CN113275029A - Heterojunction catalyst for photocatalytic coenzyme regeneration and preparation method thereof - Google Patents
Heterojunction catalyst for photocatalytic coenzyme regeneration and preparation method thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention discloses a heterojunction catalyst for photocatalytic coenzyme regeneration, which consists of three components, namely melamine, titanium dioxide (P25) and tannic acid, wherein the mass ratio of the three components is 100: 10: (1-20). The coating of polyphenol-P25 grows on the surface of melamine by utilizing the interface self-assembly action of polyphenol substances, and then the pre-assembled substances are calcined by utilizing a calcination method according to a certain program to obtain the photocatalyst g-C3N4@ C-P25. The pre-assembly of the surface polyphenol coating creates more heterojunction interfaces, and the C group converted by polyphenol promotes the heterojunction interfacesThe method has mild conditions and simple process, and regulates and controls the addition of the tannic acid, and selects a proper amount of the tannic acid to reduce the aggregation of P25 particles on the surface and increase the light absorption efficiency, thereby improving the regeneration performance of the photocatalytic coenzyme.
Description
Technical Field
The invention relates to photocatalyst preparation, in particular to a heterojunction catalyst for photocatalytic coenzyme regeneration and a preparation method thereof.
Background
The enzyme catalysis has the advantages of high activity, high efficiency, mild reaction conditions and the like, and is widely applied to the field of chemical synthesis. The oxidoreductase accounts for 25% of all enzyme types, and has a great application potential in the field of chiral medicine and fine chemical synthesis, redox equivalents are required to participate in electron transfer in the process of participating in catalytic reaction, the most common redox equivalents in the nature are NAD (P) H, about 80% of redox reactions require the participation of coenzyme NAD (P) H to complete catalytic reaction, and then the coenzyme factors are expensive, and the method for regenerating the photocatalytic coenzyme is green and efficient, and can realize the efficient regeneration of the coenzyme. In the process of regenerating the photocatalytic coenzyme, the method is mainly divided into three parts, namely light absorption, electron transfer and interface reaction. The problem difficult to solve is the transmission and utilization of electrons, electrons and holes generated under the excitation of light are separated, and the electrons can complete NAD on the active sites on the surface of the catalyst+But the electrons cannot be transferred to the active site for utilization due to the rapid recombination of electron holes. Designing a heterojunction is a simple and effective way to improve the charge separation of a photocatalyst, and by combining two semiconductors with different band structures, a photo-generated electron hole can be independently transferred to a more energetically favorable position, more precisely, a more negative valence band position correction of the conduction band position. The polyphenol is self-assembled on the surface of the material to form a coating to construct a heterostructure, and the amount of the polyphenol is regulated and controlled, so that the structure of the photocatalyst is regulated and controlled.
The construction of P25 coating on melamine is completed on the surface by utilizing the interfacial self-assembly effect of polyphenol, and g-C is obtained by a calcination method3N4@ C-P25 photocatalyst. Wherein the C group in the catalyst is in g-C3N4Plays an important role with P25, and effectively promotes electron transmissionAnd the regeneration performance of the coenzyme is improved.
Disclosure of Invention
The invention aims to provide a heterojunction catalyst for photocatalytic coenzyme regeneration and a preparation method thereof. The preparation raw materials are cheap and easy to obtain, and the preparation process is simple and easy to implement.
In order to achieve the purpose, the heterojunction catalyst for regenerating the photocatalytic coenzyme provided by the invention comprises three components, namely melamine, titanium dioxide (P25) and Tannic Acid (TA), wherein the mass ratio of the three components is 100: 10: (1-20).
The heterojunction catalyst was prepared as follows:
step one, mixing melamine and titanium dioxide particles in a container according to the mass ratio of 10:1, and adding deionized water to obtain a suspension, wherein the mass volume ratio of the mixture to the deionized water is 110mg ml-1Carrying out ultrasonic dispersion on the suspension; then placing the dispersed suspension on a magnetic stirrer for stirring;
step two, in the stirring process, quickly adjusting the concentration to 4-80 mg ml-1Adding the aqueous solution of Tannic Acid (TA), a common polyphenol, into the suspension, wherein the mass ratio of tannic acid to melamine is (1-20): 100, when the color of the suspension liquid is changed from white to orange, continuously stirring for 5-10 min; then centrifugally washing and collecting particles (named as melamine @ polyphenenol-P25 in the invention), treating the collected particles with liquid nitrogen, freeze-drying, and grinding into powder;
thirdly, placing the powder in a crucible, sealing the crucible by using tin foil paper, and then placing the crucible in a muffle furnace for calcining to obtain a product, namely the heterojunction catalyst3N4@C-P25。
Further, in the step one, the suspension is placed in an ultrasonic cleaning machine with the ultrasonic frequency of 30-50 kHz for ultrasonic treatment for 20-30 min in the ultrasonic dispersion process; the stirring speed ranges from 700 r/min to 900r/min, and the stirring time is 1 min to 3 min.
In the second step, the mass ratio of tannic acid to melamine is preferably 1: 20; the freeze-drying process of the particles treated with liquid nitrogen is as follows: placing in a freeze dryer at-40 deg.C for 10-12 hr.
In the third step, the calcining process conditions are as follows: firstly firing at 300 ℃ for 1 hour, then firing at 400 ℃ for 1 hour, and finally firing at 500 ℃ for 4 hours, wherein the heating rate of the heating process is 5 ℃/min.
Compared with the prior art, the preparation method of the heterojunction catalyst for photocatalytic coenzyme regeneration provided by the invention has the advantages that the coating of polyphenol-P25 grows on the surface of melamine by utilizing the interface self-assembly action of polyphenol substances, and then the pre-assembled substance is calcined according to a certain program by utilizing a calcination method to obtain the photocatalyst g-C3N4@ C-P25. According to the invention, more heterojunction interfaces are created by pre-assembling the surface polyphenol coating, the transfer process of electrons of the heterojunction interfaces is promoted by C groups converted by polyphenol, so that the regeneration efficiency of the photocatalytic coenzyme is obviously improved. g-C existing in the prior art3N4Compared with the technology of regenerating the photocatalytic coenzyme, the photocatalyst g-C prepared in the invention3N4The @ C-P25 has obvious improvement on the performance of coenzyme regeneration.
Drawings
FIG. 1 is a TEM photograph of a melamine @ polyphenol-P25 precursor obtained during the preparation process of the present invention;
FIG. 2 shows g-C prepared in example 1 of the present invention3N4TEM photographs of @ C-P25;
FIG. 3 is g-C3N4，P25，g-C3N4-P25，g-C3N4-C-P25，g-C3N4A graph of the photocatalytic NADH regeneration performance of @ C-P25;
FIG. 4 shows g-C prepared in examples 1-4 of the present invention3N4Photocatalytic N of @ C-P25-XADH regeneration performance map.
Detailed Description
The design idea of the invention is as follows: modifying the surface of the carbon nitride material by utilizing the self-assembly of polyphenol to construct a P25 coating to form g-C3N4The heterostructure of @ C-P25. Wherein polyphenol (tannin TA) contains abundant phenolic hydroxyl, self-polymerization of polyphenol is utilized to form a coating on the surface of melamine, P25 particles are bonded in a bionic manner, and photocatalyst g-C is formed by a calcining method3N4@ C-P25; the product g-C finally obtained3N4In the @ C-P25, the mass ratio of melamine to titanium dioxide (P25) to Tannic Acid (TA) is 100: 10: (1-20).
The technical solutions of the present invention are further described in detail with reference to the accompanying drawings and specific embodiments, which are only illustrative of the present invention and are not intended to limit the present invention.
Comparative example 1: photocatalyst g-C3N4-preparation of P25 by the following steps:
step one, mixing 1g of melamine and 100mg of P25 in a mortar and grinding until a uniform powder is formed;
step two, calcining the powder obtained in the step one by the following calcining procedure:
firstly firing at 300 ℃ for 1 hour, then firing at 400 ℃ for 1 hour, and finally firing at 500 ℃ for 4 hours, wherein the heating rate in the heating process is 5 ℃/min, and the finally obtained product is the photocatalyst g-C3N4-P25。
The photocatalyst g-C shown in FIG. 33N4NADH regeneration performance of P25.
Comparative example 2: photocatalyst g-C3N4-preparation of C-P25 by the following steps:
step one, mixing 1g of melamine, 100mg of P25 and 50mg of TA into uniform powder;
step two, calcining the powder obtained in the step one by the same calcining procedure as the comparative example 1 to finally obtain the photocatalyst g-C3N4-C-P25。
The photocatalyst g-C shown in FIG. 33N4NADH regeneration performance of C-P25.
Example 1: photocatalyst g-C3N4The preparation method of @ C-P25-50 comprises the following steps:
step one, mixing 1g of melamine and 100mg of P25 in a 25ml beaker, then adding 10ml of deionized water, and placing the obtained suspension in an ultrasonic cleaning machine with ultrasonic frequency of 40kHz for ultrasonic treatment for 20 min; then the dispersed suspension is placed on a magnetic stirrer, the stirring speed is 800r/min, and the stirring time is 3 min.
Step two, in the stirring process, rapidly adding 2.5ml with the concentration of 20mg ml-1Adding the tannic acid aqueous solution into the suspension, stirring for 5min when the solution turns from white to orange, centrifuging and washing for 2 times, collecting the granules (melamine @ polyphenol-P25), freeze-drying the granules in a freeze-drying machine for 12 hr at-40 deg.C for one night, and grinding the freeze-dried granules into powder (g-C)3N4@ C-P25, FIG. 3 shows this g-C3N4@ C-P25NADH regeneration performance.
Step three, placing the powder into a crucible, sealing the crucible by using tin foil paper, and then placing the crucible into a muffle furnace for calcining, wherein the calcining process conditions are as follows: firstly firing at 300 ℃ for 1 hour, then firing at 400 ℃ for 1 hour, and finally firing at 500 ℃ for 4 hours, wherein the heating rate in the heating process is 5 ℃/min, and the final product is the photocatalyst g-C3N4@ C-P25-50 (named g-C because the amount of TA added in the preparation process is 50 mg)3N4@C-P25-50)。
FIG. 1 is a TEM image of a pre-calcined melamine @ polyphenenol-P25 precursor in the preparation of example 1, and FIG. 2 is a g-C obtained in the preparation of example 13N4TEM image of @ C-P25, from which g-C can be seen3N4Successful preparation of @ C-P25, where P25 is uniformly distributed in g-C3N4In (1).
This embodiment 1 is shown in FIG. 4Preparation of the resulting photocatalyst g-C3N4The photocatalytic coenzyme regeneration performance of @ C-P25-50 was 68.5%.
Example 2: photocatalyst g-C3N4The preparation of @ C-P25-10, example 2, was essentially the same as example 1 except that: the concentration of tannic acid in step two of example 1 was adjusted from 20mg ml-1Changed to 4mg ml-1That is, the amount of TA added in the preparation process is 10mg, and the final product prepared is the photocatalyst g-C3N4@C-P25-10。
FIG. 4 shows the photocatalysts g-C prepared in example 23N4The photocatalytic coenzyme regeneration performance of @ C-P25-10 was about 57%.
Example 3: photocatalyst g-C3N4The preparation of @ C-P25-100, example 3, was essentially the same as example 1 except that: the concentration of tannic acid in step two of example 1 was adjusted from 20mg ml-1Changed to 40mg ml-1Namely, the amount of TA added in the preparation process is 100mg, and the finally prepared product is the photocatalyst g-C3N4@C-P25-100。
In FIG. 4, g-C can be seen3N4The photocatalytic coenzyme regeneration performance of @ C-P25-100 is about 57%.
Example 4: photocatalyst g-C3N4The preparation of @ C-P25-200, example 4, was essentially the same as example 1 except that: the concentration of tannic acid in step two of example 1 was adjusted from 20mg ml-1Changed to 80mg ml-1That is, the amount of TA added in the preparation process is 200mg, and the final product prepared is g-C3N4@C-P25-200。
In FIG. 4, g-C can be seen3N4The photocatalytic coenzyme regeneration performance of @ C-P25-200 is about 56%.
It can be seen from the graph of NADH regeneration performance shown in FIG. 3 that: photocatalyst g-C3N4-P25 and g-C3N4The photocatalytic reaction activity of-C-P25 is lower than that of g-C3N4@ C-P25.
From the photocatalytic NADH regeneration performance diagram shown in FIG. 4, it can be seen that: in the invention, the design of the catalyst is carried out by regulating and controlling the addition amount of TA, and the addition amounts of TA relative to 1000mg of melamine in examples 1-4 are respectively 10, 50, 100 and 200mg, wherein the photocatalyst g-C prepared in the examples3N4The photocatalytic coenzyme regeneration performance of @ C-P25-50 is optimal.
In conclusion, according to the TEM image corresponding to example 1 and the coenzyme regeneration performance images corresponding to the above examples 1-4 and comparative examples 1-2, it is found that P25 is coated on the surface of melamine by biomimetic adhesion through the self-polymerization of polyphenol, and finally, the photocatalyst g-C is obtained by calcination3N4@ C-P25 (series). Wherein the C group is in g-C3N4And P25, the catalyst is designed by regulating the addition amount of TA (the mass ratio of TA to melamine is (1-20): 100), and the NADH regeneration performance test is carried out on the catalyst, and the highest performance can be seen in the conditions of adding 50mg of TA (namely the mass ratio of TA to melamine is 1:20) in figures 3 and 4. g-C when small amounts of C groups are introduced3N4The interface between the P25 nanoparticle and the P25 can not be completely covered by C groups, so that the improvement of the electron transfer efficiency is not high, when the amount of TA is increased to 50mg, the C in the prepared catalyst is sufficiently coordinated with all P25 nanoparticles, the electron transfer between the electron and the P25 interface is ensured, and if the amount of TA is further increased, the self-polymerization is caused to influence the light absorption effect, and the improvement of the NADH regeneration efficiency is not facilitated. Therefore, the invention utilizes the bionic adhesion of polyphenol to carry out the design of the heterojunction catalyst, the preparation process is simple, the structure of the catalyst is regulated and controlled by changing the adding amount of TA, the successful preparation of the catalyst is finally proved by a TEM image, and the NADH regeneration efficiency obtained by a performance diagram is nearly 70 percent.
Claims (7)
1. A heterojunction catalyst for photocatalytic coenzyme regeneration is characterized by comprising three components of melamine, titanium dioxide and tannic acid, wherein the mass ratio of the three components is 100: 10: (1-20).
2. A method of preparing a heterojunction catalyst as claimed in claim 1, comprising the steps of:
step one, mixing melamine and titanium dioxide particles in a container according to the mass ratio of 10:1, and adding deionized water to obtain a suspension, wherein the mass volume ratio of the mixture to the deionized water is 110mg ml-1Carrying out ultrasonic dispersion on the suspension; then placing the dispersed suspension on a magnetic stirrer for stirring;
step two, in the stirring process, quickly adjusting the concentration to 4-80 mg ml-1Adding the tannic acid aqueous solution into the suspension, wherein the mass ratio of tannic acid to melamine is (1-20): 100, when the color of the suspension liquid is changed from white to orange, continuously stirring for 5-10 min; then centrifugally washing and collecting particles, treating the collected particles with liquid nitrogen, freeze-drying, and grinding into powder;
and step three, placing the powder in a crucible, sealing the crucible by using tin foil paper, and then placing the crucible in a muffle furnace for calcining to obtain a product, namely the heterojunction catalyst.
3. The preparation method of the heterojunction catalyst according to claim 2, wherein in the step one, the ultrasonic dispersion process is to place the suspension in an ultrasonic cleaner with an ultrasonic frequency of 30 to 50kHz for ultrasonic treatment for 20 to 30 min.
4. The preparation method of the heterojunction catalyst according to claim 2, wherein in the first step, the stirring speed ranges from 700 r/min to 900r/min, and the stirring time is 1 min to 3 min.
5. The method for preparing a heterojunction catalyst according to claim 2, wherein in the second step, the mass ratio of tannic acid to melamine is 1: 20.
6. the method for preparing a heterojunction catalyst according to claim 2, wherein in the second step, the freeze-drying process of the particles treated with liquid nitrogen comprises: placing in a freeze dryer at-40 deg.C for 10-12 hr.
7. The method for preparing a heterojunction catalyst according to claim 2, wherein in the third step, the calcination process conditions are as follows: firstly firing at 300 ℃ for 1 hour, then firing at 400 ℃ for 1 hour, and finally firing at 500 ℃ for 4 hours, wherein the heating rate of the heating process is 5 ℃/min.
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