CN106902797A - 表面负载光催化活性层的轻质泡沫陶瓷复合材料 - Google Patents
表面负载光催化活性层的轻质泡沫陶瓷复合材料 Download PDFInfo
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- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
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- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
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- 238000002360 preparation method Methods 0.000 description 5
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- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
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- 208000035126 Facies Diseases 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000005245 sintering Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- -1 polytetrafluoroethylene Polymers 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B01J35/56—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
本发明涉及一种表面负载光催化活性层的轻质泡沫陶瓷复合材料，其构成是在轻质泡沫陶瓷表面负载一层具有光催化功能的二氧化钛活性层。将光催化活性层负载于表面丰富且可漂浮于水面的多孔载体(轻质泡沫陶瓷)，可望获得一种光催化性能良好的复合材料，能够有效地通过光催化的方式降解水体中的有机污染物。所用多孔载体是采用以天然沸石粉末为主要原料制备的轻质泡沫陶瓷，通过溶胶‑凝胶法负载二氧化钛活性层。
Description
技术领域：
本发明涉及一种表面负载光催化活性层的轻质泡沫陶瓷复合材料，尤其涉及一种适用于水体中有机污染物光催化降解的轻质泡沫陶瓷复合材料。
背景技术：
染料废液必须得到有效处理，否则排放的染料污染物会对环境产生严重的危害([1]王侃，陈英旭，叶芬霞.SiO2负载的TiO2光催化剂可见光催化降解染料污染物[J].催化学报,2004,25(12):931-936.)。二氧化钛可以催化降解有机物，可望应用于染料污水的降解([2]Zhang Weijin,He Yunqiu,Qi Qiang.Preparation of porous TiO2 filmofphotocatalyst by microemulsion templating[J].Journal of Functional Materials,2005,10(36):1590-1593.[3]张平，莫尊理，张春，等.磁响应性TiO2/石墨烯纳米复合材料的合成及光催化性能[J].材料工程,2015,43(3):72-77.)。目前纳米TiO2的应用主要有两种形式：悬浮相型和负载型。悬浮相型是以悬浮的TiO2粉末为催化剂进行光催化降解，但这种悬浮体在水中易凝聚失去活性，尤其是使用后的粉末状催化剂不易回收，造成二次污染([4]Zhao Cui hua,Chen Jianhua,Shan Zhi qiang.An experimental study of effectsof different substrateson photocatalytic activity of loaded TiO 2thin films[J].Industrial Water&Wastewater,2004,35(3):15-16.[5]Tian H,Ma J F,Li K,etal.Hydrothermal synthesis of S-doped TiO2 nanoparticles and theirphotocatalytic ability for degradation of methyl orange[J].CeramicsInternational,2009,35(3):1289-1292.]。因此，后来的光催化氧化重点转移到二氧化钛的固定化技术和制备膜的研究上，即负载型催化氧化法([6]H.Zhang,R.L.Zong,J.C.Zhaoand Y.F.Zhu.Dramatic visible photocatalytic degradation performances due tosynergetic effect of TiO2 with PANI[J].Environment Science&Technology,2008,42(10):3803–3807.[7]Sun Zhi bo,Yin Yi dong,Fan Nai ying,et al.Study onpreparation of loaded TiO2 and its photocatalytic performances for NO2[J].Journal of Functional Materials,2014,45(S):99-103.]。所采用的载体有玻璃、钛板、玻璃纤维、沸石、硅胶等，负载法的固定化技术一般采用二氧化钛粉末的直接浸涂和溶胶-凝胶浸渍提拉成膜两大类([6]H.Zhang,R.L.Zong,J.C.Zhao and Y.F.Zhu.Dramaticvisible photocatalytic degradation performances due to synergetic effect ofTiO2 with PANI[J].Environment Science&Technol ogy,2008,42(10):3803–3807.[8]Zheng Shukai,Wu Guohao,Zhang Junying,et al.Energy band structure andphotocatalytic activityof Sn-doped TiO2 thin film[J].Journal of MaterialsEngineering,2014,42(1):70-74.[9]Tao Liqin,Zhao Yi xia,Kang Wei min,etal.Preparation of titanium dioxide loaded on polytetrafluoroethylenesuperfine-fiber andits photocatalytic performance[J].Journal of the ChineseCerami c Society,2016,44(1):89-94.]。已有的负载方法虽然具有一定效果，但是载体结构性能不够理想，负载***比表面小，催化活性明显低于悬浮体法([8]Zheng Shukai,WuGuohao,Zhang Junying,et al.Energy band structure and photocatalyticactivityof Sn-doped TiO2 thin film[J].Journal of Materials Engineering,2014,42(1):70-74.]。因此，目前二氧化钛光催化氧化污水处理技术向工业化应用的关键点仍然集中在固定TiO2纳米结构的载体选择和有效的固定技术上。
本发明采用无毒无害的天然沸石为主要原料制备多孔结构的轻质泡沫陶瓷，通过其负载光催化活性层的方法，获得便于回收、不易产生二次污染并对水体中有机污染物能够有效进行光催化降解的新型光催化复合材料。
发明内容：
本发明的目的在于提供一种表面负载光催化活性层的泡沫陶瓷复合材料，特别是一种表面负载二氧化钛光催化活性层的轻质泡沫陶瓷复合材料。制备方法采用溶胶-凝胶工艺：首先将轻质泡沫陶瓷置于二氧化钛溶胶中浸渍，干燥后在一定条件下烧结，如此在陶瓷表面获得一层具有光催化活性的二氧化钛活性层。
本发明中的表面负载光催化活性层的泡沫陶瓷复合材料，其特征在于：其泡沫陶瓷基体为通孔网络结构(参见图1)，基体表面负载了一层具有光催化活性的二氧化钛(参见图2)。
本发明以天然沸石为主要原料制备的轻质泡沫陶瓷为基体，采用溶胶-凝胶工艺，以钛酸四丁酯为钛源制取溶胶，通过浸渍、干燥、烧结，在陶瓷表面负载二氧化钛光催化活性层。提供的制备条件是：待用二氧化钛溶胶陈化24-48小时，基体浸渍后的干燥温度为60℃，接下来的烧结温度为300-500℃。
本发明制备的二氧化钛活性层负载轻质泡沫陶瓷复合材料，具有良好的光催化性能，可以直接用作水体中有机污染物降解的光催化材料。
附图说明：
图1泡沫陶瓷基体形貌。
图2基体表面负载二氧化钛层形貌。
具体实施方式：
实施例1：首先将无水乙醇(分析纯)、钛酸四丁酯、乙酰丙酮(分析纯)、去离子水、硝酸(分析纯)按体积比77:25:3.8:2.5:1配制二氧化钛溶胶，具体操作如下：依次将乙酰丙酮、钛酸四丁酯缓慢滴入乙醇中(乙醇用量为总量的三分之二)配成A溶液，然后依次将去离子水、硝酸先后滴入乙醇中(乙醇用量为总量的三分之一)配成B溶液，最后将B溶液缓慢滴入A溶液中。上述过程均在磁力搅拌条件下进行。混合液陈化48小时，得到待用溶胶。将自行研制的块状轻质泡沫陶瓷样品投入上述溶胶，超声振荡20min使其充分浸渍，取出后在烘箱中于60℃干燥1h，得到表面负载二氧化钛凝胶的多孔样品。重复负载三次，得到具有一定厚度的均匀凝胶层。将上述样品放入电热箱中，以1.5℃/min的升温速度将温度从室温提高到400℃，保温30min。炉冷后取出样品，得到负载二氧化钛活性层的样品。
实施例2：甲基橙具有染料类化合物的典型结构，本发明即采用浓度为20mg/L的甲基橙溶液作为染料有机物污染的废水模型。光催化降解光源采用波长为365nm的500W紫外灯，溶液吸光度采用UV-9100紫外分光光度计测量。量取50ml甲基橙溶液置于烧杯中，投入1.0g负载复合样品。测出紫外灯照射5min、10min、15min、20min、25min、30min时烧杯中溶液的吸光度(表1)，并由吸光度计算出甲基橙的降解率(对应于溶液的脱色率)，结果一同列于表1。吸光度与降解率的关系为：降解率(％)＝(A0－A)/A0，式中A0为原液吸光度，A为经光催化降解后溶液吸光度。实验显示，紫外照射30min后，甲基橙光降解率可达99％以上，溶液变为无色透明。
表1负载制品对甲基橙溶液的降解率(脱色率)
对比例：在上述实施例中将负载二氧化钛的泡沫陶瓷制品换成未经负载的泡沫陶瓷制品，其他条件不变，所得降解率见表2。可见在溶液中放入未经负载的样品，紫外光照射下甲基橙仍有一定的降解。这是由于紫外光本身直接对甲基橙的作用，而不是未负载泡沫陶瓷制品的光催化效果。
表2未经负载制品对甲基橙溶液的降解率(脱色率)
Claims (3)
1.一种表面负载光催化活性层的轻质泡沫陶瓷复合材料，其特征在于：该产品为轻质泡沫陶瓷表面负载一层光催化活性层的多孔复合材料，可漂浮于水面；其中轻质泡沫陶瓷作为活性层负载的载体，而表面负载的活性层具有光催化的功能。
2.权利要求1所述的表面负载光催化活性层的轻质泡沫陶瓷复合材料，其表面活性层是具有光催化活性的二氧化钛，采用溶胶-凝胶法制得。
3.权利要求1所述的表面负载光催化活性层的轻质泡沫陶瓷复合材料，适用于水体中有机污染物的光催化降解，并因其可漂浮于水面而具有便于打捞、回收的优点。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109437412A (zh) * | 2018-12-21 | 2019-03-08 | 河海大学 | 一种生态纤维及制备方法与应用 |
| CN109776083A (zh) * | 2018-12-26 | 2019-05-21 | 古一（广东）建材有限公司 | 一种具有复合功能的多级孔陶瓷材料及其制备方法 |
| CN111285429A (zh) * | 2020-02-29 | 2020-06-16 | 西南石油大学 | 一种低透光度污水光催化处理复合板及其制备方法 |
| EP4331721A1 (en) | 2022-08-31 | 2024-03-06 | Calistair SAS | Catalytic system with photocatalyst and gas depollution apparatus containing the same |
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| CN109437412B (zh) * | 2018-12-21 | 2021-09-17 | 河海大学 | 一种生态纤维及制备方法与应用 |
| CN109776083A (zh) * | 2018-12-26 | 2019-05-21 | 古一（广东）建材有限公司 | 一种具有复合功能的多级孔陶瓷材料及其制备方法 |
| CN111285429A (zh) * | 2020-02-29 | 2020-06-16 | 西南石油大学 | 一种低透光度污水光催化处理复合板及其制备方法 |
| EP4331721A1 (en) | 2022-08-31 | 2024-03-06 | Calistair SAS | Catalytic system with photocatalyst and gas depollution apparatus containing the same |
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