Co 3 O 4 spinel has been widely investigated as a promising catalyst for the oxidation of volatile organic compounds (VOCs). However, the roles of tetrahedrally coordinated Co 2+ sites (Co 2+ T d ) and octahedrally coordinated Co 3+ sites (Co 3+ O h ) still remain elusive, because their oxidation states are strongly influenced by the local geometric and electronic structures of the cobalt ion. In this work, we separately studied the geometrical-site-dependent catalytic activity of Co 2+ and Co 3+ in VOC oxidation on the basis of a metal ion substitution strategy, by substituting Co 2+ and Co 3+ with inactive or low-active Zn 2+ (d 0 ), Al 3+ (d 0 ), and Fe 3+ (d 5 ), respectively. Raman spectroscopy, X-ray absorption fine structure (XAFS), and in situ DRIFTS spectra were thoroughly applied to elucidate the active sites of a Co-based spinel catalyst. The results demonstrate that octahedrally coordinated Co 2+ sites (Co 2+ O h ) are more easily oxidized to Co 3+ species in comparison to Co 2+ T d , and Co 3+ are responsible for the oxidative breakage of the benzene rings to generate the carboxylate intermediate species. CoO with Co 2+ O h and ZnCo 2 O 4 with Co 3+ O h species have demonstrated good catalytic activity and high TOF Co values at low temperature. Benzene conversions for CoO and ZnCo 2 O 4 are greater than 50% at 196 and 212 °C, respectively. However, CoAl 2 O 4 with Co 2+ T d sites shows poor catalytic activity and a low TOF Co value. In addition, ZnCo 2 O 4 exhibits good durability at 500 °C and strong H 2 O resistance ability.

Ru/CeO2 catalysts with different amounts of surface oxygen vacancies were prepared by changing the morphology of CeO2. The conversion of Ce4+ to Ce3+ and the formation of Ru–O–Ce bonds led to enhancement of the amount of oxygen vacancies. Ru species of low crystallinity enriched with Ru4+ ions exist on the surface of CeO2 nanorods, while metallic Ru particles exist on CeO2 nanocubes. The low crystallinity of Ru species and high concentration of oxygen vacancies enhanced the adsorption of hydrogen and nitrogen and also led to desorption of surface hydrogen in the form of H2. Therefore, Ru/CeO2 nanorods showed high ammonia synthesis activities. On the contrary, lower catalytic activity was observed over Ru/CeO2 nanocubes catalyst because H2 and N2 adsorption was less favorable plausibly due to the large particle size of Ru species and low concentration of oxygen vacancies, and most of the hydrogen species were consumed in H2O formation.

The industrial synthesis of ammonia (NH3) using iron-based Haber-Bosch catalyst requires harsh reaction conditions. Developing advanced catalysts that perform well at mild conditions (<400 °C, <2 MPa) for industrial application is a long-term goal. Here we report a Co-N-C catalyst with high NH3 synthesis rate that simultaneously exhibits dynamic and steady-state active sites. Our studies demonstrate that the atomically dispersed cobalt weakly coordinated with pyridine N reacts with surface H2 to produce NH3 via a chemical looping pathway. Pyrrolic N serves as an anchor to stabilize the single cobalt atom in the form of Co1-N3.5 that facilitates N2 adsorption and step-by-step hydrogenation of N2 to *HNNH, *NH-NH3 and *NH2-NH4. Finally, NH3 is facilely generated via the breaking of the *NH2-NH4 bond. With the co-existence of dynamic and steady-state single atom active sites, the Co-N-C catalyst circumvents the bottleneck of N2 dissociation, making the synthesis of NH3 at mild conditions possible.

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