A Cu₂O‐derived Polymeric Carbon Nitride Heterostructured Catalyst for the Electrochemical Reduction of Carbon Dioxide to Ethylene

Abstract

The electroreduction of carbon dioxide to hydrocarbons has been proposed as a promising way to utilize CO2 and maintain the ecosystem carbon balance. However, the selective reduction of CO2 to C2 hydrocarbons is still challenging. In this study, a highly efficient heterostructured catalyst has been developed, composed of a carbon nitride (CN)‐encapsulated copper oxide hybrid (CuxO/CN). The interaction between the metal and carbon nitride in the heterostructured catalysts improves the intrinsic electrical conductivity and the charge transfer processes at metal–support interfaces. A remarkable enhancement in the selectivity of hydrocarbons is achieved with these modified Cu‐based electrocatalysts, with an onset potential of −0.4 V and high C2H4 faradaic efficiency of 42.2 %, and these catalysts can also effectively suppress H2 evolution during the CO2 reduction reaction. This work provides a simple and cost‐effective method for synthesizing CN‐encapsulated catalysts that provides the possibility of efficiently converting CO2 into C2 hydrocarbons.

Efficiently Electroreducing CO2 to Ethylene on Heterostructured CeO2/CuO

“…X-ray photoelectron spectroscopy (XPS) was carried out to probe the composition and valence state of the catalyst. As shown in Figure a, the Cu2p spectrum exhibits two contributions, 2p3/2 and 2p1/2, located at ∼933 and ∼954 eV, which can be assigned to Cu 2+ . The Cu LMM Auger peak (Figure S6) located at ∼568.6 eV further reveals that only Cu 2+ species exist in our catalysts .…”

“…As shown in Figure 4a, the Cu2p spectrum exhibits two contributions, 2p3/2 and 2p1/2, located at ∼933 and ∼954 eV, which can be assigned to Cu 2+ . 39 The Cu LMM Auger peak (Figure S6) located at ∼568.6 eV further reveals that only Cu 2+ species exist in our catalysts. 40 Comparing with CeO 2 / CuO-50%, the binding energy of Cu2p in CuO shifts from 933.2 to 932.9 eV, providing evidence of an interaction between CuO and CeO 2 species.…”

Electro‐Synthesis of Organic Compounds with Heterogeneous Catalysis

“…A highly efficient heterostructured catalyst was developed by Lin et al, composed of a carbon nitride‐encapsulated copper oxide hybrid (Cu x O/CN). [ 164 ] In such a heterostructure, the metal and CN interaction enhance the intrinsic electrical conductivity and the charge transfer processes at the metal–support interfaces. Despite the high C 2 H 4 FE of 42.2%, these modified Cu‐based electrocatalysts offer remarkable enhancements in hydrocarbon selectivity and can also suppress the generation of H 2 during the eCO 2 RR.…”

g-C3N4 Nanosheet Supported CuO Nanocomposites for the Electrochemical Carbon Dioxide Reduction Reaction

“…The nature of the catalyst support can also influence product selectivity. Recent studies suggest that N-doped carbon supports can stabilize Cu in a Cu–N coordination environment during electrolysis and shows the product selectivity toward ethanol or other C2 products. − Cu on N-doped carbon has also been used in thermal catalysis and shows enhanced stability, and there are reports utilizing N-doped carbon as a catalyst support for electrocatalysis. − A theoretical study of Cu dimer on C 2 N predicts a favored product of C 2 H 4 . We hypothesize that the N-doped carbon support for CO 2 RR will stabilize the intermediate states of CO 2 adsorbates and the catalysts, which leads to specific CO 2 RR products, owing to the coordination between the N and the d-orbitals of the metal atoms.…”