CN111203230B - 一种Pd/FeOOH@RGO皮克林乳液及其催化碳碳偶联反应的应用 - Google Patents
一种Pd/FeOOH@RGO皮克林乳液及其催化碳碳偶联反应的应用 Download PDFInfo
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Abstract
本发明公开了一种Pd/FeOOH@RGO皮克林乳液及其催化Suzuki碳碳偶联反应的应用。本发明采用水和有机溶剂同时作为溶剂，用五羰基铁还原氧化石墨和金属氯化物，没有加入任何其它还原剂，一步法反应制得Pd/FeOOH@RGO，然后以Pd/FeOOH@RGO作为乳化剂，可稳定多种水油体系形成皮克林乳液。本发明制备的皮克林乳液稳定性强，用于催化卤代苯及其衍生物的Suzuki碳碳偶联反应，催化反应效果好，可循环利用，有效解决了有机化学反应体系的底物在水溶液中溶解性差，催化剂活性低，适用范围窄和分离困难等问题，符合绿色环保的合成理念，在催化领域有着巨大的应用前景。
Description
技术领域
本发明属于催化技术领域，具体涉及一种Pd/FeOOH@RGO皮克林乳液，以及该乳液在催化卤代芳烃与苯硼酸的Suzuki碳碳偶联反应中的应用。
背景技术
长期以来，在实验室和工业上使用有机溶剂进行化学反应，有毒有机溶剂的排放和贵金属的流失造成了严重的环境污染。面对环境保护的重大压力，为实现可持续发展，有机化学反应的绿色化已经成为化学工作者面临的重大挑战。水作为有机合成反应溶剂具有操作简单、使用安全、成本低廉及不污染环境等优点。因此，在倡导绿色化学的今天，在水溶液中进行有机反应已成为近年来工业界和学术界研究的热点。而在水溶液中进行反应往往会受到底物溶解性、底物稳定性、催化剂活性等因素的限制。故水溶液中的有机反应一般需选择在水中稳定的底物，还需要添加助溶剂、相转移催化剂、或采用水溶性的金属催化剂和配体等，用以提高反应活性或底物溶解性。而这些方法中对催化剂合成设计、所选用的体系都有严格的限制，故适用的范围比较窄。因而，开发一种适用范围广、产物易于分离及催化剂可回收使用的绿色催化体系，是人们共同的希望。
乳液代表了一类重要的自组装双亲体系，是两种互不相溶的液体(如油和水) 在表面活性剂分子界面膜作用下形成的分散体系。乳液已在洗涤剂、燃料、萃取、环境保护、有机合成、高分子化学、生物化学及纳米材料制备等领域有了广泛的研究。与相转移催化相似，乳液在有机合成中普遍存在表面活性剂从产物中分离不彻底、乳液组分以及催化剂回收再利用困难等问题，因此严重限制了乳液等表面活性剂聚集体在有机合成上的应用。如果既能体现乳液在有机合成中的优点，又能简化破乳分离操作，解决乳液分离难题，实现组分(油、水、催化剂等)回收，将对油 /水非均相催化、拓宽乳液应用等领域有重要的意义。
固态颗粒稳定乳状液的现象由英国科学家Ramsden和Pickering于上世纪初首先发现。因此人们将固体颗粒稳定的乳状液称为Pickering乳液(皮克林乳液)。与传统表面活性剂稳定的乳液相比较，Pickering乳液具有其自身的优势：(1)大大降低表面活性剂的用量，甚至可以不用表面活性剂，体系只需过滤操作就能实现分离，既节约成本，又简化破乳分离操作；(2)稳定性强，普通表面活性剂分子稳定的乳状液是热力学不稳定体系。
钯催化的偶联反应具有高的选择性、官能团适用范围广等强大的优势，使得钯催化偶联反应成为形成新的C-C、C-X键的最重要的方法之一。由于使用钯的成本较高，均相的钯催化剂难于回收和重新利用，同时基于环保和可持续发展的立足点，发展催化偶联反应的非均相钯催化剂尤为重要。而且，在钯催化偶联反应中往往需要配体，而这些报道过的配体通常都是不易合成且十分耗时。再者，有机反应通常很难在水相中反应。
发明内容
本发明的目的是提供一种Pd/FeOOH@RGO皮克林乳液，及其在催化卤代芳烃与苯硼酸的Suzuki碳碳偶联反应中的应用。
针对上述目的，本发明采用的Pd/FeOOH@RGO皮克林乳液由下述方法制备得到：
1、将氧化石墨超声分散于去离子水中，得到浓度为1～15mg/mL的氧化石墨分散液；在搅拌条件下，向所述氧化石墨分散液中加入氯化钯，并加入体积浓度为 1.5～135mL/L的五羰基铁的乙腈溶液，在密闭条件50～80℃反应1～3小时，反应完后过滤、洗涤、干燥，得到纳米羟基氧化铁/钯/石墨烯三元复合材料，记为 Pd/FeOOH@RGO；其中，所述氧化石墨与氯化钯的质量比为5～1300:1，氧化石墨与五羰基铁的质量体积比为0.01～5g:1mL。
2、将Pd/FeOOH@RGO超声分散于去离子水中，得到浓度为1～5mg/mL的 Pd/FeOOH@RGO分散液；在搅拌条件下，向Pd/FeOOH@RGO分散液中加入有机溶剂，用均质机震荡制得Pd/FeOOH@RGO皮克林乳液。
上述步骤1中，优选氧化石墨与氯化钯的质量比为50～300:1，优选氧化石墨与五羰基铁的质量体积比为0.03～1g:1mL。
上述步骤2中，优选去离子水与有机溶剂的体积比为1:0.5～1.5，所述的有机溶剂为甲苯、二甲苯、环己烷、苯乙烯、正丁醇、异丁醇、正庚烷、正己烷、氯仿、氯化苄中任意一种。
本发明Pd/FeOOH@RGO皮克林乳液在催化Suzuki碳碳偶联反应中的应用，具体方法为：向Pd/FeOOH@RGO皮克林乳液中加入卤代芳烃、苯硼酸或对甲基苯硼酸、无水碳酸钾，在50～80℃下搅拌反应，反应结束后将反应液离心分液，有机相经无水硫酸镁干燥、减压浓缩、硅胶柱纯化，得到Suzuki碳碳偶联产物；水相过滤得Pd/FeOOH@RGO，重复使用。
上述应用中，所述的卤代芳烃为卤代苯、C1～C4烷氧基取代的卤代苯、C1～C6烷基取代的卤代苯、卤代萘、卤代噻吩等中任意一种。
上述应用中，优选卤代芳烃与苯硼酸或对甲基苯硼酸、无水碳酸钾的摩尔比为 1:1.1～1.2:1.2～1.5，Pd/FeOOH@RGO中金属钯的摩尔量为卤代芳烃摩尔量的 0.01％～0.5％。
本发明的有益效果如下：
本发明采用水和有机溶剂同时作为溶剂，用五羰基铁还原氧化石墨和金属氯化物，没有加入任何其它还原剂，一步法反应制得Pd/FeOOH@RGO。羟基氧化铁和金属粒子以纳米级负载在石墨烯表面，粒径小且在石墨烯表面分布均匀，稳定性和分散性好。其中纳米羟基氧化铁形貌为纳米带状，在氧化石墨烯表面呈现单分散状态分布。该方法合成步骤少，生产成本低，易于实现工业化生产。
本发明制备的Pd/FeOOH@RGO具有良好的两亲性，而且通过羟基氧化铁比例的调节可实现复合材料表面润湿性的调控，同时该复合材料兼具高催化活性的金属物种，以其制备的皮克林乳液稳定性强，制备方法简单，催化Suzuki碳碳偶联反应效率高，可循环利用，有效解决了有机化学反应体系的底物在水溶液中溶解性差、催化剂活性低、适用范围窄和分离困难等问题，为钯催化偶联反应开辟了一条简单、高效、环境友好的新路线，在催化领域有着巨大的应用前景。
附图说明
图1是不同有机相所形成的Pd/FeOOH@RGO皮克林乳的偏光显微镜照片图，其中a为正庚烷、b为甲苯、c为二甲苯、d为环己烷、e为苯乙烯、f为正丁醇、g 为异丁醇、h为正己烷、i为氯仿、j为氯化苄。
图2是不同温度下Pd/FeOOH@RGO皮克林乳液加热2h的偏光显微镜照片图，其中a为40℃、b为60℃、c为80℃、d为90℃。
图3是不同pH下Pd/FeOOH@RGO皮克林乳液放置2h的偏光显微镜照片图，其中a为pH＝1、b为pH＝5、c为pH＝12、d为pH＝14。
具体实施方式
下面结合附图和实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
1、将125mg氧化石墨(GO)加入15mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入1mg氯化钯，然后移至150mL 圆底烧瓶中，加入15mL体积浓度16.7mL/L的五羰基铁的乙腈溶液，在密闭条件下60℃反应3小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到纳米羟基氧化铁/钯/石墨烯三元复合材料，记为Pd/FeOOH@RGO。
2、称取10mg Pd/FeOOH@RGO，超声分散于2mL去离子水中，得到浓度为 5mg/mL的Pd/FeOOH@RGO分散液。在搅拌条件下，向Pd/FeOOH@RGO分散液中加入2mL正庚烷，用均质机震荡制得Pd/FeOOH@RGO皮克林乳液。
本实施例的甲苯也可用等体积的甲苯、二甲苯、环己烷、苯乙烯、正丁醇、异丁醇、正己烷、氯仿或氯化苄替换，制成Pd/FeOOH@RGO皮克林乳液。采用偏光显微镜照片对不同有机溶剂制得的Pd/FeOOH@RGO皮克林乳液的稳定性进行观察，结果见图1。如图可见，Pd/FeOOH@RGO可稳定多种类型的皮克林乳液，有机相包括极性溶剂和非极性溶剂、质子性溶剂和非质子性溶剂、饱和烃类溶剂和不饱和烃类溶剂，具有极其优秀的普适性，乳液液滴分散均匀，大小均一。
将上述在正庚烷中制得的Pd/FeOOH@RGO皮克林乳液分别在40℃、60℃、 80℃、90℃下加热2h，采用偏光显微镜照片观察乳液的温度稳定性，结果见图2。如图可见，Pd/FeOOH@RGO稳定的皮克林乳液具有优秀的温度稳定性。
将上述在正庚烷中制得的Pd/FeOOH@RGO皮克林乳液分别用HCl或NaOH 调节pH为1、5、12、14，常温放置2h。采用偏光显微镜照片观察不同pH下乳液的稳定性，结果见图3。无论是在酸性条件下，还是在碱性条件下，乳液保持稳定，乳液酸碱的耐受性优秀，适用范围宽。
实施例2
1、将25mg氧化石墨加入5mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入5mg氯化钯，然后移至150mL圆底烧瓶中，加入15mL体积浓度5mL/L五羰基铁的乙腈溶液，在密闭条件下50℃反应2 小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到Pd/FeOOH@RGO。
2、称取10mg Pd/FeOOH@RGO，超声分散于2mL去离子水中，得到浓度为 5mg/mL的Pd/FeOOH@RGO分散液。在搅拌条件下，向Pd/FeOOH@RGO分散液中加入2mL正庚烷，用均质机震荡制得Pd/FeOOH@RGO皮克林乳液。
实施例3
1、将25mg氧化石墨加入5mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入5mg氯化钯，然后移至150mL圆底烧瓶中，加入15mL体积浓度20mL/L五羰基铁的乙腈溶液，在密闭条件下50℃反应 2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到Pd/FeOOH@RGO。
2、称取10mg Pd/FeOOH@RGO，超声分散于10mL去离子水中，得到浓度为 1mg/mL的Pd/FeOOH@RGO分散液。在搅拌条件下，向Pd/FeOOH@RGO分散液中加入10mL正庚烷，用均质机震荡制得Pd/FeOOH@RGO皮克林乳液。
实施例4
将25mg氧化石墨加入5mL去离子水中，超声分散得到氧化石墨分散液。在搅拌条件下，向氧化石墨分散液中加入5mg氯化钯，然后移至150mL圆底烧瓶中，加入15mL体积浓度50mL/L五羰基铁的乙腈溶液，在密闭条件下50℃反应2小时，反应完后过滤，用去离子水洗涤，冷冻干燥，得到Pd/FeOOH@RGO。
2、称取10mg Pd/FeOOH@RGO，超声分散于2.5mL去离子水中，得到浓度为4mg/mL的Pd/FeOOH@RGO分散液。在搅拌条件下，向Pd/FeOOH@RGO分散液中加入3mL正庚烷，用均质机震荡制得Pd/FeOOH@RGO皮克林乳液。
实施例5
称取实施例1中制得的Pd/FeOOH@RGO 10mg，超声分散于2mL去离子水中，得到浓度为5mg/mL的Pd/FeOOH@RGO分散液；在搅拌条件下，向 Pd/FeOOH@RGO分散液中加入2mL正丁醇，用均质机震荡制得Pd/FeOOH@RGO 皮克林乳液，然后向该Pd/FeOOH@RGO皮克林乳液中加入1mmol对甲氧基溴苯、 1.2mmol苯硼酸、1.5mmol无水碳酸钾，在80℃下磁力搅拌反应2h。将反应液离心分液，有机相经无水硫酸镁干燥、减压浓缩、硅胶柱纯化，得到产物4-甲氧基联苯，经气相色谱检测产率90％。水相经过滤得Pd/FeOOH@RGO，重复使用。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.56(t,J＝8.4Hz,4H),7.43(t,J＝7.6Hz,2H), 7.32(t,J＝7.3Hz,1H),7.00(d,J＝8.6Hz,2H),3.86(s,4H)；13C NMR(101MHz,CDCl3) δ159.15,140.84,133.79,128.75,128.19,126.73,114.21,55.37。
实施例6
称取实施例1中制得的Pd/FeOOH@RGO 10mg，超声分散于2mL去离子水中，得到浓度为5mg/mL的Pd/FeOOH@RGO分散液；在搅拌条件下，向 Pd/FeOOH@RGO分散液中加入2mL正丁醇，用均质机震荡制得Pd/FeOOH@RGO 皮克林乳液，然后向该Pd/FeOOH@RGO皮克林乳液中加入1mmol对甲氧基碘苯、 1.2mmol苯硼酸、1.5mmol无水碳酸钾，在80℃下磁力搅拌反应2h，将反应液离心分液，有机相经无水硫酸镁干燥、减压浓缩、硅胶柱纯化，得到产物4-甲氧基联苯，经气相色谱检测产率为90％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.56(t,J＝8.4Hz,4H),7.43(t,J＝7.6Hz,2H), 7.32(t,J＝7.3Hz,1H),7.00(d,J＝8.6Hz,2H),3.86(s,4H)；13C NMR(101MHz,CDCl3) δ159.15,140.84,133.79,128.75,128.19,126.73,114.21,55.37。
实施例7
称取实施例1中制得的Pd/FeOOH@RGO 10mg，超声分散于2mL去离子水中，得到浓度为5mg/mL的Pd/FeOOH@RGO分散液；在搅拌条件下，向 Pd/FeOOH@RGO分散液中加入2mL甲苯，用均质机震荡制得Pd/FeOOH@RGO 皮克林乳液，然后向该Pd/FeOOH@RGO皮克林乳液中加入1mmol溴苯、1.2mmol 苯硼酸、1.5mmol无水碳酸钾，在80℃下磁力搅拌反应2h，将反应液离心分液，有机相经无水硫酸镁干燥、减压浓缩、硅胶柱纯化，得到产物联苯，经气相色谱检测产率为90％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.66–7.59(m,4H),7.50–7.42(m,4H),7.40– 7.34(m,2H)；13CNMR(101MHz,CDCl3)δ141.32,128.88,127.34,127.28。
实施例8
称取实施例1中制得的Pd/FeOOH@RGO 10mg，超声分散于2mL去离子水中，得到浓度为5mg/mL的Pd/FeOOH@RGO分散液；在搅拌条件下，向 Pd/FeOOH@RGO分散液中加入2mL正庚烷，用均质机震荡制得Pd/FeOOH@RGO 皮克林乳液，然后向该Pd/FeOOH@RGO皮克林乳液中加入1mmol对甲氧基溴苯、 1.2mmol对甲基苯硼酸、1.5mmol无水碳酸钾，在80℃下磁力搅拌反应2h，用将反应液离心分液，有机相经无水硫酸镁干燥、减压浓缩、硅胶柱纯化，得到产物4,4- 二甲氧基联苯，经气相色谱检测产率为82％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.53(d,J＝8.6Hz,2H),7.47(d,J＝8.0Hz,2H), 7.24(d,J＝7.9Hz,2H),6.98(d,J＝8.6Hz,2H),3.86(s,3H),2.40(s,3H)；13C NMR(101 MHz,CDCl3)δ157.86,132.46,132.26,128.38,126.81,125.35,113.09,20.03。
实施例9
称取实施例1中制得的Pd/FeOOH@RGO 10mg，超声分散于2mL去离子水中，得到浓度为5mg/mL的Pd/FeOOH@RGO分散液；在搅拌条件下，向 Pd/FeOOH@RGO分散液中加入2mL正庚烷，用均质机震荡制得Pd/FeOOH@RGO 皮克林乳液，然后向该Pd/FeOOH@RGO皮克林乳液中加入1mmol 2-溴噻吩、1.2 mmol苯硼酸、1.5mmol无水碳酸钾，在80℃下磁力搅拌反应2h，将反应液离心分液，有机相经无水硫酸镁干燥、减压浓缩、硅胶柱纯化，得到产物邻苯噻吩，经气相色谱检测产率为76％。
所得产物用Bruker Avance型超导傅立叶数字化核磁共振谱仪进行表征，表征数据为：1H NMR(400MHz,CDCl3)δ7.63(d,J＝7.7Hz,2H),7.39(t,J＝7.6Hz,2H), 7.30(dt,J＝8.2,3.6Hz,3H),7.13(m,1H)；13C NMR(101MHz,CDCl3)δ143.38, 133.35,127.84,126.96,126.42,124.91,123.76,122.03。
Claims (10)
1.一种Pd/FeOOH@RGO皮克林乳液，其特征在于该皮克林乳液由下述方法制备得到：
（1）将氧化石墨超声分散于去离子水中，得到浓度为1～15 mg/mL的氧化石墨分散液；在搅拌条件下，向所述氧化石墨分散液中加入氯化钯，并加入体积浓度为1.5～135 mL/L的五羰基铁的乙腈溶液，在密闭条件50～80 ℃反应1～3小时，反应完后过滤、洗涤、干燥，得到纳米羟基氧化铁/钯/石墨烯三元复合材料，记为Pd/FeOOH@RGO；其中，所述氧化石墨与氯化钯的质量比为5～1300:1，氧化石墨与五羰基铁的质量体积比为0.01～5 g:1 mL；
（2）将Pd/FeOOH@RGO超声分散于去离子水中，得到浓度为1～5 mg/mL的Pd/FeOOH@RGO分散液；在搅拌条件下，向Pd/FeOOH@RGO分散液中加入有机溶剂，用均质机震荡制得Pd/FeOOH@RGO皮克林乳液。
2.根据权利要求1所述的Pd/FeOOH@RGO皮克林乳液，其特征在于：步骤（1）中，所述的氧化石墨与氯化钯的质量比为50～300:1。
3.根据权利要求1或2所述的Pd/FeOOH@RGO皮克林乳液，其特征在于：步骤（1）中，所述的氧化石墨与五羰基铁的质量体积比为0.03～1 g:1 mL。
4.根据权利要求1所述的Pd/FeOOH@RGO皮克林乳液，其特征在于：步骤（2）中，所述的去离子水与有机溶剂的体积比为1:0.5～1.5。
5.根据权利要求1或4所述的Pd/FeOOH@RGO皮克林乳液，其特征在于：步骤（2）中，所述的有机溶剂为甲苯、二甲苯、环己烷、苯乙烯、正丁醇、异丁醇、正庚烷、正己烷、氯仿、氯化苄中任意一种。
6.权利要求1所述的Pd/FeOOH@RGO皮克林乳液在催化Suzuki碳碳偶联反应中的应用。
7.根据权利要求6所述的Pd/FeOOH@RGO皮克林乳液在催化Suzuki碳碳偶联反应中的应用，其特征在于：向Pd/FeOOH@RGO皮克林乳液中加入卤代芳烃、苯硼酸或对甲基苯硼酸、无水碳酸钾，在50～80 ℃下搅拌反应，反应结束后将反应液离心分液，有机相经无水硫酸镁干燥、减压浓缩、硅胶柱纯化，得到Suzuki碳碳偶联产物；水相过滤得Pd/FeOOH@RGO，重复使用。
8.根据权利要求7所述的Pd/FeOOH@RGO皮克林乳液在催化Suzuki碳碳偶联反应中的应用，其特征在于：所述的卤代芳烃为卤代苯、C1～C4烷氧基取代的卤代苯、C1～C6烷基取代的卤代苯、卤代萘、卤代噻吩中任意一种。
9.根据权利要求7所述的Pd/FeOOH@RGO皮克林乳液在催化Suzuki碳碳偶联反应中的应用，其特征在于：所述的Pd/FeOOH@RGO中金属钯的摩尔量为卤代芳烃摩尔量的0.01%～0.5%。
10.根据权利要求7所述的Pd/FeOOH@RGO皮克林乳液在催化Suzuki碳碳偶联反应中的应用，其特征在于：所述卤代芳烃与苯硼酸或对甲基苯硼酸、无水碳酸钾的摩尔比为1:1.1～1.2:1.2～1.5。
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| CN102527407A (zh) * | 2010-12-08 | 2012-07-04 | 江南大学 | 两亲磁性载钯纳米氧化铁及其乳液的制备与应用 |
| CN104667945A (zh) * | 2015-01-10 | 2015-06-03 | 安徽大学 | 一种负载型钯催化剂Fe3O4/SiO2/Pd的制备及在Suzuki反应中的应用 |
| CN104744311A (zh) * | 2015-04-20 | 2015-07-01 | 河北美星化工有限公司 | 一种联苯肼酯的合成方法 |
| CN106582710A (zh) * | 2016-11-24 | 2017-04-26 | 济南大学 | 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 |
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| JP2010522078A (ja) * | 2007-03-23 | 2010-07-01 | エージェンシー フォー サイエンス，テクノロジー アンド リサーチ | パラジウム触媒 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527407A (zh) * | 2010-12-08 | 2012-07-04 | 江南大学 | 两亲磁性载钯纳米氧化铁及其乳液的制备与应用 |
| CN104667945A (zh) * | 2015-01-10 | 2015-06-03 | 安徽大学 | 一种负载型钯催化剂Fe3O4/SiO2/Pd的制备及在Suzuki反应中的应用 |
| CN104744311A (zh) * | 2015-04-20 | 2015-07-01 | 河北美星化工有限公司 | 一种联苯肼酯的合成方法 |
| CN106582710A (zh) * | 2016-11-24 | 2017-04-26 | 济南大学 | 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 |
Non-Patent Citations (3)
| Title |
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| In situ biosynthesis of palladium nanoparticles on Artemisia abrotanum extract-modified graphene oxide and its catalytic activity for Suzuki coupling reactions;Mirmehdi Hashemi Salehi et al.;《Polyhedron》;20190307;第165卷;132-137 * |
| One-pot hydrothermal synthesis of magnetically recoverable palladium/reduced graphene oxide nanocomposites and its catalytic applications in cross-coupling reactions;Wenzhi Fu et al.;《Journal of Colloid and Interface Science》;20170228;第497卷;83-92 * |
| 磁性纳米催化剂的研究进展;郭祖鹏等;《精细化工中间体》;20110828;第41卷(第04期);18-25+29 * |
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