Enhanced Light Alkane Oxidation under Impurity-Containing Conditions by Low-Coordinated Co–O Structures Boosting C–H Bond Activation,ACS Catalysis

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Enhanced Light Alkane Oxidation under Impurity-Containing Conditions by Low-Coordinated Co–O Structures Boosting C–H Bond Activation
ACS Catalysis ( IF 11.3 ) Pub Date : 2024-09-09 , DOI: 10.1021/acscatal.4c03638
Fan Dang ₁ , Zeyu Jiang ₁ , Yadi Wang ₁ , Jialei Wan ₁ , Chunli Ai ₁ , Mingjiao Tian ₁ , Yanfei Jian ₁ , Han Xu ₁ , Reem Albilali ₂ , Jiaguo Yu ₃ , Chi He _{1,

4}

Affiliation

Anthropogenic light alkanes pose significant environmental and health hazards; however, achieving their efficient catalytic oxidation, particularly under industrial conditions with impurities, remains a huge challenge. Tuning the coordinated structure of metal atoms is a promising strategy for improving their low-temperature efficiency for stable C–H bond activation. Herein, we propose a one-step method for precisely modulating the coordination structures of Co atoms in a Co₃O₄ catalyst by controlling the diverse nucleation rates of Co(OH)_x species. The Co₃O₄-L catalyst with the lowest Co–O bonding exhibits exceptional catalytic performance, achieving complete oxidation of 1000 ppm propane and methane at just 179 and 290 °C, respectively. This performance is far superior to that of known catalysts, which typically require over 250 and 350 °C for 90% conversion of propane and methane, respectively. Additionally, Co₃O₄-L demonstrates excellent activity and stability in the presence of multiple organic components, as well as SO₂ and H₂O. The promoted electron-pair interactions between σ/σ* C–H orbitals and d orbitals of low-coordinated Co²⁺ species by sufficient low saturation sites strengthens the adsorption and activation of light alkanes and facilitates the cleavage of the C–H bond, ultimately reducing the reaction energy barrier. The high stability and antitoxicity are due to the abundant surface dangling bond-induced structural stability and rapid oxygen replenishment, which is facilitated by high electron transport capacity. This study establishes a solid foundation for further exploration of effective catalytic platforms for light alkanes under impurity-containing conditions.

中文翻译：

低配位 Co-O 结构促进 C-H 键活化，增强含杂质条件下的轻质烷烃氧化

人为轻烷烃对环境和健康造成重大危害；然而，实现它们的有效催化氧化，特别是在含有杂质的工业条件下，仍然是一个巨大的挑战。调整金属原子的配位结构是提高其低温效率以稳定 C-H 键激活的一种有前途的策略。在此，我们提出了一种一步法，通过控制Co(OH) _x物种的不同成核速率来精确调节Co ₃ O ₄催化剂中Co原子的配位结构。具有最低Co-O键的Co ₃ O ₄ -L催化剂表现出卓越的催化性能，分别在179和290°C下实现1000 ppm丙烷和甲烷的完全氧化。该性能远远优于已知催化剂，后者通常需要超过 250°C 和 350°C 才能实现丙烷和甲烷 90% 的转化率。此外，Co ₃ O ₄ -L 在多种有机成分以及 SO ₂和 H ₂ O 存在下表现出优异的活性和稳定性。 σ/σ* C–H 轨道和d轨道之间促进的电子对相互作用低配位Co ²⁺物种通过足够的低饱和位点增强了轻质烷烃的吸附和活化，并促进C-H键的裂解，最终降低反应能垒。高稳定性和抗毒性是由于丰富的表面悬挂键引起的结构稳定性和快速的氧补充，这是由高电子传输能力促进的。该研究为进一步探索含杂质条件下轻质烷烃的有效催化平台奠定了坚实的基础。

更新日期：2024-09-09

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