CN116212931A - Visible light driven seawater in-situ Fenton system and application thereof in rapid degradation of organic micro-pollutants in water - Google Patents

Visible light driven seawater in-situ Fenton system and application thereof in rapid degradation of organic micro-pollutants in water Download PDF

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CN116212931A
CN116212931A CN202310299650.XA CN202310299650A CN116212931A CN 116212931 A CN116212931 A CN 116212931A CN 202310299650 A CN202310299650 A CN 202310299650A CN 116212931 A CN116212931 A CN 116212931A
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visible light
seawater
fenton oxidation
degradation
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李心忠
骆盼盼
刘春杰
薛涵与
夏建荣
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Minjiang University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Abstract

The invention discloses a visible light driven seawater in-situ Fenton system and application thereof in rapid degradation of organic micropollutants in water, wherein hydroxy functional double doping g-C is adopted 3 N 4 In-situ photo Fenton oxidation system is constructed by taking seawater, air and ferrous salt as raw materials for a visible light catalyst, the oxidation system is continuously added into aqueous solution containing BPA and/or TC and/or CIP, and light is exerted under the drive of visible lightSynergistic effect of oxidation/Fenton oxidation, i.e. reduction of Fe by photogenerated electrons 3+ Is Fe 2+ Increase Fe 3+ /Fe 2+ Along with the new path, the photo-generated holes and active oxygen species generated by Fenton oxidation participate in the oxidative degradation of the organic substrate. The method does not need to add hydrogen peroxide, is rapid and efficient in degradation, does not generate iron mud in the process, has small ferric salt consumption, and realizes rapid and efficient degradation of BPA, TC and CIP in the water phase under the environment-friendly low-carbon condition.

Description

Visible light driven seawater in-situ Fenton system and application thereof in rapid degradation of organic micro-pollutants in water
Technical Field
The invention belongs to the technical field of chemical products and preparation thereof, and in particular relates to visible light driven seawater generation H 2 O 2 Constructing a Fenton oxidation system by in-situ coupling light with ferrous salt; the method for rapidly and efficiently degrading antibiotics tetracycline hydrochloride (TC), ciprofloxacin (CIP) and environmental hormone bisphenol A (BPA) in water under the conditions of room temperature, normal pressure, neutral or weak acid reaction by the constructed light Fenton system.
Background
Fenton oxidation was carried out in 1896 French chemists Fenton uses Fe 2+ salt/H 2 O 2 The system, when oxidizing tartaric acid, finds that the oxidation mechanism is a two-step reaction: 1) H 2 O 2 Oxidation of Fe 2+ Ion generation of hydroxyl radicals and Fe 3+ Ions; 2) Fe (Fe) 3+ The ions react with hydrogen peroxide to generate Fe 2+ Passing Fe 3+ /Fe 2+ Circulation is carried out to enable the reaction system to continuously generate oxidation-reduction potential as high as (E) 0 =2.8v), which serves as a strong oxidizing active species, captures protons of organic compounds, generates organic radicals, and the unstable organic radicals are further degraded into non-toxic small molecules, and finally mineralized into inorganic substances such as carbon dioxide and water. Fenton oxidation has the outstanding characteristics of strong oxidizing capability, universality of organic substrates, simple process and the like, so that the Fenton oxidation is widely applied to the aspects of organic sewage treatment and the field of environmental treatment, in particular to the treatment of organic pollutants which are difficult to biodegrade such as pesticides, antibiotics and the like [ J Pignatelo,E Oliveros.AMackay.Advance oxidation process for organic contamiant destruction based on the Fenton reaction and related chemistry[J]Critical reviews in environmental science and technology,2006,36(1):1–84.]. Fe in traditional homogeneous Fenton oxidation 2+ The regeneration reaction rate is slower, a large amount of iron mud is generated in practical application, the consumption of ferric salt is increased, and new solid waste is introduced into the water body. Furthermore, in order to promote the progress of the reaction, it is necessary to control the pH of the system within a narrow range of 2.0 to 3.5, which results in H 2 O 2 Greatly reduces the utilization rate of the sewage and simultaneously lengthens the sewage treatment process flow. In order to solve the problems of the traditional homogeneous Fenton oxidation reaction, heterogeneous Fenton oxidation is developed, and a solid Fe-based catalyst is introduced to replace Fe 2+ Ions, catalyzing H at the surface interface thereof 2 O 2 The generation of hydroxyl free radicals avoids the generation of iron mud in the reaction on one hand, and realizes the recycling of the in-situ catalyst on the other hand. Such as Chen et al [ H Chen, Z zhang. Heterogenesis Fenton-like catalytic degradation of2,4-dichlorophenoxyacetic acid in water with FeS [ J ]]Chem.Eng.J.,2015,273:481–489.]FeS is adopted as a heterogeneous catalyst, the herbicide 2,4-dichlorophenoxyacetic acid in the water phase is degraded, the removal rate can reach 70.4%, and the pH range of the reaction is expanded from 2.0 to 6.5.FeS is recycled for 5 times, and the catalytic active matrix is kept unchanged. The reported disadvantage is degradation times as long as 300min. Aiming at mass transfer limitation existing in heterogeneous Fenton oxidation system, shi et al [ J Shi, L Zhang. Fe@Fe ] 2 O 3 core shell nanowires enchanced Fenton oxidation by accelerating the Fe(3)/Fe(2)[J]Water Res.,2014,59:145-153.]Core-shell structure Fe@Fe with nanowire morphology is prepared 2 O 3 Fe in the core during the degradation reaction is activated by molecular oxygen to form superoxide radical (. O) 2 - )，·O 2 - Fe in shell layer formed in reaction 3+ Reduction to Fe 2+ Promote Fe 3+ /Fe 2+ The generation of hydroxyl free radicals is effectively improved, the generation of hydroxyl free radicals is improved by 38 times compared with the conventional homogeneous Fenton oxidation, and the generation of hydroxyl free radicals is improved by 2-4 orders of magnitude compared with a common iron-based Fenton catalyst. The results show that the medicine is effective inExcessively increase Fe 3+ /Fe 2+ The following of new paths is an effective way to increase Fenton oxidation. The insufficient heterogeneous Fenton reaction depends on solid interface iron activation H to a great extent 2 O 2 ROS (reactive oxygen species) generation, such that H 2 O 2 The dosage is greatly increased. Heterogeneous photo Fenton oxidation, such as Huang et al [ X Huang, H Zhou, X Yue. Novel magnetic Fe ] has been developed using photo-generated electrons in the semiconductor photocatalytic process as a reducing agent 3 O 4 /FeOOH nanocomposites and their enhanced mechanism for tetracycline hydrochloride removal in the visble photo-Fenton process[J]ACS Omega,2021,6(13):9095–489103.]Magnetic Fe is prepared by adopting hydrothermal synthesis 3 O 4 alpha-FeOOH heterojunction, utilizing the photocatalytic activity of FeOOH unit to generate photo-generated electron and hole, and reducing Fe by photo-generated electron 3+ Is Fe 2+ The photo-generated holes oxidize the TC molecules adsorbed on the surface, so that the photo/chemical synergistic oxidation effect is exerted, and the TC is deeply degraded into carbon dioxide and water. Qian et al [ Qian X, wu Y, feOOH quantum dots coulped g-C 3 N 4 for visible light driving photo-fentonl degradation of organics pollutants[J]Appl.Catal.B:Environ.,2018,237:513-520]From g-C with good visible light response and chemical and thermal stability 3 N 4 Starting from the original, the amino functional groups rich in the structure are used as active sites, and the amorphous FeOOH quantum dots are introduced to construct FeOOH/g-C 3 N 4 Heterogeneous photocatalytic system, in contrast to pure photocatalytic system g-C 3 N 4 The mineralization efficiency of the phenol is improved by 7 times. However, all the above reports require grade H of the external processing industry 2 O 2 Constructing a Fenton oxidation system and industrial H 2 O 2 The synthesis process of (a) generally adopts a main anthraquinone method (AQ method), has the problems of long process flow, multi-step catalytic reaction, high energy consumption, high environmental pollution, safety risk (explosion) in the production process and the like, and simultaneously has the industrial H 2 O 2 The Fenton oxidation can not be transported for a long distance and stored for a long time, so that the large-scale industrial degradation application of organic pollutants is limited. With water and O abundant on earth 2 Is used as a resource, utilizes sunlight as energy and is communicated withCross O 2 Reduction or oxidation of water to H 2 O 2 The method is an ideal synthesis method with environmental protection, low carbon and high efficiency. Hao et al [ Hao A, luhan J.improved H 2 O 2 photogenration by KOH-dopted g-C 3 N 4 under visible light irradiation due to synergistic effect ofN defects and Kmodification[J]Applied surfaced science 2020,527.]Introducing KOH into g-C using doping strategy 3 N 4 In the bulk structure, inorganic alkali doped g-C is obtained 3 N 4 Taking the catalyst as a visible light photocatalyst, taking isopropanol as a proton donor, and synthesizing H from pure water and pure oxygen under an acidic condition (pH=3) 2 O 2 Yield 704. Mu. Mol/g.h. Ye et al [ YuYe, cheng Wen, et al, visble-light driven efficient over H ] 2 O 2 production on modificed grapgitic carbon nitride under ambient conditions[J]Appl.Catal.B:Environ.,2021,285,119726.]The amino functional group in the carbon nitride structure is utilized, the conjugated molecular anthraquinone is introduced through covalent bond, the conjugated molecular anthraquinone plays a role of serving as a storage of photo-generated electrons, the effective separation of the photo-generated electrons is promoted, isopropanol is used as a proton donor, and the method starts from pure water and pure oxygen, and H 2 O 2 Reaching 75. Mu.M/h. The above report reveals photocatalytic molecular oxygen reduction synthesis of H 2 O 2 The disadvantage is (1) that the practical application is limited from pure water and pure oxygen; (2) the photo-generated holes generated during the photocatalytic process are not utilized effectively, etc. Gopakumar et al [ A Gopakumar, P Ren, J.Chen, et al, ligin supported heterogeneous photocatalyst for the direct generation ofH ] 2 O 2 from seawater[J]J.Am.Chem.Soc.,2022,144,2603-2613.]The lignin loaded nano BiOBr with good thermal stability and biodegradability is used as a photocatalyst, and H is directly synthesized from seawater through an oxygen reduction path (OPP) 2 O 2 Reaction for 7h gave 4085. Mu.M. The disadvantage is that the reaction is carried out under alkaline conditions and pure oxygen is used as O 2 Sources, easy loss of active ingredients of the catalytic system, and the like.
Based on the defects of the prior art, the invention constructs the high-crystallinity porous-morphology hydroxyl from the crystal engineering and the modification and functionalization of the carbon nitride molecular structureFunctionalized carbon nitride; directly taking seawater as raw material and air as O 2 The source uses environment-friendly ethanol or lactic acid as an additive to reduce O by using photo-generated electrons under the conditions of room temperature and normal pressure 2 H occurs in situ 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the The invention directly generates H in seawater 2 O 2 Adding ferrous salt solution into the system to construct an in-situ photo Fenton oxidation system, (1) generating photo-generated electrons to reduce Fe under the drive of visible light 3+ Is Fe 2+ Promote Fe of the system 3+ /Fe 2+ The circulation speed, (2) the strong oxidation effect of the photo-generated holes generated in the photocatalysis is exerted, and the strong oxidation effect and active oxidation species generated in Fenton oxidation are involved in the degradation of organic pollutants together, so that the Fenton oxidation efficiency and the efficiency are improved at the same time; the invention utilizes seawater to generate H in situ 2 O 2 Gets rid of Fenton oxidation to industry H 2 O 2 The dependence of the organic pollutant in the water body is reduced, and the industrial H is eliminated 2 O 2 The safety risks in transportation, storage and use are realized, and the ideal targets of greenness, low carbon and high efficiency are realized.
Disclosure of Invention
One of the purposes of the invention is to take supermolecule constructed by dicyandiamide or melamine cyanurate and citric acid or tartaric acid or sorbitol or mannitol or dipentaerythritol as a precursor, ammonium oxalate or ammonium oxalate, ammonium malonate, ammonium succinate, ammonium adipate and ammonium sebacate as a gas phase template agent and a structure modifier, and potassium chloride or potassium chloride/lithium chloride as an introduced ion source and a hot molten salt, and implant nano carbon quantum dots, potassium ions or potassium/lithium into g-C at the same time through in-situ thermal polymerization reaction 3 N 4 In the framework, a hydroxyl functional carbon quantum dot/ion double-doped high crystallinity g-C is provided 3 N 4 。
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the hydroxyl functional double-doped high-crystallinity carbon nitride comprises the following steps: takes melamine cyanurate (abbreviated as MCR) and citric acid (abbreviated as ca) as raw materials, and obtains a supermolecule precursor and supermolecule through hydrothermal reactionThe molecular precursor and potassium chloride or potassium chloride/lithium chloride, a gas phase template agent ammonium oxalate (expressed as 1) or ammonium oxalate (expressed as 2) or ammonium malonate (expressed as 3) or ammonium succinate (expressed as 4) or ammonium adipate (expressed as 6) or ammonium sebacate (expressed as 6) are subjected to in-situ thermal polymerization to implant nano carbon quantum dots, potassium ions or potassium/lithium into g-C simultaneously 3 N 4 In the framework, the inner part of the framework, obtaining a series of hydroxyl-functionalized potassium/citric acid doped g-C3N4 (abbreviated as K/ca@g-C3N 4-MCR-1-6) or a series of hydroxyl-functionalized potassium/lithium/citric acid doped g-C3N4 (abbreviated as K/Li/ca@g-C3N 4-MCR-1-6) or a series of hydroxyl-functionalized potassium/tartaric acid doped g-C3N4 (abbreviated as K/ta@g-C3N 4-MCR-1-6) or a series of hydroxyl-functionalized potassium/lithium/tartaric acid doped g-C3N4 (abbreviated as K/Li/ta@g-C3N 4-MCR-1-6) or a series of hydroxyl-functionalized potassium/sorbitol doped g-C3N4 (K/sb@g-C3N 4 @ room @ MCR-1-6) or series of hydroxyl-functionalized potassium/lithium/sorbitol doped g-C3N4 (abbreviated as K/Li/sb@g-C3N 4-MCR-1-6) or series of hydroxyl-functionalized potassium/mannitol doped g-C3N4 (abbreviated as K/ma@g-C3N 4-MCR-1-6) or series of hydroxyl-functionalized potassium/lithium/mannitol doped g-C3N4 (abbreviated as K/Li/ma@g-C3N 4-MCR-1-6) or series of hydroxyl-functionalized potassium/dipentaerythritol doped g-C3N4 (abbreviated as K/dp@g-C3N 4-MCR-1-6) or series of hydroxyl-functionalized potassium/lithium/dipentaerythritol doped g-room C3N4 (abbreviated as K/Li/dp@g-C3N 4-MCR-1-6).
Further, hydroxy-functionalized double doped g-C 3 N 4 The synthesis of (2) comprises the following steps:
sequentially adding dicyandiamide or melamine cyanurate, citric acid or tartaric acid or sorbitol or mannitol or dipentaerythritol and deionized water into a hydrothermal synthesis reaction kettle, reacting for 12-18 hours at 180-200 ℃, and slowly removing water under vacuum to obtain a supermolecule precursor; fully mixing and grinding a supermolecule precursor, potassium chloride or a mixture of potassium chloride and lithium chloride and a gas-phase template agent, placing the mixture in an atmosphere box-type muffle furnace, continuously introducing nitrogen, controlling the heating rate to be 2.0 ℃/min, heating to 550-650 ℃, and reacting for 3-5 h; the crude product is fully ground, fully washed by deionized water and ethanol and dried in vacuum until the weight is constant, thus obtaining the target product; the gas phase template agent is ammonium oxalate or ammonium malonate or ammonium succinate or ammonium adipate or ammonium sebacate.
It is a second object of the present invention to provide an application: hydroxy-functionalized double doping g-C 3 N 4 Is a photocatalyst, directly takes seawater as raw material and takes air as O 2 The source, ethanol or lactic acid is used as additive, and H is generated under the neutral or weak acidic condition of visible light, room temperature, normal pressure 2 O 2 Adding the generated H into the ferrous salt solution in situ 2 O 2 In the method, a visible light driven seawater in-situ light Fenton oxidation system is constructed. The method specifically comprises the following steps:
s300: in a quartz reaction flask equipped with magnetic stirring, 20mg of hydroxy-functionalized double-doped g-C are added sequentially 3 N 4 50mL of raw seawater, 5mL of ethanol or lactic acid, bubbling air, dark reacting for 0.5-1.5H, starting a 300 xenon lamp light source (matched with a 420nm optical filter), controlling the air introducing speed to be 5mL/min, and reacting for 3-5H to generate H 2 O 2 12.5mL of ferrous sulfate or ferrous chloride or ferrous nitrate aqueous solution was added.
Another object of the present invention is to provide a method for synthesizing H from seawater 2 O 2 The in-situ photo Fenton oxidation system constructed with ferrous salt is used for rapidly degrading antibiotics tetracycline hydrochloride (TC), ciprofloxacin (CIP) and environmental hormone bisphenol A (BPA) in water. The method specifically comprises the following steps:
s301: continuously adding the in-situ photo Fenton oxidation system constructed in the step S300 into an aqueous solution containing BPA, TC and CIP, starting a 300 xenon lamp light source (matched with a 420nm optical filter), continuously bubbling air at a speed of 5ml/min, and reacting for 15-45 min. TC, CIP, BPA single-component aqueous solution is degraded for 15min, and the degradation rates are 98%,95% and 92% respectively; the TC and CIP and BPA bi-component aqueous solution is degraded for 30min, the degradation rates of the TC and the CIP are respectively 92% and 87%, the degradation rates of the TC and the BPA are respectively 90% and 80%, and the degradation rates of the CIP and the BPA are respectively 95% and 90%; TC, CIP, BPA three components of the aqueous solution are degraded for 45min, and the degradation rates of TC, CIP and BPA are 95%, 90% and 86% respectively.
The invention uses self-assembled supermolecule of dicyandiamide or melamine cyanurate and citric acid or tartaric acid or sorbitol or mannitol or dipentaerythritolIs a precursor, and is subjected to in-situ thermal polymerization with potassium chloride or a mixture of potassium chloride and lithium chloride, ammonium oxalate or ammonium succinate or ammonium adipate or ammonium sebacate to construct a series of hydroxyl functional carbon quantum dots/ion double-doped porous morphology g-C 3 N 4 . Double doping porous g-C with synthesized hydroxy group 3 N 4 Is heterogeneous visible light catalyst, and air is O 2 The source, under the environmental condition (room temperature and normal pressure), ethanol or lactic acid is used as additive to generate H 2 O 2 Adding the generated H into the ferrous salt aqueous solution in situ 2 O 2 The 300 xenon lamp light source (matched with a 420nm optical filter) is started, air is continuously bubbled in, and the rapid and efficient degradation of antibiotics TC and CIP in the water phase and the environmental hormone BPA under the conditions of low carbon and green are realized.
The invention has the beneficial effects that:
1. hydroxy-functionalized double doped porous g-C 3 N 4 As heterogeneous visible light catalyst, air is directly used as O 2 The source generates H directly from seawater under the reaction conditions of room temperature, normal pressure, neutrality or weak acidity 2 O 2 And adding ferrous salt aqueous solution in situ to obtain the photo Fenton oxidation system. The system does not need external processing industry H 2 O 2 Reduces the application cost of the Fenton oxidation system and eliminates the industrial H 2 O 2 Safety risks in transportation, storage and use.
2. The Fenton oxidation system constructed in situ is continuously added into an aqueous solution containing TC, CIP, BPA single component or double component or ginseng component, a 300 xenon lamp light source (matched with a 420nm optical filter) is started, air is bubbled in, the Fenton oxidation system is degraded for 15-45 min, and the degradation rate of TC, CIP, BPA under the environmental reaction (room temperature, normal pressure, neutral or weak acidity) is 86% -98%.
3. After the oxidative degradation is finished, the system is kept stand for 2 to 5 hours, supernatant liquid is separated, lower liquid is centrifugally separated, solid matters are collected, and the mixture is sequentially washed by water, washed by ethanol and dried in vacuum at 60 ℃ until the weight is constant, and hydroxy functional double-doped porous g-C 3 N 4 The catalyst can be regenerated and recycled for three times, and the catalytic activity is basically unchanged.
4. Hydroxy-functionalized g-C 3 N 4 The potassium ion and the lithium ion are introduced in the structure synthesis. (1) By using the precursor potassium chloride or the mixture of potassium chloride and lithium chloride, the thermal polycondensation process can generate-OH in situ - Realize g-C 3 N 4 Introducing hydroxyl functional groups on the surface, wherein the introduction of the hydroxyl functional groups leads to g-C 3 N 4 The original hydrophobic surface is converted into hydrophilic, so that water molecules can smoothly enter g-C 3 N 4 The surface and molecular oxygen diffused to the surface generate H through a double electron reduction (2 e-ORR) path 2 O 2 The method comprises the steps of carrying out a first treatment on the surface of the (2) The outer empty orbitals of potassium ions and lithium ions can be combined with g-C 3 N 4 The nitrogen atoms in the structure are coordinated and combined to play the role of a node, thereby realizing g-C 3 N 4 The cross-linking of the units between the surfaces expands a conjugated system and realizes the wide spectrum high absorption of light and the high generation of photo-generated carriers; (3) plays a role of thermal eutectic salt, and induces and generates high crystallinity g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the (4) The ionic effect is exerted, and the problem of salt in hydrogen peroxide generated by taking seawater as a raw material is solved.
5. Hydroxy-functionalized g-C 3 N 4 Carbon quantum dots are introduced in the structure synthesis. (1) The carbon quantum has rich pi electrons, and is filled in g-C through intermolecular forces such as pi-pi accumulation 3 N 4 Further expands the absorption of the target compound to light and improves the generation of photo-generated carriers. Meanwhile, the device is used as a photon electron reservoir, so that the problem of mismatching of the chemical reaction speed of the surface interface and the generation speed of photo-generated electrons can be effectively solved; (2) the size of the carbon quantum is in nano scale, g-C 3 N 4 The electron conducting wire can play a role of photo-generated electrons in the structure, so that the transmission of the photo-generated electrons from the body to the surface is promoted, the recombination of photo-generated holes is reduced, and the photon yield is improved; (3) the introduction of the carbon quantum dots realizes the regulation and control of the morphology of the target compound in the nanometer scale, and the product with the specific surface and micropores increased simultaneously is obtained, so that the catalytic activity and the selectivity of the surface-interface chemical conversion are improved.
Drawings
FIG. 1 shows a hydroxy-functionalized double doping g-C according to the invention 3 N 4 Is a synthetic route of (2);
FIG. 2 is a hydroxy-functionalized double doping g-C 3 N 4 Is a structural schematic diagram of (a);
FIG. 3 is a scanning electron microscope image of K/ca@g-C3N 4-MCR-1;
FIG. 4 is a scanning electron microscope image of K/Li/ca@g-C3N 4-MCR-5;
FIG. 5 is a K/ca@g-C3N4-MCR-1XPS graph.
Detailed Description
The invention is further illustrated below in connection with specific examples, but the invention is not limited to these examples.
Example 1: synthesis of hydroxy-functionalized Potassium/citric acid doped g-C3N4 (K/ca@g-C3N 4-MCR-1)
Step S101: in a hydrothermal synthesis reaction kettle, 5g Melamine Cyanurate (MCR), 1.25g citric acid and 100mL deionized water are sequentially added, and the mixture is subjected to hydrothermal reaction at 180 ℃ for 12 hours. Slowly evaporating to remove water to obtain the supermolecule precursor. Mixing 5g of precursor, 7.5g of potassium chloride and 4g of ammonium oxalate thoroughly, and grinding. The mixture is placed in an atmosphere muffle furnace, 15ml/min of nitrogen is continuously introduced, the heating speed is controlled to be 2.0 ℃/min, the mixture is heated to 550 ℃, and the temperature is kept for 4 hours. The crude product is fully ground, fully washed by deionized water and ethanol and dried in vacuum until the weight is constant, thus obtaining the target product.
FT-IR(KBr)，ν/cm －1 ：3440，2988，2831，1598，1512，1492，1440，1365，1174。
XRD：11，27，43，52，58，69，75
Example 2: synthesis of hydroxyl-functionalized Potassium/citric acid doped g-C3N4 (K/ca@g-C3N 4-MCR-2-6) ammonium oxalate, ammonium malonate, ammonium succinate, ammonium adipate, ammonium sebacate were replaced with ammonium oxalate, otherwise as in example 1.
Example 3: synthesis of hydroxy-functionalized Potassium/lithium/citric acid doped g-C3N4 (K/Li/ca@g-C3N 4-MCR-1)
5g of MCR,1.25g of citric acid and 100mL of deionized water are sequentially added into a hydrothermal synthesis reaction kettle, and hydrothermal reaction is carried out at 180 ℃ for 16h. Slowly evaporating to remove water to obtain the supermolecule precursor. 4g of precursor, 5.5g of potassium chloride, 2.0g of lithium chloride and 4g of ammonium oxalate are taken, fully mixed and ground in a glove box. The mixture is placed in an atmosphere muffle furnace, 15ml/min of nitrogen is continuously introduced, the heating speed is controlled to be 2.0 ℃/min, the mixture is heated to 550 ℃, and the temperature is kept for 4 hours. The crude product is fully ground, fully washed by deionized water and ethanol and dried in vacuum until the weight is constant, thus obtaining the target product.
FT-IR(KBr)，ν/cm －1 ：3446，2992，2829，2151,1596，1490，1440，1397，1364，1247，1174,1001，800。
XRD：28，42，51，59，70，77
Application example 1: K/Li/ca@g-C3N4-MCR-1 catalyzed raw seawater air reduction synthesis H 2 O 2
Into a quartz reaction flask equipped with magnetic stirring, 20mg of K/Li/ca@g-C3N4-MCR-1, 50ml of raw seawater, 5ml of ethanol and bubbling air were sequentially added for dark reaction for 1.5h. Under the irradiation of a 300 xenon lamp light source (provided with a 420nm optical filter), controlling the air inlet speed to be 5ml/min for reacting for 5h and H 2 O 2 Yield 550. Mu. Mol/g.h. When lactic acid is used to replace ethanol, other conditions are the same as those of H 2 O 2 Yield 380. Mu. Mol/g.h.
TABLE 1-1 hydroxy functionalized double doped g-C3N4 (partially) catalyzed raw seawater synthesis H 2 O 2 Results
Figure BDA0004144591500000071
Figure BDA0004144591500000081
Note that: [1] ethanol is used as an additive; [2] lactic acid as additive
Application example 2: in-situ photo Fenton rapid degradation aqueous phase TC, CIP and BPA monocomponent system
25ml FeSO 4 The aqueous solution (concentration: 2.78 g/L) was added to H produced in example 1 2 O 2 The solution was stirred thoroughly and then was continuously introduced into 25ml of an aqueous TC solution (TC concentration: 50 mg/L), and a 300 xenon lamp light source (equipped with a 420nm filter) was turned on continuouslyBubbling air to react for 15min, and the TC degradation rate is 97.3%. The TC aqueous solution was increased to 50ml, and the TC degradation rate was 94.8% under the same conditions as above.
Replacing the TC aqueous solution with 25ml of CIP aqueous solution with the concentration of 20mg/L, and carrying out the same conditions as above, wherein the CIP degradation rate is 92.4%;
25ml of aqueous BPA solution with a concentration of 50mg/L was replaced with aqueous TC solution, and the degradation rate of BPA was 82.7% under the same conditions as above.
Application example 3: in-situ photo Fenton rapid degradation TC, CIP, BPA bi-component system in water phase
The TC aqueous solution in application example 2 was replaced with an equal volume mixture of TC and CIP aqueous solutions having concentrations of 50mg/L and 20mg/L, respectively, and the degradation rates of TC and CIP were 93.4% and 88.1% respectively, under the same conditions as in application example 2 except that air was continuously bubbled through for 30 minutes.
The aqueous solution of TC and aqueous solution of BPA in application example 2 was replaced with an equal volume of the mixture of TC and aqueous solution of BPA in concentrations of 50mg/L, with the other conditions being the same, and the degradation rates of TC and aqueous solution of BPA were 97.7% and 91.2%, respectively.
The TC aqueous solution in application example 2 was replaced with an equal volume mixture of CIP and BPA aqueous solutions having concentrations of 50mg/L and 20mg/L, respectively, with the other conditions being the same, and degradation rates of CIP and BPA were 90.1% and 86.9%, respectively.
Application example 4: in-situ photo Fenton rapid degradation TC, CIP, BPA three-component system in aqueous phase
The TC aqueous solution in application example 2 was replaced with an equal volume mixture of TC, BPA and CIP aqueous solutions having concentrations of 50mg/L, 50mg/L and 20mg/L, respectively, and the degradation rates of TC, CIP and BPA were 95.6%, 91.2% and 87.4% respectively, in the same manner as in application example 2 except for the reaction for 45min.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (4)

1. A hydroxyl-functionalized double doped carbon nitride, characterized by: the hydroxyl functional double-doped carbon nitride introduces hydroxyl functions to the surfaceg-C with porous morphology, wherein alkali metal K or Li and carbon quantum dots are simultaneously introduced into a bulk structure of the energy group 3 N 4 。
2. The method for preparing hydroxyl-functionalized double doped carbon nitride according to claim 1, wherein: the method comprises the following steps: sequentially adding dicyandiamide or melamine cyanurate, citric acid or tartaric acid or sorbitol or mannitol or dipentaerythritol and deionized water into a hydrothermal synthesis reaction kettle, reacting for 12-18 hours at 180-200 ℃, and slowly removing water under vacuum to obtain a supermolecule precursor; fully mixing and grinding a supermolecule precursor, potassium chloride or a mixture of potassium chloride and lithium chloride and a gas-phase template agent, placing the mixture in an atmosphere box-type muffle furnace, continuously introducing nitrogen, controlling the heating rate to be 2.0 ℃/min, heating to 550-650 ℃, and reacting to 3-5 h; the crude product is fully ground, fully washed by deionized water and ethanol and dried in vacuum until the weight is constant, thus obtaining the target product; the gas phase template agent is ammonium oxalate or ammonium malonate or ammonium succinate or ammonium adipate or ammonium sebacate.
3. The hydroxy-functionalized double doped carbon nitride according to claim 1, for constructing a visible light driven seawater in situ photo Fenton oxidation system, wherein: hydroxy-functionalized double doping g-C 3 N 4 Is a photocatalyst, directly takes seawater as raw material and takes air as O 2 A source for generating H under visible light, room temperature, normal pressure and neutral or weakly acidic conditions 2 O 2 In situ addition of an aqueous solution of a ferrous salt to the H produced 2 O 2 Obtaining a visible light driven seawater in-situ light Fenton oxidation system in the solution; the ferrous salt is ferrous sulfate or ferrous chloride or ferrous nitrate.
4. The application of the visible light driven seawater in-situ photo Fenton oxidation system as claimed in claim 3, wherein: the visible light driven seawater in-situ light Fenton oxidation system is used for degrading organic micro pollutants in water; the organic micro-pollutants comprise one or more of tetracycline hydrochloride, ciprofloxacin and environmental hormone bisphenol A.
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