阅读说明：本技术 一种Pt修饰的Au/CuSe切向异质纳米材料及其制备方法 (A kind of tangential heterogeneous nano material and preparation method thereof of the Au/CuSe of Pt modification ) 是由 马良 陈相柏 于 2019-08-14 设计创作，主要内容包括：本发明涉及一种Pt修饰的Au/CuSe切向异质纳米材料的制备方法,包括：S1.在十六烷基三甲基溴化氨体系下制备纳米金胶体溶液；S2.采用水相合成法以金纳米球为生长基底,硒氢化钠和乙酸铜为前驱体,抗坏血酸为还原剂,十六烷基三甲基溴化氨为表面活性剂,真空下反应得到Au/CuSe切向异质纳米材料水溶液；S3.在金纳米球和二维硒化铜纳米盘表面生长Pt纳米颗粒,得到Pt修饰的Au/CuSe切向异质纳米材料。本发明利用全水相方法制备了Pt修饰的Au/CuSe切向异质纳米材料,制备出的异质纳米材料形貌稳定可控,双等离激元耦合效应明显,在紫外-可见-近红外区间有显著的光子吸收,光催化产氢气性能优异。(The present invention relates to a kind of preparation methods of the tangential heterogeneous nano material of Au/CuSe of Pt modification, comprising: S1. prepares nano Au colloid liquid solution under cetyl trimethyl bromination ammono-system；S2. use aqueous phase synthesis method using gold nanosphere as growth substrate, sodium hydrogen selenide and copper acetate are presoma, and ascorbic acid is reducing agent, and cetyl trimethyl ammonia bromide is surfactant, and reaction obtains Au/CuSe tangentially heterogeneous nano material aqueous solution under vacuum；S3. Pt nano particle is grown in gold nanosphere and two-dimentional copper selenide nanometer panel surface, obtains the Au/CuSe of Pt modification tangentially heterogeneous nano material.The present invention is prepared for the tangential heterogeneous nano material of Au/CuSe of Pt modification using whole water phase method, the heterogeneous appearance of nano material prepared is stably and controllable, double phasmon coupling effects are obvious, there is significant photonic absorption between ultraviolet-visible-near infrared region, and Photocatalyzed Hydrogen Production gas is had excellent performance.)

1. a kind of preparation method of the tangential heterogeneous nano material of the Au/CuSe of Pt modification, which comprises the steps of:

S1. nano Au colloid liquid solution is prepared under cetyl trimethyl bromination ammono-system, wherein the partial size of gold nanosphere is 18 ~22nm；

S2. sodium hydrogen selenide solution is prepared, uses aqueous phase synthesis method using the gold nanosphere as growth substrate, with sodium hydrogen selenide and second Sour copper is presoma, using ascorbic acid as reducing agent, using cetyl trimethyl ammonia bromide as surfactant, in hexa-methylene Reaction grows two-dimentional copper selenide nanometer plate in gold nanosphere tangential direction under vacuum under the conditions of tetramine is existing, after reaction It is centrifuged and solid product is resuspended in deionized water and obtain Au/CuSe tangentially heterogeneous nano material aqueous solution, in reaction system The gold nanosphere, sodium hydrogen selenide, copper acetate, ascorbic acid, hexa and cetyl trimethyl ammonia bromide it is dense Degree be respectively 25.96~31.76nM, 0.52~0.87mM, 0.48~0.90mM, 8.08~15.01mM, 8.08~15.01mM, 19.63~26.56mM, reaction temperature are 85~95 DEG C, and the reaction time is 7.5~8.5h；

S3. using the Au/CuSe of step S2 preparation, tangentially heterogeneous nano material is with potassium platinic chloride as growth substrate in water phase Platinum source, using ascorbic acid as reducing agent, cetyl trimethyl ammonia bromide is surfactant, in gold nanosphere and two-dimentional selenizing Copper nanometer panel surface grows Pt nano particle, obtains the tangential heterogeneous nano material aqueous solution of Au/CuSe of Pt modification；

S4. by Au/CuSe that the Pt is modified, tangentially heterogeneous nano material aqueous solution is centrifuged to obtain solid product, and solid is produced Object is cleaned and dried to obtain the Au/CuSe of Pt modification tangentially heterogeneous nano material.

2. a kind of preparation method of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 1, feature It is, step S1 includes:

Chlorauric acid solution, cetyl trimethyl bromination ammonia solution and sodium borohydride solution hybrid reaction are obtained nanogold by S1.1 Seed solution；

S1.2 by chlorauric acid solution, ascorbic acid solution, that cetyl trimethyl bromination ammonia solution is mixed to get the first mixing is molten Liquid, the nanogold seed solution prepared by step S1.1 are added in first mixed solution, and adjusting pH to 11.3~ 11.7, reaction obtains the nano Au colloid liquid solution.

3. a kind of preparation method of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 2, feature It is, the sodium borohydride solution is sodium borohydride mixture of ice and water.

4. a kind of preparation method of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 3, feature It is, the volume of chlorauric acid solution, cetyl trimethyl ammonia bromide and sodium borohydride solution is respectively 500 μ in step S1.1 L, when 8mL and 600 μ L, the concentration of the chlorauric acid solution, cetyl trimethyl ammonia bromide and sodium borohydride solution is respectively 0.048~0.052M, 0.17~0.23M and 0.009~0.011M, the reaction time is 2~2.5h, during the reaction with 1000 Rev/min stirring.

5. a kind of preparation method of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 4, feature It is, nanogold seed solution, chlorauric acid solution, ascorbic acid solution and cetyl trimethyl ammonia bromide are molten in step S1.2 When the volume of liquid is respectively 30 μ L, 6mL, 3.5mL, 30mL, the chlorauric acid solution, ascorbic acid solution and cetyl front three The concentration of base ammonia bromide is respectively 4.5~5.5mM, 8~16mM and 0.17~0.23M, and the reaction time is 1~2h, and reaction is completed Afterwards, reaction product 10000rpm/min is centrifuged 15min, precipitating is dispersed in deionized water again.

6. a kind of preparation side of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 1-5 Method, which is characterized in that the sodium hydrogen selenide solution the preparation method comprises the following steps: sodium borohydride is soluble in water, be placed in -6~-4 DEG C it is cold Freeze 6~10min, selenium powder is added in above-mentioned sodium borohydride aqueous solution, it is molten to obtain the sodium hydrogen selenide up to being completely dissolved for stirring The molar ratio of liquid, the sodium borohydride and the selenium powder is 1.9~2.1:1, the concentration of the sodium hydrogen selenide is 0.75~ 0.125M。

7. a kind of preparation side of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 1-5 Method, which is characterized in that the specific steps of step S2 are as follows: prepare sodium hydrogen selenide solution, the nanogold colloid that will be prepared in step S1 Solution concentration is adjusted to 45~55nM, and takes the nano Au colloid liquid solution after 5mL adjusting, and 1mL ascorbic acid is added, and 1mL six is sub- It is mixed that tetramine, 1mL cetyl trimethyl ammonia bromide, 60 μ L sodium hydrogen selenide solution and 600 μ L copper acetate solutions obtain second Solution is closed, second mixed solution is transferred in reaction vessel and is encapsulated, is placed in a vacuum drying oven and is vacuumized and be warming up to 85~95 DEG C of 7.5~8.5h of reaction, the ascorbic acid, hexa solution, cetyl trimethyl bromination ammonia solution, The concentration of sodium hydrogen selenide Solutions Solution and copper acetate solution be respectively 870~130mM, 70~130mM, 170~230mM, 75~ 125mM and 7~13mM.

8. a kind of preparation side of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 1-5 Method, which is characterized in that the specific steps of step S3 are as follows: Xiang Suoshu Au/CuSe is tangentially added ten in heterogeneous nano material aqueous solution Six alkyl trimethyl bromination ammonia solutions and ascorbic acid solution, obtain third mixed solution, and the third mixed solution is placed in Then 60~80 DEG C of 0.8~1.2h of reaction are added chloroplatinic acid potassium solution and obtain the 4th mixed solution, continue in 60~80 DEG C anti- Answer 2.5~3.5h, Au/CuSe described in the 4th mixed solution tangentially heterogeneous nano material, cetyl trimethyl bromination The concentration of ammonia, ascorbic acid and potassium platinic chloride is respectively 14~21 μ g/mL, 0.19~0.15M, 5.85~7.60M, 26.31 ~32.16nM.

9. a kind of preparation side of the tangential heterogeneous nano material of the Au/CuSe of Pt modification according to claim 1-5 Method, which is characterized in that step S4 the specific steps are the tangential water-soluble liquid coolings of heterogeneous nano material of the Au/CuSe for modifying the Pt But 8000~10000rpm is centrifuged 5 minutes and obtains solid product after, and solid matter with deionized water and ethyl alcohol are alternately cleaned, set The tangential heterogeneous nano material of 60~70 DEG C of Au/CuSe for keeping obtaining for 10~12 hours the Pt modification in air dry oven.

10. a kind of tangential heterogeneous nano material of the Au/CuSe of Pt modification, which is characterized in that by any one of claim 1~9 institute The preparation method stated is prepared.

Technical field

The present invention relates to technical field of inorganic nano-material preparation, and in particular to a kind of Au/CuSe of Pt modification is tangentially different Matter nano material and preparation method thereof.

Background technique

The heterogeneous nano material of metal-semiconductor based on phasmon has outstanding photoelectric conversion and photonic absorption etc. Characteristic shows huge application potential in photocatalysis field.In the metal-semiconductor heterogeneous photochemical catalyst reported at present, Phasmon carrier is mostly metal nanocrystal, and the donor of phasmon is limited in heterojunction structure, is significantly limited heterogeneous Catalyst light captures ability and photoelectric conversion efficiency.In addition, the heterogeneous nano material of the metal-semiconductor reported at present is mostly two groups Part, the carrier transfer path of metal and semiconductor is limited, leads to that Carrier recombination rate is very fast, utilization rate is relatively low, and light is urged It is lower to change activity.

Summary of the invention

In order to solve the above-mentioned technical problem the present invention provides a kind of Au/CuSe of Pt modification with efficient catalytic performance Tangential heterogeneous nano material and preparation method thereof.

The technical scheme to solve the above technical problems is that a kind of tangential heterogeneous nanometer of the Au/CuSe of Pt modification The preparation method of material, includes the following steps:

S1. nano Au colloid liquid solution is prepared under cetyl trimethyl bromination ammono-system, wherein the partial size of gold nanosphere For 18~22nm；

S2. sodium hydrogen selenide solution is prepared, uses aqueous phase synthesis method using the gold nanosphere as growth substrate, with sodium hydrogen selenide It is presoma with copper acetate, using ascorbic acid as reducing agent, using cetyl trimethyl ammonia bromide as surfactant, in six Asias Reaction grows two-dimentional copper selenide nanometer plate, reaction knot in gold nanosphere tangential direction under vacuum under the conditions of tetramine is existing It is centrifuged after beam and solid product is resuspended in deionized water and obtain Au/CuSe tangentially heterogeneous nano material aqueous solution, reactant Gold nanosphere described in system, sodium hydrogen selenide, copper acetate, ascorbic acid, hexa and cetyl trimethyl ammonia bromide Concentration be respectively 25.96~31.76nM, 0.52~0.87mM, 0.48~0.90mM, 8.08~15.01mM, 8.08~ 15.01mM, 19.63~26.56mM, reaction temperature are 85~95 DEG C, and the reaction time is 7.5~8.5h；

S3. using the Au/CuSe of step S2 preparation, tangentially heterogeneous nano material is growth substrate in water phase, with chloroplatinic acid Potassium is platinum source, and using ascorbic acid as reducing agent, cetyl trimethyl ammonia bromide is surfactant, in gold nanosphere and two dimension Copper selenide nanometer panel surface grows Pt nano particle, obtains the tangential heterogeneous nano material aqueous solution of Au/CuSe of Pt modification；

S4. by Au/CuSe that the Pt is modified, tangentially heterogeneous nano material aqueous solution is centrifuged to obtain solid product, and will consolidate Body product cleaning is dried to obtain the Au/CuSe of Pt modification tangentially heterogeneous nano material.

The copper ion that copper acetate generates is under the action of cetyl trimethyl ammonia bromide and ascorbic acid, in nano gold spherical Surface complexing, and with sodium hydrogen selenide generate CuSe, the CuSe of generation under the booster action of cetyl trimethyl ammonia bromide Gold nanosphere tangential direction grows two-dimentional copper selenide nanometer plate, obtains Au/CuSe tangentially heterogeneous nano material, potassium platinic chloride Pt nano particle is reduced to by ascorbic acid, Pt nano particle is under the action of cetyl trimethyl ammonia bromide in Au and CuSe Surface growth, keeps the cutting orientation structure of Au/CuSe constant during the growth process, thus construct with metal and it is nonmetallic etc. from The tangential heterogeneous nano material of three component Au/CuSe/Pt of excimer close coupling effect.Present invention utilizes whole water phase methods to be prepared for The tangential heterogeneous nano material of Au/CuSe of Pt modification, the heterogeneous appearance of nano material prepared is controllable, double phasmons coupling effects Should be obvious, increased using the synergistic effect of the bis- phasmon coupled resonances of Au and CuSe and Pt nano particle and double phasmons The Photocatalyzed Hydrogen Production gas performance of strong heterojunction structure.

Further, step S1 includes:

S1.1 is received chlorauric acid solution, cetyl trimethyl bromination ammonia solution and sodium borohydride solution hybrid reaction Rice gold seeds solution；

Chlorauric acid solution, ascorbic acid solution, cetyl trimethyl bromination ammonia solution are mixed to get first and mixed by S1.2 Solution is closed, the nanogold seed solution prepared by step S1.1 is added in first mixed solution, adjusts pH to 11.3 ~11.7, reaction obtains the nano Au colloid liquid solution.

Beneficial effect using above-mentioned further scheme is that the particle size of this method gold nanosphere obtained is more equal It is even and controllable, it, can be with by the ratio of each substance in control seed and the first mixed solution during seed growth Control produces various sizes of gold nanosphere.

Further, the sodium borohydride solution is sodium borohydride mixture of ice and water.

The beneficial effect for using above-mentioned further scheme is to control the temperature of reaction to slow down the rate of reaction, to make to plant Sub slowly growth, so that the uniform particle sizes of gold nanosphere are controllable.

Further, in step S1.1 chlorauric acid solution, cetyl trimethyl ammonia bromide and sodium borohydride solution volume Respectively 500 μ L, 8mL and when 600 μ L, the chlorauric acid solution, cetyl trimethyl ammonia bromide and sodium borohydride solution Concentration is respectively 0.048~0.052M, 0.17~0.23M and 0.009~0.011M, and the reaction time is 2~2.5h, is being reacted It is stirred in journey with 1000 revs/min.

Further, nanogold seed solution, chlorauric acid solution, ascorbic acid solution and cetyl front three in step S1.2 When the volume of bromide ammonia solution is respectively 30 μ L, 6mL, 3.5mL, 30mL, the chlorauric acid solution, ascorbic acid solution and ten The concentration of six alkyl trimethyl ammonia bromides is respectively 4.5~5.5mM, 8~16mM and 0.17~0.23M, and the reaction time is 1~ Reaction product 10000rpm/min is centrifuged 15min, precipitating is dispersed in deionized water again by 2h after the reaction was completed.

Beneficial effect using above-mentioned further scheme is the nanogold particle that can control to obtain 18~22nm.

Further, the sodium hydrogen selenide solution the preparation method comprises the following steps: sodium borohydride is soluble in water, be placed in -6~-4 DEG C it is cold Freeze 6~10min, selenium powder is added in above-mentioned sodium borohydride aqueous solution, it is molten to obtain the sodium hydrogen selenide up to being completely dissolved for stirring The molar ratio of liquid, the sodium borohydride and the selenium powder is 1.9~2.1:1, the concentration of the sodium hydrogen selenide is 0.75~ 0.125M。

Further, the specific steps of step S2 are as follows: prepare sodium hydrogen selenide solution, take the nanogold colloid prepared in step S1 Solution (concentration is about 45~55nM), and the nano Au colloid liquid solution after 5mL adjusting is taken, 1mL ascorbic acid is added, 1mL six is sub- It is mixed that tetramine, 1mL cetyl trimethyl ammonia bromide, 60 μ L sodium hydrogen selenide solution and 600 μ L copper acetate solutions obtain second Solution is closed, second mixed solution is transferred in reaction vessel and vacuumizes encapsulation, is placed in a vacuum drying oven 85~95 DEG C React 7.5~8.5h, the ascorbic acid, hexa solution, cetyl trimethyl bromination ammonia solution, sodium hydrogen selenide The concentration of Solutions Solution and copper acetate solution is respectively 870~130mM, 70~130mM, 170~230mM, 75~125mM and 7 ~13mM.

Further, the specific steps of step S3 are as follows: Xiang Suoshu Au/CuSe is tangentially added ten in heterogeneous nano material aqueous solution Six alkyl trimethyl ammonia bromides and ascorbic acid solution, obtain third mixed solution, and the third mixed solution is placed in 70 DEG C 1h is reacted, chloroplatinic acid potassium solution is then added and obtains the 4th mixed solution, in 70 DEG C of the reaction was continued 3h, the 4th mixing is molten Au/CuSe described in liquid tangentially heterogeneous nano material, cetyl trimethyl ammonia bromide, ascorbic acid and potassium platinic chloride it is dense Degree is respectively 14~21 μ g/mL, 0.19~0.15M, 5.85~7.60M, 26.31~32.16nM.

Further, step S4 the specific steps are the tangential heterogeneous nano material aqueous solutions of the Au/CuSe for modifying the Pt 8000~10000rpm is centrifuged 5 minutes and obtains solid product after cooling, and solid matter with deionized water and ethyl alcohol are alternately cleaned, It is placed in air dry oven and keeps obtaining the Au/CuSe tangentially heterogeneous nano material in 10~12 hours for 60~70 DEG C.

The tangential heterogeneous nano material of the Au/CuSe for the Pt modification being prepared the present invention also provides above-mentioned preparation method.

The morphology controllable of the tangential heterogeneous nano material of the Au/CuSe of Pt prepared by the present invention modification, using gold nanosphere and The Photocatalyzed Hydrogen Production gas of the double phasmon coupled resonances of copper selenide and Pt and double phasmon synergistic effect enhancing heterojunction structures Performance.

Detailed description of the invention

Fig. 1 is the transmission electron microscopy of the tangential heterogeneous nano material of Au/CuSe of Pt modification prepared by the embodiment of the present invention 3 Mirror photo, wherein Fig. 1 (a) and 1 (c) is conventional transmission electron microscope photo, and Fig. 1 (b) is the scanning of angle of elevation angle annular dark field Transmission electron microscope photo；

Fig. 2 is the extinction spectra of the tangential heterogeneous nano material of Au/CuSe of prepared Pt modification in the embodiment of the present invention 3 Figure；

Fig. 3 is the Au/CuSe tangentially heterogeneous nano material, Au/ of prepared Pt modification in invention embodiment 3 CuSe tangentially heterogeneous nano material and Pt/CuSe Photocatalyzed Hydrogen Production gas velocity rate.

Specific embodiment

Principles and features of the present invention are described below in conjunction with drawings and the specific embodiments, example is served only for solving The present invention is released, is not intended to limit the scope of the present invention.

It is aqueous solution unless otherwise instructed below in all solution.