CN110227527A - 一种制备可见光响应掺杂TiO2的高温熔融盐方法 - Google Patents
一种制备可见光响应掺杂TiO2的高温熔融盐方法 Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 26
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
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- B01J27/24—Nitrogen compounds
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Abstract
本发明提供一种可见光响应掺杂TiO2的高温熔融盐方法，包含以下步骤：将固态盐置于密闭的耐高温坩埚中加热，使其熔融成离子液体；将含非金属元素的前驱物和含钛的前驱物材料混合均匀，置入熔融盐中反应，反应过程在惰性气体气氛中进行；将所得产物先放入去离子水中浸泡再用去离子水和乙醇离心清洗数次，烘干后得到光催化材料。本发明方法所得光催化材料的紫外可见吸收光谱(UV‑vis)吸收明显增强，同时荧光性能大大增强，促进了光催化性能，同时反应过程中气体污染小，原材料价格低廉且可反复使用，适于工业化生产。
Description
技术领域
本发明涉及一种新型的高温熔融盐制备功能材料方法，从而提高其光电催化性能。
背景技术
光催化技术能将有机污染物矿化成二氧化碳和水等无毒小分子，从而实现高效、快捷、无害化的环境污染治理和生态修复，在环境领域具有广阔发展前景。在各类光催化剂中，二氧化钛因其强氧化性、高吸附性和超亲水性，且材料本身化学性质稳定、廉价无毒等多种优质特性而备受研究者的关注。已证实是有效的光催化剂，但由于纯二氧化钛仅在紫外光区域(波长≤365nm)有吸收，带隙较宽(3.2eV)，只能被紫外光激发，而且其光生电子和空穴容易复合，导致太阳光的利用率和量子转换效率较低，极大地限制了其在环境净化方面的实际应用。因此，提高二氧化钛对太阳光的利用率，增加其可见光吸收性能的研究日益活跃，针对二氧化钛改性方法的研究主要包括染料敏化、金属离子掺杂、非金属离子掺杂、半导体复合、贵金属沉积等.其中非金属元素掺杂改性的二氧化钛光催化剂突显出化学性质稳定，毒性较小、制备工艺成熟等特点，是一种不错的选择。影响光催化过程中太阳能利用率的关键在于所选半导体材料的能级结，外来离子的掺入能够改变TiO2的能级结构，从而引起其光电性质的重大改变。因此深入研究非金属元素掺杂TiO2纳米结构中光生电荷的激发、分离、迁移及复合等复杂的物理化学过程，对于提高光催化效率，揭示表面光催化反应本质具有重大的理论和实际意义。
而目前纳米光催化材料的合成方法，如高温热解、高温高压合成、电化学沉积等方法，得到的纳米光催化材料普遍存在不稳定、易团聚等缺点，极大地影响了纳米光催化材料的应用性能。因此为了得到结构更加稳定、性能更优的层状纳米光催化材料，对其制备方法还需进一步研究和改进。
发明内容
在此背景下，本发明的目的在于提供了一种制备可见光响应掺杂TiO2的高温熔融盐方法，通过该方法制备的纳米光催化材料结构更加稳定且光催化性能性能更优。
一种制备可见光响应掺杂TiO2的高温熔融盐方法，在高温熔盐里煅烧前驱物得到目的功能材料，包含以下步骤：
(1)将固态盐置于密闭的耐高温坩埚中加热，使其熔融成离子液体；
(2)将含非金属元素的前驱物和含钛的前驱物材料混合均匀，置入熔融盐中反应，反应过程在惰性气体气氛中进行；
(3)将所得产物先放入去离子水中浸泡再用去离子水和乙醇离心清洗数次，烘干后得到光催化材料。
优选地，所述含钛的前驱物材料包括偏钛酸、硫酸钛、钛酸四丁酯、四氯化钛。
优选地，所述非金属元素为碳、氮、磷、硫元素中任一种或多种。
优选地，所述含碳元素的前驱物材料包括尿素、三聚氰胺。
优选地，所述盐为选自氯化物盐、氟化物盐、碳酸盐、硝酸盐、硫酸盐的的一元、二元、三元或多元盐。
优选地，所述氯化物盐选自LiCl，NaCl，KCl、CaCl2和MgCl2，所述氟化物盐选自LiF，NaF，KF、CaF2和MgF2，所述碳酸盐选自Li2CO3、Na2CO3、K2CO3、CaCO3和MgCO3，所述硝酸盐选自LiNO3、NaNO3、KNO3、Ca(NO3)2和Mg(NO3)2，所述硫酸盐选自Li2SO4、Na2SO4、K2SO4、CaSO4和MgSO4。
优选地，所述盐为摩尔比为47.5:15:37.5的LiCl，NaCl，KCl三元氯化物盐，或摩尔比为43.5:31.5:25的Li2CO3，Na2CO3，K2CO3三元碳酸盐。上述摩尔比的三元氯化物盐或三元碳酸盐的共熔点最低，其中摩尔比为47.5:15:37.5的LiCl、NaCl、KCl三元氯化物盐的熔点为399℃，摩尔比为43.5:31.5:25的Li2CO3、Na2CO3、K2CO3三元碳酸盐的熔点为393℃。
优选地，步骤(1)中盐的处理步骤为：将盐称好机械混合均匀放入坩埚中升温至200—300℃后保温12—48h烘干盐中水分，继续升温至盐熔点以上，保温至盐完全融化。
优选地，步骤(1)升温过程的升温速率为5—10℃/min。
优选地，步骤(2)中将前驱物置入熔融盐的方法为：将前驱物用泡沫镍或泡沫铜包覆，缠到钼丝上，浸入高温熔融盐中。
优选地，步骤(2)中前驱物在熔融盐中的反应时间为30—120min，反应温度为400-800℃。
本发明还提供了一种可见光响应掺杂TiO2光催化材料，采用上述的方法制备得到。
上述可见光响应掺杂TiO2光催化材料应用于光催化水分解产氢，二氧化碳还原和甲醛降解等光催化领域。
本发明的高温熔融盐方法，是在高温离子环境下制备可见光响应掺杂的TiO2光催化材料。作为高温离子液体，熔盐是均匀的离子介质，存在于夹层之间的离子稳定层状晶格，从而形成有序分层结构的形成/维持。作为液体反应介质，熔融盐对含氧和含杂原子(例如C/N)物质具有强溶解能力，导致这种物质的迁移和反应能力增强,从而得到结构更稳定、使用性能更加优良的光催化材料，性能测试证实，采用本发明所述的方法得到的光催化材料的紫外可见吸收光谱(UV-vis)吸收明显增强，同时荧光性能大大增强，促进了光催化性能。作为高温反应具有高热容量的介质，熔盐为热解反应提供独特的惰性气氛。与气态介质中的热解相比，在液态熔盐热解中预计会提高能量效率和更均匀的反应。在高温离子的液态环境中，材料的前驱体受热快且均匀，得到的均一的材料形貌。大部分前驱体受热分解过程会产生其他气体污染物，而当反应在高温熔融盐液体中进行时，可以有效地减少气体污染物的排放。在此合成过程中所使用的熔融盐是目前市售的碱金属氯化物盐、碳酸盐等，价格低廉且可以反复使用，降低了生产成本。
附图说明
图1为实施例3制得的熔盐碳掺杂二氧化钛材料和对比例1制得的碳掺杂二氧化钛材料的XRD对比图；
图2为实施例3制得的熔盐碳掺杂二氧化钛材料的SEM图；
图3为对比例1制得的碳掺杂二氧化钛材料的SEM图；
图4为实施例3制得熔盐碳掺杂二氧化钛材料的TEM图；
图5为对比例1制得碳掺杂二氧化钛材料的TEM图；
图6为实施例3制得熔盐碳掺杂二氧化钛材料和对比例1制得的碳掺杂二氧化钛材料的UV-vis对比图；
图7为实施例3制得熔盐碳掺杂二氧化钛材料和对比例1制得的碳掺杂二氧化钛材料PL对比图。
具体实施方式
下面通过实施例，对本发明作进一步具体的说明。
实施例1
称取LiCl、NaCl、KCl(摩尔比为47.5:15:37.5)共500g混合均匀后放入石英坩埚中，5℃/min升温至300℃保温24h除去盐中的水分，然后10℃/min升温至520℃，保温半小时使盐完全熔化并形成均匀的混盐。称取2g三聚氰胺粉末，用压片机压制成片，用泡沫镍包裹后绑在钼丝上，放入高温熔融盐中反应60min，反应在Ar的惰性气氛下进行。将泡沫镍取出放入去离子水中浸泡24h后，剥去泡沫镍，收集产物。将所得产物用去离子水和乙醇离心清洗各4次，转速5000r/min，时间为3min。然后将产物在80℃下烘干，得到熔盐碳化氮纳米材料。
实施例2
称取LiCl、NaCl、KCl(摩尔比为47.5:15:37.5)共500g混合均匀后放入石英坩埚中，5℃/min升温至300℃保温24h除去盐中的水分，然后10℃/min升温至520℃，保温半小时至盐完全熔化并形成均匀的混盐。称取2g偏钛酸(TiO(OH)2)粉末，用压片机制成片，用泡沫铜包裹后放入高温熔融盐中反应60min，反应在Ar的惰性气氛下进行。将泡沫镍取出放入去离子水中浸泡24h后，剥去泡沫铜，收集产物。将所得产物用去离子水和乙醇离心清洗各4次，转速5000r/min，时间为3min。然后将产物在80℃下烘干，得到熔盐二氧化钛纳米光催化材料。
实施例3
称取LiCl、NaCl、KCl(摩尔比为47.5:15:37.5)共500g混合均匀后放入石英坩埚中，在300℃下烘干24h除去盐中的水分，然后10℃/min升温至520℃，保温至盐完全融化。称取2g偏钛酸(TiO(OH)2)粉末和100mg三聚氰胺粉末混合均匀，用压片机压制成片，用泡沫镍包裹后放入高温熔融盐中反应60min，反应在N2气氛中进行。将泡沫镍取出放入去离子水中浸泡24h后，剥去泡沫镍，收集产物。将所得产物用去离子水和乙醇离心清洗各4次，转速5000r/min，时间为3min。然后将产物在80℃下烘干，得到熔盐二氧化钛/碳化氮复合纳米光催化材料。
对比例1
与实施例3的区别仅在于：不使用熔融盐体系，直接焙烧偏钛酸/三聚氰胺片子，且反应时间延长至90min，所得产物为二氧化钛/碳化氮复合光催化纳米材料。
性能测试与表征：
将实施例3和对比例1提供的熔盐二氧化钛/碳化氮复合纳米光催化纳米材料和二氧化钛/碳化氮复合光催化纳米材料分别进行XRD、SEM、TEM、UV-vis、PL表征。
XRD表征：采用荷兰Panalytical分析仪器公司的X’PERT-PRO MPD型X射线衍射仪(XRD，CuKα射线，λ＝0.15406nm)测试熔盐复合材料的晶型结构。
从图1可以看出碳化氮/二氧化钛复合材料在25.3°、37.9°48.3°、53.8°、55.2°、62.7°和37.9°处具有明显的特征衍射峰，但熔盐碳掺杂二氧化钛材料的峰强度明显高于对比例中的碳掺杂二氧化钛材料。且在25.3°处，熔盐碳掺杂二氧化钛材料主峰稍微向右移动，这是在熔盐里复合材料产生了特殊层间作用，从而使二氧化钛纳米光催化材料的可见光吸收加强。
SEM表征：采用日本JEOL公司的JSM-7600F型场发射电子显微镜，观察所制备熔盐材料的形貌结构。
图2和图3分别为实施例3和对比例1制得的纳米光催化材料的SEM图，由以上SEM图可以看出由本发明采用高温熔盐制得碳掺杂二氧化钛材料结构更明显，不易团聚，更加稳定。
TEM表征：采用日本东京电子型号为JEM2100F的仪器测试，观察所制备熔盐材料的形貌结构。
图4和图5分别为实施例3和对比例1制得纳米光催化材料的TEM图。
UV-vis表征：采用日本Shimadzu公司的UV-2550分光光度计测试复合材料的吸收光强度。
图6为实施例3制得熔盐碳掺杂二氧化钛材料和对比例1制得的碳化碳掺杂二氧化钛材料的UV-vis对比图，由图中可以看出高温熔盐制得的碳掺杂二氧化钛材料可见光吸收明显增强。
PL表征：采用日本JEOL公司的F-4500FL分光光度计测试熔盐复合材料的荧光强度。
由图7中可以看出高温熔盐制得碳掺杂二氧化钛材料荧光强度明显增强。
上述具体实施方式用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都落入本发明的保护范围。
Claims (10)
1.一种制备可见光响应掺杂TiO2的高温熔融盐方法，其特征在于：在高温熔盐里煅烧前驱物得到目的功能材料，包含以下步骤：
(1)将固态盐置于密闭的耐高温坩埚中加热，使其熔融成离子液体；
(2)将含非金属元素的前驱物和含钛的前驱物材料混合均匀，置入熔融盐中反应，反应过程在惰性气体气氛中进行；
(3)将所得产物先放入去离子水中浸泡再用去离子水和乙醇离心清洗数次，烘干后得到光催化材料。
2.根据权利要求1所述的一种制备可见光响应掺杂TiO2的高温熔融盐方法，其特征在于：所述含钛的前驱物材料包括偏钛酸、硫酸钛、钛酸四丁酯、四氯化钛。
3.根据权利要求1所述的一种制备可见光响应碳掺杂TiO2的高温熔融盐方法，其特征在于：所述非金属元素为碳、氮、磷、硫元素中任一种或多种。
4.根据权利要求3所述的一种制备可见光响应碳掺杂TiO2的高温熔融盐方法，其特征在于：所述含碳元素的前驱物材料包括尿素、三聚氰胺。
5.根据权利要求1所述的一种制备可见光响应掺杂TiO2的高温熔融盐方法，其特征在于：所述盐为选自氯化物盐、氟化物盐、碳酸盐、硝酸盐、硫酸盐的一元、二元、三元或多元盐。
6.根据权利要求5所述的一种制备可见光响应掺杂TiO2的高温熔融盐方法，其特征在于：所述氯化物盐选自LiCl，NaCl，KCl、CaCl2和MgCl2，所述氟化物盐选自LiF，NaF，KF、CaF2和MgF2，所述碳酸盐选自Li2CO3、Na2CO3、K2CO3、CaCO3和MgCO3，所述硝酸盐选自LiNO3、NaNO3、KNO3、Ca(NO3)2和Mg(NO3)2，所述硫酸盐选自Li2SO4、Na2SO4、K2SO4、CaSO4和MgSO4。
7.根据权利要求1所述的一种制备可见光响应掺杂TiO2的高温熔融盐方法，其特征在于：所述盐为摩尔比为47.5:15:37.5的LiCl，NaCl，KCl三元氯化物盐，或摩尔比为43.5:31.5:25的Li2CO3，Na2CO3，K2CO3三元碳酸盐。
8.根据权利要求1所述的一种制备可见光响应掺杂TiO2的高温熔融盐方法，其特征在于：步骤(1)中盐的处理步骤为：将盐称好机械混合均匀放入坩埚中升温至200—300℃后保温12—48h烘干盐中水分，继续升温至盐熔点以上，保温至盐完全融化。
9.根据权利要求1所述的一种制备可见光响应掺杂TiO2的高温熔融盐方法，其特征在于：步骤(2)中将前驱物置入熔融盐的方法为：将前驱物用泡沫镍或泡沫铜包覆，缠到钼丝上，浸入高温熔融盐中。
10.一种可见光响应掺杂TiO2光催化材料，其特征在于：采用权利要求1-9任一项所述的方法制备得到。
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| CN112973705B (zh) * | 2021-03-22 | 2022-11-01 | 江西理工大学 | 一种稀土Er掺杂NiO的光催化材料、制备方法及应用 |
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