CN107961798B - 一种Rh@CuSiO3芯鞘结构催化剂制备方法 - Google Patents
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Abstract
本发明公开了一种Rh@CuSiO3纳米结构加氢催化剂及其制备方法。此Rh@CuSiO3加氢催化剂的制备过程为:首先,采用水热的方法,在乙醇-水体系中合成硅酸盐纳米管,通过调控实验条件控制合成硅酸铜纳米管;然后,使用浸渍法在硅酸铜纳米管内负载金属铑。通过此法制备的Rh@CuSiO3加氢催化剂通过耦合芯鞘材料的结构限域效应及其组件之间的协同效应,可提高活性组分的分散度及其与载体的相互作用,从而提升催化加氢反应性能,具有广泛的应用前景。
Description
技术领域
本发明涉及一种Rh@CuSiO3纳米结构贵金属催化剂及其制备方法,该催化剂利用限域作用使Rh物种以纳米颗粒形式存在,具有较高的Rh活性组分数量和热稳定性,可用于CO2催化加氢反应。
背景技术
CO2催化加氢反应能够转化生产多种低碳化合物,对环境保护和工业生产皆有重要意义。目前为止,CO2催化加氢的催化剂通常为多相体系,主要可以分为铜、贵金属以及双金属为活性组分的负载型催化剂。其中,Rh等典型的贵金属具有较强的H2解离和加氢反应能力,而金属Rh在元素周期表中处于易使CO分解形成高级碳氢化合物的元素(Fe、Co)和不使CO分解产生甲醇的元素(Pd,Pt和Ir)之间,具有独特的生成C2含氧化合物的特性,有利于使CO氢化形成甲醇、乙醇等醇类含氧化合物。因此,Rh基催化剂是目前研究最广泛的CO2催化加氢制低碳醇的非均相贵金属催化剂。然而,Rh基催化剂在CO2加氢过程中容易引起晶粒迁移、烧结和Rh活性组分不稳定,从而导致反应活性低、稳定性差、反应条件苛刻等问题。因此,设计构筑特殊形貌结构和表面化学性质的新型Rh基催化剂,通过结构限域效应使Rh纳米颗粒高度分散,并使金属和载体形成强相互作用,是CO2加氢反应获得高活性的关键。
芯鞘结构材料是目前非常热门的国际前沿研究领域之一。鞘结构规整,一定程度上孔道尺寸可调,对金属纳米颗粒起到空间限域作用,以提高金属的分散度,避免活性金属在反应条件下迁移、烧结,因此,用来合成高效稳定的CO2加氢催化剂。此外,形成鞘结构的氧化物、硅酸盐等材料或添加的助剂可以通过消除某些副产活性中心,改变晶面间距来影响活性组分的电子性质,从而提高催化剂的活性和目标产物选择性。
硅酸盐材料的基本结构是硅-氧四面体,其中硅原子占据中心,四个氧原子占据四角,由于其结构上的特点,硅酸盐材料具有极其优异的热稳定性和良好的结构稳定性,在功能材料方面广泛应用于催化剂载体。在CO2催化加氢合成低碳醇的催化体系中,铜基催化剂已有着广泛研究,因此,在催化体系中引入金属铜,使用硅酸铜作为鞘腔的材料,在鞘腔壁上引入金属铜作为反应另外的活性位点,有利于反应进行。
发明内容
针对Rh基催化剂在CO2加氢制低碳醇反应过程中易发生晶粒迁移、烧结及活性组分Rh的热稳定性差等问题,本发明设计应用常规的氧化物、硅酸盐等材料,开发低成本、操作简单的芯鞘结构Rh基纳米反应器催化剂,耦合芯鞘结构材料的限域效应及其组件之间的协同效应,提高活性组分的分散度及其与载体的相互作用,从而达到提升反应活性和稳定性的目的。
为解决上述技术问题,本发明制备了一种Rh@CuSiO3纳米催化剂。在此种具有芯鞘结构的纳米催化剂中,活性组分Rh的负载量可通过改变相应前躯体的负载量进行调控,同时选择在催化剂体系中引入金属铜,使用硅酸铜作为鞘腔的材料,在鞘腔壁上引入金属铜作为反应另外的活性位点,有助于CO2加氢生成低碳醇产物。
本发明提供的Rh@CuSiO3纳米催化剂的制备工艺过程,具体步骤是:
1)制备硅酸铜鞘腔:
将1.5克Cu(NO3)2•6H2O加入水中溶解,然后加入25%的氨水使溶液先生成沉淀然后再溶解,随后加入乙醇搅拌,10min后,将之前配好的0.5mol/L的NaSiO3•9H2O溶液加入10mL到溶液中,形成蓝色沉淀,搅拌180min,之后转移至150mL水热釜中,移至烘箱中473K下水热处理12~36小时,然后取出冷却、过滤、洗涤、干燥、焙烧后,既得CuPNTs;
2)金属铑的填充:
将0.1g固体RhCl3加入25ml无水乙醇中,超声以帮助溶解。待RhCl3固体全部溶解后,倒入事先称好的0.5 g CuPNTs,继续超声,待CuPNTs全部溶解后,再超声20 min即从超声清洗仪中取出;
3)Rh@CuSiO3催化剂制备:
在步骤2)所得样品中加入25ml去离子水,搅拌、静置,分层后将下层溶液分入若干表面皿,80℃烘干后,在470℃下焙烧3.5h。
与现有技术相比,本发明的有益效果是:
1、有效地解决了Rh基催化剂在CO2加氢反应过程中易发生晶粒迁移、烧结及活性组分Rh的热稳定性差等问题;
2、实现了Rh基催化剂中活性组分Rh负载量可调变;
3、催化剂独特的芯鞘结构空腔体积较普通核壳结构催化剂孔道体积增大,从而可获得比普通核壳结构催化剂更大的气体通量。
附图说明
图1是本发明方法制备Rh@CuSiO3纳米催化剂的TEM图;
图2是实施例1制备的3%Rh@CuSiO3纳米催化剂的TEM图;
图3是实施例2制备的7%Rh@CuSiO3纳米催化剂的TEM图;
图4是实施例3制备的10%Rh@CuSiO3纳米催化剂的TEM图;
具体实施方式(实施例)
下面结合实施例和附图对本发明作进一步说明。
实施例1
将1.5克Cu(NO3)2•6H2O加入水中溶解,然后加入25%的氨水使溶液先生成沉淀然后再溶解,随后加入乙醇搅拌,10min后,将之前配好的0.5mol/L的NaSiO3•9H2O溶液加入10mL到溶液中,形成蓝色沉淀,搅拌180min,之后转移至150mL水热釜中,移至烘箱中473K下水热处理12~36小时,然后取出冷却、过滤、洗涤、干燥、焙烧后,既得CuPNTs。再将0.032g固体RhCl3加入25ml无水乙醇中,超声以帮助溶解。待RhCl3固体全部溶解后,倒入事先称好的0.5g CuPNTs,继续超声,待CuPNTs全部溶解后,再超声20 min即从超声清洗仪中取出。加入25ml去离子水,搅拌、静置,分层后将下层溶液分入若干表面皿,80℃烘干后,在470℃下焙烧3.5h。
实施例2
本实施例是在实施例1的基础上改变负载的活性组分的负载量。
将1.5克Cu(NO3)2•6H2O加入水中溶解,然后加入25%的氨水使溶液先生成沉淀然后再溶解,随后加入乙醇搅拌,10min后,将之前配好的0.5mol/L的NaSiO3•9H2O溶液加入10mL到溶液中,形成蓝色沉淀,搅拌180min,之后转移至150mL水热釜中,移至烘箱中473K下水热处理12~36小时,然后取出冷却、过滤、洗涤、干燥、焙烧后,既得CuPNTs。再将0.077g固体RhCl3加入25ml无水乙醇中,超声以帮助溶解。待RhCl3固体全部溶解后,倒入事先称好的0.5g CuPNTs,继续超声,待CuPNTs全部溶解后,再超声20 min即从超声清洗仪中取出。加入25ml去离子水,搅拌、静置,分层后将下层溶液分入若干表面皿,80℃烘干后,在470℃下焙烧3.5h。
实施例3
本实施例是在实施例1的基础上改变负载的活性组分的负载量。
将1.5克Cu(NO3)2•6H2O加入水中溶解,然后加入25%的氨水使溶液先生成沉淀然后再溶解,随后加入乙醇搅拌,10min后,将之前配好的0.5mol/L的NaSiO3•9H2O溶液加入10mL到溶液中,形成蓝色沉淀,搅拌180min,之后转移至150mL水热釜中,移至烘箱中473K下水热处理12~36小时,然后取出冷却、过滤、洗涤、干燥、焙烧后,既得CuPNTs。再将0.113g固体RhCl3加入25ml无水乙醇中,超声以帮助溶解。待RhCl3固体全部溶解后,倒入事先称好的0.5g CuPNTs,继续超声,待CuPNTs全部溶解后,再超声20 min即从超声清洗仪中取出。加入25ml去离子水,搅拌、静置,分层后将下层溶液分入若干表面皿,80℃烘干后,在470℃下焙烧3.5h。
Claims (5)
1.一种Rh@CuSiO3催化剂,其特征在于:所述催化剂为芯鞘结构的CO2加氢催化剂,其制备方法包括以下步骤:
1)制备硅酸铜鞘腔:
将1.5克Cu(NO3)2•6H2O加入水中溶解,然后加入25%的氨水使溶液先生成沉淀然后再溶解,随后加入乙醇搅拌,10min后,将之前配好的0.5mol/L的NaSiO3•9H2O溶液加入10mL到溶液中,形成蓝色沉淀,搅拌180min,之后转移至150mL水热釜中,移至烘箱中473K下水热处理12~36小时,然后取出冷却、过滤、洗涤、干燥、焙烧后,即得CuPNTs;
2)金属铑的填充:
将0.1g固体RhCl3加入25ml无水乙醇中,超声,待RhCl3固体全部溶解后,倒入事先称好的0.5gCuPNTs,继续超声,待CuPNTs全部溶解后,再超声20min;
3)Rh@CuSiO3催化剂制备:
在步骤2)所得样品中加入25ml去离子水,搅拌、静置,分层后将下层溶液分入若干表面皿,80℃烘干后,在470℃下焙烧3.5h。
2.根据权利要求1所述的Rh@CuSiO3催化剂,其特征在于形成CuPNTs鞘腔。
3.根据权利要求1所述的Rh@CuSiO3催化剂,其特征在于采用毛细作用原理填充金属铑。
4.根据权利要求1所述的Rh@CuSiO3催化剂,其特征在于通过改变相应前躯体的负载量以调控活性组分Rh的负载量。
5.根据权利要求1所述的Rh@CuSiO3催化剂,其特征在于将制得的催化剂进行焙烧以除去Cl原子,并使催化剂性能更稳定。
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"Theoretical Study of Methanol Synthesis from CO2 Hydrogenation on Metal-Doped Cu(111) Surfaces";Yixiong Yang等;《The Journal of Physical Chemistry C》;20111212;第249页右栏第1段、第254页右栏第2段 * |
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