CN107952465B - 一种环己烷选择性氧化的复合催化剂、制备方法及应用 - Google Patents
一种环己烷选择性氧化的复合催化剂、制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种制备简便,无贵金属掺杂,成本低,光催化活性高的介孔石墨氮化碳修饰铁掺杂二氧化钛光催化剂的制备方法。该方法是先在介孔SBA‑15模板作用下生成二维介孔石墨氮化碳,然后和含四价钛和三价铁的醇溶胶反应,产物在空气下干燥后煅烧,在二维介孔石墨氮化碳孔内原位复合铁掺杂二氧化钛纳米晶,制备了孔石墨氮化碳修饰铁掺杂二氧化钛复合催化剂Fe‑TiO2/m‑C3N4。本发明可通过改变m‑C3N4,四价钛和三价铁前驱物的质量比来制备不同组成的Fe‑TiO2/m‑C3N4复合催化剂,调节复合物的带隙宽度。本发明催化剂可用于环己烷光催化选择性氧化制备环己醇和环己酮。
Description
技术领域
本发明涉及光催化氧化领域,具体涉及一种用于环己烷选择性氧化的复合催化剂及其制备方法与应用。
背景技术
由环己醇和环己酮(KA油)选择性氧化是合成己二酸和己内酰胺的主要途径,己二酸和己内酰胺是生产高聚物尼龙6和尼龙66的重要原料。目前工业获得环己醇和环己醇的路线是环己烷和氧气高温高压(170℃,1MPa)下在助催化剂作用下氧化。为了获得较高的选择性(85%),环己烷的转化率往往需严格控制在10%以下,否则会生成过多的深度氧化产物(CO2)。因此,在工业上,需不断分离氧化产物,补充重新活化的催化剂,从而造成这一路线成本很高,危险性高,环境污染严重。光催化路线可以在室温和常压下进行,条件温和,能有效利用太阳能,清洁环保,环己烷光催化氧化合成环己醇和环己酮是一种有应用前景的绿色合成方法。
和其他半导体光催化剂相比,TiO2价格便宜,光催化活性高,光稳定性好,是一类广泛使用的光催化剂。但纯TiO2的禁带宽度宽(3.2eV),需要<380nm波长的紫外光激发才能使电子跃迁至导带,引发光催化反应。在太阳光谱中,只有5%位于紫外光区,开发具有可见光激发活性的TiO2催化剂可以克服TiO2光催化剂的应用瓶颈,更有效利用太阳能。通过掺杂修饰TiO2结构,调变TiO2价带和导带位置,可以使TiO2在可见光辐射下产生光催化活性。在不同掺杂TiO2中,Fe掺杂TiO2更具吸引力,因为Fe在地球上丰度高,来源丰富,Fe3+的离子半径和Ti4+很接近,能更好地置换到TiO2晶格中,形成“陷阱中心”,能有效捕获光生电子,阻止光生电子和空穴的复合。将两种合适的半导体复合形成异质结构,能有效改善光催化性能,有效促进光生电子和空穴在界面的分离。石墨结构氮化碳(g-C3N4)具有聚合层状结构,根据合成条件不同,禁带宽度为2.4~2.8eV。g-C3N4在可见光辐射下能产生光生电子和空穴(光生载流子),有较好的可见光响应性,但光生载流子易复合,且单独作为光催化剂的g-C3N4的活性低。通过g-C3N4和Fe-TiO2复合的异质结结构,可以调节复合催化剂的能带结构,抑制光生载流子的复合,促进光生载流子在异质结界面的迁移,提高光催化活性。
复合催化剂微观结构,吸附性能和表面性质对光催化活性有重要影响。通过控制条件,形成比表面积大的多孔纳米复合材料,能有效提高异质结界面面积,有利于反应物和光生载流子在催化剂表面吸附和反应。目前光催化剂的实用用途主要集中在有机污染物废水处理、NOx废气降解等方面,用于化学品的绿色合成方面还很少,通过g-C3N4和Fe-TiO2的合适匹配,能产生光催化性能好的复合催化剂,有望实现由环己烷光催化氧化合成环己醇和环己酮的工业生产。
发明内容
本发明的目的是提供一种用于选择性光催化氧化环己烷的复合催化剂的制备方法,以及该复合催化剂,介孔石墨氮化碳修饰铁掺杂二氧化钛的纳米复合材料:Fe-TiO2/m-C3N4在可见光辐射下环己烷选择性氧化制备环己醇和环己酮中的应用。
本发明所采用的技术方案:一种用于环己烷选择性氧化的复合催化剂的制备方法,所述复合催化剂为介孔石墨氮化碳修饰铁掺杂二氧化钛的纳米复合材料Fe-TiO2/m-C3N4,所述Fe-TiO2/m-C3N4的制备步骤为:
(1)将反应量的SBA-15和含氮有机物水溶液混合搅拌后100℃下烘干;在N2气氛下500℃煅烧充分,然后用10%HF溶液溶蚀SBA-15模板,得到介孔石墨氮化碳m-C3N4;
(2)将m-C3N4、Ti(OR)4(R=-C2H5,-CH(CH3)2,-C4H9中的一种)、Fe(NO3)3和丁醇混合,加热到50℃,搅拌充分,然后冷却至室温,搅拌;分离的固体60℃下干燥;然后在350~600℃下煅烧充分,得到Fe-TiO2/m-C3N4复合催化剂;所述的m-C3N4、Ti(OR)4、Fe(NO3)3和丁醇的质量体积比为0.5g :0.022~0.032mol :0.001~0.003mol :20mL。
所述的含氮有机物为单氰胺、二氰胺、三嗪、三聚氰胺、六次甲基四胺和尿素中的一种或两种。
所述的含氮有机物水溶液摩尔浓度为5.3~7.5mmol/mL,SBA-15在含氮有机物水溶液的含量是0.8g/mL。
一种按照所述的制备方法制备的Fe-TiO2/m-C3N4复合催化剂。
所述的制备方法制备的Fe-TiO2/m-C3N4复合催化剂在环己烷光催化制备环己醇和环己酮中的应用
本发明和其他技术相比,其有益的技术效果是:
原料来源丰富,便宜,制备简单,稳定性好。制备过程中无有害有毒中间物产生,复合催化剂化学稳定性,光稳定性好。本发明制备的Fe-TiO2/m-C3N4复合催化剂为介孔纳米复合结构,形貌晶相可控,比表面高,吸附性能好。在可见光辐射下环己烷选择性氧化制备环己醇和环己酮的催化过程中具有很好的选择性,能抑制CO2的生成,产物中酮产物比例较高。
具体实施方式
实施例1.
将2.9g单氰胺溶于10g水中形成7mmol/mL的水溶液,取1mL溶液加入0.8gSBA-15混合,搅拌1h,然后100℃下烘干。在N2气氛下500℃煅烧4h,得到的黄色固体用10%HF溶液缓慢搅拌处理4h,过滤,用水和乙醇充分洗涤,80℃下烘干12h得到介孔石墨氮化碳m-C3N4。取0.5g制备的m-C3N4和7.48g Ti(OC4H9)4,0.4gFe(NO3)3.9H2O和20mL正丁醇混合,加热到50℃,搅拌3h,冷却至室温,继续搅拌1h,固体离心分离,60℃下干燥12h。干燥后的产物在然后在N2气氛下350℃下煅烧3h得Fe-TiO2/m-C3N4催化剂。
实施例2.
将1.93g双氰胺和3.78g三聚氰胺溶于10g水中形成5.3mmol/mL(含氮有机物)的水溶液,取1mL溶液加入0.8gSBA-15混合,搅拌1h,然后100℃下烘干。在N2气氛下500℃煅烧4h,得到的黄色固体用10%HF溶液缓慢搅拌处理4h,过滤,用水和乙醇充分洗涤,80℃下烘干12h得到介孔石墨氮化碳m-C3N4。取0.5g制备的m-C3N4和7.94g Ti(OCH(CH3)2)4,0.6gFe(NO3)3.9H2O和20mL正丁醇混合,加热到50℃,搅拌3h,冷却至室温,继续搅拌1h,固体离心分离,60℃下干燥12h。干燥后的产物在然后在N2气氛下400℃下煅烧3h得Fe-TiO2/m-C3N4催化剂。
实施例3.
将1.8g尿素和3.78g三聚氰胺溶于10g水中形成5.3mmol/mL(含氮有机物)的水溶液,取1mL溶液加入0.8gSBA-15混合,搅拌1h,然后100℃下烘干。在N2气氛下500℃煅烧4h,得到的黄色固体用10%HF溶液缓慢搅拌处理4h,过滤,用水和乙醇充分洗涤,80℃下烘干12h得到介孔石墨氮化碳m-C3N4。取0.5g制备的m-C3N4和6.84g Ti(OC2H5)4,0.7gFe(NO3)3.9H2O和20mL正丁醇混合,加热到50℃,搅拌3h,冷却至室温,继续搅拌1h,固体离心分离,60℃下干燥12h。干燥后的产物在然后在N2气氛下420℃下煅烧3h得Fe-TiO2/m-C3N4催化剂。
实施例4.
将2.16g尿素和2.8g六次甲基四胺溶于10g水中形成5.6mmol/mL(含氮有机物)的水溶液,取1mL溶液加入0.8gSBA-15混合,搅拌1h,然后100℃下烘干。在N2气氛下500℃煅烧4h,得到的黄色固体用10%HF溶液缓慢搅拌处理4h,过滤,用水和乙醇充分洗涤,80℃下烘干12h得到介孔石墨氮化碳m-C3N4。取0.5g制备的m-C3N4和9.84g Ti(OC4H9)4,0.9gFe(NO3)3.9H2O和20mL正丁醇混合,加热到50℃,搅拌3h,冷却至室温,继续搅拌1h,固体离心分离,60℃下干燥12h。干燥后的产物在然后在N2气氛下450℃下煅烧3h得Fe-TiO2/m-C3N4催化剂。
实施例5.
将8.69g三聚氰胺溶于10g水中形成6.2mmol/mL(含氮有机物)的水溶液,取1mL溶液加入0.8gSBA-15混合,搅拌1h,然后100℃下烘干。在N2气氛下500℃煅烧4h,得到的黄色固体用10%HF溶液缓慢搅拌处理4h,过滤,用水和乙醇充分洗涤,80℃下烘干12h得到介孔石墨氮化碳m-C3N4。取0.5g制备的m-C3N4和9.42g Ti(OC4H9)4,0.8gFe(NO3)3.9H2O和20mL正丁醇混合,加热到50℃,搅拌3h,冷却至室温,继续搅拌1h,固体离心分离,60℃下干燥12h。干燥后的产物在然后在N2气氛下500℃下煅烧3h得Fe-TiO2/m-C3N4催化剂。
实施例6
将10.51g均三嗪溶于10g水中形成7.5mmol/mL(含氮有机物)的水溶液,取1mL溶液加入0.8gSBA-15混合,搅拌1h,然后100℃下烘干。在N2气氛下600℃煅烧4h,得到的黄色固体用10%HF溶液缓慢搅拌处理4h,过滤,用水和乙醇充分洗涤,80℃下烘干12h得到介孔石墨氮化碳m-C3N4。取0.5g制备的m-C3N4和7.3g Ti(OC2H5)4,1.2gFe(NO3)3.9H2O和20mL正丁醇混合,加热到50℃,搅拌3h,冷却至室温,继续搅拌1h,固体离心分离,60℃下干燥12h。干燥后的产物在然后在N2气氛下600℃下煅烧3h得Fe-TiO2/m-C3N4催化剂。
实施例7、 Fe-TiO2/m-C3N4催化剂在可见光辐射下环己烷选择性氧化制备环己醇和环己酮中的催化实验
1-6实施例中合成的Fe-TiO2/m-C3N4催化剂在可见光辐射下环己烷选择性氧化催化测试方法:将25mL环己烷、250mg催化剂和22μL水混合后放入50mL石英两口烧瓶中,烧瓶一口接冷凝管,冷凝管顶部接导气管将反应生成的CO2导入到含Ba(OH)2溶液的吸收瓶中;一口接鼓泡装置通入标准大气压下的空气(高纯空气来自高压钢瓶,O2:N2=1:4)。将反应瓶固定于磁力搅拌台上,整个装置放入自制暗箱中。在暗反应阶段搅拌1h达到吸附平衡,然后打开光源(300W氙灯,置于冷阱,循环水冷却),反应瓶前置滤光片,隔离波长<420nm的光,在室温下反应4h。
产物分析:反应后液体离心分离催化剂后,用气相色谱仪以十六烷为内标,分析环己醇和环己酮总产率(色谱条件:氢火焰检测器,毛细管柱SE-30,柱温:110℃,汽化:200℃,检测器温:230℃)。生成CO2的确定通过将反应后Ba(OH)2吸收瓶的溶液离心分离沉淀后,用0.01mol/L的HCl标准溶液滴定,确定吸收CO2后Ba(OH)2的浓度,从而确定CO2的量。
对比例1、Fe掺杂TiO2催化剂Fe-TiO2制备及可见光辐射下环己烷选择性氧化制备环己醇和环己酮中的催化实验
10.2gTi(OC4H9)4,1.01g的Fe(NO3)3.9H2O和20mL丁醇混合,加热到50℃,搅拌3h,然后冷却至室温,搅拌1h。分离的固体60℃下干燥12h。然后在N2气氛下500℃下煅烧3h得Fe-TiO2,上述制备的Fe-TiO2催化剂,Fe含量为5.8%质量百分比。
将上述制备的Fe-TiO2按实施例7所述实验方法进行催化实验,并将结果与1-6实施例的Fe-TiO2/m-C3N4进行对比。
表1 催化剂催化活性评价
从上述实施例和对比例反应结果可以看出,本发明方法制备的Fe-TiO2/m-C3N4复合催化剂在可见光辐射下环己烷选择性氧化制备环己醇和环己酮的催化过程中具有很好的选择性,能抑制CO2的生成,产物中酮产物比例较高。
Claims (4)
1.一种用于环己烷选择性氧化的复合催化剂的制备方法,所述复合催化剂为介孔石墨氮化碳修饰铁掺杂二氧化钛的纳米复合材料Fe-TiO2/m-C3N4,其特征在于,所述Fe-TiO2/m-C3N4的制备步骤为:
(1)将反应量的SBA-15和含氮有机物水溶液混合搅拌后100℃下烘干;在N2气氛下500℃煅烧充分,然后用10%HF溶液溶蚀SBA-15模板,得到介孔石墨氮化碳m-C3N4;所述的含氮有机物水溶液摩尔浓度为5.3~7.5mmol/mL,SBA-15在含氮有机物水溶液中的含量是0.8g/mL;
(2)将m-C3N4、 Ti(OR)4、Fe(NO3)3和丁醇混合,加热到50℃,搅拌充分,然后冷却至室温,搅拌;分离的固体60℃下干燥;然后在350~600℃下煅烧充分,得到Fe-TiO2/m-C3N4复合催化剂;所述的m-C3N4、Ti(OR)4、Fe(NO3)3和丁醇的用量比为0.5g :0.022~0.032mol :0.001~0.003mol :20mL;R=-C2H5, -CH(CH3)2, -C4H9中的一种。
2.根据权利要求1所述的制备方法,其特征在于,所述的含氮有机物为单氰胺、二氰胺、三嗪、三聚氰胺、六次甲基四胺和尿素中的一种或两种。
3.一种按照权利要求1所述的制备方法制备的Fe-TiO2/m-C3N4复合催化剂。
4.权利要求1所述的制备方法制备的Fe-TiO2/m-C3N4复合催化剂在环己烷光催化制备环己醇和环己酮中的应用。
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