CN112452324A - 一种银钌双金属掺杂石墨烯催化剂及其制备方法与应用 - Google Patents
一种银钌双金属掺杂石墨烯催化剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种银钌双金属掺杂石墨烯催化剂及其制备方法与应用,该催化剂包括石墨烯载体,石墨烯载体上负载有银、钌纳米颗粒,银、钌纳米颗粒质量比为0.5~1:0.6~1.1,银、钌纳米颗粒直径为100~800nm。该催化剂的制备方法包括以下步骤:(1)制备石墨烯;(2)将AgBF4与RuCl3溶于乙二醇,加入石墨烯,在水热条件下进行反应;(3)冷却,离心,洗涤,真空干燥得到产物;(4)焙烧。该催化剂作为催化剂应用在双酚F或1‑苯基‑3‑对硝基苯基‑丙酮的合成过程中。该催化剂用于双酚F合成中时具有优异的催化性能,显著提高双酚F的产率,副反应产物有效降低;用于1‑苯基‑3‑对硝基苯基‑丙酮合成中时具有优异的催化性能,产物化学选择性为100%,产率大于90%,能够回收再利用。
Description
技术领域
本发明涉及一种催化剂及其制备方法与应用,更具体地,涉及一种银钌双金属掺杂石墨烯催化剂及其制备方法与应用。
背景技术
双酚F经由苯酚和丙酮原位缩合所制得,是十分重要的有机化工中间体。双酚F产品主要由二羟基二苯基甲烷的3种异构体组成,其独特的化学结构特性,所合成的聚酯树脂、聚碳树脂、环氧树脂、以及作为酚醛树脂改性剂和阻燃剂,它们的耐热性、耐湿性、加工性及注塑浇注性能均超过了以双酚A为原料制成的同类产品。双酚F的衍生产品的优异性能,使其广泛地应用于电子级环氧树脂、高固体涂料、注塑与浇注特种低黏度树脂、高性能聚酯树脂和聚碳酸酯的合成,以及酚醛树脂的改性剂和高性能阻燃剂等方面,其产品具有极大的开发价值和广阔的应用前景。双酚F早在1970年就已经能够制备,但双酚F的合成过程较为繁琐,一般采用酸性催化剂催化反应,反应过程不易控制,同时副反应所生成的酚醛树脂较多,导致在合成反应的设计中,使用大比例的苯酚作为原料,从而使得生产成本一直较高。
发明内容
发明目的:本发明的目的是提供一种便于控制反应过程、反应后副产物少的银钌双金属掺杂石墨烯催化剂,本发明的另一目的是提供该催化剂的制备方法,本发明的另一目的是提供该催化剂的应用。
技术方案:本发明所述的银钌双金属掺杂石墨烯催化剂,包括石墨烯载体,石墨烯载体上负载有银、钌纳米颗粒,银、钌纳米颗粒质量比为0.5~1:0.6~1.1,银、钌纳米颗粒直径为100~800nm。
本大明所述的银钌双金属掺杂石墨烯催化剂的制备方法,包括以下步骤:
(1)制备石墨烯;
(2)将AgBF4与RuCl3溶于乙二醇,然后加入石墨烯,调节混合液pH至7~11,置于80~200℃的水热条件下进行反应;
(3)反应结束后,冷却,离心,洗涤,真空干燥得到产物;
(4)将产物进行焙烧,最后在真空干燥器中保存。
其中,步骤1包括以下步骤:
(11)利用酸处理石墨,然后加入二乙酸碘苯进行氧化,得到氧化石墨烯水溶液;
(12)利用超声波震荡氧化石墨烯水溶液至清晰无颗粒,
(13)在氧化石墨烯水溶液中加入二硝基苯肼,并在50~150℃回流,经过滤、烘干即得石墨烯。
其中,步骤11中石墨和二乙酸碘苯的质量比为6~12:1,步骤中13中二硝基苯肼与氧化石墨烯水溶液中的石墨质量比为1~5:6~12。
其中,步骤2中AgBF4和RuCl3的质量比为1:1~1.1,AgBF4和RuCl3在冰浴条件下进行搅拌溶解,AgBF4和石墨烯的质量比为1~3:5~10,步骤4中产物在300~500℃下焙烧,焙烧4~10h。
本发明所述的银钌双金属掺杂石墨烯催化剂作为催化剂应用在双酚F的合成过程中。
本发明所述的银钌双金属掺杂石墨烯催化剂作为催化剂应用在1-苯基-3-对硝基苯基-丙酮的合成过程中。
工作原理:银与钌金属元素可以在此制备过程中还原成纳米粒子;同时,该制备过程反应时间相对较短,且AgBF4与RuCl3转化率较高,生成的对应纳米粒子较多,产率较高,同时,由于“银效应”的因素,在使用含有配阴离子银试剂的时候,特别是在含有另外一种金属的时候,非常容易快速的生成纳米粒子。
有益效果:本发明与现有技术相比,其显著优点是:1、催化剂用于双酚F合成中时具有优异的催化性能,能够较好选择性地获得产物,显著提高双酚F的产率,副反应产物有效降低;2、该催化剂能够回收再利用,降低了成本与能耗,具有良好的应用前景;3、催化剂用于1-苯基-3-对硝基苯基-丙酮合成中时具有优异的催化性能,产物的化学选择性为100%,产率大于90%。
附图说明
图1是实施例1制得的催化剂的3μm扫描电镜图;
图2是实施例1制得的催化剂的1μm扫描电镜图。
具体实施方式
实施例1
制备石墨烯负载银钌双金属催化剂:
先用5mL的37%盐酸处理6.0g石墨,加入1.5g二乙酸碘苯进行氧化,然后用超声波震荡至氧化石墨烯水溶液至清晰无颗粒,加入1g二硝基苯肼在50℃回流30h,经过滤、烘干即得石墨烯,将1.0g的AgBF4与1.1g的RuCl3溶于10mL乙二醇,在冰浴的条件下搅拌,待固体全部溶解后,撤去冰浴;加入5g石墨烯,调节混合液pH至7,置于80℃的水热条件下,反应2h;反应结束后,冷却,离心,洗涤,真空干燥得到产物;将产物在高温马弗炉中焙烧,先升温至500℃,温度稳定后维持4h,最后在真空干燥器中保存,即得到银钌双金属掺杂石墨烯催化剂AgRu/石墨烯。图1、图2为AgRu/石墨烯的扫描电镜图,可以看出采用含有配阴离子银试剂的双金属纳米粒子,颗粒比较均匀,产物中,银、钌纳米颗粒粒径约为500nm,形貌比较美观;因此,所获得的催化剂有可能会有比较高的催化剂活性。
合成双酚F:
将1.0mol苯酚、80mgAgRu/石墨烯催化剂加入到反应容器中,室温下搅拌均匀,加入100mL二甲苯,再慢慢的加入5mL的37%甲醛水溶液、0.3mL质量分数10%的浓盐酸,加热至120℃,反应时间为8小时。反应结束后将得到的反应液分层,油层为反应粗产品,同时通过过滤可回收石墨烯负载银钌双金属催化剂。把所得粗产品旋蒸回收溶剂二甲苯、减压蒸馏回收剩余的苯酚,剩余产品用回收的二甲苯重新结晶一次,即可得到双酚F。双酚F的产率为67%。
实施例2
制备石墨烯负载银钌双金属催化剂:
先用12mL的37%盐酸处理9.0g石墨,加入1.5g二乙酸碘苯进行氧化,然后用超声波震荡至氧化石墨烯水溶液至清晰无颗粒,加入3g二硝基苯肼在100℃回流10h,经过滤、烘干即得石墨烯,将2.0g的AgBF4与2.2g的RuCl3溶于14mL乙二醇,在冰浴的条件下搅拌,待固体全部溶解后,撤去冰浴;加入8g石墨烯,调节混合液pH至7,置于80℃的水热条件下,反应2h;反应结束后,冷却,离心,洗涤,真空干燥得到产物;将产物在高温马弗炉中焙烧,先升温至400℃,温度稳定后维持6h,最后在真空干燥器中保存,即得到银钌双金属掺杂石墨烯催化剂AgRu/石墨烯。
合成双酚F:
将1.0mol苯酚、80mgAgRu/石墨烯催化剂加入到反应容器中,室温下搅拌均匀,加入100mL二甲苯,再慢慢的加入5mL的37%甲醛水溶液、0.3mL质量分数10%的浓盐酸,加热至140℃,反应时间为8小时。反应结束后将得到的反应液分层,油层为反应粗产品,同时通过过滤可回收石墨烯负载银钌双金属催化剂。把所得粗产品旋蒸回收溶剂二甲苯、减压蒸馏回收剩余的苯酚,剩余产品用回收的二甲苯重新结晶一次,即可得到双酚F。双酚F的产率为71%。
实施例3
制备石墨烯负载银钌双金属催化剂:
先用15mL的37%盐酸处理12.0g石墨,加入1.8g二乙酸碘苯进行氧化,然后用超声波震荡至氧化石墨烯水溶液至清晰无颗粒,加入5g二硝基苯肼在50℃回流20h,经过滤、烘干即得石墨烯,将3.0g的AgBF4与3.3g的RuCl3溶于20mL乙二醇,在冰浴的条件下搅拌,待固体全部溶解后,撤去冰浴;加入10g石墨烯,调节混合液pH至11,置于80℃的水热条件下,反应2h;反应结束后,冷却,离心,洗涤,真空干燥得到产物;将产物在高温马弗炉中焙烧,先升温至300℃,温度稳定后维持10h,最后在真空干燥器中保存,即得到银钌双金属掺杂石墨烯催化剂AgRu/石墨烯。
合成双酚F:
将1.0mol苯酚、80mgAgRu/石墨烯催化剂加入到反应容器中,室温下搅拌均匀,加入100mL二甲苯,再慢慢的加入5mL的37%甲醛水溶液、0.3mL质量分数10%的浓盐酸,加热至140℃,反应时间为12小时。反应结束后将得到的反应液分层,油层为反应粗产品,同时通过过滤可回收石墨烯负载银钌双金属催化剂。把所得粗产品旋蒸回收溶剂二甲苯、减压蒸馏回收剩余的苯酚,剩余产品用回收的二甲苯重新结晶一次,即可得到双酚F。双酚F的产率为74%。
实施例4
制备石墨烯负载银钌双金属催化剂:
先用15mL的37%盐酸处理12.0g石墨,加入1.8g二乙酸碘苯进行氧化,然后用超声波震荡至氧化石墨烯水溶液至清晰无颗粒,加入5g二硝基苯肼在50℃回流20h,经过滤、烘干即得石墨烯,将3.0g的AgBF4与3.3g的RuCl3溶于20mL乙二醇,在冰浴的条件下搅拌,待固体全部溶解后,撤去冰浴;加入10g石墨烯,调节混合液pH至11,置于80℃的水热条件下,反应2h;反应结束后,冷却,离心,洗涤,真空干燥得到产物;将产物在高温马弗炉中焙烧,先升温至300℃,温度稳定后维持10h,最后在真空干燥器中保存,即得到银钌双金属掺杂石墨烯催化剂AgRu/石墨烯。
合成1-苯基-3-对硝基苯基-丙酮:
氮气保护下,在25mL Schlenk管中加入240mg浓度为2mmol苯乙酮、368mg浓度为2.4mmol的4-硝基苯甲醇、80mg的AgRu/石墨烯催化剂、326mg浓度为1.0mmol的碳酸铯,加入5.0mL叔戊醇;反应液置于110℃反应48h,产生的溶液用300~400目硅胶柱分离,洗脱液为1:5的乙酸乙酯/石油醚,旋转蒸发除去溶剂后,即得到对应产物:1-苯基-3-对硝基苯基-丙酮,产物选择性为100%,产率:91%。
Claims (9)
1.一种银钌双金属掺杂石墨烯催化剂,其特征在于,包括石墨烯载体,所述石墨烯载体上负载有银、钌纳米颗粒,所述银、钌纳米颗粒质量比为0.5~1:0.6~1.1,所述银、钌纳米颗粒直径为100~800nm。
2.一种权利要求1所述的银钌双金属掺杂石墨烯催化剂的制备方法,其特征在于,包括以下步骤:
(1)制备石墨烯;
(2)将AgBF4与RuCl3溶于乙二醇,然后加入石墨烯,调节混合液pH至7~11,置于80~200℃的水热条件下进行反应;
(3)反应结束后,冷却,离心,洗涤,真空干燥得到产物;
(4)将产物进行焙烧,最后在真空干燥器中保存。
3.根据权利要求2所述的银钌双金属掺杂石墨烯催化剂的制备方法,其特征在于,所述步骤1包括以下步骤:
(11)利用酸处理石墨,然后加入二乙酸碘苯进行氧化,得到氧化石墨烯水溶液;
(12)利用超声波震荡氧化石墨烯水溶液至清晰无颗粒,
(13)在氧化石墨烯水溶液中加入二硝基苯肼,并在50~150℃回流,经过滤、烘干即得石墨烯。
4.根据权利要求3所述的银钌双金属掺杂石墨烯催化剂的制备方法,其特征在于,所述步骤11中石墨和二乙酸碘苯的质量比为6~12:1。
5.根据权利要求3所述的银钌双金属掺杂石墨烯催化剂的制备方法,其特征在于,所述步骤中13中二硝基苯肼与氧化石墨烯水溶液中的石墨质量比为1~5:6~12。
6.根据权利要求2所述的银钌双金属掺杂石墨烯催化剂的制备方法,其特征在于,所述步骤2中AgBF4和RuCl3的质量比为1:1~1.1,AgBF4和RuCl3在冰浴条件下进行搅拌溶解,AgBF4和石墨烯的质量比为1~3:5~10。
7.根据权利要求2所述的银钌双金属掺杂石墨烯催化剂的制备方法,其特征在于,所述步骤4中产物在300~500℃下焙烧,焙烧4~10h。
8.一种权利要求1所述的银钌双金属掺杂石墨烯催化剂在双酚F的合成过程中作为催化剂的应用。
9.一种权利要求1所述的银钌双金属掺杂石墨烯催化剂在1-苯基-3-对硝基苯基-丙酮的合成过程中作为催化剂的应用。
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