CN114011472A - 一种负载型铂纳米簇催化剂的制备及其烷烃无氧脱氢中的应用 - Google Patents
一种负载型铂纳米簇催化剂的制备及其烷烃无氧脱氢中的应用 Download PDFInfo
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Abstract
本发明提供了一种负载型铂纳米簇催化剂在烷烃无氧脱氢反应的应用。所述催化剂以氧化物为载体,以铂纳米簇为活性组分,铂纳米簇单分散于氧化物载体上,所述铂纳米簇由配体和铂原子组成;所述配体为有机磷和硫醇中的至少一种;所述铂原子为双原子或多原子。催化剂制备方法包括:(1)制备双原子或多原子铂纳米簇;(2)将双原子或多原子铂纳米簇负载于载体上;(3)催化剂的后处理。本发明制备的催化剂具有高分散的纳米级别的铂纳米簇,在丙烷等烷烃无氧脱氢反应中,对烯烃具有较高的选择性。
Description
技术领域
本发明属于贵金属纳米簇催化领域,具体涉及一种负载型双原子和多原子铂纳米簇催化剂的制备方法及其在烷烃无氧脱氢中的应用。
技术背景
烯烃作为一种重要的有机单体原料,例如,乙烯、丙烯和苯乙烯等被广泛用于各种塑料、树脂、橡胶的合成,是与人类的生活和生产密切相关。铂基纳米粒子催化剂,是一种广泛应用于烷烃脱氢的催化剂。由于相对较低的转化率和目标产物的选择性,铂原子利用率低等问题。因此,开发一种高分散、高稳定性的、高活性位点的铂催化剂是催化烷烃脱氢制烯烃的关键。Liu等通过将ZnO加入Pt/Al2O3中提高丙烷脱氢的选择性,并且降低催化剂的成本(ACS Catal.2016,6,2158-2162)。
到目前为止,美国UOP公司开发的铂锡合金催化剂(Pt3Sn/Al2O3)被认为是该反应的最佳催化剂之一,但是由于在高温脱氢过程中商业Pt3Sn合金催化剂不可避免要发生烧结与积碳导致催化剂快速失活。同时,Pt3Sn合金催化剂只有表面Pt原子参与反应,Pt原子的利用率较低。
综上所述,对于目前研究中常见的各种催化剂,存在以下几个问题:(1)底物转化率低;(2)目标产物选择性不够高;(3)催化剂容易反应失活。
发明内容
基于以上催化剂存在的问题,本发明提供了一种负载型双原子和多原子铂纳米簇催化剂,将其用于烷烃无氧脱氢反应,提高了产物烯烃的选择性,同时提高了催化剂的稳定性。
本发明技术方案具体如下:
一方面,本发明提供了一种负载型双原子和多原子铂纳米簇催化剂在烷烃无氧脱氢反应中的应用,所述催化剂以氧化物为载体,以铂纳米簇为活性组分,所述铂纳米簇单分散于氧化物载体上,所述铂纳米簇由配体和铂原子组成;所述配体为有机磷和硫醇中的至少一种;所述铂原子为双原子或多原子。
基于以上技术方案,优选的,所述催化剂中,活性组分与载体的质量比为0.1%~1.0%。
基于以上技术方案,优选的,所述铂纳米簇的尺寸为0.5~2nm,其原子个数为2-100。
基于以上技术方案,优选的,所述氧化物为Al2O3、TiO2、MgO、SiO2中的一种或多种。
基于以上技术方案,优选的,所述有机磷为三苯基膦、双磷中的至少一种;所述硫醇为苯乙硫醇、金刚烷硫醇中的至少一种。
基于以上技术方案,优选的,所述催化剂在使用前进行焙烧预处理,预处理气氛为体积百分比为1%~50%的H2/N2,预处理温度为50~700℃,预处理时间为0.5~12h。
基于以上技术方案,优选的,所述无氧脱氢反应中,反应温度为400~700℃,反应时间为0.1h~120h,催化剂活性组分与丙烷的摩尔比为1∶1~5000。在所述条件下,丙烷的转化率≥20%,烯烃的选择性>95%。
另一方面,本发明提供了一种上述催化剂的制备方法,所述方法包括如下步骤:
(1)制备双原子或多原子铂纳米簇;
双原子铂纳米簇的制备方法为:将铂前驱体、有机磷或者硫醇配体加入醇或二氯甲烷中,4-30℃搅拌1~24h,然后离心,洗涤,干燥,得到双原子铂纳米簇;
多原子铂纳米簇的制备方法为:将铂前驱体、有机磷或者硫醇配体加入醇或二氯甲烷中,4-30℃搅拌1~24h,然后加入还原剂还原,离心,洗涤,干燥,得到多原子铂纳米簇;
(2)制备负载型双原子或多原子铂催化剂:将步骤(1)得到的铂纳米簇分散于醇或二氯甲烷中,于室温条件下搅拌5min~1200min,然后加入载体,继续搅拌0.5~24h后,离心,干燥,得到固体样品;
(3)催化剂的焙烧:将步骤(2)得到的固体样品在空气或惰性气氛中50℃~800℃焙烧1h~24h,得到所述负载型铂纳米簇催化剂。
基于以上技术方案,优选的,步骤(1)中,制备双原子铂纳米簇时,铂前驱体、配体的摩尔比例为1∶0.01~100;制备多原子铂纳米簇时,所述铂前驱体、配体、还原剂的摩尔比例为1∶0.01~100∶1~200。所述铂前驱体为氯铂酸或四氯铂酸钾;所述还原剂为硼氢化钠或者硼烷叔丁胺络合物;所述醇或二氯甲烷的用量为1mL~20mL。
基于以上技术方案,优选的,步骤(1)中,干燥条件为:20~80℃下真空干燥1h~48h;洗涤方式为:正己烷25~40℃洗涤。
基于以上技术方案,优选的,步骤(2)中,干燥温度为25~120℃,干燥时间为1h~24h;步骤(1)、(2)中,所述醇为甲醇和乙醇中的至少一种。
有益效果
(1)本发明中,催化剂的活性组分为具有双原子或者多原子的铂纳米簇,此种纳米簇能够提供更多的活性位,使得催化剂具有更高的活性。
(2)本发明中,双原子和多原子铂纳米簇是由有机配体保护的,有机配体中含有的硫、磷等元素,能够改变铂纳米簇的电子结构,从而提高烯烃的选择性和催化剂的稳定性,为烷烃无氧脱氢反应的进一步工业化应用提供了一种新的解决方案。
附图说明
图1为实施例1所制得的双原子铂纳米簇的HRTEM;
图2为实施例3所制得的多原子铂纳米簇的HRTEM;
图3为实施例1、3、4中催化剂的丙烷脱氢反应活性。
具体实施方式
下面结合具体实施例进行进一步描述,以使本发明的优点和特征更易于被本领域技术人员理解。如无特别说明,以下实施例所用的原料均为可市购的常规原料。
实施例1
(1)将50mg四氯铂酸钾溶于10mL的乙醇中,随后加入80mg三苯基膦和40mg硫醇配体。将上述溶液在室温条件下搅拌0.5小时。之后,将溶液旋干,加入正己烷洗涤,在真空干燥箱内烘干,50℃干燥2h;得到双原子铂纳米簇。图1是双原子铂的电镜图,从图中可以看出双原子纳米簇。
(2)将5mg双原子铂纳米簇分散于去二氯甲烷或者乙醇中,于20℃搅拌1h;然后加入1g载体,继续搅拌6h后,离心,干燥,干燥时间为12h,干燥温度为50℃,得到干燥后得到的样品Pt2/Al2O3。将150mg的催化剂置于反应管中,在体积百分比为30%的H2/N2气氛,550℃的条件下预处理90分钟。
(3)上述催化剂在550℃,氮气平衡,C3H8和H2比例为1∶1,流速为50ml·min-1的条件下反应,反应时间为2小时。丙烷的转化率为8%,丙烯的选择性为96%。
实施例2
(1)将50mg四氯铂酸钾溶于20mL的乙醇中,随后加入80mg硫醇配体。将上述溶液在室温条件下搅拌0.5小时。然后加入20mg硼氢化钠溶于4ml的水溶液,搅拌6小时。之后,将溶液旋干,加入正己烷洗涤,在真空干燥箱内烘干,干燥温度为50℃,干燥时间为6h;得到多原子铂纳米簇。
(2)将5mg多原子铂纳米簇分散于去二氯甲烷或者乙醇中,于20℃搅拌1h;然后加入1g载体Al2O3,继续搅拌6h后,离心,干燥,干燥时间为12h,干燥温度为50℃,得到干燥后得到的样品。将所得催化剂于氮气气氛中550℃焙烧2h,得到催化剂Pt25/Al2O3。将150mg的催化剂Pt25/Al2O3置于反应管中,在体积百分比为30%的H2/N2气氛,550℃的条件下预处理90分钟。
(3)上述催化剂在550℃,氮气平衡,C3H8和H2比例为1∶1,流速为50ml·min-1的条件下反应,反应时间为2小时。丙烷的转化率为24%,丙烯选择性为97%。
实施例3
(1)将实施例1步骤(2)干燥后的样品在预处理前于氮气气氛中600℃焙烧2h,得到催化剂Pt2/Al2O3-N2-600。将150mg的催化剂置于反应管中,在体积百分比为30%的H2/N2气氛,550℃的条件下预处理90分钟。图2是铂纳米簇的电镜图,从图中可以看出多原子纳米簇,其纳米簇的尺寸大约为1nm,其金属铂原子个数为25左右。
(2)上述催化剂在550℃,氮气平衡,C3H8和H2比例为1∶1,流速为50ml·min-1的条件下反应,反应时间为2小时。丙烷的转化率为20%,丙烯选择性为93%。
实施例4
(1)将实施例1步骤(2)干燥后的样品在预处理前于空气气氛中600℃焙烧2h,得到催化剂Pt2/Al2O3-O2-600。将150mg的催化剂置于反应管中,在体积百分比为30%的H2/N2气氛,550℃的条件下预处理90分钟
(2)上述催化剂在550℃,氮气平衡,C3H8和H2比例为1∶1,流速为50ml·min-1的条件下反应,反应时间为2小时。丙烷的转化率为5%,丙烯选择性为90%。
实施例5
将实施例1、3、4制备的催化剂用于稳定性测试,反应温度为550℃,氮气平衡,C3H8和H2比例为1∶1,流速为50ml·min-1的条件下反应,反应时间为40小时,丙烷的转化率为20%,丙烯选择性为94%。
对比例
(1)将20mg四氯铂酸钾溶于水中,然后加入1.8g Al2O3中搅拌4小时,离心,干燥,干燥时间为12h,干燥温度为50℃,干燥后得到的样品Pt-NP/Al2O3。将150mg的催化剂置于反应管中,在H2气氛下200℃焙烧2小时。
(2)上述催化剂在550℃,氮气平衡,C3H8和H2比例为1∶1,流速为50ml·min-1的条件下反应,反应时间为2小时。丙烷的转化率为23%,丙烯选择性为80%。
Claims (10)
1.一种负载型铂纳米簇催化剂在烷烃无氧脱氢反应的应用,其特征在于,所述催化剂以氧化物为载体,以铂纳米簇为活性组分,所述铂纳米簇单分散于氧化物载体上,所述铂纳米簇由配体和铂原子组成;所述配体为有机磷和硫醇中的至少一种;所述铂原子为双原子或多原子。
2.根据权利要求1所述的应用,其特征在于,活性组分的含量为载体0.1~1.0wt%。
3.根据权利要求1所述的应用,其特征在于,所述铂纳米簇的尺寸为0.5~2nm,所述铂纳米簇中铂原子的个数为2~100。
4.根据权利要求1所述的应用,其特征在于,所述氧化物为Al2O3、TiO2、SiO2、MgO中的至少一种。
5.根据权利要求1所述的应用,其特征在于,所述有机磷为三苯基膦、双磷中的至少一种;所述硫醇为苯乙硫醇、金刚烷硫醇中的至少一种。
6.根据权利要求1所述的应用,其特征在于,所述催化剂在使用前进行焙烧预处理,预处理气氛为体积百分比为1%~50%的H2/N2,预处理温度为50~700℃,预处理时间为0.5~12h。
7.根据权利要求1所述的应用,其特征在于,所述烷烃无氧脱氢反应中,反应温度为400~700℃,反应时间为0.1h~120h;催化剂活性组分与烷烃的摩尔比为1∶1~5000。
8.一种权利要求1-7任一所述的应用中所述催化剂的制备方法,其特征在于,所述方法包括如下步骤:
(1)制备双原子或多原子铂纳米簇;
双原子铂纳米簇的制备方法为:将铂前驱体、有机磷或者硫醇配体加入醇或二氯甲烷中,4-30℃搅拌1~24h,然后离心,洗涤,干燥,得到双原子铂纳米簇;
多原子铂纳米簇的制备方法为:将铂前驱体、有机磷或者硫醇配体加入醇或二氯甲烷中,4-30℃搅拌1~24h,然后加入还原剂还原,离心,洗涤,干燥,得到多原子铂纳米簇;
(2)制备负载型双原子或多原子铂催化剂:将步骤(1)得到的铂纳米簇分散于醇或二氯甲烷中,于室温条件下搅拌5min~1200min,然后加入载体,继续搅拌0.5~24h后,离心,干燥,得到固体样品;
(3)催化剂的焙烧:将步骤(2)得到的固体样品在空气或惰性气氛中50℃~800℃焙烧1h~24h,得到所述负载型铂纳米簇催化剂。
9.根据权利要求8所述的制备方法,其特征在于:步骤(1)中,制备双原子铂纳米簇时,铂前驱体、配体的摩尔比例为1∶0.01~100;制备多原子铂纳米簇时,铂前驱体、配体、还原剂的摩尔比例为1∶0.01~100∶1~200;所述铂前驱体为氯铂酸、四氯铂酸钾中的至少一种;所述还原剂为硼氢化钠、硼烷叔丁胺络合物中的至少一种;所述醇或二氯甲烷的用量为1mL~20mL。
10.根据权利要求8所述的制备方法,其特征在于:步骤(1)中,洗涤方式为:采用正己烷在25~40℃下洗涤;干燥条件为:20~80℃下真空干燥1h~48h;步骤(2)中,干燥温度为25~120℃,干燥时间为1h~24h;步骤(1)、(2)中,所述醇为甲醇和乙醇中的至少一种。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114700089A (zh) * | 2022-04-11 | 2022-07-05 | 江南大学 | 一种MoS2负载的双原子催化剂及其制备方法与应用 |
CN115626671A (zh) * | 2022-11-02 | 2023-01-20 | 华南理工大学 | 多功能的双配体铂纳米粒子及其制备方法与应用 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100167078A1 (en) * | 2008-12-26 | 2010-07-01 | Il Doo Kim | Nano powder, nano ink and micro rod, and the fabrication methods thereof |
CN106588539A (zh) * | 2016-11-24 | 2017-04-26 | 中国石油大学(华东) | 使用修饰型铂催化剂催化乙烷氧化脱氢制乙烯的方法 |
AU2016363675A1 (en) * | 2015-11-30 | 2018-07-19 | Adelaide Research And Innovation | Photocatalytic conversion of carbon dioxide and water into substituted or unsubstituted hydrocarbon(s) |
CN110627030A (zh) * | 2019-09-19 | 2019-12-31 | 西安交通大学 | 一种磷化铂纳米催化剂及其制备方法和在电催化氧还原中的应用 |
CN110882708A (zh) * | 2019-12-09 | 2020-03-17 | 大连理工大学 | 一种丙烷脱氢催化剂及其制备方法 |
CN112237945A (zh) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | 一种用于乙炔氢氯化的贵金属原子簇催化剂的制备及应用 |
CN112599801A (zh) * | 2020-12-16 | 2021-04-02 | 中国石油大学(华东) | 一种配体保护Pt6亚纳米团簇及其制备方法以及一种催化剂及其制备方法和应用 |
CN112973681A (zh) * | 2019-12-16 | 2021-06-18 | 中国科学院大连化学物理研究所 | 一种金属纳米团簇催化剂在醇一步法制备缩醛中的应用 |
-
2021
- 2021-11-22 CN CN202111390829.3A patent/CN114011472A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100167078A1 (en) * | 2008-12-26 | 2010-07-01 | Il Doo Kim | Nano powder, nano ink and micro rod, and the fabrication methods thereof |
AU2016363675A1 (en) * | 2015-11-30 | 2018-07-19 | Adelaide Research And Innovation | Photocatalytic conversion of carbon dioxide and water into substituted or unsubstituted hydrocarbon(s) |
CN106588539A (zh) * | 2016-11-24 | 2017-04-26 | 中国石油大学(华东) | 使用修饰型铂催化剂催化乙烷氧化脱氢制乙烯的方法 |
CN112237945A (zh) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | 一种用于乙炔氢氯化的贵金属原子簇催化剂的制备及应用 |
CN110627030A (zh) * | 2019-09-19 | 2019-12-31 | 西安交通大学 | 一种磷化铂纳米催化剂及其制备方法和在电催化氧还原中的应用 |
CN110882708A (zh) * | 2019-12-09 | 2020-03-17 | 大连理工大学 | 一种丙烷脱氢催化剂及其制备方法 |
CN112973681A (zh) * | 2019-12-16 | 2021-06-18 | 中国科学院大连化学物理研究所 | 一种金属纳米团簇催化剂在醇一步法制备缩醛中的应用 |
CN112599801A (zh) * | 2020-12-16 | 2021-04-02 | 中国石油大学(华东) | 一种配体保护Pt6亚纳米团簇及其制备方法以及一种催化剂及其制备方法和应用 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114700089A (zh) * | 2022-04-11 | 2022-07-05 | 江南大学 | 一种MoS2负载的双原子催化剂及其制备方法与应用 |
CN114700089B (zh) * | 2022-04-11 | 2023-01-06 | 江南大学 | 一种MoS2负载的双原子催化剂及其制备方法与应用 |
CN115626671A (zh) * | 2022-11-02 | 2023-01-20 | 华南理工大学 | 多功能的双配体铂纳米粒子及其制备方法与应用 |
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