CN113526607A - Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application - Google Patents

Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application Download PDF

Info

Publication number
CN113526607A
CN113526607A CN202010344416.0A CN202010344416A CN113526607A CN 113526607 A CN113526607 A CN 113526607A CN 202010344416 A CN202010344416 A CN 202010344416A CN 113526607 A CN113526607 A CN 113526607A
Authority
CN
China
Prior art keywords
cds
nanotube
electrode
tio
solid phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202010344416.0A
Other languages
Chinese (zh)
Inventor
崔骏
何小松
郑明霞
席北斗
傅雪梅
丁鸿羽
孙源媛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chinese Research Academy of Environmental Sciences
Original Assignee
Chinese Research Academy of Environmental Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chinese Research Academy of Environmental Sciences filed Critical Chinese Research Academy of Environmental Sciences
Priority to US16/926,398 priority Critical patent/US20200378018A1/en
Publication of CN113526607A publication Critical patent/CN113526607A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a carbon-point-based organic matter degradation synchronous heavy metal reduction photocatalytic electrode and a preparation method and application thereof, belonging to the field of multifunctional environmental materials and water treatment. Aiming at the problem that the photocatalytic electrode has insufficient reduction capability of organic matter degradation synchronous heavy metal, the invention constructs the photocatalytic electrode with a Z-shaped heterojunction structure by taking CDs as an electronic assistant, improves the directional transfer capability of photoproduction electrons, inhibits the recombination efficiency of photoproduction electrons and holes, realizes the purpose of improving the reduction capability of the photocatalytic electrode organic matter degradation synchronous heavy metal, and provides scientific basis and technical support for researching and developing high-efficiency photocatalytic electrode materials and ensuring water quality safety.

Description

Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application
Technical Field
The invention belongs to the technical field of sewage treatment, relates to a multifunctional environmental material and application thereof in the field of water treatment, and particularly relates to a photocatalytic electrode for synchronously degrading organic matters and reducing heavy metals based on a carbon point electronic auxiliary agent and a preparation method and application thereof.
Background
If organic matters and heavy metals coexist in water bodies such as industrial wastewater, domestic sewage, agricultural sewage and the like and cannot be effectively treated, the public health and the water environment quality are seriously influenced. Countries around the world also severely limit the concentration of organic matter and heavy metals in water environments. However, due to the characteristics of complex organic matter structure, strong stability, poor biodegradability, strong heavy metal ion solubility, high toxicity and the like, the synchronous removal of heavy metals by degrading the organic matters becomes one of the key and difficult problems in the field of water treatment, and new challenges are provided for the research and development of water treatment technologies and materials. Therefore, the research and development of the technology for synchronously removing the heavy metals by degrading the organic matters and the preparation of the environmental materials corresponding to the technology have important significance for water quality safety guarantee and water environment improvement.
The photocatalysis technology converts solar energy into electric energy through catalytic materials, achieves the purpose of synchronously removing heavy metals by degrading organic matters, and is considered as a green and environment-friendly water treatment technology. The technical principle is that when a photocatalytic material is contacted with a solution containing organic matters and heavy metals, under the excitation of light, electrons in the material generate energy level transition and respectively transit from a valence band/highest occupied orbit to a conduction band/lowest vacant orbit to generate photo-generated electrons and holes. Both the photo-generated electrons and the holes have the capacity of generating a high-activity intermediate for oxidizing organic matters by reacting with a medium. Meanwhile, the photo-generated electrons have the ability to reduce heavy metal ions. In order to increase the contact area of the catalyst and pollutants and improve the photocatalytic efficiency, the catalyst is mostly in the form of powder (CN201711002731. X; CN 201610534511.0; CN 201610512021.0). And the powder catalyst is difficult to recover and is easy to generate the problem of secondary pollution. Therefore, researchers prepare the powder catalyst into an electrode, and the problem of difficult recovery is avoided. However, the catalytic electrode loses the advantage of large specific surface area as compared with the powder catalyst, resulting in a decrease in catalytic efficiency (Applied Catalysis B: Environmental,2015,164, 217-341; Chemical Engineering Journal,2018,344, 332-341). Meanwhile, the powder catalyst is not tightly combined with the substrate, so that the powder catalyst is easy to fall off and generates a secondary pollution problem. Therefore, the research and development of the high-efficiency and stable catalytic electrode have good development prospect.
The catalytic electrodes are generally classified into i-type, ii-type, direct Z-type and indirect Z-type heterojunction structures according to the band structure of the electrode components. As is well known, compared with I-type and II-type heterojunction structures, the Z-type heterojunction structure has the characteristics of strong electron transfer capability, difficulty in recombination of photo-generated electrons and holes and the like due to the special structure, and shows good potential of organic matter degradation and synchronous heavy metal removal. However, in the indirect Z-type heterojunction, metal atoms (Ag, Au, Bi, etc.) are often used as electron mediators (cn201310612197.x), and partial metal oxides, metal sulfides, etc. are also used as electron mediators. Carbon Dots (CDs) are widely used to enhance the light absorption properties of photocatalytic materials due to their highly efficient light absorption properties (CN 201710903335.8). In addition, CDs also have strong electron transfer capacity and the potential to serve as electron transport media. However, CDs are extremely unstable due to their good water solubility and small size. It is very soluble in water during the photocatalytic process, resulting in a decrease in catalytic efficiency (Carbon,2014,68, 718-724). This also becomes a limiting factor in the construction of photocatalytic electrodes based on carbon dots having a Z-type heterojunction structure. Therefore, the invention takes CDs as an electronic assistant, realizes high-efficiency organic matter degradation and synchronous heavy metal removal by improving the binding capacity of the CDs with the semiconductor I and the semiconductor II, and provides theoretical reference for the preparation of the Z-type heterojunction photocatalytic electrode.
Disclosure of Invention
Aiming at the problem that the existing photocatalytic electrode has insufficient reduction capability of organic matter degradation synchronous heavy metal, the invention provides a method for constructing a photocatalytic electrode with a Z-shaped heterojunction structure by using Carbon Dots (CDs) as an electron transport layer (namely an electron assistant), and aims to improve the reduction capability of organic matter degradation synchronous heavy metal of the photocatalytic electrode by directionally strengthening the transfer capability of photo-generated electrons and inhibiting the recombination efficiency of the photo-generated electrons and holes.
In order to achieve the above object, in one aspect, the present invention provides a method for preparing a photocatalytic electrode for simultaneous heavy metal reduction based on organic matter degradation at carbon sites, comprising:
forming a Carbon Dot (CDs) electron transport layer on the semiconductor i;
and forming a semiconductor II on the carbon dot electron transport layer.
In some embodiments, the step of forming a carbon dot electron transport layer on a semiconductor i comprises:
soaking the semiconductor I in a mixed solution of mercaptopropionic acid (MPA) with the volume fraction of 10% -30% (such as 15%, 20% or 25%) and CDs with the volume fraction of 1-10g/L (such as 2g/L, 5g/L or 8g/L) (preferably, the soaking time is 24-48h), and taking out to obtain the semiconductor I-CDs electrode.
In some embodiments, the semiconductor I is TiO2Nanotubes or Fe2O3Nanotubes, and the like.
In some embodiments, the TiO2TiO prepared by nanotube anodic oxidation method2Nanotubes of said Fe2O3The nanotube is Fe prepared by anodic oxidation2O3A nanotube.
In some embodiments, the semiconductor ii is an organic semiconductor or an inorganic semiconductor, wherein the organic semiconductor is polyaniline, reduced graphene oxide, carbon nitride, or the like; the inorganic semiconductor is WO3、MoS2And the like.
It will be appreciated by those of ordinary skill in the art that carbon dots conventionally prepared in the art can be used to achieve the objects of the present invention. In some embodiments, a method of making a carbon dot comprises: dissolving glucose in concentrated H2SO4Heating for 3-5h (e.g. 3.5h, 4h or 4.5h) at 180-220 deg.C (e.g. 190 deg.C, 200 deg.C or 210 deg.C), cooling to room temperature, adjusting pH of the mixed solution to 6.9-7.1, centrifuging, collecting supernatant, passing through a solid phase extraction column, blowing off the extract with nitrogen, and freeze-drying (e.g. freeze-drying for 24-48h) to obtain carbon dot solid particles.
For example, in some embodiments, CDs are prepared as follows: dissolving 1-5g of glucose in 150-200 mL of concentrated H with mass fraction of 98%2SO4In (1), glucose-H2SO4The mixed solution is placed in a reaction kettle with a polytetrafluoroethylene inner container, heated for 3-5h at the temperature of 180-220 ℃, and naturally cooled to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 6.9-7.1, and centrifuging for 10-20min (e.g. 15min) under the conditions of 10000-. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step included rinsing the solid phase extraction column with 20mL of methanol, and then washing the solid phase extraction column with 40mL of ultrapure waterResidual methanol in (1); the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; the elution step includes rinsing the solid phase extraction column with 20mL of methanol to desorb the CDs and obtain a highly pure CDs-methanol solution. And (4) blowing off the extract by using nitrogen, and freeze-drying for 24-48h to obtain the CDs solid particles.
In some embodiments, the semiconductor ii is polyaniline, which can be formed on the CDs electron transport layer by in situ electropolymerization.
For example, in some embodiments, TiO is prepared by an in situ electropolymerization process2When the nano tube-CDs-PANI photocatalysis electrode is adopted, TiO is respectively used2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.1-0.5M (such as 0.2M) aniline and 0.01-0.1M (such as 0.05M) citric acid, and the electrolyte is subjected to oxygen removal treatment for 30min by using nitrogen before in-situ electropolymerization. The aniline is electropolymerized in situ using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 10-30 cycles). Drying the polymerized working electrode for 24-48h at 40-80 ℃ to obtain TiO2nanotube-CDs-PANI photocatalytic electrode.
In some embodiments, the semiconductor II is WO3WO may be formed on the carbon dot electron transport layer by electrodeposition3。
For example, in some embodiments, TiO is prepared by an electrodeposition process2nanotube-CDs-WO3When the electrode is photocatalyzed, TiO is used respectively2nanotube-CDs electrode, platinum sheet and Ag/AgCl as working electrode, counter electrode and reference electrode, and electrolyte solution at 20-30mM (e.g. 25mM) Na concentration2WO4And 20-40mM (e.g., 30mM) H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 100-200s (for example 150s), the obtained electrode is solidified for 12-24h at the temperature of 40-80 ℃, and TiO is obtained2nanotube-CDs-WO3A photocatalytic electrode.
In some embodiments, the semiconductor ii is carbon nitride, which can be formed on the CDs electron transport layer by a hydrothermal process.
For example, in some embodiments, Fe is produced by a hydrothermal process2O3When the nano tube-CDs-carbon nitride photocatalysis electrode is adopted, the prepared Fe2O3Soaking the nanotube-CDs electrode in aqueous solution containing melamine (mass fraction of 10% -30%), and keeping the temperature at 80 ℃ for 24-72h to obtain Fe2O3nanotube-CDs-carbon nitride photocatalytic electrode.
In another aspect, the invention provides a photocatalytic electrode prepared by the preparation method.
In another aspect, the present invention provides a method for degrading organic substances while reducing heavy metals by using the photocatalytic electrode, including:
and immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals, and performing organic pollutant degradation and heavy metal reduction under the illumination condition.
In some embodiments, the reaction conditions are as follows: the illumination intensity is more than 50mW cm-2The wavelength is more than 200 nm; electrode working area to solution volume ratio: 1-10cm2 L-1(ii) a Concentration of organic contaminants: less than 1M; concentration of heavy metal: less than 10M; reaction time: 30-120min (e.g., 60min or 90 min).
Compared with the existing photocatalytic electrode, the invention has the advantages that:
(1) compared with the existing photocatalysis electrode, the photocatalysis electrode not only takes CDs as light absorption materials, but also takes CDs as electron assistants, thereby improving the directional migration capability of photo-generated electrons, and avoiding the problem of reduction efficiency of heavy metal in organic matter degradation synchronization caused by electron-hole pair recombination.
(2) Aiming at the problem that CDs are good in water solubility and easy to dissolve, and the synchronous heavy metal reduction capacity of organic matter degradation is insufficient, mercaptopropionic acid (MPA) is introduced, the binding energy of carbon points and a semiconductor I and a semiconductor II is improved, and the long-term, efficient and stable synchronous heavy metal reduction capacity of organic matter degradation of a photocatalytic electrode is guaranteed.
Drawings
The drawings are only for purposes of illustrating and explaining the present invention and are not to be construed as limiting the scope of the present invention. Wherein:
FIG. 1 is an XPS plot of CDs obtained in an example of the present invention;
FIG. 2 is a transmission electron micrograph of CDs obtained according to an embodiment of the present invention;
FIG. 3 is a scanning electron micrograph of (a) TiO2Nanotube, (b) TiO2nanotube-CDs, (c) TiO2nanotube-CDs-WO3，(d)TiO2nanotube-CDs-PANI;
FIG. 4 shows TiO obtained in example of the present invention2nanotube-CDs-PANI electrode structure diagram;
FIG. 5 shows (a) TiO obtained in example of the present invention2nanotube-CDs-WO3And (b) TiO2A graph of light absorption properties of nanotube-CDs-PANI;
FIG. 6 shows (a) TiO obtained in example of the present invention2nanotube-CDs-WO3And (b) TiO2Photoelectric conversion performance diagram of nanotube-CDs-PANI;
FIG. 7 shows Fe obtained in example of the present invention2O3Scanning electron micrographs of nanotube-CDs-carbon nitride;
FIG. 8 shows Fe obtained in example of the present invention2O3Photoelectric conversion performance diagram of the nanotube-CDs-carbon nitride photocatalytic electrode;
FIG. 9 is a graph showing the degradation effect of organic substances according to an embodiment of the present invention;
FIG. 10 is a graph showing the reduction effect of heavy metals according to the embodiment of the present invention;
FIG. 11 is a graph showing the effect of degrading organic substances in comparative example 1 of the present invention;
FIG. 12 is a graph showing the effect of reducing heavy metals in comparative example 1 of the present invention;
FIG. 13 is a graph showing the effect of degrading organic substances in comparative example 2;
FIG. 14 is a graph showing the effect of reducing heavy metals in comparative example 2 of the present invention.
Detailed Description
In order to make the aforementioned features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below, but the present invention is not limited thereto.
Some embodiments of the invention employ TiO2TiO is prepared by using nano tube as semiconductor I and Polyaniline (PANI) as organic semiconductor II2The nanotube-CDs-PANI photocatalytic electrode adopts TiO2Nanotubes as semiconductors I, WO3Preparation of TiO as inorganic semiconductor II2nanotube-CDs-WO3A photocatalytic electrode.
As shown in fig. 1: the high resolution spectrum of C1s of CDs can resolve 3 distinct characteristic peaks, located at 284.5eV, 286.2eV and 288.1eV, respectively, indicating the presence of C-C (C ═ C), C-O and C ═ O at the surface of CDs, consistent with the characteristics of CDs.
As shown in fig. 2: the diameter of CDs is mainly distributed in the range of 2-4nm, and the interplanar spacing is 0.21nm as seen from the lattice fringes, and the exposed surface of CDs is the (100) plane. The successful synthesis of CDs can be demonstrated by combining FIG. 1 and FIG. 2.
As shown in fig. 3: from FIG. 3a, significant TiO is observed2Nanotube array structure, TiO2The nanotubes have an outer diameter of about 90nm and an inner diameter of about 80 nm. It can be observed from FIG. 3b that a large amount of polymerized CDs are adsorbed on the wall of the surface nanotube. From FIG. 3c, TiO can be observed2The surface of the nanotube-CDs electrode is successfully loaded with a large amount of WO3And (3) nanoparticles. From FIG. 3d, TiO can be observed2A large number of PANI nanowires were successfully loaded on the surface of the nanotube-CDs electrode.
As shown in fig. 4: mercaptopropionic acid (MPA) having both-COOH and-SH functional groups, respectively, in association with TiO2Nanotubes are connected to CDs to ensure TiO2Stability of nanotube-CDs photocatalytic electrodes. CDs and PANI can be synthesized by PANI-H-O-CQDs-O-TiO2Connection in the forms of PANI-N.O-CQDs, PANI-N.H bond.O-CQDs, PANI-H.O-CQDs and the like to ensure TiO2Stability of nanotube-CDs-PANI.
As shown in fig. 5: compared with TiO2Nanotubes, TiO2nanotube-CDs-PANI and TiO2nanotube-CDs-WO3The band gap width of the photocatalytic electrode is obviously reduced, and the pair is 200-8The light absorption capacity in the range of 00nm is obviously improved, particularly the absorption capacity to visible light and near infrared light with the wavelength of more than 420nm is obviously enhanced, and the good potential photocatalysis performance is shown.
As shown in fig. 6: compared with TiO2Nanotubes, TiO2nanotube-CDs-PANI and TiO2nanotube-CDs-WO3The photoelectric conversion performance of the photocatalytic electrode is obviously improved by 8.1 times and 18.8 times respectively, and good potential photocatalytic performance is shown.
In other embodiments of the invention, Fe is used2O3Preparation of Fe with nanotube as semiconductor I and carbon nitride as semiconductor II2O3nanotube-CDs-carbon nitride photocatalytic electrode.
From FIG. 7, it can be observed that Fe is conspicuous2O3nanotube-CDs-carbon nitride structure, Fe2O3The nanotubes have an outer diameter of about 80nm and an inner diameter of about 70 nm. First, it was observed that a large amount of polymerized CDs was adsorbed on the surface nanotube walls. In addition, carbon nitride nanoparticles having a diameter of about 100nm were observed. It is worth to say that it is exposed to Fe2O3The influence of magnetism causes an astigmatism phenomenon which is inevitable when the observation is carried out by a scanning electron microscope.
As shown in fig. 8: compared with Fe2O3Nanotubes of Fe2O3The photoelectric conversion performance of the nanotube-CDs-carbon nitride photocatalytic electrode is obviously improved by 4.1 times, and the good potential photocatalytic performance is shown.
It is to be understood that the semiconductor I and the semiconductor II in the present invention are not limited to the semiconductor materials in the embodiments.
Example 1:
the preparation method of CDs is as follows: 2.5g of glucose were dissolved in 150mL of concentrated H with a mass fraction of 98%2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 3 hours at 180 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Get onThe clear liquid passes through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step is divided into four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of TiO by anodic oxidation2Nanotube of TiO2Soaking the nanotube in a mixed solution of mercaptopropionic acid (MPA) with the volume fraction of 10% and CDs (cadmium sulfide) with the volume fraction of 7g/L for 24 hours, and taking out to obtain TiO2nanotube-CDs electrodes.
Preparation of TiO by in situ electropolymerization2nanotube-CDs-PANI photocatalytic electrodes, respectively made of TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.2M aniline and 0.05M citric acid, and nitrogen is used for carrying out oxygen removal treatment on the electrolyte for 30min before in-situ electropolymerization. The in-situ electropolymerization of aniline was carried out using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 10 cycles). Drying the polymerized working electrode for 48 hours at 40 ℃ to obtain TiO2nanotube-CDs-PANI photocatalytic electrode.
Preparation of TiO by electrodeposition2nanotube-CDs-WO3Photocatalytic electrodes, respectively with TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are taken as a working electrode, a counter electrode and a reference electrode, and the electrolyte is 25mM Na2WO4And 30mM H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 150s, the obtained electrode is solidified for 24h at the temperature of 60 ℃, and TiO is obtained2nanotube-CDs-WO3A photocatalytic electrode.
Using prepared photocatalystsCarrying out an organic matter degradation synchronous heavy metal reduction experiment on the electrode: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 1 mu M; heavy metal concentration (hexavalent chromium): 0.68 mM; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: in loading CDs and PANI, CDs and WO3Then, the degradation effect of the photocatalytic electrode on organic matters is from 21 percent (TiO)2Nanotube) to 100% (TiO)2nanotube-CDs-PANI) and 84% (TiO)2nanotube-CDs-WO3) And shows excellent organic matter degrading effect.
As shown in fig. 10: in loading CDs and PANI, CDs and WO3Then, the effect of the photocatalytic electrode on heavy metal reduction is from 10 percent (TiO)2Nanotube) to 76% (TiO)2nanotube-CDs-PANI) and 57% (TiO)2nanotube-CDs-WO3) And shows excellent heavy metal reduction effect.
Example 2:
the preparation method of CDs is as follows: dissolving 1g glucose in 200mL concentrated H with mass fraction of 98%2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 5 hours at the temperature of 200 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts(ii) a And the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of TiO by anodic oxidation2Nanotube of TiO2Soaking the nanotube in a mixed solution of 30% mercaptopropionic acid (MPA) and 10g/L CDs for 48h, and taking out to obtain TiO2nanotube-CDs electrodes.
Preparation of TiO by in situ electropolymerization2nanotube-CDs-PANI photocatalytic electrodes, respectively made of TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.2M aniline and 0.05M citric acid, and nitrogen is used for carrying out oxygen removal treatment on the electrolyte for 30min before in-situ electropolymerization. The in-situ electropolymerization of aniline was carried out using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 20 cycles). Drying the polymerized working electrode for 36h at the temperature of 60 ℃ to obtain TiO2nanotube-CDs-PANI photocatalytic electrode.
Preparation of TiO by electrodeposition2nanotube-CDs-WO3Photocatalytic electrodes, respectively with TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are taken as a working electrode, a counter electrode and a reference electrode, and the electrolyte is 25mM Na2WO4And 30mM H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 150s, the obtained electrode is solidified for 24h at the temperature of 40 ℃, and TiO is obtained2nanotube-CDs-WO3A photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic compoundsSubstance concentration (carbamazepine): 100 mu M; heavy metal concentration (hexavalent chromium): 68 mM; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: in loading CDs and PANI, CDs and WO3Then, the degradation effect of the photocatalytic electrode on organic matters is from 21 percent (TiO)2Nanotube) to 100% (TiO)2nanotube-CDs-PANI) and 79% (TiO)2nanotube-CDs-WO3) And shows excellent organic matter degrading effect.
As shown in fig. 10: in loading CDs and PANI, CDs and WO3Then, the effect of the photocatalytic electrode on heavy metal reduction is from 10 percent (TiO)2Nanotube) to 73% (TiO)2nanotube-CDs-PANI) and 56% (TiO)2nanotube-CDs-WO3) And shows excellent heavy metal reduction effect.
Example 3:
the preparation method of CDs is as follows: dissolving 5g glucose in 150mL concentrated H with mass fraction of 98%2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 5 hours at 220 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of TiO by anodic oxidation2Nanotube of TiO2Soaking the nanotubes in a mixed solution of 25% mercaptopropionic acid (MPA) and 6g/L CDs for 24hTaking out to obtain TiO2nanotube-CDs electrodes.
Preparation of TiO by in situ electropolymerization2nanotube-CDs-PANI photocatalytic electrodes, respectively made of TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.2M aniline and 0.05M citric acid, and nitrogen is used for carrying out oxygen removal treatment on the electrolyte for 30min before in-situ electropolymerization. The in-situ electropolymerization of aniline was carried out using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 30 cycles). Drying the polymerized working electrode for 24 hours at the temperature of 80 ℃ to obtain TiO2nanotube-CDs-PANI photocatalytic electrode.
Preparation of TiO by electrodeposition2nanotube-CDs-WO3Photocatalytic electrodes, respectively with TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are taken as a working electrode, a counter electrode and a reference electrode, and the electrolyte is 25mM Na2WO4And 30mM H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 150s, the obtained electrode is solidified for 24h at the temperature of 80 ℃, and TiO is obtained2nanotube-CDs-WO3A photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 1M; heavy metal concentration (hexavalent chromium): 0.68M; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: in loading CDs and PANI, CDs and WO3Then, the degradation effect of the photocatalytic electrode on organic matters is from 21 percent (TiO)2Nanotube) to 100% (TiO)2nanotube-CDs-PANI) and 81% (TiO)2Nano metertube-CDs-WO3) And shows excellent organic matter degrading effect.
As shown in fig. 10: in loading CDs and PANI, CDs and WO3Then, the effect of the photocatalytic electrode on heavy metal reduction is from 10 percent (TiO)2Nanotube) to 71% (TiO)2nanotube-CDs-PANI) and 53% (TiO)2nanotube-CDs-WO3) And shows excellent heavy metal reduction effect.
Example 4:
the preparation method of CDs is as follows: 3g of glucose were dissolved in 180mL of 98% strength by mass concentrated H2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 4 hours at 190 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of TiO by anodic oxidation2Nanotube of TiO2Soaking the nanotube in a mixed solution of mercaptopropionic acid (MPA) with the volume fraction of 18% and CDs with the volume fraction of 7g/L for 36h, and taking out to obtain TiO2nanotube-CDs electrodes.
Preparation of TiO by in situ electropolymerization2nanotube-CDs-PANI photocatalytic electrodes, respectively made of TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.2M aniline and 0.05M citric acid, and nitrogen is used for carrying out oxygen removal treatment on the electrolyte for 30min before in-situ electropolymerization.The in-situ electropolymerization of aniline was carried out using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 15 cycles). Drying the polymerized working electrode for 24 hours at the temperature of 60 ℃ to obtain TiO2nanotube-CDs-PANI photocatalytic electrode.
Preparation of TiO by electrodeposition2nanotube-CDs-WO3Photocatalytic electrodes, respectively with TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are taken as a working electrode, a counter electrode and a reference electrode, and the electrolyte is 25mM Na2WO4And 30mM H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 150s, the obtained electrode is solidified for 18h at the temperature of 60 ℃, and TiO is obtained2nanotube-CDs-WO3A photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 1M; heavy metal concentration (hexavalent chromium): 6.8M; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: in loading CDs and PANI, CDs and WO3Then, the degradation effect of the photocatalytic electrode on organic matters is from 21 percent (TiO)2Nanotube) to 100% (TiO)2nanotube-CDs-PANI) and 85% (TiO)2nanotube-CDs-WO3) And shows excellent organic matter degrading effect.
As shown in fig. 10: in loading CDs and PANI, CDs and WO3Then, the effect of the photocatalytic electrode on heavy metal reduction is from 10 percent (TiO)2Nanotube) to 79% (TiO)2nanotube-CDs-PANI) and 58% (TiO)2nanotube-CDs-WO3) And shows excellent heavy metal reduction effect.
Example 5:
the preparation method of CDs is as follows: dissolving 2g glucose in 150mL concentrated H with mass fraction of 98%2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 3 hours at the temperature of 200 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of TiO by anodic oxidation2Nanotube of TiO2Soaking the nanotube in a mixed solution of mercaptopropionic acid (MPA) with the volume fraction of 10% and CDs with the volume fraction of 10g/L for 48 hours, and taking out to obtain TiO2nanotube-CDs electrodes.
Preparation of TiO by in situ electropolymerization2nanotube-CDs-PANI photocatalytic electrodes, respectively made of TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.2M aniline and 0.05M citric acid, and nitrogen is used for carrying out oxygen removal treatment on the electrolyte for 30min before in-situ electropolymerization. The in-situ electropolymerization of aniline was carried out using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 10 cycles). Drying the polymerized working electrode for 24 hours at the temperature of 60 ℃ to obtain TiO2nanotube-CDs-PANI photocatalytic electrode.
Preparation of TiO by electrodeposition2nanotube-CDs-WO3Photocatalytic electrodes, respectively with TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as working electrodes and pairsAn electrode and a reference electrode, the electrolyte is 25mM Na2WO4And 30mM H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 150s, the obtained electrode is solidified for 12h at the temperature of 60 ℃, and TiO is obtained2nanotube-CDs-WO3A photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 10 mu M; heavy metal concentration (hexavalent chromium): 0.68 mM; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: in loading CDs and PANI, CDs and WO3Then, the degradation effect of the photocatalytic electrode on organic matters is from 21 percent (TiO)2Nanotube) to 100% (TiO)2nanotube-CDs-PANI) and 84% (TiO)2nanotube-CDs-WO3) And shows excellent organic matter degrading effect.
As shown in fig. 10: in loading CDs and PANI, CDs and WO3Then, the effect of the photocatalytic electrode on heavy metal reduction is from 10 percent (TiO)2Nanotube) to 73% (TiO)2nanotube-CDs-PANI) and 57% (TiO)2nanotube-CDs-WO3) And shows excellent heavy metal reduction effect.
Example 6:
the preparation method of CDs is as follows: 4g of glucose were dissolved in 180mL of 98% strength by mass concentrated H2SO4In (1), glucose-H2SO4The mixed solution is placed in a reaction kettle with a polytetrafluoroethylene inner container, heated for 3 hours at the temperature of 180-220 ℃, and naturally cooled to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7 at 12000r/minCentrifuge for 15 min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of TiO by anodic oxidation2Nanotube of TiO2Soaking the nanotube in a mixed solution of 25% mercaptopropionic acid (MPA) and 15g/L CDs for 48h, and taking out to obtain TiO2nanotube-CDs electrodes.
Preparation of TiO by in situ electropolymerization2nanotube-CDs-PANI photocatalytic electrodes, respectively made of TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.2M aniline and 0.05M citric acid, and nitrogen is used for carrying out oxygen removal treatment on the electrolyte for 30min before in-situ electropolymerization. The in-situ electropolymerization of aniline was carried out using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 20 cycles). Drying the polymerized working electrode for 24 hours at the temperature of 60 ℃ to obtain TiO2nanotube-CDs-PANI photocatalytic electrode.
Preparation of TiO by electrodeposition2nanotube-CDs-WO3Photocatalytic electrodes, respectively with TiO2The nanotube-CDs electrode, the platinum sheet and the Ag/AgCl are taken as a working electrode, a counter electrode and a reference electrode, and the electrolyte is 25mM Na2WO4And 30mM H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 150s, the obtained electrode is solidified for 12h at the temperature of 60 ℃, and TiO is obtained2nanotube-CDs-WO3A photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 10 mu M; heavy metal concentration (hexavalent chromium): 0.68 mM; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: in loading CDs and PANI, CDs and WO3Then, the degradation effect of the photocatalytic electrode on organic matters is from 21 percent (TiO)2Nanotube) to 100% (TiO)2nanotube-CDs-PANI) and 85% (TiO)2nanotube-CDs-WO3) And shows excellent organic matter degrading effect.
As shown in fig. 10: in loading CDs and PANI, CDs and WO3Then, the effect of the photocatalytic electrode on heavy metal reduction is from 10 percent (TiO)2Nanotube) to 76% (TiO)2nanotube-CDs-PANI) and 56% (TiO)2nanotube-CDs-WO3) And shows excellent heavy metal reduction effect.
Example 7:
the preparation method of CDs is as follows: 4g of glucose were dissolved in 180mL of 98% strength by mass concentrated H2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 3 hours at 180 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step included washing the solid phase extraction column with 40mL of ultrapure water,dissolving impurities such as inorganic salt and the like; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of Fe by anodic oxidation2O3Nanotubes of Fe2O3Soaking the nanotube in a mixed solution of 25% mercaptopropionic acid (MPA) and 15g/L CDs for 48h, and taking out to obtain Fe2O3nanotube-CDs electrodes.
Carbon nitride is formed on the CDs electron transport layer by a hydrothermal method. Prepared Fe2O3Soaking the nanotube-CDs electrode in 10% melamine aqueous solution, and keeping the temperature at 80 ℃ for 24h to obtain Fe2O3nanotube-CDs-carbon nitride photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 10 mu M; heavy metal concentration (hexavalent chromium): 0.68 mM; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: after loading CDs and carbon nitride, the degradation effect of the photocatalytic electrode on organic matters is from 6 percent (Fe)2O3Nanotube) to 70% (Fe)2O3nanotube-CDs-carbon nitride), showing excellent organic matter degradation effect.
As shown in fig. 10: after loading CDs and carbon nitride, the effect of the photocatalytic electrode on heavy metal reduction is from 4 percent (Fe)2O3Nanotube) to 79% (Fe)2O3nanotube-CDs-carbon nitride), showing excellent heavy metal reduction effect.
Example 8:
the preparation method of CDs is as follows: 4g of glucose were dissolved in 180mL of 98% strength by mass concentrated H2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 3 hours at 220 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enrichment step comprises passing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of Fe by anodic oxidation2O3Nanotubes of Fe2O3Soaking the nanotube in a mixed solution of 25% mercaptopropionic acid (MPA) and 15g/L CDs for 48h, and taking out to obtain Fe2O3nanotube-CDs electrodes.
Carbon nitride is formed on the CDs electron transport layer by a hydrothermal method. Prepared Fe2O3Soaking the nanotube-CDs electrode in 30% melamine aqueous solution, and keeping the temperature at 80 ℃ for 72h to obtain Fe2O3nanotube-CDs-carbon nitride photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; working area of electrode and solutionProduct ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 10 mu M; heavy metal concentration (hexavalent chromium): 0.68 mM; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 9: after loading CDs and carbon nitride, the degradation effect of the photocatalytic electrode on organic matters is from 6 percent (Fe)2O3Nanotubes) to 65% (Fe)2O3nanotube-CDs-carbon nitride), showing excellent organic matter degradation effect.
As shown in fig. 10: after loading CDs and carbon nitride, the effect of the photocatalytic electrode on heavy metal reduction is from 4 percent (Fe)2O3Nanotube) to 66% (Fe)2O3nanotube-CDs-carbon nitride), showing excellent heavy metal reduction effect.
Comparative example 1
Preparation of TiO by anodic oxidation2Nanotubes, preparation of TiO by in situ electropolymerization2nanotube-PANI photocatalytic electrodes, respectively made of TiO2The nanotube electrode, the platinum sheet and the Ag/AgCl are used as a working electrode, a counter electrode and a reference electrode, the electrolyte is an acetone solution with the concentration of 0.2M aniline and 0.05M citric acid, and nitrogen is used for carrying out oxygen removal treatment on the electrolyte for 30min before in-situ electropolymerization. The in-situ electropolymerization of aniline was carried out using cyclic voltammetry (potential: 0-0.8V; number of polymerization cycles: 15 cycles). Drying the polymerized working electrode for 24 hours at the temperature of 60 ℃ to obtain TiO2nanotube-PANI photocatalytic electrode.
Preparation of TiO by electrodeposition2nanotube-WO3Photocatalytic electrodes, respectively with TiO2The nanotube electrode, the platinum sheet and the Ag/AgCl are taken as a working electrode, a counter electrode and a reference electrode, and the electrolyte is 25mM Na2WO4And 30mM H2O2Aqueous solution of HNO with concentration of 0.01M3The pH of the solution was adjusted to 1.4. + -. 0.1. The deposition voltage is-0.437VAg/AgClThe deposition time is 150s, the obtained electrode is solidified for 18h at the temperature of 60 ℃, and TiO is obtained2nanotube-WO3A photocatalytic electrode.
Organic matter using prepared photocatalysis electrodeDegradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 1M; heavy metal concentration (hexavalent chromium): 6.8M; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 11: in the respective loading of PANI and WO3Then, the degradation effect of the photocatalytic electrode on organic matters is from 21 percent (TiO)2Nanotube) to 29% (TiO)2nanotube-PANI) and 23% (TiO)2nanotube-WO3) But the organic matter degradation promoting effect is not obvious.
As shown in fig. 12: in the respective loading of PANI and WO3Then, the effect of the photocatalytic electrode on heavy metal reduction is from 10 percent (TiO)2Nanotube) to 12% (TiO)2nanotube-PANI) and 11% (TiO)2nanotube-WO3) But the heavy metal reduction promotion effect is not obvious.
It can be seen that the invention can significantly improve the efficiency of reducing heavy metals in the process of degrading organic matters by introducing CDs as electronic assistants into the photocatalytic electrode.
Comparative example 2:
the preparation method of CDs is as follows: 4g of glucose were dissolved in 180mL of 98% strength by mass concentrated H2SO4In (1), glucose-H2SO4Placing the mixed solution in a reaction kettle with an inner container made of polytetrafluoroethylene, heating for 3 hours at 220 ℃, and naturally cooling to room temperature. Using NaCO3Adjusting the pH value of the mixed solution to 7, and centrifuging for 15min under the condition of 12000 r/min. Taking the supernatant, passing through a solid phase extraction column (Oasis HLB,3cc/60mg, Waters), and the extraction step comprises four steps of activation, enrichment, separation and elution. Specifically, the activation step includes rinsing the solid phase extraction column with 20mL of methanol, and then washing the residual methanol in the solid phase extraction column with 40mL of ultrapure water; the enriching step comprisesPassing 20mL of the CDs solution through a solid phase extraction column; the separation step comprises washing the solid phase extraction column with 40mL of ultrapure water to dissolve impurities such as inorganic salts; and the elution step comprises the steps of rinsing the solid phase extraction column by using 20mL of methanol, desorbing CDs to obtain a high-purity CDs-methanol solution, blowing off the extraction liquid by using nitrogen, and freeze-drying for 48 hours to obtain CDs solid particles.
Preparation of Fe by anodic oxidation2O3Nanotube of 2 Fe2O3Soaking the nanotubes in a mixed solution containing 25% mercaptopropionic acid (MPA) by volume fraction and 15g/L CDs (carbon nanotubes) without mercaptopropionic acid) for 48h, and taking out to obtain Fe2O3nanotube-CDs electrodes.
Carbon nitride is formed on the CDs electron transport layer by a hydrothermal method. Prepared Fe2O3Soaking the nanotube-CDs electrode in 30% melamine aqueous solution, and keeping the temperature at 80 ℃ for 72h to obtain Fe2O3nanotube-CDs-carbon nitride photocatalytic electrode.
The prepared photocatalytic electrode is used for carrying out an organic matter degradation synchronous heavy metal reduction experiment: immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals with certain concentration, and irradiating the working surface of the photocatalytic electrode with simulated sunlight to degrade the organic pollutants and reduce the heavy metals. The specific conditions are as follows: illumination intensity of 100mW cm-2The wavelength is more than 420 nm; electrode working area to solution volume ratio: 7.5cm2 L-1(ii) a Organic concentration (carbamazepine): 10 mu M; heavy metal concentration (hexavalent chromium): 0.68 mM; reaction time: 60 min; the pH value of the reaction system does not need to be adjusted; the reaction system does not need aeration.
As shown in fig. 13: fe without addition of MPA2O3The degradation effect of the nanotube-CDs-carbon nitride photocatalytic electrode on organic matters is from 6 percent (Fe)2O3Nanotubes) to 25% and, after MPA addition, Fe2O3The degradation effect of the nanotube-CDs-carbon nitride on the organic matters is further improved to 65%, and the fact that the addition of MPA is beneficial to the fixation of CDs and can further improve the degradation effect of the organic matters is proved.
As shown in fig. 14: fe without addition of MPA2O3The heavy metal reduction effect of the nanotube-CDs-carbon nitride photocatalytic electrode is from 4 percent (Fe)2O3Nanotubes) to 12% and, after MPA addition, Fe2O3The reduction effect of the nanotube-CDs-carbon nitride on heavy metals is further improved to 66%, which proves that the addition of MPA is beneficial to the fixation of CDs and can further improve the reduction effect of heavy metals.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a photocatalytic electrode for synchronously reducing heavy metals based on organic matter degradation of carbon dots is characterized by comprising the following steps:
forming a Carbon Dot (CDs) electron transport layer on the semiconductor i;
and forming a semiconductor II on the carbon dot electron transport layer.
2. The production method according to claim 1, wherein the step of forming a carbon dot electron transport layer on the semiconductor i comprises:
soaking the semiconductor I in a mixed solution of mercaptopropionic acid (MPA) with the volume fraction of 10% -30% (such as 15%, 20% or 25%) and CDs with the volume fraction of 1-10g/L (such as 2g/L, 5g/L or 8g/L) (preferably, the soaking time is 24-48h), and taking out to obtain the semiconductor I-CDs electrode.
3. The method according to claim 1, wherein the semiconductor I is TiO2Nanotubes or Fe2O3A nanotube.
4. The production method according to claim 3, wherein the TiO2TiO prepared by nanotube anodic oxidation method2Nanotubes of said Fe2O3The nanotube is Fe prepared by anodic oxidation2O3A nanotube.
5. The preparation method according to claim 1, wherein the semiconductor II is an organic semiconductor or an inorganic semiconductor, wherein the organic semiconductor is polyaniline, reduced graphene oxide or carbon nitride; the inorganic semiconductor is WO3Or MoS2。
6. The method of claim 1, wherein the method of preparing the carbon dots comprises: dissolving glucose in concentrated H2SO4Heating at 180-220 deg.C (such as 190 deg.C, 200 deg.C or 210 deg.C) for 3-5h (such as 3.5h, 4h or 4.5h), cooling to room temperature, adjusting pH of the mixed solution to 6.9-7.1, centrifuging, collecting supernatant, passing through a solid phase extraction column, blowing off the extract with nitrogen, and freeze-drying (such as freeze-drying for 24-48h) to obtain carbon dot solid particles.
7. The method of claim 6, wherein the solid phase extraction column is an HLB solid phase extraction column, preferably the step of extracting comprises: rinsing the solid phase extraction column with methanol, and then washing residual methanol in the solid phase extraction column with ultrapure water; passing the CDs solution through a solid phase extraction column; washing the solid phase extraction column with ultrapure water; the solid phase extraction column was rinsed with methanol to desorb the CDs, yielding a high purity CDs-methanol solution.
8. A photocatalytic electrode produced by the production method according to any one of claims 1 to 7.
9. A method for degrading organic substances while reducing heavy metals by using the photocatalytic electrode of claim 8, comprising:
and immersing the photocatalytic electrode into a solution containing organic pollutants and heavy metals, and performing organic pollutant degradation and heavy metal reduction under the illumination condition.
10. The process of claim 9, wherein the reaction conditions are as follows: the illumination intensity is more than 50mW cm-2The wavelength is more than 200 nm; electrode working area to solution volume ratio: 1-10cm2L-1(ii) a Concentration of organic contaminants: less than 1M; concentration of heavy metal: less than 10M; reaction time: 30-120min (e.g., 60min or 90 min).
CN202010344416.0A 2020-04-16 2020-04-27 Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application Pending CN113526607A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US16/926,398 US20200378018A1 (en) 2020-04-16 2020-07-10 Carbon dots-based photocatalytic electrode for simultaneous organic matter degradation and heavy metal reduction and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2020102988637 2020-04-16
CN202010298863 2020-04-16

Publications (1)

Publication Number Publication Date
CN113526607A true CN113526607A (en) 2021-10-22

Family

ID=78094205

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010344416.0A Pending CN113526607A (en) 2020-04-16 2020-04-27 Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application

Country Status (1)

Country Link
CN (1) CN113526607A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114715984A (en) * 2022-03-28 2022-07-08 昆明理工大学 Self-cleaning luminous photoelectric cooperative catalysis electrode and application thereof
CN114768808A (en) * 2022-05-27 2022-07-22 重庆理工大学 Preparation method and application of carbon quantum dot doped iron-based oxide photo-Fenton catalyst

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070181179A1 (en) * 2005-12-21 2007-08-09 Konarka Technologies, Inc. Tandem photovoltaic cells
CN102992311A (en) * 2012-12-10 2013-03-27 福州大学 Method for preparing graphene quantum dots through carbon nano tube
CN105185601A (en) * 2015-09-28 2015-12-23 华南理工大学 Titanium dioxide nanotube/polyaniline composite electrode, preparation and application thereof
CN108315012A (en) * 2018-02-01 2018-07-24 东北林业大学 A kind of carbon quantum dot and its preparation method and application
CN109980100A (en) * 2017-12-27 2019-07-05 Tcl集团股份有限公司 Luminescent material and preparation method thereof and QLED device
CN110424064A (en) * 2019-09-03 2019-11-08 哈工大新材料智能装备技术研究院（招远）有限公司 Modified pbo fiber of a kind of graphene quantum dot and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070181179A1 (en) * 2005-12-21 2007-08-09 Konarka Technologies, Inc. Tandem photovoltaic cells
CN102992311A (en) * 2012-12-10 2013-03-27 福州大学 Method for preparing graphene quantum dots through carbon nano tube
CN105185601A (en) * 2015-09-28 2015-12-23 华南理工大学 Titanium dioxide nanotube/polyaniline composite electrode, preparation and application thereof
CN109980100A (en) * 2017-12-27 2019-07-05 Tcl集团股份有限公司 Luminescent material and preparation method thereof and QLED device
CN108315012A (en) * 2018-02-01 2018-07-24 东北林业大学 A kind of carbon quantum dot and its preparation method and application
CN110424064A (en) * 2019-09-03 2019-11-08 哈工大新材料智能装备技术研究院（招远）有限公司 Modified pbo fiber of a kind of graphene quantum dot and preparation method thereof

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
LIN ZHOU ET AL: "Insight into the effect of ligand-exchange on colloidal CsPbBr3 perovskite quantum dot/mesoporous-TiO2 composite-based photodetectors: much faster electron injection", 《JOURNAL OF MATERIALS CHEMISTRY C》 *
SOLMAZ FEIZPOOR ET AL: "Integration of carbon dots and polyaniline with TiO", 《JOURNAL OF PHOTOCHEMISTRY & PHOTOBIOLOGY A: CHEMISTRY》 *
刘斌 等: "《中药成分体内代谢与分析研究》", 31 August 2011, 中国中医药出版社 *
李垚 等: "《新型功能材料制备原理与工艺》", 31 August 2017, 哈尔滨工业大学出版社 *
梅邱峰 等: "二氧化钛Z型异质结光催化剂", 《无机化学学报》 *
黄华丽: "光电催化水分解体系中α-Fe2O3纳米棒光阳极的制备及改性研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114715984A (en) * 2022-03-28 2022-07-08 昆明理工大学 Self-cleaning luminous photoelectric cooperative catalysis electrode and application thereof
CN114715984B (en) * 2022-03-28 2024-03-22 昆明理工大学 Self-cleaning luminous photoelectric synergistic catalytic electrode and application thereof
CN114768808A (en) * 2022-05-27 2022-07-22 重庆理工大学 Preparation method and application of carbon quantum dot doped iron-based oxide photo-Fenton catalyst
CN114768808B (en) * 2022-05-27 2023-12-08 重庆理工大学 Preparation method and application of carbon quantum dot doped iron-based oxide photo-Fenton catalyst

Similar Documents

Publication Publication Date Title
US20200378018A1 (en) Carbon dots-based photocatalytic electrode for simultaneous organic matter degradation and heavy metal reduction and use thereof
Guo et al. Z-scheme heterojunction g-C3N4@ PDA/BiOBr with biomimetic polydopamine as electron transfer mediators for enhanced visible-light driven degradation of sulfamethoxazole
Wang et al. The precursor-guided hydrothermal synthesis of CuBi2O4/WO3 heterostructure with enhanced photoactivity under simulated solar light irradiation and mechanism insight
Tao et al. Multi-layered porous hierarchical TiO2/g-C3N4 hybrid coating for enhanced visible light photocatalysis
Yu et al. Novel Fe2 (MoO4) 3/g-C3N4 heterojunction for efficient contaminant removal and hydrogen production under visible light irradiation
Ranganathan et al. Study of photoelectrochemical water splitting using composite films based on TiO2 nanoparticles and nitrogen or boron doped hollow carbon spheres as photoanodes
Bai et al. D35-TiO2 nano-crystalline film as a high performance visible-light photocatalyst towards the degradation of bis-phenol A
Qin et al. Dye-sensitized TiO2 film with bifunctionalized zones for photocatalytic degradation of 4-cholophenol
Wu et al. Promising materials for photocatalysis‐self‐Fenton system: properties, modifications, and applications
Hu et al. Engineered photocatalytic fuel cell with oxygen vacancies-rich rGO/BiO1− xI as photoanode and biomass-derived N-doped carbon as cathode: Promotion of reactive oxygen species production via Fe2+/Fe3+ redox
CN104959141B (en) A kind of loaded Cu/Cu2The redox graphene of O photochemical catalysts/amorphous carbon composite and its preparation method and application
Gu et al. Heterojunction photocatalyst of cavity shaped Bi2S3/g-C3N4 for bisphenol a degradation: Regulation of internal electric field via assistance of interfacial functional groups
Wang et al. Persulfate activation of CuS@ Ti3C2-based MXene with Bi-active centers toward Orange II removal under visible light
Lin et al. Facile preparation of a novel modified biochar-based supramolecular self-assembled g-C3N4 for enhanced visible light photocatalytic degradation of phenanthrene
Peng et al. Construction of a Z-scheme gC 3 N 4/NBGO/BiVO 4 heterostructure with visible-light driven photocatalytic degradation of tetracycline: efficiency, reaction pathway and mechanism
CN113526607A (en) Organic matter degradation synchronous heavy metal reduction photocatalysis electrode based on carbon dots and application
Cheng et al. Construction of hollow In 2 S 3/CdIn 2 S 4 heterostructures with high efficiency for Cr (vi) reduction
Bu et al. Fabrication of novel Z-scheme LaCoO3/activated biochar/Ag3PO4 heterojunctions for intensifying visible-light-catalytic degradation of bisphenol A
CN112121866A (en) Photocatalyst and preparation method thereof
Cai et al. rGO-modified BiOX (X= Cl, I, Br) for enhanced photocatalytic eradication of gaseous mercury
Yan et al. Uranium extraction by a graphene-based asymmetric electrode configuration through combined complexation, electro-adsorption, and photocatalytic reduction
Sharma et al. Controllable functionalization of g-C3N4 mediated all-solid-state (ASS) Z-scheme photocatalysts towards sustainable energy and environmental applications
Hao et al. Solar-responsive photocatalytic activity of amorphous TiO2 nanotube-array films
Yang et al. A general strategy via photoelectrocatalytic oxygen reduction for generating singlet oxygen with carbon bridged carbon-nitride electrode
CN111957328A (en) Catalyst module, preparation method and application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination