通过改变酸性氧还原双活性位点上的氧吸附构型和反应途径来打破萨巴蒂尔顶点

IF 30.8 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Pan Guo, Bo Liu, Fengdi Tu, Yunkun Dai, Ziyu Zhang, Yunfei Xia, Miao Ma, Yunlong Zhang, Lei Zhao and Zhenbo Wang
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引用次数: 0

摘要

单原子催化剂是氧还原反应(ORR)中铂基催化剂的理想替代品。然而,在单活性位点上发生多步质子耦合电子传递的 ORR 过程遵循线性比例关系,因此很难突破萨巴蒂尔的限制。在本文中,我们通过构建具有类铂吸附构型的二原子活性位点,将 ORR 过程从缓慢的联合途径转换为有利的解离途径,从而使热力学极限势能突破萨巴蒂尔顶点。理论计算和原位表征充分证实了 O2 在 Ru-Fe 双基点上的类铂吸附构型,它能直接裂解 O-O 键,避免形成 *OOH 中间体,从而提高 ORR 动力学。因此,精心设计的具有双活性位点的 Ru 和 Fe 共掺杂催化剂(Ru,Fe-NC DAS)具有非凡的 ORR 催化性能,在酸性介质中的半波电位高达 0.843 V,在 H2/O2 燃料电池中的峰值功率密度达到破纪录的 1.152 W cm-2,居迄今为止报道的非铂催化剂之首。这项工作为设计高效原子分散催化剂和引导相应的催化反应机制提供了一种新方法。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Breaking Sabatier's vertex via switching the oxygen adsorption configuration and reaction pathway on dual active sites for acidic oxygen reduction†

Breaking Sabatier's vertex via switching the oxygen adsorption configuration and reaction pathway on dual active sites for acidic oxygen reduction†

Single-atom catalysts are promising alternatives to platinum-based catalysts for the oxygen reduction reaction (ORR). However, the ORR process with multiple-step proton-coupled electron transfer occurring on a single-active site follows the linear scaling relation, making it difficult to break through Sabatier's limitation. Herein, we switch the ORR process from a sluggish associative pathway to a favorable dissociative one by constructing diatomic active sites with a Pt-like adsorption configuration, enabling the thermodynamic limit potential to break through Sabatier's vertex. Theoretical calculations and in situ characterization fully corroborate the Pt-like adsorption configuration of O2 on Ru–Fe dual sites, which renders the direct cleavage of O–O bonds and avoids the formation of *OOH intermediates, thus boosting the ORR kinetics. Consequently, the well-designed Ru and Fe co-doped catalysts with dual active sites (Ru, Fe-NC DAS) deliver extraordinary ORR catalytic performance, as manifested by the high half-wave potential of 0.843 V in an acid medium and a record-breaking peak power density of 1.152 W cm−2 in H2/O2 fuel cells, ranking at the top level of non-Pt catalysts reported so far. This work provides a new approach for designing highly efficient atomically dispersed catalysts and steering the corresponding catalytic reaction mechanisms.

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来源期刊
Energy & Environmental Science
Energy & Environmental Science 化学-工程:化工
CiteScore
50.50
自引率
2.20%
发文量
349
审稿时长
2.2 months
期刊介绍: Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences." Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).
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