Dual-Sites Tandem Catalysts for C–N Bond Formation via Electrocatalytic Coupling of CO₂ and Nitrogenous Small Molecules

Abstract

The electrocatalytic carbon dioxide reduction (ECR) to fuels and feedstocks driven by renewable energy is a promising approach to alleviate the environmental and energy crisis. Recently, high-performance ECR catalysts for producing simple products has been achieved. However, the producing of chemicals with high industrial significance still remains challenging. Coupling the reduction of CO 2 and nitrogenous small molecules (N 2 , NO 2 , NH 3 etc.) is one potential solution and is currently attracting increased interest. Here, we propose a rational perspective of constructing heterogeneous dual-active site catalysts (DACs) for the C−N coupling in ECR, which could provide isolated dual sites for coupling the C and N intermediates and thus improve the C−N coupling efficiency. In this Perspective, by investigating the possible pathway of C− N coupling reaction in the co-reduction process of CO 2 with nitrogenous molecules and the reported strategies for building DACs, we discuss and project the potential strategies and challenges for the in-depth construction of C−N coupling tandem DACs systems. These insights may open up opportunities to develop high-efficiency DACs for diverse coupling electrocatalytic reactions and offer higher economic benefits and broader application prospects of electrocatalysis.

Identifying and tailoring C–N coupling site for efficient urea synthesis over diatomic Fe–Ni catalyst

“…Above results indicate that owing to the structural simplicity of the active centers, the single-atom system possesses the intrinsic disadvantages to handle the complex catalytic reaction involving multiple reactants and intermediate species 31 . The construction of diatomic site configurations has emerged as the feasible strategy to realize the coordinated adsorption and activation, and efficient electrocatalytic coupling reaction.…”

Accessing Organonitrogen Compounds via C–N Coupling in Electrocatalytic CO2 Reduction

“…A key would be to optimize the binding strength between the coupling intermediates and the catalyst to favor the chemical coupling with respect to the electrochemical reduction. One strategy could be to develop a dual-site catalyst where one type of sites is active for CO 2 reduction and the other for N precursor reduction, which has been discussed by Fu et al recently . This may allow independent optimization of the CO 2 and N precursor reductions.…”

“…One strategy could be to develop a dual-site catalyst where one type of sites is active for CO 2 reduction and the other for N precursor reduction, which has been discussed by Fu et al recently. 37 This may allow independent optimization of the CO 2 and N precursor reductions. It could also offer an opportunity to increase the coupling efficiency by positioning these two sites adjacent to each other.…”

“…In the past three decades, particularly the past few years, there have been a notable number of studies in this area that have yielded amide and amine products from N-integrated electrochemical CO 2 reduction reactions. Although some examples in this area have been touched upon in a couple of recent reviews of electrocatalytic processes and/or catalyst materials development, ,, there has not yet been a dedicated review on this topic with a focus on catalytic reactivity and reaction mechanisms.…”

Understanding the Site‐Selective Electrocatalytic Co‐Reduction Mechanism for Green Urea Synthesis Using Copper Phthalocyanine Nanotubes

“…and CO 2 through the formation of CN bond coupling. [ 14,17–24 ] And finally, for the suppression of hydrogen evolution reaction (HER), choice of electrolyte and catalyst are very crucial for electrochemical urea synthesis. [ 14 ] In this regard, electrocatalyst having multiple active sites and selectivity toward both nitrogen reduction reaction (NRR) and carbon dioxide reduction reaction under the similar potential window may be effective for urea synthesis in water medium at standard temperature and pressure (STP).…”