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用于氧去极化阴极应用的高活性和稳定的 Fe-N-C 催化剂。

Highly Active and Stable Fe-N-C Catalyst for Oxygen Depolarized Cathode Applications.

机构信息

Department of Chemistry and Chemical Biology and ‡Department of Biology, Northeastern University , Boston, Massachusetts 02115, United States.

出版信息

Langmuir. 2017 Sep 19;33(37):9246-9253. doi: 10.1021/acs.langmuir.7b00643. Epub 2017 May 2.

Abstract

Anion immunity toward the oxygen reduction reaction (ORR) has tremendous implications in electrocatalysis with applications for fuel cells, metal-air batteries, and oxygen depolarized cathodes (ODCs) in the anodic evolution of chlorine. The necessity of exploring ORR catalysts with immunity to anion adsorption is particularly significant considering that platinum group metal (PGM) catalysts are costly and highly vulnerable to impurities such as halides. Herein, we report a metal organic framework (MOF)-derived Fe-N-C catalyst that exhibits a dramatically improved half-wave potential of 240 mV compared to the state-of-the-art RhS/C catalyst in a rotating disk electrode in the presence of Cl. The Fe-N active sites in Fe-N-C are intrinsically immune to Cl poisoning, in contrast to Pt/C, which is severely susceptible to Cl poisoning. As a result, the activity of Fe-N-C decreases only marginally in the presence of Cl, far exceeding that of Pt/C. The viability of this catalyst as ODCs is further demonstrated in real-life hydrochloric acid electrolyzers using highly concentrated HCl solution saturated with Cl gas as the electrolyte. The introduction of Fe-N-C materials as ODC catalysts here overcomes the limitations of (i) the low intrinsic ORR activity of RhS/C as the state-of-the-art ODC catalyst; (ii) the vulnerability to Cl poisoning of Pt/C as the state-of-the-art ORR catalyst; and (iii) the high cost of precious metals in these two materials, resulting in a cost-effective ODC catalyst with the overall performance exceeding that of all previously reported materials.

摘要

阴离子对氧还原反应(ORR)的抗扰性在电催化中具有重要意义,可应用于燃料电池、金属空气电池和阳极析氯中的氧去极化阴极(ODC)。考虑到铂族金属(PGM)催化剂成本高昂且极易受到卤化物等杂质的影响,探索对阴离子吸附具有抗扰性的 ORR 催化剂尤为重要。在此,我们报告了一种金属有机骨架(MOF)衍生的 Fe-N-C 催化剂,与最先进的 RhS/C 催化剂相比,在旋转圆盘电极中存在 Cl 时,其半波电位显著提高了 240 mV。与极易受到 Cl 毒化的 Pt/C 相比,Fe-N-C 中的 Fe-N 活性位点本质上对 Cl 具有抗扰性。因此,在 Cl 存在下,Fe-N-C 的活性仅略有下降,远远超过 Pt/C。该催化剂作为 ODC 的可行性在使用充满 Cl 气体的高浓度 HCl 溶液作为电解质的实际盐酸电解槽中得到了进一步证明。在此,将 Fe-N-C 材料作为 ODC 催化剂引入克服了以下限制:(i) 作为最先进的 ODC 催化剂的 RhS/C 的固有 ORR 活性低;(ii) 作为最先进的 ORR 催化剂的 Pt/C 易受 Cl 毒化;(iii) 这两种材料中贵金属的成本高,导致具有整体性能超过所有先前报道的材料的具有成本效益的 ODC 催化剂。

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