High-Performance Hydroxide Exchange Membrane Fuel Cell Comprising an Atomic Layer-Deposited Silver Cathode.

Atomic layer deposition (ALD) is emerging as an efficient tool for the precise manufacture of catalysts, owing to its sophisticated surface tailoring capabilities. To overcome the techno-economic limitations of fuel cell electric vehicles (FCEVs), which are considered suitable alternatives to battery electric vehicles (BEVs), the development of cost-efficient high-performance catalysts is essential. In this study, we successfully fabricated a Pt-free cathode for a hydroxide exchange membrane fuel cell (HEMFC) with excellent oxygen reduction activity under extremely low loading of Ag electrocatalysts using ALD. Microstructural analysis confirmed that the surface modification by ALD-Ag nanoparticles exhibited excellent step coverage characteristics on porous carbon nanotubes (CNTs). An HEMFC comprising a CNT cathode surface-decorated with ALD-Ag nanoparticles delivered a high peak power density of 2154 mW mgAg-1 in an alkaline environment at 65 °C. This study demonstrates the applicability of ALD for the manufacture of highly active low-cost electrocatalysts for high-performance HEMFCs.

Condensing water vapor to droplets generates hydrogen peroxide.

It was previously shown [J. K. Lee et al., Proc. Natl. Acad. Sci. U.S.A, 116, 19294-19298 (2019)] that hydrogen peroxide (H2O2) is spontaneously produced in micrometer-sized water droplets (microdroplets), which are generated by atomizing bulk water using nebulization without the application of an external electric field. Here we report that H2O2 is spontaneously produced in water microdroplets formed by dropwise condensation of water vapor on low-temperature substrates. Because peroxide formation is induced by a strong electric field formed at the water-air interface of microdroplets, no catalysts or external electrical bias, as well as precursor chemicals, are necessary. Time-course observations of the H2O2 production in condensate microdroplets showed that H2O2 was generated from microdroplets with sizes typically less than ∼10 µm. The spontaneous production of H2O2 was commonly observed on various different substrates, including silicon, plastic, glass, and metal. Studies with substrates with different surface conditions showed that the nucleation and the growth processes of condensate water microdroplets govern H2O2 generation. We also found that the H2O2 production yield strongly depends on environmental conditions, including relative humidity and substrate temperature. These results show that the production of H2O2 occurs in water microdroplets formed by not only atomizing bulk water but also condensing water vapor, suggesting that spontaneous water oxidation to form H2O2 from water microdroplets is a general phenomenon. These findings provide innovative opportunities for green chemistry at heterogeneous interfaces, self-cleaning of surfaces, and safe and effective disinfection. They also may have important implications for prebiotic chemistry.

Magnetic Weyl Semimetal in K_{2}Mn_{3}(AsO_{4})_{3} with the Minimum Number of Weyl Points.

The "hydrogen atom" of magnetic Weyl semimetals, with the minimum number of Weyl points, has received growing attention recently due to the possible presence of Weyl-related phenomena. Here, we report a nontrivial electronic structure of the ferromagnetic alluaudite-type compound K_{2}Mn_{3}(AsO_{4})_{3}. It exhibits only a pair of Weyl points constrained in the z direction by the twofold rotation symmetry, leading to extremely long Fermi arc surface states. In addition, the study of its low-energy effective model results in the discovery of various topological superconducting states, such as the hydrogen atom of a Weyl superconductor. Our Letter provides a feasible platform to explore the intrinsic properties related to Weyl points, and the related device applications.

Spontaneous generation of hydrogen peroxide from aqueous microdroplets.

We show H2O2 is spontaneously produced from pure water by atomizing bulk water into microdroplets (1 µm to 20 µm in diameter). Production of H2O2, as assayed by H2O2-sensitve fluorescence dye peroxyfluor-1, increased with decreasing microdroplet size. Cleavage of 4-carboxyphenylboronic acid and conversion of phenylboronic acid to phenols in microdroplets further confirmed the generation of H2O2 The generated H2O2 concentration was ∼30 µM (∼1 part per million) as determined by titration with potassium titanium oxalate. Changing the spray gas to O2 or bubbling O2 decreased the yield of H2O2 in microdroplets, indicating that pure water microdroplets directly generate H2O2 without help from O2 either in air surrounding the droplet or dissolved in water. We consider various possible mechanisms for H2O2 formation and report a number of different experiments exploring this issue. We suggest that hydroxyl radical (OH) recombination is the most likely source, in which OH is generated by loss of an electron from OH- at or near the surface of the water microdroplet. This catalyst-free and voltage-free H2O2 production method provides innovative opportunities for green production of hydrogen peroxide.

Magnetic Semimetals and Quantized Anomalous Hall Effect in EuB_{6}.

Exploration of the novel relationship between magnetic order and topological semimetals has received enormous interest in a wide range of both fundamental and applied research. Here we predict that "soft" ferromagnetic material EuB_{6} can achieve multiple topological semimetal phases by simply tuning the direction of the magnetic moment. Explicitly, EuB_{6} is a topological nodal-line semimetal when the moment is aligned along the [001] direction, and it evolves into a Weyl semimetal with three pairs of Weyl points by rotating the moment to the [111] direction. Interestingly, we identify a composite semimetal phase featuring the coexistence of a nodal line and Weyl points with the moment in the [110] direction. Topological surface states and anomalous Hall conductivity, which are sensitive to the magnetic order, have been computed and are expected to be experimentally observable. Large-Chern-number quantum anomalous Hall effect can be realized in its [111]-oriented quantum-well structures.

Topological semimetal in honeycomb lattice LnSI.

Recognized as elementary particles in the standard model, Weyl fermions in condensed matter have received growing attention. However, most of the previously reported Weyl semimetals exhibit rather complicated electronic structures that, in turn, may have raised questions regarding the underlying physics. Here, we report promising topological phases that can be realized in specific honeycomb lattices, including ideal Weyl semimetal structures, 3D strong topological insulators, and nodal-line semimetal configurations. In particular, we highlight a semimetal featuring both Weyl nodes and nodal lines. Guided by this model, we showed that GdSI, the long-perceived ideal Weyl semimetal, has two pairs of Weyl nodes residing at the Fermi level and that LuSI (YSI) is a 3D strong topological insulator with the right-handed helical surface states. Our work provides a mechanism to study topological semimetals and proposes a platform for exploring the physics of Weyl semimetals as well as related device designs.

The Use of Contact Mode Atomic Force Microscopy in Aqueous Medium for Structural Analysis of Spinach Photosynthetic Complexes.

To investigate the dynamics of photosynthetic pigment-protein complexes in vascular plants at high resolution in an aqueous environment, membrane-protruding oxygen-evolving complexes (OECs) associated with photosystem II (PSII) on spinach (Spinacia oleracea) grana membranes were examined using contact mode atomic force microscopy. This study represents, to our knowledge, the first use of atomic force microscopy to distinguish the putative large extrinsic loop of Photosystem II CP47 reaction center protein (CP47) from the putative oxygen-evolving enhancer proteins 1, 2, and 3 (PsbO, PsbP, and PsbQ) and large extrinsic loop of Photosystem II CP43 reaction center protein (CP43) in the PSII-OEC extrinsic domains of grana membranes under conditions resulting in the disordered arrangement of PSII-OEC particles. Moreover, we observed uncharacterized membrane particles that, based on their physical characteristics and electrophoretic analysis of the polypeptides associated with the grana samples, are hypothesized to be a domain of photosystem I that protrudes from the stromal face of single thylakoid bilayers. Our results are interpreted in the context of the results of others that were obtained using cryo-electron microscopy (and single particle analysis), negative staining and freeze-fracture electron microscopy, as well as previous atomic force microscopy studies.

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction.

The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS2 nanofilms through electrochemical intercalation of Li(+) ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity.

Variation of energy density of states in quantum dot arrays due to interparticle electronic coupling.

Subnanometer-resolved local electron energy structure was measured in PbS quantum dot superlattice arrays using valence electron energy loss spectroscopy with scanning transmission electron microscopy. We found smaller values of the lowest available transition energies and an increased density of electronic states in the space between quantum dots with shorter interparticle spacing, indicating extension of carrier wave functions as a result of interparticle electronic coupling. A quantum simulation verified both trends and illustrated the wave function extension effect.

Quantifying Geometric Strain at the PbS QD-TiO2 Anode Interface and Its Effect on Electronic Structures.

Quantum dots (QDs) show promise as the absorber in nanostructured thin film solar cells, but achieving high device efficiencies requires surface treatments to minimize interfacial recombination. In this work, lead sulfide (PbS) QDs are grown on a mesoporous TiO2 film with a crystalline TiO2 surface, versus one coated with an amorphous TiO2 layer by atomic layer deposition (ALD). These mesoporous TiO2 films sensitized with PbS QDs are characterized by X-ray and electron diffraction, as well as X-ray absorption spectroscopy (XAS) in order to link XAS features with structural distortions in the PbS QDs. The XAS features are further analyzed with quantum simulations to probe the geometric and electronic structure of the PbS QD-TiO2 interface. We show that the anatase TiO2 surface structure induces PbS bond angle distortions, which increases the energy gap of the PbS QDs at the interface.

Enhanced Step Coverage of TiO2 Deposited on High Aspect Ratio Surfaces by Plasma-Enhanced Atomic Layer Deposition.

Plasma-enhanced atomic layer deposition (PEALD) provides multiple benefits compared to thermal ALD including lower possible process temperature and a wider palette of possible materials. However, coverage of high aspect ratio (AR) structures is limited due to the recombination rates of the radical plasma species. We study the limits of conformality in 1:30 AR structures for TiO2 based on tetrakis(dimethylamido)titanium (TDMA-Ti) and O2 plasma through variation in plasma exposure and substrate temperature. Extending plasma exposure duration and decreasing substrate temperature within the ALD window both serve to improve the conformality of the deposited film, with coverage >95% achievable. Additionally, the changes in morphology of the TiO2 were examined with crystallites of anatase and brookite found.

Rapid and controllable flame reduction of TiO2 nanowires for enhanced solar water-splitting.

We report a new flame reduction method to generate controllable amount of oxygen vacancies in TiO2 nanowires that leads to nearly three times improvement in the photoelectrochemical (PEC) water-splitting performance. The flame reduction method has unique advantages of a high temperature (>1000 °C), ultrafast heating rate, tunable reduction environment, and open-atmosphere operation, so it enables rapid formation of oxygen vacancies (less than one minute) without damaging the nanowire morphology and crystallinity and is even applicable to various metal oxides. Significantly, we show that flame reduction greatly improves the saturation photocurrent densities of TiO2 nanowires (2.7 times higher), α-Fe2O3 nanowires (9.4 times higher), ZnO nanowires (2.0 times higher), and BiVO4 thin film (4.3 times higher) in comparison to untreated control samples for PEC water-splitting applications.

Sol-flame synthesis of cobalt-doped TiO2 nanowires with enhanced electrocatalytic activity for oxygen evolution reaction.

Doping nanowires (NWs) is of crucial importance for a range of applications due to the unique properties arising from both impurities' incorporation and nanoscale dimensions. However, existing doping methods face the challenge of simultaneous control over the morphology, crystallinity, dopant distribution and concentration at the nanometer scale. Here, we present a controllable and reliable method, which combines versatile solution phase chemistry and rapid flame annealing process (sol-flame), to dope TiO2 NWs with cobalt (Co). The sol-flame doping method not only preserves the morphology and crystallinity of the TiO2 NWs, but also allows fine control over the Co dopant profile by varying the concentration of Co precursor solution. Characterizations of the TiO2:Co NWs show that Co dopants exhibit 2+ oxidation state and substitutionally occupy Ti sites in the TiO2 lattice. The Co dopant concentration significantly affects the oxygen evolution reaction (OER) activity of TiO2:Co NWs, and the TiO2:Co NWs with 12 at% of Co on the surface show the highest OER activity with a 0.76 V reduction of the overpotential with respect to undoped TiO2 NWs. This enhancement of OER activity for TiO2:Co NWs is attributed to both improved surface charge transfer kinetics and increased bulk conductivity.

Three-dimensional nanostructured bilayer solid oxide fuel cell with 1.3 W/cm(2) at 450 °C.

Obtaining high power density at low operating temperatures has been an ongoing challenge in solid oxide fuel cells (SOFC), which are efficient engines to generate electrical energy from fuels. Here we report successful demonstration of a thin-film three-dimensional (3-D) SOFC architecture achieving a peak power density of 1.3 W/cm(2) obtained at 450 °C. This is made possible by nanostructuring of the ultrathin (60 nm) electrolyte interposed with a nanogranular catalytic interlayer at the cathode/electrolyte interface. We attribute the superior cell performance to significant reduction in both the ohmic and the polarization losses due to the combined effects of employing an ultrathin film electrolyte, enhancement of effective area by 3-D architecture, and superior catalytic activity by the ceria-based interlayer at the cathode. These insights will help design high-efficiency SOFCs that operate at low temperatures with power densities that are of practical significance.

Spatial variation of available electronic excitations within individual quantum dots.

Quantum dots (QDs) allow for manipulation of the position and energy levels of electrons at sub-10 nm length scales through control of material chemistry, size, and shape. It is known from optical studies that the bandgap of semiconductor QDs increases as their size decreases due to the narrowing of the quantum confinement potential. The mechanism of quantum confinement also indicates that the localized properties within individual QDs should depend on their shape in addition to their size, but direct observations of this effect have proven challenging due to the limited spatial resolution of measurement techniques at this scale and the ability to remove contributions from the surroundings. Here we present experimental evidence of spatial variations in the lowest available electron transition energy within a series of single electrically isolated QDs due to a dome-shaped geometry, measured using electron energy-loss spectroscopy in a (scanning) transmission electron microscope [(S)TEM-EELS]. We observe a consistent increase in the energy onset of electronic excitations from the lateral center of the dot toward the edges, which we attribute purely to shape. This trend is in qualitative agreement with a simple quantum simulation of the local density of states in a dome-shaped QD.

Atomic layer deposition of platinum catalysts on nanowire surfaces for photoelectrochemical water reduction.

The photocathodic hydrogen evolution reaction (HER) from p-type Si nanowire (NW) arrays was evaluated using platinum deposited by atomic layer deposition (ALD) as a HER cocatalyst. ALD of Pt on the NW surface led to a highly conformal coating of nanoparticles with sizes ranging from 0.5 to 3 nm, allowing for precise control of the Pt loading in deep submonolayer quantities. The catalytic performance was measured using as little as 1 cycle of Pt ALD, which corresponded to a surface mass loading of ∼10 ng/cm(2). The quantitative exploration of the lower limits of Pt cocatalyst loading reported here, and its application to high-surface-area NW photoelectrodes, establish a general approach for minimizing the cost of precious-metal cocatalysts for efficient and affordable solar-to-fuel applications.

Ultra-thin platinum catalytic electrodes fabricated by atomic layer deposition.

Because noble metal catalysts (e.g. Pt) are one of the main contributors to low-temperature (<500 °C) fuel cell costs, significant efforts have been made to lower the noble metal loading in constructing fuel cell electrodes. In this work, ultra-thin (∼10 nm) platinum (Pt) cathode/catalyst layers were patterned by atomic layer deposition (ALD) and tested as catalytic electrodes (cathode) for low-temperature solid oxide fuel cells. We found that 180 cycles or approximately 10 nm of ALD Pt, with a Pt loading of only 0.02 mg cm(-2), were sufficient for the purpose of a catalytic cathode. Furthermore, this ALD Pt resulted in fuel cell performance comparable to that achieved by 80 nm-thick sputtered Pt. Transmission electron microscope (TEM) observations revealed the optimized number of ALD cycles of Pt for the catalytic electrode, which renders both contiguity and high triple-phase boundary (TPB) density. This result suggests the ability to significantly reduce Pt loading, thereby reducing the cost, and furthermore, can be easily applied to high performance fuel cells with complex 3-D structures.

Enhancing oxide ion incorporation kinetics by nanoscale Yttria-doped ceria interlayers.

Interlayering 17.5 nm of Yttria-doped ceria (YDC) thin films between bulk yttria-stabilized-zirconia electrolyte and a porous Pt cathode enhanced the performance of low-temperature solid oxide fuel cells. The added YDC interlayer (14.11% doped Y(2)O(3)) was fabricated by atomic layer deposition and reduced the cathode/electrolyte interfacial resistances while increasing the exchange current density j(0) by a factor of 4 at operating temperatures between 300-500 °C. Tafel plots and the fitted impedance data suggest that the charge transfer coefficient α of interlayered SOFCs was 1.25 times higher, and the electrode/interfacial activation energy was reduced from 0.85 to 0.76 eV.

Atomic layer deposition of lead sulfide quantum dots on nanowire surfaces.

Quantum dots provide unique advantages in the design of novel optoelectronic devices owing to the ability to tune their properties as a function of size. Here we demonstrate a new technique for fabrication of quantum dots during the nucleation stage of atomic layer deposition (ALD) of PbS. Islands with sub-10 nm diameters were observed during the initial ALD cycles by transmission electron microscopy, and in situ observations of the coalescence and sublimation behavior of these islands show the possibility of further modifying the size and density of dots by annealing. The ALD process can be used to cover high-aspect-ratio nanostructures, as demonstrated by the uniform coating of a Si nanowire array with a single layer of PbS quantum dots. Photoluminescence measurements on the quantum dot/nanowire composites show a blue shift when the number of ALD cycles is decreased, suggesting a route to fabricate unique three-dimensional nanostructured devices such as solar cells.

In vivo O2 measurement inside single photosynthetic cells.

The oxygen evolution of single cells was investigated using a nano-probe with an ultra-micro electrode (UME) in a submicron sized system in combination with a micro-fluidic system. A single cell was immobilized in the micro-fluidic system and a nano-probe was inserted into the cytosolic space of the single cell. Then, the UME was used for an in vivo amperometric experiment at a fixed potential and electrochemical impedance spectroscopy to detect oxygen evolution of the single cell under various light intensities.