CN105565899A - 一种具有可见光催化功能的半透明蜂窝陶瓷的制备 - Google Patents
一种具有可见光催化功能的半透明蜂窝陶瓷的制备 Download PDFInfo
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Abstract
本发明提供了一种具有可见光催化功能的半透明蜂窝陶瓷的制备,将光催化剂薄膜负载于半透明蜂窝陶瓷载体上,包括半透明蜂窝陶瓷载体制备和负载光催化剂薄膜的制备二个步骤:先制备对可见光半透明的氧化铝蜂窝陶瓷载体,然后采用溶胶-凝胶法将稀土和氮共掺杂的TiO2溶胶负载于载体上,经烧结形成厚度为纳米级的均匀、透明光催化剂薄膜。本发明载体的催化剂薄膜能响应可见光发挥催化作用,二是载体对可见光也具有半透明性,因而能有效利用可见光,提高光催化效率,从而为实现太阳光的光催化治理污染提供了一种实用材料。
Description
技术领域
本发明涉及可见光透明及光催化功能陶瓷的制备,属于无机非金属材料制造技术领域。
背景技术
一般陶瓷因为内部存在杂质和气孔是不透明的。如果选用高纯原料,并通过特定工艺排除气孔就可能获得透明陶瓷,其工艺包括粉体制备、成型、烧结以及后处理等。目前国内外已先后开发出Al2O3、Y2O3、MgO、CaO、TiO2、ThO2、ZrO2等氧化物透明陶瓷,以及AlN、ZnS、ZnSe、MgF2、CaF2等非氧化物透明陶瓷。透明陶瓷不仅具有较好的透明性,而且还具有耐腐蚀,耐高温、高强度、介电性能优良、低电导率、高热导性等性能,已成为一种新型的、备受瞩目的功能材料,逐渐在照明技术、光学、特种仪器制造、无线电子技术及高温技术等领域获得日益广泛的应用。
近年来有关文献已有很多报道,代表性的论文有“透明陶瓷材料现状与发展”,“透明陶瓷—无机材料研究与发展重要方向之一”,“透明氧化铝陶瓷的制备和体视学在其性能表征中的作用”,“透明氧化铝陶瓷管工艺艺术报告”、“透明氧化铝陶瓷”和“氧化物透明陶瓷的中国专利申请现状分析”等;有关透明陶瓷的发明专利也较多,如“作为GaN基LED的衬底材料的Al2O3透明陶瓷及其制备方法,ZL201110329850.2”,“一种Ti掺杂α-Al2O3透明陶瓷热释光材料的制备方法,ZL201310134408.3”,“一种LED用透明陶瓷荧光基板的制备方法,ZL201210156770.6”,“C掺杂α-Al2O3透明陶瓷热释光和光释光材料的制备方法,ZL200910052018.5”,“一种铕、镝离子共掺杂的铝酸锶透明陶瓷的合成方法,ZL201310036296.8”,“透明氮氧化铝陶瓷的制备工艺,ZL200710013606.9”等。
有关掺杂TiO2光催化剂在各种载体上负载的发明专利也比较多,如“TiO2负载S掺杂TiO2可见光催化剂及其制备方法,ZL201110158746”,“炻器载体上钕/氮共掺杂TiO2可见光响应催化膜及制备,ZL201210248894.7”,“Lu、N共掺杂TiO2光催化蜂窝陶瓷网的制备方法,ZL201310348060.8”等。另外,至今只发现与本发明相同发明人提出并公示的“一种可见光半透明三维蜂窝陶瓷网的制备方法CN105198474A”的发明专利,其它有关报道尚未发现。
但是,至今尚未见到国内外有关具有可见光催化功能的半透明蜂窝陶瓷报道。更未见到用该技术和材料治理废气和废水的报道。
发明内容
本发明的目的是:旨在提供一种具有可见光催化功能的半透明蜂窝陶瓷,它是半透明蜂窝陶瓷载体与具有可见光催化功能透明薄膜的结合,能有利于利用可见光催化,有利于可见光的利用,从而为利用太阳光实施光催化治理环境污染提供一种实用技术和材料。
本发明的技术方案是:一种具有可见光催化功能的半透明蜂窝陶瓷的制备,使将光催化剂薄膜负载于半透明蜂窝陶瓷载体上,包括半透明蜂窝陶瓷载体的制备和负载光催化剂薄膜的制备等二个步骤:
(1)制备半透明蜂窝陶瓷载体
原料准备:基体原料为(自制的或市售的)高纯度、超细度α-Al2O3;烧结助剂为MgO和和XT2O3;将基体原料与适量Mg和XT的硝酸盐混合,以乙醇或为分散介质,球磨后在350~500℃煅烧使XT硝酸盐分解成氧化物;其它添加剂包括粘结剂,润滑剂,消泡剂等;蒸馏水;
制备样品干坯体:先将上述原料按照一定比例进行机械混合、捏合,然后真空脱气练制2~3次使之塑性转变,并在室温下陈腐20~30h形成塑性泥料;泥料在15~30MPa压力下经过模具挤压成型,得到湿坯体;湿坯体经过195~210℃射频干燥0.4~0.5h,最后切割成厚度为6mm~15mm的蜂窝陶瓷干坯体样品;
样品烧成:干坯体采用二次烧成,第一次是将样品置于(碳棒)加热炉内在空气气氛中煅烧,以230~260℃/h速度升温到1100~1300℃,保持2h,冷却至室温;第二次是将第一次煅烧的样品置于硅钼棒电炉内并用氢气流保护或在真空状态下煅烧,以80~120℃/h由室温升温至380~420℃,然后以50~80℃/h升温至1400~1600℃,再以20~40℃升温至1700~1900℃保温1~3h;然后以300℃/h降温至1100~1300℃,以150℃/h降至300~500℃,再以40~50℃/h降至室温,得到半透明三维蜂窝陶瓷成品。
(2)XT和N共掺杂TiO2光催化剂薄膜的负载
XT和N共掺杂TiO2溶胶的制备:①将钛酸正丙酯或钛酸正丁酯缓慢滴加入pH为1~3的无水乙醇和冰乙酸的混合溶液中,室温下搅拌0.5~2h得到溶液A,其中钛酸正丙酯或正丁酯∶无水乙醇∶冰乙酸=11.53~23.04∶51.97~65.12∶0.69~7.13(质量比);②将尿素、XT(NO3)2·6H2O溶于无水乙醇和去离子水中,混合搅拌得到溶液B,其中尿素∶XT(NO3)2·6H2O∶无水乙醇∶去离子水=0.23~0.85∶0.01~0.61∶14.87~26.12∶0.69~3.54(质量比);③将溶液A缓慢滴加至置于冰水浴的溶液B中,不断搅拌得到掺杂TiO2溶胶,继续搅拌0.5~1h。
共掺杂TiO2溶胶的负载:将制得的半透明蜂窝陶瓷载体用稀酸、稀碱、乙醇、蒸馏水超声清洗,干燥后浸渍于上述制备的掺杂TiO2溶胶中,采用浸渍-提拉法在载体上负载湿膜,然后在60~100℃下干燥20min,冷却至室温。最后将样品置于程序控温炉内以3℃/min速度升温至300~700℃热处理,保温1~5h,自然冷却,得到负载了XT和N共掺杂TiO2光催化薄膜的半透明蜂窝陶瓷成品。
载体中高纯度、超细度α-Al2O3的制备:将纯度4N(含量99.99%)的AlNH4(SO4)2·xH2O(x=6~24),通过程序升温至1100~1300℃煅烧,然后研磨,得到纯度大于99.95%、平均晶粒0.1~0.5μm的α-Al2O3。
制备载体所用基体原料、烧结助剂和在混合物中的质量组份数:基体原料为α-Al2O3,95~100;烧结助剂前驱物Mg(NO3)2·6H2O为0.1~0.6,以及2种XT(NO3)3·6H2O,0.1~0.4,其中XT为镧La、钇Y、铈Ce和镨Pr等。
制备载体所用添加剂的名称和在混合物中的质量组份数:粘结剂为羟基丙基纤维素或羟基甲基(或乙基)纤维素等,2~8;润滑剂为甘油、乙二醇或丙三醇等,2~7;消泡剂为正丁醇或乙醇等,1~5;蒸馏水为18~28。
制备载体时,对混合原料进行真空脱气炼制的真空度为-0.095~-0.099MPa,使之高效除去除泥料中的气泡。
制备载体时,挤压模具的横截面为正方形或矩形或圆,其边长或圆的直径为60mm~200mm,模具槽宽0.2~1.2mm,孔密度为100~300孔/平方英寸。
TiO2溶胶中掺杂的XT(NO3)2·6H2O,其中XT为镧La,铈Ce,镨Pr,钕Nd,钐Sm,铕Eu,钆Gd,镝Dy,铒Er和钇Y中的1种或1种以上。
TiO2溶胶中掺杂的体系组分的质量比为XT∶N∶TiO2=0.01~0.16∶0.40~1.88∶97.94~99.54。
在载体上负载溶胶时,采用浸渍-提拉步骤可以反复多次,以得到所需要厚度的薄膜,涂层厚度为17.3~25.4μm。
本发明的有益效果:本发明在严格控制原料的配比、制备工艺和烧成制度等条件下,采用优化的陶瓷工艺制得了对可见光半透明的蜂窝陶瓷载体,再用溶胶-凝胶法在载体上负载了能响应可见光催化的掺杂TiO2薄膜,使得到的产品能大大提高可见光的利用率和光催化反应效率。与现有的非透明的蜂窝陶瓷载体比较有明显的效率的提高,可以使整个表面积的材料发挥催化作用,尤其是本发明的光谱对象是可以光频谱(包括红外光谱)。可以预见,该材料的发明对于采用光催化技术治理污染,特别是对利用太阳实施光催化将会起到极大的促进,该技术和器件可以治理废气和废水,也将会带来良好的经济和社会效益。
具体实施方式
1、半透明蜂窝陶瓷载体的制备
将基体原料α-Al2O3,烧结助剂Mg和稀土的前躯体硝酸盐按适量比例混合,并在在400~500℃煅烧使硝酸盐分解,得到的氧化物粉末再与适量粘结剂,润滑剂,消泡剂和蒸馏水混合,通过机械混合、捏合后再经过真空脱气练制,使之高效除去除泥料中的气泡,再通过陈腐使之形成塑性泥料;泥料在15~30MPa压力下经过模具挤压成型,得到湿坯体;湿坯体经过射频干燥后切割成一定厚度的蜂窝陶瓷干坯体。
干坯体采用二次烧成,第一次是在空气气氛中1100~1300煅烧1~2h;第二次是在真空状态或氢气流保护下,采用程序升温法至1700~1900℃煅烧,保持1~4h;然后采用程序降温法冷却至室温,得到半透明蜂窝陶瓷成品。
(1)原料
基体原料为高纯度、超细度α-Al2O3粉体,制备方法是将纯度4N(含量99.99%)的AlNH4(SO4)2·xH2O(x=6~24),通过程序升温至1100~1300℃煅烧,然后研磨,得到纯度大于99.95%、平均晶粒0.1~0.5μm的α-Al2O3。
烧结助剂的前躯体为Mg(NO3)2·6H2O和2种XT(NO3)3·6H2O,均为分析纯,式中XT为镧La、钇Y、铈Ce和镨Pr等。在以下“(2)原料混合与处理中”,硝酸盐通过焙烧即得到烧结助剂MgO及2种XT2O3粉体。
添加剂:润滑剂为甘油或丙三醇等,粘结剂为羟基丙基纤维素或羟基甲基(或乙基)纤维素等,消泡剂为正丁醇或乙醇等,均为分析纯。
蒸馏水。
(2)原料混合与处理
上述原料按以下质量份数混合:基体原料为α-Al2O3的质量份数为95~100;烧结助剂前驱物Mg(NO3)2·6H2O为0.1~0.6,2种XT(NO3)3·6H2O为0.1~0.4,其中XT为镧La、钇Y、铈Ce和镨Pr等。原料经过机械混合捏合,然后在真空度-0.095~-0.099MPa下脱气练制2~3次,使之高效除去除泥料中的气泡,并在15~30℃下陈腐20~30h形成塑性泥料。
(3)干坯体制备
塑性泥料在15~30MPa压力下经过模具挤压得到湿坯体,模具横截面为正方形或矩形或圆,其边长或圆的直径为60mm~200mm,模具槽宽0.2~1.2mm,孔密度为100~300孔/平方英寸;湿坯体经过195~210℃射频干燥0.4~0.5h,最后切割成厚度为6mm~15mm的蜂窝陶瓷干坯体。
(4)烧成
干坯体采用二次烧成,第一次是在空气气氛中1100~1300煅烧1~2h;第二次是在真空状态或氢气流保护下,采用程序升温法至1700~1900℃煅烧,保持1~4h;然后采用程序降温法冷却至室温,得到半透明蜂窝陶瓷成品。
2、XT/N共掺杂TiO2光催化剂薄膜的负载与焙烧
以钛酸正丙酯或钛酸正丁酯、尿素、六水合硝酸稀土盐、以及无水乙醇、冰乙酸和去离子水为原料,采用溶胶/凝胶法制得XT和N掺杂的TiO2溶胶;然后将制得的半透明蜂窝陶瓷载体浸渍于掺杂的TiO2溶胶中,数分钟后提拉起载体晾干,此时在载体上形成了溶胶湿膜,其浸渍-提拉过程可进行多次,直至达到所需的负载量。然后将样品置于程序控温炉内在300~700℃焙烧,得到负载了XT/N共掺杂TiO2光催化薄膜的半透明蜂窝陶瓷成品。具体步骤:
(1)XT和N共掺杂TiO2溶胶的制备
将钛酸正丙酯或钛酸正丁酯缓慢滴加入pH为1~3的无水乙醇和冰乙酸的混合溶液中,室温下搅拌0.5~2h得到溶液A,其中钛酸正丙酯或正丁酯∶无水乙醇∶冰乙酸=11.53~23.04∶51.97~65.12∶0.69~7.13(质量比);
将尿素、XT(NO3)2·6H2O溶于无水乙醇和去离子水中,混合搅拌得到溶液B,其中尿素∶XT(NO3)2·6H2O∶无水乙醇∶去离子水=0.23~0.85∶0.01~0.61∶14.87~26.12∶0.69~3.54(质量比);
将A液缓慢滴加至置于冰水浴的B液中,不断搅拌得到掺杂TiO2溶胶,继续搅拌0.5~1h。
(2)共掺杂TiO2溶胶的负载和焙烧
将制得的半透明蜂窝陶瓷载体用稀酸、稀碱、乙醇、蒸馏水超声清洗,干燥后浸渍于上述制备的掺杂TiO2溶胶中,采用浸渍-提拉法在载体上负载湿膜,然后在60~100℃下干燥20min,冷却至室温;
最后将样品置于程序控温炉内以3℃/min速度升温至300~700℃热处理,保温1~5h,自然冷却,得到负载了XT和N共掺杂TiO2光催化薄膜的半透明蜂窝陶瓷成品。
3、检测
(1)用游标尺、直尺、天平分别测量样品的几何尺寸、体积密度、孔密度和壁厚。
(2)用压力机测定样品的抗压强度。
(3)用721分光光度法测量样品的透光率,测定波长为645nm,样品切割成片状。
(4)用SEM(扫描电子显微镜)测定XT/N共掺杂TiO2光催化膜的厚度和形态。
(5)用UV-Vis漫反射光谱测定光催化膜的吸收光谱。
(6)亚甲基蓝水溶液的光降解试验:将负载掺杂TiO2光催化膜的半透明蜂窝陶浸入亚甲基蓝溶液中,以模拟日光的500W氙灯为光源进行光解,测定亚甲基蓝吸光度变化,得出甲基蓝的光解脱色率。
实施例1:半透明蜂窝陶瓷载体之一。
按照上述实施方式制得可见光半透明蜂窝陶瓷载体40件,制作方法和样品测得的各种参数如下:
(1)原料及混合质量份
基体原料为α-Al2O3,是将纯度为4N(含量99.99%)的AlNH4(SO4)2·xH2O(x=6~24),通过程序升温至1200℃煅烧,然后研磨,得到纯度大于99.95%、平均晶粒0.1~0.5μm的α-Al2O3,在混合原料中的质量组份数为100。
烧结助剂:Y(NO3)3·6H2O在混合原料中的质量组份数为0.2,La(NO3)3·6H2O为0.2,Mg(NO3)2·6H2O为0.4,试剂均为分析纯。
润滑剂为甘油,在混合原料中的质量组份数为3;粘结剂为羟基丙基纤维素,质量组份数为5;消泡剂为正丁醇,质量组份数为3;蒸馏水的质量组份数为22;试剂均为分析纯。
(2)原料混合与处理
将上述原料混匀混合捏合,然后在真空度为-0.098MPa下脱气练制3次使之塑性转变,并在20℃下陈腐25h形成塑性泥料。
(3)模具挤压成湿坯体
挤压模具的横截面为正方形,其边长为100mm,模具槽宽1.2mm,孔密度为200孔/平方英寸,塑性泥料经过模具挤压成型得到湿坯体。
(4)干坯体制备和切割
湿坯体经过205℃射频干燥0.5h得到干坯体,最后切割成厚度为10mm的三维蜂窝陶瓷网干坯体。
(6)烧成
干坯体采用二次烧成,第一次是将试样置于碳棒加热炉内在空气气氛中预烧,以250℃/h速度升温到1200℃,保持2h,冷却;第二次是将预烧后的试样置于硅钼棒电炉中并在氢气流保护下烧结,先以100℃/h由室温升温至400℃,并以60℃/h升温至1600℃,以30℃升温至1800℃,保温2h;然后以300℃/h降温至1200℃,并以150℃/h降至400℃,最后以50℃/h降至室温,得到半透明蜂窝陶瓷载体。
(7)检测
用游标尺、直尺、天平分别测样品:外观尺寸为100mm×100mm×10mm,壁厚1.1mm,孔密度200孔/平方英寸,体积密度0.65g/cm3。
用压力机测定样品的强度:轴向抗压强度75Mpa,径向抗压强度25Mpa。
用721分光光度计测量样品的透光率:将样品切割成10mm×10mm×1mm的薄片,测定波长为645nm,测得透光率为20%。
实施例2:半透明蜂窝陶瓷载体之二。
将实施例1中烧结助剂的质量份数减半,即Y(NO3)3·6H2O为0.1,La(NO3)3·6H2O为0.1,Mg(NO3)2·6H2O为0.2,而基体原料为氧化铝,润滑剂为甘油、粘结剂为羟基丙基纤维素、消泡剂为正丁醇以及蒸馏水的质量份数不变。同时原料混合与处理、干坯体制备和切割、烧成制度等工艺和检测项目也与实施例1保持相同。对制得三维蜂窝陶瓷网样品进行检测结果为:
外观尺寸、壁厚、轴向和径向抗压强度、体积密度等指标与实施例1样品相同,但样品的透光率下降为8%,表明烧结助剂量对透光率等性能的影响较大。
实施例3:负载了Ga/N共掺杂TiO2光催化剂薄膜的半透明蜂窝陶瓷。
(1)半透明蜂窝陶瓷载体制备同实施例1。
(2)钆/氮共掺杂TiO2溶胶的制备:①将钛酸正丙酯缓慢滴加入pH为2的无水乙醇和冰乙酸的混合溶液中,室温下搅拌1h得到溶液A,其中钛酸正丙酯或正丁酯∶无水乙醇∶冰乙酸=15.5∶59.7∶4.1(质量比);②将尿素、Gd(NO3)2·6H2O溶于无水乙醇和去离子水中,混合搅拌得到溶液B,其中尿素∶Gd(NO3)2·6H2O∶无水乙醇∶去离子水=0.52∶0.35∶20.8∶0.45(质量比);③将A液缓慢滴加至置于冰水浴的B液中,不断搅拌得到掺杂TiO2溶胶,继续搅拌0.5h。
(3)共掺杂TiO2溶胶的负载
将实施例1制得的半透明蜂窝陶瓷载体之一分别用稀酸、稀碱、乙醇、蒸馏水超声清洗,干燥后浸渍于上述制备的掺杂TiO2溶胶中,采用浸渍-提拉法在载体上负载湿膜,重复2次,然后在80℃下干燥20min,冷却至室温。
(4)烧成
将样品置于程序控温炉内以3℃/min速度升温至500℃热处理,保温3h,自然冷却,得到负载了Ga/N共掺杂TiO2光催化薄膜的半透明蜂窝陶瓷成品。
(5)检测
样品的外观尺寸,壁厚,孔密度,轴向和径向抗压强度,体积密度,透光率等数据与实施例1的检测结果相同。
SEM测定表明,钆/氮共掺杂TiO2催化剂晶粒约为15~30nm,光催化膜膜面平整,膜的厚度为300~400nm,掺杂的颗粒排列整齐。
UV-Vis漫反射光谱测定表明,纯TiO2粉末的吸收波长低于387nm,而钆/氮共掺杂TiO2吸收带红移至600nm,因而能有效利用可见光。
将负载掺杂TiO2光催化膜的半透明蜂窝陶浸入亚甲基蓝溶液中,以模拟日光的500W氙灯为光源进行光解,测定亚甲基蓝吸光度变化,得出甲基蓝的光解脱色率为93.2%。
实施例4:负载Dy/N共掺杂TiO2光催化剂薄膜的半透明蜂窝陶瓷。
(1)半透明蜂窝陶瓷载体制备同实施例1。
(2)镝/氮共掺杂TiO2溶胶的制备:所用试剂、用量和步骤与实施例3中“钆/氮共掺杂TiO2溶胶的制备”相同,只是以Dy(NO3)2·6H2O代替了Gd(NO3)2·6H2O。
(3)共掺杂TiO2溶胶的负载、烧成步骤和检测方法均与实施例3相同。
样品的检测结果如下:
样品的外观尺寸,壁厚,孔密度,轴向和径向抗压强度,体积密度,透光率等数据与实施例1的检测结果相同。
样品催化剂薄膜厚度,薄膜中晶粒大小,催化剂薄膜对可见光吸收等测定结果与实施例3的结果基本相同。以得到的样品做光催化亚甲基蓝溶液试验,得出甲基蓝的光解脱色率为90.8%,表明镝/氮共掺杂TiO2光催化亚甲基蓝的脱色效果与钆/氮共掺杂TiO2也基本相同。原因是钆、镝都是稀土元素,内部结构相似,二者在TiO2中的存在方式和光催化方式也相同。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
1.一种具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征是将光催化剂薄膜负载于半透明蜂窝陶瓷载体上,包括半透明蜂窝陶瓷载体制备和负载光催化剂薄膜的制备二个步骤:
(1)制备半透明蜂窝陶瓷载体
原料准备:基体原料为高纯度、超细度α-Al2O3;烧结助剂为MgO和XT2O3(XT为稀土元素,下同);将基体原料与适量Mg和XT的硝酸盐混合,以乙醇或为分散介质,球磨后在350~500℃煅烧使Mg和XT硝酸盐分解成氧化物;其它添加剂包括粘结剂,润滑剂,消泡剂等;蒸馏水;
制备样品干坯体:先将上述原料按照一定比例进行机械混合、捏合,然后真空脱气练制2~3次使之塑性转变,并在室温下陈腐20~30h形成塑性泥料;泥料在15~30MPa压力下经过模具挤压成型,得到湿坯体;湿坯体经过195~210℃射频干燥0.4~0.5h,最后切割成厚度为6mm~15mm的蜂窝陶瓷干坯体样品;
样品烧成:干坯体采用二次烧成,第一次是将样品置于加热炉内在空气气氛中煅烧,以230~260℃/h速度升温到1100~1300℃,保持2h,冷却至室温;第二次是将第一次煅烧的样品置于硅钼棒电炉内并用氢气流保护或在真空状态下煅烧,以80~120℃/h由室温升温至380~420℃,然后以50~80℃/h升温至1400~1600℃,再以20~40℃升温至1700~1900℃保温1~3h;然后以300℃/h降温至1100~1300℃,以150℃/h降至300~500℃,再以40~50℃/h降至室温,得到半透明蜂窝陶瓷成品;
(2)XT和N共掺杂TiO2光催化剂薄膜的负载
XT和N共掺杂TiO2溶胶的制备:①将钛酸正丙酯或钛酸正丁酯缓慢滴加入pH为1~3的无水乙醇和冰乙酸的混合溶液中,室温下搅拌0.5~2h得到溶液A,其中质量比:钛酸正丙酯或正丁酯∶无水乙醇∶冰乙酸=11.53~23.04∶51.97~65.12∶0.69~7.13;②将尿素、XT(NO3)2·6H2O溶于无水乙醇和去离子水中,混合搅拌得到溶液B,其中尿素∶XT(NO3)2·6H2O∶无水乙醇∶去离子水=0.23~0.85∶0.01~0.61∶14.87~26.12∶0.69~3.54;③将溶液A缓慢滴加至置于冰水浴的溶液B中,不断搅拌得到掺杂TiO2溶胶,继续搅拌0.5~1h;
共掺杂TiO2溶胶的负载:将制得的半透明蜂窝陶瓷载体用稀酸、稀碱、乙醇、蒸馏水超声清洗,干燥后浸渍于上述制备的掺杂TiO2溶胶中,采用浸渍-提拉法在载体上负载湿膜,然后在60~100℃下干燥20min,冷却至室温;最后将样品置于程序控温炉内以3℃/min速度升温至300~700℃热处理,保温1~5h,自然冷却,得到负载了XT和N共掺杂TiO2光催化薄膜的半透明蜂窝陶瓷成品。
2.根据权利要求1所述具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征在于载体中高纯度、超细度α-Al2O3的制备:将纯度4N即质量含量99.99%的AlNH4(SO4)2·xH2O(x=6~24),通过程序升温至1100~1300℃煅烧,然后研磨,得到纯度大于99.95%、平均晶粒0.1~0.5μm的α-Al2O3。
3.根据权利要求1所述具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征在于制备载体所用基体原料、烧结助剂和在混合物中的质量组份数:基体原料为α-Al2O3,95~100;烧结助剂前驱物Mg(NO3)2·6H2O为0.1~0.6,以及2种XT(NO3)3·6H2O,0.1~0.4,其中XT为镧La、钇Y、铈Ce、镨Pr、钕Nd、钐Sm、铕Eu、钆Gd、镝Dy、铒Er和钇Y中选择1种或1种以上。
4.根据权利要求1所述具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征在于制备载体所用添加剂在混合物中的质量组份数:粘结剂为羟基丙基纤维素或羟基甲基(或乙基)纤维素等,2~8;润滑剂为甘油、乙二醇或丙三醇,2~7;消泡剂为正丁醇或乙醇,1~5;蒸馏水为18~28。
5.根据权利要求1所述具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征在于制备载体时,对混合原料进行真空脱气炼制的真空度为-0.095~-0.099MPa,使之高效除去除泥料中的气泡。
6.根据权利要求1所述具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征在于制备载体时,挤压模具的横截面为正方形或矩形或圆,其边长或圆的直径为60mm~200mm,模具槽宽0.2~1.2mm,孔密度为100~300孔/平方英寸。
7.根据权利要求3所述具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征在于TiO2溶胶中掺杂的体系组分的质量比为XT∶N∶TiO2=0.01~0.16∶0.40~1.88∶97.94~99.54。
8.根据权利要求1所述具有可见光催化功能的半透明蜂窝陶瓷的制备,其特征在于在载体上负载溶胶时,采用浸渍-提拉步骤反复多次直到需要厚度的薄膜,需要的厚度为17.3~25.4μm。
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