Mixtures of phenols/ketones and urea show eutectic behavior upon gentle heating. These mixtures possess liquid-crystalline-like phases that can be processed. The architecture of phenol/ketone acts as structure-donating motif, while urea serves as melting-point reduction agent. Condensation at elevated temperatures results in nitrogen-containing carbons with remarkably high nitrogen content of mainly pyrazinic nature.
The synthesis, characterization, and electrocatalytic properties of mesoporous carbon materials doped with nitrogen atoms and iron are reported and compared for the catalyzed reduction of oxygen gas at fuel cell cathodes. Mixtures of common and inexpensive organic precursors, melamine, and formaldehyde were pyrolyzed in the presence of transition-metal salts (e.g., nitrates) within a mesoporous silica template to yield mesoporous carbon materials with greater extents of graphitization than those of others prepared from small-molecule precursors. In particular, Fe,N-doped carbon materials possessed high surface areas (∼800 m/g) and high electrical conductivities (∼19 S/cm), which make them attractive for electrocatalyst applications. The surface compositions of the mesoporous Fe,N-doped carbon materials were postsynthetically modified by acid washing and followed by high-temperature thermal treatments, which were shown by X-ray photoelectron spectroscopy to favor the formation of graphitic and pyridinic nitrogen moieties. Such surface-modified materials exhibited high electrocatalytic oxygen reduction activities under alkaline conditions, as established by their high onset and half-wave potentials (1.04 and 0.87 V, respectively vs reversible hydrogen electrode) and low Tafel slope (53 mV/decade). These values are superior to many similar transition-metal- and N-doped carbon materials and compare favorably with commercially available precious-metal catalysts, e.g., 20 wt % Pt supported on activated carbon. The analyses indicate that inexpensive mesoporous Fe,N-doped carbon materials are promising alternatives to precious metal-containing catalysts for electrochemical reduction of oxygen in polymer electrolyte fuel cells.
Risk research for nanomaterials is currently prioritized by means of expert workshops and other deliberative processes. However, analytical techniques that quantify and compare alternative research investments are increasingly recommended. Here, we apply value of information and portfolio decision analysis-methods commonly applied in financial and operations management-to prioritize risk research for multiwalled carbon nanotubes and nanoparticulate silver and titanium dioxide. We modify the widely accepted CB Nanotool hazard evaluation framework, which combines nano- and bulk-material properties into a hazard score, to operate probabilistically with uncertain inputs. Literature is reviewed to develop uncertain estimates for each input parameter, and a Monte Carlo simulation is applied to assess how different research strategies can improve hazard classification. The relative cost of each research experiment is elicited from experts, which enables identification of efficient research portfolios-combinations of experiments that lead to the greatest improvement in hazard classification at the lowest cost. Nanoparticle shape, diameter, solubility and surface reactivity were most frequently identified within efficient portfolios in our results.
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