CN-116553688-B - FeOCl/Ti3C2TxChlorine-removing electrode material, and preparation method and application thereof

Abstract

The invention discloses a FeOCl/Ti 3 C 2 T x dechlorination electrode material, a preparation method and application thereof, wherein FeOCl powder is prepared by taking FeCl 3 ·6H 2 O as a raw material through pyrolysis, the FeOCl powder is suspended in acetonitrile solution after being washed by acetone, an MAX phase is formed by etching precursor of HCl and LiF, a Ti 3 C 2 T x water suspension with single-layer or few-layer is obtained after ultrasonic stripping of etching products, and the Ti 3 C 2 T x water suspension is obtained after mixing with FeOCl acetonitrile suspension, vacuum suction filtration and natural drying. The invention firstly utilizes the high Cl ‑ theoretical storage capacity of FeOCl, combines the excellent conductivity and film forming property of two-dimensional layered Ti 3 C 2 T x , obtains the FeOCl/Ti 3 C 2 T x dechlorination electrode material through electrostatic self-assembly, has excellent self-supporting capability, is directly used as a dechlorination electrode, shows the advantages of high dechlorination capacity, quick dechlorination rate and low energy consumption, and is used in the fields of sea water desalination and industrial wastewater treatment.

Inventors

• MA JIE
• LEI JINGJING

Assignees

• 同济大学

Dates

Publication Date

20260512

Application Date

20230515

Claims (9)

1. 1. The FeOCl/Ti 3 C 2 T x chlorine removal electrode material is characterized by being a flexible self-supporting film material with a micropore and mesopore structure, and is obtained by electrostatic self-assembly of a Ti 3 C 2 T x two-dimensional lamellar material and FeOCl powder, wherein the surface of the Ti 3 C 2 T x two-dimensional lamellar material is corrugated, and the sections of the Ti 3 C 2 T x two-dimensional lamellar material are stacked layer by layer; The preparation method of the FeOCl/Ti 3 C 2 T x chlorine-removing electrode material comprises the following steps: (1) Placing FeCl 3 ·6H 2 O into a corundum crucible with a flat bottom and a cover, and heating in a muffle furnace to obtain FeOCl powder; (2) Centrifugally washing FeOCl powder with acetone, and vacuum drying; (3) Mixing LiF and HCl in a polytetrafluoroethylene reactor, and stirring to obtain a solution A; (4) Adding MAX-Ti 3 AlC 2 into the solution A, heating in water bath, and stirring to obtain a mixed solution B; (5) Centrifugally washing the mixed solution B by using HCl, and collecting precipitate A; (6) After the sediment A is centrifugally washed by deionized water, repeatedly performing water intercalation expansion treatment, and collecting sediment B; (7) Adding ethanol into the precipitate B, performing ultrasonic treatment, centrifuging, and collecting precipitate C; (8) Adding deionized water into the precipitate C, shaking uniformly, performing ultrasonic treatment, centrifuging, and collecting the supernatant; (9) Repeating the step (8) to collect the upper liquid; (10) Measuring the concentration of the collected upper liquid, and diluting to obtain a suspension A; (11) Taking FeOCl after vacuum drying in the step (2), adding acetonitrile, and carrying out ultrasonic treatment to obtain a suspension B; (12) And mixing and stirring the suspension A and the suspension B, vacuum filtering, and drying to obtain the FeOCl/Ti 3 C 2 T x dechlorination electrode material.
2. 2. The FeOCl/Ti 3 C 2 T x dechlorination electrode material of claim 1, characterized in that the specific surface area of the FeOCl/Ti 3 C 2 T x dechlorination electrode material is 52.618 m 2 /g.
3. 3. The FeOCl/Ti 3 C 2 T x chlorine-removing electrode material as claimed in claim 1, wherein, In the step (1), feCl 3 ·6H 2 O with the mass of 1g is uniformly paved at the bottom of a flat-bottom corundum crucible with a cover, the length of 120 mm, the width of 60 mm and the height of 18 mm, the temperature rising rate of a muffle furnace is 5 ℃ per minute, the temperature rises to 220 ℃, and the temperature is kept at 3 h; And/or in the step (2), washing until the washing liquid is colorless; and/or in step (3), the mass of LiF is 2 g, the HCl concentration is 9 mol/L, the volume is 40 mL, the polytetrafluoroethylene reactor volume is 100 mL, the stirring time is 30min, and the rotating speed is 400 rpm; And/or in the step (4), the addition amount of MAX-Ti 3 AlC 2 is 2 g, the water bath heating temperature is 35 ℃, and the stirring time is 24h; and/or in the step (5), the HCl concentration is 1 mol/L, and the washing times are 4 times; And/or in the step (6), the centrifugal speed is 3500 rpm, the duration time is 10 min each time, the washing times are not less than 10 times, and the pH value of the washing liquid is not less than 6.
4. 4. The FeOCl/Ti 3 C 2 T x chlorine-removing electrode material of claim 1, wherein in step (6), the water intercalation expansion treatment operation comprises adding deionized water to the precipitate, mixing uniformly with a vortex oscillator, centrifuging, not pouring supernatant, mixing uniformly again, centrifuging, repeating for not less than 20 times, until the precipitate expands.
5. 5. The FeOCl/Ti 3 C 2 T x dechlorination electrode material of claim 1, wherein in step (7), the ethanol addition amount is 40 mL, the ultrasonic time is 1h, the ultrasonic condition is argon atmosphere, the ice bath, the centrifugal rotation speed is 10000 rpm, and the duration time is 10 min.
6. 6. The FeOCl/Ti 3 C 2 T x dechlorinated electrode material of claim 1, wherein in step (8), deionized water is added in an amount of 20: 20mL, the ultrasound time is 20: 20 min, the ultrasound conditions are argon atmosphere, the ice bath, the centrifugation speed is 3500: 3500 rpm, and the duration is 5: 5 min.
7. 7. The FeOCl/Ti 3 C 2 T x chlorine-removing electrode material according to claim 1, wherein in the step (10), the method for measuring the concentration of the upper liquid comprises the steps of taking 5mL upper liquid, carrying out suction filtration, naturally drying, weighing the mass of the film, calculating to obtain the concentration of the upper liquid, and diluting to the concentration of the suspension A of 0.5 mg/mL according to the measured concentration of the upper liquid.
8. 8. The FeOCl/Ti 3 C 2 T x chlorine-removing electrode material as claimed in claim 1, wherein, In the step (11), the mass of FeOCl is 10 mg, the volume of acetonitrile is 20 mL, and the ultrasonic time is 30 min; And/or in the step (12), measuring the volume of the suspension A to be 40mL, mixing and stirring the suspension A and the suspension B for 5min hours, and adopting a polyvinylidene fluoride pumping filter membrane with the pore diameter of 0.22 mu m, wherein the drying condition is natural drying.
9. 9. Use of the FeOCl/Ti 3 C 2 T x dechlorination electrode material of any one of claims 1 to 8 as anode material in a capacitive deionisation process.

Description

FeOCl/Ti 3C2Tx dechlorination electrode material, and preparation method and application thereof Technical Field The invention belongs to the technical field of environmental materials, and particularly relates to a FeOCl/Ti 3C2Tx dechlorination electrode material, a preparation method and application thereof. Background As an electrochemical water treatment technology with wide prospect, the Capacitive Deionization (CDI) technology has the advantages of energy conservation, easy operation, continuous operation, long cycle life and the like. The basic principle of the CDI technology is that ions are moved to an electrode with opposite charges by applying an external electric field, meanwhile, the electrode is controlled to charge and discharge, and the ion concentration at the electrode is changed to realize ion removal. The current research focus on CDI electrode materials is mostly focused on the design of cathode materials, while there is less research on dechlorinated anode materials. The traditional CDI dechlorination electrode material is carbon materials such as active carbon, carbon aerogel and carbon nano tubes, but the carbon materials adopt an electric double layer mechanism to store ions, have low capacity, have serious homoionic rejection effect and side reaction, and have lower charge efficiency. With the rapid development of the field of energy storage batteries in recent years, faraday electrode materials are coming into the field of view of researchers, which have higher adsorption capacities. Currently, faraday chlorine-removing electrode materials mainly comprise Ag/AgCl and Bi/BiOCl. The Ag/AgCl electrode is high in price, the conductivity of the conversion product AgCl is poor, the chlorine removal rate is slow, and the Bi/BiOCl electrode can undergo large volume change in the charging and discharging processes, so that the cycling stability of the electrode is poor. In view of the foregoing, there is a need for developing a novel CDI chlorine removal electrode having high chlorine removal capacity, fast chlorine removal rate, and excellent cycle performance. Disclosure of Invention Aiming at the defects in the prior art, the primary purpose of the invention is to provide a FeOCl/Ti 3C2Tx dechlorination electrode material, wherein the FeOCl/Ti 3C2Tx dechlorination electrode material with excellent self-supporting capability is obtained through electrostatic self-assembly by utilizing the high Cl - theoretical storage capacity of FeOCl for the first time and combining the excellent conductivity and film forming property of two-dimensional layered Ti 3C2Tx. The second purpose of the invention is to provide a preparation method of the FeOCl/Ti 3C2Tx dechlorination electrode material, which comprises the steps of preparing FeOCl powder by taking FeCl 3·6H2 O as a raw material and carrying out pyrolysis, suspending in acetonitrile solution for ultrasonic treatment after washing by acetone, carrying out ultrasonic stripping by adopting an HCl and LiF etching precursor MAX phase (Ti 3AlC2), obtaining a single-layer or less-layer Ti 3C2Tx aqueous suspension after ultrasonic stripping of an etching product, mixing the FeOCl acetonitrile suspension and the Ti 3C2Tx aqueous suspension, carrying out vacuum suction filtration, and naturally drying. The third purpose of the invention is to provide the application of the FeOCl/Ti 3C2Tx dechlorination electrode material, which can be directly used as a dechlorination electrode in the fields of sea water desalination and industrial wastewater treatment, and has the advantages of high dechlorination capacity, rapid dechlorination rate and low energy consumption. In order to achieve the above purpose, the invention adopts the following technical scheme: The invention provides a FeOCl/Ti 3C2Tx dechlorination electrode material which is a flexible self-supporting film material with a micropore and mesopore structure, and is obtained by electrostatic self-assembly of a Ti 3C2Tx two-dimensional lamellar material and FeOCl powder, wherein the surface of the Ti 3C2Tx two-dimensional lamellar material is corrugated, and the sections of the Ti 3C2Tx two-dimensional lamellar material are stacked layer by layer. Preferably, the specific surface area of the FeOCl/Ti 3C2Tx chlorine-removing electrode material is 52.618m 2/g. The invention also provides a preparation method of the FeOCl/Ti 3C2Tx dechlorination electrode material, which comprises the following steps: (1) Placing FeCl 3·6H2 O into a corundum crucible with a flat bottom and a cover, and heating in a muffle furnace to obtain FeOCl; (2) Centrifugally washing FeOCl with acetone, and drying in vacuum; (3) Mixing LiF and HCl in a polytetrafluoroethylene reactor, and stirring to obtain a solution A; (4) Adding MAX-Ti 3AlC2 into the solution A, heating in water bath, and stirring to obtain a mixed solution B; (5) Centrifugally washing the mixed solution B by using HCl, and collecting precipitate A; (6) After th