阅读说明：本技术 二维MoS2负载Cu的光催化剂的制备方法 (Two-dimensional MoS2Preparation method of Cu-loaded photocatalyst ) 是由 谢宇 曾德栋 李时迁 刘玉应 凌云 于 2019-09-16 设计创作，主要内容包括：本发明涉及二维MoS_2负载Cu的光催化剂的制备方法,通过二维MoS_2负载Cu,制得了一种高催化性能的纳米材料,其光催化制氢性能活性很高,且本身拥有很好的环保性能,在合成和光催化过程中既对环境不会造成污染,对使用者也不会造成任何伤害。(The invention relates to a two-dimensional MoS 2 Method for preparing Cu-loaded photocatalyst by two-dimensional MoS 2 The Cu is loaded, so that the nano material with high catalytic performance is prepared, the photocatalytic hydrogen production performance and activity are high, the nano material has good environmental protection performance, and the environment is not polluted and the user is not hurt in the synthesis and photocatalytic processes.)

1. Two-dimensional MoS₂A method for preparing a Cu-loaded photocatalyst is characterized in that: the method comprises the following steps:

(1) Two-dimensional MoS₂The preparation of (1):

20mg of ammonium tetrathiomolybdate ((NH) were weighed out₄)₂MoS₄) Adding 20ml of N, N-Dimethylformamide (DMF), carrying out ultrasonic treatment for 45min, pouring the yellow solution into a 50ml polytetrafluoroethylene reaction kettle, reacting for 10h in a forced air drying oven at 200 ℃, naturally cooling to room temperature after the reaction is finished, centrifuging, separating, washing precipitates respectively with deionized water and absolute ethyl alcohol for 3 times, and finally carrying out freeze drying for 12h to obtain the two-dimensional MoS₂Marked N-MoS₂；

(2) Two-dimensional MoS₂Preparation of loaded Cu:

0.5g of the N-MoS prepared in the preceding step was weighed₂added to 28.51477ml Cu (NO)₃)₂Eighty percent by volume of ethylene glycol solution, wherein C_CuSubjecting to ultrasonic treatment at 0.0002630215g/ml for 30min to obtain black suspension, adjusting pH to 8-9 with 0.2M NaOH solution under stirring, and subjecting to oil bath at 75 deg.C and magnetic stirringCooling and refluxing the suspension in a stirrer for 5h, respectively washing the suspension with deionized water and absolute ethyl alcohol for 3 times after the suspension is naturally cooled to room temperature, then carrying out vacuum drying on the product in a vacuum drying box at the temperature of 80 ℃ for 48h, and finally calcining the dried product in a tubular furnace at the calcining heating rate of 1 ℃/min for 2h under the conditions of nitrogen protection and the temperature of 400 ℃ to prepare the two-dimensional MoS₂Cu-supported catalyst, labeled E-Cu-N-MoS₂。

Technical Field

The invention relates to a two-dimensional MoS₂A preparation method of a Cu-loaded photocatalyst belongs to the technical field of photocatalytic materials.

Background

MoS₂As a typical layered transition metal sulfurThe compound has been widely applied in the fields of light conversion, photocatalysis and the like, and has great prospect for degrading organic pollutants and preparing energy hydrogen. MoS₂The structure of the edge of (1) is relatively complex, sulfur has high unsaturation, and the activity of the reaction is extremely high, so that the attention and the research on the sulfur are widely drawn.

At present, most of catalysts widely used for degrading environmental pollutants in the field of photocatalysis are N-type semiconductor materials of metal oxides, particularly titanium dioxide, although titanium dioxide is cheap and nontoxic, the titanium dioxide can only absorb ultraviolet range of sunlight due to the forbidden band width of more than 3eV, the absorptivity of the titanium dioxide to the sunlight is 3% -5%, and the utilization rate of the titanium dioxide to the sunlight is seriously influenced. The band gap width of the molybdenum disulfide is about 1.29eV, the molybdenum disulfide can well absorb visible light of sunlight, the chemical property of the molybdenum disulfide is stable, and the molybdenum disulfide is not easy to react with other substances at normal temperature, so that the molybdenum disulfide has great research significance and application potential in the field of photocatalysis. Molybdenum disulfide has a huge specific surface area, is porous, is unsaturated, and is easy to combine with other atoms, so that the molybdenum disulfide is a hot spot for researching photocatalytic semiconductors.

Disclosure of Invention

The invention aims to load Cu into two-dimensional MoS through glycol solution₂the prepared nano material with high catalytic performance has high activity of photocatalytic hydrogen production performance, has good environmental protection performance, and can not cause environmental pollution and harm to users in the synthesis and photocatalytic processes.

the technical scheme adopted by the invention is as follows:

Two-dimensional MoS₂The preparation method of the supported Cu photocatalyst is prepared by a solvothermal method and comprises the following steps:

(1) Two-dimensional MoS₂The preparation of (1):

20mg of ammonium tetrathiomolybdate ((NH) were weighed out₄)₂MoS₄) 20ml of N, N-Dimethylformamide (DMF) are added, ultrasound is carried out for 45min, and the yellow solution is poured into 50mlThe polytetrafluoroethylene reaction kettle is put into an electric heating forced air drying oven for reaction for 10 hours, the reaction temperature is 200 ℃, after the reaction is finished, the reaction kettle is naturally cooled to room temperature, centrifuged, separated, precipitated and respectively washed by deionized water and absolute ethyl alcohol for 3 times, and finally freeze-dried for 12 hours to obtain two-dimensional MoS₂Marked N-MoS₂；

(2) Two-dimensional MoS₂Preparation of loaded Cu:

0.5g of the N-MoS prepared in the preceding step was weighed₂Added to 28.51477ml Cu (NO)₃)₂In a glycol solution of (2), wherein C_Cu0.0002630215g/ml, performing ultrasonic treatment for 30min to obtain black suspension, adjusting the pH of the suspension to 8-9 with 0.2M NaOH solution under the condition of continuous stirring, performing cooling reflux under a 75 ℃ oil bath kettle and a magnetic stirrer, reacting for 5h, naturally cooling the suspension to room temperature, washing with deionized water and absolute ethanol for 3 times respectively, vacuum drying the product in a vacuum drying box at 80 ℃ for 48h, calcining the dried product at 400 ℃ under the protection of inert gas, calcining in a tubular furnace at the temperature rise rate of 1 ℃/min for 2h to obtain the two-dimensional MoS₂Cu-supported catalyst, labeled E-Cu-N-MoS₂。

The volume fraction of the ethylene glycol solution was 80%.

the invention prepares two-dimensional MoS₂The Cu-loaded photocatalyst has stronger photocatalytic hydrogen evolution performance. The two-dimensional MoS is prepared by a solvothermal method and a calcination method₂Supported Cu photocatalysts, i.e. Cu-N-MoS₂The compound expands the absorption range of ultraviolet and visible light, enhances the absorption of light, inhibits the recombination of photo-generated electron-hole pairs and improves the photocatalytic hydrogen evolution performance of the product in the photocatalytic process; Cu-N-MoS₂The compound can be recycled for multiple times in a photocatalytic hydrogen evolution circulation experiment, so that good stability is maintained; Cu-N-MoS₂The compound has adsorbability and good application prospect in adsorbing pollutants.

The invention has the advantages that:

1. Two-dimensional MoS₂The Cu-supported catalyst hasThe photocatalyst has strong photocatalytic hydrogen evolution performance, has good environmental protection performance, and does not cause pollution to the environment and harm to users in the synthesis and photocatalytic processes.

2、N-MoS₂The photocatalytic hydrogen production speed is 1.059 mmoleg^-1h^-1，Cu-N-MoS₂The photocatalytic hydrogen production rate is 1.283mmolg^-1h^-1E-Cu-N-MoS prepared from eighty percent by volume of ethylene glycol solution₂The speed of the photocatalytic hydrogen production is 1.596 mmoleg^-1h^-1By the pair N-MoS₂Literature and Cu-N-MoS₂Comparison of photocatalytic hydrogen production shows that two-dimensional MoS loaded with Cu in ethylene glycol solution₂The photocatalytic hydrogen evolution efficiency is obviously much higher; the literature reports that the hydrogen production rate of the photocatalyst is 0.24mmolg^-1h^-1and the actual hydrogen production rate is 1.596 mmoleg^-1h^-1Compared with the hydrogen production rate reported in the literature, the hydrogen production rate of the product prepared by the method is dozens of times higher. By the pair N-MoS₂And Cu-N-MoS₂Comparing the adsorption quantity of rhodamine to obtain the Cu-loaded two-dimensional MoS₂The adsorption capacity of rhodamine can be improved.

3. The prepared E-Cu-N-MoS₂The composite has small particle size and large surface area, and can provide more active sites for photocatalytic hydrogen evolution.

4. The two-dimensional MoS₂No one has prepared the Cu-supported catalyst product before its production.

5. The invention adopts glycol solution as synthetic E-Cu-N-MoS₂The solvent of the complex is favorable for the transmission of ions in the solution and is favorable for Cu in N-MoS₂Loading, thereby effectively improving Cu-N-MoS₂The photocatalytic performance of the compound enhances the hydrogen production efficiency, and the subsequent hydrogen production performance experiment proves.

drawings

FIG. 1 is a two-dimensional MoS of the present invention₂a Cu-loaded catalyst hydrogen evolution performance diagram (A) and a rhodamine adsorption diagram (B).

FIG. 2 is a catalyst transmission diagram of the product of the present invention, and A is N-MoS₂Drawing (1) ofB is Cu-N-MoS₂FIG. C is E-Cu-N-MoS₂。

Detailed Description