Toward Efficient Carbon and Water Cycles: Emerging Opportunities with Single-Site Catalysts Made of 3d Transition Metals.

Advances in the chemical and electrochemical transformation of carbon and water are vital for delivering affordable and environmentally friendly energy sources and chemicals. Central to this challenge is the performance of materials. Traditionally, noble metal particles or metal complexes have been used as catalysts for many reactions. Recently, 3d transition-metal single-site catalysts (3dTM-SSCs) have emerged as potentially transformational candidates for the next-generation high-performance noble-metal-free catalysts. Designing catalysts at the molecular level can lead to a more efficient utilization of metal atoms and at the same time enhance catalytic performance under harsh reaction conditions. Despite this promise, several fundamental issues remain, in particular the structural evolution of 3dTM-SSCs during the synthesis, the molecular-level insights into the structure of the active sites, catalytic mechanisms, and the long-term cycling stability. Here, the material chemistries that facilitate the 3dTM-SSCs generation through a controlled pyrolytic synthesis are discussed, with focus on elucidating the underlying performance descriptors that can tune the catalytic properties in various critical reactions in carbon and water cycles. The current challenges and possible solutions for improving these novel catalytic materials are also highlighted.