Irradiance-Controlled Photoassisted Synthesis of Sub-Nanometre Sized Ruthenium Nanoparticles as Co-Catalyst for TiO2 in Photocatalytic Reactions.
TL;DR: In this paper, the effect of the variation of the incident irradiance and photodeposition rate on the photocatalytic properties of ruthenium nanoparticles supported on TiO2 was evaluated by using the degradation of formic acid in water under UV-A light.
Abstract: Photoassisted synthesis is as a highly appealing green procedure for controlled decoration of semiconductor catalysts with co-catalyst nanoparticles, which can be carried out without the concourse of elevated temperatures, external chemical reducing agents or applied bias potential and in a simple slurry reactor. The aim of this study is to evaluate the control that such a photoassisted method can exert on the properties of ruthenium nanoparticles supported on TiO2 by means of the variation of the incident irradiance and hence of the photodeposition rate. For that purpose, different Ru/TiO2 systems with the same metal load have been prepared under varying irradiance and characterized by means of elemental analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. The photocatalytic activity of the so-obtained materials has been evaluated by using the degradation of formic acid in water under UV-A light. Particles with size around or below one nanometer were obtained, depending on the irradiance employed in the synthesis, with narrow size distribution and homogeneous dispersion over the titania support. The relation between neutral and positive oxidation states of ruthenium could also be controlled by the variation of the irradiance. The obtained photocatalytic activities for formic acid oxidation were in all cases higher than that of undecorated titania, with the sample obtained with the lowest irradiation giving rise to the highest oxidation rate. According to the catalysts characterization, photocatalytic activity is influenced by both Ru size and Ru0/Ruδ+ ratio.
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TL;DR: In this paper , the feasibility of alveolar open-cell β-SiC foams as catalyst support for solar hydrogen production was explored, by means of photo assisted synthesis, on TiO2-coated foams.
Abstract: In this work, we have explored the feasibility of alveolar open-cell β-SiC foams as catalyst support for solar hydrogen production. For that purpose, Pt and Ru nanoparticles have been obtained, by means of photoassisted synthesis, on TiO2-coated foams and tested in gas-phase hydrogen production from water-ethanol mixtures in a tubular reactor coupled to a compound parabolic solar collector (CPC). Subnanometre-sized metal or metal/oxide nanoparticles are obtained for Pt/TiO2/SiC and Ru/TiO2/SiC foams, respectively, where co-catalyst nanoparticles decorate the TiO2 coating which in turn is attached to the SiC foam through an amorphous SiO2 washcoat formed by SiC pre-calcination. In solar photocatalytic reactions, all of the assayed foam-supported photocatalysts are active for the production of hydrogen, with Pt/TiO2 ones being the most active and foam pore size exerting little influence on hydrogen outcome. In the best conditions, 14 % UV-to-hydrogen (equivalent to 0.49 % solar-to-hydrogen) conversion efficiency, with photonic efficiency higher than 30 %, is attained.
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TL;DR: In this paper, high-resolution gold-valence-band photoemission spectra were obtained by the use of monochromatized k-ensuremath-alpha (kα) radiation and a single-crystal specimen.
Abstract: High-resolution gold-valence-band photoemission spectra were obtained by the use of monochromatized $\mathrm{Al} K\ensuremath{\alpha}$ radiation and a single-crystal specimen. After background and scattering corrections were made, the results were compared directly with broadened theoretical density-of-states functions. The following conclusions were drawn: (i) Relativistic band-structure calculations are required to fit the spectrum. (ii) Both the Korringa-Kohn-Rostoker calculation of Connolly and Johnson and the relativistic-augmented-plane-wave calculation by Christensen and Seraphin give density-of-states results that (after broadening) follow the experimental curve closely. (iii) Of the theoretical functions available to date, those with full Slater exchange agree best with experiment (perhaps because of a cancellation of errors). Fractional ($\frac{2}{3} or \frac{5}{6}$) exchange gives $d$ bands that are too wide. (iv) Eastman's 40.8-eV ultraviolet photoemission spectrum is similar to the x-ray spectrum, suggesting little dependence on photon energy above 40 eV. (v) Both (ii) and (iv) imply an absence of strong matrix-element modulation in the photoemission spectrum of gold.
5,238 citations
TL;DR: The research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible.
Abstract: Since the 1970s, splitting water using solar energy has been a focus of great attention as a possible means for converting solar energy to chemical energy in the form of clean and renewable hydrogen fuel. Approaches to solar water splitting include photocatalytic water splitting with homogeneous or heterogeneous photocatalysts, photoelectrochemical or photoelectrocatalytic (PEC) water splitting with a PEC cell, and electrolysis of water with photovoltaic cells coupled to electrocatalysts. Though many materials are capable of photocatalytically producing hydrogen and/or oxygen, the overall energy conversion efficiency is still low and far from practical application. This is mainly due to the fact that the three crucial steps for the water splitting reaction: solar light harvesting, charge separation and transportation, and the catalytic reduction and oxidation reactions, are not efficient enough or simultaneously. Water splitting is a thermodynamically uphill reaction, requiring transfer of multiple electrons, making it one of the most challenging reactions in chemistry. This Account describes the important roles of cocatalysts in photocatalytic and PEC water splitting reactions. For semiconductor-based photocatalytic and PEC systems, we show that loading proper cocatalysts, especially dual cocatalysts for reduction and oxidation, on semiconductors (as light harvesters) can significantly enhance the activities of photocatalytic and PEC water splitting reactions. Loading oxidation and/or reduction cocatalysts on semiconductors can facilitate oxidation and reduction reactions by providing the active sites/reaction sites while suppressing the charge recombination and reverse reactions. In a PEC water splitting system, the water oxidation and reduction reactions occur at opposite electrodes, so cocatalysts loaded on the electrode materials mainly act as active sites/reaction sites spatially separated as natural photosynthesis does. In both cases, the nature of the loaded cocatalysts and their interaction with the semiconductor through the interface/junction are important. The cocatalyst can provide trapping sites for the photogenerated charges and promote the charge separation, thus enhancing the quantum efficiency; the cocatalysts could improve the photostability of the catalysts by timely consuming of the photogenerated charges, particularly the holes; most importantly, the cocatalysts catalyze the reactions by lowering the activation energy. Our research shows that loading suitable dual cocatalysts on semiconductors can significantly increase the photocatalytic activities of hydrogen and oxygen evolution reactions, and even make the overall water splitting reaction possible. All of these findings suggest that dual cocatalysts are necessary for developing highly efficient photocatalysts for water splitting reactions.
2,236 citations
TL;DR: In this article, an empirical set has been developed, based upon data from 135 compounds of 62 elements, for which the sensitivity factors are based on intensity ratios of spectral lines with F1s as a primary standard, value unity, and K2p3/2 as a secondary standard.
Abstract: Quantitative information from electron spectroscopy for chemical analysis requires the use of suitable atomic sensitivity factors. An empirical set has been developed, based upon data from 135 compounds of 62 elements. Data upon which the factors are based are intensity ratios of spectral lines with F1s as a primary standard, value unity, and K2p3/2 as a secondary standard. The data were obtained on two instruments, the Physical Electronics 550 and the Varian IEE-15, two instruments that use electron retardation for scanning, with constant pass energy. The agreement in data from the two instruments on the same compounds is good. How closely the data can apply to instruments with input lens systems is not known. Calculated cross-section data plotted against binding energy on a log-log plot provide curves composed of simple linear segments for the strong lines: 1s, 2p3/2, 3d5/2 and 4f7/2. Similarly, the plots for the secondary lines, 2s, 3p3/2, 4d5/2 and 5d5/2, are shown to be composed of linear segments. Theoretical sensitivity factors relative to F1s should fall on similar curves, with minor correction for the combined energy dependence of instrumental transmission and mean free path. Experimental intensity ratios relative to F1s were plotted similarly, and best fit curves were calculated using the shapes of the theoretical curves as a guide. The intercepts of these best fit curves with appropriate binding energies provide sensitivity factors for the strong lines and the secondary lines for all of the elements except the rare earths and the first series of transition metals. For these elements the sensitivity factors are lower than expected, and variable, because of multi-electron processes that vary with chemical state. From the data it can be shown that many of the commonly-accepted calculated cross-section data must be significantly in error—as much as 40% in some cases for the strong lines, and far more than that for some of the secondary lines.
1,817 citations
TL;DR: In this article, it was pointed out that the spectra of X-ray induced fast photoelectrons from metal should have a characteristic skew line shape resulting from Kondo-like many-electron interactions of the metallic conduction electrons with the accompanying deep hole in the final state.
Abstract: It is pointed out that the spectra of X-ray induced fast photoelectrons from metal should have a characteristic skew line shape resulting from Kondo-like many-electron interactions of the metallic conduction electrons with the accompanying deep hole in the final state. The same line shape should also occur for the discrete line spectra of X-rays emitted from metals. This mechanism could account for the well-known asymmetries observed for K alpha lines.
1,773 citations
TL;DR: Various cocatalysts, such as the biomimetic, metal-based,Metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area.
Abstract: Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.
1,365 citations