サブナノメートルRh-Co二原子触媒が温和条件下でニトリル水素化を高効率化 (Sub-Nanometer Rh-Co Dual-Atom Catalyst Boosts Nitrile Hydrogenation Under Mild Conditions)

2026-05-09 中国科学院(CAS)

中国科学院金属研究所、北京大学、重慶大学の共同研究チームは、ロジウム(Rh)とコバルト(Co)から成る異種二原子触媒「Rh1Co1/ND@G」を開発し、ニトリル水素化反応における活性と選択性の両立を実現した。ニトリル水素化は医薬品や農薬などに用いられる二級アミン製造の重要反応だが、従来の貴金属触媒では副反応による低選択性や高温・高圧条件が課題だった。研究チームは欠陥グラフェン上にRh原子を固定後、Co錯体を導入する段階的固定化法により、原子間距離約2.55ÅのRh-Co対を形成。333K、0.6MPaという温和条件下でベンゾニトリルからジベンジルアミンへの水素化を行い、4068 h-1の高い反応速度と98%以上の選択性を達成した。反応機構解析では、Rhが水素分子活性化、Coがニトリル吸着を担い、協働作用により反応障壁を低減することが示された。高耐久性や広い基質適用性も確認され、グリーンケミストリー向け高性能触媒設計への応用が期待される。

サブナノメートルRh-Co二原子触媒が温和条件下でニトリル水素化を高効率化 (Sub-Nanometer Rh-Co Dual-Atom Catalyst Boosts Nitrile Hydrogenation Under Mild Conditions)
Catalyst structural characterization. (a‑c) HAADF-STEM images, (d) interatomic distance distribution. (Image by IMR)

<関連情報>

ニトリル水素化反応を相乗的に促進する二原子Rh-Co触媒 Dual-atom Rh-Co catalysts for synergistically boosting nitrile hydrogenation

Jiawei Chen,Hongqiu Chen,Xiangbin Cai,Yue Wang,Mi Peng,Bo Sun,Jiangyong Diao,Geng Sun,Ding Ma & Hongyang Liu
Nature Communications  Published:25 March 2026
DOI:https://doi.org/10.1038/s41467-026-69778-2  Unedited version

Abstract

Single-atom catalysts have found widespread application in selective hydrogenation reactions partially due to their well-defined active site structures, which ensure exceptional chemical selectivity. However, the limited binding sites on single-atom catalysts hinder their application in hydrogenating larger multidentate substrates (e.g., benzonitrile). In this work, we introduced a heteronuclear Rh-Co dual-atom catalyst stabilized on the defective graphene supports (Rh1Co1/ND@G), which resolves the activity-selectivity trade-off in nitrile hydrogenation reaction. The Rh1 site primarily activates H2, whereas the Co1 site synergistically optimizes the adsorption of benzonitrile. The cooperative interaction between Rh-Co dual sites enhances the activation of the C ≡ N bond, significantly reducing the apparent activation energy compared to Rh SACs. The Rh1Co1/ND@G catalyst achieves exceptional performance under mild reaction conditions, delivering a TOF of 4068 h-1 with >98% dibenzylamine selectivity, surpassing all previous reported heterogeneous catalysts. Remarkably, the Rh1Co1/ND@G catalyst still maintains robust catalytic performance even after 12 cycles. This work not only presents a breakthrough in dual-atom catalyst design for nitrile hydrogenation, but also opens an avenue for developing high-performance industrial hydrogenation catalysts.

0500化学一般
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