A Modeling Study of PEM Fuel Cell with Novel Catalyst Monolayers under Low Platinum Loading

Cost is a major barrier to commercialization of polymer electrolyte membrane (PEM) fuel cells. Catalyst layers (CLs) contribute to a major portion of PEM fuel cell cost due to the...

Using pH dependence to understand mechanisms in electrochemical CO reduction

Electrochemical conversion of CO(2) into hydrocarbons and oxygenates is envisioned as a promising path towards closing the carbon cycle in modern technology. To this day, however, the reaction mechanisms towards the plethora of products are disputed, complicating the search for novel catalyst materials. In order to conclusively identify the rate-limiting steps in CO reduction on Cu, we analyzed the mechanisms on the basis of constant potential DFT kinetics and experiments at a wide range of pH values (3 - 13). We find that *CO dimerization is energetically favoured as the rate limiting step towards multi-carbon products. This finding is consistent with our experiments, where the reaction rate is nearly unchanged on an SHE potential scale, even under acidic conditions. For methane, both theory and experiments indicate a change in the rate-limiting step with electrolyte pH from the first protonation step in acidic/neutral conditions to a later one in alkaline conditions. We also show, through a detailed analysis of the microkinetics, that a surface combination of *CO and *H is inconsistent with the measured current densities and Tafel slopes. Finally, we discuss the implications of our understanding for future mechanistic studies and catalyst design.

Magnetic composite of γ-Fe2O3 hollow sphere and palladium doped nitrogen-rich mesoporous carbon as a recoverable catalyst for C–C coupling reactions

In this article, palladated-magnetic nitrogen doped porous carbon was prepared from nano magnetic γ-Fe2O3 hollow sphere (h-Fe2O3) with high specific surface area and pore volume. To the purpose, initially h-Fe2O3 was prepared and covered with glucose via hydrothermal treatment with subsequent polymerization of organic shell. The polymerization of melamine-resorcinol–formaldehyde (MRF) was achieved in the presence of Cl-functionalized glucose coated h-Fe2O3 (h-Fe2O3@glu-MRF). Next, the prepared magnetic core–shell hollow sphere was palladated followed by carbonization to yield Pd@h-Fe2O3@C introducing more pores in its structure. The resulted compound, Pd@h-Fe2O3@C, was fully characterized, showing that carbonization process expressively increased the specific surface area. The resulted Pd@h-Fe2O3@C was successfully used for promoting C–C coupling reactions under mild reaction conditions as a heterogeneous catalyst and its activity was compared with some prepared control catalysts. This novel catalyst was magnetically separated simply by a magnet bar and recycled and reused at least in five consecutive runs, without considerable loss of its activity. It is note mentioning that, high recyclability with low Pd leaching are another gains of this protocol.