Carbon Nanotubes as a Solid-State Electron Mediator for Visible-Light-Driven Z-Scheme Overall Water Splitting.

So-called Z-scheme systems, which typically comprise an H2 evolution photocatalyst (HEP), an O2 evolution photocatalyst (OEP), and an electron mediator, represent a promising approach to solar hydrogen production via photocatalytic overall water splitting (OWS). The electron mediator transferring photogenerated charges between the HEP and OEP governs the performance of such systems. However, existing electron mediators suffer from low stability, corrosiveness to the photocatalysts, and parasitic light absorption. In the present work, carbon nanotubes (CNTs) were shown to function as an effective solid-state electron mediator in a Z-scheme OWS system. Based on the high stability and good charge transfer characteristics of CNTs, this system exhibited superior OWS performance compared with other systems using more common electron mediators. The as-constructed system evolved stoichiometric amounts of H2 and O2 at near-ambient pressure with a solar-to-hydrogen energy conversion efficiency of 0.15%. The OWS reaction was also promoted in the case that this CNT-based Z-scheme system was immobilized on a substrate. Hence, CNTs are a viable electron mediator material for large-scale Z-scheme OWS systems.

Nanoparticulate TiN Loading to Promote Z-Scheme Water Splitting Using a Narrow-Bandgap Nonoxide-Based Photocatalyst Sheet.

Some oxide-based particulate photocatalyst sheets exhibit excellent activity during the water-splitting reaction. The replacement of oxide photocatalysts with narrow-bandgap photocatalysts based on nonoxides could provide the higher solar-to-hydrogen energy conversion efficiencies that are required for practical implementation. Unfortunately, the activity of nonoxide-based photocatalyst sheets is low in many cases, indicating the need for strategies to improve the quality of nonoxide photocatalysts and the charge transfer process. In this work, single-crystalline particulate SrTaO2 N is studied as an oxygen evolution photocatalyst for photocatalyst sheets applied to Z-scheme water splitting, in combination with La5 Ti2 Cu0.9 Ag0.1 O7 S5 and Au as the hydrogen evolution photocatalyst and conductive layer, respectively. The loading of SrTaO2 N with CoOx provided increases activity during photocatalytic water oxidation, giving an apparent quantum yield of 15.7% at 420 nm. A photocatalyst sheet incorporating CoOx -loaded SrTaO2 N is also found to promote Z-scheme water splitting under visible light. Notably, the additional loading of nanoparticulate TiN on the CoOx -loaded SrTaO2 N improves the water splitting activity by six times because the TiN promotes electron transfer from the SrTaO2 N particles to the Au layer. This work demonstrates key concepts related to the improvement of nonoxide-based photocatalyst sheets based on facilitating the charge transfer process through appropriate surface modifications.

Efficient and stable visible-light-driven Z-scheme overall water splitting using an oxysulfide H2 evolution photocatalyst.

So-called Z-scheme systems permit overall water splitting using narrow-bandgap photocatalysts. To boost the performance of such systems, it is necessary to enhance the intrinsic activities of the hydrogen evolution photocatalyst and oxygen evolution photocatalyst, promote electron transfer from the oxygen evolution photocatalyst to the hydrogen evolution photocatalyst, and suppress back reactions. The present work develop a high-performance oxysulfide photocatalyst, Sm2Ti2O5S2, as an hydrogen evolution photocatalyst for use in a Z-scheme overall water splitting system in combination with BiVO4 as the oxygen evolution photocatalyst and reduced graphene oxide as the solid-state electron mediator. After surface modifications of the photocatalysts to promote charge separation and redox reactions, this system is able to split water into hydrogen and oxygen for more than 100 hours with a solar-to-hydrogen energy conversion efficiency of 0.22%. In contrast to many existing photocatalytic systems, the water splitting activity of the present system is only minimally reduced by increasing the background pressure to 90 kPa. These results suggest characteristics suitable for applications under practical operating conditions.

Sub-50 nm perovskite-type tantalum-based oxynitride single crystals with enhanced photoactivity for water splitting.

A long-standing trade-off exists between improving crystallinity and minimizing particle size in the synthesis of perovskite-type transition-metal oxynitride photocatalysts via the thermal nitridation of commonly used metal oxide and carbonate precursors. Here, we overcome this limitation to fabricate ATaO2N (A = Sr, Ca, Ba) single nanocrystals with particle sizes of several tens of nanometers, excellent crystallinity and tunable long-wavelength response via thermal nitridation of mixtures of tantalum disulfide, metal hydroxides (A(OH)2), and molten-salt fluxes (e.g., SrCl2) as precursors. The SrTaO2N nanocrystals modified with a tailored Ir-Pt alloy@Cr2O3 cocatalyst evolved H2 around two orders of magnitude more efficiently than the previously reported SrTaO2N photocatalysts, with a record solar-to-hydrogen energy conversion efficiency of 0.15% for SrTaO2N in Z-scheme water splitting. Our findings enable the synthesis of perovskite-type transition-metal oxynitride nanocrystals by thermal nitridation and pave the way for manufacturing advanced long-wavelength-responsive particulate photocatalysts for efficient solar energy conversion.

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.

Transition-metal (oxy)nitride photocatalysts for water splitting.

Solar-driven water splitting based on particulate semiconductor materials is studied as a technology for green hydrogen production. Transition-metal (oxy)nitride photocatalysts are promising materials for overall water splitting (OWS) via a one- or two-step excitation process because their band structure is suitable for water splitting under visible light. Yet, these materials suffer from low solar-to-hydrogen energy conversion efficiency (STH), mainly because of their high defect density, low charge separation and migration efficiency, sluggish surface redox reactions, and/or side reactions. Their poor thermal stability in air and under the harsh nitridation conditions required to synthesize these materials makes further material improvements difficult. Here, we review key challenges in the two different OWS systems and highlight some strategies recently identified as promising for improving photocatalytic activity. Finally, we discuss opportunities and challenges facing the future development of transition-metal (oxy)nitride-based OWS systems.

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.

Co-doping of a La5Ti2Cu0.9Ag0.1O7S5 photocatalyst (λ < 700 nm) with Ga and Al to enhance photocatalytic H2 evolution.

La5Ti2Cu0.9Ag0.1O7S5 (LTCA) (λ < 700 nm) can function as a photocatalyst for H2 evolution. Co-doping LTCA with Ga3+ and Al3+ at Ti4+ sites effectively enhanced the H2 evolution activity of LTCA, yielding an apparent quantum efficiency of 18% at 420 nm. The activity of this material was greater than that previously reported for Ga-doped LTCA by a factor of 1.6. Such activity enhancement is attributed to increasing the population of long-lived photogenerated electrons and facilitating the electron transfer to the cocatalyst. This work significantly improved the LTCA-based photocatalyst for H2 evolution, making it a promising material for future application in non-sacrificial Z-scheme water splitting.

Narrow-Band-Gap Particulate Photocatalysts for One-Step-Excitation Overall Water Splitting.

ConspectusSunlight-driven one-step-excitation overall water splitting (OWS) using a single particulate photocatalyst is a simple and cost-effective approach to producing sustainable hydrogen on a large scale, providing an important impetus to achieving a carbon-neutral society. Technoeconomic studies have determined that a minimum solar-to-hydrogen (STH) energy conversion efficiency of 5% must be achieved to allow this process to be economically competitive. Meeting this goal will require the fabrication of particulate photocatalysts comprising composites of semiconductors and cocatalysts that are sufficiently active under sunlight. A one-step-excitation OWS system based on a metal oxide semiconductor having a wide bandgap was first reported in 1980, and the performance of such systems has been improved significantly over the past decade. In particular, work by the authors' group increased the apparent quantum yield (AQY) obtainable for ultraviolet (UV)-active SrTiO3 to more than 90% in 2020. However, the STH conversion efficiency of a photocatalyst that absorbs only UV light (that is, λ < 400 nm) is limited to 1.7% even at an AQY of unity. It is therefore highly important to develop one-step-excitation OWS processes utilizing narrow bandgap photocatalysts having absorption edge wavelengths equal to or longer than 500 nm. Such systems would be expected to meet the desired 5% STH energy conversion efficiency once a constant AQY of approximately 63% is obtained.This Account summarizes the development and application of narrow-band-gap (oxy)nitride and oxysulfide photocatalysts in the authors' laboratory that are able to split water in response to wavelengths as high as 500 to 650 nm via single-step photoexcitation. At first, the authors briefly recount the key steps required to progress from the initial utilization of a UV-active SrTiO3 photocatalyst as an OWS-active material to the realization of an AQY of almost unity. Multiple design and refinement strategies applied to both the semiconductor and cocatalysts associated with this benchmark photocatalyst are summarized, providing insights into the rational design of narrow-band-gap OWS-active photocatalysts. Furthermore, the necessity, target, and current status of developing narrow-band-gap OWS-active photocatalysts are discussed, followed by a comprehensive discussion of progress in the fabrication of OWS-active (oxy)nitride and oxysulfide photocatalysts with absorption edge wavelengths at up to the range of 500-650 nm in our laboratory. Specific examples are used to show the importance of several factors. First, adjusting the properties of the semiconducting material based on designing appropriate precursors, optimizing the synthetic conditions and aliovalent doping is described. Second, loading of efficient dual cocatalysts is examined. Lastly, the effectiveness of coating the particulate photocatalysts with surface nanolayers is addressed. Deficits related to the performance of present-day photocatalysts are also evaluated. Expectations with regard to future improvements of (oxy)nitride- and oxysulfide-based photocatalysts as a means of increasing the AQY are considered. The strategies summarized in this Account are expected to promote the development of nonsacrificial long-wavelength-responsive photosynthesis systems using water as a hydrogen/oxygen source.

A perspective on two pathways of photocatalytic water splitting and their practical application systems.

Photocatalytic water splitting has been widely studied as a means of converting solar energy into hydrogen as an ideal energy carrier in the future. Systems for photocatalytic water splitting can be divided into one-step excitation and two-step excitation processes. The former uses a single photocatalyst while the latter uses a pair of photocatalysts to separately generate hydrogen and oxygen. Significant progress has been made in each type of photocatalytic water splitting system in recent years, although improving the solar-to-hydrogen energy conversion efficiency and constructing practical technologies remain important tasks. This perspective summarizes recent advances in the field of photocatalytic overall water splitting, with a focus on the design of photocatalysts, co-catalysts and reaction systems. The associated challenges and potential approaches to practical solar hydrogen production via photocatalytic water splitting are also presented.

Overall Water Splitting by a SrTaO2N-Based Photocatalyst Decorated with an Ir-Promoted Ru-Based Cocatalyst.

The development of narrow-bandgap photocatalysts for one-step-excitation overall water splitting (OWS) remains a critical challenge in the field of solar hydrogen production. SrTaO2N is a photocatalytic material having a band structure suitable for OWS under visible light (λ ≤ 600 nm). However, the presence of defects in the oxynitride and the lack of cocatalysts to promote simultaneous hydrogen and oxygen evolution make it challenging to realize OWS using this material. The present work demonstrates a SrTaO2N-based particulate photocatalyst for OWS. This photocatalyst, which was composed of single crystals, was obtained by nitriding SrCl2 and Ta2O5 together with NaOH, with the latter added to control the formation of defects. The subsequent loading of bimetallic RuIrOx nanoparticles accelerated charge separation and allowed the SrTaO2N photocatalyst to exhibit superior OWS activity. This research presenting the strategies of controlling the oxygen sources and promoting the cocatalyst function is expected to expand the range of potential OWS-active oxynitride photocatalysts and permit the design of efficient cocatalysts for photocatalytic OWS.

Enhanced Overall Water Splitting by a Zirconium-Doped TaON-Based Photocatalyst.

Solar-powered one-step-excitation overall water splitting (OWS) using semiconducting materials is a simple means of achieving scalable and sustainable hydrogen production. While tantalum oxynitride (TaON) is one of the few photocatalysts capable of promoting OWS via single-step visible-light excitation, the efficiency of this process remains extremely poor. The present work employed 15 nm amorphous Ta2 O5 ⋅3.3 H2 O nanoparticles as a new precursor together with Zr doping and an optimized nitridation duration to synthesize a TaON-based photocatalyst with reduced particle sizes and low defect densities. Upon loading with Ru/Cr2 O3 /IrO2 cocatalysts, this material exhibited stoichiometric water splitting into hydrogen and oxygen, with an order of magnitude improvement in efficiency. Our findings demonstrate the importance of inventing/selecting the appropriate synthetic precursor and of defect control for fabricating active OWS photocatalysts.

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.

Pre-Analytical Modification of Serum miRNAs: Diagnostic Reliability of Serum miRNAs in Hemolytic Diseases.

Circulating microRNAs (miRNAs) are useful biomarkers of hemolysis. Since blood cells are the main origins of circulating miRNAs, we evaluated blood cell-related pre-analytical modification of the miRNA signatures during blood drawing and serum processing. The levels of miRNA before and after ex vivo blood drawing were analyzed with the reverse transcriptase-based polymerase chain reaction method. Furthermore, the changes of miRNA signatures caused by different time-lag between blood drawing and serum preparation by 24 h were evaluated. Finally, we compared the miRNA levels between leftover samples and samples of hemolytic diseases. Blood drawing procedure induced increments of red blood cell (RBC)-related miRNAs (miR-451a, miR-486) about 2-fold. One hour standing of blood samples before serum separation induced almost the same increases in RBC-related miRNAs. To test the clinical usefulness of miR-451a as a biomarker of hemolytic diseases, we analyzed miRNAs of samples from 10 normal subjects, 30 leftover samples in the clinical laboratory, and 20 samples from patients with hemolytic diseases. Serum miR-451a significantly increased in patients with hemolytic anemia more than the levels of pre-analytical modification. In conclusion, the pre-analytical modification of serum miRNAs did not disturb the usefulness of RBC-derived miRNAs as biomarkers of hemolytic diseases.

Use of metamodels for rapid discovery of narrow bandgap oxide photocatalysts.

New photocatalysts are traditionally identified through trial-and-error methods. Machine learning has shown considerable promise for improving the efficiency of photocatalyst discovery from a large potential pool. Here, we describe a multi-step, target-driven consensus method using a stacking meta-learning algorithm that robustly predicts bandgaps and H2 evolution activities of photocatalysts. Trained on small datasets, these models can rapidly screen a large space (>10 million materials) to identify promising, non-toxic compounds as candidate water splitting photocatalysts. Two effective compounds and two controls possessing optimal bandgap values (∼2 eV) but not photoactivity as predicted by the models were synthesized. Their experimentally measured bandgaps and H2 evolution activities were consistent with the predictions. Conspicuously, the two compounds with strong photoactivities under UV and visible light are promising visible-light-driven water splitting photocatalysts. This study demonstrates the power of machine learning and the potential of big data to accelerate discovery of next-generation photocatalysts.

Microelectrode-based transient amperometry of O2 adsorption and desorption on a SrTiO3 photocatalyst excited under water.

Oxygen evolution at water-solid interfaces is a key reaction for sustainable energy production. Although some intermediate states have been detected in transient absorption spectroscopy, the O2 evolution kinetics after the multi-step, four-electron oxidation of water remain unknown. In this study, transient amperometry with a microelectrode was applied to operando O2 detection over Al-doped SrTiO3 particles doubly loaded with RhCrOx and CoOy cocatalysts, an efficient photocatalyst for the overall water-splitting reaction. Electrochemical O2 detection at intervals of 0.1 s unexpectedly indicated instantaneous O2 adsorption and desorption in addition to steady, photocatalytic O2 evolution on the photocatalyst modified under intense light irradiation. We hypothesized that electrons excited in the conduction band were transferred to O2 in water thorough Ti cations neighboring an oxygen anion vacancy on the modified Al-doped SrTiO3. The negatively charged O2 was then bound to the Ti cations. It was neutralized and released when shaded through electron back-transfer to the conduction band. The hypothesized mechanism for O2 adsorption and desorption was compared with the photoinduced O2 desorption known to occur on anion vacancies of TiO2(110). The microelectrode-based transient amperometry demonstrated in this paper will be applied to many other phenomena at liquid-solid interfaces.

Photocatalytic solar hydrogen production from water on a 100-m2 scale.

The unprecedented impact of human activity on Earth's climate and the ongoing increase in global energy demand have made the development of carbon-neutral energy sources ever more important. Hydrogen is an attractive and versatile energy carrier (and important and widely used chemical) obtainable from water through photocatalysis using sunlight, and through electrolysis driven by solar or wind energy1,2. The most efficient solar hydrogen production schemes, which couple solar cells to electrolysis systems, reach solar-to-hydrogen (STH) energy conversion efficiencies of 30% at a laboratory scale3. Photocatalytic water splitting reaches notably lower conversion efficiencies of only around 1%, but the system design is much simpler and cheaper and more amenable to scale-up1,2-provided the moist, stoichiometric hydrogen and oxygen product mixture can be handled safely in a field environment and the hydrogen recovered. Extending our earlier demonstration of a 1-m2 panel reactor system based on a modified, aluminium-doped strontium titanate particulate photocatalyst4, we here report safe operation of a 100-m2 array of panel reactors over several months with autonomous recovery of hydrogen from the moist gas product mixture using a commercial polyimide membrane5. The system, optimized for safety and durability, and remaining undamaged on intentional ignition of recovered hydrogen, reaches a maximum STH of 0.76%. While the hydrogen production is inefficient and energy negative overall, our findings demonstrate that safe, large-scale photocatalytic water splitting, and gas collection and separation are possible. To make the technology economically viable and practically useful, essential next steps are reactor and process optimization to substantially reduce costs and improve STH efficiency, photocatalyst stability and gas separation efficiency.

Surface Modifications of (ZnSe)0.5(CuGa2.5Se4.25)0.5 to Promote Photocatalytic Z-Scheme Overall Water Splitting.

Charge separation is crucial for an efficient artificial photosynthetic process, especially for narrow-bandgap metal sulfides/selenides. The present study demonstrates the application of a p-n junction to particulate metal selenides to enhance photocatalytic Z-scheme overall water splitting (OWS). The constructed p-n junction of CdS-(ZnSe)0.5(CuGa2.5Se4.25)0.5 significantly boosted charge separation. A thin TiO2 coating layer also was introduced to inhibit photocorrosion of CdS and suppress the backward reaction of water formation from hydrogen and oxygen. By employing Pt-loaded TiO2/CdS-(ZnSe)0.5(CuGa2.5Se4.25)0.5 as a hydrogen evolution photocatalyst (HEP), we assembled a Z-scheme OWS system, together with BiVO4:Mo and Au as an oxygen evolution photocatalyst and electron mediator, respectively. An apparent quantum yield of 1.5% at 420 nm was achieved, which is by far the highest among reported particulate photocatalytic Z-scheme OWS systems with metal sulfides/selenides as HEPs. The present work demonstrates that a well-tailored p-n junction structure is effective for promoting charge separation in photocatalysis and opens new pathways for the development of efficient artificial photosynthesis systems involving narrow bandgap photocatalysts.

Simultaneously Tuning the Defects and Surface Properties of Ta3N5 Nanoparticles by Mg-Zr Codoping for Significantly Accelerated Photocatalytic H2 Evolution.

The simultaneous control of the defect species and surface properties of semiconducting materials is a crucial aspect of improving photocatalytic performance, yet it remains challenging. Here, we synthesized Mg-Zr-codoped single-crystalline Ta3N5 (Ta3N5:Mg+Zr) nanoparticles by a brief NH3 nitridation process, exhibiting photocatalytic water reduction activity 45 times greater than that of pristine Ta3N5 under visible light. A coherent picture of the relations between the defect species (comprising reduced Ta, nitrogen vacancies and oxygen impurities), surface properties (associated with dispersion of the Pt cocatalyst), charge carrier dynamics, and photocatalytic activities was drawn. The tuning of defects and simultaneous optimization of surface properties resulting from the codoping evidently resulted in the generation of high concentrations of long-lived electrons in this material as well as the efficient migration of these electrons to evenly distributed surface Pt sites. These effects greatly enhanced the photocatalytic activity. This work highlights the importance and feasibility of improving multiple properties of a catalytic material via a one-step strategy.