Michael G. Walter

Bio: Michael G. Walter is an academic researcher from University of North Carolina at Charlotte. The author has contributed to research in topics: Porphyrin & Ohmic contact. The author has an hindex of 17, co-authored 38 publications receiving 9058 citations. Previous affiliations of Michael G. Walter include California Institute of Technology & Portland State University.

Solar Water Splitting Cells

Abstract: Energy harvested directly from sunlight offers a desirable approach toward fulfilling, with minimal environmental impact, the need for clean energy. Solar energy is a decentralized and inexhaustible natural resource, with the magnitude of the available solar power striking the earth’s surface at any one instant equal to 130 million 500 MW power plants.1 However, several important goals need to be met to fully utilize solar energy for the global energy demand. First, the means for solar energy conversion, storage, and distribution should be environmentally benign, i.e. protecting ecosystems instead of steadily weakening them. The next important goal is to provide a stable, constant energy flux. Due to the daily and seasonal variability in renewable energy sources such as sunlight, energy harvested from the sun needs to be efficiently converted into chemical fuel that can be stored, transported, and used upon demand. The biggest challenge is whether or not these goals can be met in a costeffective way on the terawatt scale.2

Porphyrins and phthalocyanines in solar photovoltaic cells

Abstract: This review summarizes recent advances in the use of porphyrins, phthalocyanines, and related compounds as components of solar cells, including organic molecular solar cells, polymer cells, and dye-sensitized solar cells. The recent report of a porphyrin dye that achieves 11% power conversion efficiency in a dye-sensitized solar cell indicates that these classes of compounds can be as efficient as the more commonly used ruthenium bipyridyl derivatives.

Photoelectrochemical Hydrogen Evolution Using Si Microwire Arrays

Abstract: Arrays of B-doped p-Si microwires, diffusion-doped with P to form a radial n+ emitter and subsequently coated with a 1.5-nm-thick discontinuous film of evaporated Pt, were used as photocathodes for H2 evolution from water. These electrodes yielded thermodynamically based energy-conversion efficiencies >5% under 1 sun solar simulation, despite absorbing less than 50% of the above-band-gap incident photons. Analogous p-Si wire-array electrodes yielded efficiencies <0.2%, largely limited by the low photovoltage generated at the p-Si/H2O junction.

Thiazolothiazole Fluorophores Exhibiting Strong Fluorescence and Viologen-Like Reversible Electrochromism

Abstract: The synthesis, electrochemical, and photophysical characterization of N,N′-dialkylated and N,N′-dibenzylated dipyridinium thiazolo[5,4-d]thiazole derivatives are reported. The thiazolothiazole viologens exhibit strong blue fluorescence with high quantum yields between 0.8–0.96. The dioctyl, dimethyl, and dibenzyl derivatives also show distinctive and reversible yellow to dark blue electrochromism at low reduction potentials. The fused bicyclic thiazolo[5,4-d]thiazole heterocycle allows the alkylated pyridinium groups to remain planar, strongly affecting their electrochemical properties. The singlet quantum yield is greatly enhanced with quaternarization of the peripheral 4-pyridyl groups (ΦF increases from 0.22 to 0.96) while long-lived fluorescence lifetimes were observed between 1.8–2.4 ns. The thiazolothiazole viologens have been characterized using cyclic voltammetry, UV–visible absorbance and fluorescence spectroscopy, spectroelectrochemistry, and time-resolved photoluminescence. The electrochromic p...

Electrical conductivity, ionic conductivity, optical absorption, and gas separation properties of ionically conductive polymer membranes embedded with Si microwire arrays

Abstract: The optical absorption, ionic conductivity, electronic conductivity, and gas separation properties have been evaluated for flexible composite films of ionically conductive polymers that contain partially embedded arrays of ordered, crystalline, p-type Si microwires. The cation exchange ionomer Nafion, and a recently developed anion exchange ionomer, poly(arylene ether sulfone) that contains quaternary ammonium groups (QAPSF), produced composite microwire array/ionomer membrane films that were suitable for operation in acidic or alkaline media, respectively. The ionic conductivity of the Si wire array/Nafion composite films in 2.0 M H_(2)SO_4(aq) was 71 mS cm^(−1), and the conductivity of the Si wire array/QAPSF composite films in 2.0 M KOH(aq) was 6.4 mS cm^(−1). Both values were comparable to the conductivities observed for films of these ionomers that did not contain embedded Si wire arrays. Two Si wire array/Nafion membranes were electrically connected in series, using a conducting polymer, to produce a trilayer, multifunctional membrane that exhibited an ionic conductivity in 2.0 M H_(2)SO)4(aq) of 57 mS cm^(−1) and an ohmic electrical contact, with an areal resistance of ~0.30 Ω cm^2, between the two physically separate embedded Si wire arrays. All of the wire array/ionomer composite membranes showed low rates of hydrogen crossover. Optical measurements indicated very low absorption (<3%) in the ion-exchange polymers but high light absorption (up to 80%) by the wire arrays even at normal incidence, attesting to the suitability of such multifunctional membranes for application in solar fuels production.

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

Abstract: As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction

Abstract: Objective evaluation of the activity of electrocatalysts for water oxidation is of fundamental importance for the development of promising energy conversion technologies including integrated solar water-splitting devices, water electrolyzers, and Li-air batteries. However, current methods employed to evaluate oxygen-evolving catalysts are not standardized, making it difficult to compare the activity and stability of these materials. We report a protocol for evaluating the activity, stability, and Faradaic efficiency of electrodeposited oxygen-evolving electrocatalysts. In particular, we focus on methods for determining electrochemically active surface area and measuring electrocatalytic activity and stability under conditions relevant to an integrated solar water-splitting device. Our primary figure of merit is the overpotential required to achieve a current density of 10 mA cm–2 per geometric area, approximately the current density expected for a 10% efficient solar-to-fuels conversion device. Utilizing ...

MoS2 Nanoparticles Grown on Graphene: An Advanced Catalyst for the Hydrogen Evolution Reaction

Abstract: Advanced materials for electrocatalytic and photoelectrochemical water splitting are central to the area of renewable energy. In this work, we developed a selective solvothermal synthesis of MoS2 nanoparticles on reduced graphene oxide (RGO) sheets suspended in solution. The resulting MoS2/RGO hybrid material possessed nanoscopic few-layer MoS2 structures with an abundance of exposed edges stacked onto graphene, in strong contrast to large aggregated MoS2 particles grown freely in solution without GO. The MoS2/RGO hybrid exhibited superior electrocatalytic activity in the hydrogen evolution reaction (HER) relative to other MoS2 catalysts. A Tafel slope of ∼41 mV/decade was measured for MoS2 catalysts in the HER for the first time; this exceeds by far the activity of previous MoS2 catalysts and results from the abundance of catalytic edge sites on the MoS2 nanoparticles and the excellent electrical coupling to the underlying graphene network. The ∼41 mV/decade Tafel slope suggested the Volmer–Heyrovsky mec...

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy

Abstract: Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.

Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions

Abstract: A fundamental change has been achieved in understanding surface electrochemistry due to the profound knowledge of the nature of electrocatalytic processes accumulated over the past several decades and to the recent technological advances in spectroscopy and high resolution imaging. Nowadays one can preferably design electrocatalysts based on the deep theoretical knowledge of electronic structures, via computer-guided engineering of the surface and (electro)chemical properties of materials, followed by the synthesis of practical materials with high performance for specific reactions. This review provides insights into both theoretical and experimental electrochemistry toward a better understanding of a series of key clean energy conversion reactions including oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The emphasis of this review is on the origin of the electrocatalytic activity of nanostructured catalysts toward the aforementioned reactions by correlating the apparent electrode performance with their intrinsic electrochemical properties. Also, a rational design of electrocatalysts is proposed starting from the most fundamental aspects of the electronic structure engineering to a more practical level of nanotechnological fabrication.