Atomic-level engineering of metal–metal interaction in intermetallic catalysts for efficient propene hydroformylation

IF 6.5 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Catalysis Pub Date : 2025-09-15 DOI:10.1016/j.jcat.2025.116431

Shuai Cui , Enze Xu , Lei Wang , Xin Song , Kelong Liu , Na Liu , Xiaolong Yan , Mingyao Li , Yusen Yang , Min Wei

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Abstract

Hydroformylation, a pivotal industrial reaction heavily reliant on Rh-based catalysts, remains limited by Rh scarcity and cost. While Co-based catalysts are potential alternatives, they still face dual challenges of insufficient activity and stability. In this work, Co-based intermetallic catalysts (CoMoIMC and CoWIMC) were synthesized through a layered double hydroxide precursor strategy. During propylene hydroformylation, CoMoIMC exhibited a butyraldehyde production rate of 105.6 mmol·g⁻¹·h⁻¹ (97 % selectivity) with >90 % activity retention over 10 cycles under mild conditions (140 °C, 4.5 MPa), outperforming conventional CoAl₂O₃ by 2.4-fold. Reactant-TPD experiments and DFT calculations revealed that the ordered Co₃Mo/Co₃W structures altered CO adsorption from hollow to top sites, reducing the desorption energy from 29.7 to 19.7 kJ·mol⁻¹ and lowering the CO insertion barrier from 1.28 to 1.09 eV. This work proposes a new strategy for preparing highly active and stable non-noble metal hydroformylation catalysts, which has a promising potential for industrial applications.

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高效丙烯氢甲酰化金属间催化剂中金属-金属相互作用的原子水平工程

氢甲酰化是一种关键的工业反应，严重依赖于Rh基催化剂，但仍然受到Rh稀缺和成本的限制。虽然钴基催化剂是潜在的替代品，但它们仍然面临着活性和稳定性不足的双重挑战。本文采用层状双氢氧化物前驱体策略合成了钴基金属间催化剂CoMoIMC和CoWIMC。在丙烯氢甲酰化过程中，CoMoIMC的丁醛产率为105 mmol·g−1·h−1（选择性为97 %），在温和条件下（140 °C, 4.5 MPa），在10个循环中保持了90 %的活性，比传统的CoAl2O3高出2.4倍。反应物- tpd实验和DFT计算表明，有序的Co3Mo/Co3W结构改变了CO从中空到顶部的吸附，将CO的解吸能从29.7降低到19.7 kJ·mol−1，将CO的插入势垒从1.28降低到1.09 eV。本研究为制备高活性、稳定的非贵金属氢甲酰化催化剂提供了一种新的策略，具有广阔的工业应用前景。

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来源期刊

Journal of Catalysis 工程技术-工程：化工

CiteScore

12.30

自引率

5.50%

发文量

447

审稿时长

31 days

期刊介绍： The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.