Rationally Designed Manganese-Based Metal-Organic Frameworks as Altruistic Metal Oxide Precursors for Noble Metal-Free Oxygen Reduction Reaction.

The sluggish oxygen reduction reaction (ORR) at the cathode is challenging and hinders the growth of hydrogen fuel cells. Concerning kinetic values, platinum is the best known catalyst for ORR; however, its less abundance, high cost, and corrosive nature warrant the development of low-cost catalysts. We report the hydrothermal synthesis of two novel Mn-based metal-organic frameworks (MOFs), [Mn2(DOT)(H2O)2]n (Mn-SKU-1) and [Mn2(DOT)2(BPY)2(THF)]n (Mn-SKU-2) (DOT = 2,5-dihydroxyterephthalate; BPY = 4,4'-bipyridine). Mn-SKU-1 contains dimeric Mn(II) centers where the two corner-shared MnO6 octahedra fuse to give rise to an infinite Mn2O10 cluster, whereas the two Mn(II) ions coordinate to DOT and BPY moieties to give rise to a pillared structure in Mn-SKU-2 and form a 3D → 3D homo-interpenetration MOF with a twofold interpenetrated net. The pyrolysis of as-synthesized Mn-MOFs at 600 °C under N2 produced exclusively porous α-Mn2O3 composites (PSKU-1 and PSKU-2), with the BET surface area of 90.8 (for PSKU-1) and 179.3 m2 g-1 (for PSKU-2). These mesoporous MOF-derived α-Mn2O3 composites were modified as cathode materials for the electrocatalytic reduction of oxygen. The onset potential for the oxygen reduction reaction was found to be 0.90 V for PSKU-1 and 0.93 V for PSKU-2 versus RHE in 0.1 M KOH solution, with the current density of 4.8 and 6.0 mA cm-2, respectively, at 1600 rpm. Based on the RDE/RRDE results, the electrocatalytic oxygen reduction occurs majorly via the four-electron process. The electrocatalyst PSKU-2 is cheap, easy to use, retains 90% of its activity after 10 h of continuous use, and offers higher recyclability than Pt/C. The onset potential maximum current density and kinetic values (Jk = 11.68 mA cm-2 and Tafel slope = 85.0 mV dec-1) obtained in this work are higher than the values reported for pure Mn2O3.

Electrochemical generation of high-valent oxo-manganese complexes featuring an anionic N5 ligand and their role in O-O bond formation.

Generation of high-valent oxomanganese complexes through controlled removal of protons and electrons from low-valent congeners is a crucial step toward the synthesis of functional analogues of the native oxygen evolving complex (OEC). In-depth studies of the water oxidation activity of such biomimetic compounds help in understanding the mechanism of O-O bond formation presumably occurring in the last step of the photosynthetic cycle. Scarce reports of reactive high-valent oxomanganese complexes underscore the impetus for the present work, wherein we report the electrochemical generation of the non-heme oxomanganese(IV) species [(dpaq)MnIV(O)]+ (2) through a proton-coupled electron transfer (PCET) process from the hydroxomanganese complex [(dpaq)MnIII(OH)]ClO4 (1). Controlled potential spectroelectrochemical studies of 1 in wet acetonitrile at 1.45 V vs. NHE revealed quantitative formation of 2 within 10 min. The high-valent oxomanganese(IV) transient exhibited remarkable stability and could be reverted to the starting complex (1) by switching the potential to 0.25 V vs. NHE. The formation of 2via PCET oxidation of 1 demonstrates an alternate pathway for the generation of the oxomanganese(IV) transient (2) without the requirement of redox-inactive metal ions or acid additives as proposed earlier. Theoretical studies predict that one-electron oxidation of [(dpaq)MnIV(O)]+ (2) forms a manganese(V)-oxo (3) species, which can be oxidized further by one electron to a formal manganese(VI)-oxo transient (4). Theoretical analyses suggest that the first oxidation event (2 to 3) takes place at the metal-based d-orbital, whereas, in the second oxidation process (3 to 4), the electron eliminates from an orbital composed of equitable contribution from the metal and the ligand, leaving a single electron in the quinoline-dominant orbital in the doublet ground spin state of the manganese(VI)-oxo species (4). This mixed metal-ligand (quinoline)-based oxidation is proposed to generate a formal Mn(VI) species (4), a non-heme analogue of the species 'compound I', formed in the catalytic cycle of cytochrome P-450. We propose that the highly electrophilic species 4 catches water during cyclic voltammetry experiments and results in O-O bond formation leading to electrocatalytic oxidation of water to hydrogen peroxide.