Particle suspension reactors and materials for solar-driven water splitting

Reactors based on particle suspensions for the capture, conversion, storage, and use of solar energy as H_2 are projected to be cost-competitive with fossil fuels. In light of this, this review paper summarizes state-of-the-art particle light absorbers and cocatalysts as suspensions (photocatalysts) that demonstrate visible-light-driven water splitting on the laboratory scale. Also presented are reactor descriptions, theoretical considerations particular to particle suspension reactors, and efficiency and performance characterization metrics. Opportunities for targeted research, analysis, and development of reactor designs are highlighted

The theory of the firm and its critics: a stocktaking and assessment

Includes bibliographical references."Prepared for Jean-Michel Glachant and Eric Brousseau, eds. New Institutional Economics: A Textbook, Cambridge, Cambridge University Press.""This version: August 22, 2005."Since its emergence in the 1970s the modern economic or Coasian theory of the firm has been discussed and challenged by sociologists, heterodox economists, management scholars, and other critics. This chapter reviews and assesses these critiques, focusing on behavioral issues (bounded rationality and motivation), process (including path dependence and the selection argument), entrepreneurship, and the challenge from knowledge-based theories of the firm

Photochemical Charge Separation in Poly(3-hexylthiophene) (P3HT) Films Observed with Surface Photovoltage Spectroscopy

Surface photovoltage spectroscopy (SPS) was used to probe photon induced charge separation in thin films of regioregular and regiorandom poly(3-hexylthiophene) (P3HT) as a function of excitation energy. Both positive and negative photovoltage signals were observed under sub-band-gap (<2.0 eV) and super-band-gap (>2.0 eV) excitation of the polymer. The dependence of the spectra on substrate work function, thermal annealing, film thickness, and illumination intensity was investigated, allowing the identification of interface, charge transfer (CT), and band-gap states in the amorphous and crystalline regions of the polymer films. The ability to probe these states in polymer films will aid the development and optimization of organic electronic devices such as photovoltaics (OPVs), light-emitting diodes (OLEDs), and field effect transistors (OFETs). The direction and size of the observed photovoltage features can be explained using the depleted semiconductor model. © 2013 American Chemical Society

Nanoscale Effects in Water Splitting Photocatalysis.

From a conceptual standpoint, the water photoelectrolysis reaction is the simplest way to convert solar energy into fuel. It is widely believed that nanostructured photocatalysts can improve the efficiency of the process and lower the costs. Indeed, nanostructured light absorbers have several advantages over traditional materials. This includes shorter charge transport pathways and larger redox active surface areas. It is also possible to adjust the energetics of small particles via the quantum size effect or with adsorbed ions. At the same time, nanostructured absorbers have significant disadvantages over conventional ones. The larger surface area promotes defect recombination and reduces the photovoltage that can be drawn from the absorber. The smaller size of the particles also makes electron-hole separation more difficult to achieve. This chapter discusses these issues using selected examples from the literature and from the laboratory of the author

Defect States Control Effective Band Gap and Photochemistry of Graphene Quantum Dots

Graphene quantum dots (GQDs) have emerged as a new group of quantum-confined semiconductors in recent years, with possible applications as light absorbers, luminescent labels, electrocatalysts, and photoelectrodes for photoelectrochemical water splitting. However, their semiconductor characteristics, such as the effective band gap, majority carrier type, and photochemistry, are obscured by defects in this material. Herein, we use surface photovoltage spectroscopy (SPS) in combination with photoelectrochemical measurements to determine the parameters that are essential to the use of GQDs as next-generation semiconductor devices and photocatalysts. Our results show that ordered GQDs (1–6 nm) behave as p-type semiconductors, based on the positive photovoltage in the SPS measurements on Al, Au, and fluorine-doped tin oxide substrates, and generate mobile charge carriers under excitation of defect states at 1.80 eV and under band gap excitation at 2.62 eV. Chemical reduction with hydrazine removes some defects and increases the effective band gap to 2.92 eV. SPS measurements in the presence of sacrificial electron donor and acceptors show that photochemical charge carriers can be extracted and promote redox reactions. A reduced GQDs photocathode supports an unprecedented photocurrent of 50 μA cm^–2 using K₃Fe­(CN)₆ as sacrificial electron acceptor. Additionally, while pristine GQDs do not photoreduce protons under visible light, hydrazine-treated GQDs generate H₂ from aqueous methanol under visible and UV light (0.04% quantum efficiency at 375 nm) without added co-catalysts. These findings are relevant to the use of GQDs in photochemical and photovoltaic energy-conversion systems

Deep eutectic solvent route synthesis of zinc and copper vanadate n-type semiconductors – mapping oxygen vacancies and their effect on photovoltage

Ternary metal oxides M2V2O7−δ (M = Zn and Cu) were synthesized by dissolving binary metal oxide precursors in an environmentally benign deep eutectic solvent (DES), which is a eutectic mixture of a hydrogen bond donor and acceptor, followed by annealing in an open crucible. The unique reaction environment provided by the evolved ammonia allows for stabilization of oxygen vacancies and reduced oxidation states of metal ions within an oxide matrix without the need for any post-treatment with flammable reducing agents. According to comprehensive characterization, including X-ray photoelectron spectroscopy (XPS), neutron powder diffraction, and UV-vis spectroscopy, oxygen deficiency is accompanied by reduced oxidation states of metal centers (Cu+ or V4+), resulting in oxides with mixed-valence metal oxidation states. The amount of oxygen vacancies can be tuned by changing the annealing temperature providing control over band gaps of ternary metal oxides and mid-gap states from reduced metal centers. All synthesized vanadates are n-type semiconductors based on negative photovoltages obtained from surface photovoltage spectroscopy (SPS). A decay of the photovoltage with increasing annealing temperatures is attributed to electron trapping and electron/hole recombination at V4+ and Cu+ mid-gap states. This work shows for the first time the impact of oxygen vacancies on the electronic structure of DES synthesized oxides for solar energy conversion applications.This article is published as Hong, Sangki, Rachel M. Doughty, Frank E. Osterloh, and Julia V. Zaikina. "Deep eutectic solvent route synthesis of zinc and copper vanadate n-type semiconductors–mapping oxygen vacancies and their effect on photovoltage." Journal of Materials Chemistry A 7, no. 19 (2019): 12303-12316. DOI: 10.1039/C9TA00957D. Copyright 2019 The Royal Society of Chemistry. Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0). Posted with permission

14.8% Quantum Efficient Gallium Phosphide Photocatalyst for Hydrogen Evolution

Gallium phosphide is an established photoelectrode material for H2 or O2 evolution from water, but particle-based GaP photocatalysts for H2 evolution are very rare. To understand the reasons, we investigated the photocatalytic H2 evolution reaction (HER) of suspended n-type GaP particles with iodide, sulfite, ferricyanide, ferrous ion, and hydrosulfide as sacrificial electron donors, and using Pt, RhyCr2-yO3, and Ni2P HER cocatalysts. A record apparent quantum efficiency of 14.8% at 525 nm was achieved after removing gallium and oxide charge trapping states from the GaP surface, adding a Ni2P cocatalyst to reduce the proton reduction overpotential, lowering the Schottky-barrier at the GaP-cocatalyst interface, adjusting the polarity of the depletion layer at the GaP-liquid interface, and optimizing the electrochemical potential of the electron donor. The work not only showcases the main factors that control charge separation in suspended photocatalysts, but it also explains why most known HER photocatalysts in the literature are based on n-type and not p-type semiconductors

Quantum Confinement Controls Photocatalysis: A Free Energy Analysis for Photocatalytic Proton Reduction at CdSe Nanocrystals

The ability to adjust the mechanical, optical, magnetic, electric, and chemical properties of materials <i>via</i> the quantum confinement effect is well-understood. Here, we provide the first quantitative analysis of quantum-size-controlled photocatalytic H₂ evolution at the semiconductor–solution interface. Specifically, it is found that the hydrogen evolution rate from illuminated suspended CdSe quantum dots in aqueous sodium sulfite solution depends on nanocrystal size. Photoelectrochemical measurements on CdSe nanocrystal films reveal that the observed reactivity is controlled by the free energy change of the system, as determined by the proton reduction potential and the quasi-Fermi energy of the dots. The corresponding free energy change can be fitted to the photocatalytic activity using a modified Butler–Volmer equation for reaction kinetics. These findings establish a quantitative experimental basis for quantum-confinement-controlled proton reduction with semiconductor nanocrystals. Electrochemical data further indicate that proton reduction occurs at cadmium sites on the dots, and that charge separation in these nanocrystals is controlled by surface effects, not by space charge layers