Tom Regier

Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction

Catalysts for oxygen reduction and evolution reactions are at the heart of key renewable-energy technologies including fuel cells and water splitting. Despite tremendous efforts, developing oxygen electrode catalysts with high activity at low cost remains a great challenge. Here, we report a hybrid material consisting of Co₃O₄ nanocrystals grown on reduced graphene oxide as a high-performance bi-functional catalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Although Co₃O₄ or graphene oxide alone has little catalytic activity, their hybrid exhibits an unexpected, surprisingly high ORR activity that is further enhanced by nitrogen doping of graphene. The Co₃O₄/N-doped graphene hybrid exhibits similar catalytic activity but superior stability to Pt in alkaline solutions. The same hybrid is also highly active for OER, making it a high-performance non-precious metal-based bi-catalyst for both ORR and OER. The unusual catalytic activity arises from synergetic chemical coupling effects between Co₃O₄ and graphene.

An Advanced Ni–Fe Layered Double Hydroxide Electrocatalyst for Water Oxidation

Highly active, durable, and cost-effective electrocatalysts for water oxidation to evolve oxygen gas hold a key to a range of renewable energy solutions, including water-splitting and rechargeable metal-air batteries. Here, we report the synthesis of ultrathin nickel-iron layered double hydroxide (NiFe-LDH) nanoplates on mildly oxidized multiwalled carbon nanotubes (CNTs). Incorporation of Fe into the nickel hydroxide induced the formation of NiFe-LDH. The crystalline NiFe-LDH phase in nanoplate form is found to be highly active for oxygen evolution reaction in alkaline solutions. For NiFe-LDH grown on a network of CNTs, the resulting NiFe-LDH/CNT complex exhibits higher electrocatalytic activity and stability for oxygen evolution than commercial precious metal Ir catalysts.

Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts.

Through direct nanoparticle nucleation and growth on nitrogen doped, reduced graphene oxide sheets and cation substitution of spinel Co(3)O(4) nanoparticles, a manganese-cobalt spinel MnCo(2)O(4)/graphene hybrid was developed as a highly efficient electrocatalyst for oxygen reduction reaction (ORR) in alkaline conditions. Electrochemical and X-ray near-edge structure (XANES) investigations revealed that the nucleation and growth method for forming inorganic-nanocarbon hybrids results in covalent coupling between spinel oxide nanoparticles and N-doped reduced graphene oxide (N-rmGO) sheets. Carbon K-edge and nitrogen K-edge XANES showed strongly perturbed C-O and C-N bonding in the N-rmGO sheet, suggesting the formation of C-O-metal and C-N-metal bonds between N-doped graphene oxide and spinel oxide nanoparticles. Co L-edge and Mn L-edge XANES suggested substitution of Co(3+) sites by Mn(3+), which increased the activity of the catalytic sites in the hybrid materials, further boosting the ORR activity compared with the pure cobalt oxide hybrid. The covalently bonded hybrid afforded much greater activity and durability than the physical mixture of nanoparticles and carbon materials including N-rmGO. At the same mass loading, the MnCo(2)O(4)/N-graphene hybrid can outperform Pt/C in ORR current density at medium overpotentials with stability superior to Pt/C in alkaline solutions.

Homogeneously dispersed, multimetal oxygen-evolving catalysts

Modulating metal oxides The more difficult step in fuel cells and water electrolysis is the oxygen evolution reaction. The search for earth-abundant materials to replace noble metals for this reaction often turns to oxides of three-dimensional metals such as iron. Zhang et al. show that the applied voltages needed to drive this reaction are reduced for iron-cobalt oxides by the addition of tungsten. The addition of tungsten favorably modulates the electronic structure of the oxyhydroxide. A key development is to keep the metals well mixed and avoid the formation of separate phases. Science, this issue p. 333 The addition of tungsten to iron cobalt oxides lowers the overpotential required for the evolution of oxygen from water. 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.

An ultrafast nickel–iron battery from strongly coupled inorganic nanoparticle/nanocarbon hybrid materials

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.

Bulk-Sensitive X-Ray Absorption Spectroscopy Free of Self-Absorption

We demonstrate a new method of x-ray absorption spectroscopy (XAS) that is bulk sensitive, like traditional fluorescence yield measurements, but is not affected by self-absorption or saturation effects. This measure of XAS is achieved by scanning the incident photon energy through an absorption edge and using an energy sensitive photon detector to measure the partial fluorescence yield (PFY). The x-ray emission from any element or core-hole excitation that is not resonant with the absorption edge under investigation is selected from the PFY. It is found that the inverse of this PFY spectrum, which we term inverse partial fluorescence yield (IPFY), is linearly proportional to the x-ray absorption cross-section without any corrections due to saturation or self-absorption effects. We demonstrate this technique on the Cu L and Nd M absorption edges of the high-Tc cuprate LNSCO by measuring the O K PFY and comparing the total electron yield, total fluorescence yield and IPFY spectra.

Chemical interaction and imaging of single Co3O4/graphene sheets studied by scanning transmission X-ray microscopy and X-ray absorption spectroscopy

Scanning transmission X-ray microscopy (STXM) has been used to investigate the chemical, electronic and structural nature of Co3O4 nanocrystals grown on single nitrogen-doped graphene sheets through spatially resolved X-ray absorption near edge structure (XANES) spectroscopy and chemical imaging. It has been found that Co3O4 nanocrystals grown on N-doped graphene were partially reduced via Co3+(Oh) to Co2+(Oh), and the reduction varies spatially on and among individual Co3O4 nanocrystal-graphene sheets. Nitrogen sites on graphene have been shown to be major and important anchoring sites for Co3O4 nanocrystals in addition to the carbon and possibly oxygen sites. Macroscopic XANES of Co L-edge and K-edge were also measured to confirm the localized STXM result that Co3+ was partly reduced in the hybrid material. These insights should account for the superior performance of the covalently coupled Co3O4/graphene hybrid in energy related applications.

Time-resolved x-ray excited optical luminescence from SnO2 nanoribbons : Direct evidence for the origin of the blue luminescence and the role of surface states

Time-resolved x-ray excited optical luminescence (XEOL) and x-ray absorption near edge structures have been employed to study the origin of the multicolor luminescence from SnO2 nanoribbons. The authors find that the yellow-green luminescence has a long lifetime while the blue luminescence a short one. The luminescence is attributed to the radiative decay of trapped electrons in oxygen vacancies just below the conduction band and electrons in the conduction band to intrinsic surface states in the band gap.

Engineering manganese oxide/nanocarbon hybrid materials for oxygen reduction electrocatalysis

AbstractManganese oxides are cost-effective and green materials with rich electrochemical properties. Continuous research efforts have been undertaken to obtain MnOx materials with improved activity and stability for catalyzing the oxygen reduction reaction (ORR). Here, we have developed a novel ORR catalyst by nucleation and growth of Mn3O4 nanoparticles on graphene oxide (GO) sheets interconnected by electrically conducting multi-walled carbon nanotubes (MWCNTs). X-ray near edge absorption structure (XANES) spectroscopy revealed the partially reduced nature of GO and strong chemical coupling between the nanoparticles and the GO sheets. Incorporation of MWCNTs was found to improve the activity and stability of the hybrid by imparting higher conductivity to the hybrid material. Furthermore, surface oxidation of the manganese oxide nanoparticles through a calcination step was found to increase the density of ORR active sites. The strongly coupled and electrically interconnected Mn3O4/nanocarbon (Mn3O4/Nano-C) hybrid is one of the most active and stable manganese oxide-based ORR catalysts and shows promise for electrochemical energy conversion applications.

Commissioning of the Spherical Grating Monochromator Soft X‐ray Spectroscopy Beamline at the Canadian Light Source

The Spherical Grating Monochromator (SGM) is a Dragon type soft x‐ray beamline designed to provide users at the Canadian Light Source (CLS) with monochromatic photons with energies between 250 and 2000 eV. Commissioning of the beamline began in the spring of 2005 and is expected to be completed in July 2006. Aspects of the commissioning process included the use of an object oriented approach to developing the beamline controls, the employment of a beam based alignment procedure and a large amount of user involvement. A description of the beamline and the commissioning techniques used is presented, along with examples of the beamline performance and capabilities.