No abstract

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.

A class of 2D covalent organic polymers (COPs) incorporating a metal (such as Fe, Co, Mn) with precisely controlled locations of nitrogen heteroatoms and holes were synthesized from various N-containing metal-organic complexes (for example, metal-porphyrin complexes) by a nickel-catalyzed Yamamoto reaction. Subsequent carbonization of the metal-incorporated COPs led to the formation of COP-derived graphene analogues, which acted as efficient electrocatalysts for oxygen reduction in both alkaline and acid media with a good stability and free from any methanol-crossover/CO-poisoning effects.

Porous covalent-organic materials (COMs) are a fascinating class of nanoporous material with high surface area and diverse pore dimensions, topologies and chemical functionalities. These materials have attracted ever-increasing attention from different field scientists, owing to their potential applications in gas storage, adsorptive separation and photovoltaic devices. The versatile networks are constructed from covalent bonds (B-O, C-C, C-H, C-N, etc.) between the organic linkers by homo-or hetero-polymerizations. To design and synthesize novel porous COMs, we first summarize their synthesis methods, mainly including five kinds of coupling reaction, i.e. boronic acid, amino, alkynyl, bromine and cyan group-based coupling reactions. Then, we review the progress of porous COMs in clean energy applications in the past decade, including hydrogen and methane storage, carbon dioxide capture, and photovoltaic applications. Finally, to improve their gas adsorptive properties, four possible strategies are proposed, and high-capacity COMs for gas storage are designed by a multiscale simulation approach.