No abstract

Replacing precious platinum with earth-abundant materials for the oxygen reduction reaction (ORR) in fuel cells has been the objective worldwide for several decades. In the last ten years, the fastestgrowing branch in this area has been carbon-based metal-free ORR electrocatalysts. Great progress has been made in promoting the performance and understanding the underlying fundamentals.Here, a comprehensive review of this field is presented by emphasizing the emerging issues including the predictive design and controllable construction of porous structures and doping configurations, mechanistic understanding from the model catalysts, integrated experimental and theoretical studies, and performance evaluation in full cells. Centering on these topics, the most upto-date results are presented, along with remarks and perspectives for the future development of carbon-based metal-free ORR electrocatalysts.

Carbon-based, metal-free catalysts showed excellent activity, durability and potential to replace Pt in acidic fuel cells.

It is still a grand challenge to develop a highly efficient nonprecious-metal electrocatalyst to replace the Pt-based catalysts for oxygen reduction reaction (ORR). Here, we propose a surfactant-assisted method to synthesize single-atom iron catalysts (SA-Fe/NG). The half-wave potential of SA-Fe/NG is only 30 mV less than 20% Pt/C in acidic medium, while it is 30 mV superior to 20% Pt/C in alkaline medium. Moreover, SA-Fe/NG shows extremely high stability with only 12 mV and 15 mV negative shifts after 5,000 cycles in acidic and alkaline media, respectively. Impressively, the SA-Fe/NG-based acidic proton exchange membrane fuel cell (PEMFC) exhibits a high power density of 823 mW cm Combining experimental results and density-functional theory (DFT) calculations, we further reveal that the origin of high-ORR activity of SA-Fe/NG is from the Fe-pyrrolic-N species, because such molecular incorporation is the key, leading to the active site increase in an order of magnitude which successfully clarifies the bottleneck puzzle of why a small amount of iron in the SA-Fe catalysts can exhibit extremely superior ORR activity.

Sulfur-stabilized intermetallic nanoparticles Nanoparticles of intermetallic alloys of platinum could have enhanced electronic properties that improve their catalytic activity, but the high temperatures needed to ensure complete atomic diffusion often lead to the growth of larger nanoparticles—sintering—with low surface area and hence low overall activity. Yang et al . show that sulfur-doped carbon supports create strong platinum-sulfur bonds that stabilize small platinum alloy nanoparticles (<5 nanometers in diameter) to temperatures up to 1000ºC. They screened libraries of platinum alloys and identified ones with high mass activity for the oxygen reduction reaction in hydrogen fuel cells. —PDS