CN116786084A - Renewable patulin adsorbent and preparation method thereof - Google Patents
Renewable patulin adsorbent and preparation method thereof Download PDFInfo
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZRWPUFFVAOMMNM-UHFFFAOYSA-N Patulin Chemical compound OC1OCC=C2OC(=O)C=C12 ZRWPUFFVAOMMNM-UHFFFAOYSA-N 0.000 title abstract description 110
- 238000001179 sorption measurement Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 7
- 230000008929 regeneration Effects 0.000 claims abstract description 6
- 238000011069 regeneration method Methods 0.000 claims abstract description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004201 L-cysteine Substances 0.000 claims description 8
- 235000013878 L-cysteine Nutrition 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 claims description 3
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- 239000011888 foil Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 claims description 3
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- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006177 thiolation reaction Methods 0.000 abstract 1
- 235000015197 apple juice Nutrition 0.000 description 9
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000008363 phosphate buffer Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- GHCZTIFQWKKGSB-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;phosphoric acid Chemical compound OP(O)(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O GHCZTIFQWKKGSB-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CCBICDLNWJRFPO-UHFFFAOYSA-N 2,6-dichloroindophenol Chemical compound C1=CC(O)=CC=C1N=C1C=C(Cl)C(=O)C(Cl)=C1 CCBICDLNWJRFPO-UHFFFAOYSA-N 0.000 description 1
- KIUMMUBSPKGMOY-UHFFFAOYSA-N 3,3'-Dithiobis(6-nitrobenzoic acid) Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(SSC=2C=C(C(=CC=2)[N+]([O-])=O)C(O)=O)=C1 KIUMMUBSPKGMOY-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3441—Regeneration or reactivation by electric current, ultrasound or irradiation, e.g. electromagnetic radiation such as X-rays, UV, light, microwaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J27/24—Nitrogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention discloses a renewable patulin adsorbent and a preparation method thereof, and the invention is characterized in that the patulin adsorbent is prepared by the method of the invention in g-C 3 N 4 grafting-SH on the surface of the material, improving the adsorption performance of the material on PAT, and simultaneously utilizing g-C 3 N 4 The material has the photocatalytic effect under visible light, realizes the recycling of the adsorbent through the process of light-shielding adsorption and photocatalytic regeneration, and reduces the cost of the adsorbent; compared with the prior common sulfhydryl functional PAT adsorbent, has the advantages of photocatalysisActive thiolation g-C 3 N 4 The method not only has high adsorption capacity and selectivity, but also solves the recycling problem which is paid attention to in the past, effectively reduces the cost of the adsorbent, and is beneficial to industrialized application and popularization.
Description
Technical Field
The invention relates to a renewable patulin adsorbent and a preparation method thereof.
Background
Patulin (PAT) is a small molecular fungus secondary metabolite, widely exists in various foods, particularly fruits and vegetables and processed products thereof, and has stronger acute and chronic toxicity. The adsorption method is a PAT removal method which is simple in operation, high in efficiency and economical, does not need high equipment investment, rarely relates to industrialization resistance caused by consumer acceptance and regulatory problems, and has great practical value and commercial potential. The traditional macroporous resin, activated carbon and other adsorbents have great negative effects on the quality of the juice and have limited PAT removal effect. Several studies in recent years have shown that breakthrough improvement of adsorption capacity and selectivity of PAT can be achieved by conjugate addition of α, β -unsaturated carbonyl groups and mercapto groups (-SH) of PAT. However, covalent bonding of PAT to-SH during adsorption results in difficult reuse of the-SH functionalized adsorbent, which limits the industrial application of this technology.
The adsorption capacity and selectivity of the traditional adsorbent to PAT are low, while the-SH functionalization can effectively improve the adsorption performance of PAT, the combination of the PAT and the SH is almost irreversible, so that the adsorbent cannot be recycled. Currently, dithiothreitol is the only reducing agent proven to be capable of achieving regeneration of the-SH adsorbent, however, it is expensive and has a certain toxicity.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a regenerable PAT adsorbent and a preparation method thereof. The invention solves the problem that the PAT adsorbent with mercapto functionalization is difficult to regenerate after being combined with PAT molecules by utilizing the advanced oxidation effect of the surface of the photocatalytic material, and realizes the reutilization of the PAT adsorbent based on the-SH functionalization.
The invention is implemented by the method of the invention in g-C 3 N 4 grafting-SH on the surface of the material, improving the adsorption performance of the material on PAT, and simultaneously utilizing g-C 3 N 4 The photocatalytic effect of the material under visible light is realized through the process of light-proof adsorption and photocatalytic regenerationThe existing adsorbent is recycled, so that the cost of the adsorbent is reduced. The key innovation of the invention is that: 1. a sulfhydryl grafting mode; 2. adsorption-photocatalysis coupling, realizing recycling of materials.
The technical scheme of the invention is as follows:
renewable g-C 3 N 4 SH adsorbent, urea as precursor material, formed into g-C by calcination 3 N 4 Glutaraldehyde is used as a cross-linking agent, L-cysteine is used as a sulfhydryl donor, and g-C 3 N 4 And modified.
Renewable g-C 3 N 4 A process for the preparation of an SH adsorbent comprising the steps of:
(1) Preparation of g-C 3 N 4
Wrapping urea with aluminum foil, placing in an alumina crucible, then placing in a muffle furnace, heating to 500-600 ℃, calcining for 1-3 h under air flow to obtain g-C 3 N 4 ；
Preferably, the temperature rising rate is 5 ℃/min;
preferably, the calcination temperature is 550 ℃ and the time is 2 hours;
(2) Mercapto grafting
g-C obtained in the step (1) 3 N 4 Dispersing in glutaraldehyde water solution, adding L-cysteine, stirring at 20-40 deg.c for reaction for 4-8 hr, rinsing the reaction mixture with deionized water, stoving to obtain g-C 3 N 4 -SH adsorbent;
preferably g-C 3 N 4 The mass ratio of the L-cysteine to the L-cysteine is 100:50 to 70, particularly preferably 100:60;
preferably, the mass fraction of the aqueous solution of glutaraldehyde is 2.5%; glutaraldehyde aqueous solution with g-C 3 N 4 The volume mass ratio of (3-5): 100, mL/mg;
the reaction is preferably carried out at a temperature of 30℃for a period of 6 hours.
The renewable g-C of the invention 3 N 4 The SH adsorbent can be recycled for the adsorption of PAT.
Specifically, g-C 3 N 4 The adsorption reaction of the SH adsorbent to the PAT is carried out under the light-shielding condition; after the adsorption reaction is completed, g-C with PAT adsorbed thereon 3 N 4 SH is degraded under illumination, so that the regeneration of the adsorbent is realized.
The technical principle of the invention is as follows:
g-C 3 N 4 the photocatalytic material has a wide absorption spectrum and can play a role in the visible light range, and can be formed by calcining a compound with high carbon and nitrogen content. The surface of the PAT-based polymer contains more amino groups, which is favorable for grafting-SH for efficient adsorption of PAT molecules by a glutaraldehyde crosslinking method. After adsorption, g-C is used 3 N 4 The photocatalytic property of the PAT-SH catalyst can conveniently and rapidly degrade the complex of PAT and-SH to regenerate the-SH, thereby realizing the recycling of the mercapto-functionalized PAT adsorbent.
The invention has the beneficial effects that:
1. compared with the prior common mercapto-functionalized PAT adsorbent, the mercapto-functionalized g-C adsorbent with photocatalytic activity 3 N 4 Not only has high adsorption capacity and selectivity, but also solves the recycling problem which is paid attention to in the past, and effectively reduces the cost of the adsorbent.
2. Although research on degradation of PAT by photocatalytic materials has been carried out, direct application of a photocatalyst to food has a great influence on food quality due to non-selective advanced oxidation of the photocatalyst. In the invention, the adsorption and photocatalysis technology is combined, and the effect of direct photocatalysis on the food quality is avoided through light-proof adsorption-photocatalysis regeneration, and the problem that the common mercapto-functionalized adsorbent is difficult to desorb and recycle after being combined with PAT, so that the adsorption treatment cost is high is solved.
3. Compared with the traditional photocatalytic material TiO 2 In contrast, g-C selected in this study 3 N 4 The absorption spectrum range is wider, photocatalysis can be realized under visible light, and the reaction condition is more convenient, so that the method is more beneficial to industrialized application and popularization.
Drawings
FIG. 1 is a schematic illustration of the process flow of the present invention.
FIG. 2g-C after calcination 3 N 4 。
FIG. 3g-C during adsorption of patulin 3 N 4 SH adsorption amount and mercapto content change curve.
FIG. 4 is g-C 3 N 4 Reusability of the SH with patulin.
Detailed Description
The present invention is further described below by way of specific examples, but the scope of the present invention is not limited thereto.
Example 1A reusable g-C 3 N 4 Preparation of-SH patulin adsorbent
The preparation method is as shown in figure 1, urea is used as a precursor substance, and light yellow g-C is formed by high-temperature calcination 3 N 4 Then glutaraldehyde is used as a cross-linking agent, L-cysteine is used as a sulfhydryl donor, and g-C 3 N 4 Modifying the material to obtain g-C 3 N 4 -SH patulin adsorbent.
The preparation method comprises the following steps:
1) Preparation of g-C 3 N 4 Materials: 10g of urea was weighed into a covered alumina crucible, wrapped with aluminum foil, and then heated to 550℃in a muffle furnace at a heating rate of 5℃per minute, and maintained under an air flow for 2 hours. Grinding and collecting the solid obtained after calcination to obtain g-C 3 N 4 . As shown in fig. 2, the calcined urea exhibited a pale yellow color. g-C due to gas generation during calcination 3 N 4 A large number of voids appear on the surface and the powder texture is fluffy. g-C after calcination 3 N 4 The yield was 3.75%.
2) Thiol grafting: weighing 100mg g-C 3 N 4 Dispersing sample in 4mL (2.5%, w/w) glutaraldehyde water solution, adding 60.6mg L-cysteine, stirring at 30deg.C and 150rpm for reaction for 6h, rinsing with deionized water for three times, and oven drying at 80deg.C to obtain g-C 3 N 4 -SH。
3) Measurement of mercapto group content: dispersing the adsorbent in pure water by ultrasonic wave, mixing 1mL of the adsorbent dispersion with 1mL of phosphate buffer (0.5M, pH 8.0) and 2mL of ellman's solution (DTNB 0.3 g/L) uniformlyAnd then reacting for 2 hours at room temperature, centrifuging, and taking the supernatant to measure the absorbance at 450nm, wherein a reagent blank is used as a reference. The method was calibrated by plotting standard curves using different concentrations of L-cysteine. The results are shown in FIG. 3, g-C 3 N 4 The initial SH-SH content was 96. Mu. Mol/g, and the PAT adsorption amount increased and the mercapto content decreased as the adsorption reaction proceeded, confirming the important role of SH in PAT removal.
Example 2g-C 3 N 4 Adsorption effect of SH adsorbent on patulin and repeated use experiment
The specific method comprises the following steps:
1) Adsorption of patulin: PAT solution (10. Mu.g/mL) was prepared with 10mM citric acid-phosphate buffer pH 4.0, the adsorbent addition was 2mg/mL, and reacted in a 30℃constant temperature shaker at 150rpm under dark conditions for 24h. The concentration of patulin after adsorption was measured by HPLC using a reversed phase chromatographic column (5 μm,4.6 mm. Times.250 mm) with a mobile phase of acetonitrile/water 1:9 (v/v) and a sample injection amount of 20. Mu.L at a column temperature of 40℃at 276 nm. The adsorption amount was calculated from the PAT concentration change before and after adsorption, and the results are shown in Table 1, g-C 3 N 4 The adsorption amount of the SH material to PAT in the buffer solution is g-C 3 N 4 3.6 times of (3).
2) Repeated usability experiment: PAT solution (4. Mu.g/mL) was prepared with 10mM citric acid-phosphate buffer pH 4.0, the adsorbent addition was 2mg/mL, and reacted under dark conditions in a 30℃constant temperature shaker at 150rpm for 12h. The adsorbent was centrifuged (8000 rpm,5 min), the supernatant was collected, the pellet was washed once with deionized water, 4mL of citric acid-phosphate buffer was added and reacted in a 30 ℃ constant temperature shaker under light at 150rpm for 12h, the adsorbent was centrifuged and washed. Repeating the above process of 'dark adsorption-light regeneration' for 4 times, and carrying out HPLC detection on PAT concentration in supernatant after 4 times of dark reaction, and calculating adsorption efficiency during recycling. As shown in FIG. 4, the adsorbent still maintains good adsorption performance at the 5 th adsorption cycle, and the adsorption efficiency is maintained at 80% or more of the first use.
Example 3g-C 3 N 4 Application of-SH adsorbent in apple juice
1) Adsorption experiment of patulin: PAT standard (10 mug/mL) is added into apple juice to obtain a simulated pollution sample, the addition amount of the adsorbent is 2mg/mL, and the mixture is reacted for 24 hours in a constant temperature shaking table at 30 ℃ under the condition of rotating at 150rpm and darkness. PAT concentration after adsorption was measured by HPLC, and the method was the same as in example 2. The results are shown in Table 1, g-C compared to the buffer 3 N 4 The adsorption amount of PAT in apple juice is reduced by 76%, which is probably due to the complex apple juice components, and some small molecular substances are bound on the surface of the adsorbent, so that the binding sites of PAT are reduced. g-C 3 N 4 SH has reduced PAT adsorption amount in apple juice compared with buffer solution, but the reduction of the PAT adsorption amount is only 30%, and the adsorption amount is unmodified g-C 3 N 4 10-fold of (A), indicates that the modification of-SH effectively improves g-C 3 N 4 Adsorption affinity and selectivity to PAT in complex apple juice systems.
2) And (3) measuring quality parameters of the juice: the color value, light transmittance, soluble solids, reducing sugar, titratable acid, total phenol and vitamin C content of the juice before and after adsorption were measured to evaluate the effect of the adsorption treatment on the juice quality. The soluble solids content of the juice was measured using a hand-held refractometer. The total acid content in the sample was quantified by titration with 0.1mol/L NaOH and the results are expressed as grams of malic acid per liter of juice. The transmittance and color values of the juice were measured by spectrophotometry at 625nm and 440nm, respectively, with distilled water as a blank. The total phenol content of the juice was determined using the Fu Lin Fen reagent. Vitamin C was measured using a standard 2, 6-dichlorophenol-indophenol dye method. The results are shown in Table 2, g-C 3 N 4 The SH material had no significant effect on key quality parameters of apple juice such as soluble solids, clarity, total acids, and total phenol content.
TABLE 1g-C 3 N 4 And g-C 3 N 4 Comparison of adsorption of SH to PAT in citrate-phosphate buffer and apple juice
TABLE 2 comparison of apple juice quality parameters before and after PAT adsorption treatment
Note that: the different letters in the table represent significant differences between groups (P < 0.05).
Claims (9)
1. Renewable g-C 3 N 4 -SH adsorbent, characterized in that said regenerable g-C 3 N 4 The SH adsorbent takes urea as a precursor substance and is calcined to form g-C 3 N 4 Glutaraldehyde is used as a cross-linking agent, L-cysteine is used as a sulfhydryl donor, and g-C 3 N 4 And modified.
2. Renewable g-C 3 N 4 -a process for the preparation of an SH adsorbent, characterized in that it comprises the steps of:
(1) Preparation of g-C 3 N 4
Wrapping urea with aluminum foil, placing in an alumina crucible, then placing in a muffle furnace, heating to 500-600 ℃, calcining for 1-3 h under air flow to obtain g-C 3 N 4 ；
(2) Mercapto grafting
g-C obtained in the step (1) 3 N 4 Dispersing in glutaraldehyde water solution, adding L-cysteine, stirring at 20-40 deg.c for reaction for 4-8 hr, rinsing the reaction mixture with deionized water, stoving to obtain g-C 3 N 4 -SH adsorbent.
3. The method according to claim 2, wherein in the step (1), the temperature rise rate is 5 ℃/min.
4. The method according to claim 2, wherein in the step (1), the calcination temperature is 550℃and the time is 2 hours.
5. The method of claim 2, wherein,in step (2), g-C 3 N 4 The mass ratio of the L-cysteine to the L-cysteine is 100:50 to 70.
6. The production method according to claim 2, wherein in the step (2), the mass fraction of the aqueous glutaraldehyde solution is 2.5%; glutaraldehyde aqueous solution with g-C 3 N 4 The volume mass ratio of (3-5): 100, mL/mg.
7. The process according to claim 2, wherein in step (2), the reaction temperature is 30℃and the reaction time is 6 hours.
8. The renewable g-C of claim 1 3 N 4 The SH adsorbent cycle is applied to the adsorption of PAT.
9. The use according to claim 8, wherein g-C 3 N 4 The adsorption reaction of the SH adsorbent to the PAT is carried out under the light-shielding condition; after the adsorption reaction is completed, g-C with PAT adsorbed thereon 3 N 4 SH is degraded under illumination, so that the regeneration of the adsorbent is realized.
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