On the Role of Sulfur for the Selective Electrochemical Reduction of CO2 to Formate on CuSx Catalysts,ACS Applied Materials & Interfaces

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On the Role of Sulfur for the Selective Electrochemical Reduction of CO2 to Formate on CuSx Catalysts
ACS Applied Materials & Interfaces ( IF 8.3 ) Pub Date : 2018-08-20 00:00:00 , DOI: 10.1021/acsami.8b08428
Yilin Deng ₁ , Yun Huang ₁ , Dan Ren _{1,

2} , Albertus D. Handoko ₃ , Zhi Wei Seh ₃ , Pussana Hirunsit ₄ , Boon Siang Yeo _{1,

2}

Affiliation

The efficient electroreduction of CO₂ has received significant attention as it is one of the crucial means to develop a closed-loop anthropogenic carbon cycle. Here, we describe the mechanistic workings of an electrochemically deposited CuS_x catalyst that can reduce CO₂ to formate with a Faradaic efficiency (FE_HCOO^_–) of 75% and geometric current density (j_HCOO^_–) of −9.0 mA/cm² at −0.9 V versus the reversible hydrogen electrode. At this potential, the formation of other CO₂ reduction products such as hydrocarbons and CO was notably suppressed (total FE < 4%). The formate intermediate (HCOO*) was identified by operando Raman spectroscopy with isotopic labeling. A combination of electrochemical and materials characterization techniques revealed that the high selectivity toward formate production can be attributed to the effect of S dopants on the Cu catalyst, rather than surface morphology. Density functional theory calculations showed that the presence of sulfur weakens the HCOO* and *COOH adsorption energies, such that the formation of *COOH toward CO is suppressed, while the formation of HCOO* toward formate is favored.

中文翻译：

硫在CuS _x催化剂上选择性电化学还原CO ₂生成甲酸酯的作用

CO ₂的有效电还原已受到广泛关注，因为它是发展闭环人为碳循环的关键手段之一。在这里，我们描述了一种电化学沉积的CuS _x催化剂的机理，该催化剂可以将CO ₂还原成甲酸盐，法拉第效率（FE _HCOO^_–）为75％，几何电流密度（j _HCOO^_–）为-9.0 mA / cm ²。 -0.9 V（相对于可逆氢电极）。在这种潜力下，其他CO ₂的形成碳氢化合物和一氧化碳等还原产物得到了显着抑制（总FE <4％）。甲酸酯中间体（HCOO *）通过同位素同位素标记拉曼光谱法进行鉴定。电化学和材料表征技术的结合表明，对甲酸生成的高选择性可以归因于S掺杂剂对Cu催化剂的影响，而不是表面形态。密度泛函理论计算表明，硫的存在会削弱HCOO *和* COOH的吸附能，从而抑制了* COOH向CO的形成，而有利于HCOO *向甲酸盐的形成。

更新日期：2018-08-20

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