To restore the natural nitrogen cycle (N-cycle), artificial N-cycle electrocatalysis with flexibility, sustainability, and compatibility can convert intermittent renewable energy (e.g., wind) to harmful or value-added chemicals with minimal carbon emissions. The background of such N-cycles, such as nitrogen fixation, ammonia oxidation, and nitrate reduction, is briefly introduced here. The discussion of emerging nanostructures in various conversion reactions is focused on the architecture/compositional design, electrochemical performances, reaction mechanisms, and instructive tests. Energy device advancements for achieving more functions as well as <i>in situ</i>/<i>operando</i> characterizations toward understanding key steps are also highlighted. Furthermore, some recently proposed reactions as well as less discussed C–N coupling reactions are also summarized. We classify inorganic nitrogen sources that convert to each other under an applied voltage into three types, namely, abundant nitrogen, toxic nitrate (nitrite), and nitrogen oxides, and useful compounds such as ammonia, hydrazine, and hydroxylamine, with the goal of providing more critical insights into strategies to facilitate the development of our circular nitrogen economy. 

https://www.sciopen.com/article_pdf/1531201054523838466.pdf

Recent advances in nanostructured heterogeneous catalysts for N-cycle electrocatalysis

Polyoxometalates (POMs) represent a class of nanomaterials, which hold enormous promise for a range of energy-related applications. Their promise is owing to their “special” structure that gives POMs a truly unique ability to control redox reactions in energy conversion and storage. One such amazing capability is their large number of redox active sites that arises from the complex three-dimensional cluster of metal-oxide ions linked together by oxygen atoms. Here, a critical review on how POMs emerged from being molecular clusters for fundamental studies, to next-generation materials for energy applications is provided. We highlight how exploiting the versatility and activity of these molecules can lead to improved performance in energy devices such as supercapacitors and batteries, and in energy catalyst applications. The potential of POMs across numerous fields is systematically outlined by investigating structure–property–performance relationships and the determinant factors for energy systems. Finally, the challenges and opportunities for this class of materials with respect to addressing our pressing energy-related concerns are identified.

Polyoxometalates (POMs): from electroactive clusters to energy materials

Improving the photocatalytic H2 evolution activity of Keggin polyoxometalates anchoring copper-azole complexes

FeS2/MoS2@RGO hybrid materials derived from polyoxomolybdate-based metal–organic frameworks as high-performance electrocatalyst for ammonia synthesis under ambient conditions

Two-dimensional (2D) metal–organic frameworks (MOFs) serve as emerging electrocatalysts due to their high conductivity, chemical tunability, and accessibility of active sites. We herein proposed a series of 2D MOFs with different metal atoms and organic linkers with the formula M3C12X12 (M = Cr, Mo, and W; X = NH, O, S, and Se) to design efficient nitrogen reduction reaction (NRR) electrocatalysts. Our theoretical calculations showed that metal atoms in M3C12X12 can efficiently capture and activate N2 molecules. Among these candidates, W3C12X12 (X = O, S, and Se) show the best NRR performance due to their high activity and selectivity as well as low limiting potential (−0.59 V, −0.14 V, and −0.01 V, respectively). Moreover, we proposed a d-band center descriptor strategy to screen out the high activity and selectivity of M3C12X12 for the NRR. Therefore, our work not only demonstrates a class of promising electrocatalysts for the NRR but also provides a strategy for further predicting the catalytic activity of 2D MOFs.

Design strategies of two-dimensional metal-organic frameworks toward efficient electrocatalysts for N2 reduction: cooperativity of transition metals and organic linkers.

Jingxiang Zhao

Papers

Polyoxometalate-based metal–organic framework-derived bimetallic hybrid materials for upgraded electrochemical reduction of nitrogen