Facile fabrication of atomically dispersed Ru-P-Ru ensembles for efficient hydrogenations beyond isolated single atoms

doi:10.1016/S1872-2067(22)64172-X

Abstract

Abstract:

It is of great significance for upgrading single-atom catalysts (SACs) to further improve their intrinsic catalytic activities while maintaining the merits of maximum atom utilization and high selectivity. Here, we report a simple and practical strategy to construct phosphorus (P) atom bridged ruthenium (Ru) ensemble (Ru-P-Ru) in carbon skeleton, which is achieved by redispersing Ru clusters with C-P species and in-situ generated PH₃. The turnover frequency of the Ru-P-Ru catalyst is 9-fold higher than that of the RuP₄ SAC in the selective hydrodeoxygenation of o-phthalic anhydride, as well as other diverse hydrogenations of C=X bonds (X = O, C, N) with good recyclability. Experimental and computational studies reveal that the d-band centers of Ru in the Ru-P-Ru are closer to the Fermi level than that of isolated Ru SAC, significantly promoting the absorption and activation of substrates. This fabrication strategy is also applicable to other M-P-M catalysts, enriching the knowledge of atomically dispersed catalysts.

Key words: Heterogeneous catalysis, P-doped mesoporous carbon, Single-atom catalyst, Ru-P-Ru ensemble, Selective hydrogenation

Chao Nie, Xiangdong Long, Qi Liu, Jia Wang, Fei Zhan, Zelun Zhao, Jiong Li, Yongjie Xi, Fuwei Li. Facile fabrication of atomically dispersed Ru-P-Ru ensembles for efficient hydrogenations beyond isolated single atoms[J]. Chinese Journal of Catalysis, 2023, 45: 107-119.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64172-X

https://www.cjcatal.com/EN/Y2023/V45/I2/107

Figures/Tables 5

Fig. 1. (a) Schematic illustration of the preparation process of Ru-P500-mPC. TEM (b) and HRTEM (c) images of Ru-P500-mPC. (d-f) HAADF-STEM image of Ru-P500-mPC sample at different magnification conditions. (g) Extracted line profile along the red solid line in (f), demonstrating the fully exposed single-atomic-layer Ru-P-Ru ensemble.

Fig. 2. (a) XANES spectra at the Ru k-edge of Ru-Px-mPC, Ru1-P-mPC, Ru foil and RuO2. (b) Deconvoluted P 2p XPS spectra of Ru-Px-mPC. All of the spectra were deconvoluted using four doublet peaks with an area ratio of 0.5 and a separation between peaks of 0.84 eV. (c) Fourier transform (FT) at the Ru k-edge of Ru-Px-mPC, Ru1-P-mPC, Ru foil and RuO2. (d) Wavelet transform of Ru-P500-mPC.

Fig. 3. (a) Selective hydrodeoxygenations of PA over different Ru-based catalysts. Reaction conditions: 2 mmol PA, mole ratio of substrate/Ru is 1200, 5 mL toluene, 4 MPa H2, 190 °C, 6 h, yields were determined by gas chromatography (GC) using decane as an internal standard. (b) TOFs of hydrodeoxygenation of PA, the values were measured in the kinetic region (conversion of PA was below 20%). (c) Time-course plots of PA conversions over Ru1-P-mPC (blue line) and Ru-P500-mPC (black line), and a hot filtration test over the latter (red line). For a hot filtration experiment, the reaction mixture was quickly centrifuged after 90 min of reaction, then the upper clear liquid proceeded to react for another 270 min. (d) Arrhenius plot for apparent activation energies of Ru1-P-mPC and Ru-P500-mPC.

Fig. 4. (a) In situ FTIR tests for the hydrogenation of PA over Ru-P500-mPC catalyst at various temperatures. (b) Top views of substrates (H2 and PA) on Ru4P9 and RuP4 sites, with the corresponding adsorption energies. (c) LDOS projected on the Ru atom of Ru1-P-mPC and Ru-P500-mPC with the Fermi level set to be zero.

Fig. 5. Ru-P500-mPC and Ru1-P-mPC catalyzed hydrogenations of (a) aldehydes and (b) quinolines, the yields with Ru1-P-mPC as the catalyst are listed in parentheses. Reaction conditions: 1 mmol substrate, substrate/Ru = 1200, 5 mL solvent. Yields are determined by GC using 1,4-dioxane as internal standard. (c) Ru-P500-mPC and Ru1-P-mPC catalyzed reductive amination of aldehydes. Reaction conditions: 2 mmol aldehydes, 3 mmol amine, 50 mg catalyst, 5 mL ethanol. For synthesis of (8a), 2 mmol substrate, 2 mL aqueous ammonia, 50 mg Ru-P500-mPC, 3 mL H2O, yield is determined by high performance liquid chromatography (HPLC). Stability test of Ru-P500-mPC in (d) hydrogenation of PA and (e) reductive amination of 4-formylbenzoic acid. Reaction conditions for (d): 2 mmol PA, substrate/Ru = 1200, 5 mL toluene, 4 MPa H2, 150 °C, 6 h. Reaction conditions for (e): 2 mmol substrate, 2 mL aqueous ammonia, 50 mg Ru-P500-mPC, 3 mL H2O, 4 MPa H2, 70 °C, 6 h.

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