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Platinum Metals Rev., 2014, 58, (1), 40

doi:10.1595/147106713x675787

PGMs in the Lab: Platinum Group Metals in Polyoxometalates

Johnson Matthey and Alfa Aesar support new platinum group metals research

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Here another researcher whose work has benefited from the support of Johnson Matthey and Alfa Aesar, A Johnson Matthey Company, is profiled. Ulrich Kortz is a Professor of Chemistry at Jacobs University in Bremen, Germany, and he is interested in the synthesis and characterisation of noble metal-containing polyoxometalates.

About the Researcher

 

Professor Ulrich Kortz

* Name: Ulrich Kortz

* Position: Professor of Chemistry

* Department: School of Engineering and Science

* University: Jacobs University

* Street: Campus Ring 1

* City: Bremen

* Post or Zip Code: 28759

* Country: Germany

* Email Address: u.kortz@jacobs-university.de

* Website: http://www.jacobs-university.de/ses/ukortz

About the Research

Polyoxometalates (POMs) are a large class of discrete, soluble metal-oxo anions of early transition metals in high oxidation states, such as tungsten(VI) or molybdenum(VI). Due to a unique combination of properties, such as thermal and oxidative stability, tunability of acidity and redox activity, solubility in various media, and ability to undergo multistep multi-electron transfers without structural changes, POMs keep attracting more and more attention in different areas of fundamental and industrial science, in particular in homogeneous and heterogeneous catalysis.

Kortz's group are world leaders in the synthesis and characterisation of noble metal-containing polyanions. They prepared the first example of a Pt(IV)-containing polyoxovanadate, [H2PtIVV9O28]5- by a facile synthetic procedure, using the Pt(IV) precursor H2Pt(OH)6. The polyanion [H2PtIVV9O28]5- was characterised in the solid state by X-ray diffraction (XRD) and in solution by 195Pt and 51V NMR spectroscopy.

Their research also includes the first example of a Pd(II)-containing heteropolyoxometalate, [Cs2Na(H2O)10Pd3(α-SbIIIW9O33)2]9- which consists of two (α-SbW9O33) moieties linked by three square planar-coordinate Pd2+ ions resulting in a sandwich type structure (Figure 1(a)). The central belt is completed by two Cs+ and a Na+ ion which occupy the vacancies between the adjacent Pd centres, resulting in a polyanion with idealised C2v symmetry (Figure 1(b)).

Fig. 1. (a)

Combined polyhedral/ball-and-stick representation of [Cs2Na(H2O)10Pd3(α-SbIIIW9O33)2]9-. The WO6 octahedra are shown in red and the balls represent palladium (blue), antimony (green), caesium (yellow), sodium (purple) and water molecules (red); (b) ball-and-stick representation of the central belt of [Cs2Na(H2O)10Pd3(α-SbIIIW9O33)2]9- (Reprinted with permission from L.-H. Bi, M. Reicke, U. Kortz, B. Keita, L. Nadjo and R. J. Clark, Inorg. Chem., 2004, 43, (13), 3915. Copyright 2004 American Chemical Society)

Combined polyhedral/ball-and-stick representation of [Cs2Na(H2O)10Pd3(α-SbIIIW9O33)2]9-. The WO6 octahedra are shown in red and the balls represent palladium (blue), antimony (green), caesium (yellow), sodium (purple) and water molecules (red); (b) ball-and-stick representation of the central belt of [Cs2Na(H2O)10Pd3(α-SbIIIW9O33)2]9- (Reprinted with permission from L.-H. Bi, M. Reicke, U. Kortz, B. Keita, L. Nadjo and R. J. Clark, Inorg. Chem., 2004, 43, (13), 3915. Copyright 2004 American Chemical Society)

 

Kortz's group have pioneered the class of polyoxopalladates with the discovery of [PdII13AsV8O34(OH)6]8-, which has the shape and dimensions of a molecular nanocube (Figure 2). Meanwhile the same group has isolated several other polypalladate derivatives of various shapes, sizes and compositions. Kortz's group has also pioneered the class of polyoxoaurates with the discovery of [AuIII4AsV4O20]8-. The Se(IV) derivative of this polyanion has also been reported very recently.

Fig. 2.

Ball-and-stick representation of [PdII13AsV8O34(OH)6]8-. The colour code of the balls is as follows: Pd (green), As (blue), O (red). Hydrogens not shown (Copyright 2013 Professor Ulrich Kortz)

Ball-and-stick representation of [PdII13AsV8O34(OH)6]8-. The colour code of the balls is as follows: Pd (green), As (blue), O (red). Hydrogens not shown (Copyright 2013 Professor Ulrich Kortz)

 

Polyoxo-noble-metalates can be used in a wide range of applications such as catalysis, analysis, medicine, biochemistry and materials science.

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Selected Publications

  1.  Y. Xiang, N. V. Izarova, F. Schinle, O. Hampe, B. Keita and U. Kortz, Chem. Commun., 2012, 48, (79), 9849 LINK http://dx.doi.org/10.1039/c2cc33795a
  2.  M. Barsukova-Stuckart, N. V. Izarova, R. A. Barrett, Z. Wang, J. van Tol, H. W. Kroto, N. S. Dalal, P. Jiménez-Lozano, J. J. Carbó, J. M. Poblet, M. S. von Gernler, T. Drewello, P. de Oliveira, B. Keita and U. Kortz, Inorg. Chem., 2012, 51, (24), 13214 LINK http://dx.doi.org/10.1021/ic301537n
  3.  N. V. Izarova, M. T. Pope and U. Kortz, Angew. Chem. Int. Ed., 2012, 51, (38), 9492 LINK http://dx.doi.org/10.1002/anie.201202750
  4.  N. V. Izarova, A. Banerjee and U. Kortz, Inorg. Chem., 2011, 50, (20), 10379 LINK http://dx.doi.org/10.1021/ic201451x
  5.  N. V. Izarova, N. Vankova, T. Heine, R. N. Biboum, B. Keita, L. Nadjo and U. Kortz, Angew. Chem. Int. Ed., 2010, 49, (10), 1886 LINK http://dx.doi.org/10.1002/anie.200905566
  6.  N. V. Izarova, N. Vankova, A. Banerjee, G. B. Jameson, T. Heine, F. Schinle, O. Hampe and U. Kortz, Angew. Chem. Int. Ed., 2010, 49, 7807 LINK http://dx.doi.org/10.1002/anie.201001738
  7.  E. V. Chubarova and U. Kortz, Exxonmobil Chemical Company, ‘Novel Heteropolyanions with Late Transition Metal Addenda Atoms and Process for their Preparation’, US Patent Appl. 2009/0,216,052
  8.  U. Lee, H.-C. Joo, K.-M. Park, S. S. Mal, U. Kortz, B. Keita and L. Nadjo, Angew. Chem. Int. Ed., 2008, 47, (4), 793 LINK http://dx.doi.org/10.1002/anie.200703082
  9.  E. V. Chubarova, M. H. Dickman, B. Keita, L. Nadjo, F. Miserque, M. Mifsud, I. W. C. E. Arends and U. Kortz, Angew. Chem. Int. Ed., 2008, 47, (49), 9542 LINK http://dx.doi.org/10.1002/anie.200803527
  10.  L.-H. Bi, M. Reicke, U. Kortz, B. Keita, L. Nadjo and R. J. Clark, Inorg. Chem., 2004, 43, (13), 3915 LINK http://dx.doi.org/10.1021/ic049736d

Additional Information

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