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通过牺牲模板法由金属有机框架衍生的碳嵌入镍纳米催化剂用于糠醛高效加氢制四氢糠醇

Carbon-embedded Ni nanocatalysts derived from MOFs by a sacrificial template method for efficient hydrogenation of furfural to tetrahydrofurfuryl alcohol.

作者信息

Su Yanping, Chen Chun, Zhu Xiaoguang, Zhang Yong, Gong Wanbing, Zhang Haimin, Zhao Huijun, Wang Guozhong

机构信息

Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, CAS Center for Excellence in Nanoscience, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, P. R. China.

出版信息

Dalton Trans. 2017 May 16;46(19):6358-6365. doi: 10.1039/c7dt00628d.

DOI:10.1039/c7dt00628d
PMID:28463366
Abstract

We report a fast and simple method for the synthesis of Ni-based metal-organic-frameworks (Ni-MOFs). Due to the existence of nickel ions and an organic ligand, the MOFs are employed as a sacrificial template for the facile preparation of carbon-embedded Ni (Ni/C) catalysts by a direct thermal decomposition method. The obtained Ni/C catalysts exhibit excellent catalytic activity for selectively transforming furfural (FAL) to tetrahydrofurfuryl alcohol (THFOL) due to the Ni nanoparticles (NPs) embedded uniformly in the ligand-derived carbon. The exemplified results illustrate that the catalytic performance of the Ni/C catalyst is greatly affected by the calcination conditions (temperature and time), composition of the Ni-MOF precursor and the catalysis conditions. The conversion of FAL and selectivity of THFOL both reached 100% under the conditions of 120 °C, 1 MPa H pressure and 120 min of hydrogenation over the Ni/C-500 catalyst, derived from the pyrolysis of Ni-MOFs (Ni : BTC mole ratio of 1.0) at 500 °C for 120 min, which exhibits an average nanoparticle size of ∼14 nm and uniform dispersion, and the highest BET surface area (∼92 m g) among all investigated Ni/C catalysts. This facilely prepared heterogeneous catalyst would be very promising for the replacement of noble metal catalysts for the efficient catalytic conversion of biomass-derived feedstocks into value-added chemicals.

摘要

我们报道了一种快速简便的合成镍基金属有机框架材料(Ni-MOFs)的方法。由于镍离子和有机配体的存在,这些MOFs被用作牺牲模板,通过直接热分解法轻松制备碳包覆镍(Ni/C)催化剂。所得的Ni/C催化剂表现出优异的催化活性,能够将糠醛(FAL)选择性转化为四氢糠醇(THFOL),这是因为镍纳米颗粒(NPs)均匀地嵌入配体衍生的碳中。示例结果表明,Ni/C催化剂的催化性能受煅烧条件(温度和时间)、Ni-MOF前驱体的组成以及催化条件的显著影响。在120℃、1MPa氢气压力和120分钟氢化条件下,由Ni-MOFs(Ni∶BTC摩尔比为1.0)在500℃热解120分钟得到平均纳米颗粒尺寸约为14nm且分散均匀、在所有研究的Ni/C催化剂中具有最高BET表面积(约92m²/g)的Ni/C-500催化剂上,FAL的转化率和THFOL的选择性均达到100%。这种简便制备的多相催化剂对于替代贵金属催化剂将生物质衍生原料高效催化转化为增值化学品具有很大的前景。

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