A Precious-Metal-Free Hybrid Electrolyzer for Alcohol Oxidation Coupled to CO 2 -to-Syngas Conversion
A Precious-Metal-Free Hybrid Electrolyzer for Alcohol Oxidation Coupled to CO 2 -to-Syngas Conversion
复制标题
用于酒精氧化与 CO 2 转化为合成气的无贵金属混合电解槽
DOI：
10.1002/ange.202002680
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发表时间：
2020
影响因子：
--
通讯作者：
Bajada M
中科院分区：
文献类型：
--
作者：
Bajada M
与从水氧化获得电子的系统相比，将CO2还原（CO2 R）与有机基质氧化相结合的电解器可以以相对较低的能量需求生产燃料和化学原料。在这里，我们报告了一个阳极混合组装的基础上（2，2，6，6-四甲基哌啶-1-基）氧基（克里思）的电催化剂改性与硅杂三环-锚（STEMPO），这是共价固定在介孔氧化铟锡（mesoITO）支架有效的醇氧化（AlcOx）。该分子阳极随后与由碳纳米管上的聚合酞菁钴组成的阴极组合，以构建混合的、无贵金属的耦合AlcOx-CO2 R电解槽。电解3小时后，甘油被选择性氧化为甘油醛，转化数（TON）为1000，法拉第效率（FE）为83%。阴极产生化学计量量的合成气，其中CO：H2比为1.25±0.25，并且总体钴基TON为894，FE为82%。该原型设备激发了将CO2 R耦合到能量需求较低且具有增值的氧化化学的非传统策略的设计和实施。
Electrolyzers combining CO2reduction (CO2R) with organic substrate oxidation can produce fuel and chemical feedstocks with a relatively low energy requirement when compared to systems that source electrons from water oxidation. Here, we report an anodic hybrid assembly based on a (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) electrocatalyst modified with a silatrane‐anchor (STEMPO), which is covalently immobilized on a mesoporous indium tin oxide (mesoITO) scaffold for efficient alcohol oxidation (AlcOx). This molecular anode was subsequently combined with a cathode consisting of a polymeric cobalt phthalocyanine on carbon nanotubes to construct a hybrid, precious‐metal‐free coupled AlcOx–CO2R electrolyzer. After three‐hour electrolysis, glycerol is selectively oxidized to glyceraldehyde with a turnover number (TON) of ≈1000 and Faradaic efficiency (FE) of 83 %. The cathode generated a stoichiometric amount of syngas with a CO:H2ratio of 1.25±0.25 and an overall cobalt‐based TON of 894 with a FE of 82 %. This prototype device inspires the design and implementation of nonconventional strategies for coupling CO2R to less energy demanding, and value‐added, oxidative chemistry.