CN115608379A - Ultraviolet light induced sulfur hybrid graphene catalytic material and preparation method thereof - Google Patents
Ultraviolet light induced sulfur hybrid graphene catalytic material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 50
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses an ultraviolet light induced sulfur hybrid graphene catalytic material and a preparation method thereof. The preparation method of the sulfur-hybridized graphene catalytic material comprises the steps of irradiating titanium dioxide by a 15-40W ultraviolet light source to excite 50-200 mL/min of carrier gas, introducing graphene oxide, a sulfur precursor and water, and carrying out low-temperature thermal annealing at 150-400 ℃ for 1-8 h, wherein the edge-type sulfur-hybridized structure accounts for more than 65% of the total sulfur-hybridized structure. According to the invention, the synergistic effect of ultraviolet light source irradiation titanium dioxide to excite carrier gas activation and low-temperature annealing is utilized, and the edge-type sulfur hybridization proportion with high catalytic activity is improved by controlling the ultraviolet light induction duration and reaction temperature under appropriate reaction conditions, so that the hybridized graphene material has more excellent catalytic activity; the method can reduce the energy consumption and operation safety of the directional regulation of the catalytic material, is favorable for deeply exploring the catalytic action mechanism of the hybrid graphene material, and has important significance in theoretical research and popularization and application of the hybrid graphene material.
Description
Technical Field
The invention belongs to the technical field of graphene catalysts, and particularly relates to an ultraviolet light induced sulfur hybrid graphene catalytic material and a preparation method thereof.
Background
Graphene, one of the most interesting materials in the new era, integrates various advantages such as excellent electrical conductivity, excellent mechanical strength, remarkable chemical stability, unrivalled thinness and transparency. With the continuous and intensive research, in order to broaden the practical application prospect of graphene materials, improve the problems of easy agglomeration and accumulation of graphene and the like, and give full play to the original characteristics of the materials, innovative materials based on graphene hybridization are paid more attention, and become a new research hotspot. Among the many hybrid elements, sulfur is considered to be a more suitable dopant for graphene due to its properties similar to carbon. The introduction of sulfur for graphene hybridization can effectively adjust the electron distribution of graphene, change the structure and element composition, adjust the physical and chemical properties of the graphene, and solve the bottleneck encountered in practical application of graphene materials, thereby releasing the potential of graphene material application.
However, studies have shown that there are four types of sulfur atoms in sulfur-hybridized graphene: sulfur adsorbed on the surface of graphene replaces the graphene carbon atoms in two different forms of sulfur or sulfur oxide, or connects two graphene sheets by forming a sulfur cluster ring. The sulfur hybridization content and the configuration of sulfur have important influence on the electrochemical activity of the sulfur-hybridized graphene material, wherein the edge sulfur (C-SO) X the-C) structure can effectively increase the active sites of the graphene material in the electrocatalytic reaction, and is beneficial to the improvement of the catalytic performance of the material. In order to effectively regulate and control the doping configuration of sulfur, the conventional thermal annealing method can promote heteroatom doping by utilizing high-temperature calcination, and is widely applied to the preparation of various hybrid graphene materials. The method can realize the adjustment of the doping type of the heteroatom by controlling the reaction temperature, but the preparation of the material with the best performance by using thermal annealing usually needs higher calcination temperature (the reaction temperature is controlled by the temperature of the reaction zone in the prior art to be higher than that of the prior art to be lower than that of the prior art>500 ℃ C.), and the energy consumption is higher. To solve this problem, improvements in thermal annealing have been madeIt is unfolded. Among a plurality of treatment methods, the ultraviolet light induction developed by the invention has the advantages of simple and easy operation, controllable defect degree, low cost, high efficiency and the like. Free radicals generated by ultraviolet light induction can attack graphene and generate defects, which is beneficial to heteroatom doping and adjustment of sulfur doping configuration. Therefore, the ultraviolet light induction method can be used for realizing the aim of preparing the material with high catalytic performance at low energy consumption.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an ultraviolet light induced sulfur hybrid graphene catalytic material and a preparation method thereof, and solves the problem of high energy consumption of a thermal annealing method in the background art.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the preparation method of the ultraviolet light induced sulfur hybrid graphene catalytic material comprises the following steps:
irradiating titanium dioxide by using a 15-40W ultraviolet light source to excite 50-200 mL/min of carrier gas to generate an active intermediate, introducing graphene oxide, a sulfur precursor and water, and carrying out low-temperature thermal annealing at 150-400 ℃ for 1-8 h to obtain the ultraviolet light-induced sulfur-hybridized graphene catalytic material.
In a preferred embodiment of the present invention, 80-90 wt% of graphene oxide, 1.50-5.00 wt% of sulfur precursor, and the balance of water are introduced.
In a preferred embodiment of the invention, a 20-35W ultraviolet light source is used for irradiating titanium dioxide to excite 80-150 mL/min carrier gas, 82-88 wt% of graphene oxide, 2.50-4.00 wt% of sulfur precursor and the balance of water are introduced, and low-temperature thermal annealing is carried out for 2-6 h at 200-350 ℃.
In a preferred embodiment of the present invention, the carrier gas is carbon monoxide or methane.
In a preferred embodiment of the present invention, the sulfur precursor is diphenyl disulfide or hexamercaptobenzene.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the ultraviolet light induced sulfur hybrid graphene catalytic material is prepared by the method.
In a preferred embodiment of the present invention, the graphene material includes an edge-type sulfur-hybridized graphene material.
In a preferred embodiment of the invention, the edge-type sulfur hybrid structure accounts for more than 65wt% of the total sulfur hybrid structure.
Compared with the background technology, the technical scheme has the following advantages:
(1) The invention excites the carrier gas to generate CO and CH by the induction of ultraviolet light 3 ·- The active intermediate is then subjected to edge reaction with graphene with higher electron density to form an activated graphene edge structure, so that the edge-type sulfur-hybridized graphene catalytic material is prepared, the preparation route is novel, the preparation method is simple and easy to operate, the sulfur hybridization controllability is high, the energy consumption is low, the efficiency is high, the loading capacity and the loading form of sulfur atoms are regulated and controlled under appropriate reaction conditions, the edge-type sulfur hybridization proportion with high catalytic activity is improved, and important technical means are provided for promoting the electrocatalytic efficiency of the hybrid material and deeply researching the heteroatom action principle.
(2) The ultraviolet light induced edge type sulfur hybrid graphene catalytic material has good electrocatalytic activity under the conditions of normal temperature and normal pressure.
(3) The invention can expand the actual application prospect of the material in the catalysis industry, is beneficial to deeply exploring the catalysis action mechanism of the hybrid graphene material, and has important significance in theoretical research and popularization and application of the hybrid graphene material.
Drawings
Fig. 1 is a transmission electron microscope image of the ultraviolet light-induced edge type sulfur hybrid graphene catalytic material in the example.
Fig. 2 is an X-ray photoelectron spectroscopy analysis diagram of the ultraviolet light-induced edge-type sulfur-hybridized graphene catalytic material in the example.
Fig. 3 is a graph of efficiency of degrading bisphenol a by using a sulfur-hybridized graphene catalytic material and a graphene catalytic material in examples and comparative examples.
Fig. 4 is a graph of the efficiency of the ultraviolet light-induced edge-type sulfur-hybridized graphene catalytic material in the example for degrading dye methyl orange and reactive black 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in more detail below with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to these embodiments.
The invention relates to an ultraviolet light induced sulfur hybrid graphene catalytic material, which utilizes the synergistic effect of ultraviolet light induction process for irradiating titanium dioxide by an ultraviolet light source to excite carrier gas activation and low-temperature annealing 3 -an intermediate, the resulting reactive intermediate then edge-reacting with graphene having a higher electron density to form an activated graphene edge structure, thereby resulting in doping of the more polysulfide atoms in the graphene structure in an edge-type hybrid manner.
The method specifically comprises the following steps:
(1) Weighing the following raw materials according to raw material components: 80-90 wt% of graphene oxide, 1.50-5.00 wt% of sulfur precursor and the balance of water;
(2) Irradiating the titanium dioxide component with carrier gas through an ultraviolet light source: irradiating titanium dioxide by a 15-40W ultraviolet light source to excite 50-200 mL/min carrier gas;
(3) And (3) introducing the excitation carrier gas obtained in the step (2) into the mixture obtained in the step (1), and carrying out low-temperature thermal annealing at the temperature of 150-400 ℃ for 1-8 h to obtain the ultraviolet light-induced sulfur hybrid graphene catalytic material, wherein the edge type sulfur hybrid structure accounts for more than 65% of the total sulfur hybrid structure.
The sulfur precursor is diphenyl disulfide or hexamercaptobenzene.
Examples
An ultraviolet light induced edge type sulfur hybrid graphene catalytic material is specifically prepared by the following steps:
(1) Weighing the following raw materials according to raw material components: 85wt% of graphene oxide, 2.0wt% of diphenyl disulfide and the balance of water;
(2) Irradiating the titanium dioxide component by carbon monoxide carrier gas through an ultraviolet light source;
(3) And (3) introducing the excitation carrier gas obtained in the step (2) into the mixture obtained in the step (1), and performing low-temperature thermal annealing at 1200 ℃ for 6 hours to obtain the ultraviolet light-induced edge-type sulfur-hybridized graphene catalytic material.
The microscopic morphology of the ultraviolet light-induced edge-type sulfur-hybridized graphene material is shown in fig. 1, and the analysis of the edge-type sulfur-hybridized morphology in the ultraviolet light-induced edge-type sulfur-hybridized graphene material is shown in fig. 2. As shown in fig. 1, the hybrid material exhibits a typical disordered carbon structure and a stacked two-dimensional (2D) nanosheet morphology. FIG. 2 is a S2 p spectrum, in which the UV-induced edge-type sulfur-hybridized graphene material has a peak at 169.0eV and an edge sulfur C-SO X The peak at 163.9eV is associated with the central sulfur C-S-C. The hybrid material prepared by the invention uses sulfur-terminated carbon-sulfur dioxide (C-SO) X C is the predominant form (66.67%).
Comparative example
The comparative examples differ from the examples in that: respectively adopting the traditional thermal annealing methods of 200 ℃, 400 ℃ and 600 ℃.
The ultraviolet light-induced edge-type sulfur-hybridized graphene catalytic material prepared in the embodiment is subjected to an electrocatalytic activity test:
the electrocatalytic degradation of bisphenol A (BPA) was performed using a potentiostatic current meter.
And evaluating the material performance by taking the BPA as a target pollutant according to the electrocatalytic oxidation degradation effect. Coating 4mg of sulfur-hybridized graphene on 2cm × 2cm carbon cloth by using a conductive adhesive, and drying the graphene to obtain an anode; a copper sheet with the thickness of 8cm multiplied by 2cm is taken as a cathode; the distance between the two was controlled to 1cm, the impressed current was adjusted using a constant potential current meter (Shanghai Xinrui) of DJS-292B, and 200ml of 10mg/L BPA solution was degraded in a 250mL beaker with 1g/L NaCl as the electrolyte, and the solution was kept stirring uniformly during the whole process using a magnetic stirrer. The switch of the potentiostatic amperemeter is turned on, and 1mL of water sample is added into a 2mL centrifuge tube filled with 1mL of methanol quencher within a set time. The liquid after the uniform mixing was subjected to filtration of impurities using a 0.22 μm filter head, and the BPA content of the filtered liquid was measured using an efficient liquid chromatograph (wawter, usa) of acquitylarc.
And (3) carrying out electrocatalytic activity test on the ultraviolet light-induced edge type sulfur hybrid graphene material to respectively obtain a BPA degradation efficiency graph of the ultraviolet light-induced edge type sulfur hybrid graphene catalytic material shown in the figure 3 and a dye degradation efficiency graph of the ultraviolet light-induced edge type sulfur hybrid graphene catalytic material shown in the figure 4. As can be seen from FIG. 3, when the ultraviolet light is used to induce the edge-type sulfur-hybridized graphene, the degradation effect of BPA is significantly better than that of the catalyst and graphene prepared by the traditional thermal annealing method. The degradation efficiency of the dye (methyl orange, reactive black 5) in FIG. 4 can reach 60-80%, which is slightly lower than the catalytic efficiency for BPA. The ultraviolet light-induced hybridization of the edge-type sulfur obviously improves the removal rate of BPA and dye, and shows the important role of the edge-type sulfur hybridization.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of an ultraviolet light induced sulfur hybrid graphene catalytic material is characterized by comprising the following steps: the method comprises the following steps:
irradiating titanium dioxide by using a 15-40W ultraviolet light source to excite 50-200 mL/min of carrier gas to generate an active intermediate, introducing graphene oxide, a sulfur precursor and water, and carrying out low-temperature thermal annealing at 150-400 ℃ for 1-8 h to obtain the ultraviolet light-induced sulfur-hybridized graphene catalytic material.
2. The preparation method of the ultraviolet light-induced sulfur-hybrid graphene catalytic material according to claim 1, characterized by comprising the following steps: and introducing 80-90 wt% of graphene oxide, 1.50-5.00 wt% of sulfur precursor and the balance of water.
3. The preparation method of the ultraviolet light-induced sulfur-hybrid graphene catalytic material according to claim 1, characterized in that: irradiating titanium dioxide by using a 20-35W ultraviolet light source to excite 80-150 mL/min of carrier gas.
4. The preparation method of the ultraviolet light-induced sulfur-hybrid graphene catalytic material according to claim 1, characterized in that: and introducing 82-88 wt% of graphene oxide, 2.50-4.00 wt% of sulfur precursor and the balance of water.
5. The preparation method of the ultraviolet light-induced sulfur-hybrid graphene catalytic material according to claim 1, characterized by comprising the following steps: low-temperature thermal annealing at 200-350 ℃ for 2-6 h.
6. The preparation method of the ultraviolet light-induced sulfur-hybrid graphene catalytic material according to claim 1, characterized by comprising the following steps: the carrier gas is carbon monoxide or methane, and the sulfur precursor is diphenyl disulfide or hexa-mercapto benzene.
7. The preparation method of the ultraviolet light-induced sulfur-hybrid graphene catalytic material according to claim 1, characterized in that: the reactive intermediates include CO and CH 3 ·- An intermediate.
8. An ultraviolet light-induced sulfur-hybridized graphene catalytic material is characterized in that: prepared by the method of any one of claims 1 to 7.
9. The ultraviolet light-induced sulfur-hybridized graphene catalytic material of claim 8, wherein: comprises an edge-type sulfur-hybridized graphene material.
10. The ultraviolet light-induced sulfur-hybrid graphene catalytic material of claim 9, wherein: the edge type sulfur hybrid structure accounts for more than 65wt% of the total sulfur hybrid structure.
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| CN115608379B CN115608379B (en) | 2024-03-29 |
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