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PtM/C (M = Ni, Cu, or Ag) electrocatalysts: effects of alloying components on morphology and electrochemically active surface areas

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Abstract

The microstructures of Pt/C and PtM/C (M = Ni, Cu, or Ag) electrocatalysts were studied using X-ray diffraction and transmission electron microscopy (TEM). The electrochemically active surface areas of the prepared materials were estimated by cyclic voltammetry in 1 M H2SO4. The materials, with metal contents ranging from 30 to 35 wt.%, were synthesized by chemically reducing the metal precursors in water–ethylene glycol solutions. The actual composition of the bimetallic nanoparticles corresponds to a theoretical (1:1) composition for the PtAg/C catalysts, whereas in the PtNi/C and PtCu/C materials, a portion of the alloying component exists in an oxide form. Decreasing the average metallic crystallite sizes from 3.5 to 1.6 nm does not increase the electrochemically active surface area. This apparent contradiction is because a majority of the PtNi and PtCu nanoparticles consist of 2–4 disordered crystallites. In addition, a portion of the PtNi or PtCu nanoparticle surface is covered by nickel or copper oxides, respectively. PtAg nanoparticles, which have a smaller size relative to other bimetallic particles according to the TEM data, are characterized by an intense platinum surface segregation. The agglomeration processes are lowest for the PtAg nanoparticles.

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Notes

  1. The specific catalytic activities of Pt and its alloys (A*m−2) decrease if the nanoparticle diameter is less than 2–3 nm. The consequence of this effect is the extreme dependence of mass activity (A*gPt −1) on the catalyst ECSA [1, 7].

  2. The Ni content in the Pt–Ni alloy as calculated using Vegard's low is less than the calculated value. However, there are no nickel oxide/hydroxide reflections in the XRD patterns of the PtNi/C sample. This result suggests that the nickel oxide/hydroxide, which contains a portion of the metal in the PtNi/C, is in an amorphous state.

  3. The initial cyclic voltammograms for the as-prepared PtAg/C catalyst in 0.5 M H2SO4 exhibit anodic and cathodic peaks at potential ranges of 0.64–0.70 and 0.45–0.52 V, respectively. Similar peaks were detected for Ag/C in the same solution. The intensities of these peaks for the as-prepared PtAg/C catalyst reduce as the number of cycles increases. We hypothesize that the behaviors of these peaks are associated with the dissolution of silver and the subsequent electroreduction (in the cathodic part of the cycle) of previously formed silver sulfate. There are no such peaks in the CVs for the standardized PtAg/C catalyst.

  4. An assembly of crystallites can exceed the formation of isotropic nanoparticles, but at the initial stages of the transformation, we could expect the formation of nanoparticles with more complex shapes.

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Acknowledgments

This work was supported by the Russian Foundation for Basic Research (grants 10-03-00474a, 11-08-00499a) and by the Ministry of Education and Science of Russia (grants no. 14.740.11.0371 and 14.132.21.1468).

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Authors and Affiliations

  1. Chemistry Department, Southern Federal University, Zorge St. 7, 344090, Rostov-on-Don, Russia

    V. E. Guterman, T. A. Lastovina & S. V. Belenov

  2. National University of Science and Technology (MISIS), Moscow, Russia

    N. Yu. Tabachkova

  3. Institute of Physics, Southern Federal University, Rostov-on-Don, Russia

    V. G. Vlasenko

  4. Institute of Microelectronics Technology and High Purity Materials RAS, Chernogolovka, Russia

    I. I. Khodos

  5. Institute of Physical and Organic Chemistry, Southern Federal University, Rostov-on-Don, Russia

    E. N. Balakshina

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  1. V. E. Guterman
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Correspondence to V. E. Guterman.

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Guterman, V.E., Lastovina, T.A., Belenov, S.V. et al. PtM/C (M = Ni, Cu, or Ag) electrocatalysts: effects of alloying components on morphology and electrochemically active surface areas. J Solid State Electrochem 18, 1307–1317 (2014). https://doi.org/10.1007/s10008-013-2314-x

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