甲醇与金表面分子吸附氧氧化偶联生成甲酸甲酯。
Oxidative Coupling of Methanol with Molecularly Adsorbed Oxygen on Au Surface to Methyl Formate.
作者信息
Sun Guanghui, Wang Fang, Jin Yuekang, Chen Xuanye, Chai Peng, Wu Longxia, Teng Bo-Tao, Huang Weixin
机构信息
Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, P. R. China.
出版信息
J Phys Chem Lett. 2021 Jul 29;12(29):6941-6945. doi: 10.1021/acs.jpclett.1c01564. Epub 2021 Jul 20.
Supported Au catalysts efficiently catalyze the oxidative coupling of methanol with O to methyl formate, in which the atomic O species (O(a)) formed via O dissociation on the Au surface has been considered as the active oxygen species. Herein we report for the first time that the oxidative coupling of methanol can occur facilely with molecularly adsorbed O species (O(a)) on a Au(997) surface at temperatures as low as around 125 K, while that with O(a) occurs at around 175 K. Both experimental and theoretical calculation results demonstrate a novel reaction mechanism of oxidative coupling of CHOH with (a) via a dioxymethylene (HCO) intermediate, resulting in the production of both HCOOCH and HCOCH. These results reveal the unique reactivity of molecularly adsorbed O species on Au surfaces for low-temperature oxidation reactions.
负载型金催化剂能有效地催化甲醇与氧气氧化偶联生成甲酸甲酯，其中通过氧气在金表面解离形成的原子氧物种（O(a)）被认为是活性氧物种。在此，我们首次报道，在低至约125 K的温度下，甲醇能与吸附在Au(997)表面的分子态氧物种（O(a)）轻松发生氧化偶联反应，而与O(a)的反应则发生在约175 K。实验和理论计算结果均表明，甲醇与（a）通过二氧亚甲基（HCO）中间体发生氧化偶联反应的新机制，生成了HCOOCH和HCOCH。这些结果揭示了吸附在金表面的分子态氧物种在低温氧化反应中独特的反应活性。
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