The energy payback time associated with the semiconductor active material is an important parameter in a photovoltaic solar cell device. Thus lowering the energy requirements for the semiconductor synthesis step or making it more energy-efficient is critical toward making the overall device economics more competitive relative to other nonpolluting energy options. In this communication, combustion synthesis is demonstrated to be a versatile and energy-efficient method for preparing inorganic oxide semiconductors such as tungsten trioxide (WO3) for photovoltaic or photocatalytic solar energy conversion. The energy efficiency of combustion synthesis accrues from the fact that high process temperatures are self-sustained by the exothermicity of the combustion process, and the only external thermal energy input needed is for dehydration of the fuel/oxidizer precursor mixture and bringing it to ignition. Importantly, we show that, in this approach, it is also possible to tune the optical characteristics of the oxide semiconductor (i.e., shift its response toward the visible range of the electromagnetic spectrum) in situ by doping the host semiconductor during the formative stage itself. As a bonus, the resultant material shows enhanced surface properties such as markedly improved organic dye uptake relative to benchmark samples obtained from commercial sources. Finally, this synthesis approach requires only very simple equipment, a feature that it shares with other "mild" inorganic semiconductor synthesis routes such as sol-gel chemistry, chemical bath deposition, and electrodeposition. The present study constitutes the first use of combustion synthesis for preparing WO3 powder comprising nanosized particles.
This review article takes a new look at the problem of characterization of structural properties and reaction dynamics of supported metal catalysts. Such catalysts exhibit an inherent complexity, particularly due to interactions with the support and the adsorbate molecules, which can be highly sensitive to environmental conditions such as pressure and temperature. Recent reports demonstrate that finite size effects such as negative thermal expansion and large bond length disorder are directly caused by these complex interactions. To uncover the atomistic features underlying the reaction mechanisms and kinetics of metal catalysts, experimental characterization must accommodate the challenging operation conditions of catalytic processes and provide insights into system attributes. The combined application of x-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) for this type of investigations will be examined, and the individual strengths and limitations of these methods will be discussed. Furthermore, spatial and temporal heterogeneities that describe real catalytic systems and can hinder their investigation by either averaging (such as XAS) or local (such as TEM) techniques alone will be addressed by conjoined, multiscale, ab initio density functional theory/molecular dynamics modeling of metal catalysts that can both support and guide experimental studies. When taken together, a new analysis scheme emerges, in which different forms of structure and dynamics can be fully characterized by combining information obtained experimentally by in situ XAS and electron microscopy as well as theoretically via modeling. V
The effect of varying the oxygen content in Sn and SnOx films during potential dependent SnOx conversion reactions and LiySn alloying relevant to Li ion battery anodes is examined. For metallic Sn films, the stresses and stability of the films are controlled by Li alloying reactions. Small, non‐contacting separated Sn particles exhibit higher electrochemical stability relative to more continuous polycrystalline films with larger particles. Metallic Sn particles develop tensile stress during LiySn de‐alloying as porous structures are formed. The amount of stress associated with lithiation and delithiation of well‐separated metallic particles decreases as a porous, easy to lithiate, material forms with cycling. During the lithiation of oxides, conversion reactions (SnOx → Sn) and the lithiation of the metallic Sn control the stress responses of the films, leading to highly potential‐dependent stress development. In particular, evidence for a multistep electrochemical mechanism, in which partially reversible lithiation of the oxygen‐containing phases is conjoined with a fully reversible lithiation of the metallic phases of the Sn, is found. The electrochemical stress analysis provides new insight into these mechanisms and delineates the extent of the reversibility of lithiation and conversion reactions of oxides.
Microcantilever stress measurements are examined to contrast and compare their attributes with those from in situ X-ray absorption spectroscopy to elucidate bonding dynamics during the oxygen reduction reaction (ORR) on a Pt catalyst. The present work explores multiple atomistic catalyst properties that notably include features of the Pt-Pt bonding and changes in bond strains that occur upon exposure to O2 in the electrochemical environment. The alteration of the Pt electronic and physical structures due to O2 exposure occurs over a wide potential range (1.2 to 0.4 V vs normal hydrogen electrode), a range spanning potentials where Pt catalyzes the ORR to those where Pt-oxide forms and all ORR activity ceases. We show that Pt-Pt surface bond strains due to oxygen interactions with Pt-Pt bonds are discernible at macroscopic scales in cantilever-based bending measurements of Pt thin films under O2 and Ar. Complementary extended X-ray absorption fine structure (EXAFS) measurements of nanoscale Pt clusters supported on carbon provide an estimate of the magnitude and direction of the in-operando bond strains. The data show that under O2 the M-M bonds elongate as compared to an N2 atmosphere across a broad range of potentials and ORR rates, an interfacial bond expansion that falls within a range of 0.23 (±0.15)% to 0.40 (±0.20)%. The EXAFS-measured Pt-Pt bond strains correspond to a stress thickness and magnitude that is well matched to the predictions of a mechanics mode applied to experimentally determined data obtained via the cantilever bending method. The data provide new quantitative understandings of bonding dynamics that will need to be considered in theoretical treatments of ORR catalysis and substantiate the subpicometer resolution of electrochemically mediated bond strains detected on the macroscale.
Energy storage is an increasingly critical component of modern technology, with applications that include energy infrastructure, transportation systems, and portable electronics. Improvements to lithium-ion battery energy/power density through the adoption of silicon anodes—promising both gravimetric and volumetric capacities that far exceed traditional carbon-based anodes—has been limited by ∼300% strains and poor coulombic efficiency during charge and discharge ((dis)charge) cycling which result in short operational lifetimes. We examine encapsulated micropore-modified silicon anodes that define lithium mass-transfer dynamics to constrain strain evolution and improve capacity retention during (dis)charge cycling. Fully integrated cells incorporating this silicon anode and a commercial grade LiCoO2 cathode maintain their capacity for 110 cycles with >99% average coulombic efficiency from cycles 5 to 100. Anodes with thicknesses up to 50 μm resulted in area-normalized capacities of up to 12.7 mAhcm−2. When the silicon anode microstructure pitch is varied, a direct relationship is found to exist between the rate capability and volumetric capacity of the anode. Helium-ion Microscopy, Secondary Ion Mass Spectrometry, and Scanning Electron Microscopy, used as ex-situ characterization methods for the evolution of the electrode's structure on cycling, reveal significant changes in nanoscale morphology that otherwise retain the essential laminate micropore motif of the initial Si anode.
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