Surface-Limited Galvanic Replacement Reactions of Pd, Pt, and Au onto Ag Core Nanoparticles through Redox Potential Tuning

Surface-Limited Galvanic Replacement Reactions of Pd, Pt, and Au onto Ag Core Nanoparticles through Redox Potential Tuning
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通过氧化还原电位调节在银核纳米颗粒上进行 Pd、Pt 和 Au 的表面限制电偶置换反应

DOI:
10.1021/acs.chemmater.1c04176
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发表时间:
2022
影响因子:
8.6
通讯作者:
Li, Christina W.
Li, Christina W.
中科院分区:
材料科学2区
文献类型:
--
作者:
Yadav, Vamakshi;Jeong, Soojin;Ye, Xingchen;Li, Christina W.

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原电池置换反应(GRR)已成为一种强大的合成策略,以获得中空和形态复杂的纳米结构。在文献中已经做了大量的工作来改变GRR的合成参数,但是实现表面自限制电流交换仍然具有挑战性。在这项工作中,我们调整的范围之间的GRR银纳米粒子和Pd,Pt,和Au离子通过定制的络合金属阳离子与有机胺和膦配体。增加结合的有机配体的数量系统地降低了金属离子的还原电位,因此降低了与Ag 0的GRR的驱动力。在每种情况下,我们能够获得具有足够低的GRR驱动力的氧化的金属-配体络合物,以限制金属沉积到Ag核的表面。该合成方法作为合成Ag@AgM或Ag@M(M = Pd、Pt、Au)核-壳纳米颗粒的一般策略,并且可以扩展到贱金属核与贵金属络合物的其他电化学置换反应。通过将Pt和Pd原子仅沉积在纳米颗粒的表面,这些材料在电催化析氢反应中表现出良好的质量活性。
Galvanic replacement reactions (GRR) have served as a powerful synthetic strategy to obtain hollow and morphologically complex bimetallic nanostructures. Extensive work has been done in the literature to vary the synthetic parameters of GRR, but achieving a surface self-limiting galvanic exchange remains challenging. In this work, we tune the extent of GRR between Ag0nanoparticles and Pd, Pt, and Au ions through tailored complexation of metal cations with organic amine and phosphine ligands. Increasing the number of bound organic ligands systematically lowers the reduction potential of the metal ion and therefore the driving force toward GRR with Ag0. In each case, we are able to obtain an oxidized metal–ligand complex with a sufficiently low GRR driving force to restrict metal deposition to the surface of the Ag core. This synthetic method serves as a general strategy to synthesize bimetallic Ag@AgM or Ag@M (M = Pd, Pt, Au) core-shell nanoparticles and may be extendable to other galvanic replacement reactions of base metal cores with noble metal complexes. By depositing the Pt and Pd atoms only at the surface of the nanoparticle, these materials exhibit good mass-activity in the electrocatalytic hydrogen evolution reaction.
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