物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2015年
1期
137-144
,共8页
金属有机骨架材料%镍%载体%前驱体%硝基苯加氢
金屬有機骨架材料%鎳%載體%前驅體%硝基苯加氫
금속유궤골가재료%얼%재체%전구체%초기분가경
Metal-organic framework%Nickel%Support%Precursor%Nitrobenzene hydrogenation
以MIL-53(Al)、MIL-96(Al)和MIL-120(Al)(MIL： Material Institute of Lavorisier)三种金属有机骨架材料为载体，采用浸渍法制备了负载廉价金属镍纳米颗粒的催化剂。将其用于催化硝基苯加氢合成苯胺反应，发现以MIL-53(Al)为载体制得的催化剂表现出优异的催化性能。采用不同的镍前驱体，如硝酸镍、醋酸镍、乙二胺合镍，制备了一系列Ni/MIL-53(Al)催化剂。通过X射线衍射、傅里叶变换红外光谱、电感耦合等离子体、N2物理吸附、H2程序升温还原、透射电镜等技术对其进行了表征，研究了镍前驱体对金属-载体相互作用、镍颗粒尺寸以及分散程度的影响。结果表明：以乙二胺合镍为镍前驱体制得的催化剂具有金属-载体相互作用适中、镍纳米颗粒更小(4-5 nm)和分布更均匀的特点，在硝基苯加氢反应中表现出优异的催化性能，硝基苯转化率达到100%。回收重复使用5次后，此催化剂仍保持催化活性，硝基苯转化率达92%。
以MIL-53(Al)、MIL-96(Al)和MIL-120(Al)(MIL： Material Institute of Lavorisier)三種金屬有機骨架材料為載體，採用浸漬法製備瞭負載廉價金屬鎳納米顆粒的催化劑。將其用于催化硝基苯加氫閤成苯胺反應，髮現以MIL-53(Al)為載體製得的催化劑錶現齣優異的催化性能。採用不同的鎳前驅體，如硝痠鎳、醋痠鎳、乙二胺閤鎳，製備瞭一繫列Ni/MIL-53(Al)催化劑。通過X射線衍射、傅裏葉變換紅外光譜、電感耦閤等離子體、N2物理吸附、H2程序升溫還原、透射電鏡等技術對其進行瞭錶徵，研究瞭鎳前驅體對金屬-載體相互作用、鎳顆粒呎吋以及分散程度的影響。結果錶明：以乙二胺閤鎳為鎳前驅體製得的催化劑具有金屬-載體相互作用適中、鎳納米顆粒更小(4-5 nm)和分佈更均勻的特點，在硝基苯加氫反應中錶現齣優異的催化性能，硝基苯轉化率達到100%。迴收重複使用5次後，此催化劑仍保持催化活性，硝基苯轉化率達92%。
이MIL-53(Al)、MIL-96(Al)화MIL-120(Al)(MIL： Material Institute of Lavorisier)삼충금속유궤골가재료위재체，채용침지법제비료부재렴개금속얼납미과립적최화제。장기용우최화초기분가경합성분알반응，발현이MIL-53(Al)위재체제득적최화제표현출우이적최화성능。채용불동적얼전구체，여초산얼、작산얼、을이알합얼，제비료일계렬Ni/MIL-53(Al)최화제。통과X사선연사、부리협변환홍외광보、전감우합등리자체、N2물리흡부、H2정서승온환원、투사전경등기술대기진행료표정，연구료얼전구체대금속-재체상호작용、얼과립척촌이급분산정도적영향。결과표명：이을이알합얼위얼전구체제득적최화제구유금속-재체상호작용괄중、얼납미과립경소(4-5 nm)화분포경균균적특점，재초기분가경반응중표현출우이적최화성능，초기분전화솔체도100%。회수중복사용5차후，차최화제잉보지최화활성，초기분전화솔체92%。
The metal-organic frameworks (MOFs), MIL-53(Al), MIL-96(Al), and MIL-120(Al) (MIL: Material Institute of Lavorisier) were synthesized and used as supports, to incorporate low-cost Ni nanoparticles (NPs) by wet impregnation. The samples were used as catalysts in the hydrogenation of nitrobenzene to aniline. The catalyst prepared with MIL- 53(Al) as a support exhibited excel ent catalytic performance. Ni/MIL- 53(Al) heterogeneous catalysts were prepared using nickel nitrate, nickel acetate, and nickel ethanediamine as precursors. Characterization by powder X-ray diffraction, Fourier-transform infrared spectroscopy, inductively coupled plasma spectroscopy, N2 sorption measurements, H2- temperature programmed reduction, and transmission electron microscopy showed that the Ni precursor affected the metal-support interaction, Ni particle size and particle distribution. The catalyst prepared using nickel ethanediamine possessed moderate metal-support interactions, smaller Ni nanoparticles (4-5 nm), and a high Ni distribution. This resulted in its superior catalytic activity, with 100% conversion of nitrobenzene in the hydrogenation. The Ni/MIL-53(Al) catalyst retained its catalytic activity after five cycles, and exhibited a nitrobenzene conversion of ~92%.
