How insignificant modifications of photocatalysts can significantly change their photocatalytic activity

Synthetic procedures, including doping, sintering and surface coating, can noticeably affect the physicochemical properties of semiconductors. Introduced changes very often translate into photocatalytic and photoelectrochemical activity alterations. However, in this work we have focused on more subtle treatments, which result in lack of changes observed using XRD, UV-vis, porosimetry, TEM or SEM. We have subjected titanium dioxide (P25, UV100) to a treatment with reducing agents used in procedures of noble metal deposition (citrate, borohydride, and photoreduction), or surface decoration with small amounts of TiO2 by atomic layer deposition (ALD; 10 to 200 deposition cycles), which presumably should be neutral to its activity. Although the "classical" characterization methods did not show any differences between the original and treated samples, spectroelectrochemical (SE-DRS) determination of the density of states (DOS) and catechol adsorption tests revealed a significant influence of such treatments on the photocatalytic activity (photogeneration of HO radicals, water reduction, and herbicide degradation) and photoelectrochemical behaviour of the studied samples. We have shown that the applied slight surface modifications of titanium dioxide ("insignificant" at the first glance) may strongly affect the activity of this material. Such often overlooked effects must be taken into account during a comparative photoactivity analysis of various semiconductors, since an insignificant surface treatment may noticeably influence surface chemistry. We have also demonstrated that SE-DRS can be considered as a useful tool to study these effects, although it can be difficult to correlate a particular treatment with recorded changes in the density of states.Peer reviewe

High Electrocatalytic Activity of Vertically Aligned Single-Walled Carbon Nanotubes towards Sulfide Redox Shuttles

Vertically aligned single-walled carbon nanotubes (VASWCNTs) have been successfully transferred onto transparent conducting oxide glass and implemented as efficient low-cost, platinum-free counter electrode in sulfide –mediated dye-sensitized solar cells (DSCs), featuring notably improved electrocatalytic activity toward thiolate/disulfide redox shuttle over conventional Pt counter electrodes. Impressively, device with VASWCNTs counter electrode demonstrates a high fill factor of 0.68 and power conversion efficiency up to 5.25%, which is significantly higher than 0.56 and 3.49% for that with a conventional Pt electrode. Moreover, VASWCNTs counter electrode produces a charge transfer resistance of only 21.22 Ω towards aqueous polysulfide electrolyte commonly applied in quantum dots-sensitized solar cells (QDSCs), which is several orders of magnitude lower than that of a typical Pt electrode. Therefore, VASWCNTs counter electrodes are believed to be a versatile candidate for further improvement of the power conversion efficiency of other iodine-free redox couple based DSCs and polysulfide electrolyte based QDSCs

The violent youth of bright and massive cluster galaxies and their maturation over 7 billion years

In this study, we investigate the formation and evolution mechanisms of the brightest cluster galaxies (BCGs) over cosmic time. At high redshift (z ∼ 0.9), we selected BCGs and most massive cluster galaxies (MMCGs) from the Cl1604 supercluster and compared them to low-redshift (z ∼ 0.1) counterparts drawn from the MCXC meta-catalogue, supplemented by Sloan Digital Sky Survey imaging and spectroscopy. We observed striking differences in the morphological, colour, spectral, and stellar mass properties of the BCGs/MMCGs in the two samples. High-redshift BCGs/MMCGs were, in many cases, star-forming, late-type galaxies, with blue broad-band colours, properties largely absent amongst the low-redshift BCGs/MMCGs. The stellar mass of BCGs was found to increase by an average factor of 2.51 ± 0.71 from z ∼ 0.9 to z ∼ 0.1. Through this and other comparisons, we conclude that a combination of major merging (mainly wet or mixed) and in situ star formation are the main mechanisms which build stellar mass in BCGs/MMCGs. The stellar mass growth of the BCGs/MMCGs also appears to grow in lockstep with both the stellar baryonic and total mass of the cluster. Additionally, BCGs/MMCGs were found to grow in size, on average, a factor of ∼3, while their average Sérsic index increased by ∼0.45 from z ∼ 0.9 to z ∼ 0.1, also supporting a scenario involving major merging, though some adiabatic expansion is required. These observational results are compared to both models and simulations to further explore the implications on processes which shape and evolve BCGs/MMCGs over the past ∼7 Gyr