Abstract
The current thermocatalytic acetylene hydrogenation process suffers from the use of excessive hydrogen and the noble metal Pd, high temperatures and overhydrogenation. Here we report an electrocatalytic semihydrogenation strategy to selectively reduce acetylene impurities to ethylene under ambient conditions. For a crude ethylene flow that contains 1 × 104 ppm acetylene, electrochemically deposited Cu dendrites exhibited a high specific selectivity of 97%, continuous production of a polymer-grade ethylene stream (4 ppm acetylene) at a large space velocity of 9.6 × 104 ml gcat–1 h–1 and excellent long-term stability. Theoretical and operando electrochemical Raman investigations revealed that the outstanding electrocatalytic acetylene semihydrogenation performance of Cu catalysts originates from its exothermic acetylene adsorption and ethylene desorption. Meanwhile, the electrocatalytic semihydrogenation strategy is universally applicable for hydrogenating other alkyne impurities to produce polymer-grade olefins, for example, propylene and 1,3-butadiene.
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The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.
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Acknowledgements
This work was financially supported by the Fundamental Research Funds for the Central Universities (Grant no. 310201911cx028 (J.Z.) and no. 3102017jc01001 (Q.Z.)), the Natural Science Foundation of Shaanxi Province (no. 2020JQ-141 (J.Z.)) and the National Natural Science Foundation of China (no. 22005245 (J.Z.)). We thank the Analytical & Testing Center of Northwestern Polytechnical University for the SEM and TEM characterizations. We also acknowledge L. Cheng and H. Liu for the Raman tests at the School of Science, Xi’an Polytechnic University.
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J.Z. designed the experiments. J.B. conducted the catalyst syntheses and performance evaluations. J.B., Z.L., L.Z. and W.M. performed the related materials characterizations. T.W. conducted the theoretical calculations. J.Z. and J.B. co-wrote the manuscript. All the authors discussed the results and commented on the manuscript.
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J.Z. and J.B. are inventors on patent application CN112301373A submitted by Northwestern Polytechnical University, which covers the selective electrocatalytic acetylene semihydrogenation for the production of polymer-grade ethylene. The other authors declare no competing interests.
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Peer review information Nature Catalysis thanks Christian Durante, Rodrigo García-Muelas and Yujin Tong for their contribution to the peer review of this work.
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Supplementary Information
Supplementary Figs. 1–23 and Table 1.
Supplementary Video 1
Electrocatalytic acetylene semihydrogenation process was powered by the electricity generated from solar irradiation.
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Statistical Source Data for Supplementary Figure 13.
Supplementary Data 2
Statistical Source Data for Supplementary Figure 14.
Supplementary Data 3
Statistical Source Data for Supplementary Figure 17.
Supplementary Data 4
Atomic coordinates of the optimised computational models.
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Statistical Source Data.
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Statistical Source Data.
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Bu, J., Liu, Z., Ma, W. et al. Selective electrocatalytic semihydrogenation of acetylene impurities for the production of polymer-grade ethylene. Nat Catal 4, 557–564 (2021). https://doi.org/10.1038/s41929-021-00641-x
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DOI: https://doi.org/10.1038/s41929-021-00641-x
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