氧合物
催化作用
甲烷
原位
金属
Atom(片上系统)
材料科学
光化学
化学
纳米技术
化学工程
无机化学
有机化学
计算机科学
嵌入式系统
工程类
作者
Wenjing Xu,Han-Xuan Liu,Yue Hu,Zhen Wang,Zheng-Qing Huang,Chuande Huang,Jian Lin,Chun‐Ran Chang,Aiqin Wang,Xiaodong Wang,Tao Zhang
标识
DOI:10.1002/anie.202315343
摘要
Direct methane conversion (DMC) to oxygenates at low temperature is of great value but remains challenging due to the high energy barrier for C-H bond activation. Here, we report that in situ decoration of Pd1-ZSM-5 single atom catalyst (SAC) by CO molecules significantly promoted the DMC reaction, giving the highest turnover frequency of 207 h-1 ever reported at room temperature and ~100 % oxygenates selectivity with H2O2 as oxidant. Combined characterizations and DFT calculations illustrate that the C-atom of CO prefers to coordinate with Pd1, which donates electrons to the Pd1-O active center (L-Pd1-O, L=CO) generated by H2O2 oxidation. The correspondingly improved electron density over Pd-O pair renders a favorable heterolytic dissociation of C-H bond with low energy barrier of 0.48 eV. Applying CO decoration strategy to M1-ZSM-5 (M=Pd, Rh, Ru, Fe) enables improvement of oxygenates productivity by 3.2-11.3 times, highlighting the generalizability of this method in tuning metal-oxo electronic structure of SACs for efficient DMC process.
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