Unassisted Photoelectrochemical H2O2 Production with In Situ Glycerol Valorization Using α-Fe2O3.

Photoelectrochemical (PEC) H2O2 production via two-electron O2 reduction is promising for H2O2 production without emitting CO2. For PEC H2O2 production, α-Fe2O3 is an ideal semiconductor owing to its earth abundance, superior stability in water, and an appropriate band gap for efficient solar light utilization. Moreover, its conduction band is suitable for O2 reduction to produce H2O2. However, a significant overpotential for water oxidation is required due to the poor surface properties of α-Fe2O3. Thus, unassisted solar H2O2 production is not yet possible. Herein, we demonstrate unassisted PEC H2O2 production using α-Fe2O3 for the first time by applying glycerol oxidation, which requires less bias compared with water oxidation. We obtain maximum Faradaic efficiencies of 96.89 ± 0.6% and 100% for glycerol oxidation and H2O2 production, respectively, with high stability for 25 h. Our results indicate that unassisted and stable PEC H2O2 production is feasible with in situ glycerol valorization using the α-Fe2O3 photoanode.

Homogeneously Mixed Cu-Co Bimetallic Catalyst Derived from Hydroxy Double Salt for Industrial-Level High-Rate Nitrate-to-Ammonia Electrosynthesis.

Electrocatalytic nitrate reduction reaction (NO3RR) presents an innovative approach for sustainable NH3 production. However, selective NH3 production is hindered by the multiple intermediates involved in the NO3RR process and the competitive hydrogen evolution reaction. Hence, the development of highly efficient NO3RR catalysts is paramount. Herein, we report highly efficient bimetallic catalysts derived from hydroxy double salt (HDS). Under NO3RR conditions, Cu1Co1-HDS undergoes in situ reconstruction, forming nanocomposites of homogeneously distributed metallic Cu0 and Co(OH)2. Reconstruction-induced Cu0 rapidly converts NO3- to NO2-, which is further hydrogenated to NH3 by Co(OH)2. Homogeneously mixed Cu and Co species maximize this synergistic effect, achieving outstanding NO3RR performance including the highest NH3 yield rate (4.625 mmol h-1 cm-2) reported for powder-type NO3RR catalysts. Integration of Cu1Co1-HDS with a commercial Si solar cell attained 4.53% solar-to-ammonia efficiency from industrial wastewater-level concentrations of NO3- (2000 ppm), demonstrating practical application potential for solar-driven NH3 production. This study provides a strategy for enhancing the NH3 yield rate by optimizing the compositions and distributions of Cu and Co.

High-Performance Electrochemical and Photoelectrochemical Water Splitting at Neutral pH by Ir Nanocluster-Anchored CoFe-Layered Double Hydroxide Nanosheets.

Highly efficient electrocatalysts for the oxygen evolution reaction (OER) in neutral electrolytes are indispensable for practical electrochemical and photoelectrochemical water splitting technologies. However, there is a lack of good, neutral OER electrocatalysts because of the poor stability when H+ accumulates during the OER and slow OER kinetics at neutral pH. Herein, we report Ir species nanocluster-anchored, Co/Fe-layered double hydroxide (LDH) nanostructures in which the crystalline nature of LDH-restrained corrosion associated with H+ and the Ir species dramatically enhanced the OEC kinetics at neutral pH. The optimized OER electrocatalyst demonstrated a low overpotential of 323 mV (at 10 mA cm-2) and a record low Tafel slope of 42.8 mV dec-1. When it was integrated with an organic semiconductor-based photoanode, we obtained a photocurrent density of 15.2 mA cm-2 at 1.23 V versus reversible hydrogen in neutral electrolyte, which is the highest among all reported photoanodes to our knowledge.

Toward practical solar hydrogen production - an artificial photosynthetic leaf-to-farm challenge.

Solar water splitting is a promising approach to transform sunlight into renewable, sustainable and green hydrogen energy. There are three representative ways of transforming solar radiation into molecular hydrogen, which are the photocatalytic (PC), photoelectrochemical (PEC), and photovoltaic-electrolysis (PV-EC) routes. Having the future perspective of green hydrogen economy in mind, this review article discusses devices and systems for solar-to-hydrogen production including comparison of the above solar water splitting systems. The focus is placed on a critical assessment of the key components needed to scale up PEC water splitting systems such as materials efficiency, cost, elemental abundancy, stability, fuel separation, device operability, cell architecture, and techno-economic aspects of the systems. The review follows a stepwise approach and provides (i) a summary of the basic principles and photocatalytic materials employed for PEC water splitting, (ii) an extensive discussion of technologies, procedures, and system designs, and (iii) an introduction to international demonstration projects, and the development of benchmarked devices and large-scale prototype systems. The task of scaling up of laboratory overall water splitting devices to practical systems may be called "an artificial photosynthetic leaf-to-farm challenge".

Aqueous-solution route to zinc telluride films for application to CO2 reduction.

As a photocathode for CO2 reduction, zinc-blende zinc telluride (ZnTe) was directly formed on a Zn/ZnO nanowire substrate by a simple dissolution-recrystallization mechanism without any surfactant. With the most negative conduction-band edge among p-type semiconductors, this new photocatalyst showed efficient and stable CO formation in photoelectrochemical CO2 reduction at -0.2--0.7 V versus RHE without a sacrificial reagent.

Understanding the preparative chemistry of atomically dispersed nickel catalysts for achieving high-efficiency H2O2 electrosynthesis.

Electrochemical hydrogen peroxide (H2O2) production via two-electron oxygen reduction reaction (2e- ORR) has received increasing attention as it enables clean, sustainable, and on-site H2O2 production. Mimicking the active site structure of H2O2 production enzymes, such as nickel superoxide dismutase, is the most intuitive way to design efficient 2e- ORR electrocatalysts. However, Ni-based catalysts have thus far shown relatively low 2e- ORR activity. In this work, we present the design of high-performing, atomically dispersed Ni-based catalysts (Ni ADCs) for H2O2 production through understanding the formation chemistry of the Ni-based active sites. The use of a precoordinated precursor and pyrolysis within a confined nanospace were found to be essential for generating active Ni-N x sites in high density and increasing carbon yields, respectively. A series of model catalysts prepared from coordinating solvents having different vapor pressures gave rise to Ni ADCs with controlled ratios of Ni-N x sites and Ni nanoparticles, which revealed that the Ni-N x sites have greater 2e- ORR activity. Another set of Ni ADCs identified the important role of the degree of distortion from the square planar structure in H2O2 electrosynthesis activity. The optimized catalyst exhibited a record H2O2 electrosynthesis mass activity with excellent H2O2 selectivity.

Fabrication of CaFe2O4/TaON heterojunction photoanode for photoelectrochemical water oxidation.

Tantalum oxynitride photoanode is fabricated and modified with calcium ferrite to form a heterojunction anode for a photoelectrochemical water splitting cell. The synthesized powders are loaded sequentially to the transparent conducting glass by electrophoretic deposition, which is advantageous to form a uniform layer and a junction structure. X-ray diffraction, UV-vis diffuse reflectance spectroscopy, scanning electron microscopy, and impedance spectroscopy analysis are conducted to investigate the structural, morphological, and electrochemical characteristics of the anode. The introduction of CaFe2O4 overlayer onto TaON electrode increases the photocurrent density about five times at 1.23 V vs reversible hydrogen electrode without any co-catalyst. Impedance spectroscopy analysis indicates that the junction formation increased photocurrent density by reducing the resistance to the transport of charge carriers and thereby enhancing the electron-hole separation. This photocurrent generation is a result of the overall water splitting as confirmed by evolution of hydrogen and oxygen in a stoichiometric ratio. From the study of different junction configurations, it is established that the intimate contact between TaON and CaFe2O4 is critical for enhanced performance of the heterojunction anode for photoelectrochemical water oxidation under simulated sun light.

Self-assembled gold nanoparticle-mixed metal oxide nanocomposites for self-sensitized dye degradation under visible light irradiation.

Gold nanoparticle (Au NP)-mixed metal oxide (MMO) nanocomposite photocatalysts for efficient self-sensitized dye degradations under visible light were prepared by an electrostatically driven self-assembly. Dihydrolipoic acid (DHLA)-capped Au NPs (building block I) were synthesized through a room temperature reaction. Their hydrodynamic size was determined as being around 4.9 nm by dynamic light scattering measurements. MMO nanoplates with lateral dimensions of 100-250 nm (building block II) were prepared by a calcination of zinc aluminum layered double hydroxides at 750 °C for 2 h in air. In a pH 7.0 aqueous solution, the DHLA-capped Au NPs had a negative zeta potential (-22 ± 3 mV); on the other hand, the MMO nanoplates had a positive zeta potential (15 ± 2 mV). Electrostatic self-assembly was achieved by stirring an aqueous solution (pH 7.0) containing DHLA-capped Au NPs and MMO nanoplates at room temperature for 1 h. The self-assembled and sequentially calcined nanocomposites exhibited the superior self-sensitized dye degradation efficiency under visible light to that of ZnO, TiO(2) (P25), or pure MMO nanoplates. The enhanced degradation efficiency could be attributed to strong coupling interactions of ZnO and ZnAl(2)O(4) phases of the MMO and the role of Au as an electron sink and mediator for formations of reactive oxidation species and as a light concentrator.

Bias-free solar hydrogen production at 19.8 mA cm-2 using perovskite photocathode and lignocellulosic biomass.

Solar hydrogen production is one of the ultimate technologies needed to realize a carbon-neutral, sustainable society. However, an energy-intensive water oxidation half-reaction together with the poor performance of conventional inorganic photocatalysts have been big hurdles for practical solar hydrogen production. Here we present a photoelectrochemical cell with a record high photocurrent density of 19.8 mA cm-2 for hydrogen production by utilizing a high-performance organic-inorganic halide perovskite as a panchromatic absorber and lignocellulosic biomass as an alternative source of electrons working at lower potentials. In addition, value-added chemicals such as vanillin and acetovanillone are produced via the selective depolymerization of lignin in lignocellulosic biomass while cellulose remains close to intact for further utilization. This study paves the way to improve solar hydrogen productivity and simultaneously realize the effective use of lignocellulosic biomass.

Three-dimensional type II ZnO/ZnSe heterostructures and their visible light photocatalytic activities.

We report a method for synthesizing three distinct type II 3D ZnO/ZnSe heterostructures through simple solution-based surface modification reactions in which polycrystalline ZnSe nanoparticles formed on the surfaces of single-crystalline ZnO building blocks of 3D superstructures. The experimental results suggested a possible formation mechanism for these heterostructures. The formation of the ZnO/ZnSe heterostructures was assumed to result from a dissolution-recrystallization mechanism. The optical properties of the 3D ZnO/ZnSe heterostructures were probed by UV-vis diffuse reflectance spectroscopy. The 3D ZnO/ZnSe heterostructures exhibited absorption in the visible spectral region. The visible photocatalytic activities of 3D ZnO/ZnSe heterostructures were much higher than those of the 3D pure ZnO structures. The activities of the 3D ZnO/ZnSe heterostructures varied according to the structures under visible light. The morphologies and exposed crystal faces of pure ZnO building blocks prior to surface modification had a significant effect on the visible light photocatalytic processes of ZnO/ZnSe heterostructures after surface modification.

Formation of amorphous zinc citrate spheres and their conversion to crystalline ZnO nanostructures.

We report a method for synthesizing zinc citrate spheres at a low temperature (90 °C) under normal atmospheric pressure. The spherical structures were amorphous and had an average diameter of ∼1.7 µm. The amorphous zinc citrate spheres could be converted into crystalline ZnO nanostructures in aqueous solutions by heating at 90 °C for 1 h. By local dissolution of the zinc citrate spheres, nucleation and growth of ZnO occurred on the surfaces of the amorphous zinc citrate spheres. The morphologies and exposed crystal faces of the crystalline ZnO nanostructures (structure I: oblate spheroid; structure II: prolate spheroid; structure III: hexagonal disk; structure IV: sphere) could be controlled simply by varying the solution composition (solutions I, II, III, or IV) in which the as-prepared amorphous zinc citrate spheres were converted. The concentration of citrate anions and solution pH played a decisive role in determining the morphologies and exposed crystal faces of the crystalline ZnO nanostructures. On the basis of experimental results, we propose a plausible mechanism for the conversion of amorphous zinc citrate spheres into the variety of observed ZnO structures.

Unassisted selective solar hydrogen peroxide production by an oxidised buckypaper-integrated perovskite photocathode.

Hydrogen peroxide (H2O2) is an eco-friendly oxidant and a promising energy source possessing comparable energy density to that of compressed H2. The current H2O2 production strategies mostly depend on the anthraquinone oxidation process, which requires significant energy and numerous organic chemicals. Photocatalyst-based solar H2O2 production comprises single-step O2 reduction to H2O2, which is a simple and eco-friendly method. However, the solar-to-H2O2 conversion efficiency is limited by the low performance of the inorganic semiconductor-based photoelectrodes and low selectivity and stability of the H2O2 production electrocatalyst. Herein, we demonstrate unassisted solar H2O2 production using an oxidised buckypaper as the H2O2 electrocatalyst combined with a high-performance inorganic-organic hybrid (perovskite) photocathode, without the need for additional bias or sacrificial agents. This integrated photoelectrode system shows 100% selectivity toward H2O2 and a solar-to-chemical conversion efficiency of ~1.463%.

Alkali-Metal-Mediated Reversible Chemical Hydrogen Storage Using Seawater.

The economic viability and systemic sustainability of a green hydrogen economy are primarily dependent on its storage. However, none of the current hydrogen storage methods meet all the targets set by the US Department of Energy (DoE) for mobile hydrogen storage. One of the most promising routes is through the chemical reaction of alkali metals with water; however, this method has not received much attention owing to its irreversible nature. Herein, we present a reconditioned seawater battery-assisted hydrogen storage system that can provide a solution to the irreversible nature of alkali-metal-based hydrogen storage. We show that this system can also be applied to relatively lighter alkali metals such as lithium as well as sodium, which increases the possibility of fulfilling the DoE target. Furthermore, we found that small (1.75 cm2) and scaled-up (70 cm2) systems showed high Faradaic efficiencies of over 94%, even in the presence of oxygen, which enhances their viability.

Exposed crystal face controlled synthesis of 3D ZnO superstructures.

We report a method for synthesizing exposed crystal face controlled 3D ZnO superstructures under mild conditions (at room temperature or 90 degrees C under 1 atm) without organic additives. The exposed crystal faces of the building blocks of the 3D structures were controlled by varying the reactant concentrations and the reaction temperatures. On the basis of the experimental results, we speculated a possible mechanism for the formation of the four distinct 3D ZnO superstructures (structures I, II, III, and IV) under the different growth conditions. The optical properties of the 3D ZnO superstructures were probed by UV-vis diffuse reflectance spectroscopy. The spectra were shifted depending on the dimensions and sizes of the building blocks of the 3D superstructures. The photocatalytic activities of the 3D superstructures varied according to the exposed crystal faces, which could be controlled by this method (structure I > structure IV > structure III > structure II).

Superaerophobic hydrogels for enhanced electrochemical and photoelectrochemical hydrogen production.

The efficient removal of gas bubbles in (photo)electrochemical gas evolution reactions is an important but underexplored issue. Conventionally, researchers have attempted to impart bubble-repellent properties (so-called superaerophobicity) to electrodes by controlling their microstructures. However, conventional approaches have limitations, as they are material specific, difficult to scale up, possibly detrimental to the electrodes' catalytic activity and stability, and incompatible with photoelectrochemical applications. To address these issues, we report a simple strategy for the realization of superaerophobic (photo)electrodes via the deposition of hydrogels on a desired electrode surface. For a proof-of-concept demonstration, we deposited a transparent hydrogel assembled from M13 virus onto (photo)electrodes for a hydrogen evolution reaction. The hydrogel overlayer facilitated the elimination of hydrogen bubbles and substantially improved the (photo)electrodes' performances by maintaining high catalytic activity and minimizing the concentration overpotential. This study can contribute to the practical application of various types of (photo)electrochemical gas evolution reactions.

High-performance and stable photoelectrochemical water splitting cell with organic-photoactive-layer-based photoanode.

Considering their superior charge-transfer characteristics, easy tenability of energy levels, and low production cost, organic semiconductors are ideal for photoelectrochemical (PEC) hydrogen production. However, organic-semiconductor-based photoelectrodes have not been extensively explored for PEC water-splitting because of their low stability in water. Herein, we report high-performance and stable organic-semiconductors photoanodes consisting of p-type polymers and n-type non-fullerene materials, which is passivated using nickel foils, GaIn eutectic, and layered double hydroxides as model materials. We achieve a photocurrent density of 15.1 mA cm-2 at 1.23 V vs. reversible hydrogen electrode (RHE) with an onset potential of 0.55 V vs. RHE and a record high half-cell solar-to-hydrogen conversion efficiency of 4.33% under AM 1.5 G solar simulated light. After conducting the stability test at 1.3 V vs. RHE for 10 h, 90% of the initial photocurrent density are retained, whereas the photoactive layer without passivation lost its activity within a few minutes.

Unassisted solar lignin valorisation using a compartmented photo-electro-biochemical cell.

Lignin is a major component of lignocellulosic biomass. Although it is highly recalcitrant to break down, it is a very abundant natural source of valuable aromatic carbons. Thus, the effective valorisation of lignin is crucial for realising a sustainable biorefinery chain. Here, we report a compartmented photo-electro-biochemical system for unassisted, selective, and stable lignin valorisation, in which a TiO2 photocatalyst, an atomically dispersed Co-based electrocatalyst, and a biocatalyst (lignin peroxidase isozyme H8, horseradish peroxidase) are integrated, such that each system is separated using Nafion and cellulose membranes. This cell design enables lignin valorisation upon irradiation with sunlight without the need for any additional bias or sacrificial agent and allows the protection of the biocatalyst from enzyme-damaging elements, such as reactive radicals, gas bubbles, and light. The photo-electro-biochemical system is able to catalyse lignin depolymerisation with a 98.7% selectivity and polymerisation with a 73.3% yield using coniferyl alcohol, a lignin monomer.

Decellularized sciatic nerve matrix as a biodegradable conduit for peripheral nerve regeneration.

The use of autologous nerve grafts remains the gold standard for treating nerve defects, but current nerve repair techniques are limited by donor tissue availability and morbidity associated with tissue loss. Recently, the use of conduits in nerve injury repair, made possible by tissue engineering, has shown therapeutic potential. We manufactured a biodegradable, collagen-based nerve conduit containing decellularized sciatic nerve matrix and compared this with a silicone conduit for peripheral nerve regeneration using a rat model. The collagen-based conduit contains nerve growth factor, brain-derived neurotrophic factor, and laminin, as demonstrated by enzyme-linked immunosorbent assay. Scanning electron microscopy images showed that the collagen-based conduit had an outer wall to prevent scar tissue infiltration and a porous inner structure to allow axonal growth. Rats that were implanted with the collagen-based conduit to bridge a sciatic nerve defect experienced significantly improved motor and sensory nerve functions and greatly enhanced nerve regeneration compared with rats in the sham control group and the silicone conduit group. Our results suggest that the biodegradable collagen-based nerve conduit is more effective for peripheral nerve regeneration than the silicone conduit.

Strong O 2p-Fe 3d Hybridization Observed in Solution-Grown Hematite Films by Soft X-ray Spectroscopies.

Photoelectrochemical (PEC) water splitting holds the potential as a direct route for solar energy conversation and storage. The performance of a PEC device is strongly influenced by the electronic properties of the photonanode surface. It has been shown that the synthesis methods can have a profound impact on the electronic properties and PEC performance of various photoelectrode materials such as hematite. Soft X-ray spectroscopic techniques, including O K-edge XAS and Fe L-edge XAS/XES, have been employed to investigate how the synthesis methods impact the electronic structure of resulting hematite materials. It is found that the hematite samples via solution regrowth methods show dramatically increased 3d-4sp band ratios in O K-edge XAS spectra and decreased relative elastic peak intensities in Fe L-edge RIXS spectra compared with samples synthesized via ALD or solution grown. The difference observed in O-K and Fe-L spectra indicated that solution regrowth strategy alters the O 2p-Fe 3d hybridization and hence the electronic structure of the hematite films, which proves to be beneficial for PEC performance of the hematite photoanode. Our findings provided new insights and potentially useful strategies for enhancing the PEC performance of photoanode materials.

Tailorable Au Nanoparticles Embedded in Epitaxial TiO2 Thin Films for Tunable Optical Properties.

The unique property of plasmonic materials to localize light into deep sub-wavelength regime has greatly driven various applications in the field of photovoltaics, sensors, and photocatalysis. Here, we demonstrate the one-step growth of an oxide-metal hybrid thin film incorporating well-dispersed gold (Au) nanoparticles (NPs) with tailorable particle shape and diameters (ranging from 2 to 20 nm) embedded in highly epitaxial TiO2 matrix, deposited using pulsed laser deposition. Incorporation of Au NPs reduces the band gap of TiO2 and enhances light absorption in the visible regime owing to the excitation of localized surface plasmons. Optical properties, including the plasmonic response and permittivity, and photocatalytic activities of the Au-TiO2 hybrid materials are effectively tuned as a function of the Au NP sizes. Such optical property tuning is well captured using full-field simulations and the effective medium theory for better understanding of the physical phenomena. The tailorable shape and size of Au NPs embedded in TiO2 matrix present a novel oxide-metal hybrid material platform for optical property tuning and highly efficient plasmonic properties for future oxide-based photocatalytic sensors and devices.