Synthesis of Co―N―C catalysts from a glucose hydrochar and their efficient hydrogenation of nitrobenzene
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摘要: 硝基苯选择性加氢反应是生产苯胺的重要方法,其关键在于开发一种具有高效选择性且低成本的绿色催化剂。本文基于葡萄糖水热炭化得到水热炭前驱体,结合尿素和硝酸钴一步高温热解制备了一种高度分散的富含Co纳米颗粒的氮掺杂多孔炭材料,将其作为催化剂用于硝基苯加氢反应。详细研究了热解温度对催化剂结构和催化活性的影响,证实了催化活性主要受催化剂的比表面积、Co掺杂量及其Co-Nx配位效应的影响。结果表明,将含10%Co源制备的前驱体800 °C热解得到的催化剂(Co@NCG-800)表现出优异的硝基苯催化加氢性能,在以异丙醇为溶剂、100 °C和1 MPa氢压下反应2.5 h时可实现硝基苯的转化,苯胺选择性高达99%。催化剂循环使用6次后的硝基苯转化率和苯胺选择性几乎保持不变。优异的循环稳定性能可归因于多孔炭材料中的氮元素和Co纳米颗粒的强相互作用,同时磁性Co纳米颗粒使得催化剂具有较好的分离特性和重复使用性。Abstract: A low-cost, green catalyst for nitrobenzene (NB) hydrogenation is needed for aniline production. We report the preparation of highly-dispersed Co particles supported on N-doped carbons by the hydrothermal treatment of glucose, followed by the pyrolysis of a mixture of urea, glucose hydrochar and cobalt nitrate in one-pot. The effect of the pyrolysis temperature on the microstructure of the catalysts was studied. Results indicated that the activity for NB hydrogenation was highly affected by the surface area, Co-loading level and Co-Nx coordination in the catalysts. Co@NCG-800 pyrolyzed at 800 °C with 10% Co in the precursor had extraordinary activity for NB hydrogenation, achieving full conversion and 99% aniline selectivity in isopropanol at 100 °C and 1 MPa H2 pressure for 2.5 h. NB conversion and aniline selectivity over the catalysts remained almost unchanged after six recycles, due to the strong coordination between the N- and Co-species. The reaction system showed not only a high NB activity but also a green and durable catalytic process, with easy operation, easy separation and catalyst reusability.
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Key words:
- Biomass glucose /
- Hydrothermal /
- Co-N-C catalysts /
- Nitrobenzene hydrogenation
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Table 1. Porous parameters for these catalysts obtained from different conditions
Catalysts [a]SBET
(m2/g)[b]Vt
(cm3/g)[c]Vmeso
(cm3/g)[d]Dave
(nm)NCG-800 204 0.16 0.13 3.19 10%Co@NCG-600 42 0.08 0.07 7.24 10%Co@NCG-700 170 0.14 0.11 3.42 10%Co@NCG-800 273 0.23 0.16 3.30 10%Co@NCG-900 196 0.19 0.14 3.92 5%Co@NCG-800 294 0.35 0.26 4.75 15%Co@NCG-800 227 0.30 0.24 5.23 Note: [a] Surface areas;
[b] Total pore volumes;
[c] Mesopore volumes for pores larger than 1.7 nm;
[d] Average pore sizes determined by 4 V/A method.Table 2. NB hydrogenation over catalysts under conditions of 120 °C and 1 MPa H2 with reaction time up to 3 h
Entry Catalysts Conversion (%) Selectivity
(%)0 Blank 0 0 1 G-HTC 0 0 2 NCG-800 11.0 >99 3 10%Co@NCG-600 86.0 >99 4 10%Co@NCG-700 95.4 >99 5 10%Co@NCG-800 100 >99 6 10%Co@NCG-900 93.7 >99 -
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