CN108816255B - 一种AZO/NaCl复合改性TiO2光触媒及其制备方法 - Google Patents
一种AZO/NaCl复合改性TiO2光触媒及其制备方法 Download PDFInfo
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Abstract
本发明公开一种AZO/NaCl复合改性TiO2高效光触媒及其制备方法，所述TiO2光触媒的粒径尺寸在5～7nm，AZO纳米粉体的粒径尺寸在17‑25nm，且均具有高结晶性。该方法利用AZO复合改性、Na离子与Cl离子双电层作用、乳液的空间位阻作用制备TiO2光触媒表面能形成高载流子传输性能和高催化性能的复合光触媒，该方法制备的光触媒可见光光催化性能好；该制备方法不需要酸碱中和改性剪切，具有工艺简单、成本低、制备周期短、环境友好等特点。可见光照下，该光触媒可用于高效去除甲醛、降解苯及其衍生物等领域，也可用于其他空气净化和环境保护等，具有良好的应用前景。
Description
技术领域
本发明涉及光触媒的制备方法，具体涉及一种AZO/NaCl复合改性TiO2光触媒及其制备方法。
背景技术
TiO2是目前应用最广泛的一种光催化半导体材料，可催化降解甲醛、甲苯或TVOC等有毒有害化合物，被广泛应用于环保领域。此外，TiO2具有优异的物理及化学的稳定性、无毒无害性和价廉等特点。但是，TiO2带隙较宽(锐钛矿为3.2eV，金红石为3.0eV)，只能在紫外线照射下产生电子空穴对，其对太阳光的利用率极低，光催化效果差。另外，TiO2光生电子空穴对较短的电子空穴扩散长度，产生的电子空穴对没有扩散到颗粒表面就被消耗掉了，也是光催化效率低\光催化活性差的重要因素。目前，如何改性TiO2使其具有较窄的禁带宽度、较长的电子空穴扩散长度，实现可见光应用、增加电荷产生率、抑制电子空穴复合，进而提高光催化性能和化学及光化学稳定的光催化剂成为研究的焦点问题(廖添,华南师范大学学报,2017:31-37)。
光触媒是一种以纳米级TiO2为代表的具有光催化功能光半导体材料的总称，通常将TiO2粉体经过球磨、搅拌、分散到水性介质中形成稳定浆料。浆料可以喷涂于墙壁、家具、沙发、天花板、窗帘等物体表面，在光线的照射作用下，催化降解有毒有害物质，能降解空气中有毒有害气体，比如甲醛；光触媒还能有效杀灭多种细菌，并能将真菌释放出的毒素分解及进行无害化处理；同时光触媒还具备除臭、抗污等功能(大地,科学新闻,2001:13-15)。光触媒材料除了TiO2，还有CdS、WO3、Fe2O3、PbS、SnO2、ZnS、SrTiO3、SiO2等。2000年以来又发现一些纳米贵金属(铂、铑、钯等)具有良好的光催化性能。但由于其中大多数金属或非氧化物材料易发生化学或光化学腐蚀变质，而贵金属材料成本过高，都不适合作为家居净化空气用光触媒。纳米TiO2的制备和性能研究倍受关注(叶凤英,硅酸盐通报,2014:277-284)。
TiO2的晶体结构有锐钛矿(Anatase)、金红石(Rutile)和板钛矿(Brookite)三种。通常，锐钛矿结构或80％的锐钛矿+20％的金红石结构具有最佳的光催化效果。尽管TiO2的实际应用非常广泛，但是如上所述，纯TiO2光催化性能由于结构局限性问题受到极大限制。即，一方面受能隙宽度的限制，使TiO2对太阳光的利用率不到5％；另一方面由于光生电子/空穴扩散长度短，光生电子/空穴对极易复合，光催化效率极低。因此就要采取合适的措施提高锐钛矿TiO2的光催化性能。一要增强TiO2对可见光的吸收，提高TiO2对可见光的利用率；二要抑制光生电子/空穴对的复合。目前，促进TiO2光催化剂产生的电子空穴对有效传输的研究仍然较少，主要方法包括：金属或非金属离子掺杂、染料敏化等(廖添,华南师范大学学报,2017:31-37)。
现有技术中制备粒径尺寸在5～7nm的高分散性、高水溶性光触媒并抑制电子空穴对的复合、提高载流子扩散长度，进而提高光催化性能一直是工艺上的热点和难点，根本原因是难以找到匹配的改性方法、难以抑制高温热处理导致的超微细TiO2晶粒生长以及颗粒尺寸过小和高比表面能过大引起的粒子团聚，团聚体尺寸通常达到几百纳米如201710881546.6所示。本发明的AZO/NaCl改性法使得光触媒的光催化效果得到了提高，保证光触媒为锐钛矿TiO2结构，且TiO2粒子尺寸极小，分散性能和环境友好性能俱佳。
发明内容
本发明提出一种可见光高效AZO/NaCl复合改性光触媒及其制备方法-即AZO/NaCl复合改性法，与其他制备方法的显著区别是该法利用AZO与Na+-Cl-的复合作用制备光触媒，即利用AZO、NaCl与纳米TiO2复合作用在光照射时提供更多的电子空穴传输通道。因为AZO是一种具有优异电子导电性能的半导体材料，电阻率可低达10-4Ω·cm，同时室温下白色AZO 的禁带宽度约为3.37eV，具有优异的光透过性能，透过率可达95％。AZO可提高光生电子空穴扩散长度，从而提高光催化性能。此外，Na正离子与Cl负离子形成的双电层作用以及AZO 乳液中丙烯酸根的静电和界面空间位阻作用，可促进光生载流子的传输，抑制TiO2的长大和聚集，所得超微细TiO2尺寸只有5～7nm，具有锐钛矿型TiO2晶体结构，且所得光触媒具有良好的可见光催化活性。该光触媒可高效去除甲醛、降解苯及其衍生物(可见光照下)，可用于空气净化和环境保护等领域，具有良好的应用前景。同时，该制备方法所得光触媒具有催化效率高、无酸碱使用、无毒无害等特点。
本发明的技术方案包括以下操作步骤：
(1)制备TiO2胶体：常温下利用去离子水溶液稀释TiO2纳米粉体至白色胶体状，获得 A胶体，其中，去离子水与TiO2的质量比为10～20:1；更优选的情况下，去离子水与TiO2的质量比为15:1；
(2)添加AZO乳液：常温下向上述白色胶体中添加AZO乳液，形成B胶体，其中， AZO乳液与TiO2的质量比为0.2～0.6:1；更优选的情况下，AZO乳液与TiO2的质量比为0.4:1；其中AZO乳液为六方铅锌矿ZnO结构，Al掺杂到ZnO晶格中形成了固溶体，没有Al及其它任何Al的氧化物的物相存在
(3)添加NaCl溶液：向B胶体中添加25～50g/L的NaCl溶液，搅拌后静置老化获得C胶体，其中，NaCl与TiO2的质量比为0.01～0.1:1；搅拌时间为0.5-2小时；静置老化时间为12-36小时；更优选的情况下，NaCl溶液浓度为36g/L，NaCl与TiO2的质量比为0.05:1；搅拌时间为1小时；静置老化时间为24小时。
光照产生的电子空穴对可以通过AZO进行扩散和分离，由于AZO具有优异的透明导电性能，不会影响光子的透射到达TiO2表面的效率，同时AZO优异的电学性能以及NaCl的双电层作用和乳液的空间位阻作用还能够使得大部分光照产生的电子和空穴快速扩散，大大提高了载流子的扩散长度。AZO的颜色为白色，具有高透明性特点，不影响白色TiO2的使用效果。电子到达粉体表面后与表面的水生成羟基自由基，该羟基自由基具有优异的氧化性能，可氧化大部分有机污染物分子。此外，空穴到达表面后与表面的氧气生成超氧离子，该离子具有强氧化性，也可氧化大部分有机污染物分子。NaCl产生Na离子和Cl离子双电层吸附在 AZO与TiO2粉体表面抑制了粉体的团聚，提高了粉体的分散性和水溶性，增大了粉体的比表面积和作用位点，从而提高了光催化性能。NaCl代替前一项发明专利201710881546.6使用的酸碱等物质，在相关内容的基础上，还减少了酸碱使用和由此形成的环境问题。
有益效果
(1)本发明所述方法不需要热处理过程，整个制备过程均在常温操作，反应条件温和，可直接获得光触媒。
(2)本发明所述AZO/NaCl改性过程完全不需要使用酸碱性溶液，环境友好。
(3)本发明所述AZO/NaCl改性方法可提高TiO2光触媒的光催化效果。
(4)本发明所述方法可制备超微细TiO2，典型的粒子尺寸在5～7nm。
(5)本发明所述方法制备的超微细TiO2具有高分散性和良好的结晶性。
(6)本发明所述方法的反应过程无需乙醇等有机溶剂的洗涤，使用的溶剂成本低，且不会造成环境污染。
(7)本发明所述方法的反应过程无需高压反应釜、球磨机等设备，工艺简单、成本低、反应周期短、反应过程易于控制且能耗低。
(8)本发明所述方法所制备得到的光触媒在可见光下具有较高的光催化降解有机物的效果。
附图说明
图1为实施例1中TiO2的XRD谱图；分析谱图可知，实施例1TiO2具有锐钛矿相TiO2晶体结构，结晶质量良好，没有其他杂质物相存在，经过谢乐公式计算可知，晶粒尺寸为6.08nm。
图2为实施例1中AZO的XRD谱图；分析谱图可知，实施例1AZO具有六方纤锌矿结构，结晶质量良好，没有其他杂质物相存在，经过谢乐公式计算可知，晶粒尺寸为22.12nm。
具体实施方式
下述非限定性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
原料TiO2纳米粉体的平均粒径约为350nm。
实施例1
量取去离子水100mL，TiO2纳米粉体10g，搅拌获得TiO2胶体。将上述原料置于单口烧瓶中，常温下向上述白色胶体中添加4g AZO乳液，其中按照文献(Chao Xu等,Micro&NanoLetters,2011,Vol.6,Iss.10,855–857)制备AZO(铝掺杂的氧化锌)粉体0.4g，AZO的晶体结构如图2所示。向上述胶体中添加25g/L的NaCl溶液20mL，其中NaCl的质量为0.5g，搅拌1小时后继续静置老化24小时，获得高效光触媒。
实施例1所述方法所用TiO2的XRD谱图如图1；分析谱图可知，实施例1TiO2具有锐钛矿相TiO2晶体结构，结晶质量良好，没有其他杂质物相存在，经过谢乐公式计算可知，晶粒尺寸为6.08nm。
实施例1所述方法所用AZO的XRD谱图如图2；分析谱图可知，实施例1AZO具有六方纤锌矿ZnO晶体结构，结晶质量良好，没有其他杂质物相存在，经过谢乐公式计算可知，晶粒尺寸为22.12nm。
对实施例1所述方法制得的光触媒进行光催化降解甲基橙实验，经测定，该光触媒在日光下24小时可将0.03g/L的甲基橙降解60％，48小时降解率可达97.5％，72小时降解率可达 100％。
对实施例1所述方法进行调整，其中省略添加AZO的步骤，制得的光触媒进行光催化降解甲基橙实验，经测定，该光触媒在日光下24小时可将0.03g/L的甲基橙降解30％，48小时降解率可达63.2％，72小时降解率可达86.5％。
对实施例1所述方法进行调整，其中省略添加NaCl的步骤，制得的光触媒进行光催化降解甲基橙实验，经测定，该光触媒在日光下24小时可将0.03g/L的甲基橙降解26.5％，48 小时降解率可达58.6％，72小时降解率可达79.5％。
通过上述“省略添加AZO”“省略添加NaCl”的实验组对比实验证明AZO和NaCl在光催化降解甲基橙方面具有显著的作用，从而突出了本方法建立的合理性和创造性。
实施例2
量取去离子水40mL，TiO2纳米粉体2g，搅拌获得TiO2胶体，将上述原料置于单口烧瓶中，常温下向上述白色胶体中添加1.2g AZO乳液，其中AZO粉体0.12g。向上述胶体中添加50g/L的NaCl溶液0.4mL，其中NaCl的质量为0.02g，搅拌0.5小时后继续静置老化12小时，获得高效光触媒。经测定，该光触媒在日光下24小时可将0.03g/L的甲基橙降解52％， 48小时降解率可达88.6％，72小时降解率可达97.5％。
实施例3
量取去离子水54mL，TiO2纳米粉体3.6g，搅拌获得TiO2胶体，将上述原料置于单口烧瓶中，常温下向上述白色胶体中添加0.8g AZO乳液，其中AZO粉体0.08g。向上述胶体中添加36g/L的NaCl溶液10ml，其中NaCl的质量为0.36g，搅拌2小时后继续静置老化36小时，获得高效光触媒。经测定，该光触媒在日光下24小时可将0.03g/L的甲基橙降解56.9％， 48小时降解率可达89.6％，72小时降解率可达98％。
通过上述“省略添加AZO”或“省略添加NaCl”的实验组对比实验证明单独引入AZO或NaCl在光催化降解甲基橙方面的作用均有所降低，从而进一步突出了本方法建立的合理性和创造性。
Claims (10)
1.一种AZO/NaCl复合改性TiO2光触媒的制备方法，其特征在于：包括以下操作步骤，
(1)用水稀释TiO2纳米粉体至白色胶体状，获得A胶体，其中，水与TiO2纳米粉体的质量比为10～20:1；
(2)向A胶体中添加AZO乳液，形成B胶体，其中，AZO乳液与TiO2的质量比为0.2～0.6:1；
(3)向B胶体中添加NaCl溶液，搅拌静置后获得C胶体，其中，NaCl与TiO2的质量比为0.01～0.1:1；
步骤(2)中，AZO乳液由铝掺杂氧化锌粉体与丙烯酸水溶液按照质量比为0.05～0.15:1组成，其中，丙烯酸水溶液为丙烯酸与水的质量比按照0.2～0.6:1混合而成；铝掺杂氧化锌粉体与丙烯酸的质量比为0.01～0.09。
2.根据权利要求1所述的制备方法，其特征在于：步骤(2)中，AZO乳液与TiO2的质量比为0.4:1。
3.根据权利要求1所述的制备方法，其特征在于：步骤(1)中，水与TiO2纳米粉体的质量比为15:1。
4.根据权利要求1所述的制备方法，其特征在于：步骤(1)中，TiO2纳米粉体的粒径为5～7nm，具有锐钛矿晶体结构。
5.根据权利要求1所述的制备方法，其特征在于：步骤(3)中，NaCl溶液的浓度为25-50g/L。
6.根据权利要求5所述的制备方法，其特征在于：步骤(3)中，NaCl溶液浓度为30-40g/L。
7.根据权利要求1所述的制备方法，其特征在于：步骤(3)中，NaCl与TiO2的质量比为0.05:1。
8.根据权利要求1所述的制备方法，其特征在于：步骤(3)中，搅拌时间为至少0.5小时。
9.如权利要求1所述制备方法获得的AZO/NaCl复合改性TiO2光触媒。
10.如权利要求9所述的AZO/NaCl复合改性TiO2光触媒在高效去除甲醛、降解苯及其衍生物的领域中应用。
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