Solution combustion synthesis (SCS) is shown to be versatile for the rapid-one-pot synthesis of three compounds and four polymorphs in the Cu−V−O ternary family: α-CuV 2 O 6 , αand β-Cu 2 V 2 O 7 , and γ-Cu 3 V 2 O 8. These compounds feature copper/vanadium stoichiometric ratios ranging from 1:1 to 3:1; their structural, electronic, optoelectronic, and photoelectrochemical attributes were comprehensively characterized by a combination of theoretical and experimental techniques. The main contribution of the present study is the demonstration that a range of stoichiometries in this compound family can be derived simply by tuning the precursor mole ratio in the SCS procedure. The Cu−V−O family of samples, derived by SCS, is shown to exemplify the strong effect of compound stoichiometry on the optoelectronic and photoelectrochemical properties. Overall, α-CuV 2 O 6 showed the best performance, rooted in the direct nature of the optical transition in this material. Finally, SCS is very timeefficient and the various compositions can be obtained in a matter of minutes, as opposed to hours or even days in classical solution-based or ceramic synthesis routes.
This review article addresses areas where solid-state chemistry concepts can contribute to the on-going search for a "magic bullet" inorganic semiconductor that can efficiently split water or reduce CO 2 . First, a methodology to visualize complex ternary oxide combinations is outlined using 31 examples based on copper in both +1 and +2 oxidation states. Then the synthetic aspects are reviewed followed by a discussion of the structural characteristics. The optoelectronic aspects are considered next, culminating the review with the state-of-the-art in the practical applicability of these materials in solar fuels photogeneration and environmental (e.g., azo dye) remediation.
The
ternary compound, CuBi2O4, a 1:1 stoichiometric
derivative of the two component oxides CuO and Bi2O3, has attracted attention from the solar water splitting and
photocatalysis communities as a p-type semiconductor
responsive to visible light. This study demonstrates that solution
combustion synthesis (SCS) can be used to prepare powders not only
of this compound but also nanocomposites with either CuO or Bi2O3 in excess. This was simply done by tuning the
SCS precursor mixture composition. The synthesized crystalline samples
were characterized by powder X-ray diffraction (with Rietveld refinement
for phase purity), diffuse reflectance UV–visible spectroscopy,
electron microscopy, and photoelectrochemical (PEC) techniques. The
band structure and photoactivity of these oxides were probed by linear
sweep voltammetry and by measuring their photoaction spectra (internal
photon-to-electron conversion efficiency vs wavelength). The photoactivity
(attributed to hydrogen evolution and CO2 photoreduction)
was considerably improved in the CuO/CuBi2O4 nanocomposites because of electron transport of the photogenerated
charge carriers between the CuBi2O4 and the
CuO nanoparticles.
Centrifuge model tests and finite element (FE) analysis have been conducted to study the penetration of spudcan foundations in uniform clay with nominally constant strength with depth. In particular, the transition between shallow penetration, with soil heaving to the ground surface, and deep penetration, with a localised flow-round mechanism, has been investigated. This transition governs the onset of back-flow and hence the depth of soil lying on the installed spudcan, which in turn influences the bearing capacity and also the potential for suction to develop and hence the uplift capacity and moment resistance of the foundation. The maximum cavity depth above the spudcan prior to any back-flow is therefore a critical issue for spudcan assessment in clay. In the centrifuge model tests, a half-spudcan model penetrating against a transparent window has been used to visualise the soil flow mechanisms around the spudcan during penetration. The formation of a cavity above the spudcan is revealed by both centrifuge modelling and FE analysis. It is found that there are three distinct penetration mechanisms during spudcan installation: during initial penetration, an open cavity is formed with vertical walls; with further penetration, soil flows partially around the spudcan into the cavity; during deep penetration, the spudcan is fully embedded and the soil flow mechanism is entirely localised. Over the wide range of normalised soil strengths explored, the soil back-flow in the second stage was shown to be due to a flow failure that was triggered by the spudcan penetration and not by wall failure, that is, the collapse of the vertical sides of the soil cavity. This observation is supported by FE analysis. The cavity depth due to flow failure is much shallower than the criterion for wall failure that is incorporated in current design guidelines. Instead, a new design chart and expression is suggested with the normalised cavity depth expressed as a function of the soil shear strength, normalised by the effective unit weight of the soil and the spudcan diameter.
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