Ru-Co单原子合金催化剂用于醇胺化: 协同效应

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

催化学报 ›› 2025, Vol. 75: 49-58.DOI: 10.1016/S1872-2067(25)64714-0

Ru-Co单原子合金催化剂用于醇胺化: 协同效应

周志同^a^,^b, 关伟翔^a, 潘晓丽^a, 张盛鑫^a^,^b, 苏杨^a, 王爱琴^a^,^*(), 张涛^a^,^b^,^*()

^a中国科学院大连化学物理研究所, 能源催化转化全国重点实验室, 辽宁大连 116023
^b中国科学院大学, 北京 100049

收稿日期:2025-02-21 接受日期:2025-03-28 出版日期:2025-08-18 发布日期:2025-07-22
通讯作者: *电子信箱: aqwang@dicp.ac.cn (王爱琴), taozhang@dicp.ac.cn (张涛).
基金资助:
国家重点研发计划(2023YFA1506603);国家自然科学基金(22209171);国家自然科学基金(22132006);国家自然科学基金(22108259);国家自然科学基金委单原子催化基础科学中心(22388102)

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

Zhou Zhitong^a^,^b, Guan Weixiang^a, Pan Xiaoli^a, Zhang Shengxin^a^,^b, Su Yang^a, Wang Aiqin^a^,^*(), Zhang Tao^a^,^b^,^*()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-02-21 Accepted:2025-03-28 Online:2025-08-18 Published:2025-07-22
Contact: *E-mail: aqwang@dicp.ac.cn (A. Wang), taozhang@dicp.ac.cn (T. Zhang).
Supported by:
National Key R&D Program of China(2023YFA1506603);National Natural Science Foundation of China(22209171);National Natural Science Foundation of China(22132006);National Natural Science Foundation of China(22108259);NSFC Center for Single-Atom Catalysis(22388102)

摘要/Abstract

摘要：

伯胺是一类重要的化工原料, 在农药、药物和染料等领域发挥着重要作用. 因此, 伯胺的合成及其应用一直是化学领域研究的重点. 醇胺化合成伯胺是一种典型的绿色化学反应过程, 其副产物仅为水, 且具有较高的原子经济性. 然而, 目前的催化体系中仍然存在一些问题, 例如高转化率下伯胺的选择性较差, 贵金属体系反应成本高, 而非贵金属体系催化活性低等. 因此, 亟需开发贵金属用量低, 同时在较温和条件下保持对伯胺高活性和高选择性的催化体系.

本工作结合贵金属的高活性以及非贵金属的低成本性特点, 开发了一种Ru-Co/ZrO₂单原子合金催化剂(SAA), 大大降低了贵金属用量, 同时保持较高的反应活性. 该催化剂在温和的条件下(0.7 MPa NH₃, 0.3 MPa H₂, 160 °C), 能够以较高的转化率(高达90%)和选择性(80%)将多种醇类化合物转化为伯胺. 活性研究结果表明, Ru和Co之间存在明显的协同作用. 再生实验结果表明, 经过5次再生反应后的催化剂, 与新鲜催化剂相比活性没有明显下降, 表现出良好的可再生性和结构稳定性. 结构表征结果表明, 催化剂经过还原处理后, Ru会在催化剂表面富集. 当Ru/Co比小于1/30时, Ru会在催化剂上形成SAA结构, 是主要的催化活性中心. 与单金属Co/ZrO₂催化剂相比, 含微量Ru的Ru-Co/ZrO₂单原子合金催化剂上底物转化速率提高了约8.4倍. 同时, 在高底物转化率下, 伯胺选择性也显著提高(从60%提高至80%). 合金化的Ru能够促进Co的分散, 增加催化剂上的活性位点. Ru的加入能够促进Co的还原, 增强与H₂的相互作用, 从而提高反应活性. 乙醇-程序升温表面反应和乙醛-程序升温脱附结果表明, SAA结构能够有效促进醇的脱氢过程, 并抑制醛中间体在催化剂上的强吸附, 减少催化剂的中毒, 因此, 与单金属Co/ZrO₂催化剂相比, 显著提高了反应活性. 与单金属Ru/ZrO₂催化剂相比, SAA结构能够调节对伯胺的吸附强度, 促进伯胺在催化剂上的脱附, 从而减少副产物仲胺的生成. 因此, 相比于单金属Co和Ru催化剂, Ru-Co/ZrO₂单原子合金催化剂展现出更好的反应活性和伯胺选择性.

综上, 本工作开发的Ru-Co/ZrO₂单原子合金催化剂显著降低了催化剂成本, 通过调节反应过程中的吸脱附行为, 能够在温和的反应条件下保持对伯胺的高活性和高选择性, 为开发高效的醇胺化反应催化剂提供了一种有前景的策略.

关键词: 醇胺化, 氨气, 单原子合金催化剂, 钌-钴, 伯胺

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

周志同, 关伟翔, 潘晓丽, 张盛鑫, 苏杨, 王爱琴, 张涛. Ru-Co单原子合金催化剂用于醇胺化: 协同效应[J]. 催化学报, 2025, 75: 49-58.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64714-0

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

图/表 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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Ru-Co单原子合金催化剂用于醇胺化: 协同效应

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

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