CN113680317A - 二氧化钛/煤基多级孔薄膜泡沫炭复合材料及制备方法 - Google Patents
二氧化钛/煤基多级孔薄膜泡沫炭复合材料及制备方法 Download PDFInfo
- Publication number
- CN113680317A CN113680317A CN202110990576.7A CN202110990576A CN113680317A CN 113680317 A CN113680317 A CN 113680317A CN 202110990576 A CN202110990576 A CN 202110990576A CN 113680317 A CN113680317 A CN 113680317A
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- Prior art keywords
- titanium dioxide
- carbon
- composite material
- foam
- coal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 94
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 91
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- 238000003775 Density Functional Theory Methods 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法、复合材料和复合材料的应用,制备方法包括步骤:将煤样分离,得到疏中质组;将疏中质组压制成块体;将压制成块体的疏中质组置入管式炉内,在惰性气体保护下,进行炭化处理,并自然降温至室温,以得到泡沫炭;将泡沫炭置入高温管式活化炉中进行活化,活化气体为水蒸气或者CO2,活化温度为700oC~950 oC,活化时间为10min~120min;采用二氧化钛悬浊液对多级孔薄膜泡沫炭进行浸渍处理;对浸渍处理后的多级孔薄膜泡沫炭进行干燥处理,得到复合材料。该制备方法简单、成本低,制备的复合材料能有效发挥光催化剂的催化活性,降解效率高、循环性好。
Description
技术领域
本发明涉及复合材料技术领域,尤其是涉及一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料及其制备方法和复合材料的应用。
背景技术
光催化降解技术可以直接利用清洁可再生的太阳能催化氧化有机污染物,且对污染物的选择性低,矿化程度高,使其在环境净化领域具有显著的优势。光催化剂二氧化钛(TiO2)在降解多种环境污染物上都表现出优异的能力,相比其它半导体光催化剂具有价廉、无毒、高活性、光辐射下的高稳定性等优势。然而,粉末状纳米二氧化钛在水溶液中易于凝聚和失活,形成悬浮液不易沉降,在实际应用中难以回收再利用。
相关技术中,通常将光催化剂二氧化钛负载在活性炭的表面来解决催化剂分离回收的问题,然而,由于活性炭是具有丰富微孔结构的吸附材料,二氧化钛负载于活性炭微孔表面后,在实际应用中,光线难以照射进入微孔道内,难以有效发挥光催化剂的催化活性,其降解有机污染物的过程实际为以吸附为主,而不是通过光催化氧化来降解有机污染物。同时,微孔主导的吸附扩散速率较慢,且多次反应后,吸附性能下降,因而使光催化剂降解效率降低,循环稳定性差。
发明内容
本发明旨在至少解决现有技术中存在的技术问题之一。为此,本发明提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,该制备方法制备得到的复合材料能有效发挥光催化剂的催化活性,降解效率高、循环性好,且制备方法简单,生产成本低。
本发明的第二个目的在于提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料,该复合材料由上述制备方法制备而成。
本发明的第三个目的在于提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料。
本发明的第四个目的在于提出了上述二氧化钛/煤基多级孔薄膜泡沫炭复合材料在光催化降解废水和/或废气中的有机污染物的用途。
在本发明的第一方面,本发明提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,包括步骤:将煤样分离,得到疏中质组;将所述疏中质组压制成块体;将压制成块体的所述疏中质组置入管式炉内,在惰性气体保护下,进行炭化处理,并自然降温至室温,以得到泡沫炭;将所述泡沫炭置入高温管式活化炉中进行活化,活化气体为水蒸气或者CO2,活化温度为700 oC ~950 oC,活化时间为10min~180min,以得到多级孔薄膜泡沫炭;采用二氧化钛悬浊液对所述多级孔薄膜泡沫炭进行浸渍处理;对浸渍处理后的所述多级孔薄膜泡沫炭进行干燥处理,得到复合材料。
根据本发明实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,具有如下优点:
(1)以煤的疏中质组为原料经过炭化工艺和活化工艺得到的层次孔薄膜泡沫炭,再通过浸渍法将二氧化钛负载在泡沫炭上,制得二氧化钛/煤基多级孔薄膜泡沫炭复合材料。该制备方法所用原料来源广泛、工艺简单、制备方法可控、生产成本低廉,并可实现规模化制备。
(2)本发明制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料,由于制备的多级孔薄膜泡沫炭具有大孔、中孔和微孔结构,且中孔率可以控制在10%~40%,在将该复合材料应用于废水或废气中的有机污染物的降解处理时,本发明中煤基多级孔薄膜泡沫炭的三维大孔泡沫交联结构有利于光线穿透,从而使负载于薄膜表面的二氧化钛能够接受光激发产生活性,提高表面利用率;而微孔和中孔结构有利于废水或废气中低浓度有机污染物在复合光催化剂表面的吸附、富集和扩散,使被降解物与光催化剂接触几率增加,产生吸附-降解协同作用。相对相关技术中,以微孔为主的活性炭基体,中孔的增加不仅有利于吸附水中大分子污染物,而且提高了吸附质在孔道中的扩散速率,从而提高了光催化降解速率和再生性能,可有效解决二氧化钛光催化剂易流失、回收困难、光利用率较低的问题,同时多级孔泡沫炭与二氧化钛的复合显著提高了复合催化剂的光催化活性,可多次循环使用。
(3)本发明中的制备方法适合各种改性或掺杂型二氧化钛,掺杂或改性二氧化钛可避免纯二氧化钛可见光相应差的缺点,由于炭材料在250nm~750 nm范围内有很好的吸收,泡沫炭与二氧化钛复合又进一步提高了该复合催化剂的可见光响应活性和光降解效率。
(4)本发明中二氧化钛/煤基多级孔薄膜泡沫炭复合材料的整体式结构,可广泛应用于气相及液相中有机污染物的光催化降解。
根据本发明的一些实施例,将所述疏中质组压制成块体前,还包括以下步骤: 在室温下使用洗涤溶剂对分离出的所述疏中质组进行洗涤;对洗涤后的所述疏中质组进行干燥处理;将干燥后的所述疏中质组研磨至100目~200目。
根据本发明的一些实施例,所述炭化处理包括:以升温速率1 oC/min ~10 oC/min升温至400~800 oC,并保持恒温1~5 h后,自然冷却到室温。
根据本发明的一些实施例,所述TiO2悬浊液的制备方法为:将纳米TiO2溶于乙醇、异丙醇、乙二醇或甲醇溶液中,搅拌10min ~120min后,超声分散10min~60 min。
根据本发明的一些实施例,采用等体积浸渍法或过量浸渍法对所述多级孔薄膜泡沫炭进行浸渍处理。
在本发明的第二方面,本发明提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料,其是由上述实施例的制备方法制备获得的。该复合材料具有的特征以及优点,在此不再赘述。
在本发明的第三方面,本发明提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料,包括泡沫炭和负载于所述泡沫炭上的二氧化钛,所述泡沫炭具有大孔、中孔和微孔,且所述中孔率为10%~40%。
根据本发明第三方面实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料,由于泡沫炭具有大孔、中孔和微孔,且中孔率为10%~40%,在将该复合材料应用于废水或废气中的有机污染物的降解处理时,泡沫炭的三维大孔泡沫交联结构有利于光线穿透,从而使负载于薄膜表面的二氧化钛能够接受光激发产生活性,提高表面利用率;而微孔和中孔结构有利于废水或废气中低浓度有机污染物在复合光催化剂表面的吸附、富集和扩散,使被降解物与光催化剂接触几率增加,产生吸附-降解协同作用。相对相关技术中,以微孔为主的活性炭基体,中孔的增加不仅有利于吸附水中大分子污染物,而且提高了吸附质在孔道中的扩散速率,从而提高了光催化降解速率和循环稳定性,可有效解决二氧化钛光催化剂易流失、回收困难、光利用率较低的问题,同时多级孔泡沫炭与二氧化钛的复合显著提高了复合催化剂的光催化活性,可多次循环使用。
根据本发明的一些实施例,所述泡沫炭的比表面积为200m2/g ~600m2/g。
根据本发明的一些实施例,所述二氧化钛的质量分数为10%~60%。
在本发明的第四方面,提出了二氧化钛/煤基多级孔薄膜泡沫炭复合材料在光催化降解废水和/或废气中的有机污染物的用途。其中,复合材料为根据本发明上述第二方面实施例或上述第三方面实施例的复合材料,该复合材料能有效发挥光催化剂的催化活性,降解效率高、循环性好。
本发明的附加方面和优点将在下面的描述中部分给出,部分将从下面的描述中变得明显,或通过本发明的实践了解到。
附图说明
本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解,其中:
图1为本发明一些实施例制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的扫描电子显微镜照图;
图2为本发明一些实施例制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料在模拟太阳光下6 h内对苯酚的光降解曲线;
图3为本发明一些实施例制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料在模拟太阳光下的循环稳定性曲线。
具体实施方式
下面详细描述本发明的实施例,所述实施例的示例在附图中示出,其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。
下面参考描述根据本发明第一方面实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法。
根据本发明第一方面实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,包括步骤:
将煤样分离,得到疏中质组;
在一些实施例中,煤样可以在自然条件下通过煤全组分族分离方法分离以得到疏中质组,煤全组分族分离方法的具体分离步骤如下:
S1:对煤样进行萃取处理:将粒度为100目~300目的煤样置于萃取器中,然后加入混合溶剂,混合溶剂的体积与煤样的质量的比值为20ml/g~300ml/g,其中,混合溶剂可以为由溶剂A和溶剂B按体积比为1:0.2~1:2配制而成,将上述煤样与上述混合溶剂在室温下搅拌10min~300mim后,萃取过程完成,得到萃取固液混合物;
S2:对步骤S1中得到的萃取固液混合物进行固液分离,分别得到萃取液和萃余物;
S3:对步骤S2中得到的萃取液进行反萃取处理:将萃取液放入至反萃取器中,再向反萃取器中加入反萃取剂C,其中,萃取液与反萃取剂的体积比为1:0.1~1:2,将萃取液与反萃取剂在室温下搅拌5mim~60mim,反萃取过程结束,反萃取过程后得到反萃取固液混合物;
S3:对步骤S2中得到的反萃取固液混合物进行处理,将反萃取固液混合物静置后进行固液分离,得到疏中质组。
根据本发明的一些实施例,溶剂A可以为:二硫化碳、氯仿、二氯甲烷、苯、甲醇、苯酚、乙醚,但不限于此。溶剂可以B为:N-甲基-2-吡咯烷酮、环已酮、二甲基亚砜、四氢呋喃、二甲基甲酰胺、二甲基乙酰胺、乙二胺、磷酸三乙脂、喹啉、吡啶,但不限于此。反萃取剂C可以为:水、正己烷,但不限于此。需要说明的是,在同一个工艺过程中,溶剂A、溶剂B和反萃取剂C必须选用三种不同的溶剂物质。
疏中质组具有分子量中等、主要含有芳香族结构化合物和较多的烷基侧链和环烷结构、密度低、炭化过程中易发泡、活化过程中易造孔的特点。具体地,疏中质组为固体状。
将疏中质组压制成块体;
在一些实施例中,可以在3MPa~15MPa压力下将疏中质组压制成厚约1mm~10mm的薄块体。
将压制成块体的疏中质组置入管式炉内,在惰性气体保护下,进行炭化处理,并自然降温至室温,以得到泡沫炭;其中,泡沫炭(foam carbon)是指泡沫状多孔质的炭素材料。泡沫炭是一种由孔泡和相互连接的孔泡壁组成的具有三维网状结构的轻质多孔材料。可选的,惰性气体可以为氮气。
疏中质组经炭化处理后得到的泡沫炭,具有丰富的大孔结构。需要说明的是,本申请中的大孔是指孔径大于50nm的孔。
将泡沫炭置入高温管式活化炉中进行活化,活化气体为水蒸气或者CO2,活化温度为700℃~950℃,活化时间为10min~180min;
例如,在一些实施例中,活化温度可以为700℃、750℃、800℃、850℃、900℃、950℃等。活化时间可以为10min、20min、30min、40min、50min、60min、70min、80min、90min、100min、110min、120min、130min、140min、150min、160min、170min、180min等。
由此,通过对泡沫炭进行活化处理,可以在泡沫炭上形成中孔和微孔,且中孔率为10%~40%,从而可以得到多级孔薄膜泡沫炭。本申请中的中孔是指孔径为2nm~50nm的孔,本申请中的微孔是指孔径小于2nm的孔。
其中,孔率可以采用如下方法测得:采用物理吸附仪测定多级孔薄膜泡沫炭的N2吸附/脱附等温线。由N2吸附/脱附等温线通过BET方程计算得到比表面积,由相对压力为0.99 时的液氮吸附值换算成液氮体积得到总孔容,T-plot 法计算微孔孔容,BJH 法计算中孔孔容,DFT 法分析孔径分布。微孔率即微孔孔容与总孔容的比值。中孔率即中孔孔容与总孔容的比值。剩下的即大孔率。
在一些实施例中,在对泡沫炭进行活化前,可以将泡沫炭切成形状规则的长方体状或立方体状。这样,可以增大泡沫炭与活化气体的接触面积,从而提高活化效率和活化效果。
采用二氧化钛悬浊液对多级孔薄膜泡沫炭进行浸渍处理;这样,可以使二氧化钛负载于泡沫炭的表面(包括泡沫炭的外表面和孔洞的内表面)。
将浸泡有活化后的泡沫炭的二氧化钛悬浊液中的液体蒸干,并干燥处理后,得到复合材料。也就是说,将含有活化后的泡沫炭的二氧化钛悬浊液进行蒸干处理,使悬浊液中的液体挥发掉,得到固定样品,然后对固体样品进行干燥处理,得到复合材料。该复合材料为二氧化钛/煤基多级孔薄膜泡沫炭复合材料。
在本申请中可以采用为过量浸渍法或等体积浸渍法进行浸渍。其中,过量浸渍法是指浸渍溶液的体积大于载体。即载体完全浸泡在浸渍溶液中。例如,在一些实施例中,可以将多级孔薄膜泡沫炭放入二氧化钛悬浊液中,浸泡第一预设时间。第一预设时间可以为10min~120min。在浸渍过程中,可以采用超声辅助分散,这样可以使得悬浊液中的二氧化钛分散均匀,有利于提高浸渍的均匀性。
在上述实施例的基础上,可以采用如下方法对浸渍后的多级孔薄膜泡沫炭进行干燥处理:将浸泡有多级孔薄膜泡沫炭的二氧化钛悬浊液中的液体蒸干,并干燥处理,包括:采用旋转蒸发仪对悬浊液进行减压旋蒸,将旋蒸后的固体样品放入鼓风干燥箱内在80 oC~110 oC下干燥1 h ~6 h。由此,可以提高多级孔薄膜泡沫炭上二氧化钛的负载量。
可以理解的是,在另一些实施例中,也可以直接将浸渍后的多级孔薄膜泡沫炭从二氧化钛悬浊液中取出,放入鼓风干燥箱内在80 oC~110 oC下干燥1 h ~6 h。这样, 同样可以得到上述复合材料。
等体积浸渍法是指载体的体积(一般情况下是指孔体积)和浸渍液的体积一致,浸渍液刚好能完全进入到孔里面。例如,在一些实施例中,可以根据多级孔薄膜泡沫炭的饱和吸水量,滴加等体积的二氧化钛悬浊液,实现对多级孔薄膜泡沫炭进行浸渍处理。
在上述实施例的基础上,将浸渍后的多级孔薄膜泡沫炭,放入鼓风干燥箱内在80 oC~110 oC下干燥1 h ~6 h,即可得到上述复合材料。工艺简单,便于实现。
根据本发明实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,具有如下优点:
(1)以煤的疏中质组为原料经过炭化工艺和活化工艺得到的层次孔薄膜泡沫炭,再通过浸渍法将二氧化钛负载在泡沫炭上,制得二氧化钛/煤基多级孔薄膜泡沫炭复合材料。该制备方法所用原料来源广泛、工艺简单、制备方法可控、生产成本低廉,并可实现规模化制备。
(2)本发明制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料,由于制备的泡沫炭具有大孔、中孔和微孔,且中孔率可以控制在10%~40%,在将该复合材料应用于废水或废气中的有机污染物的降解处理时,本发明中煤基多级孔薄膜泡沫炭的三维大孔泡沫交联结构有利于光线穿透,从而使负载于薄膜表面的二氧化钛能够接受光激发产生活性,提高表面利用率;而微孔和中孔结构有利于废水或废气中低浓度有机污染物在复合光催化剂表面的吸附、富集和扩散,使被降解物与光催化剂接触几率增加,产生吸附-降解协同作用。相对相关技术中,以微孔为主的活性炭基体,中孔的增加不仅有利于吸附水中大分子污染物,而且提高了吸附质在孔道中的扩散速率,从而提高了光催化降解速率和循环稳定性,可有效解决二氧化钛光催化剂易流失、回收困难、光利用率较低的问题,同时多级孔泡沫炭与二氧化钛的复合显著提高了复合催化剂的光催化活性,可多次循环使用。
(3)本发明中的制备方法适合各种改性或掺杂型二氧化钛,掺杂或改性二氧化钛可避免纯二氧化钛可见光相应差的缺点,由于炭材料在250nm ~750 nm范围内有很好的吸收,泡沫炭与二氧化钛复合又进一步提高了该复合催化剂的可见光响应活性和光降解效率。
(4)本发明中二氧化钛/煤基多级孔薄膜泡沫炭复合材料的整体式结构,可广泛应用于气相及液相中有机污染物的光催化降解。
根据本发明的一些实施例,将疏中质组压制成块体前,还包括以下步骤:在室温下使用洗涤溶剂对分离出的疏中质组进行洗涤;对洗涤后的疏中质组进行干燥处理;将干燥后的疏中质组研磨至100目~200目。由此,可以将残留在疏中质组表面的溶剂洗涤干净,同时,将疏中质组研磨至100目~200目,可以方便地对疏中质组进行压块处理。
根据本发明的一些实施例,炭化处理包括:以升温速率1 oC/min ~10 oC/min升温至400 oC ~800 oC,并保持恒温1~5 h后,自然冷却到室温。
根据本发明的一些实施例,二氧化钛悬浊液的制备方法为:将纳米二氧化钛溶于乙醇、异丙醇、乙二醇或甲醇溶液中,搅拌10 min ~120min后,超声分散10 min~60 min。例如,在一些实施例中,二氧化钛悬浊液的制备过程可以为:将粉末状纳米二氧化钛,溶于无水乙醇中,搅拌10min ~120min,并超声处理10min ~60min。这样,可以使得二氧化钛更加均匀的分散在无水乙醇中,提高了悬浊液的均匀性,有利于提高浸渍效果,提高多级孔薄膜泡沫炭上二氧化钛的负载量。同时,采用、乙醇、异丙醇、乙二醇或甲醇为悬浊液的溶液,由于乙醇、异丙醇、乙二醇或甲醇溶液挥发,从而可以方便地将样品与溶液分离。
其中,纳米二氧化钛可以为纳米纯二氧化钛、改良型纳米二氧化钛或掺杂型纳米二氧化钛。
表1为本发明一些实施例制备的煤基多级孔薄膜泡沫炭的孔结构参数。
表1煤基多级孔薄膜泡沫炭的孔结构参数
图1为本发明一些实施例制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的扫描电子显微镜图。从图1中可以看出,多级孔薄膜泡沫炭的孔泡直径在20μm~100μm左右(这里说明的是大孔的尺寸,中孔和微孔的尺寸在扫描电子显微镜照片中是看不到的,只能由N2吸附表征可以得到),薄壁厚度(即薄膜的厚度)为1μm -3μm。在泡沫炭薄膜表面以及孔道周围均匀负载了纳米级二氧化钛。
图2为本发明一些实施例制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料在模拟太阳光下6 h内对苯酚的光降解曲线。从图2中可以看出,复合材料在1小时暗吸附后对苯酚的脱除率达到57%,光照2小时后对苯酚的脱除率即达到97%。表明该复合材料具有较快的降解速率和优异的光降解活性。
图3为本发明一些实施例制备的二氧化钛/煤基多级孔薄膜泡沫炭复合材料在模拟太阳光下的循环稳定性曲线。图3为复合材料循环使用四次的光催化结果。每次光降解结束后用去离子水对催化剂进行清洗、过滤、干燥等一系列操作,结果表明循环使用四次后催化剂的总降解率仍达到97%,表明了该复合材料具有良好的循环稳定性。
从图2和图3可以看出,本实施例制备的复合材料具有优异的催化活性和良好的循环稳定性,表明该复合材料具有良好的光催化性能,并且这种良好的光催化性能是通过吸附-降解协同机制实现的。
该复合材料的光催化降解机理为:首先,有机物分子在泡沫炭微孔-中孔中发生吸附,进而扩散转移到二氧化钛光催化剂表面,增加局部浓度,使被降解物与光催化剂接触几率增加。然后,在光照条件下,二氧化钛受带隙光激发产生电子-空穴对,光生电子和光生空穴能够与水或氧气反应产生高活性氧化物种,使污染物最终矿化为H2O和CO2等小分子。微孔为主导的吸附扩散速率较慢,反应时间长,且多次反应后,吸附性能下降。此外,大分子吸附质无法进入微孔结构进行吸附。
可以理解的是,若多级孔泡沫炭中微孔过多,会使其过程变成实际以吸附为主,而不是通过光催化本身来降解有机污染物。
吸附之于光催化,是完全不同的两种技术,吸附会对环境产生二次污染,而光催化降解则是一种高级的绿色无二次污染的技术。同时微孔过多,会降低光催化降解速率,也会影响催化剂的循环稳定性。从图2和图3的模拟结果可以看出,该复合材料具有适宜的微孔、中孔及大孔分布,从而使催化剂具备了优良的光催化性能。
下面描述根据本发明实施例的制备多孔碳材料的方法的三个具体实施例。
实施例1
本实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,包括步骤:
将粒度为200目的煤样置于萃取器中,加入CS2和NMP(体积比1:1)室温下搅拌120min后,对萃取固液混合物进行固液分离,将萃取液放入至反萃取器中,向反萃取器中加入反萃取剂H2O,并在室温下搅拌60 min后得到反萃取固液混合物,将反萃取固液混合物静置后进行固液分离,固相即为疏中质组;
依次用乙醇和水对疏中质组进行洗涤,总洗涤时间可以为1h,洗涤后在烘箱中于80℃进行干燥;
将干燥后的疏中质组研磨至200目,每次称取0.5 g的疏中质组在油压机上以5MPa压力压制成厚约3 mm的薄块体;
将薄块体状的疏中质组放入管式炉中,在N2气氛下发泡(炭化),制备出薄膜泡沫炭。炭化升温程序:从室温升到 600℃,升温速率为5℃/min,600℃下恒温2 h 后,自然降温到室温;
将制备好的泡沫炭切成一定体积的的立方体,将切好的泡沫炭置于瓷舟中,然后放入管式炉中进行水蒸气活化,活化温度750℃,水蒸气进样速率为0.1 mL/min,活化时间60 min,得到多级孔薄膜泡沫炭;
称取100 mg N掺杂TiO2,将其分散到10 mL的乙醇中,得到乙醇的悬浊液,搅拌30min,超声30 min。称取0.5 g多级孔薄膜泡沫炭加入到乙醇悬浊液中,继续超声30 min,然后将样品在旋转蒸发仪上减压旋蒸,液体蒸干旋蒸后,将固体样品放入鼓风干燥箱内110℃下干燥3 h,得到氮掺杂二氧化钛/煤基多级孔薄膜泡沫炭复合材料。
本实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,包括步骤:
将粒度为200目的煤样置于萃取器中,加入CS2和NMP(体积比1:1)室温下搅拌120min后,对萃取固液混合物进行固液分离,将萃取液放入至反萃取器中,向反萃取器中加入反萃取剂H2O,并在室温下搅拌60 min后得到反萃取固液混合物,将反萃取固液混合物静置后进行固液分离,固相即为疏中质组;
依次用乙醇和水对疏中质组进行洗涤,总洗涤时间可以为1h, 洗涤后在烘箱中于80℃进行干燥;
将干燥后的疏中质组研磨至200目,每次称取0.5 g的疏中质组在油压机上以5MPa压力压制成厚约3 mm的薄块体;
将薄块体状的疏中质组放入管式炉中,在N2气氛下发泡(炭化),制备出薄膜泡沫炭。炭化升温程序:从室温升到 600℃,升温速率为5℃/min,600℃下恒温2 h 后,自然降温到室温;
将制备好的泡沫炭切成一定体积的的立方体,将切好的泡沫炭置于瓷舟中,然后放入管式炉中进行水蒸气活化,活化温度800℃,水蒸气进样速率为0.1 mL/min,活化时间40min,得到多级孔薄膜泡沫炭;
称取100 mg N掺杂TiO2,将其分散到10 mL的乙醇中,得到乙醇的悬浊液,搅拌30min,超声30 min。称取0.5 g多级孔薄膜泡沫炭加入到乙醇悬浊液中,继续超声30 min,然后将样品在旋转蒸发仪上减压旋蒸,液体蒸干旋蒸后,将固体样品放入鼓风干燥箱内110℃下干燥3 h,得到氮掺杂二氧化钛/煤基多级孔薄膜泡沫炭复合材料。
实施例3
本实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,包括步骤:
将粒度为200目的煤样置于萃取器中,加入CS2和NMP(体积比1:1)室温下搅拌120min后,对萃取固液混合物进行固液分离,将萃取液放入至反萃取器中,向反萃取器中加入反萃取剂H2O,并在室温下搅拌60 min后得到反萃取固液混合物,将反萃取固液混合物静置后进行固液分离,固相即为疏中质组;
依次用乙醇和水对疏中质组进行洗涤,总洗涤时间可以为1h, 洗涤后在烘箱中于80℃进行干燥;
将干燥后的疏中质组研磨至200目,每次称取0.5 g的疏中质组在油压机上以5MPa压力压制成厚约3 mm的薄块体;
将薄块体状的疏中质组放入管式炉中,在N2气氛下发泡(炭化),制备出薄膜泡沫炭。炭化升温程序:从室温升到 600℃,升温速率为5℃/min,600℃下恒温2 h 后,自然降温到室温;
将制备好的泡沫炭切成一定体积的的立方体,将切好的泡沫炭置于瓷舟中,然后放入管式炉中进行水蒸气活化,活化温度850℃,水蒸气进样速率为0.1 mL/min,活化时间20min,得到多级孔薄膜泡沫炭;
称取100 mg N掺杂TiO2,将其分散到10 mL的乙醇中,得到乙醇的悬浊液,搅拌30min,超声30 min。称取0.5 g多级孔薄膜泡沫炭加入到乙醇悬浊液中,继续超声30 min,然后将样品在旋转蒸发仪上减压旋蒸,液体蒸干旋蒸后,将固体样品放入鼓风干燥箱内110℃下干燥3 h,得到氮掺杂二氧化钛/煤基多级孔薄膜泡沫炭复合材料。
在本发明的第二方面,本发明提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料,其是由上述实施例的制备方法制备获得的。该复合材料具有的特征以及优点,在此不再赘述。
在本发明的第三方面,本发明提出一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料,包括泡沫炭和负载于泡沫炭上的二氧化钛,泡沫炭具有大孔、中孔和微孔,且中孔率为10%~40%。
根据本发明第三方面实施例的二氧化钛/煤基多级孔薄膜泡沫炭复合材料,由于泡沫炭具有大孔、中孔和微孔,且中孔率为10%~40%,在将该复合材料应用于废水或废气中的有机污染物的降解处理时,泡沫炭的三维大孔泡沫交联结构有利于光线穿透,从而使负载于薄膜表面的二氧化钛能够接受光激发产生活性,提高表面利用率;而微孔和中孔结构有利于废水或废气中低浓度有机污染物在复合光催化剂表面的吸附、富集和扩散,使被降解物与光催化剂接触几率增加,产生吸附-降解协同作用。相对相关技术中,以微孔为主的活性炭基体,中孔的增加不仅有利于吸附水中大分子污染物,而且提高了吸附质在孔道中的扩散速率,从而提高了光催化降解速率和循环稳定性,可有效解决二氧化钛光催化剂易流失、回收困难、光利用率较低的问题,同时多孔级泡沫炭与二氧化钛的复合显著提高了复合催化剂的光催化活性,可多次循环使用。
根据本发明的一些实施例,泡沫炭的比表面积为200 m2/g ~600 m2/g。
根据本发明的一些实施例,二氧化钛的质量分数为10%~60%。
在本发明的第四方面,提出了二氧化钛/煤基多级孔薄膜泡沫炭复合材料在光催化降解废水和/或废气中的有机污染物的用途。其中,复合材料为根据本发明上述第二方面实施例或上述第三方面实施例的复合材料,该复合材料能有效发挥光催化剂的催化活性,降解效率高、循环性好。
在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示意性实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
尽管已经示出和描述了本发明的实施例,本领域的普通技术人员可以理解:在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由权利要求及其等同物限定。
Claims (10)
1.一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料的制备方法,其特征在于,包括步骤:
将煤样分离,得到疏中质组;
将所述疏中质组压制成块体;
将压制成块体的所述疏中质组置入管式炉内,在惰性气体保护下,进行炭化处理,并自然降温至室温,以得到泡沫炭;
将所述泡沫炭置入高温管式活化炉中进行活化,活化气体为水蒸气或者CO2,活化温度为700 oC ~950 oC,活化时间为10min~180min,以得到多级孔薄膜泡沫炭;
采用二氧化钛悬浊液对所述多级孔薄膜泡沫炭进行浸渍处理;
对浸渍处理后的所述多级孔薄膜泡沫炭进行干燥处理,得到复合材料。
2.根据权利要求1中所述的制备方法,其特征在于,将所述疏中质组压制成块体前,还包括以下步骤:
在室温下使用洗涤溶剂对分离出的所述疏中质组进行洗涤;
对洗涤后的所述疏中质组进行干燥处理;
将干燥后的所述疏中质组研磨至100目~200目。
3.根据权利要求1 所述的制备方法,其特征在于,所述炭化处理包括:以升温速率1 oC/min ~10 oC/min升温至400 oC ~800 oC,并保持恒温1~5 h后,自然冷却到室温。
4.根据权利要求1中所述的制备方法,其特征在于,所述二氧化钛悬浊液的制备方法为:将纳米二氧化钛溶于乙醇、异丙醇、乙二醇或甲醇溶液中,搅拌10min ~120min后,超声分散10 min~60 min。
5.根据权利要求1-4中任一项所述的制备方法,其特征在于,采用等体积浸渍法或过量浸渍法对所述多级孔薄膜泡沫炭进行浸渍处理。
6.一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料,其特征在于,其是由权利要求1-4中任一项所述的制备方法制备获得的。
7.一种二氧化钛/煤基多级孔薄膜泡沫炭复合材料,其特征在于,包括泡沫炭和负载于所述泡沫炭上的二氧化钛,所述泡沫炭具有大孔、中孔和微孔,且所述中孔率为10%~40%。
8.根据权利要求7所述的复合材料,其特征在于,所述泡沫炭的比表面积为200 m2/g ~600 m2/g。
9.根据权利要求7所述的复合材料,其特征在于,所述二氧化钛的质量分数为10%~60%。
10.权利要求6-9所述的二氧化钛/煤基多级孔薄膜泡沫炭复合材料在光催化降解废水和/或废气中的有机污染物的用途。
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