Cadmium (Cd) is a priority pollutant in aquatic ecosystems because of its highly toxic effects at low concentrations. Recent work has highlighted that at sublethal concentrations, Cd can impair the ability of fish to respond to important sensory cues. In the present study, we examined whether chronic exposure to environmentally relevant concentrations of waterborne Cd (1, 2.5 and 5 μg/L) can result in reproductive impairment in fathead minnows (Pimephales promelas) as measured by the standard Organization for Economic Cooperation and Development (OECD) 21-day reproductive assay. In addition, we also evaluated the effects of chronic waterborne Cd exposure on Cd accumulation in target tissues (liver and ovary) and plasma estradiol level in females and on the reproductive behaviour of fathead minnows. We found that the standard endpoints used in the OECD reproductive assays (e.g., egg production, number of spawning attempts, brood size) are more sensitive to Cd exposure than behavioural endpoints; however, the traditional method of interpreting reproductive impairment may underestimate toxic effects. Cadmium accumulation in liver and ovary of fish increased with increasing Cd exposure concentrations; however, plasma estradiol level remained unaffected. Reproductive capacity in fathead minnows decreased at waterborne Cd concentrations as low as 1 μg/L. The findings of our study have important implications for understanding the effects of chronic Cd exposure in metal-impacted feral fish populations.

An efficient 1,4-addition of TMSCN to aromatic enones has been achieved in excellent yields (91-99%) by CsF (1 mol%) as the catalyst and H 2 O (4 equiv) as the additive in refluxing dioxane within 2-7 hours.

The U.S. Department of Energy recently announced its first Energy Earthshot on Clean Hydrogen, with a cost target of $1/kg-H2 by 2031. Assuming future utility-scale grid electricity prices from photovoltaics ($0.02/kWh), 80% of the cost of H2 would come from performing low-temperature water electrolysis at its thermoneutral voltage, with zero additional overpotential. This fact motivates alternative, less-expensive means of using light to generate mobile charge carriers than photovoltaics, and reactor designs with exceedingly low capital costs, like those we recently invented. Systems using low capital cost reactors benefit from low-voltage operation, which represents a paradigm shift from current state-of-the-art electrolyzers that aim to operate at high current densities. Analytical models predict that solar photocatalytic water splitting inherently operates at low voltages through use of an ensemble of optically thin photoabsorbers each operating at a low rate. Collectively the ensemble exhibits larger overall solar-to-hydrogen conversion efficiencies in comparison to optically thick designs. In efforts to attain these predicted higher efficiencies, we are performing detailed studies on the properties of state-of-the-art doped SrTiO3 and BiVO4 photocatalyst particles. During my talk, I will share our recent efforts in atomic-layer deposited ultrathin oxide coatings to impart redox selectivity and materials stability, single-photocatalyst-particle current–potential behavior and mobile charge carrier properties, and atomic-level information on dopant distributions and materials interfaces obtained from electron microscopies and X-ray spectroscopies. Collectively, our discoveries provide new design guidelines and additional research pathways for the development of effective composite materials to serve as active components in techno-economically viable artificial photosynthetic devices.

Similar to natural photosynthesis, Z-scheme photocatalytic water splitting relies on two different light absorbing components that are coupled by a redox active mediator that shuttles charge between them. Such a two-absorber system possesses several advantages over single absorber photocatalytic system, including higher theoretical solar-to-hydrogen conversion efficiency, relaxed band alignment requirements, and the potential for inherently safe operation whereby H2 and O2 evolution occur in separated compartments. However, a major disadvantage and challenge for Z-scheme photocatalysis is that the presence of a redox mediator introduces two undesirable back-reactions on top of parasitic H2 oxidation and O2 reduction reactions that can occur in a single absorber photocatalytic system. Previous research efforts have identified the use of semi-permeable oxide coatings as an attractive approach to suppress these thermodynamically favored redox reactions while still permitting the desired water splitting and mediator redox reactions to occur. Here, we present a combined experimental and computational approach based on model thin films that is used to (i) probe the performance limits of oxide-encapsulated photocatalysts, (ii) quantify the effects of coating defects on performance, and (iii) guide the rational design of coatings aimed at maximizing the solar-to-hydrogen conversion efficiency of a target photocatalytic system. This work specifically focusses on the development of silicon and titanium oxide coatings for Z-scheme water splitting based on a Fe(II)/Fe(III) mediator, showing that the best coatings can achieve selectivities > 90 % towards the H2 and O2 evolution reactions over undesired Fe(II)/Fe(III) back reactions. Another key finding from this work is that coating defects can have a significant influence on the performance of encapsulated electrodes, as revealed by scanning electrochemical microscopy (SECM) measurements that were used to locally quantify the parasitic back reaction rates around individual defects to determine their impact on the global selectivity of an encapsulated electrode.

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