Understanding the Activation Mechanism of RhCrO Cocatalysts for Hydrogen Evolution with Nanoparticulate Electrodes.

Mixed oxides of Rh-Cr (RhCrO), containing Rh and Cr cations, are commonly used as cocatalysts for the hydrogen evolution reaction (HER) on particulate photocatalysts. The precise physicochemical mechanisms of the HER at the catalytic sites of these oxides are not well understood. In this study, model cocatalyst electrodes, composed of nanoparticulate RhCrO, were fabricated to investigate the physicochemical mechanisms of the HER.

An Oxysulfide Photocatalyst Evolving Hydrogen with an Apparent Quantum Efficiency of 30 % under Visible Light.

Photocatalytic water splitting is a simple means of converting solar energy into storable hydrogen energy. Narrow-band gap oxysulfide photocatalysts have attracted much attention in this regard owing to the significant visible-light absorption and relatively high stability of these compounds. However, existing materials suffer from low efficiencies due to difficulties in synthesizing these oxysulfides with suitable degrees of crystallinity and particle sizes, and in constructing effective reaction sites.

Flux-Assisted Synthesis of Y Ti O S for Photocatalytic Hydrogen and Oxygen Evolution Reactions.

Photocatalytic water splitting is an ideal means of producing hydrogen in a sustainable manner, and developing highly efficient photocatalysts is a vital aspect of realizing this process. The photocatalyst Y Ti O S (YTOS) is capable of absorbing at wavelengths up to 650 nm and exhibits outstanding thermal and chemical durability compared with other oxysulfides. However, the photocatalytic performance of YTOS synthesized using the conventional solid-state reaction (SSR) process is limited owing to the large particle sizes and structural defects associated with this synthetic method.

Mechanistic Insights into Enhanced Hydrogen Evolution of CrO /Rh Nanoparticles for Photocatalytic Water Splitting.

The hydrogen evolution reaction (HER) of Rh nanoparticles (RhNP) coated with an ultrathin layer of Cr-oxides (CrO ) was investigated as a model electrode for the Cr O /Rh-metal core-shell-type cocatalyst system for photocatalytic water splitting. The CrO layer was electrodeposited over RhNP on a transparent conductive fluorine-doped tin oxide (FTO) substrate. The CrO layer on RhNP facilitates the electron transfer process at the CrO /RhNP interface, leading to the increased current density for the HER.

Local charge carrier dynamics of a particulate Ga-doped LaTiCuAgOS photocatalyst and the impact of Rh cocatalysts.

Visible-light responsive photocatalytic materials are expected to be deployed for practical use in photocatalytic water splitting. One of the promising materials as a p-type semiconductor, oxysulfides, was investigated in terms of the local charge carrier behavior for each particle by using a home-built time-resolved microscopic technique in combination with clustering analysis. We could differentiate electron and hole trapping to the surface states and the following recombination on a micron-scale from the nanosecond to microsecond order.

Thermoelectrochemical Cells Based on Ferricyanide/Ferrocyanide/Guanidinium: Application and Challenges.

Ferricyanide/ferrocyanide/guanidinium-based thermoelectrochemical cells have been investigated under different loading conditions in this work. Compared with ferricyanide/ferrocyanide-based devices, the device with guanidinium-added electrolytes shows higher power and energy densities. We observed that the enhanced performance is not due to the ionic Seebeck effect of guanidinium but because of the configuration entropy change resulting from the selective binding of Gdm to Fe(CN).

Unveiling charge dynamics of visible light absorbing oxysulfide for efficient overall water splitting.

Oxysulfide semiconductor, YTiOS, has recently discovered its exciting potential for visible-light-induced overall water splitting, and therefore, imperatively requires the probing of unknown fundamental charge loss pathways to engineer the photoactivity enhancement. Herein, transient diffuse reflectance spectroscopy measurements are coupled with theoretical calculations to unveil the nanosecond to microsecond time range dynamics of the photogenerated charge carriers. In early nanosecond range, the pump-fluence-dependent decay dynamics of the absorption signal is originated from the bimolecular recombination of mobile charge carriers, in contrast, the power-law decay kinetics in late microsecond range is dominated by hole detrapping from exponential tail trap states of valence band.

Deciphering the capacitance frequency technique for performance-limiting defect-state parameters in energy-harvesting perovskites.

With emerging thin-film PIN-based optoelectronics devices, a significant research thrust is focused on the passivation of trap states for performance enhancement. Among various methods, the capacitance frequency technique (CFT) is widely employed to quantify the trap-state parameters; however, the trapped charge-induced electrostatic effect on the same is not yet established for such devices. Herein, we present a theoretical methodology to incorporate such effects in the CF characteristics of well-established, but not limited to, carrier-selective perovskite-based PIN devices.

Insight into the effect of the configuration entropy of additives on the Seebeck coefficient.

Thermogalvanic cells have attracted considerable attention because of their potential to directly convert waste heat into electricity by using redox reactions under continuous operation with a simple, cost-effective design. An increase in the Seebeck coefficient owing to the interactions between the redox ions and the additives has been reported in recent studies. The configuration entropy of the small additives coordinated to a large ion is calculated to analyze the Seebeck coefficient obtained from the entropy difference between the redox pairs.

Photocatalytic water splitting with a quantum efficiency of almost unity.

Overall water splitting, evolving hydrogen and oxygen in a 2:1 stoichiometric ratio,  using particulate photocatalysts is a potential means of achieving scalable and economically viable solar hydrogen production. To obtain high solar energy conversion efficiency, the quantum efficiency of the photocatalytic reaction must be increased over a wide range of wavelengths and semiconductors with narrow bandgaps need to be designed. However, the quantum efficiency associated with overall water splitting using existing photocatalysts is typically lower than ten per cent.

Predictive Modeling of Ion Migration Induced Degradation in Perovskite Solar Cells.

With excellent efficiencies being reported from multiple laboratories across the world, device stability and the degradation mechanisms have emerged as the key aspects that could determine the future prospects of perovskite solar cells. However, the related experimental efforts remain scattered due to the lack of any unifying theoretical framework. In this context, here we provide a comprehensive analysis of ion migration effects in perovskite solar cells.