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Abstract Despite the pivotal roles played by halide ions (e. g., Cl−and Br−) in directing the evolution of seeds into metal nanocrystals with diverse shapes, it is still unclear how halides affect the reduction kinetics of a salt precursor and thus the outcome of a synthesis. Here we report a quantitative analysis of the multiple roles played by halides in controlling the growth behaviors of Pd seeds with cubic and octahedral shapes, respectively. Our quantitative measurements clearly indicate the existence of a transition point around 10−3 mM min−1for the reduction rate, which separates the reduction into two distinctive pathways (solutionversussurface) for the formation of completely different products. More significantly, we demonstrate that the speciation, reduction kinetics, and reduction pathway of a Pd(II) precursor can all be manipulated by varying the type and/or amount of halides introduced into a synthesis for the deterministic formation of a specific product. This work represents a critical step forward in achieving a quantitative understanding of the multiple roles of halides involved in the shape‐controlled synthesis of Pd nanocrystals, with the knowledge potentially extendible to other noble metals and their alloys.
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One‐Pot Polyol Synthesis and Scalable Production of Rh−Pd Alloy Nanorods with Tunable Compositions
Abstract Combining different precious metals to generate alloy nanocrystals with desirable shapes and compositions remains a challenge because of the low miscibility between these metals and/or the different reduction potentials of their salt precursors. Specifically, Rh and Pd are considered to be immiscible in the bulk solid over the entire composition range. Here we demonstrate that Rh−Pd alloy nanorods with well‐distributed and tunable compositions can be synthesized using a one‐pot polyol method. The success of our synthesis relies on the introduction of bromide as a coordination ligand to tune the redox potentials of Rh(III) and Pd(II) ions for the achievement of co‐reduction. The atomic ratio of the Rh−Pd alloy nanorods can be facilely tuned by changing the molar feeding ratio between the two precursors. We also systematically investigate the effects of water on the morphology of the Rh−Pd alloy nanocrystals. In an attempt to promote future use of these alloy nanorods, we successfully scale up their synthesis in a continuous‐flow reactor with no degradation to the product quality.
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- Award ID(s):
- 2219546
- PAR ID:
- 10435624
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemNanoMat
- Volume:
- 9
- Issue:
- 12
- ISSN:
- 2199-692X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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