Photoinduced interfacial electron transfer from perovskite quantum dots to molecular acceptors for solar cells.

Bandgap-engineered inorganic and hybrid halide perovskite (HP) films, nanocrystals, and quantum dots (PQDs) are promising for solar cells. Fluctuations of photoinduced electron transfer (PET) rates affect the interfacial charge separation efficiencies of such solar cells. Electron donor- or acceptor-doped perovskite samples help analyze PET and harvest photogenerated charge carriers efficiently. Therefore, PET in perovskite-based donor-acceptor (D-A) systems has received considerable attention. We analyzed the fluctuations of interfacial PET from MAPbBr3 or CsPbBr3 PQDs to classical electron acceptors such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 1,2,4,5-tetracyanobenzene (TCNB) at single-particle and ensemble levels. The significantly negative Gibbs free energy changes of PET estimated from the donor-acceptor redox potentials, the donor-acceptor sizes, and the solvent dielectric properties help us clarify the PET in the above D-A systems. The dynamic nature of PET is apparent from the decrease in photoluminescence (PL) lifetimes and PL photocounts of PQDs with an increase in the acceptor concentrations. Also, the acceptor radical anion spectrum helps us characterize the charge-separated states. Furthermore, the PL blinking time and PET rate fluctuations (108 to 107 s-1) provide us with single-molecule level information about interfacial PET in perovskites.

A poly(3,4-propylenedioxythiophene)/carbon micro-sphere-bismuth nanoflake composite and multifunctional Co-doped graphene for a benchmark photo-supercapacitor.

Efficient storage of sunlight in the form of charge is accomplished by designing and implementing a photo-supercapacitor (PSC) with a novel, cost-effective architecture. Sulfur (S)- and nitrogen (N)-doped graphene particles (SNGPs) are incorporated in a TiO2/CdS photoanode. The beneficial effects of SNGPs such as the high electrical conductance promoting fast electron transfer to TiO2, a suitably positioned conduction band that maximizes charge separation, and its' ability to absorb red photons translate into a power conversion efficiency of 9.4%, for the champion cell. A new composite of poly(3,4-propylenedioxythiophene)/carbon micro-sphere-bismuth nanoflakes (PProDOT/CMS-BiNF) is integrated with the photoanode to yield the PSC. The photocurrent produced under 1 sun irradiance is directed to the supercapacitor, wherein, the synergy between the faradaic and electrical double layer charge accumulation mechanisms of PProDOT and CMS-BiNF bestows storage parameters of an areal capacitance of 104.6 mF cm-2, and energy and power densities of 9 µW h cm-2 and 0.026 mW cm-2. An overall photo-conversion and storage efficiency of 6.8% and an energy storage efficiency of 72% exhibited by the PSC are much superior to those delivered by a majority of the PSCs reported in the literature on the otherwise highly efficient perovskite solar cell or the expensive Ru dye based solar cells.

A photoanode with plasmonic nanoparticles of earth abundant bismuth for photoelectrochemical reactions.

A wide range of technologies has been developed for producing hydrogen economically and in greener ways. Photoelectrochemical water splitting using photoelectrodes submerged in a bath electrolyte forms a major route of hydrogen evolution. The efficacy of water splitting is improved by sensitizing metal oxide photoelectrodes with narrow bandgap semiconductors that efficiently absorb sunlight and generate and transport charge carriers. Here we show that the efficiencies of photocurrent generation and photoelectrochemical hydrogen evolution by the binary TiO2/Sb2S3 anode increase by an order of magnitude upon the incorporation of the earth-abundant plasmonic bismuth nanoparticles into it. The ternary electrode TiO2/Bi nanoparticle/Sb2S3 illuminated with sunlight provides us with a photocurrent density as high as 4.21 mA cm-2 at 1.23 V, which is fourfold greater than that of the binary electrode and tenfold greater than that of pristine TiO2. By using bismuth nanoparticles, we estimate the incident photon to current conversion efficiency at 31% and solar power conversion efficiency at 3.85%. Here the overall impact of bismuth nanoparticles is attributed to increases in the open-circuit voltage (860 mV), which is by expediting the transfer of photogenerated electrons from Sb2S3 nanoparticles to the TiO2 electrode, and short-circuit current (9.54 mA cm-2), which is by the plasmonic nearfield effect. By combining the cost-effective plasmonic bismuth nanoparticles with the narrow bandgap Sb2S3 on the TiO2 electrode, we develop a stable, ternary photoanode and accomplish high-efficiency photocurrent generation and hydrogen evolution.