Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene
Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene
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DOI：
10.1021/jp306172k
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发表时间：
2013-04
影响因子：
3.7
通讯作者：
V. Tripkovic;M. Vanin;Mohammedreza Karamad;M. Björketun;K. Jacobsen;K. Thygesen;J. Rossmeisl
中科院分区：
文献类型：
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作者：
V. Tripkovic;M. Vanin;Mohammedreza Karamad;M. Björketun;K. Jacobsen;K. Thygesen;J. Rossmeisl
研究了类卟啉金属功能化石墨烯结构作为二氧化碳和一氧化碳还原为甲烷或甲醇的可能催化剂。后过渡金属(Cu、Ag、Au、Ni、Pd、Pt、Co、Rh、Ir、Fe、Ru、Os)和一些p(B、Al、Ga)、S(Mg)金属构成了卟啉环的中心。由于活性中心的电子性质不同，与扩展的金属表面相比，催化性能有明显的不同。然而，偏爱结合氢成为反应过程中的一个主要障碍。这个问题的一个可能的解决方案是减少CO而不是二氧化碳。根据反应中间体的标度关系建立了火山图，并由此推断出具有最高过电势的反应步骤。结果表明，Rh-卟啉功能化石墨烯催化剂对CO合成甲醇的催化活性最高，过电势为0.22V。
Porphyrin-like metal-functionalized graphene structures have been investigated as possible catalysts for CO2 and CO reduction to methane or methanol. The late transition metals (Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Ru, Os) and some p (B, Al, Ga) and s (Mg) metals comprised the center of the porphyrin ring. A clear difference in catalytic properties compared to extended metal surfaces was observed owing to a different electronic nature of the active site. The preference to bind hydrogen, however, becomes a major obstacle in the reaction path. A possible solution to this problem is to reduce CO instead of CO2. Volcano plots were constructed on the basis of scaling relations of reaction intermediates, and from these plots the reaction steps with the highest overpotentials were deduced. The Rh–porphyrin-like functionalized graphene was identified as the most active catalyst for producing methanol from CO, featuring an overpotential of 0.22 V. Additionally, we have also examined the hydrogen evolution and o...