氮掺杂碳纳米笼固载钌纳米粒子的费托合成性能

doi:10.6023/A22030139

摘要/Abstract

费托合成可以将来源广泛的合成气转化为低碳烯烃和燃油等高附加值化学品, 是后石油时代的重要化工过程, 而发展高性能的催化剂是该工程产业化的关键. 以具有高比表面积和高氮含量的氮掺杂碳纳米笼(NCNC)为载体, 采用等体积浸渍法制备了Ru的质量分数为20%的Ru/NCNC催化剂, 所得Ru纳米颗粒均匀分散, 相比于未掺杂碳纳米笼负载的Ru催化剂(Ru/CNC), Ru纳米粒子尺寸更小且分布更集中. Ru/NCNC催化剂展现出优异的费托合成催化性能, 在0.5 MPa和220 ℃的温和条件下, 具有高的催化活性、高的C₅₊选择性(55.7%)、低的CH₄选择性(13.5%)和高的催化稳定性(60 h, CO转化率保持在≈33%), 显著优于Ru/CNC. 这可归因于N掺杂提高了Ru活性中心的数量和电子态密度以及表面碱性, 增强了金属-载体相互作用, 进而提高Ru/NCNC的催化活性、长链产物(C₅₊)选择性、抗烧结能力和催化稳定性. 本研究提供了一条通过掺杂碳载体设计提升费托合成催化剂性能的有效策略.

关键词: 费托合成, 钌, 氮掺杂碳纳米笼, 锚定作用, 金属-载体相互作用

Fischer-Tropsch synthesis (FTS) is an important heterogeneous catalytic process in post-petroleum era, which can convert syngas from natural gas, coals and biomass into high value-added chemicals such as low-carbon olefins and fuel oil. In general, the target products have low selectivity owing to the limitation of Anderson-Schulz-Flory distribution law. The selectivity of target products can be adjusted by controlling the composition and structure of catalysts, supports and promotors. Carbon materials have been used as the remarkable supports due to the merits of rich morphological structure, high specific surface area, easily-regulated surface properties by doping and modification, good stability and so forth. Herein, taking advantage of the high specific surface area and high N content of N-doped carbon nanocages (NCNC), Ru/NCNC catalysts is prepared by equal volume impregnation method. As compared, Ru/CNC catalyst is prepared using undoped carbon nanocages (CNC) as support. Ru nanoparticles with ca. 3.9 nm in size were homogeneously dispersed on NCNC. The Ru nanoparticles on NCNC have the smaller sizes and more narrow distribution than those on CNC owing to the anchoring effect of nitrogen dopants for the former. The Ru/NCNC catalyst showed excellent catalytic performance, including good catalytic activity, high selectivity of C₅₊ products (55.7%), low selectivity of CH₄ (13.5%) and high stability (60 h, CO conversion maintained at the level of ≈33%), evidently surpassing Ru/CNC. Such excellent FTS performance of Ru/NCNC can be attributed to the following reasons. (i) N doping increases the number of catalytic centers and density of electronic states of metallic Ru, and subsequently improving the catalytic activity, inhibiting the hydrogenation of intermediate products, increasing the chain growth possibility, and finally producing more long-chain products (C₅₊). (ii) N doping enhances the surface alkalinity of nanocages and then is conducive to inhibiting the formation of CH₄. (iii) The metal-support interaction is enhanced due to the participation of N, leading to significantly improved anti-sintering ability and catalytic stability. This finding provides a promising strategy for developing high-performance FTS catalysts via designing N-doped carbon supports.

Key words: Fischer-Tropsch synthesis, ruthenium, nitrogen-doped carbon nanocage, anchoring effect, metal-support interaction

引用此文

齐志豪, 高福杰, 周常楷, 曾誉, 吴强, 杨立军, 王喜章, 胡征. 氮掺杂碳纳米笼固载钌纳米粒子的费托合成性能[J]. 化学学报, 2022, 80(8): 1100-1105.

Zhihao Qi, Fujie Gao, Changkai Zhou, Yu Zeng, Qiang Wu, Lijun Yang, Xizhang Wang, Zheng Hu. Ruthenium Nanoparticles Anchored on Nitrogen-Doped Carbon Nanocages for Fischer-Tropsch Synthesis[J]. Acta Chimica Sinica, 2022, 80(8): 1100-1105.

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图/表 5

图1. 碳基纳米笼负载Ru催化剂的形貌和结构表征 (a) NCNC的TEM和HRTEM照片. (b, c) Ru/NCNC和Ru/CNC的TEM和HRTEM照片以及粒子分布统计图. (d) Ru/NCNC, Ru/CNC, NCNC和CNC的XRD谱.

Figure 1. Morphology and structure characterization of Ru catalysts supported on carbon-based nanocages (a) TEM and HRTEM images of NCNC. (b, c) TEM and HRTEM images and particle size distributions of Ru/NCNC and Ru/CNC. (d) XRD patterns of Ru/NCNC, Ru/CNC, NCNC and CNC.

图2. Ru/NCNC、Ru/CNC和NCNC的XPS谱 (a) Ru/NCNC和NCNC的N 1s精细谱. (b) Ru/NCNC和Ru/CNC的Ru 3p精细谱

Figure 2. XPS spectra of Ru/NCNC, Ru/CNC and NCNC (a) Deconvolved N 1s spectra of Ru/NCNC and NCNC. (b) Deconvolved Ru 3p spectra of Ru/NCNC and Ru/CNC

Sample	CO Conversion/%	TOF	Selectivity/%					O/P
Sample	CO Conversion/%	TOF	CH₄	C₂~C₄	C₅~C₁₀	C₁₁~C₂₀	C₅₊	O/P
Ru/CNC	18.6	0.68	54.5	25.8	19.7	0	19.7	0.52
Ru/NCNC	33.8	0.90	13.5	30.8	48.0	7.7	55.7	3.39

表1. Ru/NCNC和Ru/CNC催化剂的费托合成性能

Table 1. FTS performance of Ru/NCNC and Ru/CNC

图3. Ru/NCNC和Ru/CNC的FTS产物分布 (a, b) Ru/NCNC和Ru/CNC的产物选择性对碳数n图. (c, d)相应的ln(Wn/n)对碳数n图, Wn是碳数为n产物的质量百分数.

Figure 3. Product distributions of FTS for Ru/NCNC and Ru/CNC catalysts (a, b) Plots of selectivity vs. carbon number (n) for Ru/NCNC and Ru/CNC. (c, d) Corresponding plots of ln(Wn/n) vs. carbon number (n) for Ru/NCNC and Ru/CNC. Wn is the mass percentage of carbon number (n).

图4. Ru/NCNC和Ru/CNC催化剂的FTS稳定性及反应60 h后的结构表征结果 (a) CO转化率随反应时间变化图. (b, c)相应的(HR)TEM和粒径分布统计图.

Figure 4. FTS stability of Ru/NCNC and Ru/CNC catalysts and their structure characterization after 60 h (a) Plot of CO conversion vs. reaction time. (b, c) Corresponding (HR)TEM images and particle size distribution.

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