The elusive photocatalytic water splitting reaction using sunlight on suspended nanoparticles: is there a way forward?

For many decades hydrogen production by photocatalytic methods has been pursued over a variety of semiconductors with probably over a thousand formulations of powder catalysts in many structures and compositions. Yet, with the exception of a few reports, water splitting to molecular hydrogen and oxygen has remained elusive. The only reproducible results are those involving other additives to water: electron donors or acceptors yielding either hydrogen or oxygen, but not both. The consequence of this is a system unrelated to water splitting but simply driven by the organic or inorganic redox potential. One may argue that thermodynamic limitations indicate that an inorganic semiconductor with a band gap within the spectrum of sunlight, and that is stable in water, cannot split water. Otherwise, it would not have existed on eart

Hydrogen production from water: past and present

Hydrogen derived from sustainable materials may be an important energy vector in a post petroleum economy. The focus of this short review article is on the most studied methods for making hydrogen from water including: electrocatalytic, photocatalytic, and thermally driven reactions on reducible oxides. Hydrogen from renewables comes at a cost. Therefore, projected process cost issues are necessary in determining the best path forward. The most important challenge in the thermally driven reaction is finding a metal oxide that can be reduced at practical temperatures with acceptable reaction kinetics while the most important challenge for photocatalytic reactions is to find a stable semiconductor-based material capable of splitting water using a large fraction of sun light

A computational study of the interaction of oxygenates with the surface of rutile TiO2_{2}(110). Structural and electronic trends

A variety of OH containing molecules in their different modes of adsorption onto the rutile TiO2(110) are studied by means of density functional theory. A special focus is given to ethanol, ethylene glycol and glycerol. The different species were analyzed with respect to the adsorption energy, work function, and atomic Bader charges. Our results show that dissociated adsorption is favored in all cases. Within these modes, the strongest binding is observed in the case of bidentate fully dissociated adsorption, followed by bidentate partially dissociated then the monodentate dissociated modes. The dependence is also noted upon charge transfer analysis. Species adsorbing with two dissociated OH groups show a negative charge which is roughly twice as large compared to those exhibiting only one dissociated group. In the case of molecular adsorption, we find a small positive charge on the adsorbate. The change in work functions obtained is found to be negative in all studied cases. We observe a trend of the work function change being more negative for glycerol (3 OH groups) followed by ethylene glycol (2 OH groups) and the remaining alcohols (1 OH group), thus indicating that the number of OH groups present is an important factor in regards to work function changes. For the complete series of adsorbates studied (methanol, ethanol, isopropanol, ethylene glycol, glycerol, hydrogen peroxide and formic acid) there is a linear relationship between the change in the work function and the adsorption energy for the molecular adsorption mode. The relationship is less pronounced for the dissociated adsorption mode for the same series

Reactions of ethanol over CeO2 and Ru/CeO2 catalysts

The reaction of ethanol has been investigated on Ru/CeO2 in steady state conditions as well as with temperature programmed desorption (TPD). High resolution transmission electron microscopy (HRTEM) images indicated that the used catalyst contained Ru particles with a mean size of ca. 1.5 nm well dispersed on CeO2 (of about 12–15 nm in size). Surface uptake of ethanol was measured by changing exposure to ethanol followed by TPD. Saturation coverage is found to be between 0.25 and 0.33 of a monolayer for CeO2 that has been prior heated with O2 at 773 K. The main reactions of ethanol on CeO2 during TPD are: re-combinative desorption of ethanol; dehydrogenation to acetaldehyde; and dehydration to ethylene. The dehydration to ethylene occurs mainly in a small temperature window at about 700 K and it is attributed to ethoxides adsorbed on surface-oxygen defects. The presence of Ru considerably modified the reaction of ceria towards ethanol. It has switched the desorption products to CO, CO2, CH4 and H2. These latter products are typical reforming products. Ethanol steam reforming (ESR) conducted on Ru/CeO2 indicated that optimal reaction activity is at about 673 K above which CO2 production declines (together with that of H2) due to reverse water gas shift. This trend was well captured during ethanol TPD where CO2 desorbed about 50 K below than CO on both oxidized and reduced Ru/CeO2 catalysts.Peer ReviewedPostprint (author's final draft

Effects of experimental parameters on the growth of GaN nanowires on Ti-film/Si(1 0 0) and Ti-foil by molecular beam epitaxy

Gallium nitride (GaN) nanostructures are used in optoelectronic applications due to their unique optical and electronic properties. For some optoelectronic applications and potential photocatalytic systems, the growth of GaN nanowires on metallic substrates instead of expensive single crystalline semiconductors can be beneficial due to specific properties of metals. In this study, GaN nanowire systems were grown on 300 nm Ti-film/Si(1 0 0) and Ti-foil by plasma assisted molecular beam epitaxy (PA-MBE) and characterized in situ by Auger electron spectroscopy (AES) and ex situ by scanning electron microscopy (SEM). Effects of (i) the nature of substrate surface, (ii) Ga flux, and (iii) substrate temperature on the growth of GaN nanowires were investigated. Nearly vertical nanowires can be grown on Ti-films covered with amorphous TiOx or TiOxNy, which is formed during the nitridation process. To grow nearly vertical nanowires on Ti-foils, pre-nitridation of the substrate surface was found to be important. The orientation of GaN nanowires grown on nitridated Ti-foil is determined by the grain alignment of the original Ti-foil, however, GaN nanowires grown on nitridated Ti-foils are uniformly oriented to one direction within an individual grain, which is most likely due to the epitaxial relation between the nanowires and the underneath grains of the polycrystalline Ti-foils. Both the orientation and nanowire density vary on different grains

Identification of Intermediates in the Reaction Pathway of SO2_{2} on the CaO Surface: From Physisorption to Sulfite to Sulfate

The interaction of CaO and Ca(OH)$_{2}$ with solvated or gaseous SO$_{2}$ plays a crucial role in the corrosion of urban infrastructure by acid rain or in the removal of SO$_{2}$ from flue gas. We carried out a combined spectroscopic and theoretical investigation on the interaction of SO$_{2}$ with a CaO(001) single crystal. First, the surface chemistry of SO$_{2}$ was investigated at different temperatures using polarization-resolved IR reflection absorption spectroscopy. Three species were identified, and an in-depth density functional theory study was carried out, which allowed deriving a consistent picture. Unexpectedly, low temperature exposure to SO$_{2}$ solely yields a physisorbed species. Only above 100 K, the transformation of this weakly bound adsorbate first to a chemisorbed sulfite and then to a sulfate occurs, effectively passivatating the surface. Our results provide the basis for more efficient strategies in corrosion protection of urban infrastructure and in lime-based desulfurization of flue gas

Letter to Editor COVID-19 outbreak and medical waste: Challenge in hand

The ongoing pandemic of  novel coronavirus disease, COVID19, which first reported in Wuhan, China, inDecember 2019, [1] and caused by severe acute respiratory syndrome coronavirus 2 (SARSCoV2) has resulted to more than 6,881,352 confirmed cases in the world, and 399,895 global deaths, as reported in 8:36am CEST, 8 June 2020. [2] It has been reported that the primary spread of COVID-19 via human transmission is during close contact, most often through small droplets spread by coughing, sneezing, and talking. [3] Researchers and health experts have discovered that wearing of appropriate face masks can significantly reduce the transmission up to the 75%

Highly acid-durable carbon coated Co3O4 nanoarrays as efficient oxygen evolution electrocatalysts

Most oxygen evolution reaction (OER) electrocatalysts are not stable in corrosive acids. Even the expensive RuO2 or IrO2, the most acid-resistant oxides, can be dissolved at an oxidative potential. Herein, we realize that the failures of OER catalysts are mostly caused by the weak interface between catalysts and the substrates. Hence, the study of the interface structure between catalysts and substrates is critical. In this work, we observe that the cheap OER catalysts Co3O4 can be more durable than the state-of-the-art RuO2 if the interface quality is good enough. The Co3O4 nanosheets deposited on carbon paper (Co3O4/CP) is prepared by electroplating of Co-species and followed by a two-step calcination process. The 1st step occurs in vacuum in order to maintain the surface integrity of the carbon paper and converts Co-species to Co(II)O. The 2nd step is a calcination in ambient conditions which enables the complete transformation of Co(II)O to Co3O4 without degrading the mechanical strength of the Co3O4-CP interface. Equally important, an in situ formation of a layer of amorphous carbon on top of Co3O4 further enhances the OER catalyst stability. Therefore, these key advances make the Co3O4 catalyst highly active toward the OER in 0.5 M H2SO4 with a small overpotential (370 mV), to reach 10 mA/cm2. The observed long lifetime for 86.8 h at a constant current density of 100 mA/cm2, is among the best of the reported in literature so far, even longer than the state-of-art RuO2 on CP. Overall, our study provides a new insight and methodology for the construction of a high-performance and high stability OER electrocatalysts in corrosive acidic environments

Evidence of Plasmonic Induced Photocatalytic Hydrogen Production on Pd/TiO2 Upon Deposition on Thin Films of Gold

H2-production from renewables using sunlight is probably the holy grail of modern science and technology. Among the many approaches for increasing reaction rates, by increasing light absorption, plasmonic materials are often invoked. Yet, most plasmonic metals on semiconductors are also good for Schottky barrier formation. In this work, we are presenting evidences of de-coupling the plasmonic from Schottky effects on photoreaction. To conduct this we have systematically changed the under-layer gold film thickness and associated particle size. On top of the thin film layer, we have deposited the exact amount of a prototypical Schottky-based photo-catalyst (Pd/TiO2). We found up to 4 times increase in the H2-production rate at a critical Au film thickness (8 nm-thick). Below this thickness, the plasmonic response is not too strong while above it, the PR decays in favor of the Drude absorption mode. The reaction requires the presence of both UV (to excite the semiconductor) and visible light (to excite Au particles) in order to obtain high hydrogen production, 800 µmol/gCatal.min (probably the highest direct hydrogen (not current) production rate reported on a performing catalyst). The enhancement origin is quantitatively traced to its computed electric field strength (EFS). Adding a dielectric (SiO2) in between the Au thin layer and the catalyst exponentially decreased the reaction rate and EFS, with increasing its thickness. This work indicates the possibility of making an active and stable photo-catalyst from fundamental concepts yet further progress on the structural (technological) front is needed to make a practical catalyst

Metal Halide Perovskites for Solar-to-Chemical Fuel Conversion

This review article presents and discusses the recent progress made in the stabilization, protection, improvement, and design of halide perovskite‐based photocatalysts, photoelectrodes, and devices for solar‐to‐chemical fuel conversion. With the target of water splitting, hydrogen iodide splitting, and CO2 reduction reactions, the strategies established for halide perovskites used in photocatalytic particle‐suspension systems, photoelectrode thin‐film systems, and photovoltaic‐(photo)electrocatalysis tandem systems are organized and introduced. Moreover, recent achievements in discovering new and stable halide perovskite materials, developing protective and functional shells and layers, designing proper reaction solution systems, and tandem device configurations are emphasized and discussed. Perspectives on the future design of halide perovskite materials and devices for solar‐to‐chemical fuel conversion are provided. This review may serve as a guide for researchers interested in utilizing halide perovskite materials for solar‐to‐chemical fuel conversion