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2. Transition metal nitrides (TMNs) are ideal candidates for noble metal catalyst supports in DMFCs because they are highly electrically conductive (metallic), thermally stable with high melting points, electrochemically stable in fuel cell operating conditions, and exhibit exceptional hardness and corrosion resistance. 21−23 However, in terms of fuel cell application, there are few publications dealing with metal nitrides as catalyst supports. The performance of a tungsten nitride supported on carbon black (W 2 N/C) as a non-noble electrocatalyst for the oxygen reduction reaction (ORR) in PEMFCs has been reported; this report concluded that the activity of the W 2 N/C catalyst toward the ORR was inferior to that of commercially available Pt/C catalysts already widely used in PEMFCs. 24 Titanium nitride (TiN) seems to be the most widely studied, but it suffers from wear and corrosion in acidic environments. 9,25,26 In contrast, chromium nitride (CrN) has high resistance to wear and corrosion. 27,28 CrN has been used as a coating material for bipolar plates in fuel cells, which is an important component of PEMFC stacks. 29,30 3. Various synthetic approaches to nanostructured metal nitrides have been reported including vapor deposition, nanopatterning, or other templating. 31−33 We recently reported a simple route for preparing mesoporous, conducting nitrides from Zn, Cd, or K-containing ternary transition metal oxides. 22,34,35 The reported nitride materials result from the condensation of atomic scale voids created by the evaporative loss of Zn or Cd, the replacement of 3 oxygen anions by 2 nitrogen anions, and, in most cases, the loss of oxygen to form water on the reduction of the transition metal. In the K case, the byproduct does not sublime away, but may be removed by washing with water. In this Article, we demonstrate a facile synthesis of mesoporous CrN with smaller pores and higher surface area than attainable using Zn- or Cd-containing precursor oxides from a potassium-containing oxide. We subsequently show that the CrN can be used as a Pt catalyst support for methanol electrooxidation, resulting in a Pt/CrN electrocatalyst that displays both higher electrocatalytic activity and higher corrosion resistance than the conventional Pt/C catalyst in PEMFCs. |
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