Highly Photoactive Polythiophenes Obtained by Electrochemical Synthesis from Bipyridine-Containing Terthiophenes

According to numerous previous reports, a Z-scheme with two photon absorbers is the most promising strategy to achieve artificial photosynthesis, but in addition to two efficient catalysts — one for oxygen evolution, the other for CO2 reduction — two different and complementary semiconducting sensitizers are required. Here we present the synthesis of two bipyridine-functionalized terthiophenes, which can be electropolymerized to give photoactive p-type semiconductors the capability to perform as photocathode in photoelectrochemical cells for water photosplitting or artificial photosynthesis. Indeed the bipyridine moiety in their structure allows the binding of transition metal carbonyl complexes employed in CO2 reduction, and their band-gap is suitable for the coupling with wide band-gap semiconductors, which have already found application as photoanodes. Finally, they are characterized by photogenerated charge carrier density between 1.1 and 1.4 × 1019 cm−3, with first-order recombination constant of 0.7–1.8 × 10−2 s−1. These figures are of the same order of magnitude of their inorganic counterparts and would therefore guarantee photoconductivity of the device and the activation of the organometallic catalysts with which they should be coupled to function as photocathodes for CO2 reduction

More than One Century of History for Photocatalysis, from Past, Present and Future Perspectives

In this review, we analyzed the history and the past and present trends in photocatalysis research, trying to outline possible scenarios for the future in the medium term. The in-depth analysis of the literature reported here—from a mere bibliometric point of view—allowed us to divide the history of photocatalysis into four different periods characterized by different maturity of the topic and different bibliometric features. The turn of the 20th century saw an explosion in scientific production, which is still continuing now and has reached more than 15,000 papers published each year. Research interest is still growing significantly, and the analysis of different keywords suggests that such growth is substantial and not merely due to “publish or perish” behavior. The analysis of the most-investigated topics in the field of photocatalysis highlighted that, during its history, the focus of the research moved from inorganic oxides to carbon and hybrid materials. Concomitantly, the investigation of the “geography” of photocatalysis allowed us to underline its evolution over the years, with the repositioning of its center of mass from the Atlantic Ocean (USA and Europe) to Asia (China and India). Photocatalysis is active as never before but still awaiting major breakthroughs, which would allow a much broader technological and commercial output. Without such breakthroughs in this decade, the growth in scientific interest could level out or even decrease

Photocatalytic performances of rare earth element-doped zinc oxide toward pollutant abatement in water and wastewater

The photocatalytic performance of pristine and rare earth elements (La, Ce, Pr, Er, Yb) doped zinc oxide was tested toward the abatement of a model pollutant in MilliQ water and wastewater matrices. ZnO doped with Ce, Er and particularly with Yb exhibited photoactivity higher than bare zinc oxide and the benchmark TiO2 P25, especially in wastewater matrix. Several electrochemical investigations were performed via chronopotentiometry and cyclic voltammetry aimed to shed light on the reasons why the diverse materials behaved differently. From the overall data a complex picture emerged, where there is not a single property of the materials evidently outperforming the others. Nonetheless, from the analysis of whole data a limited role of doping emerged for La and Pr, doping with Er improved the photocurrent, doping with Yb favored a better accumulation of photoelectrons, and doping with Ce promoted a faster electron transfer