Yang Shao-Horn

A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles

An electronic property of metal oxides was used to guide development of a catalyst for prospective use in energy applications. The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba0.5Sr0.5Co0.8Fe0.2O3–δ (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an eg symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an eg occupancy close to unity, with high covalency of transition metal–oxygen bonds.

Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries

The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ-orbital (e(g)) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ orbital and metal-oxygen covalency on the competition between O(2)(2-)/OH(-) displacement and OH(-) regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

Synthesis and Activities of Rutile IrO2 and RuO2 Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions

The activities of the oxygen evolution reaction (OER) on iridium-oxide- and ruthenium-oxide-based catalysts are among the highest known to date. However, the OER activities of thermodynamically stable rutile iridium oxide (r-IrO2) and rutile iridium oxide (r-RuO2), normalized to catalyst mass or true surface area are not well-defined. Here we report a synthesis of r-IrO2 and r-RuO2 nanoparticles (NPs) of ∼6 nm, and examine their OER activities in acid and alkaline solutions. Both r-IrO2 and r-RuO2 NPs were highly active for OER, with r-RuO2 exhibiting up to 10 A/goxide at 1.48 V versus reversible hydrogen electrode. When comparing the two, r-RuO2 NPs were found to have slightly higher intrinsic and mass OER activities than r-IrO2 in both acid and basic solutions. Interestingly, these oxide NPs showed higher stability under OER conditions than commercial Ru/C and Ir/C catalysts. Our study shows that these r-RuO2 and r-IrO2 NPs can serve as a benchmark in the development of active OER catalysts for electrolyzers, metal-air batteries, and photoelectrochemical water splitting applications.

Instability of Pt ∕ C Electrocatalysts in Proton Exchange Membrane Fuel Cells A Mechanistic Investigation

Equilibrium concentrations of dissolved platinum species from a Pt/C electrocatalyst sample in 0.5 M H2SO4 at 80°C were found to increase with applied potential from 0.9 to 1.1 V vs reversible hydrogen electrode. In addition, platinum surface area loss for a short-stack of proton exchange membrane fuel cells PEMFCs operated at open-circuit voltage 0.95 V was shown to be higher than another operated under load 0.75 V. Both findings suggest that the formation of soluble platinum species such as Pt 2+ plays an important role in platinum surface loss in PEMFC electrodes. As accelerated platinum surface area loss in the cathode from 63 to 23 m 2 /gPt in 100 h was observed upon potential cycling, a cycled membrane electrode assembly MEA cathode was examined in detail by incidence angle X-ray diffraction and transmission electron microscopy TEM to reveal processes responsible for observed platinum loss. In this study, TEM data and analyses of Pt/C catalyst and cross-sectional MEA cathode samples unambiguously confirmed that coarsening of platinum particles occurred via two different processes: i Ostwald ripening on carbon at the nanometer scale, which is responsible for platinum particle coarsening from 3t o6 nm on carbon, and ii migration of soluble platinum species in the ionomer phase at the micrometer scale, chemical reduction of these species by crossover H2 molecules, and precipitation of platinum particles in the cathode ionomer phase, which reduces the weight of platinum on carbon. It was estimated that each process contributed to 50% of the overall platinum area loss of the potential cycled electrode.

Platinum-gold nanoparticles: a highly active bifunctional electrocatalyst for rechargeable lithium-air batteries.

PtAu nanoparticles (NPs) were shown to strongly enhance the kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in rechargeable Li-O(2) cells. Li-O(2) cells with PtAu/C were found to exhibit the highest round-trip efficiency reported to date. During ORR via xLi(+) + O(2) + xe(-) --> Li(x)O(2), the discharge voltage with PtAu/C was considerably higher than that of pure carbon and comparable to that of Au/C. During OER via Li(x)O(2) --> xLi(+) + O(2) + xe(-), the charge voltages with PtAu/C fell in the range from 3.4 to 3.8 V(Li), which is slightly lower than obtained with Pt. It is hypothesized that PtAu NPs exhibit bifunctional catalytic activity, having surface Au and Pt atoms primarily responsible for ORR and OER kinetics in Li-O(2) cells, respectively.

High-power lithium batteries from functionalized carbon-nanotube electrodes

Energy storage devices that can deliver high powers have many applications, including hybrid vehicles and renewable energy. Much research has focused on increasing the power output of lithium batteries by reducing lithium-ion diffusion distances, but outputs remain far below those of electrochemical capacitors and below the levels required for many applications. Here, we report an alternative approach based on the redox reactions of functional groups on the surfaces of carbon nanotubes. Layer-by-layer techniques are used to assemble an electrode that consists of additive-free, densely packed and functionalized multiwalled carbon nanotubes. The electrode, which is several micrometres thick, can store lithium up to a reversible gravimetric capacity of approximately 200 mA h g(-1)(electrode) while also delivering 100 kW kg(electrode)(-1) of power and providing lifetimes in excess of thousands of cycles, both of which are comparable to electrochemical capacitor electrodes. A device using the nanotube electrode as the positive electrode and lithium titanium oxide as a negative electrode had a gravimetric energy approximately 5 times higher than conventional electrochemical capacitors and power delivery approximately 10 times higher than conventional lithium-ion batteries.

Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes

The kinetics of the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) on polycrystalline platinum [Pt(pc)] and high surface area carbon-supported platinum nanoparticles (Pt/C) were studied in 0.1 M KOH using rotating disk electrode (RDE) measurements. After corrections of noncompensated solution resistance from ac impedance spectroscopy and of hydrogen mass transport in the HOR branch, the kinetic current densities were fitted to the Butler-Volmer equation using a transfer coefficient of α = 0.5, from which HOR/HER exchange current densities on Pt(pc) and Pt/C were obtained, and the HOR/HER mechanisms in alkaline solution were discussed. Unlike the HOR/HER rates on Pt electrodes in alkaline solution, the HOR/HER rates on a Pt electrode in 0.1 M HClO 4 were limited entirely by hydrogen diffusion, which renders the quantification of the HOR/HER kinetics impossible by conventional RDE measurements. The simulation of the hydrogen anode performance based on the specific exchange current densities of the HOR/HER at 80°C illustrates that in addition to the oxygen reduction reaction cell voltage loss on the cathode, the slow HOR kinetics are projected to cause significant anode potential losses in alkaline fuel cells for low platinum loadings (> 130 mV at 0.05 Mg pt /CM 2 anode and 1.5 A/cm 2 anode ), contrary to what is reported for proton exchange membrane fuel cells.

Carbon Nanotube/Manganese Oxide Ultrathin Film Electrodes for Electrochemical Capacitors

Multiwall carbon nanotube (MWNT)/manganese oxide (MnO2) nanocomposite ultrathin film electrodes have been created via redox deposition of MnO2 on layer-by-layer (LbL)-assembled MWNT films. We demonstrate that these LbL-assembled MWNT (LbL-MWNT)/MnO2 thin films consist of a uniform coating of nanosized MnO2 on the MWNT network structure using SEM and TEM, which is a promising structure for electrochemical capacitor applications. LbL-MWNT/MnO2 electrodes yield a significantly higher volumetric capacitance of 246 F/cm3 with good capacity retention up to 1000 mV/s due to rapid transport of electrons and ions within the electrodes. The electrodes are generated with two simple aqueous deposition processes: the layer-by-layer assembly of MWNTs followed by redox deposition of MnO2 at ambient conditions, thus providing a straightforward approach to the fabrication of high-power and -energy electrochemical capacitors with precise control of electrode thickness at nanometer scales.

Layer-by-layer assembly of all carbon nanotube ultrathin films for electrochemical applications.

All multiwall carbon nanotube (MWNT) thin films are created by layer-by-layer (LBL) assembly of surface functionalized MWNTs. Negatively and positively charged MWNTs were prepared by surface functionalization, allowing the incorporation of MWNTs into highly tunable thin films via the LBL technique. The pH dependent surface charge on the MWNTs gives this system the unique characteristics of LBL assembly of weak polyelectrolytes, controlling thickness and morphology with assembly pH conditions. We demonstrate that these MWNT thin films have randomly oriented interpenetrating network structure with well developed nanopores using AFM and SEM, which is an ideal structure of functional materials for various applications. In particular, electrochemical measurements of these all-MWNT thin film electrodes show high electronic conductivity in comparison with polymer composites with single wall nanotubes, and high capacitive behavior with precise control of capacity.

Toward the rational design of non-precious transition metal oxides for oxygen electrocatalysis

In this Review, we discuss the state-of-the-art understanding of non-precious transition metal oxides that catalyze the oxygen reduction and evolution reactions. Understanding and mastering the kinetics of oxygen electrocatalysis is instrumental to making use of photosynthesis, advancing solar fuels, fuel cells, electrolyzers, and metal–air batteries. We first present key insights, assumptions and limitations of well-known activity descriptors and reaction mechanisms in the past four decades. The turnover frequency of crystalline oxides as promising catalysts is also put into perspective with amorphous oxides and photosystem II. Particular attention is paid to electronic structure parameters that can potentially govern the adsorbate binding strength and thus provide simple rationales and design principles to predict new catalyst chemistries with enhanced activity. We share new perspective synthesizing mechanism and electronic descriptors developed from both molecular orbital and solid state band structure principles. We conclude with an outlook on the opportunities in future research within this rapidly developing field.