CN101522306A - 二氧化硅基复合光催化剂及其制造方法 - Google Patents
二氧化硅基复合光催化剂及其制造方法 Download PDFInfo
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- CN101522306A CN101522306A CNA2007800361385A CN200780036138A CN101522306A CN 101522306 A CN101522306 A CN 101522306A CN A2007800361385 A CNA2007800361385 A CN A2007800361385A CN 200780036138 A CN200780036138 A CN 200780036138A CN 101522306 A CN101522306 A CN 101522306A
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- Prior art keywords
- base composite
- composite photocatalyst
- silica base
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- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 78
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Abstract
本发明提供一种二氧化硅基复合光催化剂及其制造方法,所述二氧化硅基复合光催化剂具有良好的水净化性能,并且能够抑制金属氧化物的析出。所述二氧化硅基复合光催化剂含有主要为以二氧化硅成分为主体的氧化物相(第1相)和二氧化钛相(第2相)的复合氧化物相,第2相的存在比例朝向表层梯度性增加,其特征在于,所述第2相含有钛酸锶和钛酸钡之中的至少一种以上的金属氧化物。
Description
技术领域
本发明涉及具有优异的光催化剂功能、电气功能和/或热催化剂功能的高强度二氧化硅基复合光催化剂及其制造方法。具体地说,本发明涉及高强度无机纤维及其制造方法,所述无机纤维具有承担力学特性的中心部(二氧化硅相),并且具有作为将各种功能用于水质净化等的环境净化材料优异的光催化剂功能。
背景技术
近年来,对使用光催化剂的水的净化进行了研究。从不使用氯、臭氧等一切对人体有害的物质的观点出发,利用光催化剂对水净化是非常安全的净化方法。在这样的用途方面,通常对光催化剂膜(将光催化剂涂布在基材上而成的膜)进行研究,但有时因该光催化剂膜上粘固了各种附着物,遮挡了光或覆盖了表面而妨碍光催化剂性能。这些附着物大多是水中存在的金属离子吸附在光催化剂纤维表面上进而又被氧化而形成的氧化物。使用专利文献1所述的纤维状光催化剂的情况下,表面积比上述光催化剂膜大,所以可以期待优异的净化性能,但是,另一方面,其存在也容易粘固附着物的问题。即,如果能够防止附着物向纤维状的光催化剂上粘固,则其作为水处理用光催化剂是非常有益的。
为了除去附着在光催化剂上的这样的金属氧化物,有时用酸进行清洗或进行削去等,但这样的方法是危险的,有时可能导致光催化剂性能降低,所以需要其他的对策。例如可以举出下述方法:如专利文献2所述那样,通过活性氧来使被处理水中的金属离子析出,并将生成的固体物质过滤除去。另外,还有如下方法:如专利文献3所述的那样,对光催化剂表面施加与金属离子的极性同极性的电位。
专利文献1:日本专利3465699号
专利文献2:日本特开2004-181409号
专利文献3:日本特开2003-285069号
但是,专利文献2所记载的方法除了需要利用光催化剂的净化装置之外还需要其他装置,所以该方法留下了装置整体的规模变大、成本增高的问题。另外,专利文献3所记载的方法也同样另外需要用于施加电位的装置。
发明内容
因此,本发明的目的是解决上述问题,提供一种二氧化硅基复合光催化剂及其制造方法,所述二氧化硅基复合光催化剂具有良好的水净化性能,并且通过简单的构成就能够抑制金属氧化物的析出。
为了实现上述目的,本发明人反复进行深入研究,结果发现,通过下述的简单构成,二氧化硅基复合光催化剂就能够具有良好的水净化性能,并且能够抑制金属氧化物的析出,其中,所述二氧化硅基复合光催化剂含有主要为以二氧化硅成分为主体的氧化物相(第1相)和二氧化钛相(第2相)的复合氧化物相,第2相的存在比例朝向表层梯度性增加,所述第2相含有钛酸锶和钛酸钡之中的至少一种以上的金属氧化物。即,本发明涉及一种二氧化硅基复合光催化剂,其含有主要为以二氧化硅成分为主体的氧化物相(第1相)和二氧化钛相(第2相)的复合氧化物相,第2相的存在比例朝向表层梯度性增加,所述二氧化硅基复合光催化剂的特征在于,所述第2相含有钛酸锶和钛酸钡之中的至少一种以上的金属氧化物。
此外,本发明涉及一种二氧化硅基复合光催化剂的制造方法,其特征在于,对改性聚碳硅烷或对所述改性聚碳硅烷、有机钛化合物和有机金属化合物的混合物进行熔融纺丝,经不熔化处理后,在空气中或氧气中进行烧制,其中所述有机金属化合物是有机锶化合物和有机钡化合物之中的至少一种以上的化合物,所述改性聚碳硅烷具有用有机钛化合物和所述有机金属化合物对具有主要以下式表示的主链骨架且数均分子量为200~10,000的聚碳硅烷进行修饰而形成的结构。
(其中,上式中的R表示氢原子、低级烷基或苯基。)
如上所述,根据本发明,能够提供一种二氧化硅基复合光催化剂及其制造方法,所述二氧化硅基复合光催化剂具有良好的水净化性能,并且通过简单的构成就能够抑制金属氧化物的析出。
附图说明
图1是示意性说明本发明的二氧化硅基复合氧化物的生成过程的图。
具体实施方式
本发明的二氧化硅基复合光催化剂中,以二氧化硅成分为主体的氧化物相(第1相)既可以是无定形的,也可以是结晶质的,并且还可以含有能够与二氧化硅形成固溶体或低共熔点化合物的金属元素或金属氧化物。对能与二氧化硅形成固溶体的金属元素(A)或者其氧化物能够与二氧化硅形成特定组成的化合物的金属元素(B)没有特别限定,例如作为(A),可以举出钛;并且,作为(B),可以举出铝、锆、钇、锂、钠、钡、钙、硼、锌、镍、锰、镁、铁等。
该第1相形成本发明得到的催化剂的内部相,起到承担力学特性的重要作用。第1相相对于二氧化硅基复合光催化剂整体的存在比例优选为98重量%~40重量%,为了充分显示出作为目的的第2相的功能且表现出高的力学特性,优选将第1相的存在比例控制在50重量%~95重量%的范围内。
在本发明中,在表现出光催化剂功能这一目的方面,第2相含有的二氧化钛起到重要的作用,另外,在本发明中,在防止金属氧化物的附着方面,第2相含有的钛酸锶和钛酸钡之中的至少一种以上的金属氧化物起到重要的作用。第2相中可以同时含有所述钛酸锶和钛酸钡。构成该催化剂的表层部的第2相相对于二氧化硅基复合光催化剂整体的存在比例优选为4重量%~60重量%,为了充分显示出各功能并同时还表现出高强度,第2相的存在比例优选控制在5重量%~50重量%的范围内。进一步优选第2相所含有的钛酸锶和钛酸钡之中的至少一种以上的金属氧化物相对于二氧化硅基复合光催化剂整体的含量为2重量%~40重量%,为了充分显示出其功能并同时还表现出高强度,所述含量优选控制在3重量%~20重量%的范围内。第2相含有的除钛以外的金属元素的存在比例优选在距催化剂表面5nm~500nm的深度存在梯度;第2相含有的二氧化钛优选晶粒粒径为15nm以下且具有光催化剂功能。
此外,本发明的二氧化硅基复合光催化剂通过在其中含有钛酸锶和钛酸钡之中的至少一种以上的金属氧化物而将光催化剂的等电点调整为8以上。本发明的二氧化硅基复合光催化剂优选是纤维状的二氧化硅基复合光催化剂纤维,但也可以是颗粒、膜、薄膜。
本发明的二氧化硅基复合光催化剂可以通过上述的方法得到,下面将其分成第1工序~第4工序进行说明。本发明的二氧化硅基复合光催化剂的生成过程示意性示于图1。
首先,第1工序是制造数均分子量为1,000~50,000的改性聚碳硅烷(用作制造二氧化硅基复合光催化剂的起始原料)的工序。
上述改性聚碳硅烷的基本制造方法与日本特开昭56-74126号极为类似,但本发明中,需要格外注意控制其中记载的官能团的结合状态。下面对此进行简单说明。
作为起始原料的改性聚碳硅烷是从具有主要以下式表示的主链骨架且数均分子量为200~10,000的聚碳硅烷和以通式M(OR′)n或MR"m(M表示钛和钛以外的金属元素,R′表示具有1~20个碳原子的烷基或苯基,R"表示乙酰丙酮根,m和n表示大于1的整数)为基本结构的有机金属化合物衍生的。作为有机金属化合物,需要使用有机钛化合物以及选自有机锶化合物和有机钡化合物之中的至少一种以上的有机金属化合物,并且优选其分子量比所形成的改性聚碳硅烷小。
(其中,上式中的R表示氢原子、低级烷基或苯基。)
用于形成二氧化钛的有机钛化合物例如有四丁氧基钛、四异丙氧基钛等。另外,形成钛酸锶的有机锶化合物有二异丙氧基锶等,形成钛酸钡的有机钡化合物有双乙酰丙酮合钡等。
此处,为了制造本发明的具有梯度组成的催化剂,需要选择仅部分上述有机金属化合物与聚碳硅烷形成键合的慢速反应条件。因此,需要在280℃以下、优选250℃以下的温度于惰性气体中进行反应。该反应条件下,上述有机金属化合物即使与聚碳硅烷发生了反应,也是以1官能性聚合物的形式键合在一起(即结合成侧链状),不会引起分子量大幅增大。结合有部分的该有机金属化合物的改性聚碳硅烷在提高聚碳硅烷和有机金属化合物的相容性方面起到重要的作用。
此外,据认为,结合有2官能以上的多个官能团的情况下,聚碳硅烷形成交联结构的同时分子量明显增大。这种情况下,反应中发生急剧的放热和熔融粘度的上升。另一方面,在仅上述1官能反应而残留有未反应的有机金属化合物的情况下,反而观察到了熔融粘度的降低。
本发明中,优选选择有意地使未反应的有机金属化合物残存的条件。本发明中,主要使用上述改性聚碳硅烷和未反应状态的有机金属化合物共存的起始原料或者上述改性聚碳硅烷和2聚物~3聚物这种程度的有机金属化合物共存的起始原料,但是,含有分子量极低的改性聚碳硅烷成分的情况下,仅改性聚碳硅烷也同样可用作本发明的起始原料。
第2工序中,使所述第1工序得到的改性聚碳硅烷、或改性聚碳硅烷和所述有机金属化合物的混合物熔融,制造纺丝原液,根据情况对其过滤,除去微凝胶、杂质等纺丝时有害的物质,通过通常使用的合成纤维纺丝用装置对其进行纺丝。进行纺丝时的纺丝原液的温度根据作为原料的改性聚碳硅烷的软化温度而有所不同,但50℃~200℃的温度范围是有利的。上述纺丝装置中,根据需要可以在喷嘴下部设置加湿加热筒。此外,通过改变从喷嘴排出的排出量和设置在纺丝机下部的高速卷绕装置的卷绕速度来调整纤维径。另外,还可以通过熔喷法或者纺粘法,不对从喷嘴排出的纤维进行卷绕,而直接将从喷嘴排出的纤维成型为毡毯形状。
除了所述熔融纺丝之外,第2工序中,还可以将所述第1工序得到的改性聚碳硅烷、或改性聚碳硅烷和所述有机金属化合物的混合物溶解在例如苯、甲苯、二甲苯或者其他能够溶化该改性聚碳硅烷和有机金属化合物的溶剂中,制造纺丝原液,并根据情况对其过滤,除去微凝胶、杂质等纺丝时有害的物质后,利用通常使用的合成纤维纺丝装置,通过干式纺丝法,对所述纺丝原液进行纺丝,控制卷绕速度下得到目的纤维。
这些纺丝工序中,根据需要,在纺丝装置上安装纺丝筒,并使该筒内的气氛为与所述溶剂之中的至少一种气体的混合气氛,或为空气、惰性气体、热空气、热惰性气体、水蒸汽、氨气、烃气体、有机硅化合物气体的气氛,由此能够控制纺丝筒中的纤维的固化。
接着,第3工序中,在氧化气氛中,对所述纺丝纤维于张力或无张力作用下进行预热,进行所述纺丝纤维的不熔化。进行该工序的目的是使纤维在后工序的烧制过程中不发生熔融,且不与邻接的纤维发生粘结。处理温度以及处理时间根据组成而有所不同,但没有特别规定,通常选择在50℃~400℃的范围内处理数小时~30小时的处理条件。另外,上述氧化气氛中,可以含有水分、氮氧化物、臭氧等提高对纺丝纤维的氧化力的物质,也可以有意地改变氧分压。
另外,根据原料中所含有的有机金属化合物的比例,有时纺丝纤维的软化温度降低到50℃以下,这种情况下,有时预先在低于上述处理温度的温度实施促进纤维表面氧化的处理。需要说明的是,据认为,该第3工序以及第2工序中,原料中所含有的低分子量化合物向纤维表面渗出,形成了目的的梯度组成的基底。
接着,第4工序中,将经所述不熔化的纤维在张力或无张力下,于500℃~1800℃的温度范围在氧化气氛中进行烧制,能够得到目的二氧化硅基复合光催化剂,其含有以二氧化硅成分为主体的氧化物相(第1相)和二氧化钛相(第2相)的复合相,第2相的构成成分的存在比例朝向表层梯度性增加。该工序中,不熔化后的纤维中所含有的有机物成分基本上被氧化了,但根据所选择的条件,有时该有机物成分以碳和碳化物的形式残留在纤维中。即使为这样的状态,如果对目的的功能没有妨碍,也可以直接使用,但有妨碍的情况下,对其进一步实施氧化处理。此时,必须选择在目的的梯度组成以及结晶结构方面不产生问题的温度、处理时间。
实施例
下面对本发明的二氧化硅基复合光催化剂纤维的实施例进行说明。
参考例1
首先,对用作本实施例的二氧化硅基复合光催化剂纤维的原料的聚碳硅烷的制造方法进行说明。首先,在5升的三口烧瓶中加入2.5升无水甲苯和400g金属钠,在氮气气流下加热到甲苯的沸点,用1小时的时间滴加1升二甲基二氯硅烷。滴加结束后,加热回流10小时,生成了沉淀物。过滤该沉淀,先用甲醇洗涤后,再用水进行洗涤,得到420g白色粉末的聚二甲基硅烷。接下来,将250g聚二甲基硅烷加入到具有水冷回流器的三口烧瓶中,在氮气气流下,于420℃加热反应30小时,得到数均分子量为1200的聚碳硅烷。
实施例1
向50g通过参考例1的方法合成的聚碳硅烷中加入100g甲苯和50g四丁氧基钛以及5g双乙酰丙酮合钡,在100℃进行1小时预热后,缓慢升温到150℃,蒸馏除去甲苯后,在该状态下反应5小时,进一步升温到250℃,反应5小时,合成出了改性聚碳硅烷。基于有意使低分子量的有机金属化合物共存在该改性聚碳硅烷中的目的,向该改性聚碳硅烷中加入5g四丁氧基钛、2g双乙酰丙酮合钡,得到改性聚碳硅烷和低分子量有机金属化合物的混合物。
使该改性聚碳硅烷和低分子量有机金属化合物的混合物溶解在甲苯中后,加入到玻璃制纺丝装置中,用氮气充分对其内部进行置换后,进行升温以蒸馏除去甲苯,在180℃进行熔融纺丝。接下来,将该纺丝纤维在空气中逐级加热到150℃,进行不熔化,然后在1200℃的空气中进行1小时烧制,由此得到实施例1的二氧化硅基复合光催化剂纤维。
根据X射线衍射结果,所得到的实施例1的二氧化硅基复合光催化剂纤维(平均直径:8μm)由无定形二氧化硅、锐钛矿型二氧化钛和钛酸钡构成,根据荧光X射线分析结果,其中二氧化硅为80重量%、二氧化钛为17重量%、钛酸钡为3重量%。另外,根据EPMA考察构成原子的分布状态,证明了其具有钛朝向表面增多的梯度组成,其中在距最外周部1μm的区域,Ti/Si(摩尔比)=0.88;在距最外周2μm~3μm的区域,Ti/Si(摩尔比)=0.17;在中心部,Ti/Si(摩尔比)=0.02。同样,证明了其具有钡朝向表面增多的梯度组成,其中,在距最外周部1μm的区域,Ba/Si(摩尔比)=0.05;在距最外周2μm~3μm的区域,Ba/Si(摩尔比)=0.02;在中心部,Ba/Si(摩尔比)=0.01。该纤维的拉伸强度为1.8GPa。并且,测定实施例1的二氧化硅基复合光催化剂纤维的ζ电位,求出等电点时,等电点是pH=8.5-9.0。
基于考察所得到的实施例1的二氧化硅基复合光催化剂纤维的防止金属氧化物附着的效果的目的,将0.2g该纤维放入直径60mm的表面皿中,在其中加入溶解有氯化铁和氯化锰的水溶液(浓度分别为10mg/l、60mg/l,pH=7.8)。从该表面皿上方照射波长254nm的紫外线24小时。照射后,从表面皿中取出纤维,使纤维干燥后,用电子显微镜观察纤维表面。其结果是没有发现纤维表面附着有金属氧化物,表现出了优异的防止附着的效果。
接着,基于考察所得到的实施例1的二氧化硅基复合光催化剂纤维的二氧化钛的晶粒粒径的目的,进行TEM(透射电子显微镜)观察。作为参考,在实施例1中,在对纺丝纤维进行不熔化之后,分别在1225℃和1250℃进行烧制来代替在1200℃进行烧制,对如此得到的各二氧化硅基复合光催化剂纤维同样地进行观察。其结果如下:在1200℃、1225℃以及1250℃烧制的二氧化硅基复合光催化剂纤维的二氧化钛的晶粒粒径分别为8nm、12nm以及20nm。
进一步基于考察所述分别在1200℃、1225℃以及1250℃烧制的二氧化硅基复合光催化剂纤维的光催化剂性能的目的,分别将0.2g各纤维放入直径60mm的表面皿中,向其中加入20毫升含有大肠菌的水(每1毫升含有100万个大肠菌)。从该表面皿的上方以1mW/cm2的强度照射3小时波长351nm的黑光。照射后,从表面皿中取出菌液,用琼脂培养基培养,考察残存大肠菌的数量,结果如下:加入了在1200℃烧制的二氧化硅基复合光催化剂纤维的情况下,残存大肠菌的数量为0个;加入了在1225℃烧制的二氧化硅基复合光催化剂纤维的情况下,残存大肠菌的数量为5个;加入了在1250℃烧制的二氧化硅基复合光催化剂纤维的情况下,残存大肠菌的数量为20个。由此表明,烧制温度低、二氧化钛的晶粒粒径小时,具有优异的光催化剂活性。
实施例2
向50g通过参考例1的方法合成的聚碳硅烷中加入100g甲苯和50g四丁氧基钛以及8g二异丙氧基锶,在100℃进行1小时预热后,缓慢升温到150℃,蒸馏除去甲苯后,在该状态下反应5小时,进一步升温到250℃,反应5小时,合成出了改性聚碳硅烷。基于有意使低分子量的有机金属化合物共存在该改性聚碳硅烷中的目的,向该改性聚碳硅烷中加入5g四丁氧基钛、4g二异丙氧基锶,得到改性聚碳硅烷和低分子量有机金属化合物的混合物。
使该改性聚碳硅烷和低分子量有机金属化合物的混合物溶解在甲苯中后,加入到玻璃制纺丝装置中,用氮气充分对其内部进行置换后,进行升温以蒸馏除去甲苯,在180℃进行熔融纺丝。接下来,将纺丝纤维在空气中逐级加热到150℃,进行不熔化,然后在1200℃的空气中进行1小时烧制,由此得到实施例2的二氧化硅基复合光催化剂纤维。
根据X射线衍射结果,所得到的实施例2的二氧化硅基复合光催化剂纤维(平均直径:8μm)由无定形二氧化硅、锐钛矿型二氧化钛和钛酸锶构成,根据荧光X射线分析结果,其中二氧化硅为80重量%、二氧化钛为16重量%、钛酸锶为4重量%。另外,根据EPMA考察构成原子的分布状态,证明了其具有钛朝向表面增多的梯度组成,其中,在距最外周部1μm的区域,Ti/Si(摩尔比)=0.85;在距最外周2μm~3μm的区域,Ti/Si(摩尔比)=0.15;在中心部,Ti/Si(摩尔比)=0.02。同样,证明了其具有锶朝向表面增多的梯度组成,其中,在距最外周部1μm的区域,Sr/Si(摩尔比)=0.06;在距最外周2μm~3μm的区域,Sr/Si(摩尔比)=0.02;在中心部,Sr/Si(摩尔比)=0.01。该纤维的拉伸强度为1.8GPa。另外,测定实施例2的二氧化硅基复合光催化剂纤维的ζ电位,求出等电点时,等电点是pH=8.0-8.5。
基于考察所得到的实施例2的二氧化硅基复合光催化剂纤维的防止金属氧化物附着的效果的目的,将0.2g该纤维放入直径60mm的表面皿中,在其中加入溶解有氯化铁和氯化锰的水溶液(浓度分别为10mg/l、60mg/l,pH=7.8)。从该表面皿上方照射波长254nm的紫外线24小时。照射后,从表面皿中取出纤维,使纤维干燥后,用电子显微镜观察纤维表面。结果没有发现纤维表面附着有金属氧化物,表现出了优异的防止附着的效果。
比较例1
向50g通过参考例1的方法合成的聚碳硅烷中加入100g甲苯和50g四丁氧基钛,在100℃进行1小时预热后,缓慢升温到150℃,蒸馏除去甲苯后,在该状态下反应5小时,进一步升温到250℃,反应5小时,合成出了改性聚碳硅烷。基于有意使低分子量的有机金属化合物共存在该改性聚碳硅烷中的目的,向该改性聚碳硅烷中加入5g四丁氧基钛,得到改性聚碳硅烷和低分子量有机金属化合物的混合物。
使该改性聚碳硅烷和低分子量有机金属化合物的混合物溶解在甲苯中后,加入到玻璃制纺丝装置中,用氮气充分对其内部进行置换后,进行升温以蒸馏除去甲苯,在180℃进行熔融纺丝。将该纺丝纤维在空气中逐级加热到150℃,进行不熔化,然后在1200℃的空气中进行1小时烧制,由此得到比较例1的二氧化硅基复合光催化剂纤维。
根据X射线衍射结果,所得到的比较例1的二氧化硅基复合光催化剂纤维(平均直径:8μm)由无定形二氧化硅和锐钛矿型二氧化钛构成,根据荧光X射线分析结果,其中二氧化硅为83重量%、二氧化钛为17重量%。另外,根据EPMA考察构成原子的分布状态,证明了其具有钛朝向表面增多的梯度组成,其中,在距最外周部1μm的区域,Ti/Si(摩尔比)=0.85;在距最外周2μm~3μm的区域,Ti/Si(摩尔比)=0.13;在中心部,Ti/Si(摩尔比)=0.04。该纤维的拉伸强度为1.8GPa。另外,测定比较例1的二氧化硅基复合光催化剂纤维的ζ电位,求出等电点时,等电点是pH=5.0-6.0。
基于考察所得到的比较例1的二氧化硅基复合光催化剂纤维的防止金属氧化物附着的效果的目的,将0.2g该纤维放入直径60mm的表面皿中,在其中加入溶解有氯化铁和氯化锰的水溶液(浓度分别为10mg/l、60mg/l,pH=7.8)。从该表面皿上方照射波长254nm的紫外线24小时。照射后,从表面皿中取出纤维,使纤维干燥后,用电子显微镜观察纤维表面。结果发现了在纤维表面上附着有大量的金属氧化物。用X射线衍射考察金属附着物,结果证明了该金属附着物是氧化铁和氧化锰。
比较例2
向50g通过参考例1的方法合成的聚碳硅烷中加入100g甲苯和50g四丁氧基钛以及5g乙酰丙酮合铁(III),在100℃进行1小时预热后,缓慢升温到150℃,蒸馏除去甲苯后,在该状态下反应5小时,进一步升温到250℃,反应5小时,合成出了改性聚碳硅烷。基于有意使低分子量的有机金属化合物共存在该改性聚碳硅烷中的目的,向该改性聚碳硅烷中加入5g四丁氧基钛、2g乙酰丙酮合铁(III),得到改性聚碳硅烷和低分子量有机金属化合物的混合物。
使该改性聚碳硅烷和低分子量有机金属化合物的混合物溶解在甲苯中后,加入到玻璃制纺丝装置中,用氮气充分对其内部进行置换后,进行升温以蒸馏除去甲苯,在180℃进行熔融纺丝。接下来,将纺丝纤维在空气中逐级加热到150℃,进行不熔化,然后在1200℃的空气中进行1小时烧制,由此得到比较例2的二氧化硅基复合光催化剂纤维。
根据X射线衍射结果,所得到的比较例2的二氧化硅基复合光催化剂纤维(平均直径:8μm)由无定形二氧化硅、锐钛矿型二氧化钛和氧化铁构成,根据荧光X射线分析结果,其中二氧化硅为80重量%、二氧化钛为16重量%、氧化铁为4重量%。另外,根据EPMA考察构成原子的分布状态,证明了其具有钛朝向表面增多的梯度组成,其中,在距最外周部1μm的区域,Ti/Si(摩尔比)=0.87;在距最外周2μm~3μm的区域,Ti/Si(摩尔比)=0.15;在中心部,Ti/Si(摩尔比)=0.03。同样,证明了其具有铁朝向表面增多的梯度组成,其中,在距最外周部1μm的区域,Fe/Si(摩尔比)=0.08;在距最外周2μm~3μm的区域,Fe/Si(摩尔比)=0.02;在中心部,Fe/Si(摩尔比)=0.01。该纤维的拉伸强度为1.7GPa。另外,测定比较例2的二氧化硅基复合光催化剂纤维的ζ电位,求出等电点时,等电点是pH=6.5-7.5。
基于考察所得到的比较例2的二氧化硅基复合光催化剂纤维防止金属氧化物附着的效果的目的,将0.2g该纤维放入直径60mm的表面皿中,在其中加入溶解有氯化铁和氯化锰的水溶液(浓度分别为10mg/l、60mg/l,pH=7.8)。从该表面皿上方照射波长254nm的紫外线24小时。照射后,从表面皿中取出纤维,使纤维干燥后,用电子显微镜观察纤维表面。结果发现了在纤维表面上附着有大量的金属氧化物。用X射线衍射考察金属附着物,结果证明了该金属附着物是氧化铁和氧化锰。
比较例3
向50g通过参考例1的方法合成的聚碳硅烷中加入100g甲苯和50g四丁氧基钛以及3g乙醇钨,在100℃进行1小时预热后,缓慢升温到150℃,蒸馏除去甲苯后,在该状态下反应5小时,进一步升温到250℃,反应5小时,合成出了改性聚碳硅烷。基于有意使低分子量的有机金属化合物共存在该改性聚碳硅烷中的目的,向该改性聚碳硅烷中加入5g四丁氧基钛、2g乙醇钨,得到改性聚碳硅烷和低分子量有机金属化合物的混合物。
使该改性聚碳硅烷和低分子量有机金属化合物的混合物溶解在甲苯中后,加入到玻璃制纺丝装置中,用氮气充分对其内部进行置换后,进行升温以蒸馏除去甲苯,在180℃进行熔融纺丝。接下来,将纺丝纤维在空气中逐级加热到150℃,进行不熔化,然后在1200℃的空气中进行1小时烧制,由此得到比较例3的二氧化硅基复合光催化剂纤维。
根据X射线衍射结果,所得到的比较例3的二氧化硅基复合光催化剂纤维(平均直径:8μm)由无定形二氧化硅、锐钛矿型二氧化钛和氧化钨构成,根据荧光X射线分析结果,其中二氧化硅为80重量%、二氧化钛为15重量%、氧化钨为5重量%。另外,根据EPMA考察构成原子的分布状态,证明了其具有钛朝向表面增多的梯度组成,其中,在距最外周部1μm的区域,Ti/Si(摩尔比)=0.85;在距最外周2μm~3μm的区域,Ti/Si(摩尔比)=0.13;在中心部,Ti/Si(摩尔比)=0.04。同样,证明了其具有钨朝向表面增多的梯度组成,其中在距最外周部1μm的区域,W/Si(摩尔比)=0.07;在距最外周2μm~3μm的区域,W/Si(摩尔比)=0.02;在中心部,W/Si(摩尔比)=0.01。该纤维的拉伸强度为1.6GPa。另外,测定比较例3的二氧化硅基复合光催化剂纤维的ζ电位,求出等电点时,等电点是pH=4.0-5.0。
基于考察所得到的比较例3的二氧化硅基复合光催化剂纤维的防止金属氧化物附着的效果的目的,将0.2g该纤维放入直径60mm的表面皿中,在其中加入溶解有氯化铁和氯化锰的水溶液(浓度分别为10mg/l、60mg/l,pH=7.8)。从该表面皿上方照射波长254nm的紫外线24小时。照射后,从表面皿中取出纤维,使纤维干燥后,用电子显微镜观察纤维表面。结果发现了在纤维表面上附着有大量的金属氧化物。用X射线衍射考察金属附着物,结果证明了该金属附着物是氧化铁和氧化锰。
Claims (6)
1.一种二氧化硅基复合光催化剂,其含有复合氧化物相,所述复合氧化物相主要为第1相即以二氧化硅成分为主体的氧化物相和第2相即二氧化钛相的复合氧化物相,第2相的存在比例朝向表层梯度性增加,该复合光催化剂的特征在于,所述第2相含有钛酸锶和钛酸钡之中的至少一种以上的金属氧化物。
2.如权利要求1所述的二氧化硅基复合光催化剂,其特征在于,相对于二氧化硅基复合光催化剂整体,第1相的存在比例为96重量%~40重量%;相对于二氧化硅基复合光催化剂整体,第2相的存在比例为4重量%~60重量%。
3.如权利要求1或2所述的二氧化硅基复合光催化剂,其特征在于,相对于二氧化硅基复合光催化剂整体,所述金属氧化物的含量为2重量%~40重量%。
4.如权利要求1~3中任一项所述的二氧化硅基复合光催化剂,其中,第2相含有的除钛以外的金属元素的存在比例在距催化剂表面5nm~500nm的深度存在梯度。
5.如权利要求1~4中任一项所述的二氧化硅基复合光催化剂,其特征在于,第2相含有的二氧化钛的晶粒粒径为15nm以下,并且该二氧化钛具有光催化剂功能。
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CN101829556A (zh) * | 2010-05-19 | 2010-09-15 | 福州大学 | 一种用于光催化除砷的钛酸钙光催化剂 |
CN102847529A (zh) * | 2012-02-09 | 2013-01-02 | 江苏大学 | 一种石墨烯/钛酸盐纳米复合可见光催化剂及其制备方法 |
CN104245115A (zh) * | 2012-04-26 | 2014-12-24 | 沙特基础工业公司 | 光催化剂、制备方法、光分解系统 |
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US10265680B2 (en) | 2016-03-04 | 2019-04-23 | Fuji Xerox Co., Ltd. | Silica particle comprising a titania coating and method for producing the same |
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JP3465699B2 (ja) * | 2000-06-13 | 2003-11-10 | 宇部興産株式会社 | シリカ基複合酸化物繊維及びその製造方法 |
JP3812481B2 (ja) * | 2001-04-05 | 2006-08-23 | 宇部興産株式会社 | 有害物質除去フィルター |
JP2003285069A (ja) | 2002-03-28 | 2003-10-07 | Hitachi Metals Ltd | 流体浄化装置 |
JP3465706B1 (ja) * | 2002-05-01 | 2003-11-10 | 宇部興産株式会社 | 可視光活性を有するシリカ基光触媒繊維及びその製造方法 |
JP2004107841A (ja) * | 2002-09-20 | 2004-04-08 | Asahi Kasei Chemicals Corp | 機能性繊維 |
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CN1491743A (zh) * | 2003-09-10 | 2004-04-28 | 武汉理工大学 | 无机耐温载体表面负载梯度复合性能光催化薄膜的材料及制备 |
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WO2008038529A1 (fr) | 2008-04-03 |
US8003562B2 (en) | 2011-08-23 |
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