CN1218787C - 激光沉积法制备纳米碳管负载金属催化剂的方法 - Google Patents
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Abstract
本发明提供一种激光沉积法制备纳米碳管负载金属催化剂的方法,即先将金属原子用脉冲激光激发为原子束,定向沉积在流动的纳米碳表面,得到均匀、牢固的纳米碳管负载金属催化剂,可应用于燃料电池、催化加氢、化学电极、F-T合成、氨合成、氢甲酰化等领域,具有较大的实施价值和重要的社会经济效益。
Description
技术领域
本发明涉及激光沉积法制备纳米碳管负载金属催化剂的方法,其特点是采用脉冲激光激发金属原子成原子束,沉积在纳米碳管表面,得到纳米碳管负载金属催化剂,具有负载均匀、结合牢固的优点,适用于燃料电池、催化加氢、化学电极、F-T合成、氨合成、氢甲酰化等领域。
背景技术
纳米碳管具有极高的强度和硬度、耐热腐蚀性好,并具有纳米尺寸和量子效应等,使得纳米碳管负载金属显示出优异的催化性能,在储氢材料、超级电容、化学反应催化剂、燃料电池催化剂、电极催化剂等方面具有良好的应用前景。纳米碳管负载金属通常采用浸渍法、离子交换法,Planeix J M等人J Am Chem Soc,1994,116:7935~7936和Appl Catal A,1998,173,175~183通过浸渍法制备了纳米碳管负载钌催化剂(Ru/CNTs)。他们把有机钌试剂溶于甲苯中,加入表面处理后的纳米碳管,充分接触后蒸去甲苯。所得固体经氮气和H2/N2处理后,即得Ru/CNTs催化剂。通过相似的方法可以把铂负载到纳米碳管上,制得纳米碳管负载Pt。Chen HB等人Appl Surf Sci,2001,180:328-335用浸渍法制备了纳米碳管负载Ru。纳米碳管先经氧化处理,再把氧化后的纳米碳管放入含有RuCl3的有机溶剂中,浸渍后,经H2还原就可得到纳米碳管负载Ru。徐才录等人科学通报,1999,44(11):1154~1156,清华大学学报(自然科学版),2001,41(2):5~7)研究了在纳米碳管上的沉积Pt。纳米碳管先进行表面处理,产生氧化基团,然后用二种方法在纳米碳管上浸渍铂:(1)在纳米碳管、水和乙醇的混合液中加入H2O2,搅拌后加入一定量的氯铂酸水溶液,再缓慢滴加Na2S2O4和NaOH,长时间搅拌后可得黑色粉末,烘干,放到密封的管式炉中在N2气氛下加热分解。(2)将氯铂酸溶于乙醇后,与纳米碳管混合,室温下搅拌、烘干,N2气氛下加热分解。Li W Z等人Carbon,2002,40:791~794研究了在含氯铂酸的乙二醇溶液中加入氧化处理的纳米碳管,高温回流,可在纳米碳管表面负载Pt。固体洗涤后在空气中干燥,就可得到含10%的纳米碳管负载Pt。Ang L M等用浸渍法Carbon,2000,38:363~372在纳米碳管表面负载了Cu和Ni。Li YH等Material Research Bulletin,2002,37:313~318研究了浸渍法在纳米碳管表面负载Ce。先把纳米碳管浸泡在HNO3和氢氟酸中,除去杂质后,所得的纳米碳管在混酸中煮沸、过滤、干燥。再将纳米碳管分散在蒸馏水中,在搅拌状态下缓慢加入CeCl3溶液,用NaOH调节pH=9,在纳米碳管表面上负载了纳米铈颗粒。金亚旭等物理化学学报,2002,18(5):459~462研究了在纳米碳管上负载金属。纳米碳管经提纯和表面处理后,与硝酸镍等体积法制备。浸渍过夜后烘干,用H2还原。TEM电镜表明:经处理的纳米碳管表面的Ni颗粒分布均匀,粒径在10nm左右。而未经处理的纳米碳管表面的金属不均匀,粒径较大。Ebbesen.T W等人AdvMater,1996,8(2):155~157研究了纳米碳管经氧化处理后,离子交换法在纳米碳管的表面负载金属。用AgNO3通过在含纳米碳管的溶液中回流,可以把Ag+交换到纳米碳管的表面上,然后用甲醛还原,就可以在纳米碳管负载上金属Ag。Bond A M等Langmuir,2000,16,6004-6012研究了在纳米碳管上离子交换固载Hg。纳米碳管的纯化氧化在H2SO4/KMnO4溶液中进行,由于H2SO4/KMnO4溶液的强氧化性,可在纳米碳管表面上形成很多活性基团,如:-COOH、-C=O、-OH。取氧化后的纳米碳管与Hg(NO3)2溶液混合搅拌,过滤后用蒸馏水洗涤,在室温真空下干燥,就可以得到Hg(II)修饰的纳米碳管。采用浸渍法和离子交换法能将金属负载到纳米碳管表面,但该方法具有很大的局限性:由于未处理纳米碳管的表面是惰性的,不能与金属离子在纳米碳管表面很好结合,因此在浸渍之前首先要对纳米碳管进行预处理,在其表面产生氧化基团,这样才能使金属离子与纳米碳管表面的氧化基团较好地结合。但纳米碳管预预处理存在操作复杂、严重污染环境和纳米碳管损失大等缺点。浸渍方法操作复杂,影响因素多,如金属离子溶液的pH值、溶液浓度、温度、浸渍时间、搅拌速度、还原剂的选择等均影响浸渍效果,并且产生大量废液,不符合绿色化要求。
发明内容
本发明的任务是克服现有技术的缺点,提供一种操作简便、无环境污染的激光沉积法制备纳米碳管负载金属催化剂的方法。
在激光沉积池(6)的底部放置纳米碳管(3),在磁力搅拌器(4)的搅拌下使(3)处于运动状态,在激光沉积池(6)的中部固定金属(2),在惰性气体(5)的保护下,激光器(1)将脉冲激光聚焦于金属(2)表面,激发金属原子成原子束,定向均匀沉积在底部的纳米碳管(3)表面,以获得纳米碳管负载金属催化剂。
采用该方法,与现有技术相比,纳米碳管不需任何预处理,避免了一系列复杂的浸渍操作,不产生任何污当物,具有绿色化特点,并且比浸渍法和离子交换法更好地将金属原子均匀、牢固地分布在纳米碳管表面,具有很大的优越性。
附图说明
图1为激光沉积法制备内米碳管负载金属的方法的工艺图
图2为激光沉积法制备纳米碳管负载金属Ni的TEM图
图3为激光沉积法制备纳米碳管负载金属Pd的TEM图
图4为离子交换法制备纳米碳管负载金属Ni的TEM图
图5为离子交换法制备纳米碳管负载金属Pd的TEM图
其中:1——为激光发生器;2——金属;3——为纳米碳管;
4——为磁力搅拌器;5——惰性气体;6——激光沉积池;
具体实施方式
实施例1
激光沉积法制备纳米碳管负载金属。纳米碳管用催化裂解法制取,所得的纳米碳管不加处理,直接置于激光沉积池底部。开动磁力搅拌,使纳米碳管处于流动状态。金属镍加工成厚为1mm,直径为10mm的圆片,置于沉积池的中央。在氦气的保护下,脉冲激光聚焦在镍片表面,并移动聚焦点,激发镍原子成原子束,向四周溅射,均匀沉积到流动的纳米碳管表面,获得纳米碳管负载金属镍,其透射电镜图(TEM图)示于图2。
实施例2
激光沉积方法同实施例1,金属为Pd,获得纳米碳管负载Pd的TEM示于图3。
实施例3
离子交换法制备纳米碳管负载金属镍。用CVD法制备纳米碳管,将制备的纳米碳管先用30%H2O2浸泡12小时,洗涤过滤后再在65%的HNO3中回流2小时,洗涤至中性后过滤出纳米碳管,烘干后得到氧化处理的纳米碳管,该过程纳米碳管的损失为55%。将1g氧化处理的纳米碳管加入到100ml的0.5%Ni(NO3)2溶液中,在60℃条件下浸泡48小时,过滤纳米碳管,烘干后放入石瑛管中在450℃、氢气流量为300ml/min的条件下还原180min,得到离子交换法制备的纳米碳管负载镍,其TEM图示于图4。
实施例4
离子交换法制备纳米碳管负载金属Pd。纳米碳管氧化处理同实施例2,将1g氧化处理的纳米碳管放烧杯中,加入16ml 0.59%的H2PdCl4水溶液,搅拌48小时,温度为45℃,过滤纳米碳管,烘干至恒重。在160℃,氢气流量为300ml/min的条件进行还原2淖小时,得到纳米碳管负载金属Pd催化剂,其TEM图示于图5。
比较图2与图4、图3与图5可以显示激光沉积法制备的纳米碳管负载金属催化剂的表面金属颗粒具有分布均匀、结合牢固等优点。而离子交换法制备的纳米碳管负载金属催化剂的表面金属颗粒分布稀疏、粒径较大。
Claims (1)
1.激光沉积法制备纳米碳管负载金属催化剂的方法,其特征是在激光沉积池(6)的底部放置纳米碳管(3),在磁力搅拌器(4)的搅拌下使纳米碳管(3)处于运动状态,在激光沉积池(6)的中部固定金属(2),在惰性气体(5)的保护下,激光器(1)将脉冲激光聚焦于金属(2)表面,激发金属原子成原子束,定向均匀沉积在底部的纳米碳管(3)表面,获得纳米碳管负载金属催化剂。
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