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Alkali ions secure hydrides for catalytic hydrogenation

Nature Catalysis volume 3, pages 703–709 (2020)Cite this article

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Abstract

Catalytic hydrogenation is one of the backbones of the chemical industry. Controlling the reaction behaviour of the activated hydrogen species over oxide-supported metal catalysts is essential. Aside from the expected addition to substrates, the activated hydrogen species would also destroy the active structures. Here we show that, with the assistance of alkali cations, the atomically dispersed Ru(iii) on Al2O3 exhibits enhanced performance in the hydrogenation of a broad range of substrates. The alkali cations facilitate the hydrogenation mediated by heterolytic hydrogen species, which not only restrain the hydride species from migrating to interfacial oxygen, thus suppressing the reduction and aggregation of ruthenium, but also stabilize the negatively charged transition states and intermediates through enhanced Columbic attraction. Distinctively, an inverse H/D isotope effect related to H2 splitting as the rate-determining step over the atomically dispersed ruthenium-catalysed hydrogenation is predicted and confirmed.

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Fig. 1: Catalysis performance and structure characterization.
Fig. 2: The critical roles of Na+ in securing hydrides and stabilizing the atomically dispersed Ru(iii).
Fig. 3: The mechanisms of catalytic hydrogenation over Ru(Na) and metallic ruthenium.

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Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request. The DFT structures can be found in Supplementary Data 1. Source data are provided with this paper.

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Acknowledgements

We thank the National Key R&D Program of China (grant nos. 2017YFA0207302, 2017YFA0207303), the NSF of China (grant nos. 21890752, 21731005, 21721001, 21573178, 21773192, 91845102) and the Fundamental Research Funds for the Central Universities (grant no. 20720180026) for financial support. N.F.Z. acknowledges support from the Tencent Foundation through the XPLORER PRIZE. We also thank the XAFS station (BL14W1) of the Shanghai Synchrotron Radiation Facility (SSRF).

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  1. The authors contributed equally: Ruixuan Qin, Lingyun Zhou.

Authors and Affiliations

  1. State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM, National & Local Joint Engineering Research Center for Preparation Technology of Nanomaterials, and National Engineering Laboratory for Green Chemical Productions of Alcohols–Ethers–Esters, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China

    Ruixuan Qin, Lingyun Zhou, Pengxin Liu, Kunlong Liu, Chaofa Xu, Yun Zhao, Gang Fu & Nanfeng Zheng

  2. Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Yue Gong & Lin Gu

  3. Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, China

    Nanfeng Zheng

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Contributions

R.X.Q. and L.Y.Z. were responsible for most of the investigations, methodology development, data collection and analysis, and writing the original manuscript. P.X.L., Y. G., K.L.L., C.F.X., Y.Z. and L.G. assisted with the data collection and analysis. N.F.Z. and G.F. were responsible for the conceptualization, funding and resources acquisition, supervising the project, and revising and editing the manuscript.

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Extended data

Extended Data Fig. 1 The atomic scale EELS of Ru(Na)-R.

The poor signal-to-noise ratio of the spectra was due to the difficulty to acquire the atomic-scale EELS of light element. The EELS in (b) is collected at the spots shown in (a). The broad peaks at ~23 eV in (b) is corelated to the bulk plasmon excitation of alumina33. Small bumps at ~23 eV located near the maxima of the spectra as highlighted in (c), should be related to the single-electron transition from the O 2p level that is perturbed by the vicinal Na ions34. The presence of both surface- and bulk-plasmon loss makes it difficult to identify these bumps straightforwardly. (d) Small bump highlighted at ~31.5 eV is attributed to the Na L2,3 edge signal, indicating the presence of Na ions nearby Ru species35. It should be noted that, due to the low intensities of the signals, Na was identified only with an approximate level of accuracy and that the assignment is supported by the literature36.

Source data

Extended Data Fig. 2 The computational models and XANES.

(a) Ru(H) and (b) Ru(Na), and (c) the comparison between the experimental XANES of Ru(Na)-R and calculated XANES of the theoretical Ru(Na) model. The inset shows the derivative XANES of both experimental and calculated XANES. The three peaks, A, B and C, correspond to the electronic transfer to the empty d (A) and p (B and C) orbitals, respectively, verifying that the theoretical model matches the experimental result very well.

Source data

Extended Data Fig. 3 The schematic diagram of the coulomb interaction.

The interaction takes place between the surface Na+ (or H+) with activated hydrogen species and corresponding electrostatic potential energy (a, b) II(II’) and (c, d) III(III’). The Ru(Na) surface displays a stronger Na+···Ha− attraction than that between H+ and Ha− on Ru(H), indicating that the surface Na+ can stabilize the hydride species. During the H transfer from Ru to O, the Ru(III) would be reduced to Ru(I) while the Ha− would be oxidized into Ha+. From viewpoint of electrostatic interaction, such a redox process is unfavorable because the attraction interaction between Ha− and Na+(H+) is replaced by the repulsion between Ha+ and Na+(H+) that is highlighted as the light red bars in (b) and (d). Considering Na+ is electronically more positive than H+, the presence of Na+ favors the formation Ha− while disfavors the formation of Ha+, nicely explaining why the introduction of Na+ can improve the reduced-sintering resistance of the atomically dispersed Ru catalysts.

Source data

Extended Data Fig. 4 Schematics of the interaction between surface Na+ and O in substrates during the hydrogenation catalysis.

The Bader charge (a.u.), bond length (Å) and electrostatic interaction energy (eV) of Na1 and the O1 illustrate the attraction between the surface Na1 and the O1 of hydrogenation intermediates and TSs, which favors the step-wise hydrogenation involved with Ru(Na).

Extended Data Fig. 5 The schematic diagram of isotopic effect.

(a) and (b) are inverse isotopic effect and normal kinetic isotopic effect for the rate-determining step of the hydrogenation reaction catalyzed by Ru(Na) and Ru(0001), respectively. The inverse kinetic isotopic effect (iKIE) is expected when (ΔZPE)TS is bigger than (ΔZPE)IS. Moreover, when the (ΔZPE)FS is also larger than (ΔZPE)IS, the inverse equilibrium isotope effect (iEIE) is also present.

Extended Data Fig. 6 The energy profiles of DMO hydrogenation on Ru(Na) (red) and Ru(H) (black) from DFT calculations.

The first step of DMO hydrogenation involves a transition state (ts3 or ts3’) by adding the H of Ru-Hδ− to the C of C = O of DMO and a hydrogenated intermediate (v or v’). The second step (>HC-O- to >HC-OH) is proceeded through a transition state (ts4 or ts4’) by adding the H of O-Hδ+ to the O of >HC-O- of hydrogenated intermediate (v or v’). For Ru(Na), the energy barriers of the first and second step of DMO hydrogenation were calculated to be 0.50 eV (ts3) and 1.00 eV (ts4), respectively. In comparison, Ru(H) need to overcome barriers of 1.10 eV (ts3’) and 0.43 eV (ts4’), respectively. From viewpoint of the effective barrier (1.00 eV vs 1.10 eV), DMO hydrogenation on Ru(Na) is expected more favorable than that on Ru(H).

Source data

Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–38, Tables 1–7, References 1–17.

Supplementary Data 1

The coordinate of DFT structures.

Source data

Source Data Fig. 1

Acetone hydrogenation turnover rate, Fourier-transform EXAFS, Wavelet transform EXAFS.

Source Data Fig. 2

XPS, FTIR, EPR and DFT energies of H2 activation and ruthenium reduction.

Source Data Fig. 3

DFT energies of acetone hydrogenation, Arrhenius plots and isotopic effect.

Source Data Extended Data Fig. 1

Na EELS

Source Data Extended Data Fig. 2

Experimental and calculated XANES.

Source Data Extended Data Fig. 3

Electrostatic potential energies.

Source Data Extended Data Fig. 6

Energies of DMO hydrogenation.

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Qin, R., Zhou, L., Liu, P. et al. Alkali ions secure hydrides for catalytic hydrogenation. Nat Catal 3, 703–709 (2020). https://doi.org/10.1038/s41929-020-0481-6

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