ABSTRACT
The oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are core steps of various energy conversion and storage systems. However, their sluggish reaction kinetics, i.e., the demanding multielectron transfer processes, still render OER/ORR catalysts less efficient for practical applications. Moreover, the complexity of the catalyst-electrolyte interface makes a comprehensive understanding of the intrinsic OER/ORR mechanisms challenging. Fortunately, recent advances of in situ/operando characterization techniques have facilitated the kinetic monitoring of catalysts under reaction conditions. Here we provide selected highlights of recent in situ/operando mechanistic studies of OER/ORR catalysts with the main emphasis placed on heterogeneous systems (primarily discussing first-row transition metals which operate under basic conditions), followed by a brief outlook on molecular catalysts. Key sections in this review are focused on determination of the true active species, identification of the active sites, and monitoring of the reactive intermediates. For in-depth insights into the above factors, a short overview of the metrics for accurate characterizations of OER/ORR catalysts is provided. A combination of the obtained time-resolved reaction information and reliable activity data will then guide the rational design of new catalysts. Strategies such as optimizing the restructuring process as well as overcoming the adsorption-energy scaling relations will be discussed. Finally, pending current challenges and prospects toward the understanding and development of efficient heterogeneous catalysts and selected homogeneous catalysts are presented.
ABSTRACT
Selective coupling of NO by a nonclassical dinuclear dinitrosyliron complex (D-DNIC) to form N2O is reported. The coupling is facilitated by the pyridinediimine (PDI) ligand scaffold, which enables the necessary denticity changes to produce mixed-valent, electron-deficient tethered DNICs. One-electron oxidation of the [{Fe(NO)2}]210/10 complex Fe2(PyrrPDI)(NO)4 (4) results in NO coupling to form N2O via the mixed-valent {[Fe(NO)2]2}9/10 species, which possesses an electron-deficient four-coordinate {Fe(NO)2}10 site, crucial in N-N bond formation. The hemilability of the PDI scaffold dictates the selectivity in N-N bond formation because stabilization of the five-coordinate {Fe(NO)2}9 site in the mixed-valent [{Fe(NO)2}]29/10 species, [Fe2(Pyr2PDI)(NO)4][PF6] (6), does not result in an electron-deficient, four-coordinate {Fe(NO)2}10 site, and hence no N-N coupling is observed.
ABSTRACT
The reduction of nitrogen oxides (NxOyn-) to dinitrogen gas by samarium(ii) iodide is reported. The polyoxoanions nitrate (NO3-) and nitrite (NO2-), as well as nitrous oxide (N2O) and nitric oxide (NO) were all shown to react with stoichiometric amounts of SmI2 in THF for the complete denitrification to N2.
ABSTRACT
Metal complexes composed of redox-active pyridinediimine (PDI) ligands are capable of forming ligand-centered radicals. In this Forum article, we demonstrate that integration of these types of redox-active sites with bioinspired secondary coordination sphere motifs produce direduced complexes, where the reduction potential of the ligand-based redox sites is uncoupled from the secondary coordination sphere. The utility of such ligand design was explored by encapsulating redox-inactive Lewis acidic cations via installation of a pendant benzo-15-crown-5 in the secondary coordination sphere of a series of Fe(PDI) complexes. Fe(15bz5PDI)(CO)2 was shown to encapsulate the redox-inactive alkali ion, Na+, causing only modest (31 mV) anodic shifts in the ligand-based redox-active sites. By uncoupling the Lewis acidic sites from the ligand-based redox sites, the pendant redox-inactive ion, Na+, can entice the corresponding counterion, NO2-, for reduction to NO. The subsequent initial rate analysis reveals an acceleration in anion reduction, confirming this hypothesis.
