CN107754778A - 石墨烯‑二氧化钛‑金属离子复合光催化剂水溶液的制备方法 - Google Patents
石墨烯‑二氧化钛‑金属离子复合光催化剂水溶液的制备方法 Download PDFInfo
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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Abstract
本发明提出了一种石墨烯‑二氧化钛‑金属离子复合光催化剂水溶液的制备方法,包括以下步骤:1)氢氧化钛固体的制备;2)将步骤1)的氢氧化钛固体及去离子水混合后进行超声分散,得到氢氧化钛分散液,然后加入过氧化氢溶液、金属离子及石墨烯进行反应,反应结束后冷却至5~20℃,即可获得复合光催化剂水溶液;其中,所述石墨烯加入到步骤2)反应体系中的终浓度为0.1mg/L~200mg/L,过氧化氢溶液与氢氧化钛固体的摩尔比为1:0.5~1.5,金属离子为化合价为+1至+4金属离子中的任意一种或者多种;金属离子与二氧化钛的摩尔比为10‑3~10‑1:1。该方法制备得到的复合光催化剂水溶液长期放置石墨烯也不会团聚沉淀,溶胶放置一年以上也无分层或沉淀物出现,稳定性好。
Description
技术领域
本发明属于二氧化钛光催化剂技术领域,具体涉及一种石墨烯/二氧化钛/金属离子复合光催化剂水溶液的制备方法。
背景技术
二氧化钛光触媒溶液涂布于各种基材表面后,在一定波长的光照射下(一般的场合为380nm以下的紫外线),通过光的吸收而形成空穴以及电子的瞬间,通常很容易与其它物质发生氧化分解反应。二氧化钛光触媒溶液的催化特征是:所形成的空穴有着很强的氧化还原作用,这个空穴直接与有机物以及水反应,会形成非常强的氢氧自由离子·OH,这个过程被称为有机物氧化过程,另外,空穴中的氧气被所产生的电子立即还原形成超级氧负自由离子·O2-,而这个自由离子也具有很强的抗菌、分解(有机物)作用,最后使之变化为对人体无害的二氧化碳和水。
氧化石墨层与层间之作用力因层间距增加而减弱,且氧化石墨烯表面产生之亲水官能基与水分子之氢链作用力,与羰基去质子化后形成之电荷相斥力,使氧化石墨可均匀分散于水中,形成单层之氧化石墨烯悬浮液。而为了得到石墨烯,需将均匀分散于水溶液之氧化石墨烯还原成“还原氧化石墨烯RGO”,将SP3链结脱氧还原成SP2链结。而大部分氧化石墨之还原,皆藉由如联胺(N2H4)等强还原剂进行还原,然而还原后的石墨烯具有较大的表面能,容易自发的聚集而沉淀,无法以稳定的悬浮液存在,其原因主要为高亲水之氧化石墨烯转变成为疏水之石墨烯,为了降低表面能,疏水之石墨烯倾向形成聚集物。
为了提升还原石墨烯悬浮液之稳定性,目前有适当利用表面活性剂修饰还原之石墨烯表面,提升亲水性;也有采用环糊精修饰或用聚氧化乙烯修饰的方法来提高石墨烯的亲水性,使之形成稳定的悬浮液。用这些方法修饰后的石墨烯加入到二氧化钛光催化剂溶液中,都会影响光催化剂溶液的稳定性。由于修饰的引入会破坏光催化的效果。
发明内容
本发明提出一种石墨烯-二氧化钛-金属离子复合光催化剂水溶液的制备方法,该方法制备得到的复合光催化剂水溶液长期放置石墨烯也不会团聚沉淀,溶胶放置一年以上也无分层或沉淀物出现,稳定性好。
本发明的技术方案是这样实现的:
一种石墨烯-二氧化钛-金属离子复合光催化剂水溶液的制备方法,包括以下步骤:
1)氢氧化钛固体的制备:
2)将步骤1)的氢氧化钛固体及去离子水混合后进行超声分散,得到氢氧化钛分散液,然后加入过氧化氢溶液、金属离子及石墨烯进行反应,反应结束后冷却即可获得复合光催化剂水溶液;
其中,所述石墨烯加入到步骤2)反应体系中的终浓度为0.1mg/L~200mg/L,过氧化氢与氢氧化钛固体的摩尔比为1:0.5~1.5,金属离子为化合价为+1至+4金属离子中的任意一种或者多种;金属离子与二氧化钛的摩尔比为10-3~10-1:1。
优选地,所述过氧化氢溶液浓度为5~60wt%;所述步骤2)反应结束后冷却至5~20℃。
优选地,所述步骤2)氢氧化钛分散液与过氧化氢溶液、金属离子及石墨烯反应具体为:
先向氢氧化钛分散液中加入石墨烯,再加入过氧化氢溶液反应24~40小时后,然后加入金属离子,待充分溶解后,再将反应液加热至90~150℃,4~20小时后,冷却得到复合光催化剂水溶液。
优选地,所述步骤2)氢氧化钛分散液与过氧化氢溶液、金属离子及石墨烯反应具体为:
先向氢氧化钛分散液中加入过氧化氢溶液,反应24~40小时后,依次加入石墨烯与金属离子,待充分溶解后,再将反应液加热至90~150℃,4~20小时后,冷却得到复合光催化剂水溶液。
优选地,所述步骤2)氢氧化钛分散液与过氧化氢溶液、金属离子及石墨烯反应具体为:
先向氢氧化钛分散液中加入过氧化氢溶液,反应开始4~20小时内加入石墨烯,氢氧化钛与过氧化氢溶液反应24~40小时后,再将反应液加热至90~150℃,再加入金属离子,待充分溶解后,继续加热,最后冷却得到复合光催化剂水溶液。
优选地,所述步骤1)氢氧化钛固体的制备方法具体为:
a、将含钛水溶液经离子交换后,加入碱溶液形成含有氢氧化钛的胶体溶液;
b、在步骤a所得的胶体溶液中加入有机酸,形成均一溶液;有机酸与胶体溶液中的氢氧化钛的摩尔比为0.01~0.2∶1;
c、从步骤b形成的均一溶液中分离出氢氧化钛固体,用去离子水冼至水层的电导率不超过10μS·CM-2。
也可以参见中国专利200410026456.1公开了一种二氧化钛光触媒复合溶液的制备方法。
优选地,所述有机酸为酒石酸、苹果酸、乳酸、柠檬酸、乙醇酸、苦杏仁酸、酪酸、碳酸、甲酸、乙酸、顺丁烯二酸、硼酸、富马酸或丙酸。
优选地,所述金属离子选自Ag+、Zn+2、Cu+2、Al+3、W+3与Ti+4中的一种或者多种。
优选地,所述石墨烯-二氧化钛-金属离子复合光催化剂水溶液的pH值为6.5~7.5。
优选地,所述石墨烯-二氧化钛-金属离子复合光催化剂水溶液中的二氧化钛的粒径大小为5nm~50nm。
本发明制备的石墨烯-二氧化钛-金属离子复合光催化剂水溶液在常温下,即使长时间保存也不会发生任何的物理及化学变化。另外此溶液的浓度通常为1.0~2.4wt%左右。在必要时根据需要可适当调整,如需要低浓度涂布液时,可将蒸馏水或去离子水稀释后使用。本发明的氧化钛粒子在常温下一般不会发生结晶。有着良好的接着性和成膜性,喷雾在基材上可以形成均一的薄膜,而且干燥之后的薄膜在水中不溶解。喷涂在白色基材上不会发黑。
本发明的有益效果:
1、本发明由于加入了石墨烯,提高了氧化钛的光催化性能,特别是在可见光范围内,较原来的纯氧化钛光催化剂有较大的提高。在应用时,特别是室内,只有可见光无紫外线照射的情况下,可以更好的发挥氧化钛的光催化作用,降低室内有害气体的浓度,改善室内空气质量。
2、本发明的制备方法由于在石墨烯/二氧化钛复合物之间加入了金属离子,提高了溶液的稳定性,长期放置石墨烯也不会团聚沉淀,本溶胶放置一年以上也无分层或沉淀物出现。
3、本发明的制备方法中某些金属离子与石墨烯的复合作用可提高产品的亲水性,产品的抗菌能力。
具体实施方式
实施例1
(一)产品制造原料液的配制
(1)将重量百分比浓度50%的四氧化钛溶液用去离子水稀释60倍,随后用离子膜处理,转变为氯化氧钛水溶液。
(2)将重量百分比浓度25%的氨水用去离子水稀释10倍,将其与(1)中所得的溶液以体积比1:6混合发生中和反应。
(3)中和反应后,将溶液的PH调至6.8,放置30分钟后用离心机除去上层水分,留下的Ti(OH)4沉淀继续用离子水清洗,直到上层液的电导率为10μs.cm-2为止,停止清洗。
(二)将(一)中得到洗净过的氢氧化钛沉淀溶解于去离子水后,用作为安定剂的苹果酸处理,加入的量为氢氧化钛量1/8(摩尔比)。苹果酸加入后,溶液的PH呈酸性,用碱性物质将PH调至7左右。
(三)用30%的过氧化氢处理(二)中得到的溶液,过氧化氢的加入量为氢氧化钛量的1.5倍(摩尔比),过氧化氢加入后,静置24小时,待反应完及过剩的过氧化氢彻底分解后,将此溶液加热至100℃,加热时间为8小时,冷却,得到白色锐钛型氧化钛溶液。
实施例2
将实施例1得到的氢氧化钛(二),加入石墨烯,浓度在成品中为30mg/L。用30%过氧化氢溶液处理上述氧氢化钛/石墨烯混合溶液。过氧化氢加入量为氢氧化钛量的1.5倍(摩尔比),过氧化氢加入后,静置24小时,待反应完及过剩的过氧化氢彻底分解后,加入AgNO3充分溶解Ag+1与TiO2的摩尔比为1×10-3:1。将此溶液在超声反应釜中加热至100℃,加热时间为10小时,冷却至5℃得到灰白透红光的石墨烯-锐钛型氧化钛-Ag+1离子复合催化剂水溶液。
实施例3
将实施例1得到的氢氧化钛(二),先用50%过氧化氢溶液处理,过氧化氢加入量为氢氧化钛量的0.5倍(摩尔比),过氧化氢加入后静止24小时,待反应完全及过剩的过氧化氢彻底分解后,加入石墨烯,浓度在成品中为30mg/L,加入W(NO3)3充分溶解W+3与TiO2摩尔比为1.5×10-2:1。将此溶液在超声反应釜中,加热至90℃,加热时间为16小时,冷却至10℃得到灰白透红光的石墨烯-锐钛型氧化钛-W+3离子复合催化剂水溶液。
实施例4
将实施例1得到的氢氧化钛(二),先用10%过氧化氢处理,过氧化氢加入量为氢氧化钛量的1.0倍(摩尔比),过氧化氢加入后静止24小时,待反应完全及过剩的过氧化氢彻底分解后,加入石墨烯,浓度在成品中为30mg/L,加入Mn(NO3)2与TiO2的摩尔比为2.6×10-2:1。将此溶液在超声反应釜中,加热至100℃,加热时间为6小时,冷却至15℃得到灰白透红光的石墨烯-锐钛型氧化钛-Mn+2复合催化剂水溶液。
实施例5
将实施例1得到的氢氧化钛(二)加入石墨烯,再加入60%过氧化氢处理40小时后,氧化氢加入量为氢氧化钛量的1.5倍(摩尔比),然后加入Mn(NO3)2与TiO2的摩尔比为1.0×10-1:1,待充分溶解后,再将反应液加热至150℃,20小时后,冷却至20℃,冷却至20℃得到灰白透红光的石墨烯-锐钛型氧化钛-Mn+2复合催化剂水溶液。
试验例
将实施例2至5制备得到的复合催化剂水溶液进行稳定性试验,长期放置石墨烯也不会团聚沉淀,本溶胶放置一年以上也无分层或沉淀物出现。
按照了JC/T1074-2008《室内空气净化功能涂覆材料净化性能》标准进行测试,结果如下:甲苯净化性能,实施例1为51%;实施例2为53%;实施例3为61%;实施例4为55%;实施例5为58%。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,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 (10)
1.一种石墨烯-二氧化钛-金属离子复合光催化剂水溶液的制备方法,其特征在于,包括以下步骤:
1)氢氧化钛固体的制备;
2)将步骤1)的氢氧化钛固体及去离子水混合后进行超声分散,得到氢氧化钛分散液,然后加入过氧化氢溶液、金属离子及石墨烯进行反应,反应结束后冷却即可获得复合光催化剂水溶液;
其中,所述石墨烯加入到步骤2)反应体系中的终浓度为0.1mg/L~200mg/L,过氧化氢与氢氧化钛固体的摩尔比为1:0.5~1.5,金属离子为化合价为+1至+4金属离子中的任意一种或者多种;金属离子与二氧化钛的摩尔比为10-3~10-1:1。
2.根据权利要求1所述的制备方法,其特征在于,所述步骤2)氢氧化钛分散液与过氧化氢溶液、金属离子及石墨烯反应具体为:
先向氢氧化钛分散液中加入石墨烯,再加入过氧化氢溶液反应24~40小时后,然后加入金属离子,待充分溶解后,再将反应液加热至90~150℃,4~20小时后,冷却得到复合光催化剂水溶液。
3.根据权利要求1所述的制备方法,其特征在于,所述步骤2)氢氧化钛分散液与过氧化氢溶液、金属离子及石墨烯反应具体为:
先向氢氧化钛分散液中加入过氧化氢溶液,反应24~40小时后,依次加入石墨烯与金属离子,待充分溶解后,再将反应液加热至90~150℃,4~20小时后,冷却得到复合光催化剂水溶液。
4.根据权利要求1所述的制备方法,其特征在于,所述步骤2)氢氧化钛分散液与过氧化氢溶液、金属离子及石墨烯反应具体为:
先向氢氧化钛分散液中加入过氧化氢溶液,反应开始4~20小时内加入石墨烯,氢氧化钛与过氧化氢溶液反应24~40小时后,再将反应液加热至90~150℃,再加入金属离子,待充分溶解后,继续加热,最后冷却得到复合光催化剂水溶液。
5.根据权利要求1至4任意一项所述的制备方法,其特征在于,所述步骤1)氢氧化钛固体的制备方法具体为:
a、将含钛水溶液经离子交换后,加入碱溶液形成含有氢氧化钛的胶体溶液;
b、在步骤a所得的胶体溶液中加入有机酸,形成均一溶液;有机酸与胶体溶液中的氢氧化钛的摩尔比为0.01~0.2∶1;
c、从步骤b形成的均一溶液中分离出氢氧化钛固体,用去离子水冼至水层的电导率不超过10μS·CM-2。
6.根据权利要求5所述的制备方法,其特征在于,所述有机酸为酒石酸、苹果酸、乳酸、柠檬酸、乙醇酸、苦杏仁酸、酪酸、碳酸、甲酸、乙酸、顺丁烯二酸、硼酸、富马酸或丙酸。
7.根据权利要求1至4任意一项所述的制备方法,其特征在于,所述金属离子选自Ag+、Zn+2、Cu+2、Al+3、W+3与Ti+4中的一种或者多种。
8.根据权利要求1至4任意一项所述的制备方法,其特征在于,所述石墨烯-二氧化钛-金属离子复合光催化剂水溶液的pH值为6.5~7.5。
9.根据权利要求1至4任意一项所述的制备方法,其特征在于,所述石墨烯-二氧化钛-金属离子复合光催化剂水溶液中的二氧化钛的粒径大小为5nm~50nm。
10.根据权利要求1至4任意一项所述的制备方法,其特征在于,所述步骤2)反应结束后冷却至5~20℃。
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王阿鸣: "石墨烯纳米复合材料的制备及光电性质研究", 《中国优秀硕士论文全文数据库》 * |
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CN115999619A (zh) * | 2021-10-21 | 2023-04-25 | 中国科学院理化技术研究所 | 一种臭氧吸附催化剂的低温光沉积制备方法 |
CN115999619B (zh) * | 2021-10-21 | 2024-04-12 | 中国科学院理化技术研究所 | 一种臭氧吸附催化剂的低温光沉积制备方法 |
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