Electrocatalyst for oxygen reduction reaction (ORR) is crucial for a variety of renewable energy applications and energy-intensive industries. The design and synthesis of highly active ORR catalysts ...with strong durability at low cost is extremely desirable but remains challenging. Here, we used a simple two-step method to synthesize cobalt oxide/carbon nanotube (CNT) strongly coupled hybrid as efficient ORR catalyst by directly growing nanocrystals on oxidized multiwalled CNTs. The mildly oxidized CNTs provided functional groups on the outer walls to nucleate and anchor nanocrystals, while retaining intact inner walls for highly conducting network. Cobalt oxide was in the form of CoO due to a gas-phase annealing step in NH3. The resulting CoO/nitrogen-doped CNT (NCNT) hybrid showed high ORR current density that outperformed Co3O4/graphene hybrid and commercial Pt/C catalyst at medium overpotential, mainly through a 4e reduction pathway. The metal oxide/carbon nanotube hybrid was found to be advantageous over the graphene counterpart in terms of active sites and charge transport. Last, the CoO/NCNT hybrid showed high ORR activity and stability under a highly corrosive condition of 10 M NaOH at 80 °C, demonstrating the potential of strongly coupled inorganic/nanocarbon hybrid as a novel catalyst system in oxygen depolarized cathode for chlor-alkali electrolysis.
Manganese oxides with rich redox chemistry have been widely used in (electro)catalysis in applications of energy and environmental consequence. While they are ubiquitous in catalyzing the oxygen ...evolution reaction (OER) and oxygen reduction reaction (ORR), redox processes occurring on the surface of manganese oxides are poorly understood. We report valence changes at OER- and ORR-relevant voltages of a layered manganese oxide film prepared by electrodeposition. X-ray absorption spectra were collected in situ in O2-saturated 0.1 M KOH using inverse partial fluorescence yield (IPFY) at the Mn L3,2-edges and partial fluorescence yield (PFY) at the O K-edge. Overall, we found reversible yet hysteretic Mn redox and qualitatively reproducible spectral changes by Mn L3,2 IPFY XAS. Oxidation to a mixed Mn3+/4+ valence preceded the oxygen evolution at 1.65 V vs RHE, while manganese reduced below Mn3+ and contained tetrahedral Mn2+ during oxygen reduction at 0.5 V vs RHE. Analysis of the pre-edge in O K-edge XAS provided the Mn–O hybridization, which was highest for Mn3+ (eg 1). Our study demonstrates that combined in situ experiments at the metal L- and oxygen K-edges are indispensable to identify both the active valence during catalysis and the hybridization with oxygen adsorbates, critical to the rational design of active catalysts for oxygen electrocatalysis.
Earth-abundant first-row (3d) transition metal–based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials substantially above thermodynamic ...requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxyhydroxides materials with an atomically homogeneous metal distribution. These gelled FeCoW oxyhydroxides exhibit the lowest overpotential (191 millivolts) reported at 10 milliamperes per square centimeter in alkaline electrolyte. The catalyst shows no evidence of degradation after more than 500 hours of operation. X-ray absorption and computational studies reveal a synergistic interplay between tungsten, iron, and cobalt in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER.
Fire-derived organic matter, often referred to as pyrogenic organic matter (PyOM), is present in the Earth's soil, sediment, atmosphere, and water. We investigated interactions of PyOM with ammonia ...(NH
) gas, which makes up much of the Earth's reactive nitrogen (N) pool. Here we show that PyOM's NH
retention capacity under ambient conditions can exceed 180 mg N g
PyOM-carbon, resulting in a material with a higher N content than any unprocessed plant material and most animal manures. As PyOM is weathered, NH
retention increases sixfold, with more than half of the N retained through chemisorption rather than physisorption. Near-edge X-ray absorption fine structure and nuclear magnetic resonance spectroscopy reveal that a variety of covalent bonds form between NH
-N and PyOM, more than 10% of which contained heterocyclic structures. We estimate that through these mechanisms soil PyOM stocks could retain more than 600-fold annual NH
emissions from agriculture, exerting an important control on global N cycling.
Vegetation fires are known to have broad geochemical effects on carbon (C) cycles in the Earth system, yet limited information is available for nitrogen (N). In this study, we evaluated how charring ...organic matter (OM) to pyrogenic OM (PyOM) altered the N molecular structure and affected subsequent C and N mineralization. Nitrogen near-edge X-ray absorption fine structure (NEXAFS) of uncharred OM, PyOM, PyOM toluene extract, and PyOM after toluene extraction were used to predict PyOM-C and -N mineralization potentials. PyOM was produced from three different plants (e.g. Maize-Zea mays L.; Ryegrass-Lollium perenne L.; and Willow-Salix viminalix L.) each with varying initial N contents at three pyrolysis temperatures (350, 500 and 700 °C). Mineralization of C and N was measured from incubations of uncharred OM and PyOM in a sand matrix for 256 days at 30 °C. As pyrolysis temperature increased from 350 to 700 °C, aromatic CN in 6-membered rings (putative) increased threefold. Aromatic CN in 6-membered oxygenated ring increased sevenfold, and quaternary aromatic N doubled. Initial uncharred OM-N content was positively correlated with the proportion of heterocyclic aromatic N in PyOM (R2 = 0.44; P < 0.0001; n = 42). A 55% increase of aromatic N heterocycles at high OM-N content, when compared to low OM-N content, suggests that higher concentrations of N favor the incorporation of N atoms into aromatic structures by overcoming the energy barrier associated with the electronic and atomic configuration of the C structure. A ten-fold increase of aromatic CN in 6-membered rings (putative) in PyOM (as proportion of all PyOM-N) decreased C mineralization by 87%, whereas total N contents and C:N ratios of PyOM had no effects on C mineralization of PyOM-C for both pyrolysis temperatures (for PyOM-350 °C, R2 = 0.15; P < 0.27; for PyOM-700 °C, R2 = 0.22; P < 0.21). Oxidized aromatic N in PyOM toluene extracts correlated with higher C mineralization, whereas aromatic N in 6-membered heterocycles correlated with reduced C mineralization (R2 = 0.56; P = 0.001; n = 100). Similarly, aromatic N in 6-membered heterocycles in PyOM remaining after toluene extraction reduced PyOM-C mineralization (R2 = 0.49; P = 0.0006; n = 100). PyOM-C mineralization increased when N atoms were located at the edge of the C network in the form of oxidized N functionalities or when more N was found in PyOM toluene extracts and was more accessible to microbial oxidation. These results confirm the hypothesis that C persistence of fire-derived OM is significantly affected by its molecular N structure and the presented quantitative structure-activity relationship can be utilized for predictive modeling purposes.
Ultrafast rechargeable batteries made from low-cost and abundant electrode materials operating in safe aqueous electrolytes could be attractive for electrochemical energy storage. If both high ...specific power and energy are achieved, such batteries would be useful for power quality applications such as to assist propelling electric vehicles that require fast acceleration and intense braking. Here we develop a new type of Ni-Fe battery by employing novel inorganic nanoparticle/graphitic nanocarbon (carbon nanotubes and graphene) hybrid materials as electrode materials. We successfully increase the charging and discharging rates by nearly 1,000-fold over traditional Ni-Fe batteries while attaining high energy density. The ultrafast Ni-Fe battery can be charged in ~2 min and discharged within 30 s to deliver a specific energy of 120 Wh kg(-1) and a specific power of 15 kW kg(-1). These features suggest a new generation of Ni-Fe batteries as novel devices for electrochemical energy storage.
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