A hydrophobic core–shell architecture was constructed to control local H2O availability on the surface of the copper-based materials, which could provide a maximum generation rate of −434 mA cm−2 towards CH4.

Electrochemical CO 2 -to-CO conversion provides a possible way to address problems associated with the greenhouse effect; however, developing low-cost electrocatalysts to mediate high-efficiency CO 2 reduction remains a challenge on account of the limited understanding of the nature of the real active sites. Herein, we reveal the Zn δ + metalloid sites as the real active sites of stable nonstoichiometric ZnO x structure derived from Zn 2 P 2 O 7 through operando X-ray absorption fine structure analysis in conjunction with evolutionary-algorithm-based global optimization. Furthermore, theoretical and experimental results demonstrated that Zn δ + metalloid active sites could facilitate the activation of CO 2 and the hydrogenation of *CO 2 , thus accelerating the CO 2 -to-CO conversion. Our work establishes a critical fundamental understanding of the origin of the real active center in the zinc-based electrocatalysts for CO 2 reduction reaction.

To rationally locate the high-performance atomically dispersed catalyst remains a challenge, albeit wide explorations in numerous critical chemical reactions. Here, taking the cohesive-energy property of metal (Ec) as the descriptor,...

Electrochemical CO 2 -to-CO conversion provides a possible way to address problems associated with the greenhouse effect; however, developing low-cost electrocatalysts to mediate high-efficiency CO 2 reduction remains a challenge on account of the limited understanding of the nature of the real active sites. Herein, we reveal the Zn δ + metalloid sites as the real active sites of stable nonstoichiometric ZnO x structure derived from Zn 2 P 2 O 7 through operando X-ray absorption fine structure analysis in conjunction with evolutionary-algorithm-based global optimization. Furthermore, theoretical and experimental results demonstrated that Zn δ + metalloid active sites could facilitate the activation of CO 2 and the hydrogenation of *CO 2 , thus accelerating the CO 2 -to-CO conversion. Our work establishes a critical fundamental understanding of the origin of the real active center in the zinc-based electrocatalysts for CO 2 reduction reaction.

The discovery of high-performance catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) has faced an enormous challenge for years. The lack of cognition about the surface active structures or centers of catalysts in complex conditions limits the development of advanced catalysts for CO 2 RR. Recently, the positive valent metal sites (PVMS) are demonstrated as a kind of potential active sites, which can facilitate carbon dioxide (CO 2 ) activation and conversation but are always unstable under reduction potentials. Many advanced technologies in theory and experiment have been utilized to understand and develop excellent catalysts with PVMS for CO 2 RR. Here, we present an introduction of some typical catalysts with PVMS in CO 2 RR and give some understanding of the activity and stability for these related catalysts.