Julia G. Buschermöhle*, Julia Müller-Hülstede, Henrike Schmies, Dana Schonvogel, Tanja Zierdt, Rene Lucka, Franz Renz, Peter Wagner and Michael Wark,
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In order to enhance the stability and activity of Fe–N–Cs, this study investigates the incorporation of tin as a second metal, resulting in Fe–Sn–N–Cs, prepared by a metal–organic framework (MOF)-based approach. Stable and highly active catalysts with total mass activities of 8.2 A g<sup>–1</sup> (Fe–Sn–N–C (1:1)) and 19.3 A g<sup>–1</sup> (Fe–Sn–N–C (1:0.3)) in 0.5 mol L<sup>–1</sup> H<sub>3</sub>PO<sub>4</sub>, drastically exceeding those of the commercial Fe–N–C catalyst PMF-014401 (Pajarito-Powder, 4.8 A g<sup>–1</sup>), are obtained by a synthesis without the need for subsequent purification steps. A stress test under harsh conditions (0.6–1.0 V<sub>RHE</sub>, 10,000 cycles, O<sub>2</sub>-saturated electrolyte) ascertains stability-enhancing effects of tin, highlighting an increase in stability in conjunction with the tin content. 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引用次数: 0
摘要
高温质子交换膜燃料电池(ht - pemfc)通常依赖于铂基催化剂,由于磷酸掺杂膜上的磷酸盐使Pt失活,因此需要高负载。作为氧还原反应的替代催化剂,金属-氮-碳(M-N-Cs)具有较高的内在活性和对磷酸盐的耐受性,具有广阔的应用前景。然而,与Pt纳米粒子相比,Pt纳米粒子在炭黑(Pt/C)上的体积活度较低,稳定性不足,限制了它们的适用性。为了提高Fe-N-Cs的稳定性和活性,本研究采用金属有机骨架(MOF)法制备了Fe-Sn-N-Cs。在0.5 mol L-1 H3PO4中,该催化剂的总质量活性分别为8.2 A g-1 (Fe-Sn-N-C(1:1))和19.3 A g-1 (Fe-Sn-N-C(1:0.3)),大大超过了商品Fe-N-C催化剂PMF-014401 (pajarto - powder, 4.8 A g-1)。在恶劣条件下(0.6-1.0 VRHE, 10,000次循环,o2饱和电解质)的压力测试确定了锡的稳定性增强作用,突出了锡含量增加的稳定性。这些结果通过显著提高无铂族金属催化剂的催化活性,为开发具有成本效益的ht - pemfc提供了有价值的贡献。
High-temperature proton exchange membrane fuel cells (HT-PEMFCs) typically rely on platinum-based catalysts, which require high loadings due to Pt deactivation by phosphates from the phosphoric acid-doped membrane. As alternative catalysts for the oxygen reduction reaction, metal–nitrogen-carbons (M–N–Cs) are promising due to their high intrinsic activity and tolerance to phosphates. However, low volumetric activity compared to Pt nanoparticles on carbon blacks (Pt/C) and insufficient stability limit their applicability. In order to enhance the stability and activity of Fe–N–Cs, this study investigates the incorporation of tin as a second metal, resulting in Fe–Sn–N–Cs, prepared by a metal–organic framework (MOF)-based approach. Stable and highly active catalysts with total mass activities of 8.2 A g–1 (Fe–Sn–N–C (1:1)) and 19.3 A g–1 (Fe–Sn–N–C (1:0.3)) in 0.5 mol L–1 H3PO4, drastically exceeding those of the commercial Fe–N–C catalyst PMF-014401 (Pajarito-Powder, 4.8 A g–1), are obtained by a synthesis without the need for subsequent purification steps. A stress test under harsh conditions (0.6–1.0 VRHE, 10,000 cycles, O2-saturated electrolyte) ascertains stability-enhancing effects of tin, highlighting an increase in stability in conjunction with the tin content. These results provide a valuable contribution to the development of cost-effective HT-PEMFCs by significantly enhancing the catalytic activity of platinum group metal-free catalysts.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.