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Acetylene hydrogenation to ethylene by water at low temperature on a Au/α-MoC catalyst

Nature Catalysis volume 6, pages 1005–1015 (2023)Cite this article

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Abstract

The hydrogenation of coal-based acetylene to ethylene is an important approach to establishing a non-oil route to ethylene production, yet it suffers from high H2 consumption as well as a high energy input. Here we report a H2-free acetylene hydrogenation process achieved by directly using water as the hydrogen source and low-cost CO as the oxygen acceptor over a Au/α-MoC catalyst. The process delivers over 99% acetylene conversion and a high ethylene selectivity of 83% at 80 °C, surpassing the hydrogenation process using H2 as the hydrogen source. Mechanistic studies have revealed that in situ-generated hydroxyl species from water dissociation at the boundary of Au and α-MoC, serving as mild reductants, enable the selective semi-hydrogenation of acetylene with residual O removed by CO. This process circumvents the need for H2 in the classical route and opens avenues for energy-efficient acetylene hydrogenation by water at low temperature.

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Fig. 1: The CO-H2O-AHE process and its reactivity.
Fig. 2: Structural and electronic characterization of the Au/α-MoC catalysts.
Fig. 3: Investigation of the CO-H2O-AHE mechanism.
Fig. 4: DFT calculations of the CO-H2O-AHE process.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information files or from the corresponding author on reasonable request. The atomic structures and vibrational frequencies for the intermediate states are available in the figshare repository (https://doi.org/10.6084/m9.figshare.22768451). Source data are provided with this paper.

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Acknowledgements

Financial support by the National Natural Science Foundation of China (grant nos. 21890753, 21988101, 22225204 and 22372019), the Strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDB36030200), the Key Research Program of Frontier Sciences of the Chinese Academy of Sciences (grant no. QYZDB-SSW-JSC020) and the Fundamental Research Funds for the Central Universities (DUT21LK09/82231014) is acknowledged. We thank the staff at the BL14W1 beamline of the Shanghai Synchrotron Radiation Facilities for assistance with the EXAFS and XANES measurements. We also thank C. Meng, W. Yu, Y. Tu and K. Zhu from DICP for help with the in situ XPS, TPD, XAS and NMR measurements.

Author information

Author notes

  1. These authors contributed equally: Rui Huang, Meihan Xia.

Authors and Affiliations

  1. State Key Laboratory of Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China

    Rui Huang, Meihan Xia, Yunlong Zhang, Chenxi Guan, Mingrun Li, Baibei Zhao, Xiaohui Hou, Yan Wei, Qiao Chen, Jingting Hu, Xiaoju Cui, Liang Yu & Dehui Deng

  2. School of Chemistry, Dalian University of Technology, Dalian, China

    Rui Huang, Chenxi Guan, Baibei Zhao, Xiaohui Hou, Yan Wei, Qiao Chen & Dehui Deng

  3. University of Chinese Academy of Sciences, Beijing, China

    Meihan Xia, Yunlong Zhang, Yao Wei, Zheng Jiang, Jingting Hu, Xiaoju Cui, Liang Yu & Dehui Deng

  4. Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, China

    Yao Wei & Zheng Jiang

  5. Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China

    Yao Wei & Zheng Jiang

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Contributions

D.D. conceived the project. R.H. carried out the experiments. M.X. and L.Y. performed the DFT calculations. Y.Z. and M.L. conducted the AC-HRTEM measurements. Yao Wei and Z.J. helped with the XAS analysis. C.G. and B.Z. helped with the kinetic measurements. X.H., Q.C., Yan Wei, J.H. and X.C. helped with other catalyst characterization. All authors contributed to the scientific discussion. R.H., M.X., L.Y. and D.D. wrote and revised the manuscript.

Corresponding authors

Correspondence to Liang Yu or Dehui Deng.

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Extended data

Extended Data Fig. 1 Screening of catalyst under different reaction conditions.

a,b, Reaction conditions: 30 mg catalyst, 80 °C, 3.2 MPa (CO/C2H2/Ar = 6:5:89), 15 ml H2O, 20 hours. c, In-situ catalytic cycle. Reaction conditions: 100 mg catalyst, 80 °C, 3.2 MPa (CO/C2H2/Ar = 6:5:89), 10 ml H2O. The reaction was cycled by charging new feed gas into the system without separating the catalyst and solution. TOF is calculated as specific mole rate of C2H4 production on per mole of Au. d, The reaction temperature and time were changed to 220 °C, and 2 hours with other conditions unchanged. e, ICP-OES results.1st and 5th mean the results after one or five cycles.

Source data

Extended Data Fig. 2 Bulk-phase structure characterizations of catalysts.

a, PXRD patterns of different catalysts before and after reaction. b,c, AC-HRTEM images and particle size distribution diagrams of 6Au/α-MoC (b) and 1Au/α-MoC (c) catalyst. It presents nearly the same size of α-MoC. The size of Au was measured by elemental mapping images in Extended Data Fig. 4.

Source data

Extended Data Fig. 3 Ex-situ and in-situ XAS spectra at the Au L3-edge of different catalysts.

a, Curve fitting parameters for Au L3-edge EXAFS for different samples. The distance of Au-Au and Au-Mo is from the crystal structure of [Au 1100138] and [Mo 4317354]; *: Average coordination number; #: distance between absorber and backscatter atoms; ǁ: difference of potential of sample and standard; ǂ: Debye-Waller factor. The data are not phase-corrected. Error bars represent the fitting error from EXAFS. b,c, Au L3-edge EXAFS (points) and the curvefit (line) for different samples in R space and k3-weighted k space. d,e, In-situ XANES (d) and Fourier-transform EXAFS spectra in the R-space (e) at the Au L3-edge for the 6Au/α-MoC catalyst during the CO-H2O-AHE reaction at 25, 80 and 100 °C. The inset shows the enlarged regions of the Au L3-edge absorption edge.

Source data

Extended Data Fig. 4 AC-HRTEM images and elemental mapping images of 6Au/α-MoC.

a,b AC-HRTEM images, c-f Elemental mapping images of Mo (c), Au (d), C (e), and O (f).

Extended Data Fig. 5 XPS of the Au/α-MoC catalysts with different Au loadings and the used 6Au/α-MoC catalyst.

a, Mo 3d5/2 XPS spectra of different catalysts. b, C 1s XPS spectra of catalysts. c, Element and component content of different catalysts fitted by XPS. Mo 3d5/2 XPS spectra (a) can be assigned to four components, which are carbide (MoC1-x), MoO2, oxycarbide (MoOxCy) and MoO3 at 228.6, 229.2, 230.1, 232.7 eV respectively22,39. C 1 s XPS spectra (b) can be deconvoluted into four components, which are carbide (MoC1-x), adventitious carbon contamination (C-C), C-O and C = O linkage at 283.4, 284.6, 286.4, and 288.3 eV respectively22,40. Au 4f7/2 XPS spectra (Fig. 2c) can be attributed to two components, which are Au0 with diameter larger than 3 nm and Auδ+ with diameter of 2 to 3 nm at 84.0 and 84.3 eV, respectively29,33,35.

Source data

Extended Data Fig. 6 Quasi in-situ XPS, DRIFT spectra and Pulse chemisorption of Au/α-MoC catalysts.

a, Quasi in-situ XPS of 6Au/α-MoC before (as-prepared) and after H2 reduction (30 ml min−1) at 300 °C, 0.1 MPa for 1 hour. The residual oxygen can be attributed to unreduced MoOx40,63. b, Comparison of in-situ DRIFT spectra for 15Au/α-MoC, 6Au/α-MoC, 1Au/α-MoC and α-MoC in CO (0.1 MPa) atmosphere. c, Competitive pulse chemisorption. The as-prepared (left) and H2-reduced (right) sample denote the catalyst before and after H2 reduction (300 °C,1 hour) followed by He purge (300 °C, 0.5 hour), respectively. Then the mixed gas of CO/C2H2/He (5/5/90, 0.1 MPa, 30 ml min−1) was pulsed through 10 mg of samples at 30 °C. d, TPD profiles of 6Au/α-MoC before and after H2 reduction at 300 °C for 1 hour. e, Schematic illustration for pulse chemisorption.

Source data

Extended Data Fig. 7 Kinetic measurements.

a,b, Kinetic isotope effect (KIE) of the CO-H2O-AHE reaction by replacing H2O or CO with D2O and 13CO, respectively. a, MS signals. b, Influence of KIE on the reaction rate determined by GC. Error bars represent the standard deviation from at least two independent measurements. c-f, Correlation between experimentally measured rC2H4 and simulated ones by assuming different rate-determining step (RDS) in the reaction model (See Supplementary Note 2).

Source data

Extended Data Fig. 8 Free energy profiles for oxygen adsorption and H2O dissociation on α-MoC(111) surface.

a, Differential adsorption energies of oxygen on α-MoC(111) surface referenced to O2 gas. b, Free energy profile for H2O dissociation to two OH* combining with a surface O* specie on the α-MoC(111) surface. c, Top and side views of the Au/α-MoC(111) model in Fig. 4d with 31 Au atoms on a 8 × 8 α-MoC slab. Cyan, grey, red and white spheres represent Mo, C, O and H atoms, respectively. d, The structures of the transition states in Fig. 4d.

Source data

Extended Data Fig. 9 DFT studies of the reactivity and selectivity.

a, Partial density of states (PDOS) for the C 2p in the adsorbed C2H4, O 2p in the adsorbed OH, and Mo 4d orbital of the corresponding adsorption sites labelled by dotted circles in the structure. b, Gibbs free paths for CH3CHO formation via Vinyl alcohol (CH2CHOH*) and CHCH3 intermediate. Gold, cyan, red, grey and white spheres represent Au, Mo, O, C and H atoms, respectively. c, Interaction energy between α-MoC and different metals. The interaction energy was calculated by (Esupported - EMoC – nμmetal)/m, in which Esupported and EMoC are the energies of the supported structure and the MoC support, respectively, and μmetal is the chemical potential of a metal atom in its bulk phase, n is the total number of metal atoms in the supported metal nanoparticle (that is 31), m is number of metal atoms bonding with the MoC surface (that is 19). The interaction energy implies the formation enthalpy of the interfacial structure, which reflects its relative thermodynamic stability.

Source data

Supplementary information

Supplementary Information

Supplementary Notes 1 and 2, Figs. 1 and 2, Tables 1–3 and references.

Supplementary Data 1

Vibrational frequencies of the transition states.

Supplementary Data 2

Optimized atomic structures of intermediate states.

Supplementary Data 3

Statistical source data for Supplementary Fig. 2.

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Huang, R., Xia, M., Zhang, Y. et al. Acetylene hydrogenation to ethylene by water at low temperature on a Au/α-MoC catalyst. Nat Catal 6, 1005–1015 (2023). https://doi.org/10.1038/s41929-023-01026-y

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