Selective Activation of Propane Using Intermediates Generated during Water Oxidation
Selective Activation of Propane Using Intermediates Generated during Water Oxidation
复制标题
使用水氧化过程中产生的中间体选择性活化丙烷
DOI：
10.1021/jacs.1c00377
复制
发表时间：
2021
影响因子：
15
通讯作者：
Goddard William A. III
中科院分区：
文献类型：
--
作者：
Zhang Haochen;Li Chunsong;Lu Qi;Cheng Mu-Jeng;Goddard William A. III
轻烷烃的电化学转化为高价值的含氧化合物为这些碳氢化合物的生态友好利用提供了一条有吸引力的途径。然而，由于C-H键裂解的高能量势垒，这种转化在环境条件下仍然非常具有挑战性。本文利用水氧化过程中产生的活性中间体作为氧化剂，从理论上研究了丙烷在一系列单原子合金上的部分氧化。研究表明，通过控制电位和pH值，可以在水氧化条件下保持表面氧原子的稳定。表面氧裂解C-H键的自由能垒可小至0.54 eV，在室温下可轻易突破。我们的计算确定了三个有希望的表面作为有效的丙烷氧化催化剂。我们的补充实验证明了丙烷在ni掺杂的Au表面上部分氧化为丙酮。我们还通过计算研究了丙酮生成的步骤。这些研究表明，利用水氧化过程中产生的中间体作为氧化剂的概念为电催化剂设计提供了一种富有成效的策略，可以有效地将碳氢化合物转化为增值化学品。
Electrochemical conversion of light alkanes to high-value oxygenates provides an attractive avenue for eco-friendly utilization of these hydrocarbons. However, such conversion under ambient conditions remains exceptionally challenging due to the high energy barrier of C–H bond cleavage. Herein, we investigated theoretically the partial oxidation of propane on a series of single atom alloys by using active intermediates generated during water oxidation as the oxidant. We show that by controlling the potential and pH, stable surface oxygen atoms can be maintained under water oxidation conditions. The free energy barrier for C–H bond cleavage by the surface oxygen can be as small as 0.54 eV, which can be surmounted easily at room temperature. Our calculations identified three promising surfaces as effective propane oxidation catalysts. Our complementary experiments demonstrated the partial oxidation of propane to acetone on Ni-doped Au surfaces. We also investigated computationally the steps leading to acetone formation. These studies show that the concept of exploiting intermediates generated in water oxidation as oxidants provides a fruitful strategy for electrocatalyst design to efficiently convert hydrocarbons into value-added chemicals.