading into a porcelain boat, placing into a tube furnace, introducing nitrogen, heating to 550 ℃ at a heating rate of 2 ℃/min, preserving heat at 550 ℃ for 4 hours, and then naturally cooling.
Taking out the calcined sample, grinding, stirring with 500ml deionized water, washing, and performing suction filtration for 4-5 times, then placing the sample obtained after the suction filtration for several times into a glass culture dish, and placing the glass culture dish into a vacuum drying oven to dry for 12 hours at 60 ℃.
Example 3
The synthesis of oxygen deficient MoO was carried out as follows 3-x Modified honeycombs g-C 3 N 4 Composite catalyst (MNCN):
dicyandiamide (1.26 g) and sodium chloride (8.77 g) are weighed and dissolved in 100mL of deionized water, the mixture is stirred in a 150mL beaker until the solid is completely dissolved, 1mL of ammonium molybdate aqueous solution with the mass fraction of 1% is dropped in the mixture and stirred for 12 hours, then the mixed solution is poured into a glass culture dish and put into a refrigerator for freezing for 12 hours, and liquid nitrogen is poured for freeze drying for 48 hours after the mixed solution is frozen into the solid.
Freeze drying, grinding, loading into porcelain boat, placing into tube furnace, and introducing N 2 Heating to 550 ℃ at a heating rate of 2 ℃/min, preserving heat at 550 ℃ for 4h, and then naturally cooling.
And taking out the calcined sample, grinding, stirring with 500mL of deionized water, washing, and performing suction filtration for 8-10 times, then placing the sample obtained after the suction filtration for several times into a glass culture dish, and placing the glass culture dish into a vacuum drying oven to dry for 12 hours at 60 ℃.
The bulk g-C prepared in examples 1 to 3 were each subjected to X-ray diffractometry (XRD) 3 N 4 Honeycomb of g-C 3 N 4 And oxygen deficient MoO 3-x Modified honeycombs g-C 3 N 4 The structure of the photocatalyst is characterized.
As shown in FIG. 1, the characteristic peaks of DCN appearing around 12 ℃ and 27 ℃ are assigned to g-C 3 N 4 (100) Crystal face and (002) crystal face. For the template method of preparation cellular NCN, g-C 3 N 4 The characteristic peak still exists, but the intensity is reduced to a certain extent.
After further compounding, the XRD peak spectra of the compound sample and the NCN sample are similar, which indicates that the structure of the NCN is not influenced by the existence of molybdenum. In addition, no characteristic peak of molybdenum species was detected in the composite sample, which may be related to a lower content and a more uniform dispersion of molybdenum. The morphology of the MNCN catalyst of example 3 was observed using a japanese model JSM-6360A scanning electron microscope.
As shown in fig. 2, the MNCN catalyst prepared in this embodiment has a honeycomb-like shape with a clearly staggered tube structure, and the corresponding element energy spectrum further detects the presence of C, N, O, mo and Na elements in the composite sample. MoO can be seen from FIG. 3 in a transmission electron microscope 3-x The nanoparticles are attached to the surface of the cellular NCN.
Photo-thermal catalysis of CO 2 Performance evaluation: the blocks g-C prepared in examples 1-3 were put into 3 N 4 Honeycomb of g-C 3 N 4 And oxygen deficient MoO 3-x Modified honeycombs g-C 3 N 4 Reduction of CO as a catalyst 2 。
20mg of catalyst was added to 2mL of the aqueous solution and uniformly dispersed by sonication. And pouring deionized water into the glass reactor, placing a beaker with the volume of 25mL, inverting a crucible cover wrapped with tin foil paper on the beaker, pouring the sample on the tin foil paper after ultrasonic dispersion, and placing the sample in an oven for drying. Photo-thermal catalysis of CO by using 300W xenon lamp as light source 2 And (4) carrying out reduction reaction.
The reaction time is 4h, after illumination, samples are taken from the glass reactor for 4 times at 1h,2h,3h and 4h in sequence, and the injection amount is 500 mu L each time.
As shown in FIG. 4, the MNCN complex sample has a CO yield of 25 mu mol/g/h. The yield was 1.9 times that of NCN.
The surface temperatures of the catalysts DCN, NCN and MNCN were detected by infrared imaging technique, as shown in fig. 5, under the same xenon lamp irradiation conditions, the MNCN rose to the highest temperature and the surface temperature reached 63.8 ℃.
Example 4
After 1.26g of dicyandiamide is freeze-dried, calcined and filtered, the yield is 0.63g, and 1.26g is g-C 3 N 4 Theoretical value, to reduce error, from formula m Mo /(m M0 +m g-C3N4 ) =1% calculated, preparing 1.16% ammonium molybdate aqueous solution by mass fraction, adding 1ml solution, namely m Mo =0.0063g, mass fraction of Mo obtained is 1%.
After 1.26g of dicyandiamide is freeze-dried, calcined and filtered, the yield is 0.63g, and 1.26g is g-C 3 N 4 Theoretical value, to reduce error, from formula m Mo /(m Mo +m g-C3N4 ) =1% calculated, preparing 1.16% ammonium molybdate aqueous solution by mass fraction, adding 0.5-2.0ml solution, namely m Mo And (4) 0.00315-0.0126g, wherein the mass fraction of the obtained Mo is 0.5-2.0%.
In-situ photothermal catalysis of CO 2 In the reduction of CO (same as example 3), the results are:
the yield of MNCN with the mass fraction of Mo being 1% is the highest, and is 25.35 mu mol/g/h;
the yield of MNCN, where the mass fraction of Mo is 2%, is 24.23. Mu. Mol/g/h, slightly less than 1% MNCN;
the yield of Mo at 0.5% by mass was 22.16. Mu. Mol/g/h, which was slightly less than 2% MNCN.
(Explanation: m) Mo Represents the mass of molybdenum, m g-C3N4 Denotes g-C 3 N 4 Quality of (2)
The invention adopts a sodium chloride template method to increase the surface area, and simultaneously, the introduced sodium ions can be used as electron donors, g-C 3 N 4 Cyano groups generated by polymerization are used as electron-withdrawing bodies to form an internal electron-withdrawing system, so that the dissociation of carriers is promoted, and the catalytic activity is improved. The cocatalyst can effectively promote the separation of photon-generated carriers in the reaction process, and the transition metal oxide serving as a hole capture site can effectively inhibit the rapid recombination of holes and electrons.
Molybdenum oxide (MoO) containing oxygen defects 3-x ) Modified g-C 3 N 4 The recombination of carriers can be suppressed as a driving force for accelerating the charge separation. At the same time, moO 3 By generating oxygen vacancy defects in Vis and NIR bands, a localized plasmon resonance (LSPR) with similar noble metals can be generated, and a semiconductor with unique photocatalysis and photo-thermal characteristics is obtained. MoO 3-x The photo-thermal conversion characteristic can effectively convert the light energy into the heat energy, so that the photo-thermal conversion characteristic can be used as a nano heater to realize the self-heating of a composite system, therebyThe temperature is increased, the cost is saved, and the synergistic catalysis of the temperature field and the optical field is realized.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
weighing dicyandiamide and sodium chloride, dissolving in water, stirring, adding a molybdate solution under the stirring condition, and stirring to prepare a mixed solution;
freezing the mixed solution, freezing and drying after the mixed solution is frozen into solid, putting the dried product into a tubular furnace for calcining and cooling to obtain a calcined sample;
grinding, washing, suction filtering and drying the calcined sample to obtain MoO 3-x Modified honeycombs g-C 3 N 4 And (4) compounding the samples.
2. The method for preparing the three-dimensional honeycomb graphite-phase carbon nitride composite photo-thermal catalyst according to claim 1, wherein the method comprises the following steps: the molar ratio of dicyandiamide to sodium chloride is 1.
3. The method for preparing the three-dimensional honeycomb-shaped graphite-phase carbon nitride composite photo-thermal catalyst according to claim 1 or 2, wherein: the molybdate is one or two of ammonium molybdate and sodium molybdate.
4. The method for preparing the three-dimensional honeycomb-shaped graphite-phase carbon nitride composite photo-thermal catalyst according to claim 3, wherein the method comprises the following steps: the molybdate solution is 1% by mass.
5. The method for preparing the three-dimensional honeycomb-shaped graphite-phase carbon nitride composite photo-thermal catalyst according to claim 4, wherein the method comprises the following steps: the freeze drying is carried out at the drying temperature of-10 to 0 ℃ for 24 to 48 hours.
6. The method for preparing the three-dimensional honeycomb-shaped graphite-phase carbon nitride composite photo-thermal catalyst according to claim 5, wherein the method comprises the following steps: the calcination is carried out at the temperature of 1-4 ℃/min from room temperature to 550-600 ℃, the temperature is kept for 4-8 h, and the calcination atmosphere range is 99% nitrogen.
7. The method for preparing the three-dimensional honeycomb-shaped graphite-phase carbon nitride composite photo-thermal catalyst according to claim 6, wherein the method comprises the following steps: and the temperature is reduced at a rate of 10 ℃/h.
8. The method for preparing the three-dimensional honeycomb graphite phase carbon nitride composite photo-thermal catalyst according to any one of claims 1, 2 and 4 to 7, wherein the method comprises the following steps: the MoO 3-x Modified honeycombs g-C 3 N 4 Composite sample of molybdenum with g-C 3 N 4 0.1-5% by mass: 1.
9. the three-dimensional honeycomb graphite phase carbon nitride composite photothermal catalyst prepared by the preparation method of any one of claims 1 to 8.
10. The three-dimensional honeycomb graphite-phase carbon nitride composite photo-thermal catalyst of claim 9 for photo-thermal catalytic reduction of CO 2 The use of (1).
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