负载掺杂纳米TiO_2耐久抗菌织物的制备与表征
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摘要
为解决特种军需及医用织物在可见光下的耐久性抗菌问题,以钛酸四丁酯为钛源、硫脲和尿素为掺杂体、棉针织布为基材,通过快速溶胶-凝胶法负载和低温热处理,制备出硫氮共掺杂纳米二氧化钛(S-N-TiO_2)可见光催化耐久性抗菌织物。利用紫外-可见漫反射吸收光谱、X射线光电子能谱和扫描电子显微镜,表征分析抗菌材料的光谱性质和微观形貌;以大肠杆菌、金黄色葡萄球菌为目标样本,采用振荡法,研究测试抗菌织物的可见光催化抗菌性能。结果表明:S、N以取代型和间隙型掺进TiO_2晶格中,使其吸收边带红移至可见光区,且吸收强度较高;抗菌织物表面包裹着一层致密的S-N-TiO_2薄膜,对金黄色葡萄球菌的抑菌率均优于AAA级,对大肠杆菌的均高于AA级。
To solve the durable antibacterial problem on special military supplies and medical textile fabric under visible light irradiation,by using tetrabutyl titanate as the Ti source,thiourea and urea as the dopant,and cotton knitted fabric as the base materials,visible light catalytic durable antibacterial cotton knitted fabric loaded with S-N co-doped nano-TiO_2( S-N-TiO_2) was prepared by fast sol-gel loading in combination with low temperature heat treatment. The light absorption properties and microstructures of the prepared samples were characterized by UV-Vis spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy. Using Escherichia coli and Staphylococcus aureus as target object,the visible light catalytic antibacterial properties of the fabric were investigated by shake flask method. The results indicate that sulfur and nitrogen atoms are incorporated into the TiO_2 lattice as substitutional and interstitial forms,which allowed light absorption band edge redshift into the visible light region and the absorption intensity was increased. The dense film of S-N-TiO_2 is coated on the surface of the fabric samples. The antibacterial rates of all the samples for Staphylococcus aureus are superior to the AAA standard,for Escherichia coli are superior to the AA standard.
To solve the durable antibacterial problem on special military supplies and medical textile fabric under visible light irradiation,by using tetrabutyl titanate as the Ti source,thiourea and urea as the dopant,and cotton knitted fabric as the base materials,visible light catalytic durable antibacterial cotton knitted fabric loaded with S-N co-doped nano-TiO_2( S-N-TiO_2) was prepared by fast sol-gel loading in combination with low temperature heat treatment. The light absorption properties and microstructures of the prepared samples were characterized by UV-Vis spectroscopy,X-ray photoelectron spectroscopy,and scanning electron microscopy. Using Escherichia coli and Staphylococcus aureus as target object,the visible light catalytic antibacterial properties of the fabric were investigated by shake flask method. The results indicate that sulfur and nitrogen atoms are incorporated into the TiO_2 lattice as substitutional and interstitial forms,which allowed light absorption band edge redshift into the visible light region and the absorption intensity was increased. The dense film of S-N-TiO_2 is coated on the surface of the fabric samples. The antibacterial rates of all the samples for Staphylococcus aureus are superior to the AAA standard,for Escherichia coli are superior to the AA standard.
引文
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[21]郭晓玲,戴杰,王向东.快速溶胶-凝胶制备硫氮共掺杂纳米二氧化钛的方法:中国,ZL201410261336.3[P].2016-06-15.GUO Xiaoling,DAI Jie,WANG Xiangdong.A method of fast sol-tel preparation of S—N codoped nano-Ti O2:China,ZL201410261336.3[P].2016-06-15.
[22]徐建华.新型纳米二氧化钵光催化材料的合成及反应研究[D].上海:复旦大学,2007:97-98.XU Jianhua.Study on the synthesis and reaction of novel nano-scale Ti O2photocatalysts[D].Shanghai:Fudan University,2007:97-98.
[23]SOUMYASHREE Pany,BRUNDABANA Naik,SATYABADI Martha,et al.Plasmon induced nano Au particle decorated over S,N-modified Ti O2for exceptional photocatalytic hydrogen evolution under visible light[J].ACS Applied Materials&Interfaces,2014,6(2):839-846.
[24]PARIDA K M,NRUPARAJ Sahu,TRIPATHI A K,et al.Gold promoted S,N-doped Ti O2:an efficient catalyst for CO adsorption and oxidation[J].Environmental Science&Technology,2010,44(11):4155-4160.
[25]DING Wuchen,LI Weixue.A first principles study of the energetics and core level shifts of anion-doped Ti O2photocatalysts[J].Chinese Journal of Catalysis,2015,36(2):181-187.
[2]孙伊,刘红.密闭舱室内微生物污染问题及其防控体系[J].载人航天,2014,20(6):543-549.SUN Yi,LIU Hong.Microbial contamination and its prevention and control system in an enclosed cabin[J].Manned Spaceflight,2014,20(6):543-549.
[3]徐绸,谢琼,辛冰牧,等.一株神舟十号飞船分离少动鞘氨醇单胞菌基因组测序结果及分析[J].载人航天,2016,22(5):651-654.XUN Chou,XIE Qiong,XIN Bingmu,et al.Genome sequence analysis of a sphingomonas paucimobilis strain from Shenzhou-10 spacecraft[J].Manned Spaceflight,2016,22(5):651-654.
[4]林宏,杜锐.夏季真菌性皮肤病病因及防治[J].解放军健康,2016(4):15.LIN Hong,DU Rui.The pathogeny and prevention of fungal skin disease in summer[J].PLA Health,2016(4):15.
[5]付留杰,刘元东,高伟.海训部队卫勤保障特点及疾病预防控制措施[J].解放军健康,2014(4):8-9.FU Liujie,LIU Yuandong,GAO Wei.The logistical support characteristics and disease prevention and control measures of navy training[J].PLA Health,2014(4):8-9.
[6]王晓明,马强,陈照立,等.多维极端环境对军事环境医学发展的新挑战[J].解放军预防医学杂志,2016,34(1):4-6.WANG Xiaoming,MA Qiang,CHEN Zhaoli,et al.New challenges of the development of military environmental medicine to multi-dimensional extreme environment[J].Journal of Preventive Medicine of Chinese People's Liberation Army,2016,34(1):4-6.
[7]肖红,施楣梧,刘丽丽.抗菌防臭纺织品相关基础性问题[J].纺织学报,2011,32(9):147-152.XIAO Hong,SHI Meiwu,LIU Lili.Fundamental issues concerning anti-bacterial and odor-resistant textiles[J].Journal of Textile Research,2011,32(9):147-152.
[8]GAO Yuan,CRANSTON Robin.Recent advances in antimicrobial treatment of textiles[J].Textile Research Journal,2008,78(1):60-72.
[9]SPITZ M G,JOHNSON W K,LESHER L L,et al.Soldier hygiene issues and use of antimicrobial textiles in the military[J].AATCC Journal of Research,2016,3(5):27-37.
[10]KOWAL Katarzyna,CRONIN Patrick,DWORNICZEK Ewa,et al.Biocidal effect and durability of nano-Ti O2coated textiles to combat hospital acquired infections[J].RSC Advances,2014,4:19945-19952.
[11]么丹阳,巫晓华,毛雪峰,等.银纳米颗粒/二氧化钛/醋酸纤维素复合纤维的制备及其性能[J].纺织学报,2016,37(4):15-20.YAO Danyang,WU Xiaohua,MAO Xuefeng,et al.Preparation and characterization of silver nanoparticles/Ti O2/cellulose acetate composite nanofibers[J].Journal of Textile Research,2016,37(4):15-20.
[12]马超,吴瑛.抗菌剂抗菌机理简述[J].中国酿造,2016,35(1):5-9.MA Chao,WU Ying.Research on antimicrobial agents and their mechanism of actions[J].China Brewing,2016,35(1):5-9.
[13]ASAHI R,MORIKAWA T,OHWAKI T,et al.Visiblelight photocatalysis in nitrogen-doped titanium oxides[J].Science,2001,293(5528):269-271.
[14]DEVI L Gomathi,KAVITHA R.A review on plasmonic metal-Ti O2composite for generation,trapping,storing and dynamic vectorial transfer of photogenerated electrons across the schottky junction in a photocatalytic system[J].Applied Surface Science,2016,360:601-622.
[15]姜洪波,高濂,张青红.铜离子掺杂对Ti O2纳米颗粒膜结构和性能的影响[J].无机材料学报,2002,17(4):787-791.JIANG Hongbo,GAO Lian,ZHANG Qinghong.Influence of Cu dopants on structure and properties of nanosized Ti O2particulate film[J].Journal of Inorganic Materials,2002,17(4):787-791.
[16]XIAO Jiadong,XIE Yongbing,CAO Hongbin,et al.Disparate roles of doped metal ions in promoting surface oxidation of Ti O2photocatalysis[J].Journal of Photochemistry and Photobiology A:chemistry,2016,315:59-66.
[17]GUO Xiaoling,DAI Jie,CUI Zhen,et al.Fabrication of N-doped Ti O2/activated carbon fiber composites with enhanced photocatalytic activity[J].Textile Research Journal,2014,84(17):1891-1900.
[18]BARKUL R P,KOLI V B,SHEWALE V B,et al.Visible active nanocrystalline N-doped anatase Ti O2particles for photocatalytic mineralization studies[J].Materials Chemistry and Physics,2016,173:42-51.
[19]WANG Yuan,ZHANG Jiawang,LIU Lixin.Visible light photocatalysis of V2O5/Ti O2nanoheterostructures prepared via electrospinning[J].Materials Letters,2012,75:95-98.
[20]SANGCHAY Weerachai,SIKONG Lek,KOOPTARNOND Kalayanee.Photochromic and selfcleaning properties of Ti O2-Ag Cl/Ti O2-x Cu thin film[J].Journal of Nanosience and Nanotechnology,2013,13(2):1448-1452.
[21]郭晓玲,戴杰,王向东.快速溶胶-凝胶制备硫氮共掺杂纳米二氧化钛的方法:中国,ZL201410261336.3[P].2016-06-15.GUO Xiaoling,DAI Jie,WANG Xiangdong.A method of fast sol-tel preparation of S—N codoped nano-Ti O2:China,ZL201410261336.3[P].2016-06-15.
[22]徐建华.新型纳米二氧化钵光催化材料的合成及反应研究[D].上海:复旦大学,2007:97-98.XU Jianhua.Study on the synthesis and reaction of novel nano-scale Ti O2photocatalysts[D].Shanghai:Fudan University,2007:97-98.
[23]SOUMYASHREE Pany,BRUNDABANA Naik,SATYABADI Martha,et al.Plasmon induced nano Au particle decorated over S,N-modified Ti O2for exceptional photocatalytic hydrogen evolution under visible light[J].ACS Applied Materials&Interfaces,2014,6(2):839-846.
[24]PARIDA K M,NRUPARAJ Sahu,TRIPATHI A K,et al.Gold promoted S,N-doped Ti O2:an efficient catalyst for CO adsorption and oxidation[J].Environmental Science&Technology,2010,44(11):4155-4160.
[25]DING Wuchen,LI Weixue.A first principles study of the energetics and core level shifts of anion-doped Ti O2photocatalysts[J].Chinese Journal of Catalysis,2015,36(2):181-187.