Pt1/FeOx single-atom catalyst with dual-valent Pt sites for water-promoted hydrogenation of nitroarenes

doi:10.1016/S1872-2067(26)65240-0

Abstract

Abstract:

Single-atom catalysts (SACs) are highly attractive for selective hydrogenation owing to their excellent chemoselectivity toward specific functional group activation, yet the inherently cationic nature of isolated metal sites often limits hydrogen activation and thus compromises activity. Herein, we report a Pt₁/FeO_x SAC prepared via atomic layer deposition of Pt onto α-Fe₂O₃ nanosheets. Dual-valent Pt atoms are identified on different surface terminations of the exposed (001) facet, and theoretically demonstrated to exhibit distinct catalytic behaviors, i.e., Pt₁^δ⁺ sites enable heterolytic H₂ activation whereas Pt₁⁰ sites facilitate a more kinetically favorable homolytic H₂ dissociation. Moreover, a water-mediated hydrogen-bonding network substantially lowers the H₂ dissociation and H* species spillover barriers and promotes remote hydrogenation. As a result, in the catalytic hydrogenation of 3-nitrostyrene, the Pt₁/FeO_x SAC exhibits approximately 24-fold higher activity relative to its water-free counterpart, while high selectivity toward 3-aminostyrene is maintained through preferential activation of nitro groups at adjacent low-valence Fe neighboring Pt single-atom sites. These findings reveal that the catalytic behavior of SACs strongly depends on the oxidation state of single atoms. Notably, metallic single-atom species with water-promoted hydrogen activation demonstrate superior hydrogenation efficiency, resulting in a markedly enhanced activity.

Key words: Nitroarene hydrogenation, Single-atom catalysts, Water effect, Hydrogen-bonding network, Selective hydrogenation

Anqi Li, Yusen Chen, Xiaoli Pan, Yujing Ren, Hongchen Cao, Guiyue Bi, Xiaofeng Yang, Aiqin Wang, Tao Zhang. Pt₁/FeO_x single-atom catalyst with dual-valent Pt sites for water-promoted hydrogenation of nitroarenes[J]. Chinese Journal of Catalysis, 2027, 92: 410-419.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65240-0

https://www.cjcatal.com/EN/Y2027/V92/I1/410

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Fig. 1. (a) H2-TPR profiles of Fe2O3 nanosheet and Pt/Fe2O3 catalyst. (b) HAADF-STEM image, (c) CO-DRIFTS and (d) in-situ XPS of Pt1/FeOx.

Fig. 2. (a) Top and side views of the geometry and charge density difference for the two Pt1/FeOx(001) models. The values for the calculated bader charges on the Pt1 are indicated. Charge accumulation and depletion are colored yellow and cyan, respectively, with the isosurface value of 0.01 e Å‒3. (b) The potential energy profiles for H2 dissociation and H species diffusion process on the two Pt1/FeOx(001) models. (c) PDOS of Pt atoms in the two Pt1/FeOx(001) models, the zero-energy corresponds to the Fermi level, and the d-band centers are shown with the dotted short lines. (d,e) The adsorption energies of H2, ‒NO2 and ‒C=C‒ group of 3-nitrostyrene on the different sites of Pt1/FeOx(001).

Fig. 3. (a) The energy barrier for H2 dissociation and H* spillover over the Pt1δ+/FeOx and Pt10/FeOx models, respectively, in the absence and presence of water. (b) The energy barrier for H* species diffusion over the O/Fe-terminated FeOx models in the absence and presence of water, respectively. (c,d) The potential energy profiles and schematic model for the H* species transferring from Pt1δ+ sites to the ‒NO2 group in the presence and absence of water. Color code: O-red; Fe-purple; Pt-blue; H-white; C-grey; N-dark blue.

Fig. 4. (a) Hydrogenation performance of 3-nitrostyrene as a function of added water content. 0.55 mmol 3-nitrostyrene, 40 mg Pt1/FeOx as catalyst, 100 μL n-octanol as internal standard, (x) mL H2O + (2‒x) mL ethanol as solvent in total. Reaction conditions: 40 °C, 0.4 MPa H2. 50 vol% water, x = 1 mL. The 3-nitrostyrene hydrogenation apparent activation energy (b), reaction order of 3-nitrostyrene (c) and H2 (d). (e) Kinetic isotope effect of H2/D2 and H2O/D2O in the hydrogenation of 3-nitrostyrene over Pt1/FeOx in ethanol or a mixture of ethanol and water (50 vol%). (f) H2-D2O isotopic exchange experiment results over Pt1/FeOx at 100 °C.

Fig. 5. (a) The mixing experiment of catalyst and WO3. Reaction conditions: 10 mg catalyst, 100 mg WO3, 2 mL solvent in total (2 mL ethanol or 1 mL ethanol + 1 mL water), 40 °C, 0.4 MPa H2, 20 min. (b) 3-Nitrostyrene hydrogenation performance over physical mixtures of PtNP/Al2O3 with Al2O3 or Fe2O3-S-230H2. Reaction conditions: 0.55 mmol 3-nitrostyrene, 30 mg PtNP/Al2O3 mixed with 30 mg support as catalyst, 100 μL n-octanol as internal standard, 2 mL ethanol or 1 mL ethanol + 1 mL water as solvent; 40 °C, 0.4 MPa H2.

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Pt₁/FeO_x single-atom catalyst with dual-valent Pt sites for water-promoted hydrogenation of nitroarenes

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