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掠入射X射线衍射:确定铜泡沫中主导的晶面,该晶面电催化二氧化碳还原为甲酸盐。

Grazing incidence X-Ray diffraction: identifying the dominant facet in copper foams that electrocatalyze the reduction of carbon dioxide to formate.

作者信息

Ahn Steven T, Sen Sujat, Palmore G Tayhas R

机构信息

School of Engineering, Brown University, 184 Hope Street, Providence, RI 02912, USA.

Department of Chemistry, Brown University, 324 Brook Street, Providence, RI 02912, USA.

出版信息

Nanoscale. 2022 Sep 22;14(36):13132-13140. doi: 10.1039/d2nr03212k.

DOI:10.1039/d2nr03212k
PMID:36052773
Abstract

Copper foams have been shown to electrocatalyze the carbon dioxide reduction reaction (CORR) to formate (HCOO) with significant faradaic efficiency (FE) at low overpotentials. Unlike the CORR electrocatalyzed at copper foils, the CORR electrocatalyzed at porous copper foams selects for HCOO essentially to the exclusion of hydrocarbon products. Formate is an environmentally friendly organic acid with many applications such as food preservation, textile processing, de-icing, and fuel in fuel cells. Thus, HCOO is an attractive product from the CORR if it is produced at an overpotential lower than that at other electrocatalysts. In this study, grazing incidence X-ray diffraction (GIXRD) was used to identify the dominant surface facet of porous copper foams that accounts for its selectivity for HCOO during the CORR. Included are data from the CORR at different temperatures using copper foams as the electrocatalyst. Under optimal reaction conditions at 2 °C, the FE for converting CO to HCOO at Cu foams approaches 50% while the FE for hydrogen gas (H) falls below 40%, a significant departure from that obtained at polycrystalline Cu foils. Computational studies by others have proposed (200) and (111) facets of Cu foils thermodynamically favour methane and other hydrocarbons, CO, HCOO from the CORR. Results from the GIXRD studies indicate Cu foams are dominated by the (111) facet, which accounts for the selectivity of Cu foams toward HCOO regardless of temperature used for the CORR.

摘要

泡沫铜已被证明能在低过电位下将二氧化碳还原反应(CORR)电催化为甲酸盐(HCOO),且具有显著的法拉第效率(FE)。与在铜箔上电催化的CORR不同,在多孔泡沫铜上电催化的CORR主要生成HCOO,基本不生成碳氢化合物产物。甲酸盐是一种环境友好型有机酸,有许多应用,如食品保鲜、纺织品加工、除冰以及燃料电池中的燃料等。因此,如果HCOO能在比其他电催化剂更低的过电位下生成,那么它就是CORR中一种有吸引力的产物。在本研究中,掠入射X射线衍射(GIXRD)被用于确定多孔泡沫铜的主要表面晶面,该晶面决定了其在CORR过程中对HCOO的选择性。其中包括以泡沫铜为电催化剂在不同温度下进行CORR的数据。在2℃的最佳反应条件下,泡沫铜将CO转化为HCOO的FE接近50%,而氢气(H)的FE低于40%,这与在多晶铜箔上获得的结果有显著差异。其他人的计算研究表明,铜箔的(200)和(111)晶面在热力学上有利于CORR生成甲烷和其他碳氢化合物、CO、HCOO。GIXRD研究结果表明,泡沫铜以(111)晶面为主,这解释了无论CORR使用何种温度,泡沫铜对HCOO的选择性。

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