Temperature gradients are generated by the sun and a vast array of technologies and can induce molecular concentration gradients in solutions via thermodiffusion (Soret effect). For ions, this leads to a thermovoltage that is determined by the thermal gradient ΔT across the electrolyte, together with the ionic Seebeck coefficient α_i. So far, redox-free electrolytes have been poorly explored in thermoelectric applications due to a lack of strategies to harvest the energy from the Soret effect. Here, we report the conversion of heat into stored charge via a remarkably strong ionic Soret effect in a polymeric electrolyte (Seebeck coefficients as high as α_i = 10 mV K⁻¹). The ionic thermoelectric supercapacitor (ITESC) is charged under a temperature gradient. After the temperature gradient is removed, the stored electrical energy can be delivered to an external circuit. This new means to harvest energy is particularly suitable for intermittent heat sources like the sun. We show that the stored electrical energy of the ITESC is proportional to (ΔTα_i)². The resulting ITESC can convert and store several thousand times more energy compared with a traditional thermoelectric generator connected in series with a supercapacitor.

Measuring temperature and heat flux is important for regulating any physical, chemical, and biological processes. Traditional thermopiles can provide accurate and stable temperature reading but they are based on brittle inorganic materials with low Seebeck coefficient, and are difficult to manufacture over large areas. Recently, polymer electrolytes have been proposed for thermoelectric applications because of their giant ionic Seebeck coefficient, high flexibility and ease of manufacturing. However, the materials reported to date have positive Seebeck coefficients, hampering the design of ultra-sensitive ionic thermopiles. Here we report an “ambipolar” ionic polymer gel with giant negative ionic Seebeck coefficient. The latter can be tuned from negative to positive by adjusting the gel composition. We show that the ion-polymer matrix interaction is crucial to control the sign and magnitude of the ionic Seebeck coefficient. The ambipolar gel can be easily screen printed, enabling large-area device manufacturing at low cost.

Photoelectrochemical (PEC) water splitting is a promising technology that uses light absorbing semiconductors to convert solar energy directly into a chemical fuel (i.e., hydrogen). PEC water splitting has the potential to become a key technology in achieving a sustainable society, if high solar to fuel energy conversion efficiencies are obtained with earth abundant materials. This review article discusses recent developments and discoveries in the mechanisms by which the localized surface plasmon resonance (LSPR) in metallic nanoparticles can increase or complement a neighbouring semiconductor in light absorption for catalytic water splitting applications. These mechanisms can mitigate the intrinsic optical limitations of semiconductors (e.g., metal oxides) for efficient solar water splitting. We identify four types of enhancement mechanisms in the recent literature: (i) light scattering, (ii) light concentration, (iii) hot electron injection (HEI), and (iv) plasmon-induced resonance energy transfer (PIRET). (i) Light scattering and (ii) light concentration are light trapping mechanisms that can increase the absorption of light with energies above the semiconductor optical band-edge. These two mechanisms are ideal to enhance the absorption of promising semiconductors with narrow bandgap energies that suffer from limited absorption coefficients and bulk charge recombination. On the other hand, (iii) HEI and the recently discovered (iv) PIRET are mechanisms that can enhance the absorption also below the semiconductor optical band-edge. Therefore, HEI and PIRET have the potential to extend the light utilization to visible and near-infrared wavelengths of semiconductors with excellent electrochemical properties, but with large bandgap energies. New techniques and theories that have been developed to elucidate the above mentioned plasmonic mechanisms are presented and discussed for their application in metal oxide photoelectrodes. Finally, other plasmonic and non-plasmonic effects that do not increase the device absorption, but affect the electrochemical properties of the semiconductor (e.g., charge carrier transport) are also discussed, since a complete understanding of these phenomena is fundamental for the design of an efficient plasmonic NP-semiconductor water splitting device.

With the aim of developing a DNA sequencing methodology, we theoretically examine the feasibility of using nanoplasmonics to control the translocation of a DNA molecule through a solid-state nanopore and to read off sequence information using surface-enhanced Raman spectroscopy. Using molecular dynamics simulations, we show that high-intensity optical hot spots produced by a metallic nanostructure can arrest DNA translocation through a solid-state nanopore, thus providing a physical knob for controlling the DNA speed. Switching the plasmonic field on and off can displace the DNA molecule in discrete steps, sequentially exposing neighboring fragments of a DNA molecule to the pore as well as to the plasmonic hot spot. Surface-enhanced Raman scattering from the exposed DNA fragments contains information about their nucleotide composition, possibly allowing the identification of the nucleotide sequence of a DNA molecule transported through the hot spot. The principles of plasmonic nanopore sequencing can be e...