Isomorphous substitution in CaAl-hydrotalcite to construct high density single-atom catalysts for selective N-Heteroarene hydrogenation

doi:10.1016/S1872-2067(24)60217-2

Abstract

Abstract:

Metal oxides as support for constructing precious metal single-atom catalysts hold great promise for a wide range of industrial applications, but achieving a high-loading of thermally stable metal single atoms on such supports has been challenging. Herein, we report an innovative strategy for the fabrication of high-density single-atoms (Rh, Ru, Pd) catalysts on CaAl-layered double hydroxides (CaAl-LDH) via isomorphous substitution. The Rh species have occupied Ca²⁺ vacancies within CaAl-LDH laminate by ion-exchange, facilitating a substantial loading of isolated Rh single-atoms. Such catalysts displayed superior performance in the selective hydrogenation to quinoline, pivotal for liquid organic hydrogen storage, and the universality for the hydrogenation of N-heterocyclic aromatic hydrocarbons was also verified. Combining the experimental results and density functional theory calculations, the pathway of quinoline hydrogenation over Rh₁CaAl-LDH was proposed. This synthetic strategy marks a significant advancement in the field of single-atom catalysts, expanding their horizons in green chemical processes.

Key words: Isomorphous substitution, High-loading, Single‐atom catalyst, Selective hydrogenation

Jieting He, Yu Liang, Binbin Zhao, Lei Liu, Qian He, Dingsheng Wang, Jinxiang Dong. Isomorphous substitution in CaAl-hydrotalcite to construct high density single-atom catalysts for selective N-Heteroarene hydrogenation[J]. Chinese Journal of Catalysis, 2025, 70: 353-362.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60217-2

https://www.cjcatal.com/EN/Y2025/V70/I3/353

Figures/Tables 6

Fig. 1. (a) Illustration scheme of synthetic procedure of 1Rh1CaAl-LDH catalyst. (b) The concentration of Ca ions and Rh ions in solution. (c) content of Rh in 1Rh1CaAl-LDH catalyst of exchange using CaAl-LDH.

Fig. 2. Structural characterization of single-atom Rh with xRh1CaAl-LDH. (a) XRD patterns of CaAl-LDH and xRh1CaAl-LDH samples. (b) In-situ DRIFTS spectra of CO adsorbed on xRh1CaAl-LDH catalysts. (c) Nitrogen adsorption-desorption isotherms of the catalysts. HRTEM image of 1Rh1CaAl-LDH (d) and 4Rh1CaAl-LDH (e). (f) STEM-EDS elemental mapping images of 4Rh1CaAl-LDH. The k2-weighted Fourier transform spectra in R space (g) and Rh K-edge XANES spectra (h) of catalysts. (i) Wavelet transform (WT) of the EXAFS spectrum of 4Rh1CaAl-LDH.

Fig. 3. Rh 3d (a) and Ca 2p (b) XPS spectra of 1Rh1CaAl-LDH catalyst. The k2-weighted Fourier transform spectra in R space of 0.8Pd1CaAl-LDH (c) and 1.6Ru1CaAl-LDH (d). Wavelet transform (WT) of the EXAFS spectrum of 0.8Pd1CaAl-LDH (e) and 1.6Ru1CaAl-LDH (f).

Fig. 4. (a) Possible products of the quinoline hydrogenation. (b) metal-normalized activity (per unit mass of Rh) of the xRhCaAl-LDH in hydrogenation of quinoline (Temperature: 80 °C; H2 Pressure: 2 MPa). (c) Effect of reaction time on hydrogenation activity with 1Rh1CaAl-LDH. (d) Hydrogenation properties of different noble metals catalysts (Reaction times are respectively: 5, 2, 1 h). (e) The comparison of noble metal catalyst performance.

Fig. 5. (a) Quinoline adsorption energies (ΔEads) of C=N over Rh1CaAl-LDH and Rh10/CaAl-LDH. (b) Proposed route for quinoline hydrogenation on Rh1CaAl-LDH.

Table 1 The catalytic hydrogenation of functional group substituted quinoline and other N-heteroarenes over 1Rh1CaAl-LDH catalyst.

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