CN102077865A - Titanium dioxide nano particle and litchi nano preservative - Google Patents
Titanium dioxide nano particle and litchi nano preservative Download PDFInfo
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- CN102077865A CN102077865A CN2010105543542A CN201010554354A CN102077865A CN 102077865 A CN102077865 A CN 102077865A CN 2010105543542 A CN2010105543542 A CN 2010105543542A CN 201010554354 A CN201010554354 A CN 201010554354A CN 102077865 A CN102077865 A CN 102077865A
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- titanium dioxide
- litchi
- lychee
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 34
- 241001629511 Litchi Species 0.000 title claims abstract 11
- 239000003755 preservative agent Substances 0.000 title abstract description 21
- 239000004408 titanium dioxide Substances 0.000 title abstract description 17
- 230000002335 preservative effect Effects 0.000 title abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 150000003608 titanium Chemical class 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims 4
- 238000009413 insulation Methods 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims 1
- 239000001488 sodium phosphate Substances 0.000 claims 1
- 239000013638 trimer Substances 0.000 claims 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 244000183278 Nephelium litchi Species 0.000 abstract description 55
- 235000015742 Nephelium litchi Nutrition 0.000 abstract description 40
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 23
- 238000004321 preservation Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
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- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
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- 239000002086 nanomaterial Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
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- 239000005416 organic matter Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
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- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
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- 244000241235 Citrullus lanatus Species 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Storage Of Fruits Or Vegetables (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种二氧化钛纳米颗粒及荔枝纳米保鲜剂。所述二氧化钛纳米颗粒是采用无机钛盐在碱性条件下水解得到的沉淀用氧化剂处理后,加入贵金属离子保温处理得到的,所述二氧化钛纳米颗粒尺寸为6~10nm,晶粒尺寸为锐钛矿相。所述荔枝纳米保鲜剂是将鲜荔枝液添加至所述二氧化钛纳米颗粒溶液中,搅拌均匀后即得。本发明将所述的掺杂纳米二氧化钛颗粒与鲜荔枝液混配得到荔枝纳米保鲜剂为绿色环保制剂,无任何毒副作用,30~60天后荔枝果实没有任何异味和变色,保持原有的新鲜味道。其成本为每公斤荔枝所用的保鲜剂为0.05元左右,具有保鲜时间长、成本低、较好的保持荔枝鲜美味道等有益效果。
The invention discloses a titanium dioxide nano particle and a litchi nano preservative. The titanium dioxide nanoparticles are obtained by using the precipitation obtained by hydrolysis of inorganic titanium salts under alkaline conditions, after being treated with an oxidant, and then adding noble metal ions for heat preservation treatment. The size of the titanium dioxide nanoparticles is 6-10 nm, and the grain size is anatase Mutually. The lychee nano preservative is obtained by adding fresh lychee liquid into the titanium dioxide nano particle solution and stirring evenly. In the present invention, the lychee nano preservative is obtained by mixing the doped nano-titanium dioxide particles with fresh lychee liquid, which is a green and environmentally friendly preparation without any toxic and side effects. After 30 to 60 days, the lychee fruit has no peculiar smell and discoloration, and the original fresh taste is maintained. . Its cost is about 0.05 yuan per kilogram of lychees, and has beneficial effects such as long fresh-keeping time, low cost, better keeping lychees delicious taste, and the like.
Description
技术领域technical field
本发明属于水果保鲜技术领域,具体涉及一种二氧化钛纳米颗粒及其在荔枝保鲜方面的应用。The invention belongs to the technical field of fruit preservation, and in particular relates to a titanium dioxide nanoparticle and its application in litchi preservation.
背景技术Background technique
荔枝成熟期正值盛夏高温季节,果实极不耐贮藏。荔枝每年因腐烂变质而造成的损失占总产量的20%以上。因此当荔枝采后必须进行贮藏保鲜。目前,在荔枝速冻冷藏保鲜方面,基本能保证果品贮存半年或更长时间。然而在常温保鲜方面,尚未取得重大突破。目前,国内外在常温贮藏研究方面主要偏重于防腐剂、保鲜剂的筛选和应用,但是保温时间一般不超过7~8d,且要结合常规的药物防腐,如苯来特、特克多、灭菌威等。由于这些药物具有一定的毒性和残留量,会影响人体健康。国外主要采用熏硫方法进行荔枝常温保鲜,虽能有效地保持果实颜色,但对某些真菌并不能完全杀灭,导致口感变差,影响人们身心健康。因此,急需研制一种无毒、防失水、防褐变、防腐、防病害和延长衰老的保鲜剂。The ripening period of litchi coincides with the high temperature season in midsummer, and the fruit is extremely intolerant to storage. The annual loss of litchi due to rot and deterioration accounts for more than 20% of the total output. Therefore must carry out storage and fresh-keeping after lychee is gathered. At present, in terms of quick-frozen and refrigerated preservation of lychee, it can basically guarantee the fruit to be stored for half a year or longer. However, no major breakthrough has been made in terms of fresh-keeping at room temperature. At present, domestic and foreign studies on storage at room temperature mainly focus on the screening and application of preservatives and preservatives, but the holding time generally does not exceed 7 to 8 days, and it must be combined with conventional drug preservation, such as benlaite, Tecdo, and methionine. Bacteria etc. Because these drugs have certain toxicity and residual amount, they will affect human health. Foreign countries mainly adopt the method of sulfur fumigation to keep litchi fresh at room temperature. Although it can effectively maintain the color of the fruit, it cannot completely kill some fungi, resulting in poor taste and affecting people's physical and mental health. Therefore, be badly in need of developing a kind of antistaling agent that is nontoxic, prevents dehydration, prevents browning, anticorrosion, prevents diseases and prolongs aging.
当前,纳米材料发展迅速,纳米材料具有很多不同于常规材料的优异特性,如高比表面积、量子效应、特殊的光、热、磁学等性质。因此,如何充分有效地将纳米材料应用于食品科学,并有效地开发和利用,是纳米材料应用的方向之一。At present, nanomaterials are developing rapidly, and nanomaterials have many excellent properties different from conventional materials, such as high specific surface area, quantum effect, special optical, thermal, magnetic and other properties. Therefore, how to fully and effectively apply nanomaterials to food science, and effectively develop and utilize them is one of the directions for the application of nanomaterials.
目前,应用于果蔬保鲜方面的纳米材料主要有纳米氧化硅、纳米二氧化钛、银系纳米材料等。适量的纳米SiOx颗粒加入可以形成纳米抗菌薄膜,利用硅氧键对CO2和O2吸附、溶解、扩散和释放作用,调节膜内外CO2和O2的交换量,从而抑制果蔬呼吸强度,起到保鲜保水的作用。纳米抗氧化剂、抗菌剂应用于保鲜包装材料可以提高新鲜果蔬的保鲜效果和延长保鲜时间。纳米系列银粉可以有效的延长抗菌时间,加速氧化果蔬释放出的乙烯,降低包装中乙烯的含量,从而达到良好的保鲜效果。而纳米TiO2具有良好的光催化性能,它一方面能够将果蔬贮藏中产生的乙烯氧化分解成二氧化碳和水;另一方面可以杀死细菌等微生物,因此可以有效延长果蔬保鲜时间。有文献报道纳米二氧化钛果蔬保鲜剂,通常是将三乙醇胺溶于水,加入纳米二氧化钛,高速搅拌,使纳米二氧化钛均匀分散于三乙醇胺水溶液中,并加热到90℃,再将巴西棕榈蜡和油酸混合,加热到90℃,搅拌均匀,将纳米二氧化钛的三乙醇胺溶液与巴西棕榈蜡和油酸混合液混和得到一种纳米果蔬保鲜剂,可分别喷涂于苹果、柑橘、香蕉、樱桃、西红柿、长茄、西瓜等各种果蔬上,在其表面形成光泽性涂膜用于保鲜;专利申请号为200610155124.2的专利申请公开了一种纳米果蔬常温保鲜剂及其制备方法,所述保鲜剂由下述重量百分比的原料组成:纳米二氧化钛0.5~10%、纳米银钛0.01~1%、白云母5~20%、对羟基苯甲酸乙酯与对羟基甲酸丙酯的混合物0.05~1%、铁粉1~5%、桂醛0.001~0.01%、活性炭2~7%,其余为载体。但上述保鲜剂都采用有机物成分,有机物长期附着于荔枝表面,通过渗透容易进入果肉中以产生不良反应,影响人体健康。At present, nano-materials used in fruit and vegetable preservation mainly include nano-silicon oxide, nano-titanium dioxide, and silver-based nano-materials. Adding an appropriate amount of nano-SiOx particles can form a nano-antibacterial film, which uses the silicon-oxygen bond to absorb, dissolve, diffuse and release CO 2 and O 2 , and adjust the exchange volume of CO 2 and O 2 inside and outside the film, thereby inhibiting the respiration intensity of fruits and vegetables. To the role of freshness and water retention. The application of nano-antioxidants and antibacterial agents in fresh-keeping packaging materials can improve the fresh-keeping effect and prolong the fresh-keeping time of fresh fruits and vegetables. Nano-series silver powder can effectively prolong the antibacterial time, accelerate the oxidation of ethylene released by fruits and vegetables, and reduce the ethylene content in packaging, so as to achieve a good fresh-keeping effect. Nano-TiO 2 has good photocatalytic performance. On the one hand, it can oxidize and decompose ethylene produced in the storage of fruits and vegetables into carbon dioxide and water; on the other hand, it can kill bacteria and other microorganisms, so it can effectively prolong the preservation time of fruits and vegetables. It has been reported in the literature that nano-titanium dioxide fruit and vegetable preservatives are usually dissolved in water with triethanolamine, added with nano-titanium dioxide, and stirred at a high speed, so that nano-titanium dioxide is evenly dispersed in the triethanolamine aqueous solution, and heated to 90 ° C, and then carnauba wax and oleic acid Mix, heat to 90°C, stir evenly, mix the triethanolamine solution of nano-titanium dioxide with carnauba wax and oleic acid mixture to obtain a nano-fruit and vegetable preservative, which can be sprayed on apples, citrus, bananas, cherries, tomatoes, long On various fruits and vegetables such as eggplant, watermelon, on its surface form glossy film and be used for keeping fresh; Raw material composition in weight percentage: 0.5-10% of nano-titanium dioxide, 0.01-1% of nano-silver titanium, 5-20% of muscovite, 0.05-1% of a mixture of ethyl p-hydroxybenzoate and propyl p-hydroxyformate, and 1% of iron powder ~5%, cinnamaldehyde 0.001~0.01%, activated carbon 2~7%, and the rest are carriers. But above-mentioned antistaling agent all adopts organic matter composition, and organic matter is attached to litchi surface for a long time, easily enters in the pulp by infiltration to produce untoward reaction, affects human health.
发明内容Contents of the invention
本发明的一个目的是克服现有纳米保鲜技术的不足,提供一种纯水溶性的二氧化钛纳米颗粒,其制备方法简单,且任何有机污染物。通过改性后可提高其在可见光下的抗菌及对荔枝的保鲜功能,延长保鲜寿命。An object of the present invention is to overcome the deficiencies of the existing nano-preservation technology, and provide a pure water-soluble titanium dioxide nanoparticle, which has a simple preparation method and is free from any organic pollutants. After modification, its antibacterial under visible light and its fresh-keeping function on litchi can be improved, and the fresh-keeping life can be prolonged.
本发明的另一个目的是将所述二氧化钛纳米颗粒与天然保鲜剂结合获得一种生态环保具有更好常温保鲜功能的纳米保鲜剂。Another object of the present invention is to combine the titanium dioxide nanoparticles with a natural antistaling agent to obtain an eco-friendly nano antistaling agent with better room temperature preservation function.
本发明的目的通过以下技术方案予以实现:The purpose of the present invention is achieved through the following technical solutions:
提供一种二氧化钛纳米颗粒,平均颗粒尺寸为6~10nm,晶相为锐钛矿相,采用无机钛盐在碱性条件下水解得到的沉淀用氧化剂处理后,加入贵金属离子保温处理得到。纳米颗粒自然稳定地均分散于水溶液中,无需任何有机分散剂和稳定剂。优选的方案是无机钛盐、氧化剂和贵金属化合物的重量比例为1~2∶10~20∶0.05~0.1。Provided is a titanium dioxide nanoparticle, the average particle size is 6-10nm, the crystal phase is anatase phase, and the precipitation obtained by hydrolyzing inorganic titanium salt under alkaline conditions is treated with an oxidant, and is obtained by adding noble metal ions for heat preservation. Nanoparticles are naturally and stably dispersed in aqueous solution without any organic dispersants and stabilizers. The preferred scheme is that the weight ratio of the inorganic titanium salt, the oxidizing agent and the noble metal compound is 1-2:10-20:0.05-0.1.
本发明所述无机钛盐优选硫酸氧钛、四氯化钛或硫酸钛;所述贵金属离子优选Ag、Ce、Gd等金属离子,可选用化合物AgNO3,Ce(NO3)3,Gd(NO3)3等;所述氧化剂为硝酸或双氧水中的一种。The inorganic titanium salt of the present invention is preferably titanyl sulfate, titanium tetrachloride or titanium sulfate; the noble metal ions are preferably Ag, Ce, Gd and other metal ions, and the compounds AgNO 3 , Ce(NO 3 ) 3 , Gd(NO 3 ) can be selected. 3 ) 3 etc.; described oxidant is a kind of in nitric acid or hydrogen peroxide.
所述水解是水解至pH值为4~8。The hydrolysis is hydrolysis to a pH value of 4-8.
本发明所述二氧化钛纳米颗粒的制备方法包括以下步骤:The preparation method of titanium dioxide nanoparticles of the present invention comprises the following steps:
(1)将无机钛盐在碱性条件下水解至pH为4~8,然后离心处理后得到白色沉淀;(1) hydrolyzing the inorganic titanium salt to a pH of 4 to 8 under alkaline conditions, and then centrifuging to obtain a white precipitate;
(2)将步骤(1)得到的白色沉淀用去离子水洗涤2~3遍后用氧化剂处理得到棕色透明液体,然后静置6~12h;(2) Wash the white precipitate obtained in step (1) with deionized water for 2 to 3 times, then treat it with an oxidant to obtain a brown transparent liquid, and then let it stand for 6 to 12 hours;
(3)将贵金属化合物加入步骤(2)所述棕色透明液体中,90~100℃保温处理4~8h,得到乳白色纳米二氧化钛溶胶;冷却备用。(3) adding the noble metal compound into the brown transparent liquid described in step (2), and heat-preserving at 90-100° C. for 4-8 hours to obtain a milky white nano-titanium dioxide sol; cool it for later use.
所述二氧化钛纳米颗粒溶液中的纳米二氧化钛颗粒质量百分数含量为1~8%,纳米颗粒的尺寸平均为6~10nm。The mass percent content of the nano-titanium dioxide particles in the titanium dioxide nano-particle solution is 1-8%, and the average size of the nano-particles is 6-10 nm.
本发明同时提供了一种荔枝纳米保鲜剂,包括上述乳白色纳米二氧化钛溶胶、水溶性分散剂和鲜荔枝液,所述水溶性分散剂为六偏磷酸钠或者三聚磷酸钠,所述鲜荔枝液是将鲜荔枝叶加水煮沸得到的水溶液经过浓缩制备得到;按重量计,水溶性分散剂为荔枝纳米保鲜剂总重量的0.3~1.5%;所述鲜荔枝液为保鲜剂总重量的3~10%;The present invention simultaneously provides a nano-preservative for lychees, comprising the above-mentioned milky white nano-titanium dioxide sol, a water-soluble dispersant and fresh lychee liquid, the water-soluble dispersant being sodium hexametaphosphate or sodium tripolyphosphate, and the fresh lychee liquid It is prepared by concentrating the aqueous solution obtained by boiling fresh lychee leaves with water; by weight, the water-soluble dispersant is 0.3-1.5% of the total weight of the litchi nano preservative; the fresh lychee liquid is 3-10% of the total weight of the preservative. %;
所述荔枝纳米保鲜剂的制备方法包括以下步骤:The preparation method of described lychee nano preservative comprises the following steps:
(A)往冷却后的乳白色纳米二氧化钛溶胶加入水溶性分散剂,搅拌均匀,得分散好的二氧化钛纳米颗粒溶液;(A) Add a water-soluble dispersant to the milky white nano-titanium dioxide sol after cooling, stir evenly, and obtain a dispersed titanium dioxide nanoparticle solution;
将鲜荔枝叶加水煮沸得到的水溶液经过浓缩后制得鲜荔枝液;Fresh lychee liquid is prepared by concentrating the aqueous solution obtained by boiling fresh lychee leaves with water;
(B)将鲜荔枝液添加至上述步骤(A)制备得到的二氧化钛纳米颗粒溶液中,搅拌均匀后即得。(B) Add fresh lychee liquid to the titanium dioxide nanoparticle solution prepared in the above step (A), and stir evenly.
步骤(A)所述鲜荔枝叶与水的重量比为1~10∶1;煮沸时间优选0.5小时~1小时;可浓缩至原来体积的一半左右。The weight ratio of fresh lychee leaves to water in step (A) is 1-10:1; the boiling time is preferably 0.5-1 hour; it can be concentrated to about half of the original volume.
所述荔枝纳米保鲜剂的使用方法是:The using method of described lychee nano preservative is:
将本发明的纳米保鲜剂装入带有喷头的容器中,然后均匀喷洒于荔枝果实表面1~2次,将处理好的荔枝果实放置于包装盒中即可。Put the nano antistaling agent of the present invention into a container with a spray head, then evenly spray it on the surface of litchi fruit for 1 to 2 times, and put the treated litchi fruit in a packaging box.
本发明的有益效果:Beneficial effects of the present invention:
本发明针对现有技术的不足,本发明提供了一种纯水性无机纳米二氧化钛荔枝保鲜剂,采用水热合成的单分散纳米颗粒,一次水热合成平均颗粒尺寸为6~10nm的锐钛矿相纳米二氧化钛颗粒。保鲜剂中无任何有害成分。为了进一步提高其可见光催化活性,还采用了掺杂技术改性纳米二氧化钛颗粒,提高其可将光下对荔枝表面微生物的抑制或杀死、以及荔枝新陈代谢所释放的乙烯等气体的降解等作用,其具有较好的光催化活性,可以有效杀死荔枝表面的细菌以及去除新陈代谢释放的乙烯气体,具有长期保鲜功能。纳米二氧化钛半导体材料在颗粒尺寸为10nm以下时能吸收紫外光产生自由载流子,这些载流子活性很强,能与颗粒表面存在的氧气和水分子结合形成自由基,这些自由基能进入微生物内部破坏其内部组织,从而杀死细菌。同时,这些自由基能够破坏有机物中的双键、芳香链使有机物裂变而生成二氧化碳和水,从而达到很好的防腐和抑制后熟等作用。本发明纳米二氧化钛光触媒保鲜剂本身为无机物,无毒、无污染,为绿色环保制剂,无任何毒副作用,30~60天后荔枝果实没有任何异味和变色,保持原有的新鲜味道。其成本为每公斤荔枝所用的保鲜剂为0.05元左右,具有保鲜时间长、成本低、较好的保持荔枝鲜美味道等有益效果,具有重大的应用和推广前景。The present invention aims at the deficiencies of the prior art, and the present invention provides a pure water-based inorganic nano-titanium dioxide lychee preservative, which adopts monodisperse nano-particles synthesized by hydrothermal, and anatase with an average particle size of 6-10 nm in one hydrothermal synthesis phase nanoparticles of titanium dioxide. There are no harmful ingredients in the preservative. In order to further improve its visible light catalytic activity, doping technology is also used to modify nano-titanium dioxide particles to improve its ability to inhibit or kill microorganisms on the surface of litchi under light, and to degrade ethylene and other gases released by litchi metabolism. It has good photocatalytic activity, can effectively kill bacteria on the surface of litchi and remove ethylene gas released by metabolism, and has a long-term fresh-keeping function. Nano-titanium dioxide semiconductor materials can absorb ultraviolet light to generate free carriers when the particle size is below 10nm. These carriers are very active and can combine with oxygen and water molecules on the particle surface to form free radicals. These free radicals can enter microorganisms Internally destroys its internal tissues, thus killing bacteria. At the same time, these free radicals can destroy the double bonds and aromatic chains in the organic matter to cause the fission of the organic matter to generate carbon dioxide and water, so as to achieve good anti-corrosion and inhibit post-ripening effects. The nano-titanium dioxide photocatalyst antistaling agent of the present invention is an inorganic substance, non-toxic, non-polluting, green and environmentally friendly preparation, without any toxic and side effects, and after 30 to 60 days, the lychee fruit has no peculiar smell and discoloration, and maintains the original fresh taste. Its cost is about 0.05 yuan per kilogram of lychees, and has beneficial effects such as long fresh-keeping time, low cost, and good preservation of lychees' delicious taste, and has great application and promotion prospects.
附图说明Description of drawings
图1本发明纳米颗粒的SEM图The SEM figure of Fig. 1 nanoparticle of the present invention
图2本发明纳米保鲜剂中纳米颗粒的X射线衍射图The X-ray diffraction figure of nanoparticle in Fig. 2 nano preservative of the present invention
具体实施方式Detailed ways
下面结合具体实施例进一步详细说明本发明。下述实施例中所使用的试验方法和设备如无特殊说明,均为常规方法;所使用的原料,如无特殊说明,为可从商业途径得到的原料。The present invention will be further described in detail below in conjunction with specific examples. The test methods and equipment used in the following examples are conventional methods unless otherwise specified; the raw materials used are commercially available raw materials unless otherwise specified.
实施例1Example 1
将10gTiCl4加入500ml水中,用浓氨水调节pH值为6.2,离心处理(4000r/min)后得到白色沉淀50g,然后将沉淀物质用去离子水洗涤2遍后加入500ml去离子水,再加入10ml硝酸(稀释至体积比浓度为30~50%)经充分搅拌1h后得到透明液体;静置6h后将0.5g AgNO3加入透明液体中,经95℃保温处理4h得到乳白色纳米二氧化钛溶胶,所得二氧化钛纳米颗粒尺寸为6~10nm,晶粒尺寸为锐钛矿相,纳米颗粒的SEM图见附图1所示。Add 10g of TiCl 4 into 500ml of water, adjust the pH value to 6.2 with concentrated ammonia water, and obtain 50g of white precipitate after centrifugation (4000r/min), then wash the precipitated substance twice with deionized water, add 500ml of deionized water, and then add 10ml Nitric acid (diluted to a concentration of 30-50% by volume) was fully stirred for 1 hour to obtain a transparent liquid; after standing for 6 hours, 0.5g AgNO3 was added to the transparent liquid, and treated at 95°C for 4 hours to obtain a milky white nano-titanium dioxide sol, and the obtained titanium dioxide The nanoparticle size is 6-10nm, and the crystal grain size is anatase phase. The SEM picture of the nanoparticle is shown in Fig. 1 .
乳白色纳米二氧化钛溶胶冷却后加入1g六偏磷酸钠搅拌均匀得分散好的溶液A;Add 1g of sodium hexametaphosphate to the milky white nano-titanium dioxide sol after cooling and stir to obtain a well-dispersed solution A;
将1g荔枝叶加入10ml水,煮沸0.5h后得水溶液,采用常规方法浓缩至5ml左右,得到鲜荔枝液5g;Add 1g of lychee leaves to 10ml of water, boil for 0.5h to obtain an aqueous solution, use conventional methods to concentrate to about 5ml, and obtain 5g of fresh lychee liquid;
将2g鲜荔枝液加入2g分散好的溶液A中,搅拌均匀后得到新鲜荔枝纳米保鲜剂。制得的保鲜剂的pH值为5~8;无有机物成分,为环保型纳米保鲜剂。Add 2 g of fresh lychee liquid into 2 g of the dispersed solution A, stir evenly to obtain the fresh lychee nano preservative. The prepared antistaling agent has a pH value of 5-8; has no organic components, and is an environment-friendly nano antistaling agent.
将本发明的纳米保鲜剂,均匀喷洒于新鲜荔枝果实表面,喷洒两次,然后将鲜荔枝果实置于常规包装容器中(不用封闭),30天后打开容器,发现荔枝果实未出现任何异味、变色、疲软等现象。The nano preservative of the present invention is evenly sprayed on the surface of fresh lychee fruit, sprayed twice, and then the fresh lychee fruit is placed in a conventional packaging container (without closing), the container is opened after 30 days, and no peculiar smell or discoloration occurs in the lychee fruit. , Weakness and so on.
实施例2Example 2
将10gTiOSO4加入500ml水中,用浓氨水调节pH为6.8,离心处理后得到(4500r/min)后得到白色沉淀56g,用去离子水洗涤白色沉淀3遍后加入500ml去离子水,再用10ml 30%(体积比浓度)浓度的双氧水经充分搅拌1h后得到透明液体,然后静置6h,将1g Ce(NO3)3加入其中,后经95℃保温处理6h,得到乳白色纳米二氧化钛溶胶,冷却后加入1.5g六偏磷酸钠搅拌均匀得分散好的纳米二氧化钛溶液;Add 10g TiOSO 4 into 500ml water, adjust the pH to 6.8 with concentrated ammonia water, obtain 56g of white precipitate after centrifugation (4500r/min), wash the white precipitate with deionized water 3 times, add 500ml of deionized water, and then use 10ml of 30 % (volume ratio concentration) concentration of hydrogen peroxide was fully stirred for 1 hour to obtain a transparent liquid, then left to stand for 6 hours, 1g Ce(NO 3 ) 3 was added to it, and then treated at 95°C for 6 hours to obtain milky white nano-titanium dioxide sol, after cooling Add 1.5g of sodium hexametaphosphate and stir to obtain a well-dispersed nano-titanium dioxide solution;
所述纳米颗粒尺寸采用透射电子显微镜检测得到,晶相通过X射线晶体衍射仪测定,二氧化钛纳米颗粒平均尺寸为6~10nm,晶相为锐钛矿相。The size of the nanoparticles is detected by a transmission electron microscope, and the crystal phase is measured by an X-ray crystal diffractometer. The average size of the titanium dioxide nanoparticles is 6-10 nm, and the crystal phase is an anatase phase.
将1g荔枝叶加入12ml水,煮沸0.5h后获得的水溶液,浓缩至5ml左右得到鲜荔枝液5g。Add 1g of lychee leaves to 12ml of water, boil the aqueous solution obtained after 0.5h, and concentrate to about 5ml to obtain 5g of fresh lychee liquid.
将2g鲜荔枝液加入3g分散好的分散好的纳米二氧化钛溶液中,经过搅拌均匀后得到新鲜荔枝纳米保鲜剂。Add 2 g of fresh lychee liquid into 3 g of dispersed nano-titanium dioxide solution, and stir evenly to obtain the fresh lychee nano-preservative.
将本发明的纳米保鲜剂,均匀喷洒于需要保鲜的新鲜荔枝果实表面两次,然后置于包装容器中,45天后打开发现荔枝果实未出现任何异味、变色、疲软等现象。The nano preservative of the present invention is evenly sprayed twice on the surface of fresh lychees that need to be kept fresh, and then placed in a packaging container. After 45 days, it is opened to find that the lychees do not have any peculiar smell, discoloration, and weakness.
实施例3Example 3
将10gTi(SO4)2加入500ml水中,用浓氨水调节pH为6.0,离心处理后得到白色沉淀,然后将沉淀物质用去离子水洗涤2遍后加入500ml去离子,再用10ml 30%浓度的双氧水经充分搅拌1h后得到透明液体,然后静止6h后将0.8g Gd(NO3)3加入其中后经95℃保温处理6h后得到乳白色纳米二氧化钛溶胶;冷却后加入1.2g三聚磷酸钠搅拌均匀得分散好的纳米二氧化钛溶液;Add 10gTi(SO 4 ) 2 into 500ml of water, adjust the pH to 6.0 with concentrated ammonia water, and obtain a white precipitate after centrifugation, then wash the precipitated material twice with deionized water, add 500ml of deionized water, and then use 10ml of 30% concentration of Hydrogen peroxide was fully stirred for 1 hour to obtain a transparent liquid, and then 0.8g Gd(NO 3 ) 3 was added to it after standing still for 6 hours, and then treated at 95°C for 6 hours to obtain a milky white nano-titanium dioxide sol; after cooling, add 1.2g sodium tripolyphosphate and stir well Get dispersed nano-titanium dioxide solution;
所述纳米颗粒尺寸采用透射电子显微镜检测得到,晶相通过X射线晶体衍射仪测定,二氧化钛纳米颗粒平均尺寸为6~10nm,晶相为锐钛矿相。The size of the nanoparticles is detected by a transmission electron microscope, and the crystal phase is measured by an X-ray crystal diffractometer. The average size of the titanium dioxide nanoparticles is 6-10 nm, and the crystal phase is an anatase phase.
将1g荔枝叶加入12ml水,煮沸30min后获得的水溶液,浓缩至4ml左右得到鲜荔枝液4.2g。Add 1g of lychee leaves to 12ml of water, boil the aqueous solution obtained after 30min, and concentrate to about 4ml to obtain 4.2g of fresh lychee liquid.
将2g鲜荔枝液加入3g分散好的纳米二氧化钛溶液中,经过搅拌均匀后得到新鲜荔枝纳米保鲜剂。Add 2 g of fresh litchi liquid into 3 g of dispersed nano-titanium dioxide solution, and stir evenly to obtain the fresh litchi nano-preservative.
将本发明的纳米保鲜剂,均匀喷洒于需要保鲜的新鲜荔枝果实表面两次。然后置于包装容器中,55天后打开发现荔枝果实未出现任何异味和变色,疲软等现象。The nano antistaling agent of the present invention is evenly sprayed on the surface of fresh litchi fruits to be preserved twice. Then place it in a packaging container, open it after 55 days and find that any peculiar smell, discoloration, and weakness do not appear in the lychee fruit.
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