Visible light driven photocatalysis mediated via ligand-to-metal charge transfer (LMCT): An alternative approach to solar activation of titania

Visible light harvesting or utilization through semiconductor photocatalysis is a key technology for solar chemical conversion processes. Although titania nanoparticles are popular as a base material of photocatalysis, the lack of visible light activity needs to be overcome. This mini-review is focused on an uncommon approach to visible light activation of titania: the ligand-to-metal charge transfer (LMCT) that takes place between TiO2 nanoparticles and surface adsorbates under visible light irradiation. We discuss a basic concept of photoinduced LMCT and the recent advances in LMCT-mediated visible light photocatalysis which has been applied in environmental remediation and solar energy conversion. Although the LMCT processes have been less investigated and limited in photocatalytic applications compared with other popular visible light activation methods such as impurity doping and dye sensitization, they provide lots of possibilities and flexibility in that a wide variety of organic or inorganic compounds can form surface complexes with TiO2 and introduce a new absorption band in the visible light region. The LMCT complexes may serve as a visible light sensitizer that initiates the photocatalytic conversion of various substrates or the self-degradation of the ligand complexes (usually pollutants) themselves. We summarized and discussed various LMCT photocatalytic systems and their characteristics. The LMCT-mediated activation of titania and other wide bandgap semiconductors has great potential to be developed as a more general method of solar energy utilization in photocatalytic systems. More systematic design and utilization of LMCT complexes on semiconductors are warranted to advance the solar-driven chemical conversion processes.open11144136Ysciescopu

Dynamic model for failures in biological systems

A dynamic model for failures in biological organisms is proposed and studied both analytically and numerically. Each cell in the organism becomes dead under sufficiently strong stress, and is then allowed to be healed with some probability. It is found that unlike the case of no healing, the organism in general does not completely break down even in the presence of noise. Revealed is the characteristic time evolution that the system tends to resist the stress longer than the system without healing, followed by sudden breakdown with some fraction of cells surviving. When the noise is weak, the critical stress beyond which the system breaks down increases rapidly as the healing parameter is raised from zero, indicative of the importance of healing in biological systems.Comment: To appear in Europhys. Let

Natural attenuation of arsenic by sediment sorption and oxidation

Arsenic sorption onto aquifer sediments was investigated in anaerobic laboratory batch and column uptake experiments and characterized by As, Fe, and Mn X-ray absorption spectroscopy (XAS) to estimate the extent and mechanism of abiotic sorption and oxidation of As(III). Batch experiments at pH 6 showed that the amount of As(III) or As(V) sorption from synthetic background porewater to sediments was similar as a function of total As concentration, but slightly more As(V) was sorbed than As(III) with increasing As concentrations. Column experiments with As(III) solutions in the absence and presence of dissolved Fe^2+ showed more As uptake in the presence of Fe but also more Fe desorption during flushout with As-free solutions such that net As uptake was similar to, or less than that of, the Fe-free experiment. Fits to bulk Fe X-ray absorption near-edge spectroscopy (XANES) spectra showed no change between unreacted and reacted sediments. Manganese XANES revealed small increases in absorption in the spectral region associated with Mn(II) after reaction, indicating sediment Mn reduction. However, XANES spectra showed that Mn is not present as Mn^(IV)O_2(s) but is probably substituted into other sediment minerals as a mixture of Mn(II,III). Quantitative analyses of As XANES spectra, which indicated mixtures of As(III) and As(V) after reaction with As(III) solutions, were used to estimate a fraction of As(V) in excess of native As(V) in the sediment (0.2 mmol kg^−1) that corresponds to sorbed As(III) oxidized to As(V). The spectroscopic and solution data indicate that the aquifer sediments have a limited abiotic capacity to oxidize As(III), which did not exceed 30% of the total amount of As sorbed and was estimated in the range of 0.025−0.4 mmol kg^−1 sediment. In the presence of dissolved Fe^2+, the precipitation of Fe(III) hydrous oxide phases will be an effective mechanism for As scavenging only if there exists sufficient dissolved oxygen in groundwater to oxidize Fe. Once the aqueous oxidative capacity is exhausted, dissolved Fe^2+ may compete with As(III) for the limited abiotic oxidation supplied by sediment Mn-bearing phases

ACREAGE RESPONSE, EXPECTED PRICE FUNCTIONS, AND ENDOGENOUS PRICE EXPECTATIONS

Taking the price of futures as a proxy for expected price, this article treats acreage planted to soybean, the price of futures, and other variables as jointly dependent. A futures price equation is embedded in a simultaneous equations model along with the consumption demand and acreage response. The model is estimated using both ordinary and three-stage least squares. Estimated price elasticities for consumption demand, demand for stocks, and acreage response equal, respectively, -.5, -1.8, and +.2 (short run) and +.59 (long run).Crop Production/Industries,

Partial scaling transform of multiqubit states as a criterion of separability

The partial scaling transform of the density matrix for multiqubit states is introduced to detect entanglement of quantum states. The transform contains partial transposition as a special case. The scaling transform corresponds to partial time scaling of subsystem (or partial Planck's constant scaling) which was used to formulate recently separability criterion for continous variables.A measure of entanglement which is a generalization of negativity measure is introduced being based on tomographic probability description of spin states.Comment: 16 pages, 5 figures, submitted to J. Phys. A: Math. Ge

Cosmological Luminosity Evolution of QSO/AGN Population

We apply the observed optical/X-ray spectral states of the Galactic black hole candidates (GBHCs) to the cosmological QSO luminosity evolution under the assumptions that QSOs and GBHCs are powered by similar accretion processes and that their emission mechanisms are also similar. The QSO luminosity function (LF) evolution in various energy bands is strongly affected by the spectral evolution which is tightly correlated with the luminosity evolution. We generate a random sample of QSOs born nearly synchronously by allowing the QSOs to have redshifts in a narrow range around an initial high redshift, black hole masses according to a power-law, and mass accretion rates near Eddington rates. The QSOs evolve as a single long-lived population on the cosmological time scale. The pure luminosity evolution results in distinct luminosity evolution features due to the strong spectral evolution. Most notably, different energy bands (optical/UV, soft X-ray, and hard X-ray) show different evolutionary trends and the hard X-ray LF in particular shows an apparent reversal of the luminosity evolution (from decreasing to increasing luminosity) at low redshifts, which is not seen in the conventional pure luminosity evolution scenario without spectral evolution. The resulting mass function of black holes (BHs), which is qualitatively consistent with the observed QSO LF evolution, shows that QSO remnants are likely to be found as BHs with masses in the range 10**8-5x10**10 solar masses. The long-lived single population of QSOs are expected to leave their remnants as supermassive BHs residing in rare, giant elliptical galaxies.Comment: 9 pages, 2 figures, ApJ