CN114570378A - CeO2包覆Ni的纳米管光热复合催化剂及制法和应用 - Google Patents
CeO2包覆Ni的纳米管光热复合催化剂及制法和应用 Download PDFInfo
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Abstract
本发明公开了一种用于光热驱动甲烷‑二氧化碳重整的CeO2包覆Ni的硅酸盐纳米管催化剂及其制备方法和应用。首先采用水热法制备了包Ni的的层状硅酸盐前驱体(Ni‑psnts),然后再使用沉淀法在Ni‑psnts上沉积一层CeO2薄层,然后经过高温煅烧和H2还原后制备得到Ni‑psnts@CeO2。在全波段光谱氙灯辐照下,该催化剂具有优异的吸光性能和非常好的光热催化CH4‑CO2重整催化活性及稳定性。本发明制备方法简单,生产成本低,用该方法制备的催化剂为太阳能驱动温室气体(CH4和CO2)减排和绿色能源转化等领域奠定了良好的基础。
Description
技术领域
本发明属于能源材料领域,尤其涉及一种CeO2包覆Ni的硅酸盐纳米管光热复合催化剂的制备方法及其应用。
背景技术
随着世界经济的快速发展与全球工业化的推进,化石能源在过去的几百年里被过度的开采与使用。由于化石能源的过度使用,人类已经向大气中排放了太多的温室气体(CH4,CO2),它们被认为是造成全球变暖的原因。CH4-CO2重整技术可以将CH4与CO2两种温室气体作为原料转化为具有更高附加值的H2和CO合成气。而以太阳能驱动的光热CH4-CO2重整技术具有更广阔的发展前景,因为该技术不仅具备传统CH4-CO2催化技术的优势,同时还能够避免温室气体的二次排放,利用清洁可再生的太阳能作为能量输入,实现太阳能到化学能的存储与利用。
早在20世纪90年代,多个国际组织报道了人类活动,尤其是温室气体的排放是全球变暖的主要原因。同一时期,Aschoft等人发表了他们在CH4-CO2重整领域的研究成果,CO2-CH4重整反应开始引起人们的广泛关注。经过20多年的研究,目前普遍认同CH4-CO2重整反应的主要活性组分集中在除金属锇(Os)外的第Ⅷ族金属元素(Rh、Ru、Ir、Pt、Pd、Fe、Co、Ni)。其中Ni金属因其储量丰富、价格低、活性高被认为是CH4-CO2重整工业应用最理想的催化剂。但是由于实现C-H键的活化在热力学和动力学上都面临着巨大的挑战,需要在较高的温度下才能实现,而Ni金属在高温下容易因烧结和积碳而失活,所以设计新的催化剂体系,保持催化剂高的活性,提高镍基催化剂的稳定性依然是研究的重点。目前的研究认为积碳是热力学上不可避免的问题,所以如何提升催化剂消除积碳的速率成为减少积碳的关键,当前的研究表明了具有氧化还原特性的氧化物载体(如CeO2)对抑制积碳生长有较好的帮助。另一方面,使用太阳能辅助Ni基催化剂进行CH4-CO2重整反应,利用Ni纳米颗粒的局部表面等离子体效应减少积碳行为的研究也有报道,虽然目前内在的机理尚不清晰,但是太阳能对CH4-CO2重整反应的促进作用值得研究。因此,我们选用以CeO2包覆Ni的硅酸盐纳米管催化剂作为光热催化CH4-CO2重整反应的研究对象。
发明内容
发明目的:本发明的目的在于提供一种用于光热CH4-CO2重整反应的高效、稳定的新型催化剂的制备方法,先采用水热法合成Ni-psnts前驱体,然后用沉淀法在前驱体上沉积一层CeO2薄层,经过高温煅烧还原后制备出Ni-psnts@CeO2。本发明的另一个目的是提供上述催化剂的应用,在全波段的氙灯光源辐照下,该催化剂具有很高的光热CH4-CO2催化重整活性和稳定性。该方法对环境、能源和材料等交叉学科领域具有广泛的实用价值和应用研究前景。。
技术方案:本发明的CeO2包覆Ni的光热复合催化剂Ni-psnts@CeO2,所述催化剂包括负载在层状硅酸盐纳米管psnts载体上的活性组分Ni和包覆在外层的助催化剂壳层CeO2。
进一步地,所述活性组分Ni的粒径为7-9nm。
本发明还公开一种CeO2包覆Ni的光热复合催化剂Ni-psnts@CeO2的制备方法,包括如下步骤:
步骤(1):将硝酸镁和硝酸镍溶解在去离子水中超声处理10~20min,然后持续搅拌形成均匀的盐溶液;偏硅酸钠溶解在去离子水中超声处理15~30min形成溶液并将其添加到上述盐溶液中,继续搅拌形成悬浊液;
步骤(2):将氢氧化钠溶解在去离子水中超声处理5~10min形成碱性溶液,将其加入到步骤(1)所述的正在搅拌的悬浊液中,再持续搅拌20~30min;然后将搅拌完成后的液体转移到带有聚四氟乙烯内衬的高压反应釜中高温处理;将所得沉淀物离心收集并使用去离子水和乙醇交替洗涤三次后干燥得到Ni-psnts前驱体;
步骤(3)称取一定量的Ni-psnts前驱体和硝酸铈加入到乙醇溶液中超声分散;将一定量的乌洛托品溶解在去离子水中并加入到上述乙醇溶液中,然后将混合溶液转移到水浴锅中加热;将得到的沉淀物离心收集并使用水和乙醇交替洗涤,然后干燥、煅烧、还原后得到最终产物。
进一步地,步骤(1)中,所述的硝酸镁和硝酸镍的摩尔量之和(Ni+Mg)与偏硅酸钠的摩尔量(Si)的比值为1~1.5。
进一步地,步骤(2)中,所述的氢氧化钠摩尔量为偏硅酸钠的15~20倍,悬浊液在加热前的pH>14,加热后的pH>11。
进一步地,步骤(2)中,所述的高温处理温度为150~250℃,处理时间为24~48h,干燥温度为60~120℃,干燥时间为8~12h。
进一步地,步骤(3)中,所述的每克Ni-psnts对应的硝酸铈添加量为1.65~1.98g,对应乙醇使用量为300~500ml。
进一步地,步骤(3)中,所述每克Ni-psnts对应的乌洛托品添加量为10~15g,对应的去离子水使用量为50~75ml。
进一步地,步骤(3)中,所述水浴加热温度为60~100℃,加热时间为5~10h;所述的干燥温度为60~100℃,煅烧温度为600~700℃,还原温度为600~750℃,还原气氛为氢气,所有升温速率均为1~5℃/min。
一种如上所述的用于光热催化CH4-CO2重整反应的光热复合催化剂的应用:复合光热催化剂在氙灯模拟的太阳光下表现出很高的光热催化活性和稳定性,持续反应100h后CO产率为120.9mmol·g-1·min-1,H2产率为136.8mmol·g-1·min-1。
光热催化CH4-CO2重整反应制备太阳能燃料的具体步骤如下:
(1)在自制的内径为6mm的光热催化反应器中装入17mg Ni-psnts@CeO2复合催化剂,在12W聚光辐照下以81.5ml·min-1的流速通入体积含量为37.2/37.4/25.4%的CH4/CO2/N2混合气。
(2)将反应器出口的气体引入气相色谱中进行气体种类与含量分析,根据色谱检测图中峰面积的大小进行定量。
发明原理:本发明将助催化剂CeO2包覆在硅酸盐负载的Ni纳米颗粒外获得Ni-psnts@CeO2复合催化剂用于光热催化CH4-CO2重整反应。CeO2的包覆作用在一定程度上限制了Ni纳米颗粒的热运动,减缓了Ni颗粒的烧结问题;由于CeO2具有良好的氧化还原特性,能够利用其晶格氧气化Ni颗粒表面的碳物种减少积碳生成,同时利用其晶格氧缺陷加速CO2活化,这使得催化剂具有较高的催化活性和稳定性。Ni-psnts@CeO2上的光热催化则进一步降低了CH4-CO2重整反应的表观活化能,使得光热催化相比于同温度下的热催化具有更高的反应速率,因此具有更广阔的发展前景。
有益效果:与现有技术相比,本发明具有如下显著优点:
(1)该催化剂制备方法简单、成本低,能够以太阳能作为唯一能量驱动,实现集温室气体转化和太阳能燃料制备及太阳能存储一体化。避免了传统热催化的高耗能和温室气体二次排放问题,有利于环境保护和新能源开发。
(2)Ni-psnts@CeO2复合催化剂的生产工艺简单、成本低、有活性高、稳定性强。
附图说明
图1是psnts@CeO2、Ni-psnts和Ni-psnts@CeO2的光谱吸收图;
图2是前驱体Ni-psnts的SEM图;
图3是Ni-psnts@CeO2的SEM图;
图4是Ni-psnts和Ni-psnts@CeO2的XRD图;
图5是催化剂的光热催化CH4-CO2重整活性测试图;
图6是psnts@CeO2、Ni-psnts和Ni-psnts@CeO2的光热催化反应和生产速率图;
图7是Ni-psnts@CeO2在光照和黑暗条件下的催化活性随温度演化曲线。
具体实施方式
下面结合附图对本发明的技术方案作进一步说明。
实施例1
催化剂的制备
(1)Ni-psnts催化剂的制备:
称取2.9486g的硝酸镁和1.1078g的硝酸镍溶解在55ml去离子水中超声处理10min,然后持续搅拌至形成均匀的盐溶液;接着将2.842g的偏硅酸钠溶解在25ml去离子水中超声处理15min形成溶液并将其添加到上述盐溶液中,继续搅拌30min形成悬浊液;然后将6.8g的氢氧化钠溶解在20ml去离子水中超声处理5min形成强碱性溶液,将其加入到上述的正在搅拌的悬浊液中形成碱性液体(Ph>14),再持续搅拌20min。然后将搅拌完成后的液体转移到带有聚四氟乙烯内衬的高压反应釜中190℃高温处理48h(Ph>11)。将所得沉淀物离心收集并使用去离子水和乙醇交替洗涤三次再60℃干燥10h得到Ni-psnts前驱体。然后将Ni-psnts前驱体转移至马弗炉中650℃煅烧6h,接着转移至管式炉中650℃氢气气氛中还原1h得到Ni-psnts催化剂。
(2)Ni-psnts@CeO2催化剂的制备:
称取500mg的Ni-psnts前驱体和990mg的硝酸铈放入150ml的乙醇溶液中,超声处理120min至形成悬浊液。然后,将5g的乌洛托品加入到20ml的去离子水中超声至完全溶解,接着在搅拌下将乌洛托品的水溶液滴加到上述的悬浊液中,然后将混合液体转移至水浴锅中70℃处理7小时。离心收集沉淀并使用去离子水和乙醇交替洗涤3次,然后转移至鼓风干燥箱中60℃干燥12h,再转移至马弗炉中600℃煅烧2h,最后转移至管式炉中在氢气气氛下650℃还原2h得到Ni-psnts@CeO2催化剂。
(3)psnts@CeO2催化剂的制备:
先制备不Ni的的psnts前驱体,将上述步骤(1)中的硝酸镍替换为相同摩尔量的硝酸镁,然后按照上述步骤(1)中的制备流程即可得到不Ni的的psnts前驱体;接着将上述步骤(2)中的Ni-psnts前驱体替换为psnts前驱体,再按照步骤(2)中的制备流程即可以得到psnts@CeO2催化剂。
实施例2
光热催化活性测试:
(1)在自制的内径为6mm的光热催化反应器中装入17mg催化剂,在12W聚光辐照下以81.5ml·min-1的流速通入体积含量为37.2/37.4/25.4%的CH4/CO2/N2混合气。
(2)将反应器出口的气体引入气相色谱中进行气体种类与含量分析,根据色谱检测图中峰面积的大小进行定量。
实施例3
热催化活性测试:
将0.017mg的催化剂置于管式炉中,以81.5ml·min-1的流速通入体积含量为37.2/37.4/25.4%的CH4/CO2/N2混合气,然后使用电加热升温(无光)到反应温度,将管式炉出口的气体引入气相色谱中进行气体种类与含量分析,根据色谱检测图中峰面积的大小进行定量。
从催化剂psnts@CeO2、Ni-psnts和Ni-psnts@CeO2的光谱吸收结果(图1)可以看出,不Ni的的psnts@CeO2在300~450nm范围内表现出较好的吸光效果,在450~2500nm波段的整体吸光性能较差,而含有Ni的Ni-psnts和Ni-psnts@CeO2在整个光谱范围内则具有较好的吸光性能,这是催化剂表面的Ni等离激元效应增强光谱吸收的结果。
从图2中的SEM图中可以看出,前驱体Ni-psnts呈纳米管状。
从图3中的SEM图中可以看出,纳米管外包裹了一层CeO2层,形成Ni-psnts@CeO2。
从图4的XRD分析结果中可以看出,Ni-psnts中的金属Ni和载体的衍射峰明显,这说明Ni在催化剂中以金属相形式存在。但是Ni-psnts@CeO2中只有CeO2的衍射峰表现明显,几乎看不到Ni的衍射峰,这说明CeO2成功覆盖在Ni的表面。
从图5中可以看出,本实验除氙灯光源作为能量输入外不提供其他外热源,也就是说该反应完全由光热驱动。
从图6中可以看出,不Ni的的psnts@CeO2几乎不具备任何催化活性,而包裹了CeO2的Ni-psnts@CeO2则表现出最高的催化活性。
从图7中可以看出,在相同温度下,Ni-psnts@CeO2上的光热反应活性要高于黑暗条件下的热催化反应活性,这说明光热催化能够降低反应的活化能从而提升反应活性。
Claims (10)
1.一种CeO2包覆Ni的硅酸盐纳米管光热复合催化剂,其特征在于,所述催化剂包括负载在层状硅酸盐纳米管psnts载体上的活性组分Ni和包覆在外层的助催化剂壳层CeO2。
2.根据权利要求1所述的CeO2包覆Ni的硅酸盐纳米管光热复合催化剂,其特征在于,所述活性组分Ni的粒径为7-9nm。
3.一种权利要求1所述的CeO2包覆Ni的硅酸盐纳米管光热复合催化剂的制备方法,其特征在于,包括如下步骤:
步骤(1):将硝酸镁和硝酸镍溶解在去离子水中超声处理10~20min,然后持续搅拌形成均匀的盐溶液;偏硅酸钠溶解在去离子水中超声处理15~30min形成溶液并将其添加到上述盐溶液中,继续搅拌形成悬浊液;
步骤(2):将氢氧化钠溶解在去离子水中超声处理5~10min形成碱性溶液,将其加入到步骤(1)所述的正在搅拌的悬浊液中,再持续搅拌20~30min;然后将搅拌完成后的液体转移到带有聚四氟乙烯内衬的高压反应釜中高温处理;将所得沉淀物离心收集并使用去离子水和乙醇交替洗涤三次后干燥得到Ni-psnts前驱体;
步骤(3)称取一定量的Ni-psnts前驱体和硝酸铈加入到乙醇溶液中超声分散;将一定量的乌洛托品溶解在去离子水中并加入到上述乙醇溶液中,然后将混合溶液转移到水浴锅中加热;将得到的沉淀物离心收集并使用水和乙醇交替洗涤,然后干燥、煅烧、还原后得到最终产物。
4.根据权利要求3所述的CeO2包覆Ni的硅酸盐纳米管光热复合催化剂的制备方法,其特征在于,步骤(1)中,所述的硝酸镁和硝酸镍的摩尔量之和与偏硅酸钠的摩尔量的比值为1~1.5。
5.根据权利要求3所述的CeO2包覆Ni的硅酸盐纳米管光热复合催化剂的制备方法,其特征在于,步骤(2)中,所述的氢氧化钠摩尔量为偏硅酸钠的15~20倍,悬浊液在加热前的pH>14,加热后的pH>11。
6.根据权利要求3所述的CeO2包覆Ni的硅酸盐纳米管光热复合催化剂的制备方法,其特征在于,步骤(2)中,所述的高温处理温度为150~250℃,处理时间为24~48h,干燥温度为60~120℃,干燥时间为8~12h。
7.根据权利要求3所述的CeO2包覆Ni的硅酸盐纳米管光热复合催化剂的制备方法,其特征在于,步骤(3)中,所述的每克Ni-psnts对应的硝酸铈添加量为1.65~1.98g,对应乙醇使用量为300~500ml。
8.根据权利要求3所述的CeO2包覆Ni的硅酸盐纳米管光热复合催化剂的制备方法,其特征在于,步骤(3)中,所述每克Ni-psnts对应的乌洛托品添加量为10~15g,对应的去离子水使用量为50~75ml。
9.根据权利要求3所述的CeO2包覆Ni的光热复合催化剂的制备方法,其特征在于,步骤(3)中,所述水浴加热温度为60~100℃,加热时间为5~10h;所述的干燥温度为60~100℃,煅烧温度为600~700℃,还原温度为600~750℃,还原气氛为氢气,所有升温速率均为1~5℃/min。
10.一种CeO2包覆Ni的硅酸盐纳米管光热复合催化剂在光热催化CH4-CO2重整反应中应用。
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