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(Invited) Boosting Non-Precious Metal Catalysts Toward the Oxygen Reduction Reaction through Ionic Liquid Modification

机译:(邀请)通过离子液体改性促进非贵金属催化剂朝向氧还原反应

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Finding cost effective catalysts for the oxygen reduction reaction (ORR) is one of the most overriding challenges in the field of electrochemistry. Carbon-based materials emerge as one of the promising candidates due to their remarkable advantages of low cost, abundant structural variety, tailorable surface chemistry, and good conductivity. Tremendous efforts have been made to improve the performance of carbon-based materials for the ORR, mainly through modifying the inherent structures of carbon by doping heteroatoms (e.g., B, N, P) or combining with metal/metal oxides. We have demonstrated recently that modifying Pt-based catalysts by a minor amount of ionic liquid (IL, e.g., [BMIM][NTf_2], [MTBD][NTf_2]) could significantly boost their ORR activity. This innovative strategy has also been successfully transferred to some non-precious metal Fe-N-C catalysts, on which an ionic liquid ([BMMIM][NTf_2]) modification is found to boost both their activity and stability. In the current contribution, we will present our latest progress toward boosting the emerging zeolitic imidazolate framework (ZIF)-derived carbons (ZDC) for the ORR using IL modification strategy. First we verified again the boosting effect of IL toward the ORR on the as-synthesized ZDC materials. The half wave potential of ORR on these ZDCs is positively shifted by up to 18 mV and their intrinsic kinetic current (@ 0.85 V) is increased by a factor of 2 after being modified with [BMMIM][NTf2]. At the same time, it is observed that the boosting effect from IL modification is highly sensitive to the exact loading amount of the IL. Exceeding a specific loading amount, however, leads to a mass transport related activity drop. Moreover, it is also unraveled that the IL takes effect by increasing electrochemically accessible surface area, as reflected by the significantly enhanced double layer capacitance of ZDCs after IL modification. These results again demonstrate the great promise of the IL modification strategy as a generic method to improve ORR catalysts, and at the same time are anticipated to form the basis for an unprecedented perspective in developing high-performing non-precious metal catalysts for low temperature fuel cell applications.
机译:寻找用于氧还原反应(ORR)的成本效益催化剂是电化学领域中最重要的挑战之一。由于其卓越的成本优势,丰富的结构品种,可定制的表面化学和良好的导电性,碳基材料作为承诺的候选人之一。已经通过通过掺杂杂原子(例如,B,N,P)或与金属/金属氧化物组合来改变碳的碳基材料的性能来提高ORR的碳基材料的性能。最近我们已经证明,通过少量的离子液体(例如,[Bmim] [Bmim] [NTF_2],[MTBD] [NTF_2])来修饰Pt基催化剂可以显着提高其ORR活性。这种创新策略也已成功转移到一些非贵金属Fe-N-C催化剂上,其中发现离子液体([Bmmim] [NTF_2])改性来提高它们的活性和稳定性。在目前的贡献中,我们将在使用IL修改策略中提高促进新兴沸石咪唑酯框架(ZIF)的碳(ZDC)的最新进展。首先,我们再次验证了IL朝向AS合成ZDC材料上的ORR的升压效果。在这些ZdC上的ORR的半波电位呈正换档,最多偏移至18mV,并且它们的固有动力电流(@ 0.85V)在用[Bmmim] [NTF2]改性后增加了2倍。同时,观察到IL修饰的升压效果对IL的精确装载量非常敏感。然而,超过特定的负载量导致大规模运输相关的活性下降。此外,还解开了IL通过增加电化学可访问的表面积来实现,如IL修改后的ZDC的显着增强的双层电容反射。这些结果再次证明了IL改性策略作为改善ORR催化剂的通用方法的巨大希望,并且预计将在开发用于低温燃料的高性能非贵金金属催化剂时形成前所未有的观点的基础细胞应用。

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