Ru-Co single-atom alloy catalysts for efficient amination of alcohols: A synergistic effect

doi:10.1016/S1872-2067(25)64714-0

Abstract

Abstract:

Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds. However, challenges remain to develop both cost-effective and efficient catalysts. In this study, we developed a Ru-Co/ZrO2 single-atom alloy catalyst which afforded diverse primary amines from alcohols in the presence of ammonia and hydrogen with exceptional conversion (up to 90%) and selectivity (80%) under mild conditions (0.7 MPa NH3, 0.3 MPa H2, 160 °C) and exhibited satisfactory stability upon regeneration. The turnover rate was approximately 8.4 times higher than that observed over the Co/ZrO2 catalyst. Characterizations indicated that the alloyed Ru facilitated the reduction of Co, strengthened the interaction with H2 and mitigated the over-strong adsorption of aldehyde intermediates. These combined effects contributed significantly to the enhanced catalytic performances. This work presents a promising strategy for the development of advanced catalysts in the amination of alcohols.

Key words: Alcohols amination, Ammonia, Single-atom alloy catalyst, Ru-Co, Primary amine

Zhou Zhitong, Guan Weixiang, Pan Xiaoli, Zhang Shengxin, Su Yang, Wang Aiqin, Zhang Tao. Ru-Co single-atom alloy catalysts for efficient amination of alcohols: A synergistic effect[J]. Chinese Journal of Catalysis, 2025, 75: 49-58.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64714-0

https://www.cjcatal.com/EN/Y2025/V75/I8/49

Figures/Tables 8

Table 1 The amination of 1-octanol over different catalysts.

Entry	Catalyst	Conv. (%)	Sel. (%)			Yield of b (%)
Entry	Catalyst	Conv. (%)	b	c	Others	Yield of b (%)
1	Ru₁-Co₁₂₀/ZrO₂	73.1	89.0	11.0	—	65.1
2	Ru₁-Co₆₀/ZrO₂	90.9	79.0	16.1	4.9	71.8
3	Ru₁-Co₃₀/ZrO₂	92.8	80.0	15.1	4.9	74.2
4	Ru₁-Co₁₀/ZrO₂	72.8	83.1	8.6	8.3	60.5
5	Ru₁-Co₁/ZrO₂	55.2	85.3	6.5	8.2	47.1
6	Co/ZrO₂	20.3	>99	n.d.	—	20.3
7^a	Ru/ZrO₂	4.8	>99	n.d.	—	4.8
8^b	Ru/ZrO₂	72.0	68.6	26.0	5.4	49.4
9	Co/ZrO₂+ Ru/ZrO₂	45.0	82.0	3.6	14.4	36.9
10	Ru₁-Co₃₀/Al₂O₃	90.4	79.3	20.7	—	71.7
11	Ru₁-Co₆₀/Al₂O₃	87.2	81.6	17.6	0.8	71.2
12	Ru₁-Co₃₀/HAP	94.2	67.8	32.2	—	63.9
13	Ru₁-Co₃₀/SiO₂	20.3	47.8	n.d.	52.2	9.7
14	Ru₁-Co₃₀/BN	13.0	>99	n.d.	—	13.0
15	Ru₁-Co₃₀/TiO₂	14.6	98.5	n.d.	1.5	14.4

Fig. 1. (a) HAADF-STEM images of Ru1-Co30/Al2O3 catalyst. Panels (1) and (2) are the line intensity profiles of the rectangular regions in (a). The elemental mapping of Co (c) and Ru (d) in the selected area (b). (e) Line scan profiles on randomly selected Co particles.

Fig. 2. (a) The normalized XANES spectra at Ru K-edge of Ru1-Co60/Al2O3 sample, with Ru foil and RuO2 as references. (b) The Fourier transform (FT) k2-weighted χ(k)-function of the EXAFS spectra at Ru K-edge.

Fig. 3. XPS in the Ru 3p (a) and Co 2p (b) core-level regions for the Ru1-Co30/ZrO2 and Ru1-Co10/ZrO2 samples.

Fig. 4. DRIFTS of CO adsorption on Ru-Co/ZrO2 and Ru/ZrO2 catalysts.

Fig. 5. H2-TPR (a) and H2-TPD (b) profiles of different samples.

Fig. 6. The signals of H2 (a) and acetaldehyde (b) detected by Ethanol-TPSR and the signals of acetaldehyde (c) detected by acetaldehyde-TPD over Ru1-Co30/ZrO2, Co/ZrO2 and Ru/ZrO2 catalysts.

Table 2 Amination of various alcohols over Ru1-Co30/ZrO2 catalyst.

Conv. (%)		Conv. (%)
92.8	80.0	85.3	79.5
80.0	73.8	66.0	86.2
74.0	79.5	82.1	89.2
62.0	92.6	98.2	78.0
86.2	93.4	85.1	99.9
97.2	97.9	46.1 ^a	52.8

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