CN113908873B - Method for selectively oxidizing glucose by photocatalysis of carbon nitride-based photocatalyst - Google Patents
Method for selectively oxidizing glucose by photocatalysis of carbon nitride-based photocatalyst Download PDFInfo
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 79
- 239000008103 glucose Substances 0.000 title claims abstract description 79
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 51
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- DSLZVSRJTYRBFB-LLEIAEIESA-N D-glucaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O DSLZVSRJTYRBFB-LLEIAEIESA-N 0.000 claims description 9
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 9
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- 239000003929 acidic solution Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 5
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- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002904 solvent Substances 0.000 claims description 4
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
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- 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
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- 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
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C07H3/02—Monosaccharides
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Abstract
The invention belongs to the field of photocatalysis and biomass-based chemicals, and discloses a method for obtaining chemicals with high added value by utilizing the photocatalysis and selective oxidation of glucose by using a composite photocatalyst Ce6@BNCN.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for preparing high-added-value chemicals by photocatalytic oxidation of glucose, which takes Ce6@BNCN as a photocatalyst and hydrogen peroxide as an oxidant.
Background
Biomass is a renewable resource widely distributed on earth and can be used as an effective substitute for fossil energy to produce chemicals with high added value. Glucose is a sugar monomer that can be obtained from biomass through a series of pretreatment processes. Gluconic acid and glucaric acid are two major oxidation products of glucose. The glucaric acid is one of 12 'most valuable biorefinery products', can be used as raw materials to synthesize a plurality of high-value products, and has great potential economic value. Currently, gluconic acid is produced by enzymatic oxidation of glucose, and the production of glucaric acid mainly uses nitric acid or a bleaching agent to oxidize glucose. However, there are significant obstacles to the practical use of these methods: for example, biochemical processes have problems of slow reaction speed and difficulty in separation of free enzymes, and chemical methods generate toxic products, resulting in secondary pollution.
The photocatalytic selective oxidation technology has the advantage of mild reaction conditions and is receiving more and more attention. Polymer semiconductor graphite phase carbon nitride (g-C) 3 N 4 ) Because of the unique semiconductor energy band structure and excellent chemical stability, the catalyst is introduced into the field of photocatalysis as a visible light catalyst without metal components, is used for producing hydrogen and oxygen by photolysis water, photocatalytic organic selective synthesis, photocatalytic degradation of organic pollutants and the like,and is attracting attention. Due to g-C 3 N 4 The method is not only cheap and stable, meets the basic requirements of people on the photocatalyst, but also has the characteristics of easy regulation and control of the chemical composition and energy band structure of the polymer semiconductor, and the like, and is considered to be one of the research directions of the photocatalytic material research field and deserves deep exploration. However, in the case of water as solvent, obtaining the desired highly selective oxidation product remains a great challenge. Although heterogeneous photocatalysis provides a gentle route for glucose conversion, it is still very difficult to control the selectivity of glucose oxidation at the C1 or C1/C6 position due to the multifunctional structure of the glucose molecule. Therefore, there is an urgent need to develop a new photocatalytic system for efficiently converting glucose into gluconic acid and glucaric acid in water.
Like many other semiconductor photocatalysts, g-C 3 N 4 The main disadvantages of (2) are low visible light utilization efficiency and high recombination rate of photo-generated charges. In view of the above problems, researchers have put forward various modification strategies through practice, including morphology regulation, element doping, semiconductor compounding, noble metal deposition, coordination with metal ions, and the like. Wherein the element doping and the defect pair g-C are introduced 3 N 4 The energy band structure can be designed and regulated to obviously improve the light absorption capacity, and inhibit the recombination of photon-generated carriers, so that the photocatalytic activity is enhanced.
Photosensitization, which is one of the main ways to extend the excitation wavelength range of photocatalysts, mainly utilizes TiO 2 The particles in the excitation wavelength range have strong adsorption of photoactive substances, and are physically or chemically adsorbed on the surface of the catalyst by adding a suitable photoactive sensitizer. The substances have larger excitation factors under the visible light, and after absorption of photons by the absorption state photoactive molecules under the irradiation of the visible light, the absorption state photoactive molecules are excited to generate free electrons, and then the excitation state photoactive molecules inject electrons into the conduction band of the semiconductor, so that the excitation wavelength range is enlarged, and the visible light can be fully utilized. At present, several common sensitizers reported in the literature are inorganic sensitizers, pure organic dyes, metal organic complexes, composite sensitizers and the like. In particular, photosensitizationThe strategy promotes the generation of singlet oxygen, simultaneously inhibits the generation of hydroxyl free radicals, improves the selectivity of the reaction, and avoids excessive oxidation.
In summary, the current method for selectively oxidizing glucose by using a photocatalyst has the problems of low conversion rate, low selectivity and excessive oxidation, and the method starts from the catalyst and the reaction medium to deeply research a catalytic reaction system and a reaction mechanism, so that the method is an effective way for improving the reaction efficiency and the selectivity of the reaction.
The invention comprises the following steps:
the invention aims to solve the problems of low reaction speed, difficult separation of free enzyme, toxic product generation and the like in the existing glucose oxidation process, and provides a method for obtaining chemicals with high added value by utilizing photocatalytic selective oxidation of glucose by using a carbon nitride and photosensitizer composite material. The composite photocatalyst Ce6@BNCN prepared by the invention can efficiently and selectively oxidize glucose into gluconic acid, glucaric acid and arabinose by photocatalysis.
According to the invention, ce6 is loaded on modified carbon nitride BNCN to prepare the composite photocatalyst Ce6@BNCN, ce6@BNCN is used as a photocatalyst, hydrogen peroxide is used as an oxidant, water is used as a solvent, and researches show that under the condition of simulating sunlight irradiation, the composite photocatalyst Ce6@BNCN has high-efficiency photocatalytic glucose oxidation capability under the condition of normal temperature and normal pressure, and can obtain gluconic acid, glucaric acid and arabinose.
In order to achieve the above purpose of the present invention, the present invention adopts the following technical scheme:
(1) The nitrogen-rich organics were placed in a covered alumina crucible and warmed to 520 c at a ramp rate of 5 c/min, calcined at this temperature for 4 hours, cooled to room temperature and then the yellow powder was collected.
(2) The prepared g-C 3 N 4 And NaBH 4 Mixing at a certain ratio, grinding, heating to 400deg.C at a heating rate of 10deg.C/min, calcining at the temperature for 1 hr, cooling the obtained powder to room temperature, washing with ethanol and deionized water for multiple times, and removing unreacted NaBH 4 Dried under vacuum at 80℃for 10h. The product was designated BNCN.
(3) A quantity of BNCN was dispersed in 200ml of an acidic solution A (1M) at room temperature, stirred magnetically for 5 hours, then filtered centrifugally and washed three times with deionized water. Finally, the yellow powder protonated pBNCN was obtained by vacuum drying at 80℃for 12 h.
(4) 0.5g of the prepared pBNCN was uniformly dispersed in 100mL of deionized water, and then a certain amount of Ce6 was added to the suspension, followed by rapid magnetic stirring at room temperature for 2 hours. Repeated centrifugal washing with deionized water was performed 5 times. After 80 hours of vacuum drying, ce6@BNCN is obtained.
(5) The composite photocatalyst Ce6@BNCN can be applied to the field of photocatalysis. Preferably, the composite photocatalyst of the present invention is applied to photocatalytic oxidation of glucose. Ce6@BNCN is used as a photocatalyst, hydrogen peroxide is used as an oxidant, water is used as a solvent under the irradiation of a 300W xenon lamp, and glucose is subjected to photocatalytic oxidation under the conditions of normal temperature and normal pressure to obtain gluconic acid, glucaric acid and arabinose.
(6) The composite photocatalyst is applied to photocatalytic oxidation of glucose, and comprises the specific steps of adding a glucose aqueous solution into a jacketed photoreaction bottle, then adding the composite photocatalyst, fully dispersing the catalyst in a reaction system under the condition of avoiding light by stirring, starting circulating condensed water, then adding a certain volume of hydrogen peroxide as an oxidant, and realizing oxidation of glucose under the irradiation of a 300W xenon lamp.
The method for obtaining the chemicals with high added value by utilizing the composite photocatalyst Ce6@BNCN to perform photocatalytic selective oxidation on glucose comprises the step of mixing one of cyanamide, dicyandiamide, melamine, urea and thiourea in any proportion.
The method for obtaining the chemicals with high added value by using the composite photocatalyst Ce6@BNCN to photo-catalyze and selectively oxidize glucose comprises the following steps of (2) g-C 3 N 4 And NaBH 4 Preferably 1-5:10, more preferably 5:2.
The method for obtaining the chemicals with high added value by utilizing the composite photocatalyst Ce6@BNCN to perform photocatalytic selective oxidation on glucose comprises the step of preparing an acidic solution A, wherein the acidic solution A comprises hydrochloric acid, nitric acid and sulfuric acid, and preferably the acidic solution A is hydrochloric acid.
The method for obtaining the chemicals with high added value by using the composite photocatalyst Ce6@BNCN to catalyze and selectively oxidize glucose, wherein the mass ratio of pBNCN to Ce6 in the step (4) is preferably 5-20:1, and more preferably, the mass ratio is 10.
The method for obtaining the chemicals with high added value by using the composite photocatalyst Ce6@BNCN to perform photocatalytic selective oxidation on glucose, wherein the concentration of the glucose aqueous solution in the step (6) is preferably 1-7mmol/L, more preferably 1-3mmol/L, and most preferably 1mmol/L.
The method for obtaining the chemicals with high added value by utilizing the composite photocatalyst Ce6@BNCN to catalyze and selectively oxidize glucose, wherein the dosage of the composite photocatalyst Ce6@BNCN in the step (6) is preferably 5-30mg, and preferably 10mg.
The method for obtaining the chemical with high added value by using the composite photocatalyst Ce6@BNCN to photo-catalyze and selectively oxidize glucose, wherein the hydrogen peroxide in the step (6) is added in an amount of preferably 10-40 microliters, and preferably 10 microliters.
Further, 30mL of 1mmol/L glucose aqueous solution is added into a jacketed photoreaction bottle, then 100mg of composite photocatalyst Ce6@BNCN is added, and the mixture is magnetically stirred for 30min under the condition of avoiding light, so that the catalyst is fully dispersed in a reaction system. 30 microliters of hydrogen peroxide was added, the circulating condensate was turned on, and the temperature of the reaction system was maintained. Under the irradiation of a 300W xenon lamp, the reaction is carried out for 2 hours, the glucose conversion rate is 65%, and the total selectivity of the product is 60%.
The invention has the advantages and beneficial effects that: the invention provides a method for obtaining chemicals with high added value by utilizing the composite photocatalyst Ce6@BNCN to perform photocatalytic selective oxidation on glucose.
Drawings
FIG. 1 is a scanning electron microscope image
FIG. 2 is a transmission electron microscope image
FIG. 3 influence of different catalysts
FIG. 4 effect of glucose substrate concentration on photocatalytic oxidation of glucose
FIG. 5 effect of catalyst amount on photocatalytic oxidation of glucose
FIG. 6 effect of Hydrogen peroxide addition on photocatalytic oxidation of glucose
FIG. 7 cycle experiment
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative, but not limiting, of the scope of the invention.
Example 1
Preparation of composite photocatalyst Ce6@BNCN
2g of melamine was placed in a covered alumina crucible, calcined in air at 520℃for 4 hours, cooled to room temperature and then collected as yellow powder. 0.4g of the prepared g-C 3 N 4 And 0.16g NaBH 4 Is ground and then calcined at 400 ℃. In a nitrogen atmosphere, the rate of pressure increase was 10deg.C/min. Cooling the obtained powder to room temperature, washing with ethanol and deionized water for several times to remove unreacted NaBH 4 Dried under vacuum at 80℃for 10h. The product was designated BNCN. BNCN (1 g) was dispersed in 200ml of hydrochloric acid solution (1M), stirred magnetically for 5 hours, then filtered centrifugally and washed three times with deionized water. Finally, the yellow powder protonated H-BNCN is obtained by vacuum drying at 80 ℃ for 12H. 0.5g of the prepared pBNCN was uniformly dispersed in 100mL of deionized water, and then 0.05g of Ce6 was added to the suspension, followed by rapid magnetic stirring at room temperature for 2 hours. Repeated centrifugal washing with deionized water was performed 5 times. And (3) drying in vacuum at 80 ℃ to obtain the composite photocatalyst Ce6@BNCN.
Example 2
Composite photocatalyst Ce6@BNCN photocatalytic selective oxidation glucose activity experiment
In the reactor was placed 30mL of 1mmol/L glucose, followed by addition of 10mg of photocatalyst. The catalyst was dispersed by sonication for 10 minutes and the suspension was magnetically stirred for 30 minutes under dark conditions before light irradiation to reach adsorption-desorption equilibrium. Then, 30. Mu.l of a 30% aqueous hydrogen peroxide solution was added to the above suspension, and the suspension was irradiated with a xenon lamp for 2 hours. And separating out the photocatalyst Ce6@BNCN after the reaction is finished to obtain a product rich in gluconic acid, glucaric acid and arabinose, wherein the glucose conversion rate is 65%, and the total selectivity of the product is 60%, which is marked as Entry1.
Example 3
Influence of the glucose substrate concentration on the photocatalytic Selective Oxidation of glucose by the Complex photocatalyst Ce6@BNCN
The procedure of example 2entry 1 was followed to change the glucose substrate concentration, and experiments were performed to photo-catalyze oxidizing glucose at 1mM,3mM,5mM, and 7mM, respectively, to examine the effect of the glucose substrate concentration on photo-catalytic oxidizing glucose, and the effect of the glucose concentration on glucose conversion and oxidation product selectivity is shown in FIG. four. It was observed that as the initial glucose concentration increased from 1 to 7 mmol.L -1 The glucose conversion gradually decreased from 62.3% to 10.7%. In all cases, the glucose concentration has a limited effect on the overall selectivity of the oxidation product with gluconic acid as the major product.
Example 4
Influence of catalyst usage on the photocatalytic selective oxidation of glucose activity of the composite photocatalyst Ce6@BNCN
According to the procedure of entry1 of example 2, experiments for photocatalytic oxidation of glucose were carried out under conditions of 5mg,10mg,20mg and 30mg, respectively, with varying amounts of catalyst, and the effect of the amount of catalyst on photocatalytic oxidation of glucose was examined, and the effect of the amount of catalyst on glucose conversion and selectivity of oxidation products was shown in FIG. five. Although the glucose conversion is higher when the amount of catalyst is low (5 mg), the overall selectivity of the oxidation product is relatively low, similar to using H in the absence of catalyst 2 O 2 The results obtained. It is notable that the catalyst dosage is increased to 10mg, the product selectivity is significantly improved, and the glucose conversion is slightly reduced. As expected, a further increase in the catalyst amount from 10mg to 30mg resulted in a significant increase in glucose conversion. In contrast to this,when the catalyst amount exceeds 10mg, the selectivity of the oxidation product tends to decrease. The optimum catalyst amount for glucose oxidation under experimental conditions was 10mg in view of the substrate conversion and the product selectivity.
Example 5
Influence of Hydrogen peroxide usage on the Activity of the Compound photocatalyst Ce6@BNCN for photocatalytic selective oxidation of glucose
According to the procedure of example 2entry 1, experiments were conducted to perform photocatalytic oxidation of glucose with hydrogen peroxide addition amounts of 10 μl,20 μl,30 μl, and 40 μl, respectively, while changing the catalyst amount, and the effect of the hydrogen peroxide addition amount on the photocatalytic oxidation of glucose was examined, and the effect of the hydrogen peroxide addition amount on the glucose conversion and the oxidation product selectivity was shown in fig. six. With H 2 O 2 A significant increase in glucose conversion was observed with increasing amounts. With H 2 O 2 The addition amount was increased from 10. Mu.L to 40. Mu.L, and the glucose conversion was increased from 51.0% to 68.6%. Notably, when H 2 O 2 At 30. Mu.L, the total selectivity of the oxidation products was the highest. Add 40. Mu. L H 2 O 2 The glucose conversion was slightly higher than when 30. Mu.L was added, but the selectivity of the oxidation product was significantly lower than the latter.
Example 6
Stability of composite photocatalyst Ce6@BNCN
The measurement of the recycling efficiency of the composite photocatalyst was performed according to the procedure of 2entry 1. And after each photocatalytic oxidation reaction, filtering the reaction system to obtain a catalyst, washing the catalyst with deionized water, performing vacuum drying, and using the dried catalyst for the next photocatalytic oxidation reaction. The stability of the composite photocatalyst was examined by measuring the 4-cycle use efficiency of the composite photocatalyst. The 1 st use of catalyst in the cycling experiment was noted Entry1 (which was the first time that the freshly prepared catalyst was used); the 2 nd use of the catalyst in the cycling experiment was noted Entry 2; the 3 rd use of the catalyst in the cycling experiments was noted Entry 3; the 4 th use of the catalyst in the cycling experiment was designated Entry 4. The experimental results are shown in table 5. The comparative experiment shows that the composite photocatalyst Ce6@BNCN is recycled for 4 times, and the change of the conversion rate of glucose and the selectivity of oxidation products is small, so that the composite photocatalyst Ce6@BNCN has good stability.
Claims (7)
1. A method for obtaining chemicals with high added value by using a composite photocatalyst Ce6@BNCN to catalyze and selectively oxidize glucose, comprising the following steps:
(1) Placing the nitrogen-rich organic matter into a covered alumina crucible, heating to 520 ℃ at a heating rate of 5 ℃/min, calcining at the temperature of 4h, cooling to room temperature, and collecting yellow powder;
(2) The prepared g-C 3 N 4 And NaBH 4 Mixing at a certain ratio, grinding, heating to 400deg.C at a heating rate of 10deg.C/min, calcining at the temperature of 1h, cooling the obtained powder to room temperature, washing with ethanol and deionized water for several times, and removing unreacted NaBH 4 Drying 10h under vacuum at 80 ℃, the product was designated BNCN;
(3) Dispersing a certain amount of BNCN into 200ml of acid solution A with the concentration of 1 mol/L at room temperature, rapidly magnetically stirring for 5 hours, centrifugally filtering, and washing with deionized water for three times; finally, vacuum drying is carried out for 12 hours at 80 ℃ to obtain yellow powdery protonated pBNCN;
(4) Uniformly dispersing the pBNCN prepared by 0.5g in 100mL deionized water, adding a certain amount of Ce6 into the suspension, and rapidly and magnetically stirring for 2 hours at room temperature; repeatedly centrifuging and washing with deionized water for 5 times; vacuum drying at 80 deg.c to obtain Ce6@BNCN;
(5) Taking Ce6@BNCN as a photocatalyst, taking hydrogen peroxide as an oxidant, taking water as a solvent under the irradiation of a 300W xenon lamp, and carrying out photocatalytic oxidation on glucose under the conditions of normal temperature and normal pressure to obtain gluconic acid, glucaric acid and arabinose;
(6) The composite photocatalyst is applied to photocatalytic oxidation of glucose, and comprises the specific steps of adding a glucose aqueous solution into a jacketed photoreaction bottle, then adding the composite photocatalyst, fully dispersing the catalyst in a reaction system under the condition of avoiding light by stirring, starting circulating condensed water, then adding a certain volume of hydrogen peroxide as an oxidant, and realizing oxidation of glucose under the irradiation of a 300W xenon lamp.
2. The method for photocatalytically selective oxidation of glucose with high value-added chemicals using the composite photocatalyst ce6@bncn according to claim 1, wherein the nitrogen-rich organic matter comprises one of cyanamide, dicyandiamide, melamine, urea, thiourea.
3. The method for photocatalytically and selectively oxidizing glucose to obtain chemicals with high added value by utilizing composite photocatalyst Ce6@BNCN as claimed in claim 1, wherein the step (2) g-C 3 N 4 And NaBH 4 The mass ratio of (2) is 1-5:10.
4. The method for photocatalytically and selectively oxidizing glucose to obtain chemicals with high added value using the composite photocatalyst ce6@bncn according to claim 1, wherein the acidic solution a comprises hydrochloric acid, nitric acid or sulfuric acid.
5. The method for photocatalytically and selectively oxidizing glucose to obtain chemicals with high added value by utilizing a composite photocatalyst Ce6@BNCN according to claim 1, wherein the mass ratio of pBNCN to Ce6 in the step (4) is 5-20:1.
6. The method for photocatalytically selective oxidation of glucose with high value-added chemicals using a composite photocatalyst ce6@bncn according to claim 1, wherein the glucose aqueous solution concentration in step (6) is 1-7 mmol/L.
7. The method for photocatalytically and selectively oxidizing glucose to obtain chemicals with high added value according to claim 1, wherein the amount of the composite photocatalyst Ce6@BNCN used in the step (6) is 5-30 mg.
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| DE102014000888A1 (en) * | 2014-01-23 | 2015-07-23 | Kevin Jablonka Josef und Danuta, als gesetzliche Vertreter des minderjährigen Jablonka | Device for the catalytic, photochemical decomposition of water for the recovery of hydrogen |
| CN110961129A (en) * | 2019-10-30 | 2020-04-07 | 广东工业大学 | Reductive carbon nitride photocatalyst and preparation method and application thereof |
| CN111889130A (en) * | 2020-07-30 | 2020-11-06 | 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 |
| CN113318764A (en) * | 2021-05-28 | 2021-08-31 | 江苏大学 | Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE102014000888A1 (en) * | 2014-01-23 | 2015-07-23 | Kevin Jablonka Josef und Danuta, als gesetzliche Vertreter des minderjährigen Jablonka | Device for the catalytic, photochemical decomposition of water for the recovery of hydrogen |
| CN110961129A (en) * | 2019-10-30 | 2020-04-07 | 广东工业大学 | Reductive carbon nitride photocatalyst and preparation method and application thereof |
| CN111889130A (en) * | 2020-07-30 | 2020-11-06 | 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 |
| CN113318764A (en) * | 2021-05-28 | 2021-08-31 | 江苏大学 | Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst |
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