一种利用葡萄柚汁液还原出硝酸银溶液中的银离子的方法 A reduction of the use of grapefruit juice solution of silver nitrate solution of silver ions method

技术领域 Technical Field

[0001] 本发明属纳米银颗粒制造领域，尤其涉及一种利用葡萄柚汁液还原出硝酸银溶液中的银离子的方法。 [0001] The present invention belongs to the manufacture of nano-silver particles, in particular to a reduction of the use of grapefruit juice solution of silver nitrate solution of silver ions approach.

背景技术 Background

[0002] 随着纳米材料的迅速发展,纳米材料的应用也越来越广泛，如在纳米涂料，纳米碳管，纳米半导体、催化材料，以及在医药、家电、纺织、环境保护等方面。 [0002] With the rapid development of nano-materials, nano-materials applications are increasingly being used, such as in nano-coatings, carbon nanotubes, nano semiconductor, catalytic materials, as well as in medicine, electronics, textile, environmental protection and other aspects. 而近年来，在纳米银方面的研究更是取得了丰厚的成果。 In recent years, in terms of research nano-silver is achieved substantial results. 无论是从制备、性质、还是应用上，纳米银无疑是一种研究最为广泛深入的材料之一。 Whether it is prepared from nature, or the application of nano-silver is certainly a one of the most extensive materials research. 纳米银材料除了具备一般的纳米材料的特性外，在光学材料方面，纳米银颗粒显著的表面等离子体共振效应，此效应能够增强纳米银颗粒内部及其周围区域的电磁场，可用于开发光子晶体材料，如纳米银半导体。 Nano-silver material addition to the general properties of nanomaterials, but in terms of optical materials, nano-silver particles significant surface plasmon resonance effect, this effect can be enhanced internal nano-silver particles and electromagnetic field around the area can be used to develop photonic crystal material , such as nano silver semiconductors. 同时，由于纳米银颗粒具有很强的荧光发射特性，可用于生物检测、标记及生物和化学传感器的开发等；在热力学性质方面，显示出尺寸效应和形状效应。 Meanwhile, the nano-silver particles have a strong fluorescence emission characteristics, can be used for biological testing, marking and development of biological and chemical sensors and the like; thermodynamic properties in terms of showing the effect size and shape effects. 随着纳米银材料尺寸的减小纳米银材料的结合能、熔解焓以及相对应的标准热力学函数如AM、△兄和Δg。 With the binding energy, melting enthalpy and standard thermodynamic functions corresponding reduction in size of nano-silver material, such as nano-silver material AM, △ brother and Δg. 均降低，而K0增大等。 They were lower, while K0 increases and so on. 纳米银材料热力学性质在各方面与块体银材料均有一定的差异性，因此研究纳米银材料的热力学性质具有极其重要的科学意义和应用价值。 Thermodynamic properties of nano-silver in all respects with the bulk silver materials have some differences, therefore the thermodynamic properties of nano-silver material has an extremely important scientific significance and value.

[0003] 纳米银的传统制备方法主要包括物理法、化学法及物理化学结合的综合方法。 Traditional production of [0003] nanosilver include an integrated approach physical, chemical and physico-chemical binding. 最早制备制备纳米银的方法是物理法，此方法制备的纳米银的纯度较高，但是产量低、资金投入大、能耗大。 Preparation method first nano-silver is a physical method, this method of preparing high purity nano-silver, but the yield is low, capital investment, high energy consumption. 主要制备方法有高能机械球磨法、光照法、辐射法、电弧法、蒸发冷凝法等。 The main preparation methods are high-energy mechanical milling method, light, radiation, arc, evaporation condensation method. Xu J,Yin JS等在-196°C的超低温下对银粉进行高能机械球磨，得到了平均粒径约为20nm的纳米银颗粒；杜勇等把金属银放在波长1064nm的Nd:YAG激光器下,通过控制光照时间制备出5-20nm的银胶体粒子。 Xu J, Yin JS, etc. at extremely low temperatures of -196 ° C high energy mechanical milling of silver, to give an average particle size of about silver nanoparticles of 20nm; DU Yong and other metal silver on the wavelength of 1064nm Nd: YAG laser under By controlling the illumination time to prepare a silver colloidal particles 5-20nm of. 所制得的银胶体的稳定性很好，放置数周也未出现聚沉物；辐射法制备纳米材料是利用电离辐射，一般是利用钴60辐射源产生的Y高能射线使水产生电离和激发，生成还原性粒子H自由基和水合电子以及氧化性粒子OH自由基。 The stability of the obtained silver colloid good place for several weeks have not coagulating substance appears; Remarks radiation method is the use of ionizing radiation nanomaterials are generally high energy use cobalt 60 radiation source Y rays produced water ionization and excitation generating reducing particle H radical and hydrated electron and oxide particles OH radicals. 利用这些还原性粒子可逐步把银离子还原为纳米银颗粒。 Reducing the use of these particles can gradually reduce silver ion nano-silver particles. 崔国士等人采用Y射线辐射液相还原制备纳米银溶胶。 Cuiguo Shi, who used Y-ray radiation phase synthesis of nanocrystalline silver sol. 在较低的吸收剂量、较高的聚乙烯醇浓度(7.5%)、较低的硝酸银浓度(0.01mol/L)和适宜的异丙醇浓度(0.5mol/L)有利于获得平均粒径较小(10_30nm)、单分散、无聚集的纳米银溶胶；段志伟等采用自行研制的直流电弧等离子体蒸发设备制备的银粉纯净无污染，属多晶型结构，呈球链状形态。 At lower absorbed dose, the higher the concentration of polyvinyl alcohol (7.5%), a lower concentration of silver nitrate (0.01mol / L) and the appropriate concentration of isopropyl alcohol (0.5mol / L) in favor of an average particle size small (10_30nm), monodisperse, non-aggregated nano silver sol; segment Zhiwei, etc. prepared by DC arc plasma evaporation device developed silver clean pollution, is a multi-crystal structure, was ball-chain form. 平均粒径在38-220nm范围内。 The average particle size in the range 38-220nm. 粒径分布窄。 Narrow particle size distribution. 最大产率比同类研究结果提高了近17倍。 The maximum yield than comparable findings increased nearly 17-fold.

[0004] 魏智强等采用阳极弧放电等离子体蒸发冷凝法制备银纳米粉末，在最佳工艺条件下:热功率3kw、气压0.3-2kPa、Ar气氛、弧电压20-30V、弧电流70-150A、水冷制备的银纳米粉末粒径在20nm左右且纯度高、分散性好。 [0004] 魏智强 such as the use of the anode arc discharge plasma evaporation condensation Preparation of silver nano powder under optimum conditions: the thermal power 3kw, pressure 0.3-2kPa, Ar atmosphere, arc voltage 20-30V, arc current 70-150A, silver nano powder size of about 20nm prepared cooling and high purity, good dispersion.

[0005] 面对物理化学法制备纳米银颗粒存在的各种弊端，再加上当今社会所追求的低碳和绿色环保生活。 [0005] The face of physical chemical method nano silver particles are present in a variety of drawbacks, plus today's society the pursuit of low-carbon and green living. 绿色还原制备纳米银颗粒成为人们追求的方向。 Green synthesis of nanocrystalline silver particles become the pursuit of direction. 发明内容 DISCLOSURE

[0006] 本发明的目的是提出一种利用葡萄柚汁液还原出硝酸银溶液中的银离子的方法。 Objective [0006] The present invention is to propose a reduction of the use of grapefruit liquid silver nitrate solution of silver ions approach.

[0007] 为了实现上述目的本发明采用如下技术方案: [0007] To achieve the above object of the present invention adopts the following technical scheme:

[0008] 一种利用葡萄柚汁液还原出硝酸银溶液中的银离子的方法，其特征在于，包括以下步骤: [0008] A reduction of the use of grapefruit liquid silver nitrate solution method of silver ions, characterized in that it comprises the following steps:

[0009] (I)取新鲜葡萄柚，去皮，取30g左右葡萄柚果粒加60g左右蒸馏水压榨后，用布氏漏斗抽滤得汁液，并用离心机低速离心制得上清液，所得上清液即为现榨葡萄柚汁液，全部放在烧杯中密封保存备用； [0009] (I) Fresh grapefruit, peeled grapefruit take about 30g 60g distilled water and add the fruit after about squeezing juice obtained Buchner funnel filtration and centrifuge low speed centrifugation to obtain the supernatant, the resulting supernatant liquid is squeezed grapefruit juice, all in a beaker sealed spare;

[0010] (2)在30°C左右的恒温水浴中，取20mL左右现榨葡萄柚汁液与20mL左右的0.01-0.lmol/L的硝酸银溶液混合均匀后在50mL的小烧杯中进行反应,将上述反应液放置48小时后，用高速离心机分离出沉淀，再用无水乙醇洗涤沉淀后并经过高速离心机离心得到产物。 [0010] (2) at a constant temperature of about 30 ° C water bath, and take about 20mL and 20mL freshly squeezed grapefruit juice was about 0.01-0.lmol / L silver nitrate solution was mixed uniformly reacted in 50mL of a small beaker , The reaction was allowed to stand for 48 hours, the precipitate was separated by high-speed centrifuge, washed with anhydrous ethanol precipitated and subjected to high-speed centrifuge to give the product.

[0011] 所述的一种利用葡萄柚汁液还原出硝酸银溶液中的银离子的方法，其特征在于，包括以下步骤: [0011] A liquid using the grapefruit juice reduction of silver nitrate solution method of silver ions, characterized in that it comprises the following steps:

[0012] ( I)取新鲜葡萄柚，去皮，取30g葡萄柚果粒加60g蒸馏水压榨后，用布氏漏斗抽滤得汁液，并用离心机低速离心制得上清液，所得上清液即为现榨葡萄柚汁液，全部放在烧杯中S封保存备用； After [0012] (I) Fresh grapefruit, peeled, take 30g 60g distilled water squeezed grapefruit fruit plus a Buchner funnel filtration to obtain juice, and low-speed centrifuge supernatant obtained by centrifugation, the resulting supernatant liquid is squeezed grapefruit juice, all in a beaker sealed and stored at S;

[0013] (2)在30°C的恒温水浴中，取20mL现榨葡萄柚汁液与20mL的0.01-0.lmol/L的硝酸银溶液混合均匀后在50mL的小烧杯中进行反应,将上述反应液放置48小时后,用高速离心机分离出沉淀，再用无水乙醇洗涤沉淀后并经过高速离心机离心得到产物。 [0013] (2) at 30 ° C in the water bath, freshly squeezed grapefruit juice was taken 20mL and 20mL of 0.01-0.lmol / L silver nitrate solution was mixed uniformly reacted in 50mL of a small beaker, the above The reaction was allowed to stand for 48 hours, the precipitate was separated by high-speed centrifuge, washed with anhydrous ethanol precipitated and centrifuged to give the product through high-speed centrifuge.

[0014] 银纳米颗粒形成机理的探讨: [0014] Silver nanoparticles formation mechanism discussed:

[0015] 葡萄柚汁液中主要含有胡萝卜素，B族维生素、维生素C，糖类、挥发油、蛋白质、谷氨酸(Glu)、天冬氨酸(Asp)、赖氨酸(Lys)、精氨酸(Arg)、苏氨酸(Thr)及有机酸等生物分子等。 [0015] The main liquid grapefruit contains carotene, B vitamins, vitamin C, carbohydrates, volatile oil, protein, glutamate (Glu), aspartic acid (Asp), lysine (Lys), arginine acid (Arg), threonine (Thr) and organic acids and other biological molecules. 由于维生素C及部分氨基酸等生物分子具有还原性，可将一价银离子还原为单质银。 Because vitamin C and some amino acids and other biological molecules with the reduction can be monovalent silver ions are reduced to elemental silver. 生成的银原子在形成晶核以及晶核不断长大的过程中，受到葡萄柚汁液中生物分子的吸附和包裹作用，降低了表面能，从而晶粒继续长大受限，最终形成尺寸为50-100纳米的类球形小颗粒。 Generated during the formation of silver atoms and nuclei in nuclei continue to grow, and by the adsorption effect of grapefruit juice were wrapped in biomolecules, reduced surface energy, and thus continue to grow grains is limited, the final size of 50 is formed -100 nm spherical granules.

[0016] 本发明的有益效果: [0016] The present invention beneficial effects:

[0017] (I)本发明用新鲜压榨的葡萄柚汁液还原出硝酸银溶液中的银离子，操作简便，步骤简单，既环保又安全而且得到的纳米银具有良好的稳定性。 [0017] (I) of the present invention with freshly squeezed grapefruit juice was the reduction of silver nitrate solution of silver ions, simple, simple steps, environmentally friendly and safe and get nanosilver has good stability. 原料容易获得且无毒害，具有良好的应用前景。 Raw materials readily available and non-toxic and has good prospects.

[0018] (2)利用葡萄柚汁液中含有的还原性有机生物分子，能够在温和条件(30°C，常压)下还原出硝酸银溶液中的一价银离子；对反应产物经过多种分析测试表明，得到类球形形貌的面心立方晶系的单质银，粒径在50-100nm之间；葡萄柚汁液中含有的有机还原生物分子对纳米银颗粒的生成起到模板和还原剂的作用，诱导和调控银纳米粒子的生成。 [0018] (2) the use of reducing organic solution containing biomolecules grapefruit juice, it is possible to restore a silver nitrate solution of monovalent silver ions under mild conditions (30 ° C, atmospheric pressure); the reaction product through a variety of analysis test showed that elemental silver spherical morphology get a face-centered cubic system, particle size between 50-100nm; organic reducing solution containing biomolecules grapefruit juice to generate silver nanoparticles play a template and a reducing agent The role of induction and regulation of the generation of silver nanoparticles.

附图说明 Brief Description

[0019] 图1为实施例1的葡萄柚汁液的红外光谱图； [0019] Figure 1 is an infrared spectrum of grapefruit juice solution of Example 1;

[0020]图2为实施例1的葡萄柚汁液的紫外可见光谱图；[0021] 图3为实施例1的反应液的紫外可见光谱图； [0020] Figure 2 is an example embodiment of a liquid grapefruit ultraviolet visible light spectrum; [0021] FIG. 3 is an embodiment of the ultraviolet-visible spectrum of the reaction solution 1;

[0022] 图4为实施例1的本发明产物的扫描电镜图； [0022] Figure 4 is a scanning electron micrograph of the product of the present invention of Example 1;

[0023] 图5为实施例1的本发明产物的X-射线衍射图。 [0023] FIG. 5 is a X- ray diffraction pattern of the product of the invention of Example 1 of the present embodiment.

具体实施方式 DETAILED DESCRIPTION

[0024] 实施例1、 [0024] Example 1,

[0025] I实验试剂及仪器 [0025] I test reagents and equipment

[0026] 试剂:硝酸银，无水乙醇，单质碘，碘化钾，以上均为分析纯；二次蒸馏水；实验所用的水果葡萄柚购于本地水果店； [0026] Reagents: silver nitrate, ethanol, elemental iodine, potassium iodide, which are all analytical grade; double distilled water; fruit grapefruit used in the experiments were purchased from the local fruit shop;

[0027] 仪器:美国NicOlet870型傅立叶变换红外光谱仪，固体KBr压片(扫描范围:4000~40001^，扫描32次，分辨率4CHT1)； [0027] Instrument: US NicOlet870 type Fourier transform infrared spectroscopy, solid KBr tablet (scan range: 4000 to 40001 ^, 32 scans, resolution 4CHT1);

[0028] TU-1901双光束紫外-可见分光光度计，北京普析通用仪器有限责任(扫描范围:19(T800nm，采样间隔:lnm，光谱带宽:2nm，扫描速度:中速，扫描次数:一次，光度模式:Abs)； [0028] TU-1901 double beam UV - visible spectrophotometer, Beijing Purkinje General Instrument Co., Ltd. (scanning range: 19 (T800nm, sampling interval: lnm, spectral bandwidth: 2nm, scan speed: the speed, the number of scans: a , photometric mode: Abs);

[0029] TD6台式多管自动平衡离心机，长沙平凡仪器有限公司(加速电压为80kV)； [0029] TD6 desktop multi-barrel automatic balance centrifuge, Changsha extraordinary Instruments (acceleration voltage of 80kV);

[0030] MAP18XAHF型X射线衍射仪，丹东射线仪器工业公司(测试电压为40kV，电流为IOOmA,扫描速度为4° /min,连续扫描)； [0030] MAP18XAHF type X-ray diffractometer, Dandong-ray machines Industries (test voltage of 40kV, current IOOmA, scanning speed of 4 ° / min, continuous scanning);

[0031] KYKY-EM3200型数字化扫描电子显微镜，北京中科科仪技术发展有限责任公司(加速电压:30kV)； [0031] KYKY-EM3200 digital scanning electron microscope, Section of Beijing Technology Development Co., Ltd. (acceleration voltage: 30kV);

[0032] 电子天平(AB104-N，Max=IOlg, d=0.1mg)； [0032] The electronic balance (AB104-N, Max = IOlg, d = 0.1mg);

[0033] HH-S6恒温水浴锅，金坛市鑫诺实验仪器厂(水温控制在30°C )。 [0033] HH-S6 temperature water bath, Jintan Sino Experimental Instrument Factory (water temperature controlled at 30 ° C).

[0034] 2葡萄柚汁液的提取 Grapefruit extract solution [0034] 2

[0035] 取新鲜葡萄柚，去皮，取30g柚子果粒加60g蒸馏水压榨成果汁。 [0035] Fresh grapefruit, peeled, plus 60g 30g of distilled water squeezed grapefruit fruit into juice. 用布氏漏斗抽滤得果汁，并用离心机低速离心制得SOmL上清液。 Buchner funnel filtration to obtain the juice, and low-speed centrifuge SOmL supernatant obtained by centrifugation. 将该实验平行进行5-10组，所得上清液全部放在烧杯中密封保存备用。 The experiments carried out in parallel 5-10 group, the resulting supernatant was placed in a beaker of all sealed spare.

[0036] 3银纳米颗粒的制取 [0036] 3 Preparation of silver nanoparticles

[0037] 取一定量的硝酸银(1.6990g)固体，放在烧杯中加入蒸馏水溶解后，转移入规格为IOOmL的容量瓶中配制成0.lmol/L的硝酸银溶液。 After the [0037] certain amount of silver nitrate (1.6990g) solids, was added to distilled water in a beaker, transferred into a volumetric flask specifications for IOOmL formulated 0.lmol / L of silver nitrate solution. 将此溶液稀释成体积均为50mL的浓度不低于0.01mol/L的一系列硝酸银溶液。 This solution was diluted to a volume of 50mL concentrations are not less than a series of silver nitrate solution 0.01mol / L of. 在30°C恒温水浴中，取20mL现榨葡萄柚汁液与20mL0.1-0.01mol/L的硝酸银溶液混合在50mL的小烧杯中进行反应。 In 30 ° C water bath, take 20mL squeezed grapefruit juice was mixed with 20mL0.1-0.01mol / L silver nitrate solution was reacted in a mixed 50mL small beaker. 定时测定反应液的紫外吸收光谱。 Timing reaction solution was measured by UV absorption spectrum. 将上述反应液放置48h后，用离心机高速离心分离出沉淀，再用无水乙醇洗涤沉淀后并经过离心机离心得到产物。 After the reaction mixture was placed above 48h, with a high speed centrifuge separated the precipitate by centrifugation, washed with anhydrous ethanol precipitated and centrifuged to give the product through. 将上述实验平行进行10-20组，以获得足够的产物，干燥后进行扫描电子显微镜、红外光谱和X-射线衍射测试。 The above experiments 10-20 parallel groups, in order to obtain sufficient product, scanning electron microscopy, infrared spectroscopy and X- ray diffraction after drying.

[0038] 4Vc含量的粗略计算 [0038] A rough calculation 4Vc Content

[0039] 取20mL现榨葡萄柚汁液、IOOmL 二次水、10mL2mol/L HAc和IOmL0.5%淀粉，将它们全部加入到250mL锥形瓶中，混合均匀后，用I2标准溶液[1/2 (I2)=0.lmol/L]进行滴定，以确定上述葡萄柚汁液中Vc的含量。 [0039] Take 20mL liquid squeezed grapefruit juice, IOOmL secondary water, 10mL2mol / L HAc and IOmL0.5% starch, they are all added to 250mL conical flask, uniformly mixed with I2 standard solution [1/2 (I2) = 0.lmol / L] was titrated to determine the above-mentioned solution Vc content of grapefruit juice. 平行滴定三次。 Three parallel titration. 所用I2标准溶液的体积分别为:1.51mL、L 57mL、L 63mL，平均体积为L 57mL。 I2 volume of standard solution used were: 1.51mL, L 57mL, L 63mL, average volume of L 57mL.

[0040]因此，Vc 含量为:Vc%=CI2VI2176.12/20=0.1543mg/mL。 [0040] Thus, Vc content: Vc% = CI2VI2176.12 / 20 = 0.1543mg / mL. [0041] 5结果与讨论 [0041] 5 Results and Discussion

[0042] 5.1葡萄柚汁液的红外光谱分析 [0042] 5.1 grapefruit juice liquid Infrared Spectroscopy

[0043] 在葡萄柚汁液中有许多种生物分子，如蛋白质、维生素和多糖等。 [0043] There are many kinds of biological molecules in grapefruit juice solution, such as protein, vitamins and polysaccharides. 图1为葡萄柚汁液汁液滴在KBr固体上，晾干后压片所测得的红外光谱图。 Figure 1 is a grapefruit juice droplets on KBr solid, dry tableting measured infrared spectra. 图中1621CHT1处吸收峰对应于蛋白酰胺I带的C=O基团的伸缩振动，1250cm-1处的吸收峰则为蛋白酰胺III带上的CN弯曲振动。 Figure 1621CHT1 absorption peak corresponding to C = O group of the amide I band stretching protein absorption peak at 1250cm-1, compared with protein amide III band CN bending vibration. 1413CHT1和1055CHT1处吸收峰则可能分别为蛋白、维生素或多糖分子中C-OH基团的弯曲振动和COC基团的不对称伸缩振动。 1413CHT1 and 1055CHT1 absorption peak may respectively asymmetric protein, vitamins or polysaccharide molecule bending vibration C-OH group and a group COC stretching vibration. 2930cm—1处可能为甲基的特征伸缩振动吸收带。 2930cm-1 may be methyl 处 characteristic stretching vibration absorption band. 3379CHT1处可能是NH中氢键的特征吸收带。 3379CHT1 at NH hydrogen bond may be characteristic absorption band.

[0044] 5.2葡萄柚汁液的紫外可见光谱分析 UV [0044] 5.2 grapefruit juice was visible spectroscopy

[0045] 图2为测得的葡萄柚汁液的紫外可见光谱图。 [0045] FIG. 2 is a UV grapefruit juice was measured in the visible light spectrum. 从图中可以看出，在210nm和280nm处出现了两个吸收峰，分别对应着蛋白质或氨基酸等肽键上C=O基η- π *的电子跃迁和蛋白酪氨酸、色氨酸或者苯基丙氨酸残基上π ^的电子跃迁，表明葡萄柚汁液中含有蛋白质、氨基酸等生物分子。 As can be seen from the figure, there were two absorption peaks at 210nm and at 280nm, corresponding to a protein or amino acid peptide bond C = O group η- π * electronic transition and protein tyrosine, tryptophan or π ^ on phenylalanine residues electronic transition indicates grapefruit juice solution containing proteins, amino acids and other biological molecules.

[0046] 5.3反应液的紫外可见光谱分析 UV [0046] 5.3 the reaction liquid visible spectroscopy

[0047] 图3为测得的放置不同时间的反应液的紫外可见光谱图。 UV reaction solution [0047] Figure 3 is measured at different times to place visible spectrum. 从图中可以看出，在440nm处明显出现了一个吸收峰，并且该吸收峰的强度随反应时间的增加而逐渐增强。 As can be seen from the figure, a marked at 440nm at an absorption peak, and the intensity of the absorption peak increases with time and the reaction gradually increased. 这个吸收峰被认为是银纳米颗粒的特征吸收峰，它是由于溶液中银纳米颗粒的径向表面增强拉曼共振引起的。 The absorption peak is considered to be characteristic absorption peak of silver nanoparticles, which is due to the solution of silver nanoparticles radial surface enhanced Raman resonance caused. 这说明随着反应时间的延长，产物银纳米颗粒的量在不断增加。 This shows that with the extension of reaction time, the amount of product silver nanoparticles is increasing.

[0048] 5.4产物的扫描电镜分析 Scanning electron microscopy (SEM) [0048] 5.4 product

·[0049] 图4为含0.05mol/L硝酸银和葡萄柚汁液的反应液在30°C条件下反应48小时所得产物的扫描电镜图。 * [0049] Figure 4 is a reaction solution containing 0.05mol / L silver nitrate solution and grapefruit juice resulting product of the reaction 48 hours at 30 ° C conditions SEM FIG. 从图中可以看出，产物为类球形的小颗粒，粒子尺寸在50-100nm之间。 As can be seen from the figure, the small spherical particles as the product, the particle size between 50-100nm. 图中出现的较大的颗粒是由于小的纳米颗粒发生聚集而形成的。 Larger particles appear in the figure is due to the small aggregation of nanoparticles formed.

[0050] 5.5产物的X-射线衍射分析 [0050] X- ray diffraction analysis of the product 5.5

[0051] 图5为含0.05mol/L硝酸银和葡萄柚汁液的反应液在30°C条件下反应48小时所得产物的X-射线衍射图。 [0051] FIG. 5 is a reaction solution containing 0.05mol / L silver nitrate solution and grapefruit reaction conditions at 30 ° C 48 hours X- ray diffraction pattern of the resulting product. 由图可见，在2 Θ为38.24° ,44.43° ,64.66° ,77.63° ,81.78°时出现了5个衍射峰，对照标准卡片(JCPDS87-0720)可以发现分别对应面心立方型银单质的(111)、( 200 )、( 220 )、( 311)和(222 )面的特征衍射，表明产物为面心立方结构的银单质。 The figure shows, in 2 Θ is 38.24 °, 44.43 °, 64.66 °, there have been five diffraction peaks 77.63 °, 81.78 °, the reference standard card (JCPDS87-0720) can be found corresponding to the face-centered cubic elemental silver (the 111), (200), (220), (311) and features (222) plane diffraction showed the product to elemental silver face-centered cubic structure.

[0052] 5.6银纳米颗粒形成机理的探讨 [0052] 5.6 investigate the formation mechanism of silver nanoparticles

[0053] 葡萄柚汁液中主要含有胡萝卜素，B族维生素、维生素C，糖类、挥发油、蛋白质、谷氨酸(Glu)、天冬氨酸(Asp)、赖氨酸(Lys)、精氨酸(Arg)、苏氨酸(Thr)及有机酸等生物分子等。 [0053] The main liquid grapefruit contains carotene, B vitamins, vitamin C, carbohydrates, volatile oil, protein, glutamate (Glu), aspartic acid (Asp), lysine (Lys), arginine acid (Arg), threonine (Thr) and organic acids and other biological molecules. 由于维生素C及部分氨基酸等生物分子具有还原性，可将一价银离子还原为单质银。 Because vitamin C and some amino acids and other biological molecules with the reduction can be monovalent silver ions are reduced to elemental silver. 生成的银原子在形成晶核以及晶核不断长大的过程中，受到葡萄柚汁液中生物分子的吸附和包裹作用，降低了表面能，从而晶粒继续长大受限，最终形成尺寸为50-100纳米的类球形小颗粒。 Generated during the formation of silver atoms and nuclei in nuclei continue to grow, and by the adsorption effect of grapefruit juice were wrapped in biomolecules, reduced surface energy, and thus continue to grow grains is limited, the final size of 50 is formed -100 nm spherical granules.

[0054] 6 结论 [0054] 6. Conclusions

[0055] 利用葡萄柚汁液中含有的多种生物分子，在温和条件下(30°C，常压)将硝酸银溶液中的一价银离子还原为单质银。 [0055] The use of a variety of grapefruit juice solution containing biomolecules, in (30 ° C, atmospheric pressure) under mild conditions in the silver nitrate solution monovalent silver ions are reduced to elemental silver. 经过多种分析测试后发现，所得产物为面心立方晶系的单质银，粒径在50-100nm之间。 After a variety of analytical testing found that the resulting product is a face-centered cubic crystal elemental silver, diameter between 50-100nm. 对银纳米颗粒的形成机理进行了探讨，表明葡萄柚汁液中含有的生物分子对单质银颗粒的生成起到模板和还原剂的作用，诱导和调控银纳米粒子的生成。 The formation mechanism of silver nanoparticles were discussed, indicating grapefruit juice solution containing biomolecules to generate elemental silver particles act as a template and a reducing agent, to induce and modulate formation of silver nanoparticles.

[0056] 实施例2、 [0056] Example 2,

[0057] 所述的一种利用葡萄柚汁液还原出硝酸银溶液中的银离子的方法，包括以下步骤: [0057] The use of grapefruit juice was a reduction of silver nitrate solution of silver ions, comprising the steps of:

[0058] (I)取新鲜葡萄柚，去皮，取30g葡萄柚果粒加60g蒸馏水压榨后，用布氏漏斗抽滤得汁液，并用离心机低速离心制得上清液，所得上清液即为现榨葡萄柚汁液，全部放在烧杯中S封保存备用； After [0058] (I) Fresh grapefruit, peeled, take 30g 60g distilled water squeezed grapefruit fruit plus a Buchner funnel filtration to obtain juice, and low-speed centrifuge supernatant obtained by centrifugation, the resulting supernatant liquid is squeezed grapefruit juice, all in a beaker sealed and stored at S;

[0059] (2)在30°C的恒温水浴中，取20mL现榨葡萄柚汁液与20mL的0.01-0.lmol/L的硝酸银溶液混合均匀后在50mL的小烧杯中进行反应,将上述反应液放置48小时后,用高速离心机分离出沉淀，再用无水乙醇洗涤沉淀后并经过高速离心机离心得到产物。 [0059] (2) at 30 ° C in the water bath, freshly squeezed grapefruit juice was taken 20mL and 20mL of 0.01-0.lmol / L silver nitrate solution was mixed uniformly reacted in 50mL of a small beaker, the above The reaction was allowed to stand for 48 hours, the precipitate was separated by high-speed centrifuge, washed with anhydrous ethanol precipitated and centrifuged to give the product through high-speed centrifuge.