CN114100598A - Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top - Google Patents

Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top Download PDF

Info

Publication number
CN114100598A
CN114100598A CN202111431065.8A CN202111431065A CN114100598A CN 114100598 A CN114100598 A CN 114100598A CN 202111431065 A CN202111431065 A CN 202111431065A CN 114100598 A CN114100598 A CN 114100598A
Authority
CN
China
Prior art keywords
photocatalytic
van der
der waals
assembling
waals heterojunction
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
CN202111431065.8A
Other languages
Chinese (zh)
Inventor
陈华军
席晓晶
赵莉
李冬
田文杰
王小庆
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.)
Luoyang Institute of Science and Technology
Original Assignee
Luoyang Institute of Science and Technology
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 Luoyang Institute of Science and Technology filed Critical Luoyang Institute of Science and Technology
Priority to CN202111431065.8A priority Critical patent/CN114100598A/en
Publication of CN114100598A publication Critical patent/CN114100598A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B01J35/396—Distribution of the active metal ingredient
    • 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
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • 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

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 relates to a method for assembling a Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top, which belongs to the field of photocatalysis and photoelectrocatalysis material synthesis and comprises the following steps: adding the nano powder photocatalytic material into a tris (hydroxymethyl) aminomethane aqueous solution, and dispersing to obtain a solution A; adding dopamine, and carrying out dopamine polymerization reaction on the surface of the powder photocatalytic material to obtain a product B; centrifugally separating, washing, drying and roasting to obtain a product C; adding the product C into deionized water, and dispersing to obtain a suspension D; and (3) immersing the carbon fiber fabric into the suspension D, and assembling the product C with the carbon fiber fabric to form the macroscopic Van der Waals heterojunction photocatalytic and photoelectrocatalysis material. The method adopts a mode from bottom to top, the powder photocatalytic material is assembled on the surface of the carbon fiber fabric through Van der Waals effect, the obtained product is easy to separate and recycle, the method is simple and easy to implement, the process is environment-friendly, the difficult problems of separating and recycling the powder photocatalyst are solved, and a new way is opened up for the industrial application of the photocatalysis.

Description

Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top
Technical Field
The invention belongs to the field of synthesis of photocatalytic and photoelectric catalytic materials, and particularly relates to a method for assembling a van der Waals heterojunction photocatalytic and photoelectric catalytic material from bottom to top.
Background
The solar photocatalysis technology has important significance in the aspects of air purification and water treatment, and is expected to solve the environmental problem. The photocatalytic process comprises light absorption, carrier separation and surface reaction, and the photocatalytic efficiency of the material mainly depends on the three processes. In the aspect of photocatalytic treatment of organic wastewater, the traditional powder photocatalytic material has high separation and recovery cost, and is also not beneficial to the design of photocatalytic reaction equipment, so that the problems hinder the industrial application of the photocatalytic material.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for assembling Van der Waals heterojunction photocatalysis and photoelectrocatalysis materials from bottom to top, which adopts a mode from bottom to top to assemble powder photocatalysis materials and macroscopic carbon fiber fabrics into a photocatalysis and photoelectrocatalysis material which is easy to separate and recycle through Van der Waals interaction, thereby solving the difficult problems of separation and recycling of the powder photocatalyst in the water treatment process.
The invention adopts the following specific scheme:
a method for assembling Van der Waals heterojunction photocatalysis and photoelectrocatalysis materials from bottom to top comprises the following steps:
(1) adding the nano powder photocatalytic material into a tris (hydroxymethyl) aminomethane aqueous solution, and performing ultrasonic dispersion to obtain a suspension solution A;
(2) adding dopamine into the solution A under stirring, and carrying out dopamine polymerization reaction on the surface of the powder photocatalytic material to obtain a product B;
(3) centrifugally separating, washing and drying the product B, and roasting the product B under the protection of argon to obtain a product C;
(4) and adding the product C into deionized water, performing ultrasonic dispersion to obtain a suspension D, immersing the carbon fiber fabric into the suspension D, and assembling the product C and the carbon fiber fabric through Van der Waals force to form a macroscopic Van der Waals heterojunction photocatalytic and photoelectric catalytic material.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top comprises the following steps of (1): the powder photocatalytic material can be zero-dimensional nanospheres, one-dimensional nanofibers or two-dimensional nanosheets, the concentration of the tris (hydroxymethyl) aminomethane is 5-15 mmol/L, and the ultrasonic dispersion time is 30-60 min.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top comprises the following steps of (2): the mass ratio of the powder photocatalytic material to the dopamine is 1: 1-3: 1, the dopamine polymerization reaction time is 4-6h, and the dopamine is subjected to polymerization reaction on the surface of the photocatalytic material to form a uniform polydopamine coating.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top is characterized in that in the step (3): the drying time is 10-12h, the roasting temperature is 400-450 ℃, the time is 10-12h, the roasting atmosphere is argon atmosphere, the flow rate of argon is 40-60SCCM, and the poly-dopamine coating on the surface of the photocatalytic material is carbonized into a carbon coating in the roasting process to form the zero-dimensional, one-dimensional or two-dimensional core-shell material.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top comprises the following steps of (4): the ultrasonic dispersion time is 30-60min, the mass ratio of the core-shell material to the carbon fiber fabric is 1: 100-2: 100, and the assembly time is 4-6 h. The amorphous carbon is adopted to carry out surface modification on the powder photocatalytic material, and the van der Waals interaction between the powder photocatalytic material and the carbon fiber fabric is enhanced, so that the photocatalytic and photoelectric catalytic material which is easy to separate and recycle is assembled.
The technical scheme of the invention obtains the following beneficial technical effects:
1. the invention adopts a mode from bottom to top, and assembles the powder photocatalytic material on the surface of the macroscopic carbon fiber fabric through Van der Waals interaction, so as to prepare the macroscopic photocatalytic and photoelectrocatalysis material which is easy to separate and recycle.
2. The material assembly strategy provided by the invention solves the difficult problems of separation and recovery of the powder photocatalyst in the actual use process, and opens up a new way for the industrial application of photocatalysis.
3. The easily separated and recycled photocatalytic and photoelectrocatalysis material assembled by Van der Waals force has excellent photocatalytic and photoelectrocatalysis cycle performance, the photoelectrocatalysis performance is greater than the sum of the photocatalysis and the electrocatalysis, and the photocatalysis have synergistic effect in the process of the photocatalysis and the photoelectrocatalysis.
Drawings
FIG. 1 is a TEM photograph of P25@ activated carbon core-shell spheres in example 1;
FIG. 2 is a graph comparing the UV-visible diffuse reflectance spectra of P25 with P25@ activated carbon core-shell sphere in example 1;
FIG. 3 is an SEM photograph of the Van der Waals heterojunction photocatalytic and photocatalytic material of P25@ activated carbon/carbon fiber fabric in example 1;
FIG. 4 is a graph comparing the effect of P25@ activated carbon/carbon fiber fabric van der Waals heterojunction on the electrocatalytic, photocatalytic and photoelectrocatalytic degradation of 2, 4-dinitrophenol in example 1;
FIG. 5 shows TiO in example 22@ TEM photograph of core-shell fibers of activated carbon;
FIG. 6 is an embodimentIn case 2, TiO2Fibres and TiO2A @ active carbon core-shell fiber photoluminescence spectrum contrast diagram;
FIG. 7 shows TiO in example 22The SEM photo picture of the @ active carbon/carbon fiber fabric van der Waals heterojunction photocatalysis and photoelectrocatalysis material;
FIG. 8 shows TiO in example 22Comparison graphs of the van der Waals heterojunction of the @ activated carbon/carbon fiber fabric on the electrocatalytic, photocatalytic and photoelectrocatalytic degradation effects of 2, 4-dinitrophenol;
FIG. 9 shows g-C in example 33N4@ TEM photograph of core-shell nanosheets of activated carbon;
FIG. 10 shows the results of example 3, g-C3N4Nanosheets and g-C3N4A @ active carbon core-shell nanosheet ultraviolet visible diffuse reflectance spectrum contrast diagram;
FIG. 11 shows the results of example 3, g-C3N4Nanosheets and g-C3N4A @ active carbon core-shell nanosheet photoluminescence spectrum contrast diagram;
FIG. 12 shows the results of example 3, g-C3N4@ active carbon/carbon fiber fabric van der Waals heterojunction photocatalytic and photoelectrocatalysis material SEM photo;
FIG. 13 shows the results of example 3, g-C3N4Comparison graphs of the van der Waals heterojunction of the @ activated carbon/carbon fiber fabric on the electrocatalytic, photocatalytic and photoelectrocatalytic degradation effects of 2, 4-dinitrophenol;
FIG. 14 shows the van der Waals heterojunction TiO of P25@ activated carbon/carbon fiber fabric in examples 1-32@ activated carbon/carbon fiber fabric van der Waals heterojunction and g-C3N4A comparison graph of the circulation stability of the 2, 4-dinitrophenol degraded by adopting the van der Waals heterojunction photoelectrocatalysis of the @ activated carbon/carbon fiber fabric;
FIG. 15 is a graph comparing the cycle stability of the photocatalytic degradation of 2, 4-dinitrophenol by the powder photocatalytic material and the van der Waals heterojunction in examples 1 to 3.
Detailed Description
A method for assembling Van der Waals heterojunction photocatalysis and photoelectrocatalysis materials from bottom to top comprises the following steps:
(1) adding the nano powder photocatalytic material into a tris (hydroxymethyl) aminomethane aqueous solution, and performing ultrasonic dispersion to obtain a suspension solution A;
(2) adding dopamine into the solution A under stirring, and carrying out dopamine polymerization reaction on the surface of the powder photocatalytic material to obtain a product B;
(3) centrifugally separating, washing and drying the product B, and roasting the product B under the protection of argon to obtain a product C;
(4) and adding the product C into deionized water, performing ultrasonic dispersion to obtain a suspension D, immersing the carbon fiber fabric into the suspension D, and assembling the product C and the carbon fiber fabric through Van der Waals force to form a macroscopic Van der Waals heterojunction photocatalytic and photoelectric catalytic material.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top comprises the following steps of (1): the powder photocatalytic material can be zero-dimensional nanospheres, one-dimensional nanofibers and two-dimensional nanosheets, the concentration of the tris (hydroxymethyl) aminomethane is 5-15 mmol/L, and the ultrasonic dispersion time is 30-60 min.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top comprises the following steps of (2): the mass ratio of the powder photocatalytic material to the dopamine is 1: 1-3: 1, the dopamine polymerization reaction time is 4-6h, and the dopamine is subjected to polymerization reaction on the surface of the photocatalytic material to form a uniform polydopamine coating.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top is characterized in that in the step (3): the drying time is 10-12h, the roasting temperature is 400-450 ℃, the time is 10-12h, the roasting atmosphere is argon atmosphere, the flow rate of argon is 40-60SCCM, and the poly-dopamine coating on the surface of the photocatalytic material is carbonized into a carbon coating in the roasting process to form zero-dimensional/one-dimensional and two-dimensional core-shell materials.
The method for assembling the van der waals heterojunction photocatalytic and photoelectrocatalysis material from bottom to top comprises the following steps of (4): the ultrasonic dispersion time is 30-60min, the mass ratio of the core-shell material to the carbon fiber fabric is 1: 100-2: 100, and the assembly time is 4-6 h. The amorphous carbon is adopted to carry out surface modification on the powder photocatalytic material, and the van der Waals interaction between the powder photocatalytic material and the carbon fiber fabric is enhanced, so that the photocatalytic and photoelectric catalytic material which is easy to separate and recycle is assembled.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
Example 1
A method for assembling Van der Waals heterojunction photocatalysis and photoelectrocatalysis materials from bottom to top comprises the following steps:
1) adding 0.020 g of zero-dimensional P25 photocatalytic material into 10 mmol/L tris (hydroxymethyl) aminomethane aqueous solution, and performing ultrasonic dispersion for 60min to obtain a suspension solution A;
2) adding 0.010 g of dopamine into the solution A under stirring, wherein the dopamine is subjected to dopamine polymerization reaction on the surface of the powder photocatalytic material, the dopamine polymerization reaction time is 5 hours, and the dopamine forms a uniform polydopamine coating on the surface of the photocatalytic material;
3) centrifugally separating a dopamine polymerization product, washing with deionized water for 3 times, drying at 90 ℃ for 10 hours, keeping argon, roasting at 400 ℃ for 12 hours, wherein the flow rate of argon is 50 SCCM in the roasting process, and a polydopamine coating on the surface of P25 is carbonized into a carbon coating to form a P25@ activated carbon core-shell sphere;
4) adding zero-dimensional P25@ activated carbon core-shell balls into deionized water, ultrasonically dispersing for 60min, immersing 1.00g of carbon fiber fabric into suspension, and assembling the zero-dimensional P25@ activated carbon core-shell balls and the carbon fiber fabric through van der Waals force under magnetic stirring to form an easily separated and recycled P25@ activated carbon/carbon fiber fabric van der Waals heterojunction photocatalytic and photoelectrocatalysis material, wherein the assembling time is 5 hours;
5) the P25@ activated carbon/carbon fiber fabric van der Waals heterojunction photocatalytic and photoelectrocatalysis material assembled by van der Waals force has excellent photocatalytic and photoelectrocatalysis cycle performances, the degradation rates of electrocatalysis, photocatalysis and photoelectrocatalysis to 2, 4-dinitrophenol within 60min are respectively 32.0%/41.5% and 99.7%, the photoelectrocatalysis performance is larger than the sum of photocatalysis and electrocatalysis, and the electrocatalysis and the photocatalysis have synergistic effect in the process of P25@ activated carbon/carbon fiber fabric van der Waals heterojunction photoelectrocatalysis.
Example 2
A method for assembling Van der Waals heterojunction photocatalysis and photoelectrocatalysis materials from bottom to top comprises the following steps:
1) 0.020 g of one-dimensional TiO2Adding the fibers into a 10 mmol/L aqueous solution of tris (hydroxymethyl) aminomethane, and performing ultrasonic dispersion for 60min to obtain a suspension solution A;
2) adding 0.010 g of dopamine into the solution A under stirring, wherein the dopamine is in powder TiO2Carrying out dopamine polymerization reaction on the surface of the fiber for 5 h, wherein the dopamine is in TiO2Forming a uniform polydopamine coating on the surface of the fiber;
3) centrifuging to separate dopamine polymerization product, washing with deionized water for 3 times, drying at 90 deg.C for 10 hr, calcining at 400 deg.C for 12 hr under the protection of argon gas, wherein the flow rate of argon gas is 50 SCCM and TiO is TiO2Carbonizing polydopamine coating on the surface of the fiber into carbon coating to form TiO2@ activated carbon core-shell fibers;
4) one-dimensional TiO is mixed2@ active carbon core-shell fiber is added into deionized water, ultrasonic dispersion is carried out for 60min, 1.00g of carbon fiber fabric is immersed into suspension, and zero-dimensional TiO is added into the suspension under magnetic stirring2The @ activated carbon core-shell fiber and the carbon fiber fabric are assembled through van der Waals force to form TiO which is easy to separate and recover2@ active carbon/carbon fiber fabric van der Waals heterojunction photocatalysis and photoelectrocatalysis material, and the assembly time is 5 h;
5) TiO assembled by van der Waals forces2The @ active carbon/carbon fiber fabric van der Waals heterojunction photocatalytic and photoelectrocatalysis material has excellent photocatalytic and photoelectrocatalysis cycle performance, the degradation rates of electrocatalysis, photocatalysis and photoelectrocatalysis to 2, 4-dinitrophenol within 70 min are respectively 24.4%/35.0% and 99.6%, the photoelectrocatalysis performance is larger than the sum of photocatalysis and electrocatalysis, TiO2The @ active carbon/carbon fiber fabric van der Waals heterojunction photoelectrocatalysis process has synergistic effect of electrocatalysis and photocatalysis.
Example 3
A method for assembling Van der Waals heterojunction photocatalysis and photoelectrocatalysis materials from bottom to top comprises the following steps:
1) 0.020 g of two-dimensional g-C3N4Adding the nanosheets into a 10 mmol/L aqueous solution of tris (hydroxymethyl) aminomethane, and ultrasonically dispersing for 60min to obtain a suspension solution A;
2) adding 0.010 g of dopamine into the solution A under stirring, wherein the g-C of dopamine is3N4Carrying out dopamine polymerization reaction on the surface of the nano sheet for 5 h, wherein the dopamine is in g-C3N4A uniform polydopamine coating is formed on the surface of the nanosheet;
3) centrifuging to separate dopamine polymerization product, washing with deionized water for 3 times, drying at 90 deg.C for 10 hr, calcining at 400 deg.C for 12 hr under argon atmosphere, wherein the flow rate of argon gas is 50 SCCM, g-C3N4Carbonizing the poly dopamine coating on the surface of the nano sheet into a carbon coating to form g-C3N4@ activated carbon core-shell nanosheets;
4) two dimensions g-C3N4Adding the @ activated carbon core-shell nanosheet into deionized water, ultrasonically dispersing for 60min, immersing 1.00g of carbon fiber fabric into the suspension, and stirring under magnetic force to obtain two-dimensional g-C3N4The g-C easy to separate and recover is formed by assembling the @ activated carbon core-shell nanosheet and the carbon fiber fabric through van der Waals force3N4@ active carbon/carbon fiber fabric van der Waals heterojunction photocatalysis and photoelectrocatalysis material, and the assembly time is 5 h;
5) g-C assembled by van der Waals forces3N4The @ activated carbon/carbon fiber fabric van der Waals heterojunction photocatalytic and photoelectrocatalysis material has excellent photocatalytic and photoelectrocatalysis cycle performance, the degradation rates of electrocatalysis, photocatalysis and photoelectrocatalysis to 2, 4-dinitrophenol within 210 min are respectively 28.6 percent, 37.5 percent and 99.8 percent, the photoelectrocatalysis performance is greater than the sum of photocatalysis and electrocatalysis, and g-C3N4The @ active carbon/carbon fiber fabric van der Waals heterojunction photoelectrocatalysis process has synergistic effect of electrocatalysis and photocatalysis.
The van der waals heterojunction photocatalytic and photocatalytic materials prepared in examples 1 to 3 were evaluated, and the results are shown in fig. 1 to 15.
TEM photographs of P25@ activated carbon core-shell spheres in example 1 of FIG. 1 show an outer activated carbon coating thickness of 3.1nm in P25.
In the embodiment 1 shown in fig. 2, P25 is compared with P25@ activated carbon core-shell sphere in the ultraviolet-visible diffuse reflection spectrum, and P25@ activated carbon core-shell sphere has a light absorption capacity in the ultraviolet and visible light regions which is significantly greater than that of P25.
In the SEM photograph of the Van der Waals heterojunction photocatalytic and photocatalytic material of P25@ activated carbon/carbon fiber fabric in the embodiment 1 in FIG. 3, it can be seen from FIG. 3 that P25@ activated carbon core-shell spheres are firmly and uniformly distributed on the surface of carbon fibers.
In the embodiment 1 of fig. 4, the electrocatalytic, photocatalytic and photoelectrocatalytic degradation effects of P25@ activated carbon/carbon fiber fabric van der waals heterojunction pair 2, 4-dinitrophenol are compared, and as can be seen from fig. 4, the photoelectrocatalytic degradation effect of P25@ activated carbon/carbon fiber fabric van der waals heterojunction pair 2, 4-dinitrophenol is greater than the sum of electrocatalytic and photocatalytic, which indicates that the electrocatalytic and photocatalytic have synergistic effects in the photoelectrocatalytic process.
FIG. 5 example 2 TiO2@ TEM photograph of core-shell fiber of activated carbon, TiO2The thickness of the activated carbon coating on the outside of the fiber was 10 nm.
FIG. 6 example 2, TiO2Fibres and TiO2Comparison of the photoluminescence spectra of @ activated carbon core-shell fibers, TiO2The strength of the photoluminescence spectrum of the @ activated carbon core-shell fiber is obviously lower than that of TiO2Fibers, illustrative of the ability of activated carbon coatings to promote photogenerated electron/hole separation, TiO2The @ activated carbon core-shell fiber has higher photoproduction electron/hole separation efficiency, thereby having higher photocatalysis and photoelectrocatalysis performances.
FIG. 7 example 2, TiO2The SEM photograph of the @ active carbon/carbon fiber fabric van der Waals heterojunction photocatalytic and photoelectrocatalysis material can be seen from figure 7, TiO2The @ activated carbon core-shell fiber is firmly and uniformly distributed on the surface of the carbon fiber.
FIG. 8 example 2, TiO2Comparison of the electrocatalytic, photocatalytic and photoelectrocatalytic degradation effects of the @ activated carbon/carbon fiber fabric van der Waals heterojunction pair 2, 4-dinitrophenol, as can be seen from FIG. 8, P25@ activated carbon/carbon fiber fabric van der Waals heterojunction pair 2, 4-dinitrophenolThe electrocatalytic degradation effect is larger than the sum of electrocatalysis and photocatalysis, which shows that the electrocatalysis and the photocatalysis have synergistic effect in the photoelectrocatalysis process.
FIG. 9 example 3 g-C3N4And @ active carbon core-shell nanosheet TEM picture.
FIG. 10 example 3, g-C3N4Nanosheets and g-C3N4Comparison of ultraviolet-visible diffuse reflectance spectra of @ activated carbon core-shell nanosheets, g-C3N4The light absorption capacity of the @ activated carbon core-shell nanosheet in ultraviolet and visible light regions is remarkably greater than g-C3N4Nanosheets.
FIG. 11 example 3, g-C3N4Nanosheets and g-C3N4Comparison of the photoluminescence spectra of @ activated carbon core-shell nanosheets, g-C3N4The photoluminescent spectral intensity of the @ activated carbon core-shell nanosheet is obviously lower than that of g-C3N4Nanosheets, indicating that the activated carbon coating can facilitate separation of photogenerated electrons/holes, g-C3N4The @ activated carbon core-shell nanosheet has higher photoproduction electron/hole separation efficiency, so that the photocatalyst and photoelectrocatalysis performance is higher.
FIG. 12 example 3, g-C3N4SEM photograph of @ active carbon/carbon fiber fabric van der Waals heterojunction photocatalytic and photoelectrocatalytic material, as can be seen from FIG. 13, g-C3N4The @ activated carbon core-shell nanosheets are firmly and uniformly distributed on the surface of the carbon fiber.
FIG. 13 example 3, g-C3N4Comparison of the effects of the @ activated carbon/carbon fiber fabric van der Waals heterojunction on electrocatalysis, photocatalysis and photoelectrocatalysis degradation of 2, 4-dinitrophenol, as can be seen from figure 8, g-C3N4The photoelectrocatalytic degradation effect of the @ activated carbon/carbon fiber fabric van der Waals heterojunction on the 2, 4-dinitrophenol is larger than the sum of electrocatalysis and photocatalysis, and the situation that the electrocatalysis and the photocatalysis have a synergistic effect in the photoelectrocatalysis process is shown.
In the embodiment 1-3 of FIG. 14, P25@ activated carbon/carbon fiber fabric van der Waals heterojunction, TiO2@ activated carbon/carbon fiber fabric van der Waals heterojunction and g-C3N4The circulation stability of the 2, 4-dinitrophenol photoelectrocatalytic degradation of the van der Waals heterojunction of the activated carbon/carbon fiber fabric is shown in figure 14, and the photoelectrocatalytic performance of 3 van der Waals heterojunctions is almost unchanged after 10 cycles, so that the material assembly strategy provided by the invention can effectively solve the problem of separation and recovery of the powder photocatalyst in the use process, and a new way is opened up for the industrial application of the photocatalysis.
In the embodiment 1-3 of fig. 15, the cycle stability of the photocatalytic degradation of 2, 4-dinitrophenol by the powder photocatalytic material and the van der waals heterojunction is shown in fig. 15, and it can be seen from fig. 15 that the photocatalytic performance of the powder photocatalytic material decreases with the increase of the cycle times, because the powder photocatalytic material cannot be completely separated and recovered in the using process, the powder photocatalytic material is easy to run off. Compared with the powder photocatalysis material, the 3 Van der Waals heterojunctions have almost no change in photocatalysis performance after 10 cycles, which shows that the material assembly strategy provided by the invention can effectively solve the difficult problems of separation and recovery of the powder photocatalyst in the use process, and opens up a new way for the industrial application of photocatalysis.
It should be noted that the above-mentioned embodiments illustrate rather than limit the scope of the invention, which is defined by the appended claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.

Claims (7)

1. A method for assembling Van der Waals heterojunction photocatalysis and photoelectrocatalysis materials from bottom to top is characterized by comprising the following steps:
(1) adding the nano powder photocatalytic material into a tris (hydroxymethyl) aminomethane aqueous solution, and performing ultrasonic dispersion to obtain a suspension solution A;
(2) adding dopamine into the suspension solution A obtained in the step (1) under stirring, and carrying out dopamine polymerization reaction on the surface of the powder photocatalytic material to obtain a product B;
(3) centrifugally separating, washing and drying the product B, and roasting the product B under the protection of argon to obtain a core-shell material, namely a product C;
(4) and adding the product C into deionized water, performing ultrasonic dispersion to obtain a suspension D, immersing the carbon fiber fabric into the suspension D, and assembling the product C and the carbon fiber fabric through Van der Waals force to form a macroscopic Van der Waals heterojunction photocatalytic and photoelectric catalytic material.
2. The method of assembling a bottom-up van der waals heterojunction photocatalytic and photocatalytic material as claimed in claim 1, wherein: in the step (1), the powder photocatalytic material is a zero-dimensional nanosphere, a one-dimensional nanofiber or a two-dimensional nanosheet.
3. The method of assembling a bottom-up van der waals heterojunction photocatalytic and photocatalytic material as claimed in claim 2, wherein: the zero-dimensional nanospheres are zero-dimensional P25 photocatalytic materials, and the one-dimensional nanofibers are one-dimensional TiO2A fiber, the two-dimensional nanosheet being a two-dimensional g-C3N4Nanosheets.
4. The method of claim 1, wherein the method further comprises the step of assembling the van der waals heterojunction photocatalytic and photocatalytic material from top to bottom, wherein the method further comprises the steps of: in the step (1), the concentration of the tris (hydroxymethyl) aminomethane is 5-15 mmol/L, and the ultrasonic dispersion time is 30-60 min.
5. The method of assembling a bottom-up van der waals heterojunction photocatalytic and photocatalytic material as claimed in claim 1, wherein: the mass ratio of the powder photocatalytic material to the dopamine is 1: 1-3: 1, and the dopamine polymerization reaction time is 4-6 h.
6. The method of assembling a bottom-up van der waals heterojunction photocatalytic and photocatalytic material as claimed in claim 1, wherein: in the step (3), the drying time is 10-12 h; the roasting temperature is 400-450 ℃, the time is 10-12h, the roasting atmosphere is argon atmosphere, and the flow rate of the argon gas is 40-60 SCCM.
7. The method of assembling a bottom-up van der waals heterojunction photocatalytic and photocatalytic material as claimed in claim 1, wherein: in the step (4), the ultrasonic dispersion time is 30-60min, the mass ratio of the core-shell material to the carbon fiber fabric is 1: 100-2: 100, and the assembly time is 4-6 h.
CN202111431065.8A 2021-11-29 2021-11-29 Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top Pending CN114100598A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111431065.8A CN114100598A (en) 2021-11-29 2021-11-29 Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111431065.8A CN114100598A (en) 2021-11-29 2021-11-29 Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top

Publications (1)

Publication Number Publication Date
CN114100598A true CN114100598A (en) 2022-03-01

Family

ID=80371131

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111431065.8A Pending CN114100598A (en) 2021-11-29 2021-11-29 Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top

Country Status (1)

Country Link
CN (1) CN114100598A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155597A (en) * 2022-08-12 2022-10-11 洛阳理工学院 Preparation method of recyclable nickel cobaltate/titanium dioxide @ AC @ CFs photocatalytic material
CN115445593A (en) * 2022-09-08 2022-12-09 洛阳理工学院 Photoelectrocatalysis material, electrochemical preparation method and application thereof

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1803291A (en) * 2006-01-20 2006-07-19 中国科学院广州地球化学研究所 Titanium dioxide/active carbon fiber photocatalyst and its preparation method and uses in air purification
CN201092541Y (en) * 2007-09-27 2008-07-30 肖东 Novel sewage water treatment device
US20080311497A1 (en) * 2007-06-18 2008-12-18 Xerox Corporation Hole blocking layer containing photoconductors
CN104923203A (en) * 2015-05-20 2015-09-23 上海应用技术学院 Composite photlocatalyst and preparation method as well as application thereof
CN105057003A (en) * 2015-08-22 2015-11-18 北京化工大学 Preparing method for titanium dioxide nanometer composite thin film
CN105110432A (en) * 2015-09-09 2015-12-02 洛阳理工学院 Preparation method of granular-activated-carbon-carried nitrogen-modified nano titanium dioxide disinfectant
CN106219687A (en) * 2016-08-15 2016-12-14 浙江大学 A kind of method of pollutant in photoelectrocatalysis reduction treatment water body
CN106694014A (en) * 2015-11-13 2017-05-24 天津大学 Nitrogen-doped nonmetallic catalyst as well as preparation method and use thereof
CN107376886A (en) * 2017-09-06 2017-11-24 北方民族大学 One kind dipping hydro-thermal method synthesis active carbon from coal load TiO2The method of composite
CN110180520A (en) * 2019-05-08 2019-08-30 陕西科技大学 A kind of recyclable mesoporous carbon@TiO2/ carbon fiber catalysis material and preparation method thereof
CN111389418A (en) * 2020-04-30 2020-07-10 浙江理工大学 Flexible carbon fiber cloth @ Cu2O@SnS2Composite material, preparation method and application
CN111420649A (en) * 2020-05-11 2020-07-17 山东省淄博生态环境监测中心 PDA modified high-adsorbability TiO2Preparation method and application of fiber catalyst
CN112495419A (en) * 2020-12-03 2021-03-16 天津大学 Method for preparing graphite phase carbon nitride based nano composite photocatalyst by utilizing polydopamine
CN112547108A (en) * 2020-12-11 2021-03-26 江南大学 Ternary composite photocatalyst for antibiotic pollution degradation and preparation method thereof
WO2021224358A1 (en) * 2020-05-05 2021-11-11 Witkowski Hubert A filter and a method for manufacturing thereof

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1803291A (en) * 2006-01-20 2006-07-19 中国科学院广州地球化学研究所 Titanium dioxide/active carbon fiber photocatalyst and its preparation method and uses in air purification
US20080311497A1 (en) * 2007-06-18 2008-12-18 Xerox Corporation Hole blocking layer containing photoconductors
CN201092541Y (en) * 2007-09-27 2008-07-30 肖东 Novel sewage water treatment device
CN104923203A (en) * 2015-05-20 2015-09-23 上海应用技术学院 Composite photlocatalyst and preparation method as well as application thereof
CN105057003A (en) * 2015-08-22 2015-11-18 北京化工大学 Preparing method for titanium dioxide nanometer composite thin film
CN105110432A (en) * 2015-09-09 2015-12-02 洛阳理工学院 Preparation method of granular-activated-carbon-carried nitrogen-modified nano titanium dioxide disinfectant
CN106694014A (en) * 2015-11-13 2017-05-24 天津大学 Nitrogen-doped nonmetallic catalyst as well as preparation method and use thereof
CN106219687A (en) * 2016-08-15 2016-12-14 浙江大学 A kind of method of pollutant in photoelectrocatalysis reduction treatment water body
CN107376886A (en) * 2017-09-06 2017-11-24 北方民族大学 One kind dipping hydro-thermal method synthesis active carbon from coal load TiO2The method of composite
CN110180520A (en) * 2019-05-08 2019-08-30 陕西科技大学 A kind of recyclable mesoporous carbon@TiO2/ carbon fiber catalysis material and preparation method thereof
CN111389418A (en) * 2020-04-30 2020-07-10 浙江理工大学 Flexible carbon fiber cloth @ Cu2O@SnS2Composite material, preparation method and application
WO2021224358A1 (en) * 2020-05-05 2021-11-11 Witkowski Hubert A filter and a method for manufacturing thereof
CN111420649A (en) * 2020-05-11 2020-07-17 山东省淄博生态环境监测中心 PDA modified high-adsorbability TiO2Preparation method and application of fiber catalyst
CN112495419A (en) * 2020-12-03 2021-03-16 天津大学 Method for preparing graphite phase carbon nitride based nano composite photocatalyst by utilizing polydopamine
CN112547108A (en) * 2020-12-11 2021-03-26 江南大学 Ternary composite photocatalyst for antibiotic pollution degradation and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HUA-JUN CHEN ET AL., 《ENVIRON. SCI.: NANO》ASSEMBLY OF RECYCLABLE TIO2@AC/CTS THROUGH VDW-INTEGRATED STRATEGY FOR PHOTOCATALYTIC AND PHOTOELECTROCATALYTIC OXIDATION, vol. 10, pages 1468 - 1481 *
HUA-JUN CHEN ET AL., 《SUSTAINABLE MATERIALS AND TECHNOLOGIES》SEPARABLE AND RECYCLABLE MESO-CARBON@TIO2/CARBON FIBER COMPOSITES FOR VISIBLE-LIGHT PHOTOCATALYSIS AND PHOTOELECTROCATALYSIS, vol. 21, pages 2 *
于竹芹 等, 《工业催化》活性炭纤维负载TI02光催化降解甲醛研究, vol. 16, no. 7, pages 71 - 74 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115155597A (en) * 2022-08-12 2022-10-11 洛阳理工学院 Preparation method of recyclable nickel cobaltate/titanium dioxide @ AC @ CFs photocatalytic material
CN115155597B (en) * 2022-08-12 2023-07-18 洛阳理工学院 Preparation method of recyclable nickel cobaltate/titanium dioxide@AC@CFs photocatalytic material
CN115445593A (en) * 2022-09-08 2022-12-09 洛阳理工学院 Photoelectrocatalysis material, electrochemical preparation method and application thereof
CN115445593B (en) * 2022-09-08 2023-12-01 洛阳理工学院 Photoelectrocatalysis material, electrochemical preparation method and application thereof

Similar Documents

Publication Publication Date Title
You et al. State-of-the-art recent progress in MXene-based photocatalysts: a comprehensive review
Cui et al. Solar photocatalytic water oxidation over Ag3PO4/g-C3N4 composite materials mediated by metallic Ag and graphene
Zhang et al. ZnO/COF S-scheme heterojunction for improved photocatalytic H2O2 production performance
CN108772108B (en) Visible light response titanium dioxide nanowire/metal organic framework/carbon nanofiber membrane and preparation method and application thereof
Chen et al. Two-dimensional heterojunction photocatalysts constructed by graphite-like C3N4 and Bi2WO6 nanosheets: enhanced photocatalytic activities for water purification
Xu et al. Surface hybridization of π-conjugate structure cyclized polyacrylonitrile and radial microsphere shaped TiO2 for reducing U (VI) to U (IV)
Yin et al. Recent progress in gC 3 N 4 based low cost photocatalytic system: activity enhancement and emerging applications
CN114100598A (en) Assembling method of Van der Waals heterojunction photocatalysis and photoelectrocatalysis material from bottom to top
CN103769167B (en) A kind of method preparing Graphene parcel cadmium sulfide nucleocapsid structure catalysis material
Su et al. Enhanced visible light photocatalytic performances of few-layer MoS2@ TiO2 hollow spheres heterostructures
Qu et al. Controllable synthesis of a sponge-like Z-scheme N, S-CQDs/Bi2MoO6@ TiO2 film with enhanced photocatalytic and antimicrobial activity under visible/NIR light irradiation
Ran et al. Core–shell BiVO 4@ PDA composite photocatalysts on cotton fabrics for highly efficient photodegradation under visible light
Ren et al. In situ synthesis of gC 3 N 4/TiO 2 heterojunction nanocomposites as a highly active photocatalyst for the degradation of Orange II under visible light irradiation
CN110064434B (en) Preparation method of intrinsic photocatalytic hollow fiber
CN106345533A (en) Preparation method of titanium dioxide/polyaniline/carbon nitride Z-form heterojunction photocatalytic material
He et al. Hydrogen bond interactions within OH-CQDs/fiber-like carbon nitride for enhanced photodegradation and hydrogen evolution
Su et al. Multifunctional MoS2 ultrathin nanoflakes loaded by Cd0. 5Zn0. 5S QDs for enhanced photocatalytic H2 production
Xu et al. Refined Z-scheme charge transfer in facet-selective BiVO4/Au/CdS heterostructure for solar overall water splitting
Yang et al. Synthesis of high-efficient g-C3N4/polydopamine/CdS nanophotocatalyst based on bioinspired adhesion and chelation
CN112619647A (en) Preparation method of Co-MOF derived cobaltosic oxide composite titanium dioxide heterojunction and application of electrolyzed water
Chen et al. TiO2 nanosheet/NiO nanorod/poly (dopamine) ternary hybrids towards efficient visible light photocatalysis
CN108686645A (en) A kind of TiO2/BiVO4The preparation method and application of heterojunction composite
CN106000460B (en) Carbon quantum dot is sensitized the amine-modified TiO of dendritic polyethyleneimine2Photochemical catalyst
Huang et al. One-step hydrothermal formation of porous N-graphyne decorated TiO2/Ti3C2 composites with enhanced photocatalytic activity
Abu-Sari et al. Visible-light-driven photocatalytic hydrogen production on defective, sulfur self-doped g-C3N4 nanofiber fabricate via electrospinning method

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