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

Mixed oxides of Rh-Cr (RhCrOx), containing Rh3+ and Cr3+ 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 RhCrOx, were fabricated to investigate the physicochemical mechanisms of the HER. Electroanalytical and X-ray photoelectron spectroscopic measurements revealed that nanoparticulate RhCrOx produces reduced Rh (Rh0) species by maintaining an electrode potential more negative than 0.03 V versus the reversible hydrogen electrode (VRHE). This results in significant enhancement of the HER activity. The catalytic activity for the HER stems from the reduced Rh species, and the inclusion of Cr3+ (CrOx) aided in the electron transfer process at the solid/liquid interface, resulting in a higher current density during the HER. To achieve a solar-to-hydrogen efficiency of over 3%, the conduction band minimum of the particulate photocatalyst should be positioned more negatively than -0.10 VRHE. Moreover, the formation of electron trap states at potentials more positive than 0.03 VRHE should be avoided. This study highlights the importance of understanding the catalytic sites on metal oxide cocatalysts. Moreover, it offers a design strategy for enhancing the efficiency of photocatalytic water splitting.

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. The present work demonstrates the production of a Gd2 Ti2 O5 S2 (λ<650 nm) photocatalyst capable of efficiently driving photocatalytic reactions. Single-crystalline, plate-like Gd2 Ti2 O5 S2 particles with atomically ordered surfaces were synthesized by flux and chemical etching methods. Ultrafine Pt-IrO2 cocatalyst particles that promoted hydrogen (H2 ) and oxygen (O2 ) evolution reactions were subsequently loaded on the Gd2 Ti2 O5 S2 while ensuring an intimate contact by employing a microwave-heating technique. The optimized Gd2 Ti2 O5 S2 was found to evolve H2 from an aqueous methanol solution with a remarkable apparent quantum efficiency of 30 % at 420 nm. This material was also stable during O2 evolution in the presence of a sacrificial reagent. The results presented herein demonstrates a highly efficient narrow-band gap oxysulfide photocatalyst with potential applications in practical solar hydrogen production.

Flux-Assisted Synthesis of Y2 Ti2 O5 S2 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 Y2 Ti2 O5 S2 (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. Herein, we report the synthesis of YTOS particles by a flux-assisted technique. The enhanced mass transfer efficiency in the flux significantly reduced the preparation time compared with the SSR method. In addition, the resulting YTOS showed improved photocatalytic H2 and O2 evolution activity when loaded with Rh and Co3 O4 co-catalysts, respectively. These improvements are attributed to the reduced particle size and enhanced crystallinity of the material as well as the slower decay of photogenerated carriers on a nanosecond to sub-microsecond time range. Further optimization of this flux-assisted method together with suitable surface modification is expected to produce high-quality YTOS crystals with superior photocatalytic activity.

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

The hydrogen evolution reaction (HER) of Rh nanoparticles (RhNP) coated with an ultrathin layer of Cr-oxides (CrOx ) was investigated as a model electrode for the Cr2 O3 /Rh-metal core-shell-type cocatalyst system for photocatalytic water splitting. The CrOx layer was electrodeposited over RhNP on a transparent conductive fluorine-doped tin oxide (FTO) substrate. The CrOx layer on RhNP facilitates the electron transfer process at the CrOx /RhNP interface, leading to the increased current density for the HER. Impedance spectroscopic analysis revealed that the CrOx layer transferred protons via the hopping mechanism to the RhNP surface for HER. In addition, CrOx restricted electron transfer from the FTO to the electrolyte and/or RhNP and suppressed the backward reaction by limiting oxygen migration. This study clarifies the crucial role of the ultrathin CrOx layer on nanoparticulate cocatalysts and provides a cocatalyst design strategy for realizing efficient photocatalytic water splitting.

Local charge carrier dynamics of a particulate Ga-doped La5Ti2Cu0.9Ag0.1O7S5 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. The map of the charge carrier type revealed that charge trapping sites for electrons and holes were spatially separated within each particle/aggregate. Furthermore, the effect of the rhodium cocatalyst was recognized as a new electron pathway, trapping to the rhodium site and the following recombination, which was delayed compared with the original electron recombination process. The Rh effect was discussed based on the phenomenological simulation, revealing a possible reason for the decay was due to the anisotropic diffusion of charge carriers in oxysulfides or the interfacial energy barrier at the interface.

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)64-. However, the device with guanidinium-added electrolyte does not show steady-state operation. The two possible reasons include (1) the difficult diffusion of Fe(CN)63- into the crystal layer of (Gdm+)n[Fe(CN)64-] at the hot electrode and (2) the difficult precipitation of (Gdm+)n[Fe(CN)64-] formed at the cold side upon the binding of the reduced Fe(CN)64- with Gdm+. Nevertheless, the performance recovers once the device is disconnected from the external loading. Due to the high thermopower after adding guanidinium, we successfully fabricate self-powered sensors by connecting four flexible cells in series. The sensors can transfer humidity, temperature, and air pressure data wirelessly using body heat. Therefore, ferricyanide/ferrocyanide/guanidinium is a promising electrolyte material for applications of low-grade energy harvesting.

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

Oxysulfide semiconductor, Y2Ti2O5S2, 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. A well-calibrated theoretical model estimates various efficiency limiting material parameters like recombination rate constant, n-type doping density and tail-states parameters. Compared to metal oxides, longer effective carrier lifetime ~6 ns is demonstrated. Different design routes are proposed to realize efficiency beyond 10% for commercial solar-to-hydrogen production from oxysulfide photocatalysts.

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. We show that the electrostatic effect of trapped charges leads to non-linear energy bands in the perovskite layer, which results in the underestimation of the trap density from existing CFT models. Consequently, a parabolic band approximation with effective length (PBAEL) model is developed to accurately predict the trap density for shallow or deep states from CFT analysis. In addition, we demonstrate that the attempt-to-escape frequency, which dictates the trapping dynamics, can be well extracted by eliminating the electrostatic effect at a reduced perovskite thickness. We believe that our work provides a unified theoretical platform for CFT to extract trap-state parameters for a broad class of organic, inorganic, and hybrid semiconductor-based thin-film devices for energy-conversion applications such as solar cells, LEDs, artificial photosynthesis, etc.

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. The recently reported increase in the Seebeck coefficient owing to the introduction of guanidinium (Gdm) or urea into the Fe(CN)64-/Fe(CN)63- electrolyte is analyzed using the theoretical results. Furthermore, qualitative and quantitative analyses were also performed to determine the influence of the affinity for the additives on the entropy difference of the redox couples and on the Seebeck coefficient. This study also demonstrates the enhancement in the Seebeck coefficient caused by a membrane isolating the binding species into an appropriate hot/cold zone.

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 cent1,2. Thus, whether a particulate photocatalyst can enable a quantum efficiency of 100 per cent for the greatly endergonic water-splitting reaction remains an open question. Here we demonstrate overall water splitting at an external quantum efficiency of up to 96 per cent at wavelengths between 350 and 360 nanometres, which is equivalent to an internal quantum efficiency of almost unity, using a modified aluminium-doped strontium titanate (SrTiO3:Al) photocatalyst3,4. By selectively photodepositing the cocatalysts Rh/Cr2O3 (ref. 5) and CoOOH (refs. 3,6) for the hydrogen and oxygen evolution reactions, respectively, on different crystal facets of the semiconductor particles using anisotropic charge transport, the hydrogen and oxygen evolution reactions could be promoted separately. This enabled multiple consecutive forward charge transfers without backward charge transfer, reaching the upper limit of quantum efficiency for overall water splitting. Our work demonstrates the feasibility of overall water splitting free from charge recombination losses and introduces an ideal cocatalyst/photocatalyst structure for efficient water splitting.

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. Specifically, we show that (a) the effect of ionic charges is almost indistinguishable from that of dopant ions, (b) ion migration could lead to simultaneous improvement in Voc and degradation in Jsc-an observation which is beyond the realm of mere parametric variation in carrier mobility and lifetime, (c) champion devices are more resilient toward the ill effects of ion migration; (d) we propose characterization schemes to determine both magnitude and polarity of ionic species, and finally, (e) we illustrate that ion migration could be differentiated from ion redistribution based on the distinct trends in performance degradation. Our results, supported by detailed numerical simulations and direct comparison with experimental data, are of broad interest and provide a much needed predictive capability toward the research on performance degradation mechanisms in perovskite solar cells.