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Cobalt carbide nanoprisms for direct production of lower olefins from syngas

Nature volume 538, pages 84–87 (2016)Cite this article

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Abstract

Lower olefins—generally referring to ethylene, propylene and butylene—are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes1,2. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks3,4,5,6,7,8,9. The ‘Fischer–Tropsch to olefins’ (FTO) process has long offered a way of producing lower olefins directly from syngas—a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas3,4,5,6,7. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson–Schulz–Flory distribution, which is characterized by a maximum C2–C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2–C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

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Figure 1: Catalytic performance of the CoMn catalyst in the initial stages of the reaction.
Figure 2: TEM images of the CoMn catalysts after reaching steady state.
Figure 3: Energy profiles for pathways that lead to the formation of CH2CH2 and CH3CH3, on different surfaces of Co2C and Co.

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Acknowledgements

This work has been supported by the Natural Science Foundation of China (grants 21403278, 21403277, 21573271, 91545112), the Shanghai Municipal Science and Technology Commission, China (grants 15DZ1170500, 14ZR1444600), Shanxi Lu’an Coal Corporation Limited, the Ministry of Science and Technology of China (grant 2016YFA0202802) and the Chinese Academy of Sciences (grant QYZDB-SSW-SLH035, the Youth Innovation Promotion Association of CAS).

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Authors and Affiliations

  1. CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201203, PR China

    Liangshu Zhong, Fei Yu, Yunlei An, Yonghui Zhao, Yuhan Sun, Zhengjia Li, Tiejun Lin, Yanjun Lin, Xingzhen Qi, Yuanyuan Dai, Qun Shen & Hui Wang

  2. School of Environmental and Chemical Engineering, Shanghai University, Shanghai, 200444, PR China

    Fei Yu & Yunlei An

  3. School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201203, PR China

    Yuhan Sun

  4. School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, PR China

    Zhengjia Li

  5. University of the Chinese Academy of Sciences, Beijing, 100049, PR China

    Yuanyuan Dai & Jinsong Hu

  6. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, PR China

    Lin Gu & Shifeng Jin

  7. Beijing National Laboratory for Molecular Sciences, Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, PR China

    Jinsong Hu

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Contributions

L.Z. and Y.S. designed the study, analysed the data and wrote the paper. F.Y. and Y.A. prepared the samples and drafted the manuscript. Y.Z. performed DFT calculations. Z.L. and T.L. studied the promoter effect. Y.L., X.Q. and Y.D. performed catalytic evaluation. L.G., J.H., S.J., Q.S. and H.W. characterized the samples. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Liangshu Zhong or Yuhan Sun.

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The authors declare no competing financial interests.

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Reviewer Information

Nature thanks M. Claeys, A. Holmen and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Extended data figures and tables

Extended Data Figure 1 Distribution of products generated by the FTO process from syngas.

a, Product distribution according to the Anderson–Schulz–Flory (ASF) model. The vertical bar shows the calculated hydrocarbon distribution for a chain-growth probability (α) of 0.46, which provides the highest proportion of C2–C4 hydrocarbons. b, Hydrocarbon distribution according to the ASF model for chain-growth probabilities of 0.3, 0.4, 0.46, 0.5, 0.6 and 0.7. c–e, Typical product plots obtained using our CoMn catalyst (showing ln(Wn/n) versus n) when the reaction was performed under a H2/CO ratio of 2 (c), 1 (d) or 0.5 (e), at a temperature of 250 °C and a pressure of 1 bar. The chain-growth probabilities were obtained by fitting the results obtained for C3–7 using the ASF model.

Source data

Extended Data Figure 2 Stability test for the CoMn catalyst.

Reaction conditions: 250 °C, 3 bar, 6,000 ml h−1 gcat−1, H2/CO = 1. The selectivity of the indicated products remains more or less constant over more than 600 h.

Source data

Extended Data Figure 3 X-ray diffraction analysis of the CoMn catalyst at different times on-stream.

a–g, Results from refinement of the X-ray diffraction patterns of catalysts at 0 h (a), 2 h (b), 4 h (c), 10 h (d), 15 h (e), 20 h (f) and 150 h (g) (‘0 h’ refers to the catalyst after reduction). The graphs show the different phases of the catalyst (Co, Co2C, CoxMn1−xO and MnO) that are present at different times on-stream. h, Quantification of the refinement results on the basis of a full Rietveld analysis. NA, not available.

Source data

Extended Data Figure 4 Catalytic performance and structure of Co2C sphere-like nanoparticles.

a, Catalytic performance of Co2C sphere-like nanoparticles with time on-stream. b, XRD pattern, c, TEM image and d, high-resolution TEM image of Co2C sphere-like nanoparticles. The Co2C was prepared by carbonizing Co3O4 with pure CO at a temperature of 250 °C and at atmospheric pressure for 24 h. The reaction was performed at 250 °C, 1 bar, 2,000 ml h−1 gcat−1, H2/CO = 2. The calculated reaction rate for such Co2C sphere-like nanoparticles was 2.8 × 10−3 mol CO h−1 gcat−1 for a CO conversion of 9.5%. The calculated reaction rate for the Co2C catalyst in ref. 18 was 8.9 × 10−4 mol CO h−1 gcat−1 (CO conversion of 2%, at 20 bar, 220 °C, 3,000 ml h−1 gcat−1, H2/CO = 2). The calculated reaction rate for the studied Co2C nanoprism catalyst was 9.4 × 10−3 mol CO h−1 gcat−1 (CO conversion of 31.8% at 250 °C, 1 bar, 2,000 ml h−1 gcat−1, H2/CO = 2).

Source data

Extended Data Figure 5 TEM images of the CoMn catalyst after reaching steady state.

a–d, Low-resolution images (a, b) and high-resolution images (c, d) showing Co2C nanoprisms (parallelepiped structures) and sphere-like nanoparticles of MnO or CoxMn1−xO. e, Scanning TEM image. f–h, EDX mapping of Co (f), Mn (g) and Co plus Mn (h). For the nanoprism particles, a higher concentration of Co and a very low concentration of Mn was observed; these results, coupled with the high-resolution TEM images of the lattice fringes, suggest that such nanoprisms are composed of Co2C. For most of the sphere-like nanoparticles, both Co and Mn were observed, indicating that these particles are composed of CoMn composite oxide (CoxMn1−xOy). For some of the sphere-like nanoparticles, only Mn was observed and the concentration of Co was very low, suggesting that these particles are composed of MnO.

Extended Data Figure 6 TEM images of the CoMn catalyst at different reaction times.

a–c, Low-resolution TEM images at 2 h (a), 10 h (b) and 20 h (c). d–f, Corresponding high-resolution TEM images. For the samples removed at 2 h, it was hard to find Co2C nanoprisms; the shape of the Co2C seemed to be irregular. At 10 h, the Co2C nanostructure seemed to be nanoprism-like, with a parallepiped shape, and the lattice fringes suggested the exposed facet of (101) geometry, although the shape was not perfect. At 20 h, Co2C nanoprisms were found.

Extended Data Figure 7 TEM, XRD and ICP analyses of the effects of Na and Mn on different Co-based catalysts.

a–c, Low-resolution TEM images of spent CoMn-A (a), CoMn-Na (b) and Co3O4 (c). d–f, Corresponding high-resolution TEM images. g, XRD patterns of spent CoMn-A, CoMn-Na and Co3O4 catalysts. h, Elemental analysis of the fresh catalysts by ICP mass spectrometry. To produce CoMn-A, CoMn catalyst (Co/Mn = 2/1) was precipitated with (NH4)2CO3. To produce CoMn-Na, CoMn catalyst (Co/Mn = 2/1) was precipitated with (NH4)2CO3 and impregnated with about 0.4 wt% of Na using Na2CO3. CoMn was prepared by precipitating CoMn catalyst (Co/Mn = 2/1) with Na2CO3. Co3O4 was prepared by precipitation using Na2CO3. We found CoMn-A to include sphere-like, face-centred-cubic, metallic Co nanoparticles. We detected Co2C nanoprisms in CoMn-Na, while Co3O4 comprised larger Co2C sphere-like nanoparticles.

Source data

Extended Data Figure 8 Catalytic performance and product distribution of different catalysts.

a, Performance of different catalysts. b–d, Product plot (ln(Wn/n) versus n) for CoMn-A (b), CoMn-Na (c) and Co3O4 (d) catalysts. CoMn-A, CoMn-Na and Co3O4 were prepared as described in Extended Data Fig. 7. MnO2 was prepared by precipitation using Na2CO3. Reaction conditions: 1 bar, 250 °C, 2,000 ml h−1 gcat−1, H2/CO = 2. There was no detectable CO conversion by MnO2.

Source data

Extended Data Figure 9 DFT study on different surfaces.

a, Top views (upper panels) and side views (bottom panels) of different surfaces: from left to right, Co2C(101), Co2C(020), Co2C(111) and Co(0001). Blue, Co atom; grey, C atom. b, Energy profiles for CH4 formation on Co2C(101), Co2C(020), Co2C(111) and Co(0001) surfaces. The intermediate state of CH2 + 2H is chosen as the zero point for all of the energy profiles.

Source data

Extended Data Table 1 Catalytic performance of CoMn catalyst in the initial stages of the FTO reaction
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Zhong, L., Yu, F., An, Y. et al. Cobalt carbide nanoprisms for direct production of lower olefins from syngas. Nature 538, 84–87 (2016). https://doi.org/10.1038/nature19786

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