CN109012693A - 一种Pd-Ni多孔纳米笼催化材料的制备方法与应用 - Google Patents
一种Pd-Ni多孔纳米笼催化材料的制备方法与应用 Download PDFInfo
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- CN109012693A CN109012693A CN201810841637.1A CN201810841637A CN109012693A CN 109012693 A CN109012693 A CN 109012693A CN 201810841637 A CN201810841637 A CN 201810841637A CN 109012693 A CN109012693 A CN 109012693A
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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Abstract
本发明公开了一种Pd‑Ni多孔纳米笼催化材料的制备方法与应用,该方法是:(1)将一定量的金属钯前体、金属镍前体、磷配体、表面活性剂和保护剂进行混合,在惰性气体氛围中搅拌并加热,反应完成后冷却至室温,得到Pd‑Ni;(2)用有机溶剂A洗涤Pd‑Ni表面残留的有机物,离心,收集沉淀,得到Pd‑Ni纳米材料;(3)将Pd‑Ni纳米材料分散在有机溶剂B中,减压蒸除溶剂,得到固体Pd‑Ni,称重后按预定的比例与载体X超声负载,减压蒸除溶剂,得到负载型的Pd‑Ni/X;(4)煅烧,冷却到室温,研磨即制得Pd‑Ni多孔纳米笼材料。本发明的原材料经济易得,无需高温高压,制备工艺简单,对生产设备没有特殊要求,能够实现大规模生产;制得的纳米笼电催化活性高,催化稳定性好。
Description
技术领域
本发明涉及纳米材料制备技术领域,涉及一种纳米笼材料,具体涉及一种Pd-Ni多孔纳米笼催化材料的制备方法与应用。
背景技术
多孔材料在材料学、化学以及物理学领域一直备受关注,随着研究的不断深入和发展成熟,已经成为跨学科的研究热点之一,多孔材料在石油化工、生物技术、环境治理净化、信息技术等重大科学技术以及工业生产领域内都有重要的应用。无机规则孔道结构纳米材料是多孔材料的重要成员,因其具有规则而均匀的孔道结构、高比表面积、高吸附量和高选择性等特点,在吸附分离、离子交换以及光学器件等众多领域被广泛应用。尤其在石油炼制、石油化工、精细化工等领域,充当重要的催化剂和催化剂载体。
纳米笼作为一种新型的纳米材料,具备高比表面、内外表面均可利用等优点,其独特的结构赋予了纳米笼系列独特的物理化学性质,有望应用于电催化、储能、分离、光学器件等诸多领域。纳米笼的制备方法主要有模板法、等离子体聚合法、化学气相沉积法等。这些方法都需要模板并涉及复杂的制备工艺或环境不友好的试剂,因而存在诸多不利因素。
发明内容
本发明的目的是提供一种Pd-Ni多孔纳米笼催化材料的制备方法,工艺流程简单,反应条件温和。
为实现上述目的,本发明采用的技术方案如下:
一种Pd-Ni多孔纳米笼催化材料的制备方法,包括以下步骤:
(1)将一定量的金属钯前体、金属镍前体、磷配体、表面活性剂和保护剂进行混合,在惰性气体氛围中搅拌并加热,反应完成后冷却至室温,得到Pd-Ni,即组分A;
(2)用有机溶剂A洗涤组分A表面残留的有机物,离心,收集沉淀,得到Pd-Ni纳米材料,即组分B;
(3)将组分B分散在有机溶剂B中,减压蒸除溶剂,得到固体Pd-Ni,称重后按预定的比例与载体X超声负载,减压蒸除溶剂,得到负载型的Pd-Ni/X,即组分C;
(4)将组分C置于管式炉内,在惰性气体氛围中煅烧,煅烧温度为200~600℃,煅烧时间为2~5h,煅烧后自然冷却到室温,研磨制得Pd-Ni多孔纳米笼材料。
优选的,所述金属钯前体为乙酰丙酮钯、氯化钯、醋酸钯、四三苯基膦合钯、草酸钯、硫酸钯、磷酸钯中的一种或多种。
优选的,所述金属镍前体为乙酰丙酮镍、氯化镍、醋酸镍、草酸镍、硫酸镍、磷酸镍中的一种或多种。
优选的,所述磷配体为三苯基膦、氧化膦中的一种或多种。
优选的,所述表面活性剂为季铵盐型、脂肪胺型、氨基酸型、甜菜碱型、磷脂中的一种或多种。更优选的为季铵盐表面活性剂,如四丁基溴化铵、十六烷基三甲基溴化铵、十二烷基三甲基溴化铵等。
优选的,所述保护剂为三辛基氧化膦、三辛基膦、甲硼烷-叔丁胺络合物中的一种或多种。
优选的,所述有机溶剂A为甲醇、乙醇、丁醇、丙醇、乙二醇、丙二醇、丁二醇中的一种或多种;所述有机溶剂B为甲苯、乙苯、二甲苯、正己烷、戊烷、丁烷、二氯甲烷、三氯甲烷、四氯化碳、乙醚、丙醚、四氢呋喃、丙酮、丁酮、二甲基亚砜、二甲基甲酰胺、乙胺、乙醇胺、二乙醇胺、三乙醇胺和三乙胺中的一种或多种。
优选的,步骤(3)中,所述载体X为Vulcan XC-72活性炭、SiO2、Al2O3、碳纳米管等中的一种。
优选的,步骤(2)中,所述离心转速为1000~10000rpm,离心时间为2~30min。
本发明的目的之二是提供上述Pd-Ni多孔纳米笼催化材料的应用。
上述制备方法获得的Pd-Ni多孔纳米笼催化材料具有高催化活性和显著的催化稳定性,可用作直接醇类燃料电池阳极催化剂,醇类阳极有甲醇、乙醇、丁醇、丙醇、乙二醇、丙二醇、丁二醇、丙三醇等;也可用作直接甲酸燃料电池阳极催化剂,还可用作电解水析氢吸氧反应的催化剂。
除此之外,本发明制得的Pd-Ni多孔纳米笼催化材料还可应用于其他催化、生物医学、环境保护、工程材料、建筑、涂料、光电、能源、信息等方面。
与现有技术相比,本发明具有如下有益效果:
1、本发明原材料经济易得,无需高温高压,制备制造工艺简单,对生产设备没有特殊要求,能够实现大规模生产;
2、本发明制得的纳米笼在甲醇燃料电池电催化方面表现出优异的活性以及显著的催化稳定性;制得的纳米笼其内部的自支撑结构在一定程度上避免了纳米粒子在电化学过程中的聚集以及载体的腐蚀,催化甲醇的质量活性达到优质的水平。
附图说明
图1为本发明实施例1制得的Pd-Ni MCs的扫描电镜图谱;
图2为本发明实施例2制得的Pd-Ni MCs的扫描电镜图谱;
图3为本发明实施例3制得的Pd-Ni MCs的扫描电镜图谱;
图4为本发明实施例2产物的X射线衍射图;
图5为本发明实施例2电氧化甲醇的循环伏安活性图(与商用Pd/C和PdNi/C对比);
图6为本发明实施例2电氧化甲醇的多次循环伏安后活性损失图(与商用Pd/C、PdNi/C和PtRu/C对比);
图7为本发明实施例1-3制得的Pd-Ni MCs的孔隙大小图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明。
实施例1
一种Pd-Ni多孔纳米笼催化材料的制备方法,包括以下步骤:
将0.2mmol的金属钯前体乙酰丙酮钯(Pd(acac)2),0.2mmol的金属镍前体乙酰丙酮镍(Ni(acac)2),0.88mmol的磷配体三苯基膦(TPP),1.5mmol表面活性剂四丁基溴化铵(TBAB)和2mmol保护剂三辛基氧化膦(TOPO)混合于带回流装置的三颈瓶中;在80℃下用氮气进行脱气处理;将反应液加热到220℃保温30min,再将反应温度提高到280℃孵育15min;反应完成后冷却至室温;
在三口烧瓶中加入40ml乙醇溶液(质量分数≥97%)与反应液混合均匀进行离心处理,离心转速10000rpm,离心时间10min,收集沉淀,并用无水乙醇反复清洗沉淀,得到Pd-Ni纳米材料;
将Pd-Ni纳米材料分散在50ml正己烷中;通过旋转蒸发仪旋干溶剂,得到固体Pd-Ni;称重,按3:7的比例量取载体Vulcan XC-72活性炭(粒径30nm)后置于圆形底瓶中,并分散在100ml正己烷中,超声处理25min;将Pd-Ni的正己烷溶液加入圆形底瓶,该混合物继续经过超声波作用30min;
经蒸发除去正己烷后,在300℃氮气气氛下利用高温管式炉煅烧2h,煅烧后自然冷却到室温,研磨得到最终的Pd-Ni多孔纳米笼材料。
将本实施例制得的Pd-Ni MCs催化材料置于扫描电子显微镜(型号FEI QuantaFEG 250)下观察,如图1所示,可以看到形成了纳米颗粒聚集体。
实施例2
一种Pd-Ni多孔纳米笼催化材料的制备方法,包括以下步骤:
将0.2mmol的金属钯前体乙酰丙酮钯(Pd(acac)2),0.2mmol的金属镍前体乙酰丙酮镍(Ni(acac)2),0.88mmol的磷配体三苯基膦(TPP),1.5mmol表面活性剂四丁基溴化铵(TBAB)和3mmol保护剂三辛基氧化膦(TOPO)混合于带回流装置的三颈瓶中;在80℃下用氦气进行脱气处理;将反应液加热到220℃保温30min,再将反应温度提高到280℃孵育15min;反应完成后冷却至室温;
在三口烧瓶中加入40ml乙醇溶液(质量分数≥97%)与反应液混合均匀进行离心处理,离心转速10000rpm,离心时间10min,收集沉淀,并对沉淀采用无水乙醇反复清洗,得到Pd-Ni纳米材料;
将Pd-Ni纳米材料分散在50ml正己烷中;通过旋转蒸发仪旋干溶剂,得到固体Pd-Ni;称重,按3:7的比例量取Vulcan XC-72活性炭后置于圆形底瓶,并分散在100ml正己烷中,超声处理25min;将Pd-Ni的正己烷溶液加入圆形底瓶,该混合物继续经过超声波作用30min;
经蒸发除去正己烷后,在300℃氦气气氛下利用高温管式炉煅烧2h,煅烧后自然冷却到室温,研磨得到最终的Pd-Ni多孔纳米笼材料。
将本实施例制得的Pd-Ni MCs催化材料置于扫描电子显微镜(型号FEI QuantaFEG 250)下观察,如图2所示,可以看到形成了多孔纳米笼。
将本实施例制得的Pd-Ni MCs催化材料置于X射线衍射仪(德国Bruker D8ADVANCE)中进行分析,如图4所示,Pd-Ni MCs的主导相为面心立方(Fcc)晶体(图4a)。当材料不含Ni(acac)2时,根据Pd的PDF卡,Pd(111)、(200)和(220)峰精确定位于面心立方Pd的位置。然而,在Pd-Ni MCs中,Pd(200)和Pd(220)的峰位发生了偏移,分别为0.2%和0.3%,这表明多孔纳米笼中有Ni的掺入,即Pd-Ni合金材料(图4b和4c)。
使用常见的三电极系统(工作电极为玻碳电极,参比电极为饱和甘汞电极,对电极为铂丝电极)进行电化学测试。
在4mg催化剂中加入4μl Nafion(5%)、380μl乙醇和380μl水溶液中,充分混合均匀,取6μl滴到直径为3mm的玻碳电极表面,在自然状态下待溶液蒸干,制得表面负载有催化剂的工作电极。
利用电化学工作站进行循环伏安测试:
(1)将表面负载有催化剂的工作电极浸泡在KOH溶液中,以PdO的还原峰为计算依据,得到Pd原子发生氧化还原反应所需要的电荷Q,最后再根据ECSA公式计算出催化剂的电化学活性表面积。
(2)将表面负载有催化剂的工作电极浸泡在0.5mol/L KOH+0.5mol/L甲醇混合溶液,测试催化剂对甲醇的电氧化活性。
(3)将表面负载有催化剂的工作电极浸泡在0.5mol/L KOH+0.5mol/L甲醇混合溶液,测试催化剂在甲醇电氧化反应中的稳定性。
图5为本发明实施例1电氧化甲醇的循环伏安活性图(与商用Pd/C和PdNi/C对比)。在图中正(右)扫峰被归因于甲醇氧化为CO2,纵坐标比表面积活性用来评判氧化甲醇的效果。Pd-Ni MCs的比活性为3.2mA/cm2,是Pd35Ni1/C和Pd/C的8.9倍和7.0倍。
图6为本发明实施例1电氧化甲醇的多次循环伏安后活性损失图(与商用Pd/C、PdNi/C和PtRu/C对比)。多次循环CV的研究可直观观测到Pd-Ni MCs耐久电催化性能。2000圈周期后的归一化电流MCs仍可贡献91.4%的活性,优于Pd-Ni/C(67%)、Pd/C(10%)和Pt-Ru/C(800次后仅剩3%)。
实施例3
一种Pd-Ni多孔纳米笼催化材料的制备方法,包括以下步骤:
将0.2mmol的金属钯前体乙酰丙酮钯(Pd(acac)2),0.2mmol的金属镍前体乙酰丙酮镍(Ni(acac)2),0.88mmol的磷配体三苯基膦(TPP),1.5mmol表面活性剂四丁基溴化铵(TBAB)和4.5mmol保护剂三辛基氧化膦(TOPO)混合于带回流装置的三颈瓶中;在80℃下用氩气进行脱气处理;将反应液加热到220℃保温30min,再将反应温度提高到280℃孵育15min;反应完成后冷却至室温;
在三口烧瓶中加入40ml乙醇溶液(质量分数≥97%)与反应液混合均匀进行离心处理(离心转速10000rpm,离心时间10min),收集沉淀,并对沉淀采用无水乙醇反复清洗,得到Pd-Ni纳米材料;
将Pd-Ni纳米材料分散在50ml正己烷中;通过旋转蒸发仪旋干溶剂,得到固体Pd-Ni;称重,按3:7的比例量取Vulcan XC-72活性炭后置于圆形底瓶,并分散在100ml正己烷中,超声处理25min;将Pd-Ni的正己烷溶液加入圆形底瓶,该混合物继续经过超声波作用30min;
经蒸发除去正己烷后,在300℃氩气气氛下利用高温管式炉煅烧2h,煅烧后自然冷却到室温,研磨得到最终的Pd-Ni多孔纳米笼材料。
将本实施例制得的Pd-Ni MCs催化材料置于扫描电子显微镜(型号FEI QuantaFEG 250)下观察,如图3所示,可以看到形成了熔融态的纳米笼。
利用氮气吸脱附实验,对不同掺量TOPO制备的材料的孔径分布进行了分析。当使用TOPO的用量分别为2.0、3.0或4.5mmol时,Brunauer-Emmett-Teller(BET)比表面积分别为54.4、72.1或101.4m2/g(表1);基于Barrett-JoynerHalenda(BJH)法的孔径分布分析表明,孔隙大小分别为76.3、92.2和97.9nm(图7)。
表1实施例1-3制得的Pd-Ni MCs的氮气吸脱附总结表
结合扫描电镜和氮气吸脱附实验,结果表明实施例1、2、3制得的不同材料因条件的改变发生了结构上的规律性变化。
实施例4
一种Pd-Ni多孔纳米笼催化材料的制备方法,包括以下步骤:
将0.2mmol的金属钯前体氯化钯,0.2mmol的金属镍前体氯化镍,0.88mmol的磷配体三苯基膦,1.5mmol表面活性剂十六烷基三甲基溴化铵和4.5mmol保护剂三辛基膦混合于带回流装置的三颈瓶中;在80℃下用氮气进行脱气处理;将反应液加热到220℃保温30min,再将反应温度提高到280℃孵育15min;反应完成后冷却至室温;
在三口烧瓶中加入40ml乙二醇溶液与反应液混合均匀进行离心处理(离心转速8000rpm,离心时间15min),收集沉淀,并对沉淀采用无水乙醇反复清洗,得到Pd-Ni纳米材料;
将Pd-Ni纳米材料分散在50ml甲苯中;通过旋转蒸发仪旋干溶剂,得到固体Pd-Ni;称重,按3:7的比例量取二氧化硅后置于圆形底瓶,并分散在100ml甲苯中,超声处理25min;将Pd-Ni的正己烷溶液加入圆形底瓶,该混合物继续经过超声波作用30min;
经蒸发除去正己烷后,在400℃氮气气氛下利用高温管式炉煅烧3h,煅烧后自然冷却到室温,研磨得到最终的Pd-Ni/SiO2多孔纳米笼材料。
实施例5
一种Pd-Ni多孔纳米笼催化材料的制备方法,包括以下步骤:
将0.2mmol的金属钯前体硫酸钯,0.2mmol的金属镍前体硫酸镍,0.88mmol的磷配体氧化膦,1.5mmol表面活性剂十六烷基三甲基溴化铵和4.5mmol保护剂三辛基膦混合于带回流装置的三颈瓶中;在80℃下用氮气进行脱气处理;将反应液加热到220℃保温30min,再将反应温度提高到280℃孵育15min;反应完成后冷却至室温;
在三口烧瓶中加入40ml丙醇溶液与反应液混合均匀进行离心处理(离心转速1000rpm,离心时间30min),收集沉淀,并对沉淀采用无水乙醇反复清洗,得到Pd-Ni纳米材料;
将Pd-Ni纳米材料分散在50ml丙酮中;通过旋转蒸发仪旋干溶剂,得到固体Pd-Ni;称重,按3:7的比例量取氧化铝后置于圆形底瓶,并分散在100ml丙酮中,超声处理25min;将Pd-Ni的正己烷溶液加入圆形底瓶,该混合物继续经过超声波作用30min;
经蒸发除去正己烷后,在600℃氮气气氛下利用高温管式炉煅烧2.5h,煅烧后自然冷却到室温,研磨得到最终的Pd-Ni/Al2O3多孔纳米笼材料。
实施例6
一种Pd-Ni多孔纳米笼催化材料的制备方法,包括以下步骤:
将0.2mmol的金属钯前体氯化钯,0.2mmol的金属镍前体硫酸镍,0.88mmol的磷配体氧化膦,1.5mmol表面活性剂十二烷基三甲基溴化铵和4.5mmol保护剂甲硼烷-叔丁胺络合物混合于带回流装置的三颈瓶中;在80℃下用氮气进行脱气处理;将反应液加热到220℃保温30min,再将反应温度提高到280℃孵育15min;反应完成后冷却至室温;
在三口烧瓶中加入40ml丙二醇溶液与反应液混合均匀进行离心处理(离心转速10000rpm,离心时间2min),收集沉淀,并对沉淀采用无水乙醇反复清洗,得到Pd-Ni纳米材料;
将Pd-Ni纳米材料分散在50ml二氯甲烷中;通过旋转蒸发仪旋干溶剂,得到固体Pd-Ni;称重,按3:7的比例量取碳纳米管后置于圆形底瓶,并分散在100ml二氯甲烷中,超声处理25min;将Pd-Ni的正己烷溶液加入圆形底瓶,该混合物继续经过超声波作用30min;
经蒸发除去正己烷后,在200℃氮气气氛下利用高温管式炉煅烧5h,煅烧后自然冷却到室温,研磨得到最终的Pd-Ni/C多孔纳米笼材料。
Claims (10)
1.一种Pd-Ni多孔纳米笼催化材料的制备方法,其特征在于,包括以下步骤:(1)将一定量的金属钯前体、金属镍前体、磷配体、表面活性剂、保护剂和溶剂进行混合,在惰性气体氛围中搅拌并加热,反应完成后冷却至室温,得到Pd-Ni,即组分A;
(2)用有机溶剂A洗涤组分A表面残留的有机物,离心,收集沉淀,得到Pd-Ni纳米材料,即组分B;
(3)将组分B分散在有机溶剂B中,减压蒸除溶剂,得到固体Pd-Ni,称重后按预定的比例与载体X超声负载,减压蒸除溶剂,得到负载型的Pd-Ni/X,即组分C;
(4)将组分C置于管式炉内,在惰性气体氛围中煅烧,煅烧温度为200~600℃,煅烧时间为2~5h,煅烧后自然冷却到室温,研磨制得Pd-Ni多孔纳米笼材料。
2.根据权利要求1所述的Pd-Ni多孔纳米笼催化材料的制备方法,其特征在于,所述金属钯前体为乙酰丙酮钯、氯化钯、醋酸钯、四三苯基膦合钯、草酸钯、硫酸钯、磷酸钯中的一种或多种;所述金属镍前体为乙酰丙酮镍、氯化镍、醋酸镍、草酸镍、硫酸镍、磷酸镍中的一种或多种。
3.根据权利要求1所述的Pd-Ni多孔纳米笼催化材料的制备方法,其特征在于,所述磷配体为三苯基膦、氧化膦中的一种或多种。
4.根据权利要求1所述的Pd-Ni多孔纳米笼催化材料的制备方法,其特征在于,所述表面活性剂为季铵盐型、脂肪胺型、氨基酸型、甜菜碱型、磷脂中的一种或多种;所述保护剂为三辛基氧化膦、三辛基膦、甲硼烷-叔丁胺络合物中的一种或多种。
5.根据权利要求1所述的Pd-Ni多孔纳米笼催化材料的制备方法,其特征在于,所述有机溶剂A为甲醇、乙醇、丙醇、丁醇、乙二醇、丙二醇、丁二醇中的一种或多种;所述有机溶剂B为甲苯、乙苯、二甲苯、正己烷、戊烷、丁烷、二氯甲烷、三氯甲烷、四氯化碳、乙醚、丙醚、四氢呋喃、丙酮、丁酮、二甲基亚砜、二甲基甲酰胺、乙胺、乙醇胺、二乙醇胺、三乙醇胺和三乙胺中的一种或多种。
6.根据权利要求1所述的Pd-Ni多孔纳米笼催化材料的制备方法,其特征在于,步骤(3)中,所述载体X为Vulcan XC-72活性炭、SiO2、Al2O3、碳纳米管中的一种。
7.根据权利要求1所述的Pd-Ni多孔纳米笼催化材料的制备方法,其特征在于,步骤(2)中,所述离心转速为1000~10000rpm,离心时间为2~30min。
8.权利要求1~7任一项所述制备方法获得的Pd-Ni多孔纳米笼催化材料。
9.权利要求1~7任一项所述制备方法获得的Pd-Ni多孔纳米笼催化材料在制备直接醇类燃料电池阳极催化剂中的应用。
10.权利要求1~7任一项所述制备方法获得的Pd-Ni多孔纳米笼催化材料在制备电解水析氢吸氧反应催化剂中的应用。
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