CN111185212B - Double-function catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen and preparation method and application thereof - Google Patents
Double-function catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen and preparation method and application thereof Download PDFInfo
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- CN111185212B CN111185212B CN201911373161.4A CN201911373161A CN111185212B CN 111185212 B CN111185212 B CN 111185212B CN 201911373161 A CN201911373161 A CN 201911373161A CN 111185212 B CN111185212 B CN 111185212B
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- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 229940120503 dihydroxyacetone Drugs 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 14
- 238000005984 hydrogenation reaction Methods 0.000 title description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 53
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 17
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 5
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 5
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims abstract description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 5
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims abstract description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 18
- 239000006227 byproduct Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003225 biodiesel Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 238000012719 thermal polymerization Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- -1 pharmacy Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 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
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a bifunctional catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen, and a preparation method and application thereof, wherein the catalyst is oxygen-doped graphite-phase carbon nitride, wherein an oxygen-doped source is at least one of ammonium acetate, ammonium formate and ammonium oxalate, and a carbon nitride precursor is at least one of urea, cyanamide, dicyandiamide, melamine and thiourea; the mass ratio of the oxygen doping source to the carbon nitride precursor is 1-10. Compared with the prior art, the invention has the following advantages: (1) the bifunctional catalyst has good selectivity; (2) The bifunctional catalyst is mild in reaction condition, and provides a green route for high-added-value utilization of glycerol; (3) The preparation method of the bifunctional catalyst is simple and efficient.
Description
Technical Field
The invention belongs to the technical field of energy recycling, and relates to a method for synthesizing dihydroxyacetone and hydrogen through photocatalysis, in particular to a bifunctional catalyst for synthesizing dihydroxyacetone and hydrogen through photocatalysis, and a preparation method and application thereof.
Background
As a green energy source with wide application prospect, the biodiesel is widely concerned and researched by people, and 1 ton of glycerin can be produced as a byproduct every 9 tons of biodiesel are produced. With the development of the biodiesel industry, the utilization of the byproduct glycerol becomes an urgent problem to be solved. The method is an important solution for changing the cheap glycerol into a high-valued chemical product.
The dihydroxyacetone has high added value, so that the dihydroxyacetone becomes a research hotspot for high-value utilization of the glycerol. Dihydroxyacetone is the simplest polyhydroxyketose, is very soluble in various solvents such as water, ether, ethanol, acetone and the like, can synthesize various organic compounds due to more functional groups and very active chemical properties, and is a very valuable chemical intermediate. The dihydroxyacetone can be used as a food additive, an antistaling agent, a leather product protective agent, an antiviral agent, a formula raw material of cosmetics and the like, is widely applied to industries of food, leather, pharmacy, cosmetics and the like, and has larger market demand.
Graphite-like phase carbon nitride (g-C) 3 N 4 ) As a typical polymer semiconductor, the compound has very suitable semiconductor band edge positions, not only meets the thermodynamic requirements of hydrogen production and oxygen production by photolysis of water, but also can effectively activate molecular oxygen to generate superoxide radicals for photocatalytic conversion of organic functional groups and photocatalytic degradation of organic pollutants. But generally prepared g-C 3 N 4 The photo-generated electrons and holes are easy to polymerize due to a massive sheet-shaped stacking structure, so that the photocatalysis performance of the photo-generated electrons and holes is poor. The g-C can be improved by adopting an oxygen doping mode 3 N 4 The problem of the recombination of photo-generated carriers is improved, the photocatalytic performance is enhanced, and the reaction activity is improved.
Disclosure of Invention
The technical problem to be solved is as follows: in order to overcome the defects of the prior art and obtain a catalyst which can efficiently utilize byproducts of the biodiesel industry or the soap making industry and obtain dihydroxyacetone and hydrogen with high added values under mild conditions, the invention provides a bifunctional catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen, and a preparation method and application thereof.
The technical scheme is as follows: the catalyst is oxygen-doped graphite-phase carbon nitride, wherein an oxygen-doped source is at least one of ammonium acetate, ammonium formate and ammonium oxalate, and a carbon nitride precursor is at least one of urea, cyanamide, dicyandiamide, melamine and thiourea; the mass ratio of the oxygen doping source to the carbon nitride precursor is 1-10.
The preparation method of the double-function catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen comprises the steps of physically mixing an oxygen doping source and a carbon nitride precursor, and synthesizing oxygen-doped graphite-like carbon nitride by adopting a thermal polymerization method to prepare the double-effect active site-containing photocatalyst.
Preferably, the method specifically comprises the following steps:
(1) Mixing an oxygen doping source and a carbon nitride precursor according to a mass ratio of 1-10; naturally cooling to room temperature after roasting is finished to obtain yellow solid, and grinding the yellow solid into powder;
(2) Performing secondary roasting on the powder collected in the step (1), placing the powder in an open container and placing the powder in a muffle furnace, wherein the roasting temperature is 500-600 ℃, the heating rate is 2-5 ℃/min, and the roasting time is 2-4h; and cooling the muffle furnace to room temperature to obtain the bifunctional catalyst.
The application of the double-function catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen in the reutilization of by-product glycerol.
Preferably, the application process of the bifunctional catalyst in the reuse of the byproduct glycerol is as follows:
(1) Placing a glycerol aqueous solution with the mass concentration of 5-50g/L into a reactor, adding a bifunctional catalyst with the mass of 1-10% of that of the glycerol, degassing for 20-50min by using oxygen under the condition of magnetic stirring, then reacting for 4-8h under the irradiation of a solar simulator at normal temperature and normal pressure in an oxygen atmosphere to obtain a mixture containing dihydroxyacetone, and collecting hydrogen;
(2) Filtering the mixture collected in the step (1), and continuously recycling the filtered solid catalyst; and (3) after the filtrate is subjected to rotary evaporation to remove water, standing, cooling and crystallizing to obtain a crystal, namely dihydroxyacetone.
Preferably, the by-product glycerol is derived from a by-product of the biodiesel industry or soap making industry.
The reaction principle of the bifunctional catalyst is as follows: the oxygen doping source is one or a compound of more than one of ammonium acetate, ammonium formate and ammonium oxalate, and the carbon nitride precursor is one or a compound of more than one of urea, cyanamide, dicyandiamide, melamine and thiourea; the mass ratio of the oxygen doping source to the carbon nitride precursor is 1-10. After the mixture is fully ground, the oxygen-doped graphite-like phase carbon nitride is obtained by a thermal polymerization method. In the reaction process, the surface of the catalyst absorbs light to form a photoproduction electron and a photoproduction cavity, wherein the photoproduction cavity is an oxidation end, and the photoproduction electron is a reduction end. The glycerol adsorbed on the surface of the catalyst can undergo oxidation-reduction reaction to form dihydroxyacetone as an oxidation product and hydrogen as a byproduct.
Has the advantages that: (1) the bifunctional catalyst of the invention has good selectivity; (2) The bifunctional catalyst has mild reaction conditions, and provides a green route for the reuse of the byproduct glycerol; (3) The preparation method of the bifunctional catalyst is simple and efficient.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, steps or conditions of the present invention may be made without departing from the spirit and scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
2g ammonium acetate and 20g urea were added to the mortar. After grinding for 20 minutes, the white powder obtained was transferred to a 50mL crucible, compacted, covered with a crucible lid and tightly wrapped with tinfoil. And (3) putting the crucible into a muffle furnace for roasting, wherein the heating rate is 8 ℃ per minute, the roasting temperature is 550 ℃, and the roasting time is 2 hours. After the baking, the mixture was naturally cooled to room temperature, and the yellow solid obtained in the crucible was taken out and ground into powder. And (3) carrying out secondary roasting on the obtained yellow powder: the yellow powder was transferred to a 50mL crucible and placed in a muffle furnace without covering the crucible lid. The heating rate was 5 ℃ per minute, the calcination temperature was 520 ℃ and the calcination time was 2 hours. And taking out the yellow powder in the crucible after the muffle furnace is cooled to the room temperature to obtain the bifunctional catalyst.
Example 2
1g of ammonium oxalate and 20g of urea were added to a mortar. After grinding for 15 minutes, the white powder obtained was transferred to a 50mL crucible, compacted, covered with a crucible lid and tightly wrapped with tinfoil. And (3) putting the crucible into a muffle furnace for roasting, wherein the heating rate is 5 ℃ per minute, the roasting temperature is 500 ℃, and the roasting time is 4 hours. After the baking, the mixture was naturally cooled to room temperature, and the yellow solid obtained in the crucible was taken out and ground into powder. And (3) carrying out secondary roasting on the obtained yellow powder: the yellow powder was transferred to a 50mL crucible and placed in a muffle furnace without covering the crucible lid. The heating rate is 2 ℃ per minute, the roasting temperature is 500 ℃, and the roasting time is 4 hours. And taking out the yellow powder in the crucible after the muffle furnace is cooled to the room temperature to obtain the bifunctional catalyst.
Example 3
The difference from example 1 is that: and replacing the carbon nitride precursor with cyanamide.
Example 4
The difference from example 1 is that: the carbon nitride precursor was replaced with melamine.
Example 5
The difference from example 1 is that: the carbon nitride precursor was replaced with thiourea.
Example 6
The difference from example 2 is that: the carbon nitride precursor is replaced by cyanamide.
Example 7
The difference from example 2 is that: the carbon nitride precursor was replaced with thiourea.
Example 8
10mL of an aqueous glycerol solution (20 g/L) was added to the reactor, followed by 2% by mass of the bifunctional catalyst based on the total mass of the reactants. Degassing with oxygen under magnetic stirring for 30min, reacting under irradiation of a sunlight simulator at normal temperature and normal pressure in oxygen atmosphere for 8h to obtain a mixture containing high value-added glycerol derivatives (dihydroxyacetone), and collecting by-product hydrogen. The obtained reaction properties are shown in Table 1, using the dihydroxyacetone selectivity and the amount of hydrogen produced as indices.
TABLE 1 reaction results for the Synthesis of dihydroxyacetone and Hydrogen gas with bifunctional catalyst
Claims (5)
1. The application of the bifunctional catalyst for photocatalytic synthesis of dihydroxyacetone and hydrogen in catalyzing glycerol to generate dihydroxyacetone is characterized in that the catalyst is oxygen-doped graphite-phase carbon nitride, wherein an oxygen doping source is at least one of ammonium acetate, ammonium formate and ammonium oxalate, and a carbon nitride precursor is at least one of urea, cyanamide, dicyandiamide, melamine and thiourea; the mass ratio of the oxygen doping source to the carbon nitride precursor is 1-10.
2. The use according to claim 1, wherein the catalyst is prepared by a process comprising: and physically mixing the oxygen doping source and the carbon nitride precursor, and synthesizing the oxygen doping graphite-like phase carbon nitride by adopting a thermal polymerization method to prepare the photocatalyst containing the double-effect active sites.
3. The use according to claim 2, characterized in that the preparation method of the catalyst comprises in particular the following steps:
(1) Mixing an oxygen doping source and a carbon nitride precursor according to a mass ratio of 1-10; naturally cooling to room temperature after roasting is finished to obtain yellow solid, and grinding the yellow solid into powder;
(2) Carrying out secondary roasting on the powder collected in the step (1), placing the powder in an open container and placing the powder in a muffle furnace, wherein the roasting temperature is 500-600 ℃, the heating rate is 2-5 ℃/min, and the roasting time is 2-4h; and cooling the muffle furnace to room temperature to obtain the bifunctional catalyst.
4. The use of claim 1, wherein the bifunctional catalyst is used for catalyzing glycerol to dihydroxyacetone as follows:
(1) Placing a glycerol aqueous solution with the mass concentration of 5-50g/L into a reactor, adding a bifunctional catalyst with the mass of 1-10% of that of the glycerol, degassing for 20-50min by using oxygen under the condition of magnetic stirring, then reacting for 4-8h under the irradiation of a solar simulator at normal temperature and normal pressure in an oxygen atmosphere to obtain a mixture containing dihydroxyacetone, and collecting hydrogen;
(2) Filtering the mixture collected in the step (1), and continuously recycling the filtered solid catalyst; and (3) after the filtrate is subjected to rotary evaporation to remove water, standing, cooling and crystallizing to obtain a crystal, namely dihydroxyacetone.
5. Use according to claim 3 or 4, characterized in that the glycerol is derived from a by-product of the biodiesel industry or soap manufacturing industry.
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| CN111545239B (en) * | 2020-05-29 | 2021-06-25 | 江南大学 | Solid catalyst for glycerol oxidation and preparation method thereof |
| CN111889130B (en) * | 2020-07-30 | 2022-12-13 | 大连工业大学 | Preparation of modified carbon nitride photocatalyst and application of modified carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of glucose |
| CN112094190B (en) * | 2020-09-28 | 2021-06-25 | 江南大学 | Method for preparing ester by photocatalytic oxidation esterification of glycerol |
| CN115043455A (en) * | 2022-06-16 | 2022-09-13 | 河海大学 | Ballast water sterilization method by coupling photocatalysis with persulfate |
| CN115518666A (en) * | 2022-09-20 | 2022-12-27 | 江苏大学 | Preparation method and application of ammonium formate modified coral-shaped wide-spectral-response carbon-nitrogen polymer photocatalyst |
| CN115739154B (en) * | 2022-11-16 | 2024-02-02 | 山东科技大学 | Carbon nitride nanomaterial with three-coordination nitrogen vacancies and preparation method and application thereof |
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