Daniel Malko

In situ electrochemical quantification of active sites in Fe–N/C non-precious metal catalysts

The economic viability of low temperature fuel cells as clean energy devices is enhanced by the development of inexpensive oxygen reduction reaction catalysts. Heat treated iron and nitrogen containing carbon based materials (Fe–N/C) have shown potential to replace expensive precious metals. Although significant improvements have recently been made, their activity and durability is still unsatisfactory. The further development and a rational design of these materials has stalled due to the lack of an in situ methodology to easily probe and quantify the active site. Here we demonstrate a protocol that allows the quantification of active centres, which operate under acidic conditions, by means of nitrite adsorption followed by reductive stripping, and show direct correlation to the catalytic activity. The method is demonstrated for two differently prepared materials. This approach may allow researchers to easily assess the active site density and turnover frequency of Fe–N/C catalysts.

The intriguing poison tolerance of non-precious metal oxygen reduction reaction (ORR) catalysts

Electrochemical devices such as fuel cells are key to a sustainable energy future. However the applicability of such under realistic conditions is not viable to date. Expensive precious metals are used as electrocatalysts and contaminants present in the operating media poison the utilized catalysts. Here the one pot synthesis of a highly active, self-supporting and surprisingly poison tolerant catalyst is reported. The polymerisation of 1,5-diaminonaphthalene provides self-assembled nanospheres, which upon pyrolysis form a catalytically active high surface area material. Tolerance to a wide range of substances that poison precious metal based catalysts combined with high electrocatalytic activity might enable numerous additional technological applications. In addition to fuel cells these could be metal–air batteries, oxygen-depolarized chlor-alkali cathodes, oxygen sensors, medical implantable devices, waste water treatment and as counter electrodes for many other sensors where the operating medium is a complex and challenging mixture.

Carbon foams from emulsion-templated reduced graphene oxide polymer composites: electrodes for supercapacitor devices

Amphiphilic reduced graphene oxide (rGO) is an efficient emulsifier for water-in-divinylbenzene (DVB) high internal phase emulsions. The polymerisation of the continuous DVB phase of the emulsion template and removal of water results in macroporous poly(divinylbenzene) (polyDVB). Subsequent pyrolysis of the poly(DVB) macroporous polymers yields ‘all-carbon’ foams containing micropores alongside emulsion templated-macropores, resulting in hierarchical porosity. The synthesis of carbon foams, or ‘carboHIPEs’, from poly(DVB) produced by polymerisation of rGO stabilised HIPEs provides both exceptionally high surface areas (up to 1820 m2 g−1) and excellent electrical conductivities (up to 285 S m−1), competing with the highest figures reported for carboHIPEs. The use of a 2D carbon emulsifier results in the elimination of post-carbonisation treatments to remove standard inorganic particulate emulsifiers, such as silica particles. It is demonstrated that rGO containing carboHIPEs are good candidates for supercapacitor electrodes where carboHIPEs derived from more conventional polymerised silica-stabilised HIPEs perform poorly. Supercapacitor devices featured a room-temperature ionic liquid electrolyte and electrodes derived from either rGO- or silica-containing poly(DVB)HIPEs demonstrated a maximum specific capacitance of 26 F g−1, an energy density of 5.2 W h kg−1 and a power density of 280 W kg−1.