Showing papers by "Nathan S. Lewis published in 2022"

Failure Modes of Platinized pn+-GaInP Photocathodes for Solar-Driven H2 Evolution.

Abstract: The long-term stability for the hydrogen-evolution reaction (HER) of homojunction pn+-Ga0.52In0.48P photocathodes (band gap = 1.8 eV) with an electrodeposited Pt catalyst (pn+-GaInP/Pt) has been systematically evaluated in both acidic and alkaline electrolytes. Electrode dissolution during chronoamperometry was correlated with changes over time in the current density-potential (J-E) behavior to reveal the underlying failure mechanism. Pristine pn+-GaInP/Pt photocathodes yielded an open-circuit photopotential (Eoc) as positive as >1.0 V vs the potential of the reversible hydrogen electrode (RHE) and a light-limited current density (Jph) of >12 mA cm-2 (1-sun illumination). However, Eoc and Jph gradually degraded at either pH 0 or pH 14. The performance degradation was attributed to three different failure modes: (1) gradual thinning of the n+-emitter layer due to GaInP dissolution in acid; (2) active corrosion of the underlying GaAs substrate at positive potentials causing delamination of the upper GaInP epilayers; and (3) direct GaAs/electrolyte contact compromising the operational stability of the device. This work reveals the importance of both substrate stability and structural integrity of integrated photoelectrodes toward stable solar fuel generation.

Polymorphic Control of Solution-Processed Cu2SnS3 Films with Thiol–Amine Ink Formulation

Abstract: There is increasing demand for tailored molecular inks that produce phase-pure solution-processed semiconductor films. Within the Cu–Sn–S phase space, Cu2SnS3 belongs to the I2–IV–VI3 class of semiconductors that crystallizes in several different polymorphs. We report the ability of thiol–amine solvent mixtures to dissolve inexpensive bulk Cu2S and SnO precursors to generate free-flowing molecular inks. Upon mild annealing, polymorphic control over phase-pure tetragonal (I4̅2m) and orthorhombic (Cmc21) Cu2SnS3 films was realized simply by switching the identity of the thiol (i.e., 1,2-ethanedithiol vs 2-mercaptoethanol, respectively). Polymorph control is dictated by differences in the resulting molecular metal–thiolate complexes and their subsequent decomposition profiles, which likely seed distinct Cu2–xS phases that template the ternary sulfide sublattice. The p-type tetragonal and orthorhombic Cu2SnS3 films possess similar experimental direct optical band gaps of 0.94 and 0.88 eV, respectively, and strong photoelectrochemical current responses. Understanding how ink formulation dictates polymorph choice should inform the development of other thiol–amine inks for solution-processed films.

Powdered MnySb1–yOx Catalysts for Cerium-Mediated Oxygen Evolution in Acidic Environments

Abstract: MnySb1–yOx powders with a series of compositions were evaluated as catalysts for chemical water oxidation in aqueous perchloric, sulfuric, or methanesulfonic acid. O2(g) evolved spontaneously over MnySb1–yOx catalyst powders that had been suspended in solutions that were pre-loaded with Ce4+ ions. The rate of O2 evolution depended on the amount, as well as the oxidation state, of the Mn in the powder. The highest O2 evolution rate was observed from the most Mn-rich catalyst, which had an effective surface oxidation state of Mn2.9+ in its rest state. The facile synthetic accessibility of such catalysts in powder form constitutes a step toward replacing Ir or Ru in Ce-mediated oxygen evolution in decoupled water splitting systems, as well as toward developing inks of earth-abundant catalysts for preparation of catalyst-coated membranes used in conventional proton-exchange membrane electrolyzers.

Strain-Based Chemiresistive Polymer-Coated Graphene Vapor Sensors

Abstract: Suspended chemiresistive graphene sensors have been fabricated using well-established nanofabrication techniques to generate sensors that are highly sensitive to pyridine and with excellent discrimination between polar and nonpolar analytes. When coated with a polymer surface layer and suspended on 3-D patterned glass electrodes, a hybrid combination of polymer and graphene yields chemiresistive vapor sensors. Expansion and contraction of the polymer layer produces strain on the suspended graphene (Gr). Hence, when organic vapors permeate into the polymer layer, the high gauge factor of the graphene induces substantial electrical resistive changes as folds and creases are induced in the graphene. The hybrid suspended polymer/Gr sensor exhibits substantial responses to polar organic vapors, especially pyridine, while also exhibiting reversibility and increased discrimination between polar and nonpolar analytes compared to previous approaches. This sensor design also allows for potential tunability in the types of polymers used for the reactive surface layer, allowing for use in a variety of potential applications.

Plastic Morphological Response to Spectral Shifts during Inorganic Phototropic Growth

Abstract: Plants exhibit phototropism in which growth is directed toward sunlight and demonstrate morphological plasticity in response to changes in the spectral distribution of the incident illumination. Inorganic phototropic growth via template-free, light-directed electrochemical deposition of semiconductor material can spontaneously generate highly ordered mesostructures with anisotropic, nanoscale lamellar features that exhibit a pitch proportional to the wavelength (λ) of the stimulating illumination. In this work, Se–Te films were generated via a two-step inorganic phototropic growth process using a series of narrowband light-emitting diode sources with discrete output wavelengths (λ0 ≠ λ1). Analogous to the plasticity observed in plants, changes in illumination wavelength from λ0 to λ1 resulted in morphological changes including feature branching, termination, and/or fusion along the growth direction. The interfacial feature pitch changed with the growth duration, in some cases in a notably nonmonotonic fashion, and eventually matched that obtained for growth using only λ1. Simulated morphologies generated by modeling light–material interactions at the growth interface closely matched the evolved structures observed experimentally, indicating that the characteristics of the optical stimulation produce the observed plastic response during inorganic phototropic growth. Examination of the interfacial electric field modulation for λ1 illumination of simplified structures, representative of those generated experimentally, revealed the interfacial light scattering and concentration behavior that directed phototropic growth away from equilibrium, as well as the emergent nature of the phenomena that reestablish equilibrium.

Experimental and Theoretical Comparison of Potential-dependent Methylation on Chemically Exfoliated WS2 and MoS2.

Abstract: Reductant-activated functionalization is shown to enhance the methylation of chemically exfoliated MoS2 (ceMoS2) and ceWS2 by introducing excess negative charge to facilitate a nucleophilic attack reaction. Relative to methylation in the absence of a reductant, the reaction produces a twofold increase in coverage of ceWS2, from 25 to 52% coverage per WS2. However, at every potential, the methyl coverage on ceWS2 was ∼20% lower than that on ceMoS2. We applied grand canonical density functional theory to show that at constant potential, more negative charge is present on 1T'-MoS2 than on 1T'-WS2, making methylation both thermodynamically and kinetically more favorable for 1T'-MoS2 than 1T'-WS2. This effect was moderated when the reactions were compared at constant charge, emphasizing the importance of comparing the reactivity of materials at nominally identical electrode potentials.

Numerical Simulation and Modeling of Hydrogen Gas Evolution on Planar and Microwire Array Electrodes

Abstract: The impact of gas evolution on the electrochemical characteristics of planar electrodes and microwire array electrodes has been analyzed using modeling and simulation. The impacts can mainly be broken into three phenomena, a shift in the local reversible hydrogen electrode potential, hyperpolarization and an increase in the solution resistance of the electrolyte. The local reversible hydrogen electrode potential shift was found to play the most important role, constituting >40% of the total potential drop between the cathode and reference electrode, following correction for cell resistance. Compared to planar electrodes, a microwire array structure reduces the impact of bubbles on the solution conductance, but the shift in the local reversible hydrogen electrode potential varies with distance from the actual electrode surface.