CN101913600A - Method for preparing graphene/semiconductor quantum dot composite material - Google Patents

Method for preparing graphene/semiconductor quantum dot composite material Download PDF

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CN101913600A
CN101913600A CN 201010264796 CN201010264796A CN101913600A CN 101913600 A CN101913600 A CN 101913600A CN 201010264796 CN201010264796 CN 201010264796 CN 201010264796 A CN201010264796 A CN 201010264796A CN 101913600 A CN101913600 A CN 101913600A
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graphene
solution
quantum dot
composite material
preparing
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CN101913600B (en )
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余家龙
王俊飞
程萍
蓝天
郭守武
陈瑞昊
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上海交通大学
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Abstract

The invention discloses a method for preparing a graphene/semiconductor quantum dot composite material, which belongs to the technical field of inorganic nano materials and prepares the graphene/semiconductor quantum dot composite material by preparing solution of single-layer graphene and solution of quantum dots and uniformly mixing the solution of graphene and the solution of quantum dots. The surfaces of the quantum dots synthesized by using mercaptan acid as a stabilizer of the invention have carboxyls, while the surfaces of graphene slices prepared by a chemical oxidation reduction process have hydroxys; therefore, the carboxyls can be bonded with the hydroxys by covalent bonds to form the graphene/quantum dot composite material. As the graphene and the quantum dots mutual soluble in water, ligand disreplacement or modification is avoided. Thus, the preparation process is simplified greatly and the cost is lowered.

Description

制备石墨烯/半导体量子点复合材料的方法 The method of preparing a graphene / semiconductor quantum dot composite

技术领域 FIELD

[0001] 本发明涉及的是一种无机纳米材料技术领域的方法,具体是一种制备石墨烯/半导体量子点复合材料的方法。 [0001] The present invention relates to the art is a method of an inorganic nanomaterials, in particular a method for graphene / composite semiconductor quantum dots prepared.

背景技术 Background technique

[0002] 石墨烯是由碳原子通过共价键结合而成的理想二维晶体,它不但具有大的比表面积(2630m2/g),而且具有优异的力学性能(杨氏模量达llOOGPa,断裂强度达125GPa)、热学性能(导热系数为5000W/m. K)和电学性能(电荷迁移率高达2X 105cm2/V. s),有望在能量存储材料、聚合物复合材料、液晶显示器件和生化传感器等方面得到应用。 [0002] Graphene is composed of carbon atoms bonded by a covalent bond over the two-dimensional crystal, it not only has a large specific surface area (2630m2 / g), but also excellent mechanical properties (Young's modulus reached llOOGPa, fracture strength of 125 GPa), thermal properties (thermal conductivity of 5000W / m. K) and electrical properties (the charge mobility of up to 2X 105cm2 / V. s), is expected in the energy storage material, a polymer composite, the liquid crystal display device and biochemical sensors and other aspects of the application.

[0003] 半导体量子点的尺寸为几纳米到几十纳米,由于量子尺寸效应,它具有分立的电子能级和尺寸依赖的能级间距和带隙,因而具有良好的光学性能,有望在光电器件、电致发光、生物荧光标记等方面得到应用。 [0003] The size of the semiconductor quantum dots is several nanometers to several tens of nanometers, due to the quantum size effect, having a discrete electron level and the energy gap and the size dependent band gap, which has a good optical performance, expected in the photovoltaic device , electroluminescent emission aspect, the biological fluorescent label applied. 其中,量子点太阳能电池由于其可调的太阳光谱吸收以及一个高能光子可产生多个电子的性质,能量转换效率有望突破Shockley-Queisser极限(33. 7% ),因此成为太阳能电池领域的研究热点之一。 Wherein the quantum dot solar cells due to its adjustable solar spectrum and a high-energy photon absorption properties may generate more electrons, the energy conversion efficiency is expected to exceed Shockley-Queisser limit (33.7%), and therefore become a hot topic in the field of solar cell one. 目前开发高效率量子点太阳能电池的挑战之一是如何使光生电子/空穴对有效分离,并使光生电子快速传输到电极表面。 One of the challenges currently developing high-efficiency quantum dot solar cells is that the photogenerated electron / hole pairs separated effectively and quickly transfer the photogenerated electrons to the electrode surface.

[0004] 利用半导体量子点的光敏特性,以及石墨烯的高电荷迁移率和大比表面积,制备石墨烯/半导体量子点复合材料,有望提供一种新型高效光电转换材料。 [0004] With the semiconductor quantum dots photosensitive characteristics, and high charge mobility and a large specific surface area graphene prepared graphene / composite semiconductor quantum dots, are expected to provide a new and efficient photoelectric conversion material.

[0005] 经过对现有技术的检索发现,中国专利申请号200910050334. 9和200910050333. 4均公开了一种制备石墨烯/硫化镉量子点复合材料的制备方法,但两者都采用了二甲亚砜作为硫化镉的硫源,因此对其它非硫化镉量子点的制备不具有普适性。 [0005] After retrieval of prior art found in Chinese patent application No. 200910050334.9 and 200910050333.4 have disclosed a preparation method for preparing a graphene / CdS quantum dot composite material, but both using dimethyl sulfoxide as a sulfur source cadmium sulfide, cadmium sulfide thus prepared other non-quantum dots does not have universality.

[0006] 进一步检索发现,中国专利申请号200910035780. 2公开了一种石墨烯与半导体纳米颗粒复合体系及其合成方法,但该技术采用的是合成工艺重复性较差、原料(有机重金属盐)毒性很大、成本昂贵的油溶性量子点,且制备过程中需要进行配体置换或修饰,因此制备工艺复杂。 [0006] Further search finds, Chinese Patent Application No. 200910035780.2 discloses a graphene composite systems with semiconductor nanoparticles and a synthesis method, but the technology is used in the synthesis process reproducibility is poor, the raw material (organic heavy metal salt) very toxic, expensive oil-soluble quantum dots, and the manufacturing process need to be modified or replaced with a ligand, so the preparation process complicated.

发明内容 SUMMARY

[0007] 本发明针对现有技术存在的上述不足,提供一种制备石墨烯/半导体量子点复合材料的方法,采用巯基酸作为稳定剂合成的水溶性量子点,这些量子点表面带有羧基,而化学氧化还原法制备的石墨烯片层表面带有羟基,通过羟基和羧基的共价结合,形成石墨烯与半导体量子点的复合材料,由于石墨烯和量子点可在水中互溶,不需要进行配体置换或修饰,因而大大简化了制备工艺,降低了成本。 [0007] The present invention addresses the above shortcomings of the prior art, there is provided a method for graphene / semiconductor quantum dot composite prepared using a water-soluble quantum dots mercapto acid as stabilizer synthesis, quantum dots surface with a carboxyl group, redox chemically prepared graphene sheets having surface hydroxyl groups, and covalently bonded by a hydroxyl group a carboxyl group, to form a composite material with graphene semiconductor quantum dots, and quantum dots graphene miscible in water, does not require ligand substitutions or modifications, which greatly simplifies the manufacturing process and reduce costs.

[0008] 本发明是通过以下技术方案实现的,本发明包括以下过程和步骤: [0008] The present invention is achieved by the following technical scheme, and the present invention includes the following process steps:

[0009] 第一步、单层石墨烯的制备:将石墨粉与硝酸钠置于低温酸性环境下搅拌混合后经强氧化反应后依次加入双氧水和去离子水,经清洗过滤后采用水合胼进行还原得到石墨烯溶液。 [0009] The first step, preparation of single graphene: graphite powder mixed with sodium nitrite placed stirred at low temperature after strong acidic conditions the oxidation reaction of hydrogen peroxide were added, and deionized water, washed and filtered for use hydrated corpus reduction of graphene solution.

[0010] 所述的强氧化反应是指:在1小时内将高锰酸钾分3-4批加入,加入时保持在不高 [0010] The oxidation reaction is strongly means: within 1 hour of potassium permanganate was added in 3-4 minutes, the addition is not maintained at a high

4于20°C的环境下剧烈搅拌,然后用水浴加热到35士3°C,搅拌反应2小时后向其中缓慢加入去离子水,得到褐色的石墨悬浮液; 4 with vigorous stirring at 20 ° C at ambient, then heated to 35 with a water bath disabilities 3 ° C, the reaction was stirred for 2 hours after which deionized water was slowly added to give a brown suspension of graphite;

[0011] 所述的双氧水是指:30wt. %双氧水; [0011] The hydrogen peroxide refers to: 30wt% hydrogen peroxide;.

[0012] 所述的清洗过滤是指:过滤后采用温度为45°C的质量百分比为3%的稀盐酸将滤饼反复洗涤3次,然后再进行离心处理并在40°C的真空干燥箱中干燥24小时后得到固体氧化石墨烯; Cleaning Filter [0012] The means: the percentage by mass was filtered using a temperature of 45 ° C was 3% of the filter cake was washed with dilute hydrochloric acid repeated three times, and then centrifuged in a vacuum oven of 40 ° C after 24 hours the resulting solid was dried graphene oxide;

[0013] 所述的还原反应是指:将固体氧化石墨烯配成浓度为0. lmg/L〜lg/L的水溶液, 超声剥离1小时后,向氧化石墨烯溶液中加入还原剂水合胼和氨水溶液,在95°C下搅拌反应1小时,得到黑色的均勻分散的石墨烯溶液。 Reduction [0013] The means: the solid graphene oxide formulated at a concentration of 0. lmg / L~lg / L of an aqueous solution, an ultrasonic stripping for 1 hour, adding a reducing agent to the hydrated corpus graphene oxide solution and aqueous ammonia solution, stirred at 95 ° C for 1 hour, to obtain a black solution uniformly dispersed graphene.

[0014] 第二步、量子点的制备:通过将硒氢化钠(NaHSe)溶液或碲氢化钠(NaHTe)溶液或H2S气体快速注入重金属的高氯酸盐、氯化物或硝酸盐与巯基酸的混合液中,经过加热处理后得到量子点溶液。 [0014] The second step, quantum dots prepared: by selenium Sodium hydride (NaHSe) solution or sodium tellurium hydride (NaHTe) was rapidly injected H2S gas or heavy metal perchlorate, chloride or nitrate with a mercapto acid mixture, after the heat treatment to obtain the quantum dot solution.

[0015] 所述的硒氢化钠溶液或碲氢化钠溶液通过以下方式制备获得:将Se粉或Te粉置于密封的试剂瓶中,快速向其中注入NaBH4水溶液,直至黑色Se或Te粉消失,得到透明的NaHSe或NaHTe水溶液; Selenium tellurium sodium hydride or sodium hydride [0015] The preparation obtained by the following manner: Se Te powder or powder placed in a sealed vial, wherein the flash implantation NaBH4 solution until disappearance of the black powder Se or Te, a clear solution NaHSe or NaHTe;

[0016] 所述的快速注入是指:在磁力搅拌和氮气保护的环境下将硒氢化钠溶液或碲氢化钠溶液或H2S气体在磁力搅拌和通N2的条件下,迅速注入混合液中,其中各物质量的摩尔比为:重金属离子:硒离子、碲离子或硫离子:巯基酸=1 : 0. 5〜1 : 1〜2. 5,经过混合搅拌均勻后,得到量子点前驱体溶液。 Rapid injection of [0016] the means: the selenium or tellurium sodium hydride or sodium hydride H2S gas through the stirring and N2 under conditions of rapid injection of the mixture under magnetic stirring in a nitrogen atmosphere with magnetic environment, wherein molar mass ratio of each substance is: heavy metal ions: selenium ions, tellurium or sulfide: mercapto acid = 1: 0. 5~1: 1 ~ 5, after mixing to homogeneity, giving a quantum dot precursor solution.

[0017] 所述的重金属包括:铬、汞或铅。 Heavy metal according to [0017] include: chromium, mercury or lead.

[0018] 所述的重金属高氯酸盐、氯化物或硝酸盐是指:浓度为10〜40mmol/L的X(ClO4)2 或XCl2或X (NO3) 2的水溶液,其中=X为铬、汞或铅; Heavy metals [0018] The perchlorate, nitrate or chloride refers to: a concentration of 10~40mmol / L of X (ClO4) 2 or XCl2 or X (NO3) 2 solution, wherein = X is chromium, mercury or lead;

[0019] 所述的混合液通过以下方式制备得到:将重金属高氯酸盐、氯化物或硝酸盐和巯基酸混合后置于三口瓶中,用IM浓度的NaOH溶液将体系的pH值调至9〜12,再持续通氮气30分钟去除空气后置于具有氮气气氛的三口瓶中保存; [0019] the obtained mixture prepared by: a heavy metal perchlorate, nitrate or mixed acid chloride group and a mercapto disposed after three-neck flask, with a IM NaOH solution concentration was adjusted to the pH of the system 9~12, nitrogen was continued after the removal of the air disposed necked flask having a nitrogen atmosphere stored for 30 min;

[0020] 所述的巯基酸包括:巯基乙酸、巯基丙酸或半胱氨酸; [0020] The mercapto acids include: thioglycolic acid, mercaptopropionic acid, or cysteine;

[0021] 所述的加热处理是指:在80-100°C水浴中回流1-20小时或在高压釜中在80-180°C下保温0. 5-2小时。 The heat treatment of [0021] means: at reflux for 1-20 hours at 80-100 ° C in a water bath or incubated at 80-180 ° C in an autoclave 0. 5-2 hours.

[0022] 第三步、石墨烯/量子点复合材料的制备:将石墨烯溶液和量子点溶液混合均勻后得到石墨烯/半导体量子点复合材料。 [0022] The third step is the preparation of a graphene / quantum dot composite: graphene quantum dot solution and the solution mixed to obtain a graphene / composite semiconductor quantum dots.

[0023] 所述的混合均勻是指:采用机械搅拌的方式混合,或 [0023] The mixed means: mechanical stirring mixed manner, or

[0024] 采用机械搅拌的方式混合后置于80-100°C水浴中进行回流1-20小时,或 [0024] After mixing by mechanical stirring manner reflux placed in a water bath at 80-100 ° C for 1-20 hours, or

[0025] 采用机械搅拌的方式混合后置于高压釜中在80_180°C进行热处理0. 5-2小时。 After [0025] The mechanical stirring manner was placed in the mixing autoclave 80_180 ° C heat treatment 0.5 5-2 hours.

[0026] 本发明的特点是利用石墨烯和量子点在水溶液中互溶的性质,并通过石墨烯表面的羟基与量子点表面的羧基的共价作用,得到石墨烯/量子点复合材料。 [0026] The features of the present invention is the use of graphene and quantum dots properties miscible in aqueous solution, by covalent interaction with hydroxycarboxylic quantum dot surface alkenyl surface graphite, graphene / quantum dot composite. 本发明所用的原料毒性较小,成本相对低廉,量子点制备工艺简单,重复性好,且量子点不需要进行配体置换或修饰,因此大大简化了制备工艺,并降低了成本。 Less toxic material used in the present invention, relatively low cost, simple process dot, repeatable, and quantum dots need not be modified or replaced with a ligand, thus greatly simplifying the manufacturing process, and reduced costs. 附图说明 BRIEF DESCRIPTION

[0027] 图1本发明所得在160°C的高压釜中生长不同时间得到的水溶性CdTe量子点的紫外-可见吸收光谱图。 UV-soluble CdTe quantum dots [0027] FIG invention obtained a grown at different times in an autoclave of 160 ° C obtained - visible absorption spectrum in FIG.

[0028] 图2为本发明所得石墨烯/CdTe量子点复合材料的AFM图,插图为相应的高度分布图。 [0028] FIG. 2 resulting graphene / CdTe quantum dot composite material of the present invention, AFM images, illustrations corresponding height profile.

[0029] 图3为本发明所得CdTe量子点在与石墨烯按不同比例复合后的荧光光谱图。 [0029] FIG. 3 CdTe quantum dots resulting graphene fluorescence spectra in different proportions according to the present invention the composite. 其中,CdTe量子点为在160°C高压釜中水热处理30分钟制备而成,图中G代表石墨烯。 Wherein, CdTe quantum dots prepared from 30 minutes hydrothermal treatment at 160 ° C in an autoclave, G represents graphene FIG.

具体实施方式 detailed description

[0030] 下面对本发明的实施例作详细说明,本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。 [0030] Hereinafter, embodiments of the present invention will be described in detail, the present embodiments In order aspect of the present invention is a premise is given and the specific operation detailed embodiments, but the scope of the present invention is not limited to the Example embodiments described below.

[0031] 实施例1 [0031] Example 1

[0032] 制备石墨烯/CdTe量子点复合材料,包括以下步骤: [0032] Preparation of graphene / CdTe quantum dot composite material, comprising the steps of:

[0033] 1)将2g粒度为500目的天然石墨粉和Ig硝酸钠置于250ml三口瓶中,在冰浴中冷却至0°C ;将50mL浓硫酸缓慢加入三口瓶中,充分搅拌30分钟,保证反应体系的温度不高于5°C ;将0. 3g高锰酸钾加入三口瓶中,充分搅拌30分钟,同时保证反应体系的温度不高于10°C ;在1小时内,再将7g高锰酸钾分3批加入三口瓶中,保证反应体系的温度不高于20°C;移走冰浴,换用水浴将反应体系温度加热到35士3°C,搅拌反应2小时,得到褐色石墨悬浮液;将90mL去离子水缓慢加入三口瓶中,体系温度迅速升高到70°C,并伴有大量气体生成,稀释的悬浮液在此温度下反应15分钟;向三口瓶中加入7mL 30w. t% H2O2和55mL 温度为40°C的去离子水,充分搅拌反应后,得到亮黄色氧化石墨烯悬浮液;将氧化石墨烯悬浮液趁热过滤,得到黄褐色滤饼,并用150mL温度为45°C的3wt. %稀盐酸溶液将滤饼洗 [0033] 1) particle size of 500 mesh 2g of natural graphite powder and 250ml three-neck flask was placed sodium Ig, was cooled to 0 ° C in an ice bath; 50mL of concentrated sulfuric acid was slowly added to the three-neck flask, stir 30 minutes. ensure that the temperature of the reaction system is not more than 5 ° C; 0. 3g of potassium permanganate was added to three-neck flask, stir for 30 minutes while maintaining the temperature of the reaction system was not higher than 10 ° C; over 1 hour, then 7g of potassium permanganate added in 3 necked flask, to ensure that the temperature of the reaction system is not higher than 20 ° C; ice bath was removed, changing the temperature of the reaction system was heated to 35 with a water bath disabilities 3 ° C, the reaction was stirred for 2 hours. graphite to give a brown suspension; and 90mL deionized water was slowly added three-neck flask, the temperature of the system rapidly rises to 70 ° C, and with a large amount of gas generated, diluted suspension to react at this temperature for 15 min; three-necked flask was added 7mL 30w t% H2O2 and 55mL temperature of 40 ° C deionized water, followed by sufficient mixing to give a bright yellow suspension graphene oxide; graphene oxide suspension was filtered hot to give a tan cake, and with 150mL temperature of 45 ° C to 3wt.% dilute hydrochloric acid solution to wash the filter cake 3次后,将其分散于600mL水中,并将经离心(转速为4000转/分,时间20分钟)后所得到的凝胶状氧化石墨转移至真空干燥箱中,在40°C保温24小时得到固体氧化石墨;将固体氧化石墨配置成0. lg/L水溶液,超声处理1小时(工作频率40kHz,功率200W),将氧化石墨剥离,得到均勻分散的氧化石墨烯溶液;取50mL均勻分散的0. lg/L氧化石墨烯溶液、 50mL去离子水、20. 6 μ L浓度为85wt. %的水合胼和350 μ L浓度为25wt %的氨水置于三口瓶中,经剧烈搅拌10分钟后,将三口瓶放入95°C油浴中加热反应1小时后得到均勻分散的黑色石墨烯溶液。 After three times, it was dispersed in 600mL water, and centrifuged (rotational speed of 4000 rev / min, 20 minutes) The resulting gel was transferred to a vacuum oven graphite oxide, and incubated at 40 ° C 24 hours to obtain a solid graphite oxide; the solid graphite oxide configured 0. lg / L solution, sonicated 1 hour (the operating frequency of 40kHz, power 200W), the graphite oxide peeled off to obtain a uniform dispersion of graphene oxide solution; 50mL taken uniformly dispersed after 0. lg / L solution of oxidized graphene, 50 mL of deionized water, μ L concentration of 20.6 to 85wt.% hydrated corpus 350 μ L and a concentration of 25wt% aqueous ammonia was placed three-neck flask, a vigorously stirred for 10 minutes after the bottle was put in three 95 ° C oil bath for 1 hour to obtain a uniform black dispersed graphene solution.

[0034] 2)取1.97g Cd(ClO4)2. 6H20、250mL水、780 μ L巯基乙酸放置于三口瓶中,溶液出现浑浊,用IM NaOH溶液将体系的ρΗ值调至9,溶液变澄清,将溶液持续通氮气30分钟去除体系中的空气,并将体系保持在氮气气氛中待用;取0.297g Te粉置于通氮气的试剂瓶中, 快速向其中注入0. 178g NaBH4和IOmL水,直至黑色Te粉消失,得到透明的NaHTe水溶液; 将NaHTe水溶液在磁力搅拌和通N2的条件下,快速注入盛有Cd盐溶液的三口瓶中,体系中各物质量的摩尔比Cd2+/Te27巯基乙酸=1 : 0.5 : 2. 4,混合搅拌均勻后,得到亮黄色的量子点前驱体溶液,将量子点前驱体溶液转移至高压釜中,并在160°C下保温30分钟,最终得到橙红色的CdTe量子点。 [0034] 2) Take 1.97g Cd (ClO4) 2. 6H20,250mL water, 780 μ L thioglycolate placed in three-neck flask, the solution appeared cloudy, with a IM NaOH solution adjusted to pH ρΗ system 9, the solution became clear the solution was continuously removed through nitrogen for 30 minutes in the air system, and the system was maintained in a nitrogen atmosphere until used; taken 0.297g Te powder reagent bottle placed in the nitrogen, and 0. 178g NaBH4 rapid injection of water thereto IOmL until the black Te powder disappeared to give a clear NaHTe water; the NaHTe aqueous solution under magnetic stirring and N2 is rapidly injected filled with Cd salt solution three-necked flask, the system of the respective physical quality molar ratio of Cd2 + / Te27 mercapto acetic acid = 1: 0.5: 2.4, the uniformly mixed and stirred to give a bright yellow solution precursor quantum dot, the quantum dot precursor solution was transferred to an autoclave, and incubated at 160 ° C 30 minutes, the resulting orange give red CdTe QDs.

[0035] 3)石墨烯/量子点复合材料的制备:将2)中得到的CdTe量子点溶液各取6份2mL,同时分别取1)中的石墨烯溶液0,0. 05,0. 1,0.2,0.4和lmL,将上述两种溶液分别混合,搅拌均勻后便得到6种不同成分的石墨烯/量子点复合材料。 Preparation of graphene / quantum dot composite material [0035] 3): A 2) obtained from each of CdTe QDs solution 6 parts 2mL, while taking the graphene solution 1) 1 0,0 05,0 respectively. , 0.2, 0.4 and lmL, the above two solutions were mixed and stirred to obtain a uniform after six kinds of different components of the graphene / quantum dot composite.

[0036] 对用上述方法制备的量子点、石墨烯/量子点复合材料进行了表征。 [0036] The quantum dots prepared by the above methods, the graphene / quantum dot composite were characterized. 图1为在160°C的高压釜中生长不同时间后得到的水溶性CdTe量子点的紫外-可见吸收光谱图,可以看出,在160°C下,当生长时间由15分钟延长到90分钟时,CdTe量子点尺寸由0. 4nm长大到3. 6nm。 Figure 1 is a UV-soluble CdTe quantum dots grown at different times after the autoclave of 160 ° C obtained - visible absorption spectrum, it can be seen, at 160 ° C, when the growth time is extended from 15 to 90 minutes when, CdTe quantum dot to grow in size 3. 6nm by a 0. 4nm. 图2为相应的石墨烯/CdTe量子点复合材料的AFM图,插图为相应的高度分布图。 FIG 2 is a corresponding graphene / CdTe quantum dot composite AFM images, illustrations corresponding height profile. 可以看出,几乎所有的量子点都分布在片状石墨烯的表面,说明量子点和石墨烯之间的共价作用很强。 As can be seen, almost all the quantum dots are distributed on the surface of the graphene sheets, described the covalent interaction between the quantum dots and graphene strong. 图3为CdTe量子点在与石墨烯按不同比例复合后的荧光光谱图。 FIG 3 is a CdTe quantum dots graphene fluorescence spectra in different proportions according to the composite. 其中, CdTe量子点为在160°C的高压釜中水热处理30分钟制备而成,G代表石墨烯。 Wherein, CdTe quantum dots prepared from 30 minutes hydrothermal treatment in an autoclave of 160 ° C, G represents graphene. 可以看出,纯CdTe量子点有很强的荧光峰,但当它与石墨烯复合后,荧光强度明显减弱,且随着石墨烯含量的提高,荧光强度逐渐降低,直至出现荧光淬灭(图3f)。 As can be seen, pure CdTe QDs have a strong fluorescence peaks, but after it graphene composite, significantly decreased fluorescence intensity, and with increasing ethylene content of the graphite, the fluorescence intensity gradually decreases, until fluorescence quenching (FIG appears 3f). 量子点的荧光峰是由电子/空穴对复合引起的,量子点与石墨烯复合后,由于石墨烯的高导电性,量子点受激产生的电子会被快速转移出去,减少了电子与空穴复合的几率,因而荧光强度降低。 Peak fluorescence quantum dots by electron / hole pair recombination caused the graphene composite quantum dots, due to the high conductivity of graphene, quantum dots generated by the excited electrons will be transferred out quickly, reducing the electrons and composite chance pocket, thus the fluorescence intensity decreases.

[0037] 实施例2 [0037] Example 2

[0038] 制备石墨烯/CdTe量子点复合材料,包括以下步骤: [0038] Preparation of graphene / CdTe quantum dot composite material, comprising the steps of:

[0039] 本实施例中的步骤1)和2)与上述实施例完全相同。 Step [0039] Example 1 of the present embodiment) and 2) the same as the above embodiment. 不同的是步骤3)中,将2)中得到的亮黄色CdTe量子点前驱体溶液与1)中石墨烯溶液混合后,转移至高压釜中在160°C 进行热处理30分钟,在石墨烯表面原位生成CdTe量子点。 Except that in step 3), a 2) obtained in bright yellow CdTe QDs precursor solution of 1) mixed graphene solution was transferred to an autoclave heat-treated for 30 minutes at 160 ° C, the surface of the graphene situ CdTe quantum dots.

[0040] 实施例3 [0040] Example 3

[0041] 制备石墨烯/HgSe量子点复合材料,包括以下步骤: [0041] Preparation of graphene / HgSe quantum dot composite material, comprising the steps of:

[0042] 1)与上述实施例1中的1)完全相同。 [0042] 1) above in Example 11) are identical.

[0043] 2)取0.948(2.35讓01)取((:104)2、2501^水、502“1^(5.77讓01)巯基丙酸放置于三口瓶中,溶液出现浑浊,用IM NaOH溶液将体系的pH值调至11.2,溶液变澄清,将溶液持续通氮气30分钟去除体系中的空气,并将体系保持在氮气气氛中待用;取0. 186g Se粉置于通氮气的试剂瓶中,快速向其中注入0. 178g NaBH4和IOmL水,直至黑色Se粉消失,得到透明的NaHSe水溶液;将NaHSe水溶液在磁力搅拌和通N2的条件下,快速注入盛有Hg盐溶液的三口瓶中,体系中各物质量的摩尔比Hg2+/Se27巯基丙酸=1 : 1 : 2. 4,混合搅拌均勻后,得到量子点前驱体溶液,将量子点前驱体溶液在100°C水浴中回流12小时,最终得到HgSe量子点。 [0043] 2) taking 0.948 (2.35 Let 01) take ((: 104) 2,2501 ^ water, 502 "1 ^ (5.77 Let 01) mercaptopropionate placed in three-neck flask, the solution appeared cloudy, with a IM NaOH solution the system was adjusted to pH 11.2, the solution became clear, the solution was maintained in a nitrogen atmosphere continuously removed through nitrogen for 30 minutes in the air system and standby system; 0. 186g Se powder takes place through the nitrogen reagent bottle in rapidly injected thereto IOmL 0. 178g NaBH4 and water until disappearance of the black Se powder, to obtain a transparent aqueous NaHSe; NaHSe the solution was stirred under N2 and pass the magnetic force, rapid injection filled with saline solution three-necked flask Hg , the system of the respective physical quality molar ratio of Hg2 + / Se27 mercaptopropionic acid = 1: 1: 2.4, after mixing to homogeneity, giving a quantum dot precursor solution, the quantum dot precursor solution was refluxed for 12 at 100 ° C in a water bath hours with final HgSe quantum dots.

[0044] 3)石墨烯/量子点复合材料的制备:将2)中得到的HgSe量子点溶液与1)中的石墨烯溶液混合,搅拌均勻后便得到石墨烯/HgSe量子点复合材料。 Preparation of graphene / quantum dot composite material [0044] 3): The mixture obtained in 2) of a quantum dot solution HgSe 1) of the graphene was stirred uniformly after graphene / quantum dot composite HgSe.

[0045] 实施例4 [0045] Example 4

[0046] 制备石墨烯/CdS量子点复合材料,包括以下步骤: [0046] Preparation of graphene / CdS quantum dot composite material, comprising the steps of:

[0047] 1)与上述实施例1中的1)完全相同。 [0047] 1) above in Example 11) are identical.

[0048] 2)取0.86g CdCl2、250mL水、1. 14g半胱氨酸放置于三口瓶中,溶液出现浑浊,用IMNaOH溶液将体系的pH值调至10,溶液变澄清,将溶液持续通氮气30分钟去除体系中的空气,并将体系保持在氮气气氛中待用;在磁力搅拌下,以N2为载气,向盛有Cd盐溶液的三口瓶中通入105mL H2S气体,体系中各物质量的摩尔比Cd2+/S27半胱氨酸=1 : 1 : 2,混合搅拌均勻后,得到量子点前驱体溶液,将量子点前驱体溶液在100°C水浴中回流1小时, 最终得到CdS量子点。 [0048] 2) Take 0.86g CdCl2,250mL water, 1. 14g cysteine ​​placed in three-neck flask, the solution appeared cloudy, with a pH adjusted solution IMNaOH system 10, the solution became clear, the solution was continuously introduced nitrogen for 30 minutes in the air removal system, and the system is kept on standby in a nitrogen atmosphere; under magnetic stirring, in N2 as a carrier gas, to be filled with saline solution three-necked flask Cd into 105mL H2S gas, each system the molar ratio of substance Cd2 + / S27 cysteine ​​= 1: 1: 2, after mixing to homogeneity, giving a quantum dot precursor solution, the precursor quantum dots was refluxed in 100 ° C water bath for 1 hour to give a final CdS quantum dots.

7[0049] 3)石墨烯/量子点复合材料的制备:将2)中得到的CdS量子点溶液与1)中的石墨烯溶液混合,搅拌均勻后便得到石墨烯/CdS量子点复合材料。 Preparation of graphene / quantum dot composite 7 [0049] 3): The mixture obtained in 2) of CdS quantum dot solution 1) of the graphene was stirred uniformly after graphene / CdS quantum dot composite.

[0050] 实施例5 [0050] Example 5

[0051] 制备石墨烯/PbSe量子点复合材料,包括以下步骤: [0051] Preparation of graphene / PbSe quantum dot composite material, comprising the steps of:

[0052] 1)与上述实施例1中的1)完全相同。 [0052] 1) above in Example 11) are identical.

[0053] 2)取1.56g Pb (NO3) 2、250mL水、780 μ L巯基乙酸放置于三口瓶中,用IM NaOH溶液将体系的PH值调至9,将溶液持续通氮气30分钟去除体系中的空气,并将体系保持在氮气气氛中待用;取0. 186g Se粉置于通氮气的试剂瓶中,快速向其中注入0. 178g NaBH4和IOmL水,直至黑色Se粉消失,得到透明的NaHSe水溶液;将NaHSe水溶液在磁力搅拌和通N2的条件下,快速注入盛有Pb盐溶液的三口瓶中,体系中各物质量的摩尔比pb2+/Se27巯基乙酸=1 : 0.5 : 2. 4,混合搅拌均勻后,得到量子点前驱体溶液,将量子点前驱体溶液在100°C水浴中回流12小时,最终得到PbSe量子点。 [0053] 2) Take 1.56g Pb (NO3) 2,250mL water, 780 μ L thioglycolate placed in three-neck flask, with a IM NaOH solution was adjusted to PH value of the system 9, and the solution was continuously removed through nitrogen for 30 min System air, and the system was maintained in a nitrogen atmosphere until used; 0. 186g Se powder takes place the vial nitrogen, rapid injection IOmL 0. 178g NaBH4 and water added until the black Se powder disappeared to give a clear the NaHSe water; the NaHSe aqueous solution under magnetic stirring and N2 is rapidly injected filled with three-necked flask Pb salt solution, the system of the respective physical quality molar ratio of pb2 + / Se27 mercapto acetic acid = 1: 0.5: 2.4 , mixing uniformly to obtain a quantum dot precursor solution, the precursor quantum dots was refluxed for 12 hours in a water bath at 100 ° C, the finally obtained PbSe quantum dots.

[0054] 3)石墨烯/量子点复合材料的制备:将2)中得到的PbSe量子点溶液与1)中的石墨烯溶液混合,搅拌均勻后便得到石墨烯/PbSe量子点复合材料。 Preparation of graphene / quantum dot composite material [0054] 3): The mixture obtained in 2) of PbSe quantum dot solution 1) of the graphene was stirred uniformly after graphene / PbSe quantum dot composite.

Claims (10)

  1. 一种制备石墨烯/半导体量子点复合材料的方法,其特征在于,包括以下过程和步骤:第一步、单层石墨烯的制备:将石墨粉与硝酸钠置于低温酸性环境下搅拌混合后经强氧化反应后依次加入双氧水和去离子水,经清洗过滤后采用水合肼进行还原得到石墨烯溶液;第二步、量子点的制备:通过将硒氢化钠溶液或碲氢化钠溶液或H2S气体快速注入重金属重金属的高氯酸盐、氯化物或硝酸盐与巯基酸的混合液中,经过加热处理后得到量子点溶液;第三步、石墨烯/量子点复合材料的制备:将石墨烯溶液和量子点溶液混合均匀后得到石墨烯/半导体量子点复合材料。 After the graphite powder was stirred with sodium nitrite placed at low mixing an acidic environment: A graphene / semiconductor quantum dots process for preparing a composite material, characterized in that it comprises the following procedures and steps: a first step of preparing graphene after strong oxidation reaction of hydrogen peroxide were added, and deionized water, washed and filtered using hydrazine hydrate reduction of graphene solution; the second step, quantum dots prepared: by selenium or tellurium sodium hydride or sodium hydride gas H2S rapid injection of heavy metals heavy metal perchlorate, nitrate and chloride or a mixture of a mercapto acid, obtained after the heat treatment quantum dot solution; preparing a third step, the graphene / quantum dot composite material: a solution of graphene quantum dot solution and uniformly mixed to obtain a graphene / composite semiconductor quantum dots.
  2. 2.根据权利要求1所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的强氧化反应是指:在1小时内将高锰酸钾分3-4批加入,加入时保持在不高于20°C的环境下剧烈搅拌,然后用水浴加热到35士3°C,搅拌反应2小时后向其中缓慢加入去离子水, 得到褐色的石墨悬浮液。 The method of preparing a graphene / semiconductor quantum dot composite material according to claim 1, characterized in that the oxidation reaction is strongly means: within 1 hour of potassium permanganate was added in 3-4 minutes, is added with vigorous stirring maintained at not more than the environment of 20 ° C, and then heated with a water bath to 35 persons 3 ° C, the reaction was stirred for 2 hours after which deionized water was slowly added to give a brown suspension of graphite.
  3. 3.根据权利要求1所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的清洗过滤是指:过滤后采用温度为45°C的质量百分比为3%的稀盐酸将滤饼反复洗涤3次,然后再进行离心处理并在40°C的真空干燥箱中干燥24小时后得到固体氧化石墨烯。 3. The method of claim 1 prepared graphene / semiconductor quantum dot composite material as claimed in claim, characterized in that said filter cleaning means: the percentage by mass was filtered using a temperature of 45 ° C was 3% diluted hydrochloric acid the filter cake was washed repeatedly three times, and then centrifuged in a vacuum oven of 40 ° C the solid obtained graphene oxide after drying for 24 hours.
  4. 4.根据权利要求1所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的还原反应是指:将固体氧化石墨烯配成浓度为0. lmg/L〜lg/L的水溶液,超声剥离1小时后,向氧化石墨烯溶液中加入还原剂水合胼和氨水溶液,在95°C下搅拌反应1小时,得到黑色的均勻分散的石墨烯溶液。 4. The method of claim 1 prepared graphene / semiconductor quantum dot composite material as claimed in claim, characterized in that said reduction means: the solid graphene oxide formulated at a concentration of 0. lmg / L~lg / after the aqueous solution L, ultrasonic peeling one hour, added to the reducing agent solution of oxidized graphene corpus and hydrated ammonia solution, the reaction was stirred at 95 ° C 1 hour to obtain a uniform black dispersed graphene solution.
  5. 5.根据权利要求1所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的硒氢化钠溶液或碲氢化钠溶液通过以下方式制备获得:将Se粉或Te粉置于密封的试剂瓶中,快速向其中注入NaBH4水溶液,直至黑色Se或Te粉消失,得到透明的NaHSe或NaHTe 水溶液。 The method of preparing a graphene / semiconductor quantum dot composite material according to claim 1, characterized in that the selenium or tellurium sodium hydride, sodium hydride obtained solution was prepared in the following manner: the powder is set Se, or Te powder in a sealed vial, wherein the flash implantation NaBH4 solution until disappearance of the black Se or Te powder, to obtain a transparent aqueous NaHSe or NaHTe.
  6. 6.根据权利要求1所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的快速注入是指:在磁力搅拌和氮气保护的环境下将硒氢化钠溶液或碲氢化钠溶液或H2S 气体在磁力搅拌和通N2的条件下,迅速注入混合液中,其中各物质量的摩尔比为:重金属离子:硒离子、碲离子或硫离子:巯基酸=1 : 0. 5〜1 : 1〜2. 5,经过混合搅拌均勻后,得到量子点前驱体溶液。 The method of preparing a graphene / semiconductor quantum dot composite material according to claim 1, characterized in that the fast-injection means: magnetic stirring and under a nitrogen blanket environment selenium tellurium hydride or sodium hydride molar ratio of H2S in a solution of sodium or magnetic stirring and under N2, the mixture is injected rapidly, wherein each of substance as: heavy metal ions: selenium ions, tellurium or sulfide: mercapto acid = 1: 0.5 ~ 1: 1 ~ 5, after mixing to homogeneity, giving a quantum dot precursor solution.
  7. 7.根据权利要求1所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的混合液通过以下方式制备得到:将重金属高氯酸盐、氯化物或硝酸盐和巯基酸混合后置于三口瓶中,用IM浓度的NaOH溶液将体系的pH值调至9〜12,再持续通氮气30分钟去除空气后置于具有氮气气氛的三口瓶中保存。 The method of preparing a graphene / semiconductor quantum dot composite material according to claim 1, wherein said mixture is prepared by obtained: the heavy metal perchlorate, chloride or nitrate and a mercapto group mixed acid placed in three-neck flask, with a IM NaOH solution concentration adjusted to pH 9~12 system, nitrogen was continued after the removal of the air disposed necked flask having a nitrogen atmosphere, stored for 30 minutes.
  8. 8.根据权利要求1或6或7所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的巯基酸包括:巯基乙酸、巯基丙酸或半胱氨酸。 The method of preparing a graphene / semiconductor quantum dot composite material according to claim 1 or 6 or 7, characterized in that the mercapto acid comprising: thioglycolic acid, mercaptopropionic acid, or cysteine.
  9. 9.根据权利要求1或6或7所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的重金属包括:铬、汞或铅。 The method of preparing a graphene / semiconductor quantum dot composite material according to claim 1 or 6 or 7, wherein said heavy metal comprising: chromium, mercury or lead.
  10. 10.根据权利要求1所述的制备石墨烯/半导体量子点复合材料的方法,其特征是,所述的混合均勻是指:采用机械搅拌的方式混合,或采用机械搅拌的方式混合后置于80-100°C水浴中进行回流1-20小时,或采用机械搅拌的方式混合后置于高压釜中在80-180°C进行热处理0. 5-2小时。 The method of preparing a graphene / semiconductor quantum dots 10. A composite material according to claim 1, characterized in that the homogeneous mixing means: mechanical stirring manner mixing, mechanical stirring or mixing the disposed manner after refluxing for 1-20 hours in a water bath at 80-100 ° C, mechanical stirring or mixing manner of 80-180 ° C was placed in the autoclave and heat-treated 0. 5-2 hours.
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