CN107803900B - 一种具有光催化活性的功能性木材的制备方法 - Google Patents
一种具有光催化活性的功能性木材的制备方法 Download PDFInfo
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Abstract
一种具有光催化降解作用的功能性木质材料的制备方法。本发明要解决木材易污染、紫外光下颜色变化大，单一催化剂光催化降解有机染料催化效率低等问题。首先用氢氧化钠溶液对木材进行表面活化；将质子化处理后的g‑C3N4通过真空浸渍的方法负载于木材表面；以氟钛酸铵和尿素为原料在负载g‑C3N4的木材表面生长TiO2，经保温，清洗等步骤得到具有光催化活性的功能性木材，本产品在紫外光照下四小时内对质量浓度为2mg/L的罗丹明B和亚甲基蓝溶液的降解率可达95％以上，能有效降低木材表面在紫外光老化后的色差变化，大幅度提升木材表面颜色稳定性，该制备技术具有工艺简单，易于操作，成本低廉以及环境友好等优点。
Description
技术领域
本发明涉及光催化降解有机染料的功能性木材的制备方法。
背景技术
木材是一种可再生循环利用的天然高分子聚合物，具有质轻、高强度、绝热、绝缘、耐冲击、隔音、调湿等许多优点，在家具、建筑等领域有着广泛的应用。然而木材存在易变色、易被污染等天然缺陷，尤其在经受长时间紫外线照射后，木材颜色变化大，严重缩短木材使用寿命。TiO2具有廉价、无毒、化学稳定性好等优点，已有学者将TiO2作为光催化剂复合于木材表面，在提高木材的传统性能的同时赋予木材如抗菌性、光催化性能等新功能。但TiO2的低量子效应和较高的电子-空穴对复合率是限制其光催化效率的主要因素。类石墨相氮化碳(g-C3N4)是一种新型非金属半导体光催化剂，由于其热稳定性和化学惰性等特性而广泛应用于分解水产氢、光解有机污染物等方面。但g-C3N4有一显著缺点，即光生电荷易复合、量子效率低，这影响了它的光催化性能。
综上所述，现有木材存在易被污染，耐紫外老化性差等问题，且g-C3N4或TiO2单一催化剂光催化降解有机染料的方法存在催化效率低、回收困难等问题。本发明通过将以三聚氰胺、尿素和氟钛酸铵为原料，通过真空浸渍和液相沉淀法在木质基材表面构建g-C3N4/TiO2复合涂层，获得具有光催化活性的功能性木材，本发明具有操作简单、产品易得、无毒、成本低廉、环境友好等优点。
发明内容
本发明所要解决的技术问题是，克服以上背景技术中提到的不足和缺陷，提供一种对光的利用率高、紫外光照射下能有效降解有机染料的功能性木材的制备方法。
本发明中具有光催化活性的功能性木材的制备方法，具体按下述步骤进行：
(1)木材的预处理：将氢氧化钠溶于去离子水中，制备质量分数为5～15wt％氢氧化钠溶液，落叶松室干锯材木片(30mm(长)×30mm(宽)×2mm(厚))在氢氧化钠溶液中以420W功率超声浸渍5～10min，对木材进行表面活化。
(2)g-C3N4的制备：称取一定量三聚氰胺加入有盖的石英坩埚中，在管式炉中升温至520～550℃，保持2～4h，自然冷却至室温，研磨，得到g-C3N4；
(3)质子化处理g-C3N4：将g-C3N4分散于18.5wt％的盐酸中，室温搅拌，600W功率下超声4～8h，将悬浊液分散于500mL去离子水中，沉降12h，离心取沉淀，用去离子水清洗至中性，烘干。
(4)将g-C3N4负载于木材表面：将质子化处理过的g-C3N4分散于无水乙醇中，420W超声处理10min，将活化处理过的木材试件置于g-C3N4乙醇悬浮液中，放入真空室内，打开真空泵10～20min，在0.09MPa真空度下真空浸渍6～18h。
(5)液相沉淀法将TiO2生长于负载有g-C3N4的木材表面：称量一定量的尿素和氟钛酸铵，溶于去离子水中，配制氟钛酸铵和尿素摩尔质量比为1:20～1:30的混合溶液。将负载有g-C3N4的木材试件和木材试件分别放入混合溶液中并在搅拌的条件下迅速升温到85～110℃，保持30～180min。自然冷却至室温，超声清洗，烘干得到对有机染料具有光催化降解作用的功能性木材。
本发明采用木材作为基材，木材是一种环保、可再生的生物质材料，木材内部分布着发达的孔隙结构，这些孔隙结构的尺寸介于纳米和微米之间，并且相互交错形成一个孔隙网络。采用氢氧化钠溶液对木材表面进行处理后，将g-C3N4成功负载于木材上。在液相沉淀反应中，采用尿素作为沉淀剂，在温度为85～110℃的条件下，反应30～180min，使TiO2颗粒牢固的生长在负载了g-C3N4的木材上，并且与g-C3N4形成异质结构。负载g-C3N4/TiO2复合涂层的木质基材的光催化性能明显优于g-C3N4或TiO2单一涂层的木质基材，g-C3N4与TiO2互相掺杂有效提高了两者的光催化活性。其原因在于g-C3N4与TiO2有匹配的能带结构，在光照下，g-C3N4中由价带跃迁到导带的光生电子迁移到TiO2的导带中，而TiO2价带上留下的空穴迁移到g-C3N4的价带上，这有效的降低了光生电子空穴对的复合率，提高了二者单独使用时的光催化效率，赋予了木材表面良好的光催化性能。本发明采用真空浸渍法和液相沉淀法在木材表面构建g-C3N4/TiO2复合涂层，得到了具有光催化活性的功能性木材。
本发明原料来源广泛，生产成本低，制备过程简单，易于操作，工艺容易控制，环境友好，能够有效的赋予木材光降解有机染料的性能。
具体实施方式
为了便于理解本发明，下文将结合较佳的实施例对本发明作更全面、细致地描述，但本发明的保护范围并不限于以下具体的实施例。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
实例1
将3g氢氧化钠溶解于27g蒸馏水中，制备10wt％氢氧化钠溶液，木材超声浸渍10min，对木材表面进行活化，去离子水清洗，烘干。称取一定量三聚氰胺加入有盖的石英坩埚中，在管式炉中升温至550℃，保持4h，自然冷却至室温，研磨，得到g-C3N4；将1g g-C3N4分散于18.5wt％的盐酸中，室温搅拌，600W功率下超声6h，将悬浊液分散于500mL去离子水中，沉降12h，离心取沉淀，用去离子水清洗至中性，烘干。将质子化处理过的g-C3N4分散于无水乙醇中，420W超声处理10min，将活化处理过的木材试件置于g-C3N4乙醇悬浮液中，放入真空室内，打开真空泵20min，在0.09MPa真空度下真空浸渍18h。蒸馏水冲洗后，清洗多次，烘干。称量一定量的尿素和氟钛酸铵，溶于去离子水中，配置浓度分别为1mol/L和0.04mol/L的混合溶液。将负载g-C3N4的木材试件放入混合溶液中并在搅拌的条件下迅速升温到100℃，保持60min。自然冷却至室温，超声清洗，烘干得到对有机染料具有光催化降解作用的功能性木材。产品对质量浓度为2mg/L的罗丹明B溶液四小时内降解率达到97.3％，对质量浓度为2mg/L亚甲基蓝溶液四小时内降解率达到96.1％，96h紫外老化后，负载g-C3N4/TiO2复合涂层的功能性木材色差变化较素材降低了34％。
实例2
将3g氢氧化钠溶解于27g蒸馏水中，制备10wt％氢氧化钠溶液，木材超声浸渍10min，对木材表面进行活化，去离子水清洗，烘干。称取一定量三聚氰胺加入有盖的石英坩埚中，在管式炉中升温至550℃，保持4h，自然冷却至室温，研磨，得到g-C3N4；将1g g-C3N4分散于18.5wt％的盐酸中，室温搅拌，600W功率下超声4h，将悬浊液分散于500mL去离子水中，沉降12h，离心取沉淀，用去离子水清洗至中性，烘干。将质子化处理过的g-C3N4分散于无水乙醇中，420W功率下超声处理10min，将活化处理过的木材试件置于g-C3N4乙醇悬浮液中，放入真空室内，打开真空泵15min，在0.09MPa真空度下真空浸渍12h。之后蒸馏水冲洗、，清洗多次，烘干。称量一定量的尿素和氟钛酸铵，溶于去离子水中，配置浓度分别为1mol/L和0.04mol/L的混合溶液。将负载g-C3N4的木材试件放入混合溶液中并在搅拌的条件下迅速升温到90℃，保持120min。自然冷却至室温，超声清洗，烘干得到对有机染料具有光催化降解作用的功能性木材。产品对质量浓度为2mg/L的罗丹明B溶液四小时内降解率达到95.5％，对质量浓度为2mg/L亚甲基蓝溶液四小时内降解率达到94.7％，96h紫外老化后，负载g-C3N4/TiO2复合涂层的功能性木材色差变化较素材降低了30％。
实例3
将3g氢氧化钠溶解于27g蒸馏水中，制备10wt％氢氧化钠溶液，木材超声浸渍10min，对木材表面进行活化，去离子水清洗，烘干。称取一定量三聚氰胺加入有盖的石英坩埚中，在管式炉中升温至550℃，保持4h，自然冷却至室温，研磨，得到g-C3N4；将g-C3N4分散于18.5wt％的盐酸中，室温搅拌，600W下超声2h，将悬浊液分散于500mL去离子水中，沉降12h，离心取沉淀，用去离子水清洗至中性，烘干。将质子化处理过的g-C3N4分散于无水乙醇中，420W功率下超声处理20min，将活化处理过的木材试件置于g-C3N4乙醇悬浮液中，放入真空室内，20min后关闭真空泵，在0.09MPa真空度下真空浸渍6h。之后，蒸馏水冲洗，清洗多次，烘干。称量一定量的尿素和氟钛酸铵，溶于去离子水中，配置浓度分别为1mol/L和0.04mol/L的混合溶液。将负载g-C3N4的木材试件放入混合溶液中并在搅拌的条件下迅速升温到90℃，保持30min。自然冷却至室温，超声清洗，烘干得到对有机染料具有光催化降解作用的功能性木材。产品对质量浓度为2mg/L的罗丹明B溶液四小时内降解率达到85.5％，对质量浓度为2mg/L亚甲基蓝溶液四小时内降解率达到84.7％，96h紫外老化后，负载g-C3N4/TiO2复合涂层的功能性木材色差变化较素材降低了22％。
实例4
将3g氢氧化钠溶解于27g蒸馏水中，制备10wt％氢氧化钠溶液，木材超声浸渍10min，对木材表面进行活化，去离子水清洗，烘干。称取一定量三聚氰胺加入有盖的石英坩埚中，在管式炉中升温至550℃，保持4h，自然冷却至室温，研磨，得到g-C3N4；将1g g-C3N4分散于18.5wt％的盐酸中，室温搅拌，600W功率下超声4h，将悬浊液分散于500mL去离子水中，沉降12h，离心取沉淀，用去离子水清洗至中性，烘干。将质子化处理过的g-C3N4分散于无水乙醇中，420W功率超声处理10min，将活化处理过的木材试件置于g-C3N4乙醇悬浮液中，放入真空室内，打开真空泵20min，在0.09MPa真空度下真空浸渍12h。蒸馏水冲洗后，清洗多次，烘干。称量一定量的尿素和氟钛酸铵，溶于去离子水中，配置浓度分别为1mol/L和0.04mol/L的混合溶液。将负载g-C3N4的木材试件放入混合溶液中并在搅拌的条件下迅速升温到100℃，保持120min。自然冷却至室温，超声清洗，烘干得到对有机染料具有光催化降解作用的功能性木材。产品对质量浓度为2mg/L的罗丹明B溶液四小时内降解率达到93.6％，对质量浓度为2mg/L亚甲基蓝溶液四小时内降解率达到91.9％，96h紫外老化后，负载g-C3N4/TiO2复合涂层的功能性木材色差变化较素材降低了31％。
Claims (6)
1.一种具有光催化活性的功能性木材的制备方法，包括以下步骤：
(1)将氢氧化钠溶于去离子水中制备氢氧化钠溶液，将木材浸渍于氢氧化钠溶液中，超声，对木材进行表面活化；
(2)取一定量三聚氰胺加入有盖的石英坩埚中，在管式炉中加热到一定温度后保温一段时间，自然冷却，研磨得到g-C3N4，将g-C3N4分散于盐酸中，室温搅拌，超声，离心，清洗至中性，烘干，得到质子化后的g-C3N4；
(3)取适量质子化后的g-C3N4粉末均匀分散于无水乙醇中，将氢氧化钠活化处理过的木材试件置于其中，真空浸渍，蒸馏水冲洗，清洗多次，烘干，得到负载g-C3N4的木材；
(4)将尿素和氟钛酸铵溶于去离子水中，配制一定浓度的混合溶液，将负载g-C3N4的木材试件放入混合溶液中并在搅拌的条件下迅速升温，保温一段时间，使TiO2生长于负载g-C3N4的木材表面，自然冷却至室温，取出木材试件，超声清洗，烘干得到对有机染料具有光催化降解作用的功能性木材。
2.根据权利要求1所述的一种具有光催化活性的功能性木材的制备方法，其特征在于步骤(1)中，对木材进行预处理，具体是将木材浸渍于浓度为5～15wt％的氢氧化钠溶液中，以420W功率超声处理5～20min。
3.根据权利要求1所述的一种具有光催化活性的功能性木材的制备方法，其特征在于步骤(2)中，质子化处理g-C3N4，具体是盐酸浓度为18.5wt％，处理时间4～8h。
4.根据权利要求1所述的一种具有光催化活性的功能性木材的制备方法，其特征在于所述步骤(3)中，所述浸渍操作具体为真空浸渍，真空度为0.09MPa～0.1MPa，浸渍时间为6～18h。
5.根据权利要求1所述的一种具有光催化活性的功能性木材的制备方法，其特征在于所述步骤(4)中，氟钛酸铵与尿素的摩尔质量比是1:20～1:30，反应温度为90～110℃，保持时间为30～180min。
6.根据权利要求1所述的一种具有光催化活性的功能性木材的制备方法，其特征在于所述步骤(3)与步骤(4)中，具体是先通过真空浸渍的方法将g-C3N4负载于木材上，之后采用液相沉淀法在负载有g-C3N4的木材表面生长TiO2。
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