Efficient Conversion of CO2 to CO Using Tin and Other Inexpensive and Easily Prepared Post-Transition Metal Catalysts
Efficient Conversion of CO2 to CO Using Tin and Other Inexpensive and Easily Prepared Post-Transition Metal Catalysts
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DOI：
10.1021/ja5121088
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发表时间：
2015-04-22
影响因子：
15
通讯作者：
Rosenthal, Joel
中科院分区：
文献类型：
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作者：
Medina-Ramos, Jonnathan;Pupillo, Rachel C.;Rosenthal, Joel
开发经济实惠的电催化剂，能够以高选择性、高效率和大电流密度将二氧化碳还原为CO，是生产液态碳基燃料的关键一步。在这项工作中，我们证明了廉价的三氟盐Sn2+、Pb2+、Bi3+和Sb3+可以作为从MeCN溶液中电沉积CO2还原阴极材料的前驱体，提供了一种通用的、简单的电沉积策略，从而简化了催化剂的合成。探讨了这四个平台在[BMIM]OTF存在下催化CO2生成CO的能力。电化学制备的锡和铋催化剂具有很高的CO析出活性、选择性和稳定性，在Eta<；250 mV的过电位下，其部分电流密度为j(CO)=5-8 mA/cm(2)。相比之下，电沉积的铅和锑催化剂不能以相同的选择性促进快速生成CO。在外加电压E=-1.95V时，铅材料的活性仅相当于锡系和铋系的10%，并且在催化过程中被迅速钝化。在类似条件下，含Sb的正极材料没有表现出将CO2转化为CO的活性。综合考虑，这项工作表明，1，3-二烷基咪唑类化合物可以促进CO的生成，但只有在与适当选择的电催化剂材料结合使用时才能实现。更广泛地说，这些结果表明，二氧化碳、咪唑促进剂和阴极表面之间的相互作用对观察到的催化都是关键的。
The development of affordable electrocatalysts that can drive the reduction of CO2 to CO with high selectivity, efficiency, and large current densities is a critical step on the path to production of liquid carbon-based fuels. In this work, we show that inexpensive triflate salts of Sn2+, Pb2+, Bi3+, and Sb3+ can be used as precursors for the electrodeposition of CO2 reduction cathode materials from MeCN solutions, providing a general and facile electrodeposition strategy, which streamlines catalyst synthesis. The ability of these four platforms to drive the formation of CO from CO2 in the presence of [BMIM]OTf was probed. The electrochemically prepared Sn and Bi catalysts proved to be highly active, selective, and robust platforms for CO evolution, with partial current densities of j(CO) = 5-8 mA/cm(2) at applied overpotentials of eta < 250 mV. By contrast, the electrodeposited Pb and Sb catalysts do not promote rapid CO generation with the same level of selectivity. The Pb material is only similar to 10% as active as the Sn and Bi systems at an applied potential of E = -1.95 V and is rapidly passivated during catalysis. The Sb-comprised cathode material shows no activity for conversion of CO2 to CO under analogous conditions. When taken together, this work demonstrates that 1,3-dialkylimidazoliums can promote CO production, but only when used in combination with an appropriately chosen electrocatalyst material. More broadly, these results suggest that the interactions between CO2, the imidazolium promoter, and the cathode surface are all critical to the observed catalysis.