Elucidating the Electrocatalytic CO2 Reduction Reaction over a Model Single-Atom Nickel Catalyst.

Designing effective electrocatalysts for the carbon dioxide reduction reaction (CO2 RR) is an appealing approach to tackling the challenges posed by rising CO2 levels and realizing a closed carbon cycle. However, fundamental understanding of the complicated CO2 RR mechanism in CO2 electrocatalysis is still lacking because model systems are limited. We have designed a model nickel single-atom catalyst (Ni SAC) with a uniform structure and well-defined Ni-N4 moiety on a conductive carbon support with which to explore the electrochemical CO2 RR. Operando X-ray absorption near-edge structure spectroscopy, Raman spectroscopy, and near-ambient X-ray photoelectron spectroscopy, revealed that Ni+ in the Ni SAC was highly active for CO2 activation, and functioned as an authentic catalytically active site for the CO2 RR. Furthermore, through combination with a kinetics study, the rate-determining step of the CO2 RR was determined to be *CO2 - +H+ →*COOH. This study tackles the four challenges faced by the CO2 RR; namely, activity, selectivity, stability, and dynamics.

Shape-Controlled Synthesis of Metal-Organic Frameworks with Adjustable Fenton-Like Catalytic Activity.

Controllable synthesis of metal-organic frameworks with well-defined morphology, composition, and size is of great importance toward understanding their structure-property relationship in various applications. Herein, we demonstrate a general strategy to modulate the relative growth rate of the secondary building units (SBUs) along different crystal facets for the synthesis of Fe-Co, Mn0.5Fe0.5-Co, and Mn-Co Prussian blue analogues (PBAs) with tunable morphologies. The same growth rate of SBUs along the {100}, {110}, and {111} surfaces at 0 °C results in the formation of spherical PBA particles, while the lowest growth rate of SBUs along the {100} surface resulting from the highest surface energy with increasing reaction temperature induces the formation of PBA cubes. Fenton reaction was used as the model reaction to probe the structure-catalytic activity relation for the as-synthesized catalysts. The cubic Fe-Co PBA was found to exhibit the best catalytic performance with reaction rate constant 6 times higher than that of the spherical counterpart. Via density functional theory calculations, the abundant enclosed {100} facets in cubic Fe-Co PBA were identified to have the highest surface energy and favor high Fenton reaction activity.