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Issue 39, 2018
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A comprehensive approach providing a new synthetic route for bimetallic electrocatalysts via isoPOMs [M/Rh(Cp*)4W8O32] (M = Rh (1) and Ir (2))

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Abstract

Polyoxometalates (POMs) are highly versatile materials if paired with various conducting supports. We here present a new prospective approach for obtaining advanced electrocatalytic systems via POMs (1 and 2) nanostructured on Ni foam (NF) to give bimetallic nanohybrid composite materials M0.4Ni0.6/WO3 (M = Rh (3) or Ir (4)). By this pathway, two rare isopolyoctatungstate-based organometallic clusters [Hx(MCp*)4W8O32yH2O (in 1, M = Rh, x = 8, y = 23; in 2, M = Ir, x = 4, y = 17.33) have been synthesized via one-pot reactions using [Cp*MCl2]2 (Cp* = pentamethylcyclopentadienyl, M = Rh or Ir) and Na2WO4·2H2O in basic conditions. Compounds 1 and 2 were successfully nanostructured on the surface of commercially available NF and were thermally reduced to M0.4Ni0.6/WO3 (M = Rh (3) or Ir (4)) after annealing at 400 °C for 8 h in a 15% H2/N2 atmosphere. Electrodes modified with the POMs 3 and 4 exhibited remarkable HER activities in a 1 M KOH solution and achieved a current density of 10 mA cm−2 at low overpotentials of about 67 and 35 mV versus RHE, with Tafel slopes of 56 and 34 mV dec−1, respectively.

Graphical abstract: A comprehensive approach providing a new synthetic route for bimetallic electrocatalysts via isoPOMs [M/Rh(Cp*)4W8O32] (M = Rh (1) and Ir (2))

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Publication details

The article was received on 07 Aug 2018, accepted on 02 Sep 2018 and first published on 03 Sep 2018


Article type: Paper
DOI: 10.1039/C8DT03227K
Citation: Dalton Trans., 2018,47, 13870-13879
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    A comprehensive approach providing a new synthetic route for bimetallic electrocatalysts via isoPOMs [M/Rh(Cp*)4W8O32] (M = Rh (1) and Ir (2))

    V. Singh, P. Ma, M. G. B. Drew, J. Wang and J. Niu, Dalton Trans., 2018, 47, 13870
    DOI: 10.1039/C8DT03227K

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