CN113233553B - Ti loaded with graphene nanoparticles4O7Method for preparing anode - Google Patents

Ti loaded with graphene nanoparticles4O7Method for preparing anode Download PDF

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CN113233553B
CN113233553B CN202110595376.1A CN202110595376A CN113233553B CN 113233553 B CN113233553 B CN 113233553B CN 202110595376 A CN202110595376 A CN 202110595376A CN 113233553 B CN113233553 B CN 113233553B
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graphene
anode
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CN113233553A (en
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林辉
肖润林
李威
吕斯濠
杨立辉
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Dongguan University of Technology
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    • 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
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

Abstract

The invention discloses Ti loaded with graphene nano particles4O7Method for producing an anode made of Ti4O7The powder and the graphene nano-particles are prepared by spark plasma sintering. The invention uses cerium dioxide as a binder to prepare titanium oxide powder (Ti)4O7) Mixing with graphene nanoparticles (GR), ball-milling to obtain mixed powder, and performing high-temperature sintering by using a spark plasma sintering technology to obtain GR @ Ti4O7Anode capable of greatly increasing Ti4O7The catalytic activity of the anode is increased, the number of the surface reaction active sites is increased, the yield of OH is improved, the internal resistance of charge transfer is greatly reduced, and Ti is promoted4O7The anode is applied to the large-scale repair of the underground water polluted by the 1, 4-dioxane, and the capability of degrading the 1, 4-dioxane is similar to that of a boron-doped diamond electrode (BDD).

Description

Ti loaded with graphene nanoparticles4O7Method for preparing anode
Technical Field
The invention relates to the technical field of electrochemistry, in particular to Ti loaded with graphene nano particles4O7A method for preparing an anode.
Background
In recent years, with the rapid development of industrial and agricultural industries, environmental pollution caused by emerging pollutants generated in the industry, which are toxic and difficult to degrade, has become more serious, and 1, 4-dioxane is one of the representatives. The traditional physical adsorption, biodegradation and the like are difficult to effectively remove the 1, 4-dioxane in the water, and the advanced oxidation technology can generate high-activity free radicals, so that the advanced oxidation technology has a good degradation effect on the pollutants. Ti4O7The electrode material is a commonly used electrode material in the advanced oxidation technology, and has a series of advantages of high conductivity, high chemical stability, wide potential window (-1.5V-2.5V) and the like. It not only can produce hydroxyl free radical, but also hasIs beneficial to the direct electron transfer of pollutants on the surface, has the characteristics of an active electrode and a non-active electrode, and is considered as an ideal sewage treatment material. But Ti4O7When used as an electrode material, the material has problems of low hydroxyl radical yield and high internal resistance of charge transfer, so that the material has general catalytic activity. Therefore, we propose a graphene nanoparticle-loaded Ti4O7A method for preparing an anode.
Disclosure of Invention
The invention aims to provide Ti loaded with graphene nanoparticles4O7A method for preparing an anode, which solves the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: ti loaded with graphene nanoparticles4O7The preparation method of the anode is characterized in that: the method comprises the following steps:
taking Ti4O7And mixing the powder, the graphene nano particles and the cerium dioxide powder, uniformly ball-milling to obtain mixed powder, and sintering at high temperature and high pressure by using discharge plasma sintering to obtain the anode.
Further, the mass fraction of the graphene nanoparticles in the mixed powder is 1-5%, and the mass fraction of the cerium dioxide powder is 6-8%.
Further, the graphene nanoparticles are graphene oxide, reduced graphene or graphene.
Further, said Ti4O7The diameter of the powder is 100 nm-1 μm.
Further, the ball milling process comprises the following steps: the ball milling speed is 1500-1800 r/min, and the ball milling time is 20-40 min.
Further, the high temperature conditions in the sintering process are as follows: the sintering temperature rise rate is 50-60 ℃/min, and the sintering temperature is 1100-1250 ℃.
Further, the high pressure conditions in the sintering process are as follows: 1 to 4 MPa.
Further, the sintering time in the sintering process is as follows: 20-30 min.
In the technical scheme, a certain proportion of titanium suboxide powder (Ti) is added4O7) Mixing with graphene nanoparticles (GR) and taking cerium oxide (CeO)2) Ball milling uniformly as binder to obtain mixed powder, placing in graphite mould of spark plasma sintering device, high-temperature sintering to obtain GR-loaded titanium suboxide (GR @ Ti)4O7Anode capable of greatly increasing the original Ti4O7The catalytic activity of the anode is increased, the number of the surface reaction active sites is increased, the yield of OH is improved, the internal resistance of charge transfer is greatly reduced, and Ti is promoted4O7The anode is applied to the large-scale repair of the underground water polluted by the 1, 4-dioxane, and the capability of degrading the 1, 4-dioxane is similar to that of a boron-doped diamond electrode (BDD).
Further, the graphene nanoparticles are zirconium nitride modified graphene, and the graphene nanoparticles are prepared from the following raw materials in parts by weight: 90-100 parts of graphene, 14.6-18.9 parts of hexadecyl trimethyl ammonium bromide, 50.4-65.5 parts of oxalic acid, 48-62 parts of ammonium fluorozirconate, 0.6-0.8 part of glass powder and 27.4-35.6 parts of bromine trifluoride.
Further, the preparation process of the graphene nanoparticles comprises the following steps:
dissolving cetyl trimethyl ammonium bromide in absolute ethyl alcohol, sequentially adding deionized water, oxalic acid and ammonium fluorozirconate, uniformly mixing, ultrasonically dispersing for 30-40 min, stirring for 3-4 h, performing spray drying at the temperature of 150-160 ℃, and roasting at the temperature of 270-320 ℃ for 55-70 min in an air atmosphere; placing the mixture in an ammonia atmosphere, reacting at 480-540 ℃ for 10-15 h at a heating rate of 2-3 ℃/min, and cooling to room temperature to obtain zirconium nitride;
ball-milling zirconium nitride and glass powder for 60-80 min, adding deionized water, tetramethylammonium hydroxide and graphene, continuing ball-milling for 30-40 min, and drying in a magnetic field at the temperature of 60-70 ℃; sintering at 900-1100 ℃ in a nitrogen atmosphere, cooling to room temperature, adding bromine trifluoride, and reacting at room temperature; and filtering, and taking the solid for acid washing, water washing and drying to obtain the graphene nano-particles.
In the technical scheme, cetyl trimethyl ammonium bromide is used as a template, spray drying is adopted, and ammonia gas is utilized for nitridation reduction to prepare spherical porous zirconium nitride, so that the spherical porous zirconium nitride has a rich mesoporous structure and excellent electrochemical properties; the preparation method comprises the steps of taking glass powder as a binding phase, mixing and sintering the glass powder and graphene, forming a compact network structure on the surface of the graphene, reacting the compact network structure with bromine trifluoride at normal temperature, removing the glass powder on the graphene after acid washing and water washing to form a porous zirconium nitride coating, fluorinating the graphene to prepare zirconium nitride modified graphene, improving the conductivity of the prepared anode, increasing the surface roughness of the modified graphene, facilitating the subsequent bonding of titanium suboxide, cerium dioxide and the graphene, and improving the electrochemical performance and stability of the prepared anode.
Compared with the prior art, the invention has the following beneficial effects:
the graphene nanoparticle-supported Ti of the invention4O7The anode is prepared by using cerium dioxide as binder and titanium oxide powder (Ti)4O7) Mixing with graphene nanoparticles (GR), ball-milling to obtain mixed powder, and performing high-temperature sintering by using a spark plasma sintering technology to obtain GR @ Ti4O7Anode capable of greatly increasing Ti4O7The catalytic activity of the anode is increased, the number of the surface reaction active sites is increased, the yield of OH is improved, the internal resistance of charge transfer is greatly reduced, and Ti is promoted4O7The anode is applied to the large-scale repair of the underground water polluted by the 1, 4-dioxane, and the capability of degrading the 1, 4-dioxane is similar to that of a boron-doped diamond electrode (BDD).
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an electron micrograph of example 1 and comparative example 1 according to the present invention;
FIG. 2 is a CV diagram of example 1 and comparative example 1 of the present invention;
FIG. 3 is EIS graphs of example 1 and comparative example 1 in the present invention;
FIG. 4 is a comparison of OH productivity of example 1 of the present invention and that of comparative example 1;
FIG. 5 is a comparison of the 1, 4-dioxane degrading ability of example 1 of the present invention as compared to comparative examples 1 and 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 100nm, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nanoparticles is 1%, the mass fraction of the cerium dioxide powder is 8%, and the ball-milling process comprises the following steps: 1800r/min, and ball milling time is 20 min; wherein the graphene nanoparticles are graphene oxide;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: the sintering heating rate is 55 ℃/min, the maximum sintering temperature is 1200 ℃, the pressure is 3MPa, and the sintering time is 20min, thus obtaining the anode.
Example 2
Taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 500nm, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nano particles is 3%, the mass fraction of the cerium dioxide powder is 7%, and the ball-milling process comprises the following steps: 1650r/min, and ball milling time of 30 min; wherein the graphene nanoparticles are reduced graphene;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: sintering temperature rise rate is 60 ℃/min, sintering temperature is 1250 ℃, pressure is 4MPa, and sintering time is 25min, so that the anode is prepared.
Example 3
Taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 1 mu m, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nanoparticles is 4%, the mass fraction of the cerium dioxide powder is 6%, and the ball-milling process comprises the following steps: 1500r/min, ball milling time 40 min;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: sintering at the heating rate of 60 ℃/min, the sintering temperature of 1100 ℃, the pressure of 1MPa and the sintering time of 20min to obtain the anode.
Example 4
Taking the following components in parts by weight for later use: 90 parts of graphene, 14.6 parts of hexadecyl trimethyl ammonium bromide, 50.4 parts of oxalic acid, 48 parts of ammonium fluorozirconate, 0.6 part of glass powder and 27.4 parts of bromine trifluoride;
dissolving cetyl trimethyl ammonium bromide in anhydrous ethanol, sequentially adding deionized water, oxalic acid and ammonium fluorozirconate, uniformly mixing, ultrasonically dispersing for 30min, stirring for 3h, spray drying at 150 ℃, and roasting at 270 ℃ for 55min in an air atmosphere; placing the mixture in an ammonia atmosphere, reacting for 10 hours at 480 ℃ at the heating rate of 2 ℃/min, and cooling to room temperature to obtain zirconium nitride;
ball-milling zirconium nitride and glass powder for 60min, adding deionized water, tetramethylammonium hydroxide and graphene, continuing ball-milling for 30min, and drying in a magnetic field at 60 ℃; sintering at 900 ℃ in a nitrogen atmosphere, cooling to room temperature, adding bromine trifluoride, and reacting at normal temperature; filtering, taking the solid, and performing acid washing, water washing and drying to obtain graphene nanoparticles;
taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 100nm, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nanoparticles is 1%, the mass fraction of the cerium dioxide powder is 8%, and the ball-milling process comprises the following steps:1800r/min, ball milling time 20 min;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: the sintering heating rate is 55 ℃/min, the maximum sintering temperature is 1200 ℃, the pressure is 3MPa, and the sintering time is 20min, thus obtaining the anode.
Example 5
Taking the following components in parts by weight for later use: 95 parts of graphene, 16.7 parts of hexadecyl trimethyl ammonium bromide, 58 parts of oxalic acid, 55 parts of ammonium fluorozirconate, 0.7 part of glass powder and 31.5 parts of bromine trifluoride;
dissolving cetyl trimethyl ammonium bromide in anhydrous ethanol, sequentially adding deionized water, oxalic acid and ammonium fluorozirconate, uniformly mixing, ultrasonically dispersing for 35min, stirring for 3.5h, spray drying at 155 ℃, and roasting at 300 ℃ for 62min in an air atmosphere; placing the mixture in an ammonia atmosphere, reacting at 510 ℃ for 12h at the heating rate of 2 ℃/min, and cooling to room temperature to obtain zirconium nitride;
ball-milling zirconium nitride and glass powder for 70min, adding deionized water, tetramethylammonium hydroxide and graphene, continuing ball-milling for 35min, and drying at 65 ℃ in a magnetic field; sintering at 1000 ℃ in a nitrogen atmosphere, cooling to room temperature, adding bromine trifluoride, and reacting at room temperature; filtering, taking the solid, and performing acid washing, water washing and drying to obtain graphene nanoparticles;
taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 100nm, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nanoparticles is 1%, the mass fraction of the cerium dioxide powder is 8%, and the ball-milling process comprises the following steps: 1800r/min, ball milling time 20 min;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: the sintering heating rate is 55 ℃/min, the maximum sintering temperature is 1200 ℃, the pressure is 3MPa, and the sintering time is 20min, thus obtaining the anode.
Example 6
Taking the following components in parts by weight for later use: 100 parts of graphene, 18.9 parts of hexadecyl trimethyl ammonium bromide, 65.5 parts of oxalic acid, 62 parts of ammonium fluorozirconate, 0.8 part of glass powder and 35.6 parts of bromine trifluoride;
dissolving cetyl trimethyl ammonium bromide in anhydrous ethanol, sequentially adding deionized water, oxalic acid and ammonium fluorozirconate, uniformly mixing, ultrasonically dispersing for 40min, stirring for 4h, spray drying at 160 ℃, and roasting at 320 ℃ for 70min in an air atmosphere; placing the mixture in an ammonia atmosphere, reacting for 15 hours at the temperature of 540 ℃ at the heating rate of 3 ℃/min, and cooling to room temperature to obtain zirconium nitride;
ball-milling zirconium nitride and glass powder for 80min, adding deionized water, tetramethylammonium hydroxide and graphene, continuing ball-milling for 40min, and drying at 70 ℃ in a magnetic field; sintering at 1100 ℃ in a nitrogen atmosphere, cooling to room temperature, adding bromine trifluoride, and reacting at room temperature; filtering, and pickling, washing and drying the solid to obtain graphene nanoparticles;
taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 100nm, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nanoparticles is 1%, the mass fraction of the cerium dioxide powder is 8%, and the ball-milling process comprises the following steps: 1800r/min, ball milling time 20 min;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: the sintering temperature rise rate is 55 ℃/min, the maximum sintering temperature is 1200 ℃, the pressure is 3MPa, and the sintering time is 20min, thus obtaining the anode.
Comparative example 1
Taking Ti4O7Mixing the powder with cerium oxide powder, wherein Ti4O7The diameter of the powder is 100nm, the powder is ball-milled uniformly to prepare mixed powder, wherein the mass fraction of the cerium dioxide powder is 8%, and the ball-milling process comprises the following steps: 1800r/min, ball milling time 20 min;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: the sintering temperature rise rate is 55 ℃/min, the maximum sintering temperature is 1200 ℃, the pressure is 3MPa, and the sintering time is 20min, thus obtaining the anode.
Comparative example 2
A conventional BDD electrode was taken as the anode of comparative example 2.
Comparative example 3
Taking the following components in parts by weight for later use: 95 parts of graphene, 16.7 parts of hexadecyl trimethyl ammonium bromide, 58 parts of oxalic acid, 55 parts of ammonium fluorozirconate and 31.5 parts of bromine trifluoride;
dissolving cetyl trimethyl ammonium bromide in anhydrous ethanol, sequentially adding deionized water, oxalic acid and ammonium fluorozirconate, uniformly mixing, ultrasonically dispersing for 35min, stirring for 3.5h, spray drying at 155 ℃, and roasting at 300 ℃ for 62min in an air atmosphere; placing the mixture in an ammonia atmosphere, reacting at 510 ℃ for 12h at the heating rate of 2 ℃/min, and cooling to room temperature to obtain zirconium nitride;
adding deionized water, tetramethylammonium hydroxide and graphene into zirconium nitride, continuously ball-milling for 35min, and drying at 65 ℃ in a magnetic field; sintering at 1000 ℃ in a nitrogen atmosphere, cooling to room temperature, adding bromine trifluoride, and reacting at room temperature; filtering, taking the solid, and performing acid washing, water washing and drying to obtain graphene nanoparticles;
taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 100nm, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nanoparticles is 1%, the mass fraction of the cerium dioxide powder is 8%, and the ball-milling process comprises the following steps: 1800r/min, ball milling time 20 min;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: the sintering heating rate is 55 ℃/min, the maximum sintering temperature is 1200 ℃, the pressure is 3MPa, and the sintering time is 20min, thus obtaining the anode.
Comparative example 4
Taking the following components in parts by weight for later use: 95 parts of graphene, 16.7 parts of hexadecyl trimethyl ammonium bromide, 58 parts of oxalic acid, 55 parts of ammonium fluorozirconate and 0.7 part of glass powder;
dissolving cetyl trimethyl ammonium bromide in anhydrous ethanol, sequentially adding deionized water, oxalic acid and ammonium fluorozirconate, uniformly mixing, ultrasonically dispersing for 35min, stirring for 3.5h, spray drying at 155 ℃, and roasting at 300 ℃ for 62min in an air atmosphere; placing the mixture in an ammonia atmosphere, reacting at 510 ℃ for 12h at the heating rate of 2 ℃/min, and cooling to room temperature to obtain zirconium nitride;
ball-milling zirconium nitride and glass powder for 70min, adding deionized water, tetramethylammonium hydroxide and graphene, continuing ball-milling for 35min, and drying at 65 ℃ in a magnetic field; sintering at 1000 ℃ in nitrogen atmosphere, and cooling to room temperature; filtering, taking the solid, and performing acid washing, water washing and drying to obtain graphene nanoparticles;
taking Ti4O7Mixing the powder, graphene nanoparticles and cerium dioxide powder, wherein Ti4O7The diameter of the powder is 100nm, the powder is uniformly ball-milled to prepare mixed powder, wherein the mass fraction of the graphene nanoparticles is 1%, the mass fraction of the cerium dioxide powder is 8%, and the ball-milling process comprises the following steps: 1800r/min, ball milling time 20 min;
sintering at high temperature and high pressure by using spark plasma sintering, wherein the sintering process comprises the following steps: the sintering heating rate is 55 ℃/min, the maximum sintering temperature is 1200 ℃, the pressure is 3MPa, and the sintering time is 20min, thus obtaining the anode.
Experiment of
The anodes obtained in examples 1 to 6 and comparative examples 1 to 4 were used to prepare samples, and the performance of the samples was measured and the measurement results were recorded:
taking a sample, carrying out electrochemical impedance spectrum test on the sample, and detecting the charge transfer resistance (omega) of the sample;
at 20mA/cm2Samples were taken as anodized 1mM Coumarin (COU) and 0.1mM Terephthalic Acid (TA), which were able to react freely with OH to form 7-hydroxycoumarin (7-COU) and 2-hydroxyterephthalic acid (2-HTA), respectively, and both were resistant to direct oxidation. Therefore, the generated concentration of 7-COU and 2-HTA reflects the generation rate of OH, and the generated concentration of 7-COU and 2-HTA after 40min of a detection test is recorded as the OH generating capacity (mu M);
taking a sample as an anode, and setting a reaction solution as follows: 1, 4-dioxane initial concentration of 1mM, current density of 20mA/cm2The supporting electrolyte is 20mM Na2SO4Detecting that the degradation rate of the 1, 4-dioxane reaches 95% time spent, reported as degradation time (min);
Figure BDA0003090805430000071
Figure BDA0003090805430000081
from the data in the table above, it is clear that the following conclusions can be drawn:
the anodes obtained in examples 1 to 6 were compared with the anodes obtained in comparative examples 1 to 4, and the results of the measurements showed that:
1. compared with example 1, comparative example 1 has no added component graphene nanoparticles, and comparative example 2 is a conventional BDD anode; compared with the comparative example 1, the anodes of the examples 1 to 6 have obviously improved OH generating capacity, obviously reduced charge transfer resistance, obviously shorter time for the degradation rate of 1, 4-dioxane to reach 95 percent, and are closer to the data of the comparative example 2, which fully shows that the invention improves the electrocatalytic activity of the prepared anodes and can improve the degradation efficiency of the 1, 4-dioxane;
2. compared with example 5, the comparative example 3 has no glass powder added, and the comparative example 4 has no bromine trifluoride added, so that the charge transfer resistance, the OH production capacity and the degradation time data are all reduced, and the modification treatment of the graphene can improve the electrocatalytic activity and stability of the prepared anode.
FIG. 1 shows example 1 (1% GR @ Ti) of the present invention4O7Anode) and comparative example 1 (Ti)4O7Anode), and FIG. 1(A) shows Ti4O7The anode surface is uneven, has a plurality of uniformly distributed small holes with micron-sized aperture, and Ti4O7The sintering condition of the powder particles is good. FIG. 1(B) shows 1% GR @ Ti4O7The surface of the anode is provided with a plurality of uniformly distributed graphene clusters, the diameters of the graphene clusters are 25-80 nm, and the graphene clusters are formed by a preparation method of ball milling and discharge plasma sintering;
FIG. 2 is a CV diagram showing 1% GR @ Ti in accordance with example 1 and comparative example 1 of the present invention4O7The current area of the anode is about Ti4O72 times of the anode, 1% GR @ Ti4O7Anode ratio Ti4O7The anode has a stronger electron transfer activity. The inset in FIG. 2 is the voltammetric charge q (in mC/cm) displayed by graphical integration2) Linear relationship with the inverse square root of the voltage. q represents the number of electrochemically active sites per region of the electrode, which plays an important role in the electrochemical oxidation performance. The slope of the q and v1/2 curves for a 1% GR @ Ti4O7 anode was 20.06 to Ti4O7The height of the anode (12.06) is much higher, which means that the doping of the GR serves to increase the electrochemically reactive active sites.
FIG. 3 is an EIS graph of 1% GR @ Ti of example 1 and comparative example 1 of the present invention4O7The charge transfer resistance of the anode was 8.42 Ω, which was significantly lower than that of the original Ti4O7The charge transfer resistance of the anode (73.87 Ω), indicating that GR doping results in 1% GR @ Ti4O7The anode impedance is significantly reduced. This result is caused by the moderate oxidation of the carbon functional groups to add oxygen-containing functional groups, thereby facilitating interfacial electron transfer.
FIG. 4 is a comparison of OH productivity of example 1 and comparative example 1 of the present invention at 20mA/cm2At a current density of (1%) GR @ Ti4O7Anode and original Ti4O7Results of anodizing 1mMCOU and 0.1 mMTA. Coumarin (COU), p-benzoquinone (p-BQ) and Terephthalic Acid (TA) are used as probes of OH, both COU and TA can freely react with OH to respectively generate 7-hydroxycoumarin (7-COU) and 2-hydroxyterephthalic acid (2-HTA), and both can resist direct oxidation. The concentration of 7-COU and 2-HTA formed reflects the rate of OH formation. 1% GR @ Ti4O7The rate of anodic generation of OH is faster, with concentrations of Ti to produce 7-COU and 2-HTA, respectively4O72.6 times and 2.8 times the anode. This indicates that the chemical bond surface formed by the GR-O-Ti bond has a stronger reactivity to generate OH, and also can prove GR @ Ti4O7The anodic oxidation pollutants have a good application prospect. In addition, p-BQ also readily reacts with. OH (k)·OH,p-BQ＝1.2×109M-1s-1) And also has a strong resistance to direct oxidation. After 40min, 1% GR @ Ti4O7Anode and original Ti4O7The degradation rates of the anode for p-BQ were 83.5% and 59.9%, respectively, also indicating 1% GR @ Ti4O7The amount of OH produced at the anode is large. These results indicate that GR doping can generate OH in situ with high selectivity, thereby enhancing the catalytic oxidation capability of the electrode.
FIG. 5 is a graph showing the comparison of the 1, 4-dioxane degrading ability of example 1 with that of comparative examples 1 and 2 in the present invention, in which the initial concentration of 1, 4-dioxane was set to 1mM and the current density was set to 20mA/cm2The supporting electrolyte is 20mM Na2SO4The experimental results are shown in fig. 5. 1% GR @ Ti4O7The reaction rate constant of the anode was 1.49X 10-2min-1Is original Ti4O7Rate constant of anodic reaction 7.7X 10-3min-1More than twice, and a reaction rate constant of 1.95 × 10 for the BDD anode-2min-1Similarly. For Ti4O7The anode, when degrading 1, 4-dioxane with an initial concentration of 1mM, has a degradation rate of 95% after 6h, and 1% GR @ Ti4O7The anode only needs 3h to reach the same degradation rate, and the time is very close to that of the BDD anode. This may indicate 1% GR @ Ti4O7Anode catalytic activity ratio of original Ti4O7The anode is much improved and is comparable to the catalytic activity of the BDD anode.
In summary, GR @ Ti obtained by the preparation method4O7The anode can greatly improve the original Ti4O7The reactive active site of the anode can improve the yield of OH, and can greatly reduce the original Ti4O7The internal resistance of electrode charge transfer can be greatly improved, and the catalytic activity of degrading 1, 4-dioxane can be greatly improved. Furthermore, GR @ Ti4O7The preparation process of the anode is simple, and the substrate Ti4O7Is particularly rich in the worldTitanium dioxide is produced, the overall manufacturing cost is much lower than that of a BDD anode, and therefore, the BDD anode is expected to be replaced for large-scale actual sewage treatment.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (7)

1. Ti loaded with graphene nanoparticles4O7The preparation method of the anode is characterized in that: the preparation of the anode comprises the following steps:
taking Ti4O7Mixing the powder, the graphene nanoparticles and the cerium dioxide powder, uniformly ball-milling to obtain mixed powder, and sintering at high temperature and high pressure by using discharge plasma to obtain an anode;
the graphene nanoparticles are zirconium nitride modified graphene;
the zirconium nitride modified graphene is prepared from the following raw materials in parts by weight: 90-100 parts of graphene, 14.6-18.9 parts of hexadecyl trimethyl ammonium bromide, 50.4-65.5 parts of oxalic acid, 48-62 parts of ammonium fluorozirconate, 0.6-0.8 part of glass powder and 27.4-35.6 parts of bromine trifluoride;
the preparation process of the zirconium nitride modified graphene comprises the following steps:
dissolving cetyl trimethyl ammonium bromide in absolute ethyl alcohol, sequentially adding deionized water, oxalic acid and ammonium fluorozirconate, uniformly mixing, ultrasonically dispersing for 30-40 min, stirring for 3-4 h, performing spray drying at the temperature of 150-160 ℃, and roasting at the temperature of 270-320 ℃ for 55-70 min in an air atmosphere; placing the mixture in an ammonia atmosphere, reacting at 480-540 ℃ for 10-15 h at a heating rate of 2-3 ℃/min, and cooling to room temperature to obtain zirconium nitride;
ball-milling zirconium nitride and glass powder for 60-80 min, adding deionized water, tetramethylammonium hydroxide and graphene, continuing ball-milling for 30-40 min, and drying in a magnetic field at the temperature of 60-70 ℃; sintering at 900-1100 ℃ in a nitrogen atmosphere, cooling to room temperature, adding bromine trifluoride, and reacting at room temperature; and filtering, and taking the solid for acid washing, water washing and drying to obtain the graphene nano-particles.
2. The graphene nanoparticle-supported Ti of claim 14O7The preparation method of the anode is characterized in that: the mass fraction of the graphene nanoparticles in the mixed powder is 1-5%, and the mass fraction of the cerium dioxide powder is 6-8%.
3. The graphene nanoparticle-supported Ti of claim 14O7The preparation method of the anode is characterized in that: the Ti4O7The diameter of the powder is 100 nm-1 μm.
4. The graphene nanoparticle-supported Ti of claim 14O7The preparation method of the anode is characterized in that: the Ti4O7The ball milling process in the mixing process of the powder, the graphene nano particles and the cerium dioxide powder is as follows: the ball milling speed is 1500-1800 r/min, and the ball milling time is 20-40 min.
5. The graphene nanoparticle-supported Ti of claim 14O7The preparation method of the anode is characterized in that: the high-temperature conditions of the spark plasma sintering process are as follows: the sintering temperature rise rate is 50-60 ℃/min, and the sintering temperature is 1100-1250 ℃.
6. The graphene nanoparticle-supported Ti of claim 14O7The preparation method of the anode is characterized in that: the high-pressure conditions of the spark plasma sintering process are as follows: 1 to 4 MPa.
7. The graphene nanoparticle-loaded Ti of claim 14O7The preparation method of the anode is characterized in that: the sintering time of the spark plasma sintering process is as follows: 20-30 min.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102190351A (en) * 2010-03-10 2011-09-21 同济大学 Electrode Ce doped PbO2 used for treating waste water and its preparation method
CN104846227A (en) * 2015-02-16 2015-08-19 苏州大学 Graphene-reinforced titanium-based composite and preparation method thereof
CN107393622A (en) * 2017-06-27 2017-11-24 宁波墨西科技有限公司 A kind of graphene Asia titanium oxide combined conductive agent and preparation method thereof
CN109678494A (en) * 2019-02-22 2019-04-26 中国科学院过程工程研究所 A kind of Asia Titanium oxide electrode piece and its preparation method and application
CN110357079A (en) * 2018-04-11 2019-10-22 广州墨羲科技有限公司 A kind of graphene composite material on nanometer of skeleton

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200313162A1 (en) * 2019-03-26 2020-10-01 Nanotek Instruments, Inc. Method of producing graphene-encapsulated graphite-supported anode active material for lithium-ion batteries

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102190351A (en) * 2010-03-10 2011-09-21 同济大学 Electrode Ce doped PbO2 used for treating waste water and its preparation method
CN104846227A (en) * 2015-02-16 2015-08-19 苏州大学 Graphene-reinforced titanium-based composite and preparation method thereof
CN107393622A (en) * 2017-06-27 2017-11-24 宁波墨西科技有限公司 A kind of graphene Asia titanium oxide combined conductive agent and preparation method thereof
CN110357079A (en) * 2018-04-11 2019-10-22 广州墨羲科技有限公司 A kind of graphene composite material on nanometer of skeleton
CN109678494A (en) * 2019-02-22 2019-04-26 中国科学院过程工程研究所 A kind of Asia Titanium oxide electrode piece and its preparation method and application

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