Methane Carboxylation Using Electrochemically Activated Carbon Dioxide.
Methane Carboxylation Using Electrochemically Activated Carbon Dioxide.
复制标题
使用电化学活性二氧化碳进行甲烷羧化。
DOI：
10.1002/anie.202305568
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Wang,Dunwei
中科院分区：
文献类型：
--
作者：
Yuan,Yucheng;Zhang,Yuhan;Li,Haoyi;Fei,Muchun;Zhang,Hongna;Santoro,John;Wang,Dunwei
从CH4和CO2直接合成CH3COOH是一种吸引人的方法，可以利用这两种以难以激活而闻名的强有力的温室气体。在这次通讯中，我们报告了一种使这种反应得以实现的综合途径。认识到CO2的热力学稳定性，我们的策略寻求首先激活CO2生成CO(通过电化学CO2还原)和O2(通过水氧化)，然后在沸石上负载Rh单原子催化剂催化氧化CH4羰基化反应。最终的结果是CH4羧化，原子经济性为100 %。以较高的选择性(~gt；80 %)和较好的产率(约3.2 g−1catin 3 h)得到了CH3COOH。同位素标记实验证实，CH3COOH是由CH4和CO2偶联生成的。这项工作是首次成功地将CO/O2的生成与氧化羰化反应相结合。这一结果有望激发更多利用预活化二氧化碳的羧化反应，这些反应利用了还原和氧化过程的两种产物，从而在合成中实现了高原子效率。
Direct synthesis of CH3COOH from CH4and CO2is an appealing approach for the utilization of two potent greenhouse gases that are notoriously difficult to activate. In thisCommunication, we report an integrated route to enable this reaction. Recognizing the thermodynamic stability of CO2, our strategy sought to first activate CO2to produce CO (through electrochemical CO2reduction) and O2(through water oxidation), followed by oxidative CH4carbonylation catalyzed by Rh single atom catalysts supported on zeolite. The net result was CH4carboxylation with 100 % atom economy. CH3COOH was obtained at a high selectivity (>80 %) and good yield (ca. 3.2 mmol g−1catin 3 h). Isotope labelling experiments confirmed that CH3COOH is produced through the coupling of CH4and CO2. This work represents the first successful integration of CO/O2production with oxidative carbonylation reaction. The result is expected to inspire more carboxylation reactions utilizing preactivated CO2that take advantage of both products from the reduction and oxidation processes, thus achieving high atom efficiency in the synthesis.