CN111747845A - Method for selectively oxidizing glucose by visible light catalysis - Google Patents

Method for selectively oxidizing glucose by visible light catalysis Download PDF

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CN111747845A
CN111747845A CN202010585888.5A CN202010585888A CN111747845A CN 111747845 A CN111747845 A CN 111747845A CN 202010585888 A CN202010585888 A CN 202010585888A CN 111747845 A CN111747845 A CN 111747845A
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hmdtn
glucose
bivo
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杨昌军
殷杰
邓克俭
张丙广
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South Central Minzu University
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Abstract

The invention belongs to the field of chemical industry, and particularly discloses a method for selectively oxidizing glucose by visible light catalysis. BiVO is adopted in the method4/CoPz(hmdtn)4Is a photocatalyst, directly takes molecular oxygen in the air as an oxidant, and can realize the effective photocatalytic oxidation of glucose in water environment to prepare high added value under the condition of the visible light illumination with the lambda being more than or equal to 420nmA chemical. The method can utilize solar energy and air to carry out the oxidation of glucose at normal temperature and normal pressure, and provides a green and energy-saving selective oxidation method for preparing high value-added chemicals by the oxidation of glucose.

Description

Method for selectively oxidizing glucose by visible light catalysis
Technical Field
The invention relates to the field of chemical industry, in particular to a method for selectively oxidizing glucose by visible light catalysis, which uses BiVO4/CoPz(hmdtn)4The photocatalyst and oxygen in the air are used as oxidantsVisible light photocatalytically oxidizes glucose to prepare high value-added chemicals.
Background
Glucose is a monosaccharide which is most widely distributed in nature, and an oxidation product of the glucose can be used as an important intermediate and a chemical product to be applied to the fields of chemical industry, food, medicine and the like. Therefore, research on obtaining high value-added chemicals through oxidation of glucose has received extensive attention. From the perspective of green chemical industry and sustainable development, the method has important significance and application value in preparing high value-added chemicals by utilizing the characteristic that glucose can be dissolved in water, taking sunlight as a driving force, taking molecular oxygen in air as an oxidant and utilizing a photocatalysis technology to realize selective oxidation of glucose under mild conditions in a water environment.
The core of the photocatalysis technology is the development of a photocatalyst. The composition of the solar spectrum is mostly visible light, the metalloporphyrin has strong absorption in a visible light region, and the inorganic semiconductor photocatalyst and the metalloporphyrin are compounded to form the composite photocatalyst, so that the utilization rate of sunlight can be improved, the separation efficiency of photo-generated electron-hole pairs can be enhanced, and the photocatalytic oxidation efficiency of the photocatalyst can be improved. The composite photocatalyst based on the inorganic semiconductor and the metalloporphyrin is applied to the photocatalytic selective oxidation reaction of glucose, renewable solar energy can be used as a light source, meanwhile, environment-friendly oxygen is used as an oxidant, the use of a strong corrosive oxidant can be avoided, the selectivity of an oxidation product is improved through optimization of photocatalytic reaction conditions, and a green and energy-saving selective oxidation method is provided for oxidation of glucose.
Disclosure of Invention
Aiming at the defects of the existing glucose oxidation method, the invention utilizes the dipping method to oxidize BiVO (BiVO) to develop a green and energy-saving method for preparing high value-added chemicals by glucose oxidation4With tetrakis (hydroxymethyl) tetrakis (1, 4-dithiin) tetraazacobalt porphyrin (CoPz (hmdtn)4) Composite photocatalyst BiVO (bismuth VO) is prepared through compounding4/CoPz(hmdtn)4And develops a composite photocatalyst BiVO4/CoPz(hmdtn)4Visible light catalytic activated molecular oxygenUse of oxidized glucose. The composite photocatalyst BiVO prepared by the invention4/CoPz(hmdtn)4The visible light photocatalysis can efficiently oxidize glucose into gluconic acid, arabinose, erythrose and formic acid.
The invention relates to a method for preparing a compound of CoPz (hmdtn)4Loaded in BiVO4Composite photocatalyst BiVO prepared on the surface4/CoPz(hmdtn)4With BiVO4/CoPz(hmdtn)4Is a visible light catalyst, takes molecular oxygen in the air as an oxidant and water as a solvent, and researches show that the composite photocatalyst BiVO is compounded under the conditions of normal temperature and normal pressure under the irradiation of visible light with the lambda being more than or equal to 420nm4/CoPz(hmdtn)4Has high-efficiency photocatalytic oxidation capacity on glucose, and can obtain gluconic acid, arabinose, erythrose and formic acid.
In order to achieve the above purpose of the present invention, the technical scheme adopted by the present invention is as follows:
composite photocatalyst BiVO with high activity4/CoPz(hmdtn)4The preparation method comprises the following steps:
BiVO (bismuth oxide) is added4Adding the mixture into a solvent A, fully dispersing, and adding a solvent B containing tetrakis (1, 4-dithiino) tetraazacobalt porphyrin to BiVO4Uniformly mixing in a dispersion system, removing the solvent, and drying in vacuum to obtain the composite photocatalyst BiVO4/CoPz(hmdtn)4。
CoPz(hmdtn)4The load of the catalyst refers to a composite photocatalyst BiVO4/CoPz(hmdtn)4Middle CoPz (hmdtn)4And BiVO4In mass percent of (1), CoPz (hmdtn)4The loading of (b) is 0.25% to 3%, preferably 0.5% to 2%.
Preferably, the BiVO4The crystal form is monoclinic scheelite type, tetragonal zircon type or tetragonal scheelite type.
More preferably, the BiVO4Is monoclinic scheelite crystal form.
The solvent A is N, N-Dimethylformamide (DMF), acetonitrile or tetrahydrofuran; preferably, solvent a is N, N-dimethylformamide.
The solvent B is the same as the solvent A. The amount of solvent a is greater than the amount of solvent B.
The composite photocatalyst BiVO of the invention4/CoPz(hmdtn)4Can be applied to the field of photocatalysis. Preferably, the composite photocatalyst is applied to photocatalytic oxidation of glucose. With BiVO4/CoPz(hmdtn)4Is a visible light catalyst, takes molecular oxygen in the air as an oxidant, and has a visible light intensity of 0.78 W.cm at lambda of more than or equal to 420nm-2-1.68W·cm-2Under the irradiation of the light source, water is used as a solvent, and glucose is subjected to photocatalytic oxidation under the conditions of normal temperature and normal pressure to obtain gluconic acid, arabinose, erythrose and formic acid.
The composite photocatalyst is applied to photocatalytic oxidation of glucose, and comprises the following specific steps:
adding glucose aqueous solution into a jacket light reaction bottle, adding a composite photocatalyst, fully dispersing the catalyst in a reaction system under the condition of keeping out of the sun by stirring, starting circulating condensed water, directly using oxygen in the air as an oxidant, and taking visible light with the lambda of more than or equal to 420nm and the visible light intensity of 0.78W cm-2-1.68W·cm-2And the oxidation of glucose is realized under the condition of illumination.
The concentration of the glucose aqueous solution is preferably 0.5 mmol.L-1-7mmol·L-1More preferably 0.5 mmol. multidot.L-1-3mmol·L-1Most preferably 0.5 to 1 mmol. multidot.L-1；
When in use, glucose in the glucose aqueous solution and the composite photocatalyst BiVO4/CoPz(hmdtn)4Middle CoPz (hmdtn)4The dosage ratio is (0.025-0.35) mmol: (0.075-0.9) mg, optimally (0.025-0.05) mmol: (0.15-0.6) mg.
Further, 50mL of 0.5 mmol. multidot.L was put into a jacketed photoreaction flask-1Adding 30mg of composite photocatalyst BiVO into the glucose aqueous solution4/CoPz(hmdtn)4(CoPz(hmdtn)4The loading amount of the catalyst is 2 percent), and the catalyst is fully dispersed in the reaction system by magnetic stirring for 30min under the condition of keeping out of the sun. And starting circulating condensate water to maintain the temperature of the reaction system unchanged. The mouth of the photoreaction bottle is opened,directly contacting with the atmosphere, and having a light intensity of 1.68W cm-2The reaction is carried out for 9 hours under the condition that the lambda is more than or equal to 420nm of visible light illumination, the conversion rate of glucose is 40.6 percent, and the selectivity of oxidation products is as follows: the selectivity of gluconic acid is 13.8%, the selectivity of arabinose is 27.1%, the selectivity of erythrose is 12.7%, and the selectivity of formic acid is 18.2%.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(1) BiVO is used in the invention4/CoPz(hmdtn)4The catalyst is a visible light catalyst, can directly perform visible light catalytic oxidation on glucose at normal temperature and normal pressure to obtain high value-added chemicals, and the condition of the photocatalytic reaction is milder than that of the traditional catalysis.
(2) The invention takes the visible light with the lambda being more than or equal to 420nm as the light source, directly takes the oxygen in the air as the oxygen source, realizes the catalytic oxidation of the glucose in the pure water environment to prepare the high value-added chemical, and provides a green and energy-saving selective oxidation method for the oxidation of the glucose.
Drawings
FIG. 1 shows CoPz (hmdtn)4Ultraviolet-visible absorption spectrum of (a).
FIG. 2 shows CoPz (hmdtn)4MALDI-TOF MS spectrum of (1).
FIG. 3 is BiVO4XRD pattern of (a).
FIG. 4 is BiVO4/CoPz(hmdtn)4(CoPz(hmdtn)4Load of 2%) and the corresponding element distribution map.
FIG. 5 is BiVO4And BiVO4/CoPz(hmdtn)4Ultraviolet-visible diffuse reflection absorption spectrum diagram.
FIG. 6 is BiVO4、CoPz(hmdtn)4And BiVO4/CoPz(hmdtn)4(CoPz(hmdtn)4Loading of 2%) of the sample.
FIG. 7 is BiVO4、CoPz(hmdtn)4And BiVO4/CoPz(hmdtn)4(CoPz(hmdtn)4Loading of 2%) was determined.
FIG. 8 is quenching agent vs BiVO4/CoPz(hmdtn)4(CoPz(hmdtn)4Loading of 2%) the effect of photocatalytic oxidation of glucose.
Detailed Description
The method for the visible light catalytic selective oxidation of glucose according to the present invention is further described below by way of specific examples, but the following should not be construed to limit the scope of the claimed invention in any way.
The main raw materials used in the following examples are as follows:
the molecular structure of the tetrakis (1, 4-dithiin) tetraazacobalt porphyrin is as follows:
Figure BDA0002554626830000041
(1) tetramethylol tetrakis (1, 4-dithiin) tetraazacobalt porphyrin (abbreviated as CoPz (hmdtn))4) The synthesis method comprises the following steps: CoPz (hmdtn)4Reference Journal of molecular catalysis A Chemical (2013,372: 114-. For the synthesized CoPz (hmdtn)4The structural characterization was performed by UV-visible absorption spectroscopy and MALDI-TOF MS as shown in FIG. 1 and FIG. 2, respectively.
(2)BiVO4The XRD pattern of the commercial product is shown in figure 3, which shows that the BiVO4Has monoclinic scheelite crystal structure.
Example 1: composite photocatalyst BiVO4/CoPz(hmdtn)4Preparation of
The operation steps are as follows: 1g of BiVO4Adding into 40mLN, N-Dimethylformamide (DMF) solvent, and magnetically stirring for 30min to make BiVO4Dispersed well in DMF. Meanwhile, 20mg of CoPz (hmdtn)4Dissolved in 10ml of a mixed solvent of DMMF and then added dropwise to the aforementioned BiVO4In a dispersed system. Continuously stirring for 24 hours, removing the solvent DMF by a reduced pressure distillation method, and after completely removing the solvent DMF, carrying out vacuum drying on the obtained sample at 60 ℃ for 12 hours to obtain the composite photocatalyst BiVO4/CoPz(hmdtn)4，CoPz(hmdtn)4The loading of (2%).
Following the same procedure, by varying CoPz (hmdtn)4Quantitatively prepare CoPz (hmdtn)4Composite photocatalyst BiVO with the load amounts of 0.25%, 0.5%, 1% and 3% respectively4/CoPz(hmdtn)4。
Composite photocatalyst BiVO4/CoPz(hmdtn)4The HAADF-STEM map of (a) and the corresponding element distribution map are shown in fig. 4. From FIG. 4, it is clear that Bi, O, V, C, N, S and Co are uniformly distributed, indicating that BiVO4And CoPz (hmdtn)4Uniformly dispersed in a composite photocatalyst BiVO4/CoPz(hmdtn)4While indicating CoPz (hmdtn)4Successfully loaded in BiVO4Of (2) is provided.
BiVO4And BiVO4/CoPz(hmdtn)4The ultraviolet-visible diffuse reflectance absorption spectrum of (a) is shown in fig. 5. Wherein: a means BiVO4(ii) a b-f denotes BiVO4/CoPz(hmdtn)4Middle CoPz (hmdtn)4The loading amounts of the components are 0.25%, 0.5%, 1%, 2% and 3% in sequence. From FIG. 5, it can be seen that the BiVO is related to pure BiVO4Compared with the prior art, the composite photocatalyst BiVO4/CoPz(hmdtn)4Has strong absorption in the visible region of 500-800nm and follows CoPz (hmdtn)4Increase of load capacity and composite photocatalyst BiVO4/CoPz(hmdtn)4The absorption of visible light is gradually enhanced. Further indicating that CoPz (hmdtn)4Successfully loaded in BiVO4Also shown are CoPz (hmdtn)4The surface modification can obviously expand BiVO4The absorption range of visible light is beneficial to effectively utilizing sunlight.
BiVO4、CoPz(hmdtn)4And composite photocatalyst BiVO4/CoPz(hmdtn)4The transient photocurrent of (a) is shown in fig. 6. As can be seen from fig. 6, the composite photocatalyst BiVO was irradiated under an LED lamp with λ 420nm4/CoPz(hmdtn)4The photocurrent of (A) is significantly higher than that of pure CoPz (hmdtn)4And pure BiVO4The composite photocatalyst has better photoproduction electron and hole separation compared with a single materialThe capability is beneficial to improving the activity of the photocatalyst.
BiVO4、CoPz(hmdtn)4And composite photocatalyst BiVO4/CoPz(hmdtn)4The electrochemical impedance spectrum of (a) is shown in FIG. 7. As can be seen from FIG. 7, it is found that4And pure BiVO4Compared with the prior art, the composite photocatalyst BiVO4/CoPz(hmdtn)4The Nyquist curve radius is smaller, and the composite photocatalyst BiVO is shown4/CoPz(hmdtn)4The photocatalyst has better photoproduction electron and hole separation and transfer capability, and is beneficial to improving the activity of the photocatalyst, which is consistent with the result of the transient photocurrent test.
Example 2: activity measurement of the composite photocatalyst prepared in example 1 for visible light photocatalytic oxidation of glucose
50mL of 1 mmol. multidot.L was put in a jacketed photoreaction flask-1Adding 30mg of composite photocatalyst BiVO into the glucose aqueous solution4/CoPz(hmdtn)4(CoPz(hmdtn)4The loading amount of the catalyst is 2 percent), and the catalyst is fully dispersed in the reaction system by magnetic stirring for 30min under the condition of keeping out of the sun. And starting circulating condensate water to maintain the temperature of the reaction system unchanged. The mouth of the photoreaction bottle is open, the bottle is directly contacted with the atmosphere, the reaction is carried out for 9 hours under the condition that the lambda is more than or equal to 420nm and the illumination is visible light, and the light intensity is 1.68W cm-2. This group is an experiment under visible light and is denoted as Entry 1. The reaction products were qualitatively and quantitatively analyzed by LC-MS and HPLC.
In addition, following the same procedure, three other sets of experiments were performed as controls: under the condition of no catalyst, investigating the oxidation of glucose only under the condition of visible light illumination, and the group is marked as Entry 2; with BiVO4The oxidation of glucose under the condition of visible light illumination is inspected for a photocatalyst, and the group is named as Entry 3; with CoPz (hmdtn)4Being a photocatalyst, CoPz (hmdtn)4The mass was 0.6mg, and the oxidation of glucose under visible light was examined, and this group was designated as Entry 4.
The results of the experiment are shown in table 1. Comparative experiments show that glucose is not oxidized in the absence of a catalyst (Entry 2); in CoPz(hmdtn)4Glucose does not oxidize in the presence of the enzyme (Entry 4); in BiVO4In the presence and under visible light, glucose can be oxidized, the conversion rate of the glucose after 9 hours of reaction is 5.1%, the oxidation products of the glucose are arabinose, erythrose and formic acid, and the selectivity of the three oxidation products is 72.5%, 9.5% and 15.5% (Entry 3); and BiVO is a composite photocatalyst4/CoPz(hmdtn)4The conversion rate of glucose reaches 33.3 percent (Entry 1) after 9 hours of reaction in the presence of visible light, and the reaction product is BiVO46.5-fold higher photocatalytic system, indicating CoPz (hmdtn)4The surface modification of (2) significantly improves the conversion rate of glucose. Meanwhile, it can be seen from comparative analysis that BiVO is a very important factor4/CoPz(hmdtn)4In the photocatalytic system, the oxidation products of glucose, except arabinose, erythrose and formic acid, also generate gluconic acid, and the selectivity of the four oxidation products of the gluconic acid, the arabinose, the erythrose and the formic acid is 17.7 percent, 39.3 percent, 17.3 percent and 21.9 percent respectively. And in BiVO4No gluconic acid was produced in the photocatalytic system, indicating that CoPz (hmdtn)4The surface modification of (2) is beneficial to the generation of gluconic acid.
Table 1. oxidation of glucose under different conditions.
Figure BDA0002554626830000061
Example 3: quenching experiment of active species in visible light catalytic system of composite photocatalyst
The effect of the active species on photocatalytic oxidation of glucose was investigated by performing a quenching experiment. The method comprises the following steps: 50mL of 1 mmol. multidot.L was put in a jacketed photoreaction flask-1Adding 30mg of composite photocatalyst BiVO into the glucose aqueous solution4/CoPz(hmdtn)4(CoPz(hmdtn)42%) under the condition of protecting from light, magnetically stirring for 30min to make catalyst fully disperse in reaction system, then adding 2.5mmol β -Carotene (abbreviated as β -Carotene), 2.5mmol isopropanol (abbreviated as IPA), 2.5mmol p-benzoquinone (abbreviated as BQ) or 2.5mmol KI. to start circulating condensed waterThe temperature of the reaction system was maintained constant. The mouth of the photoreaction bottle is open, the bottle is directly contacted with the atmosphere, the reaction is carried out for 9 hours under the condition that the lambda is more than or equal to 420nm and the illumination is visible light, and the light intensity is 1.68W cm-2. The reaction product was quantitatively analyzed by HPLC. Addition of quencher KI for detection of active species h+Influence on photocatalytic oxidation of glucose, addition of a quencher β -Carotene for detecting active oxygen species1O2The effect on photocatalytic oxidation of glucose; adding a quenching agent BQ for detecting active oxygen species O2 -The effect on photocatalytic oxidation of glucose; the addition of the quencher IPA was to examine the effect of the active oxygen species OH on the photocatalytic oxidation of glucose.
The results of the experiment are shown in FIG. 8. Comparative experiments show that when h is added+The conversion rate of glucose is reduced from 33.3% to 8.7% by using the quencher KI; adding into1O2The conversion rate of glucose was reduced from 33.3% to 7.6% when the quenching agent β -Carotene was added2 -The conversion rate of glucose is reduced from 33.3% to 6.4% when the quencher BQ is used; when the OH quencher IPA was added, the glucose conversion decreased from 33.3% to 19%. Indicates h+、1O2、·O2 -However, the effect of the quencher IPA on the conversion of glucose was small compared to the quenchers KI, β -Carotene and BQ, indicating that the quencher IPA had a small effect on the conversion of glucose1O2、·O2 -And h+Is the main active species in this photocatalytic process.
Example 4: CoPz (hmdtn)4Influence of load on photocatalytic oxidation of glucose by composite photocatalyst
The composite photocatalyst BiVO was changed according to the procedure of example 2Entry 14/CoPz(hmdtn)4Middle CoPz (hmdtn)4The loading amounts are respectively in CoPz (hmdtn)4Experiments with photocatalytic oxidation of glucose at loadings of 0.25%, 0.5%, 1%, 2%, and 3% examined CoPz (hmdtn)4Effect of loading on photocatalytic oxidation of glucose. CoPz (hmdtn)4The load of 0.25 percent is recorded as Entry 1; CoPz (hm)dtn)4Recording the load amount of 0.5% as Entry 2; CoPz (hmdtn)4The loading of 1% was designated as Entry 3. CoPz (hmdtn)4Recording the load as Entry4 when the load is 2%; CoPz (hmdtn)4The loading of 3% was designated as Entry 5.
The results of the experiment are shown in table 2. Comparative experiments show that with CoPz (hmdtn)4The loading is increased, the conversion rate of glucose is increased and then decreased when CoPz (hmdtn)4At a loading of 0.5%, the conversion of glucose reached 38.7% (Entry 2). CoPz (hmdtn)4The load has no influence on the types of glucose oxidation products, and the oxidation products are gluconic acid, arabinose, erythrose and formic acid. However, CoPz (hmdtn)4The loading affects the selectivity of the various oxidation products, when CoPz (hmdtn)4At loadings above 1% this favors the production of gluconic and erythrose but not arabinose, e.g. CoPz (hmdtn)4At a loading of 2%, the selectivity for gluconic acid reached 17.7%, for erythrose 17.3%, and for arabinose 39.3% (Entry 4).
TABLE 2 CoPz (hmdtn)4The loading capacity influences the photocatalytic oxidation of glucose by the composite photocatalyst.
Figure BDA0002554626830000081
Example 5: influence of glucose concentration on photocatalytic oxidation of glucose by composite photocatalyst
The procedure of example 2Entry 1 was followed, with changing the concentration of glucose as a reaction substrate, at a glucose concentration of 0.5 mmol. multidot.L-1、1mmol·L-1、3mmol·L-1、5mmol·L-1And 7 mmol. L-1The experiment of photo-catalytic oxidation of glucose is carried out under the condition of (1), and the influence of the glucose concentration on the photo-catalytic oxidation of glucose by the composite photocatalyst is examined. The glucose concentration is 0.5 mmol.L-1Is recorded as Entry 1; the glucose concentration is 1 mmol.L-1Is recorded as Entry 2; the glucose concentration is 3 mmol.L-1Is recorded as Entry 3; the glucose concentration is 5 mmol.L-1Is recorded as Entry 4;the glucose concentration is 7 mmol.L-1Denoted Entry 5.
The results of the experiment are shown in table 3. Comparative experiments show that the conversion of glucose decreases with increasing glucose concentration. The glucose concentration has no influence on the kind of its oxidation products, i.e., gluconic acid, arabinose, erythrose, and formic acid, but the selectivity of the oxidation products is influenced by the glucose concentration. When the glucose concentration is 0.5 mmol.L-1The total selectivity to the four oxidation products was 71.8%. When the glucose concentration is higher than 0.5 mmol.L-1In the process, the total selectivity of four oxidation products is obviously improved and can reach over 96 percent. The selectivity of gluconic acid is firstly increased and reduced along with the increase of the glucose concentration, and when the glucose concentration is 1 mmol.L-1The selectivity to gluconic acid was 17.7%. The selectivity of arabinose increased with increasing glucose concentration, indicating that increasing glucose concentration favors the production of arabinose. The selectivity of erythrose is increased and decreased firstly, when the concentration of glucose is 3 mmol.L-1The erythrose selectivity was 21.9%. The glucose concentration has a smaller effect on the selectivity to formic acid.
Table 3. effect of glucose concentration on photocatalytic oxidation of glucose by the composite photocatalyst.
Figure BDA0002554626830000091
Example 6: influence of light intensity on photocatalytic oxidation of glucose by composite photocatalyst
The procedure of example 2Entry 1 was followed to change the intensity of visible light at a light intensity of 0.78 W.cm, respectively-2、1.08W·cm-2、1.38W·cm-2And 1.68 W.cm-2The experiment of photocatalytic oxidation of glucose was conducted under the conditions of (1) to examine the influence of the light intensity of visible light on the photocatalytic oxidation of glucose.
The results of the experiment are shown in table 4. The comparative experiment shows that the conversion rate of the glucose increases along with the increase of the intensity of the visible light, and the oxidation process of the glucose is a photocatalytic oxidation process. At the same time, the selectivity of the glucose oxidation products is substantially unaffected by the light intensity.
Table 4. effect of light intensity on photocatalytic oxidation of glucose by a composite photocatalyst.
Figure BDA0002554626830000092
Example 7: investigating the stability of the composite photocatalyst
The recycling efficiency of the composite photocatalyst was measured according to the procedure of example 2Entry 1. And after each photocatalytic oxidation reaction is finished, 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. And (3) investigating the stability of the composite photocatalyst by measuring the 4-time recycling efficiency of the composite photocatalyst. The 1 st use of the catalyst in the recycle experiment is denoted Entry 1 (which was the first use of the freshly prepared catalyst for the previous time); the 2 nd use of the catalyst in the recycle experiment is denoted Entry 2; the 3 rd use of the catalyst in the recycle experiment is denoted Entry 3; the 4 th use of the catalyst in the recycle experiment is denoted Entry 4.
The results of the experiment are shown in Table 5. A comparison experiment shows that the composite photocatalyst BiVO4/CoPz(hmdtn)4After 4 times of recycling, the change of the conversion rate of glucose and the selectivity of the oxidation product is small, and the composite photocatalyst BiVO is shown4/CoPz(hmdtn)4Has better stability.
TABLE 5 composite photocatalyst BiVO4/CoPz(hmdtn)4The recycling efficiency of (2).
Figure BDA0002554626830000101

Claims (6)

1. A method for selectively oxidizing glucose by visible light catalysis is characterized in that: BiVO is adopted in the method4/CoPz(hmdtn)4The composite photocatalyst is a visible light photocatalyst, and the molecular oxygen in the air is used as oxygenA reagent, under the irradiation of visible light with lambda being more than or equal to 420nm, water is used as a solvent, and glucose is oxidized to prepare a high value-added chemical;
the high value-added chemicals are gluconic acid, arabinose, erythrose and formic acid;
the BiVO4/CoPz(hmdtn)4To convert CoPz (hmdtn)4Loaded in BiVO4The above.
2. The method of claim 1, wherein the CoPz (hmdtn)4The loading amount of the catalyst is 0.25-3%.
3. The method of claim 1, wherein the BiVO is4The crystal form is monoclinic scheelite type, tetragonal zircon type or tetragonal scheelite type.
4. The method of claim 1, wherein the BiVO is4/CoPz(hmdtn)4The preparation method comprises the following steps:
BiVO (bismuth oxide) is added4Adding the mixture into a solvent A, fully dispersing, and adding a solvent B containing tetrakis (1, 4-dithiino) tetraazacobalt porphyrin to BiVO4Uniformly mixing in a dispersion system, removing the solvent, and drying in vacuum to obtain the composite photocatalyst BiVO4/CoPz(hmdtn)4。
5. The method according to claim 4, wherein the solvent A is the same as the solvent B and is N, N-dimethylformamide, acetonitrile or tetrahydrofuran.
6. The method according to any one of claims 1 to 5, wherein the method is: adding a composite photocatalyst into a glucose aqueous solution, stirring to fully disperse the catalyst in a reaction system, directly using oxygen in the air as an oxidant, and taking visible light with the lambda of more than or equal to 420nm and the visible light intensity of 0.78W-cm-2-1.68 W·cm-2Under irradiation of (a) to effect oxidation of glucose.
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