CN110052242B - Load carbon quantum dot/W18O49Preparation method of photocatalytic renewable porous carbon adsorbent - Google Patents

Load carbon quantum dot/W18O49Preparation method of photocatalytic renewable porous carbon adsorbent Download PDF

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CN110052242B
CN110052242B CN201910342029.0A CN201910342029A CN110052242B CN 110052242 B CN110052242 B CN 110052242B CN 201910342029 A CN201910342029 A CN 201910342029A CN 110052242 B CN110052242 B CN 110052242B
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quantum dot
carbon quantum
porous carbon
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adsorbent
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CN110052242A (en
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王滨松
于晨阳
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Heilongjiang University
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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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • 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
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
    • 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
    • B01J20/30—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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols

Abstract

The invention discloses a loaded carbon quantum dot/W18O49A preparation method of a photocatalytic renewable porous carbon adsorbent relates to the technical field of material preparation, and comprises the following steps: (1) performing hydrothermal reaction on furfural wastewater, soaking the obtained precursor carbon material in KOH aqueous solution, and calcining to obtain a porous carbon adsorbent; (2) mixing citric acid and urea for hydrothermal reaction, filtering, dialyzing, and freeze-drying to obtain carbon quantum dots, and preparing a carbon quantum dot ethanol solution; (3) mixing WCl6Dissolving in absolute ethyl alcohol, adding polyethylene glycol, carbon quantum dot ethanol solution and porous carbon adsorbent into the mixture, performing hydrothermal reaction, and separating to obtain loaded carbon quantum dot/W18O49A photocatalytic regenerable porous carbon adsorbent. The method realizes the recycling of the furfural wastewater, the effective treatment of the phenol-containing wastewater and the photocatalytic regeneration recycling of the porous carbon material, and has good production and application values.

Description

Load carbon quantum dot/W18O49Preparation method of photocatalytic renewable porous carbon adsorbent
Technical Field
The invention relates to the technical field of material preparation, in particular to a method for preparing porous carbon-loaded carbon quantum dots/W by using high-concentration furfural wastewater as a carbon source18O49A method for preparing a renewable adsorbent by using a photocatalyst.
Background
With the rapid development of national economy, phenol as an important chemical raw material is widely applied to industries such as oil refining, coal conversion, petrochemical industry, medicines, pesticides and the like, and phenol has carcinogenicity, teratogenicity and difficult biodegradability, so that phenol-containing wastewater is discharged into the environment without treatment and seriously threatens human health. At present, the phenol-containing wastewater treatment becomes a hot problem in the field of wastewater treatment, the adsorption of a porous carbon material is widely concerned due to the advantages of high efficiency, easy operation and cyclic utilization, but the porous carbon material is favorable for the adsorption of organic pollutants due to the large aperture and high specific surface area, the regeneration is difficult after the adsorption saturation, the secondary utilization cannot be realized, the generated solid waste is directly discharged into the environment, the serious secondary pollution can be caused, and the method is not suitable for treating the high-concentration phenol wastewater; and most porous carbon materials are prepared from coal, petroleum, biomass and the like, and the preparation process has high energy consumption and releases harmful gases, so that the preparation method is not beneficial to environmental protection and energy conservation.
Materials with Near Infrared (NIR) shielding properties, particularly transition metal oxide nanostructures, are of increasing interest to researchers. W18O49The photocatalyst has strong and tunable local plasma resonance effect in the near-infrared light wavelength range of 780-2526nm, so that the photocatalyst has good light absorption performance in the near-infrared region of sunlight, but pure W18O49When the photocatalyst is used, electron holes are easy to recombine at the defect position, and the photocatalytic activity is greatly reduced.
Disclosure of Invention
In order to solve the problems, the invention provides a load carbon quantum dot/W18O49The preparation method of the photocatalytic renewable porous carbon adsorbent comprises the following steps:
(1) preparation of porous carbon material: carrying out hydrothermal reaction on high-concentration furfural wastewater, filtering to obtain a solid to obtain a precursor carbon material, soaking the precursor carbon material in a KOH aqueous solution, drying and calcining to obtain a porous carbon adsorbent taking the high-concentration furfural wastewater as a carbon source;
(2) preparing the carbon quantum dots: mixing citric acid and urea for hydrothermal reaction, cooling to room temperature, filtering by using a needle filter, dialyzing the filtered filtrate, and freeze-drying the obtained solution to obtain carbon quantum dots; dissolving the obtained carbon quantum dots in absolute ethyl alcohol, wherein 0.05g of carbon quantum dots are contained in 10mL of solution to obtain carbon quantum dot ethyl alcohol solution;
(3) supported carbon quantum dot/W18O49Preparing a photocatalytic renewable porous carbon adsorbent: mixing WCl6Dissolving in absolute ethanol (WCl6Adding into anhydrous ethanol, and placing in a magnetic stirrerStirring vigorously until WCl6Completely dissolving in absolute ethyl alcohol), adding polyethylene glycol, the carbon quantum dot ethanol solution prepared in the step (2) and the porous carbon adsorbent prepared in the step (1) into the mixture, uniformly mixing, adding the mixture into a high-temperature reaction kettle, carrying out hydrothermal reaction, and separating the mixture obtained after the reaction to obtain the loaded carbon quantum dot/W18O49A photocatalytic regenerable porous carbon adsorbent.
The high-concentration furfural wastewater in the step (1) is furfural wastewater under a primary distillation tower containing 15% by volume of furfural.
And (2) carrying out hydrothermal reaction in the step (1), wherein the reaction temperature is 200 ℃, and the reaction time is 8 h.
The concentration of the KOH aqueous solution in the step (1) is 1.12 g/mL; the soaking time is 10-18 h.
And (2) calcining under the protection of nitrogen, wherein the heating rate is 3 ℃/min, the calcining temperature is 800 ℃, and the constant-temperature calcining time at 800 ℃ is 1 h.
The mass ratio of the citric acid to the urea in the step (2) is 1: 4.
And (3) carrying out hydrothermal reaction in the step (2), wherein the reaction temperature is 160 ℃, and the reaction time is 6 h. The reaction vessel is a polytetrafluoroethylene reaction kettle.
And (3) the aperture of the needle type filter membrane in the step (2) is 0.22 mu m.
The dialysis in the step (2) adopts a dialysis bag for dialysis, and the molecular weight is 500-100 Da.
WCl in step (3)6The concentration in absolute ethyl alcohol is 0.005g/mL, the WCl6The mass to volume ratio of the polyethylene glycol is 1:100g/mL, the volume ratio of the polyethylene glycol to the carbon quantum dot ethanol solution is 2:1, and the mass to volume ratio of the porous carbon adsorbent to the carbon quantum dot ethanol solution is 1:10 g/mL;
and (3) a PPL (para-polyphenol) lining high-temperature reaction kettle is arranged in the high-temperature reaction kettle.
And (3) carrying out hydrothermal reaction at 240 ℃ for 20 h.
The separation in the step (3) is specifically as follows: centrifuging the obtained mixture, taking the precipitate, washing the precipitate with absolute ethanol, re-suspending, centrifuging, taking the precipitate, repeating the operation twice, and vacuum-drying the obtained precipitate at 70 ℃.
Advantageous effects
Firstly, the porous carbon adsorbent is prepared by using the high-concentration furfural wastewater as a carbon source, so that the recycling of the high-concentration furfural wastewater is realized, and the purposes of cyclic utilization of the adsorbent, treatment of the high-concentration phenol wastewater, environmental protection and pollution control are achieved.
Second, the present invention utilizes W18O49After the photocatalyst is compounded with the carbon quantum dots, the charge transfer rate of the carbon quantum dots is improved, so that photo-generated electrons on the carbon quantum dots can be transferred to W more quickly and effectively18O49The surface of the photocatalyst is adopted, so that the charge separation rate is improved, and the catalytic activity is further improved. Carbon quantum dots/W18O49The photocatalyst material is loaded on the prepared porous carbon adsorbent to prepare the loaded carbon quantum dot/W18O49The photocatalytic renewable porous carbon adsorbent has good stability and photocatalytic regeneration capacity, and has a good adsorption effect on phenol wastewater.
In summary, the invention utilizes high-concentration furfural wastewater to prepare the porous carbon material and load carbon quantum dots/W18O49Preparation of supported carbon quantum dot/W with renewable performance by photocatalyst material18O49The photocatalytic renewable porous carbon adsorbent solves the problem of the existing pure W18O49The photocatalyst has no strong phenol adsorption and photocatalytic degradation capability under near infrared light, and the traditional activated carbon material has the problems of poor phenol adsorption effect, no regeneration performance and incapability of recycling. The invention realizes the recycling of high-concentration furfural wastewater, the effective treatment of phenol-containing wastewater and the photocatalytic regeneration recycling of porous carbon materials, and has good production and application values. Using carbon quantum dots/W18O49The photocatalyst material is loaded on the porous carbon material, so that the porous carbon material with saturated adsorption is regenerated by photocatalysis, and the cyclic utilization of the adsorbent is realized. The addition of the carbon quantum dots improves the separation efficiency of photoproduction electrons and promotes the photoproduction electronsElectron-hole separation is carried out to W18O49The photocatalyst has better photocatalytic performance and can enable W to be18O49The crystal is better crystallized on the surface and in the aperture of the porous carbon material, and the compounding efficiency is improved. The adsorption results are compared to show that the three-phase composite sample loads the carbon quantum dots/W18O49Photocatalytic renewable porous carbon adsorbent and pure W18O49Photocatalyst, carbon quantum dot/W18O49Compared with three samples of the photocatalyst material and the porous carbon adsorbent, the adsorption performance is improved to a certain extent, and the removal efficiency of 500mg/L phenol after 180min can reach more than 80%. And the research of adsorption kinetics and adsorption isotherm is carried out on the sample, and the sample conforms to the pseudo-second-order adsorption kinetics and Langmuir adsorption isotherm. The prepared adsorbent has a good treatment effect on high-concentration phenol wastewater, and can be regenerated in a photocatalytic manner. The regeneration test of five cycles can show that the difference of the adsorption performance does not exceed 6 percent, which indicates that the sample has better regeneration performance.
Drawings
FIG. 1 is a graph comparing the adsorption performance of four materials on phenol;
FIG. 2 is a graph of the change in phenol concentration over the course of 5 cycle repetitions for four materials;
FIG. 3 Supported carbon Quantum dots/W18O49Scanning electron microscope images of photocatalytic renewable porous carbon adsorbent samples; FIG. a is a low power graph, and FIG. b is a high power graph;
FIG. 4 Supported carbon Quantum dots/W18O49Transmission electron micrographs of the photocatalytic regenerable porous carbon adsorbent; the figure a is a low-power figure and a partial enlarged figure, and the figure b is a high-power figure.
Detailed Description
Example 1 Supported carbon Quantum dots/W18O49Preparing a photocatalytic renewable porous carbon adsorbent:
(1) preparation of porous carbon material: preparing a precursor carbon material by using high-concentration furfural wastewater as a carbon source through a hydrothermal method, carrying out hydrothermal reaction on the high-concentration furfural wastewater for 8 hours at the temperature of 200 ℃, and preparing the precursor carbon materialThe precursor carbon material is subjected to KOH activation to enable the carbon material to have larger specific surface area and adsorption capacity, and the precursor carbon material which is soaked in KOH and dried is placed in N2Calcining at 800 ℃ under protection, heating up at a rate of 3 ℃/min, and calcining at constant temperature for 1h to obtain a porous carbon adsorbent taking high-concentration furfural wastewater as a carbon source;
the high-concentration furfural wastewater is furfural wastewater under a primary distillation tower containing 15% by volume of furfural;
the concentration of the KOH aqueous solution is 1.12 g/mL; the soaking time is 10 h.
(2) Preparing the carbon quantum dots: in a 50mL Teflon reactor, 1g of citric acid and 4g of urea were added. Carrying out hydrothermal reaction for 6h at the temperature of 160 ℃. Cooling to room temperature, adsorbing and filtering the supernatant by using a pinhole filter, adopting a filter membrane with the aperture of 0.22 mu m, dialyzing by using a dialysis bag (molecular weight: 500-100Da) after filtering to obtain carbon quantum dots (CD), and dissolving the carbon quantum dots in absolute ethyl alcohol, wherein 0.05g of carbon quantum dots are contained in each 10mL of solution to obtain the carbon quantum dot ethanol solution.
(3) Supported carbon quantum dot/W18O49Preparing a photocatalytic renewable porous carbon adsorbent: 0.2g of WCl6Dissolving in 40mL absolute ethyl alcohol, placing on a magnetic stirrer, and stirring vigorously6After completely dissolving in absolute ethanol, 20mL of polyethylene glycol (PEG) and 10mL of the carbon quantum dot ethanol solution prepared in step (2) were introduced into the mixture, 1.0g of the porous carbon adsorbent prepared in step (1) was added, the mixture was stirred, mixed uniformly, charged into a 100mL PPL (para-polyphenolic phenol) lined high-temperature reaction kettle, and subjected to hydrothermal treatment at 240 ℃ for 20 hours. And centrifuging the mixture in the reaction kettle after reaction, reserving the centrifuged blue solid, repeatedly washing and centrifuging for 3 times by using absolute ethyl alcohol, and removing organic matter impurities in the product. Finally, the obtained solid is dried in vacuum at 70 ℃ to obtain the loaded carbon quantum dot/W18O49Photocatalytic renewable porous carbon adsorbent (carbon quantum dot/W for short)18O49Carbon).
Comparative example
(3) Pure W18O49Photocatalyst and carbon quantumdot/W18O49Preparation of photocatalyst material:
a) pure W18O49Preparation of the photocatalyst: 0.2g of WCl6Dissolving in 40mL of anhydrous ethanol, introducing 20mL of polyethylene glycol (PEG) into the mixture, vigorously stirring until the mixture is completely dissolved to obtain a photocatalyst precursor, and performing hydrothermal treatment at 240 ℃ for 20h to obtain pure W18O49Photocatalyst sample (W for short)18O49)。
b) Carbon quantum dot/W18O49Preparation of photocatalyst material sample: namely, after introducing 10mL of the carbon quantum dot ethanol solution prepared in the step (2) of the example into the photocatalyst precursor, the photocatalyst precursor was subjected to hydrothermal treatment at 240 ℃ for 20 hours to obtain carbon quantum dots/W18O49Photocatalyst material sample (carbon quantum dot/W for short)18O49)。
Performance testing and analysis:
1) adsorption Performance test
In order to analyze the phenol adsorption performance of the material, the prepared loaded carbon quantum dot/W is selected18O49Photocatalytic renewable porous carbon adsorbent, pure W18O49Photocatalyst, carbon quantum dot/W18O49The photocatalyst material and the porous carbon adsorbent are respectively used as the 'adsorbent' to carry out adsorption performance test on the simulated phenol wastewater: putting 0.05g of adsorbent into 50mL of phenol solution with the concentration of 500mg/L to obtain a mixture, pouring the mixture into a 100mL beaker, placing the beaker on a constant-temperature magnetic stirrer, taking a small amount (equal amount) of the mixture for filtering at 0min, 30min, 60min, 90min, 120min, 150min and 180min respectively, taking 2mL of solution after filtering, fixing the volume to a 200mL volumetric flask, and measuring the phenol concentration in the solution by using a 4-aminoantipyrine direct spectrophotometry (HJ 503-.
2) Test for regeneration Performance
In order to analyze the photocatalytic regeneration performance of the material, the prepared load carbon quantum dot/W is selected18O49Photocatalytic renewable porous carbon adsorbent, pure W18O49Photocatalyst, carbon quantum dot/W18O49The photocatalytic regeneration performance is tested by respectively using four materials, namely a photocatalyst material and a porous carbon adsorbent, as the adsorbents: putting 0.05g of adsorbent into 50mL of 500mg/L phenol solution, putting the solution into a beaker, putting the beaker on a constant-temperature magnetic stirrer, stirring the solution at room temperature for 30min to adsorb pollutants, measuring the phenol concentration of the solution according to the method in the step 1) at 0min, 15 min and 30min respectively, then centrifugally separating the adsorbent from the solution, putting the separated adsorbent (separated solid) into a glass vessel, irradiating the adsorbent for 30min by using a 200W infrared lamp as a near infrared light source at a position 20cm away from a light source, after the photocatalytic reaction, adding the adsorbent into 50mL of 500mg/L phenol solution again, repeating the adsorption experiment, and repeating the cycle for 5 times.
And (4) analyzing results:
FIG. 1 shows that four comparative samples load carbon quantum dots/W within 180min18O49Photocatalytic renewable porous carbon adsorbent, pure W18O49Photocatalyst, carbon quantum dot/W18O49The comparative graph of the adsorption effect of the photocatalyst material and the porous carbon adsorbent on 500mg/L phenol solution. As can be seen from the figure, the sample prepared after compounding the porous carbon material is compared with pure W18O49The adsorption effect of the photocatalyst on phenol is obviously improved, and carbon quantum dots and W are added18O49After the recombination, the adsorption removal efficiency of phenol is about 40%, which means that the carbon material has an important effect on the adsorption capacity of the sample. Porous carbon adsorbent and carbon quantum dot/W generated after high-concentration furfural wastewater is carbonized and activated by KOH18O49After the photocatalyst material is compounded, the removal rate of phenol is greatly improved and can reach more than 80%.
The adsorption time of the sample in FIG. 2 is controlled at 30min, and after each adsorption, the sample is illuminated for 30min for regeneration experiment, and then the adsorbent is separated from the solution by centrifugation. After drying, the sample was recovered and used as an adsorbent to perform adsorption test again, and the cycle was repeated for 5 times, and the removal efficiency was 65.3%, 62.7%, 64%, 61.9% and 60%, respectively.
As can be seen from the figure, after 5 regeneration cycles, the removal efficiency of the sample to phenol still has not too obvious change, the absorption performance loss is within 6%, and the removal efficiency can still reach more than 60% within 30 min. Indicating the loading of carbon quantum dots/W18O49The photocatalytic regenerable porous carbon adsorbent is stable during adsorption and photocatalytic regeneration. From this, it can be concluded that the carbon quantum dots/W are supported18O49The photocatalytic renewable porous carbon adsorbent has very good stability.
FIG. 3 shows the carbon quantum dot/W loading18O49SEM images of photocatalytic regenerable porous carbon adsorbent samples, where panel a is a low power panel of photocatalytic regenerable adsorbent and panel b is a high power panel of adsorbent surface pore size. As can be seen from the figure, in the pores formed by the activated porous carbon, the carbon quantum dots/W18O49The photocatalyst is distributed in the three samples, and the success of compounding the three samples is proved.
FIG. 4 shows the carbon quantum dot/W loading18O49Transmission electron micrographs of samples of photocatalytic regenerable porous carbon adsorbent are shown. As can be seen from the figure, a large number of pore channels exist in the three-phase compounded sample, and a porous carbon spherical structure is formed on the surface of the sample after the compounding. The carbon quantum dots/W can be seen from the direction of the arrows circled in the figure18O49The high power of the photocatalyst material pellet is shown in the right figure, and clear lattice stripes can be seen from the line shape of the pellet surface, the lattice spacing is 0.23nm, and W18O49The characteristic peaks of the (511) crystal face of the photocatalyst are matched. Description of W18O49The photocatalyst is successfully loaded on the surface of the carbon quantum dot, and the carbon quantum dot/W is proved18O49The photocatalyst material successfully enters the pore channels of the porous carbon material sample and is combined.

Claims (9)

1. Load carbon quantum dot/W18O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of porous carbon material: carrying out hydrothermal reaction on high-concentration furfural wastewater, filtering to obtain a solid to obtain a precursor carbon material, soaking the precursor carbon material in a KOH aqueous solution, drying and calcining to obtain a porous carbon adsorbent taking the high-concentration furfural wastewater as a carbon source;
(2) preparing the carbon quantum dots: mixing citric acid and urea for hydrothermal reaction, cooling to room temperature, filtering by using a needle filter, dialyzing the filtered filtrate, and freeze-drying the obtained solution to obtain carbon quantum dots; dissolving the obtained carbon quantum dots in absolute ethyl alcohol, wherein 0.05g of carbon quantum dots are contained in each 10mL of solution to obtain a carbon quantum dot ethyl alcohol solution;
(3) supported carbon quantum dot/W18O49Preparing a photocatalytic renewable porous carbon adsorbent: mixing WCl6Dissolving in absolute ethyl alcohol, adding polyethylene glycol, the carbon quantum dot ethanol solution prepared in the step (2) and the porous carbon adsorbent prepared in the step (1) into the mixture, uniformly mixing, adding the mixture into a high-temperature reaction kettle, carrying out hydrothermal reaction, and separating the mixture obtained after the reaction to obtain the loaded carbon quantum dot/W18O49A photocatalytic regenerable porous carbon adsorbent;
wherein the high-concentration furfural wastewater in the step (1) is furfural wastewater under a primary distillation tower containing 15% by volume of furfural.
2. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: and (2) carrying out hydrothermal reaction in the step (1), wherein the reaction temperature is 200 ℃, and the reaction time is 8 h.
3. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: and (2) calcining under the protection of nitrogen, wherein the heating rate is 3 ℃/min, the calcining temperature is 800 ℃, and the constant-temperature calcining time at 800 ℃ is 1 h.
4. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: the mass ratio of the citric acid to the urea in the step (2) is 1: 4.
5. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: carrying out hydrothermal reaction in the step (2), wherein the reaction temperature is 160 ℃, and the reaction time is 6 h; the reaction vessel is a polytetrafluoroethylene reaction kettle.
6. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: WCl in step (3)6The concentration in absolute ethyl alcohol is 0.005g/mL, the WCl6The ratio of the mass of the porous carbon adsorbent to the volume of the carbon quantum dot ethanol solution is 1:100g/mL, the ratio of the mass of the porous carbon adsorbent to the volume of the carbon quantum dot ethanol solution is 2:1, and the ratio of the mass of the porous carbon adsorbent to the volume of the carbon quantum dot ethanol solution is 1:10 g/mL.
7. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: and (3) carrying out hydrothermal reaction at 240 ℃ for 20 h.
8. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: the separation in the step (3) is specifically as follows: centrifuging the obtained mixture, taking the precipitate, washing the precipitate with absolute ethanol, re-suspending, centrifuging, taking the precipitate, repeating the operation twice, and vacuum-drying the obtained precipitate at 70 ℃.
9. The supported carbon quantum dot/W of claim 118O49The preparation method of the photocatalytic renewable porous carbon adsorbent is characterized by comprising the following steps: the concentration of the KOH aqueous solution in the step (1) is 1.12 g/mL; the soaking time is 10-18h(ii) a The aperture of the needle type filter membrane in the step (2) is 0.22 mu m; the dialysis in the step (2) adopts a dialysis bag for dialysis, and the molecular weight is 500-100 Da.
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