Dynamic (Sub)surface-Oxygen Enables Highly Efficient Carbonyl-Coupling for Electrochemical Carbon Dioxide Reduction.

Nowadays, high-valent Cu species (i.e., Cuδ +) are clarified to enhance multi-carbon production in electrochemical CO2 reduction reaction (CO2RR). Nonetheless, the inconsistent average Cu valence states are reported to significantly govern the product profile of CO2RR, which may lead to misunderstanding of the enhanced mechanism for multi-carbon production and results in ambiguous roles of high-valent Cu species. Dynamic Cuδ + during CO2RR leads to erratic valence states and challenges of high-valent species determination. Herein, an alternative descriptor of (sub)surface oxygen, the (sub)surface-oxygenated degree (κ), is proposed to quantify the active high-valent Cu species on the (sub)surface, which regulates the multi-carbon production of CO2RR. The κ validates a strong correlation to the carbonyl (*CO) coupling efficiency and is the critical factor for the multi-carbon enhancement, in which an optimized Cu2O@Pd2.31 achieves the multi-carbon partial current density of ≈330 mA cm-2 with a faradaic efficiency of 83.5%. This work shows a promising way to unveil the role of high-valent species and further achieve carbon neutralization.

Activating dynamic atomic-configuration for single-site electrocatalyst in electrochemical CO2 reduction.

One challenge for realizing high-efficiency electrocatalysts for CO2 electroreduction is lacking in comprehensive understanding of potential-driven chemical state and dynamic atomic-configuration evolutions. Herein, by using a complementary combination of in situ/operando methods and employing copper single-atom electrocatalyst as a model system, we provide evidence on how the complex interplay among dynamic atomic-configuration, chemical state change and surface coulombic charging determines the resulting product profiles. We further demonstrate an informative indicator of atomic surface charge (φe) for evaluating the CO2RR performance, and validate potential-driven dynamic low-coordinated Cu centers for performing significantly high selectivity and activity toward CO product over the well-known four N-coordinated counterparts. It indicates that the structural reconstruction only involved the dynamic breaking of Cu-N bond is partially reversible, whereas Cu-Cu bond formation is clearly irreversible. For all single-atom electrocatalysts (Cu, Fe and Co), the φe value for efficient CO production has been revealed closely correlated with the configuration transformation to generate dynamic low-coordinated configuration. A universal explication can be concluded that the dynamic low-coordinated configuration is the active form to efficiently catalyze CO2-to-CO conversion.

MOF-Templated Sulfurization of Atomically Dispersed Manganese Catalysts Facilitating Electroreduction of CO2 to CO.

To reach a carbon-neutral future, electrochemical CO2 reduction reaction (eCO2RR) has proven to be a strong candidate for the next-generation energy system. Among potential materials, single-atom catalysts (SACs) serve as a model to study the mechanism behind the reduction of CO2 to CO, given their well-defined active metal centers and structural simplicity. Moreover, using metal-organic frameworks (MOFs) as supports to anchor and stabilize central metal atoms, the common concern, metal aggregation, for SACs can be addressed well. Furthermore, with their turnability and designability, MOF-derived SACs can also extend the scope of research on SACs for the eCO2RR. Herein, we synthesize sulfurized MOF-derived Mn SACs to study effects of the S dopant on the eCO2RR. Using complementary characterization techniques, the metal moiety of the sulfurized MOF-derived Mn SACs (MnSA/SNC) is identified as MnN3S1. Compared with its non-sulfur-modified counterpart (MnSA/NC), the MnSA/SNC provides uniformly superior activity to produce CO. Specifically, a nearly 30% enhancement of Faradaic efficiency (F.E.) in CO production is observed, and the highest F.E. of approximately 70% is identified at -0.45 V. Through operando spectroscopic characterization, the probing results reveal that the overall enhancement of CO production on the MnSA/SNC is possibly caused by the S atom in the local MnN3S1 moiety, as the sulfur atom may induce the formation of S-O bonding to stabilize the critical intermediate, *COOH, for CO2-to-CO. Our results provide novel design insights into the field of SACs for the eCO2RR.