CN106560243A - 一种抗菌金属离子/载钛羟基磷灰石纳米光催化剂及其制备方法 - Google Patents
一种抗菌金属离子/载钛羟基磷灰石纳米光催化剂及其制备方法 Download PDFInfo
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- CN106560243A CN106560243A CN201610518881.5A CN201610518881A CN106560243A CN 106560243 A CN106560243 A CN 106560243A CN 201610518881 A CN201610518881 A CN 201610518881A CN 106560243 A CN106560243 A CN 106560243A
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- Prior art keywords
- metal ions
- antibacterial metal
- antibacterial
- titanium supported
- titanium
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- A—HUMAN NECESSITIES
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- Chemical & Material Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
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- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
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Abstract
本发明公开了一种抗菌金属离子/载钛羟基磷灰石纳米光催化剂,为一种部分Ca2+被抗菌金属离子以及Ti4+所取代的羟基磷灰石纳米材料,所述抗菌金属离子包括Cu2+、Zn2+以及Ag+,在制备时各金属离子的原始投加摩尔比为n(Ti+metal)/n(Ca+Ti+metal)=0.1‑0.5,其中“metal”指抗菌金属离子。该纳米材料具有速效杀菌功能,长效杀菌功能,且有较高防霉能力,在无光照条件下,可瞬间发挥超强杀菌作用,在1分钟内的杀菌率达到96%以上,在3‑4分钟内达到99%以上;此外,在可见光照射下,30分钟后可去除甲醛气体80%以上。
Description
技术领域
本发明涉及光催化技术和抗菌金属游离型离子浓缩技术领域,特别涉及一种抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
背景技术
纳米光催化剂作为一种纳米仿生技术,广泛用于环境净化,自清洁材料,先进新能源,癌症医疗,高效率抗菌等多个前沿领域。最具代表性的纳米光催化剂是二氧化钛(TiO2),但是,TiO2是典型的紫外光响应光催化剂,只能利用380nm左右的紫外光能量来进行催化反应。而太阳光中的紫外光占比不足5%,并且,TiO2在紫外灯以外的人造光源下更是无法发挥作用。因此,TiO2的应用普及受到了极大的限制。
在此背景下,众多的研究人员通过金属离子、或阴离子的掺杂,或者通过添加有机或无机敏化剂,对TiO2进行改性,以使改性后TiO2能够利用长波区域(400~600nm)光源发挥光催化效应,用于分解空气和水中的污染物,以达到净化环境的目的。但是,金属离子掺杂改性TiO2的能带结构一般表现为一种不纯能级,光生电子-空穴在此能级上不易迁移,同时掺杂的金属离子本身成为电子-空穴复合点位,电子-空穴在此点位复合的结果,导致量子效率低下,即光催化活性低下。而阴离子掺杂的改性TiO2,比如用氮取代部分氧得到的TiO2-xNy光催化材料,虽然提高了在可见光区域的光催化效率,但是作为改性物注入的阴离子在光照下极易分解,导致阴离子掺杂改性TiO2的不稳定性,限制了材料的实际应用。由于综上所述的问题,近年来出现了TiO2与高吸附材料结合在一起 的复合型光催化剂。其中,二氧化钛/羟基磷灰石复合光催化材料最受关注。
羟基磷灰石(hydroxyapatite,简称HAP)是一种白色、微溶于水的弱碱性磷酸钙盐。羟基磷灰石具有独特的结构和成分,使其对微生物、病毒和有机物具有很强的吸附性。而当其与TiO2的结合时,使该复合材料在可见光区域呈现出光催化作用。比如:(1)Teraoka等通过化学沉淀法在羟基磷灰石单晶体表面沉积了TiO2,并证实该材料能同时发挥羟基磷灰石对污染物的高吸附能力和TiO2光催化分解污染物的能力。(2)Chusuei发现羟基磷灰石-TiO2复合材料在可见光,甚至是黑暗条件下也具有光催化降解能力。此外,近年来人们对羟基磷灰石在抗菌材料中的应用研究也给予了热切的关注,首先是负载金属离子的纳米羟基磷灰石材料,比如:(3)利用羟基磷灰石中Ca2+离子易与其他金属离子发生置换的特性制备而得的载银羟基磷灰石,在可见光的照射下能显示较强的光催化活性。由于银离子的因素,在黑暗条件下也显示了一定的抗菌性能。
上述(1)~(3)三个研究所述的载钛、或载银/羟基磷灰石材料都是单一金属离子置换的产物。由于各种抗菌金属离子对不同微生物所显示的抗菌优势不同,单一金属离子置换的羟基磷灰石材料虽然在一定时间内显示出一定的抗菌活性,但是,作为消毒剂,该活性缺乏瞬间发挥作用的“速效性”,尤其是“对霉菌的抑制能力尚缺”。而且,载银羟基磷灰石材料中的银离子是贵金属,又极易氧化变色,因而为提高抗菌活性而需要大量使用,不仅成本高昂,而且还会因变色影响产品外观,不宜商品化。然而,降低使用浓度又会导致产品杀菌功能的低下。
发明内容
本发明的目的在于提供一种抗菌金属离子/载钛羟基磷灰石纳米光催化剂, 是一种负载多种金属的载钛羟基磷灰石纳米材料,显示出杀菌功能的速效性和长效性、又有较高防霉能力,同时在太阳光或普通灯光的照射下还能分解甲醛、甲苯、氮氧化物、硫氧化物等挥发性有机气体、分解细菌内毒素等有害有机污染物。
本发明的目的是通过以下技术方案实现的:
一种抗菌金属离子/载钛羟基磷灰石纳米光催化剂,为一种部分Ca2+被抗菌金属离子以及Ti4+所取代的羟基磷灰石纳米材料,所述抗菌金属离子包括Cu2+、Zn2+以及Ag+,在制备时各金属离子的原始投加摩尔比为n(Ti+metal)/n(Ca+Ti+metal)=0.1-0.5,其中“metal”指抗菌金属离子,将原始投料量控制在上述范围内可保证产品的结晶度。
本发明的另一目的在于提供制备上述抗菌金属离子/载钛羟基磷灰石纳米光催化剂的方法。
通过将所述抗菌金属离子的水溶液与载钛羟基磷灰石纳米材料中Ca2+进行离子置换制备得到最终产品,或者将(NH4)2HPO4缓慢加入至所述抗菌金属离子的水溶液、含钛水溶液/水溶胶以及Ca2+的混合液中经水热法合成得到最终产品。
进一步地,所述抗菌金属离子的水溶液通过以下步骤配制而成:
(1)配制抗菌金属离子盐混合液,采用人造沸石颗粒为载体,在30℃-60℃通过离子吸附制备复合金属离子负载人造沸石;
(2)采用去离子水将人造沸石中抗菌金属离子溶出,制得抗菌金属阳离子的水溶液。
进一步地,上述步骤(1)包括以下具体步骤:
(1a)将配制的抗菌金属离子盐溶液加入水热反应釜中混合搅拌;优选地,Ag+、Cu2+以及Zn2+三种离子摩尔比为n(Ag):n(Cu):n(Zn)=(1-2):40:50;
(1b)在抗菌金属离子盐混合液中加入人造沸石,并在30℃-60℃不断搅拌3-6h;
(1c)进行固液分离后,使用去离子水通过离心法对固体部分进行洗涤,洗涤次数为2-3次,并将固体部分烘干。
进一步地,所述步骤(2)中,将人造沸石置于去离子水中,不断搅拌2-3个小时,充分溶解出颗粒内的抗菌金属离子,静置30分钟后,倒出上清液备用,控制抗菌金属离子的总浓度c(metal)=0.01-0.04mol/L。
进一步地,通过以下具体步骤进行抗菌金属离子与Ca2+的离子置换:
(Ⅰ)将所述载钛羟基磷灰石纳米材料加入抗菌金属离子水溶液中,在30℃-60℃搅拌4小时以上;
(Ⅱ)采用逐渐升温的方式,将水热反应温度提升至40℃-90℃,陈化24-72小时;
(Ⅲ)固液分离后,将固体部分在70-90℃真空干燥得到抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
进一步地,所述载钛羟基磷灰石纳米材料通过以下步骤制备:
(i)以钛酸正丁酯为原料溶解于醇溶液中,加酸调节pH至2-3;
(ii)向步骤(i)所得溶液中缓慢加入Ca(NO3)2,n(Ti)/n(Ca+Ti)摩尔比为0.1-0.5;
(iii)向步骤(ii)所得溶液中缓慢加入(NH4)2HPO4,n(Ca+Ti)/n(P)摩尔比为1-2;
(iv)用氨水调节溶液pH至9-11;
(v)固液分离后,将固体部分干燥得到载钛羟基磷灰石纳米材料。
本发明的有益效果在于:(1)多种抗菌金属离子负载的载钛羟基磷灰石纳米材料具有速效杀菌功能,具有杀菌长效性,且有较高防霉能力,在无光照条 件下,可瞬间发挥超强杀菌作用,在1分钟内的杀菌率达到96%以上,在3-4分钟内达到99%以上;此外,在可见光照射下,30分钟后可去除甲醛气体80%以上。
(2)采用去离子水将复合抗菌颗粒中金属抗菌离子溶出,获得高度浓缩的多种游离型抗菌金属阳离子的混合液,并且,可根据需要以调节复合抗菌颗粒与去离子水的比例,来随意调节该混合液的浓度,该混合金属离子液用于制取多离子负载羟基磷灰石纳米材料时,排除了干扰载钛羟基磷灰石稳定性的阴离子。
(3)制备载钛羟基磷灰石纳米材料时采用钛酸正丁酯(C16H36O4Ti)作为反应物,通过简单的水解步骤,制得二氧化钛[-OTiO-]水性溶胶。进一步,将硝酸钙[Ca(NO3)2]和磷酸氢二胺添加入制得的二氧化钛[-OTiO-]水性溶胶中,可直接制得纳米级载钛羟基磷灰石材料。该方法避免了最终反应产物中氯离子残留的可能性,并可减少制作流程中的洗涤次数,降低了反应物(原材料)和生成物(产品)的损耗率。
具体实施方式
下面结合实施例对本发明构思作进一步说明;
实施例1
第一步抗菌金属离子负载人造沸石的制备
(1)原料配方
a.硝酸银(AgNO3)
b.硝酸铜[Cu(NO3)2]
c.硝酸锌[Zn(NO3)2·6H2O]
d.人造沸石
e.去离子水
(2)加工流程
制备过程如下:
a.配制硝酸银(AgNO3)水溶液:将的AgNO3(1.7g,0.01mol)完全溶解于100ml的去离子水中,放置在暗处备用;
b.配制硝酸铜Cu(NO3)2水溶液:将Cu(NO3)2(75g,0.4mol)溶解于200ml的去离子水中,放置在暗处备用;
c.在内壁涂有聚四氟乙烯的反应釜中加入700ml的去离子水,将已静置了1-2小时以上的AgNO3水溶液和Cu(NO3)2水溶液倒入反应釜,充分搅拌混合;
d.为防止后续负载于人造沸石上的银离子和铜离子的氧化变色,将硝酸锌分批次加入,第一次添加硝酸锌[Zn(NO3)2·6H2O]:将硝酸锌(75g,0.25mol)缓慢地加入盛有AgNO3和Cu(NO3)2混合液的反应釜中,不断搅拌近20-30分钟,使试剂完全溶解;
e.在反应釜中加入人造沸石(1.37mol),继续不断搅拌3小时;
f.采用高速离心机,进行固液分离;
g.第二次添加去离子水750ml;
h.第二次添加硝酸锌[Zn(NO3)2·6H2O]:将硝酸锌(74g,0.25mol)再次缓慢地加入反应釜中,不断搅拌近3小时;
i.再一次采用高速离心机进行固液分离;
j.使用去离子水和离心法对固体部分进行洗涤,重复2-3次;
l.使用烘干法对固体进行烘干、备用。
第二步载钛羟基磷灰石纳米材料的制备
(1)原料
a.钛酸正丁酯(C16H36O4Ti)、无水乙醇(C2H5OH)、聚乙二醇(PEG)、2%硝酸(HNO3)溶液
b.硝酸钙[Ca(NO3)2]、磷酸氢二胺[(NH4)H2PO4]、氨水
(2)制作流程
制备过程如下:
a.将钛酸正丁酯(ρ=0.996g/mL,10ml,0.03mol)溶解于70ml无水乙醇中,加入1.0g聚乙二醇-6000混合均匀,在加入4ml冰醋酸和10mL蒸馏水,缓慢滴加2%的硝酸溶液调节pH值至2-3之间,制得[-OTiO-]水性溶胶;
b.将硝酸钙[Ca(NO3)2]缓慢地添加到的[-OTiO-]水性溶胶中,控制Ti/(Ca+Ti)的摩尔比百分比0.26;
c.将(NH4)H2PO4缓慢地滴加到[-OTiO-]/Ca(NO3)2溶液中,控制(Ca+Ti)/P的摩尔比为1.67-1.7;
d.采用25%的氨水调节溶液的pH值至9-10的弱碱性;
e.离心、水洗,反复三次;
f.将滤渣(反应产物)放入90℃的恒温箱中真空干燥,再经研磨即得载钛羟基磷灰石纳米材料。
第三步抗菌金属离子/载钛羟基磷灰石纳米光催化剂
(1)材料
a.抗菌金属离子负载人造沸石
b.载钛羟基磷灰石纳米材料
(2)操作流程
a.将抗菌金属离子负载人造沸石以1.0%-5.0%的浓度置于去离子水中,30℃-60℃下不间断地搅拌2-3个小时,充分溶解出颗粒内的抗菌金属离子,静置30分钟后,倒出上清液,测试上清液中的Ag+、Zn2+、Cu2+的含量,适度稀释,将混合阳离子的总浓度为调节至0.01mol/L后备用;
b.将第二步制得的纳米载钛羟基磷灰石纳米材料,边搅拌边添加至上述抗菌金属离子混合液中(600mL),在30℃-60℃搅拌近4个小时以上,;
c.采用逐渐升温的方式,将水热反应温度升至40℃-90℃的范围,达到目的温度后,陈化24小时;
d.采用离心法进行固液分离;
f.将滤渣(产物)放入70℃-90℃的恒温箱中真空干燥,再经研磨即得抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
实施例2
(1)材料
a.抗菌金属离子液
b.市场销售的羟基磷灰石纳米材料
c.正钛酸H4TiO4(也可用二氢氧化钛Ti(OH)2、三氢氧化钛H3TiO3,或三者的混合物)
d.硝酸溶液(2%的浓度)
(2)操作流程
a.抗菌金属离子液采用实施例1中所述方法制备得到;
b.将正钛酸H4TiO4(2.32g,0.024mol)溶解于100ml的2%的硝酸水溶液中,制得H4TiO4/硝酸溶液;
c.将从市场采购的羟基磷灰石纳米材料直接添加入到H4TiO4/硝酸溶液中,控制Ti/(Ca+Ti)的摩尔比为0.2。在室温搅拌30分钟后,采用超声波处理30分钟,之后陈化24小时,将固体分离干燥、研磨制得载钛羟基磷灰石纳米材料;
d.将上述(c)制得的载钛羟基磷灰石纳米材料加入(a)制得的抗菌金属离子液中,控制(Ti+Metal)/(Ca+Ti+Metal)的摩尔比在0.3。在室温搅拌30分钟后,采用超声波处理30分钟,之后陈化24小时,将固体分离并干燥、研磨制得抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
实施例3
(1)材料
a.抗菌金属离子液
b.[-OTiO-]水性溶胶
c.硝酸钙[Ca(NO3)2]、磷酸氢二胺[(NH4)H2PO4]、氨水
(2)操作流程
a.抗菌金属离子液采用实施例1中所述方法制备得到;
b.[-OTiO-]水性溶胶采用实施例1中所述方法制备得到;
c.将制得的抗菌金属离子液与[-OTiO-]水性溶胶混合,Metal/Ti的摩尔比为1/5,在40℃搅拌近4-6个小时,制得金属离子掺杂二氧化钛水性溶胶;
d.加入硝酸钙[Ca(NO3)2]、控制Ti/(Ca+Ti)的摩尔比为0.26。再将(NH4)H2PO4缓慢地滴加到“金属抗菌离子/[-OTiO-]/Ca(NO3)2混合溶液”中,控制(Ca+Ti)/P的摩尔比为1.67-1.7;
e.采用氨水调节溶液的pH值至9-10的弱碱性;
f.在一定温度下陈化24小时;
g.经洗涤、过滤、烘干和研磨得到产物抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
实施例4
(1)材料
a.硝酸银、硝酸铜、硝酸锌
b.H4TiO4/硝酸溶液
c.硝酸钙[Ca(NO3)2]、磷酸氢二胺[(NH4)H2PO4]、氨水
(2)操作流程
a.H4TiO4/硝酸溶液采用实施例2中所述方法制备得到;
b.将硝酸银(0.17g,0.001mol)、硝酸铜(7.5g,0.04mol)、硝酸锌(14.87g,0.05mol)加入H4TiO4/硝酸溶液(0.02mol/L,4.5L)中;
c.加入硝酸钙[Ca(NO3)2]、控制(Ti+Metal)/[Ca+(Ti+Metal)]的摩尔比为0.3。再将(NH4)H2PO4缓慢地滴加到“抗菌离子液/[-OTiO-]/Ca(NO3)2混合溶液”中,控制(Ca+Ti)/P的摩尔比为1.67-1.7;
d.采用氨水调节溶液的pH值至9-10的弱碱性;
e.在一定温度下陈化24小时;
f.加入事先配置好的氧化锌溶液,充分搅拌,一方面可包裹位于复合材料表面的银离子和铜离子,防止其变色,另一方面氧化锌本身具有抗菌和光催化作用;
g.经洗涤、过滤、烘干和研磨得到产物抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
实施例5
(1)原料
a.四氯化钛(TiCl4)
b.羟基磷灰石纳米粉末
c.氨水
(2)制作流程
a.四氯化钛(TiCl4)配制成1mol/L的水溶液;用0.5mol/L的氨水调节该溶液的pH至12-13,之后将溶液陈化24小时。用去离子水洗涤沉淀3-5次,即得Ti(OH)4胶体;
b.将2g Ti(OH)4胶体与羟基磷灰石纳米粉末混合,控制(Ca+Ti)/P的摩尔比为1.67-1.7,加入150ml去离子水,采用25%的氨水调节溶液的pH值至9-10的弱碱性,将混合溶液置于200ml容积的高压釜中,在190℃水热反应8小时;
c.反应后,采用离心法进行固液分离,并用去离子水洗涤、过滤沉淀至滤液呈中性;
d.将滤渣(反应产物)放入90℃的恒温箱中真空干燥,再经研磨即得载钛羟基磷灰石纳米材料。
实施例6
在重复实施例1操作的基础上,仅将抗菌金属离子Ag+、Cu2+以及Zn2+摩尔比例改为2:40:50,得到抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
实施例7
对上述实施例所得材料进行性能测试,得到结果如下:
将实施例1所得抗菌金属离子/载钛羟基磷灰石纳米光催化剂进行灭菌试验,得到下表1所示结果。
表1抗菌金属离子/载钛羟基磷灰石纳米光催化剂灭菌试验结果
名称 | 处理前 | 处理1分钟后 |
ATP测试值 | 5356 | 223 |
注:由于ATP测试受到样品中灰尘等其他杂质的干扰,测得数据比菌落形成法(残留活菌数的可视化方法)的测试数据高,即:过低评估了样品的消毒结果。
将实施例1所得抗菌金属离子/载钛羟基磷灰石纳米光催化剂进行杀菌试验,得到下表2所示结果。
表2抗菌金属离子/载钛羟基磷灰石纳米光催化剂杀菌试验结果
菌种 | 1小时杀菌率(%) | 4小时杀菌率(%) | 72小时杀菌率(%) |
大肠杆菌 | ﹥99 | 99.99 | —— |
金色葡萄球菌 | ﹥99 | 99.99 | —— |
白色念珠菌 | ﹥99 | 99.99 | |
枯草芽孢杆菌 | —— | —— | 94.27 |
黑曲霉菌 | —— | —— | 88.78 |
注:由广东微生物分析检测中心提供检测数据
将实施例5所得载钛羟基磷灰石纳米光催化剂进行灭菌试验,得到下表3所示结果。
表3载钛羟基磷灰石纳米光催化剂杀菌试验结果
菌种 | 24小时杀菌率(%) |
大肠杆菌 | 97.8 |
金色葡萄球菌 | 99.9 |
上述实验结果明显显示,单种金属钛离子加载羟基磷灰石的杀菌率,明显低于抗菌金属离子/载钛羟基磷灰石材料。
将实施例1所得抗菌金属离子/载钛羟基磷灰石纳米光催化剂进行最小杀菌浓度(MBC)的测定,测定方法可参考“载铜锌纳米羟基磷灰石的抗菌性能及机理研究”(无机材料学报,21(1),2006)中所述方法,得出如下表4所示测定结果。
表4载钛羟基磷灰石纳米光催化剂的MBC测定结果
注:对比例1在李吉东等发表的“载铜纳米羟基磷灰石的制备及抗菌性能评价”(功能材料,2006,37(4),635)中有记载;对比例2在赵彩霞等发表的“载钛(Ⅳ)锌(Ⅱ)纳米羟基磷灰石的制备及抗菌性研究”(无机材料学报,2009,24(6),1243)中有记载。
从上述结果可知,本发明的无机抗菌剂载钛羟基磷灰石纳米催化剂材料相比于现有的单抗菌金属离子负载的载钛羟基磷灰石或者单抗菌金属离子负载的羟基磷灰石具有极其优异的抗菌活性。
Claims (8)
1.一种抗菌金属离子/载钛羟基磷灰石纳米光催化剂,为一种部分Ca2+被抗菌金属离子以及Ti4+所取代的羟基磷灰石纳米材料,所述抗菌金属离子包括Cu2+、Zn2+以及Ag+,在制备时各金属离子的原始投加摩尔比为n(Ti+metal)/n(Ca+Ti+metal)=0.1-0.5,其中“metal”指抗菌金属离子。
2.一种制备权利要求1中抗菌金属离子/载钛羟基磷灰石纳米催化剂的方法,其特征在于,通过将所述抗菌金属离子的水溶液与载钛羟基磷灰石纳米材料中Ca2+进行离子置换制备得到最终产品,或者将(NH4)2HPO4缓慢加入至所述抗菌金属离子的水溶液、含钛水溶液/水溶胶以及Ca2+水溶液的混合液中经水热法合成得到最终产品。
3.根据权利要求2所述的制备抗菌金属离子/载钛羟基磷灰石纳米催化剂的方法,其特征在于,所述抗菌金属离子的水溶液通过以下步骤配制而成:
(1)配制抗菌金属离子盐混合液,采用人造沸石颗粒为载体,在30℃-60℃通过离子吸附制备复合金属离子负载人造沸石;
(2)采用去离子水将人造沸石中抗菌金属离子溶出,制得抗菌金属阳离子的水溶液。
4.根据权利要求3所述的制备抗菌金属离子/载钛羟基磷灰石纳米催化剂的方法,其特征在于,步骤(1)包括以下具体步骤:
(1a)将配制的抗菌金属离子盐溶液加入水热反应釜中混合搅拌;
(1b)在抗菌金属离子盐混合液中加入人造沸石,并在30℃-60℃不断搅拌3-6h;
(1c)进行固液分离后,使用去离子水通过离心法对固体部分进行洗涤,洗涤次数为2-3次,并将固体部分烘干。
5.根据权利要求3或4所述的制备抗菌金属离子/载钛羟基磷灰石纳米催化剂的方法,其特征在于,步骤(1)的所述抗菌金属离子盐溶液中Ag+、Cu2+以及Zn2+三种离子摩尔比为n(Ag):n(Cu):n(Zn)=(1-2):40:50。
6.根据权利要求3所述的制备抗菌金属离子/载钛羟基磷灰石纳米催化剂的方法,其特征在于,所述步骤(2)中,将人造沸石置于去离子水中,不断搅拌2-3个小时,充分溶解出颗粒内的抗菌金属离子,静置30分钟后,倒出上清液备用,测试上清液中的Ag+、Zn2+、Cu2+的含量,控制抗菌金属离子的总浓度c(metal)=0.01-0.04mol/L。
7.根据权利要求2所述的制备抗菌金属离子/载钛羟基磷灰石纳米催化剂的方法,其特征在于,通过以下具体步骤进行抗菌金属离子与Ca2+的离子置换:
(Ⅰ)将所述载钛羟基磷灰石纳米材料加入抗菌金属离子水溶液中,在30℃-60℃搅拌4小时以上;
(Ⅱ)采用逐渐升温的方式,将水热反应温度提升至40℃-90℃,陈化24-72小时;
(Ⅲ)固液分离后,将固体部分在70-90℃真空干燥得到抗菌金属离子/载钛羟基磷灰石纳米光催化剂。
8.根据权利要求2或7所述的制备抗菌金属离子/载钛羟基磷灰石纳米催化剂的方法,其特征在于,所述载钛羟基磷灰石纳米材料通过以下步骤制备:
(i)以钛酸正丁酯为原料溶解于醇溶液中,加酸调节pH至2-3;
(ii)向步骤(i)所得溶液中缓慢加入Ca(NO3)2,控制n(Ti)/n(Ca+Ti)摩尔比为0.1-0.5;
(iii)向步骤(ii)所得溶液中缓慢加入(NH4)2HPO4,n(Ca+Ti)/n(P)摩尔比为1-2;
(iv)用氨水调节溶液pH至9-11;
(v)固液分离后,将固体部分干燥、研磨得到载钛羟基磷灰石纳米材料。
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