Energy-Efficient and Self-Powered Green Ammonia Synthesis by Electrochemical Nitrate Reduction Combined with Hydrazine Oxidation.

To achieve the global goal of carbon neutrality, recently, emphasis has been placed on developing green ammonia production method to replace the Haber-Bosch process. Nitrate reduction reaction (NO3 RR) has received considerable attention, especially for electrochemically producing ammonia from nitrate and simultaneously purifying wastewater. This study first demonstrates that the combination of NO3 RR with hydrazine oxidation reaction (HzOR) is an energy efficient green ammonia production method, which overcomes the sluggish water oxidation limitation. Tungsten phosphide (WP) nanowires (NWs) are prepared as cathode NO3 RR electrocatalysts, which exhibit a high Faradaic efficiency in both neutral (≈93%) and alkaline (≈85%) media. Furthermore, they show a high bifunctional activity in anodic reactions and exhibit a low potential 0.024 V for generating a current density of 10 mA cm-2 in HzOR. The overall NO3 RR-HzOR required an impressively low potential of 0.24 V for generating a current density of 10 mA cm-2 ; this potential is much lower than those required for NO3 RR-OER (1.53 V) and NO3 RR-UOR (1.31 V). A self-powered ammonia production system, prepared by assembling an NO3 RR-HzOR with a perovskite solar cell, displays a high ammonia production rate of 1.44 mg cm-2  h-1 . A single PV cell provides enough driving voltage in the PV-EC due to low required potential. This system facilitates unassisted green ammonia synthesis with a low energy consumption and also allows upcycling of wastewater to produce useful fuel.

NiMoFe and NiMoFeP as Complementary Electrocatalysts for Efficient Overall Water Splitting and Their Application in PV-Electrolysis with STH 12.3.

Complementary water splitting electrocatalysts used simultaneously in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can simplify water splitting systems. Herein, earth-abundant NiMoFe (NMF) and phosphorized NiMoFeP (NMFP) are synthesized as complementary overall water splitting (OWS) catalysts. First, NMF is tested as both the HER and OER promoter, which exhibits low overpotentials of 68 (HER) and 337 mV (OER). A quaternary NMFP is then prepared by simple phosphorization of NMF, which shows a much lower OER overpotential of 286 mV. The enhanced OER activity is attributed to the unique surface/core structure of NMFP. The surface phosphate acts as a proton transport mediator and expedites the rate-determining step. With the application of OER potential, the NMFP surface is composed of Ni(OH)2 and FeOOH, active sites for OER, but the inner core consists of Ni, Mo, and Fe metals, serving as a conductive electron pathway. OWS with NMF-NMFP requires an applied voltage of 1.452 V to generate 10 mA cm-2 , which is one of the lowest values among OWS results with transition-metal-based electrocatalysts. Furthermore, the catalysts are combined with tandem perovskite solar cells for photovoltaic (PV)-electrolysis, producing a high solar-to-hydrogen (STH) conversion efficiency of 12.3%.

Au-Coated Honeycomb Structure as an Efficient TCO-Free Counter-Electrode for Quantum-Dot-Sensitized Solar Cells.

This study reports the fabrication of a Petri dish patterned with cylindrical micro-cavities that are produced using a one-step solvent-immersion phase-separation process. The developed 3D honeycomb Petri dish is coated with a Au film through a sputtering method to be an efficient Au-coated FTO-free electrode for quantum-dot-sensitized solar cells. Due to the high specific active surface area of the electrode with the Au-coated honeycomb structure, the energy conversion efficiency of devices that use this electrode is 5.2 % compared to 4.4 and 4.7 % by devices using an Au-coated flat Petri dish and an Au-coated FTO electrode, respectively. This design strategy offers excellent potential for the fabrication of highly efficient counter electrodes with FTO-free substrates of flexible photovoltaic devices.

Environmentally benign synthesis of CuInS2/ZnO heteronanorods: visible light activated photocatalysis of organic pollutant/bacteria and study of its mechanism.

Due to its high light absorption coefficient and appropriate bandgap, CuInS2 (CIS) has been receiving much attention as an absorber material for thin film solar cells and also as a visible light photocatalyst. Herein we present heterostructured CIS/ZnO nanorods (NRs) in an attempt to enhance light absorption and facilitate charge separation/transfer in the photocatalysis system. CIS nanoparticles (NPs) were directly deposited on ZnO nanorod arrays (NRAs) to fabricate heterostructured CIS/ZnO NRAs using an environmentally benign, non-hydrazine solution reaction. These heterostructured NRAs are immobilized on FTO glass, which has additional merits of recyclability and bias-applicability. The ideal type-II band structure of CIS/ZnO enables efficient charge separation/transfer, which is confirmed by PL (photoluminescence) decay measurements. Also, the 1D-ZnO NR structure facilitates fast charge transfer along with enhancing light absorption via light scattering. These synergistic effects improved the photocatalytic activity in both organic dye and bacteria decomposition. The photodecomposition efficiency was further enhanced with an aid of external bias. The underlying photocatalytic mechanism was also investigated through controlled experiments under various scavenging conditions. The results suggest that reactive oxygen species (ROS) formed by multistep reduction of O2 play a main role in photocatalysis, while hole-induced photodecomposition is relatively deactivated due to the band structure of the heterostructures of CIS/ZnO.

Solution-processed Cu2ZnSnS4 superstrate solar cell using vertically aligned ZnO nanorods.

One-dimensional (1D) zinc oxide (ZnO) nanostructures are considered to be promising materials for use in thin film solar cells because of their high light harvesting and charge collection efficiencies. We firstly report enhanced photovoltaic performances in Cu2ZnSnS4 (CZTS) thin film solar cells prepared using ZnO nanostructures. A CdS-coated, vertically well-aligned ZnO nanorod (NR) array was prepared via a hydrothermal reaction and nanocrystal layer deposition (NCLD) and was used as a transparent window/buffer layer in a CZTS thin film photovoltaic. A light absorber CZTS thin film was prepared on the CdS/ZnO NRs in air by depositing a non-toxic precursor solution that was annealed in two steps at temperatures up to 250 °C. The crystallized CZTS phase completely infiltrated the CdS/ZnO NR array. The nanostructured ZnO array provided improved light harvesting behavior compared to a thin film configuration by measuring UV-vis transmittance spectroscopy. The prepared CZTS/CdS/ZnO NR device exhibited a solar energy conversion efficiency of 1.2%, which is the highest efficiency yet reported for nanostructured superstrate CZTS solar cells.

Environmentally benign and efficient Ag2S-ZnO nanowires as photoanodes for solar cells: comparison with CdS-ZnO nanowires.

In this work, we develop a low-temperature, facile solution reaction route for the fabrication of quantum-dot-sensitized solar cells (QDSSCs) containing Ag(2)S-ZnO nanowires (NWs), simultaneously ensuring low manufacturing costs and environmental safety. For comparison, a CdS-ZnO NW photoanode was also prepared using the layer-by-layer growth method. Ultraviolet photoelectron spectroscopy analysis revealed type-II band alignments for the band structures of both photoanodes which facilitate electron transfer/collection. Compared to CdS-ZnO QDSSCs, Ag(2)S-ZnO QDSSCs exhibit a considerably higher short-circuit current density (J(sc)) and a strongly enhanced light-harvesting efficiency, but lower open-circuit voltages (V(oc)), resulting in almost the same power-conversion efficiency of 1.2 %. Through this work, we demonstrate Ag(2)S as an efficient quantum-dot-sensitizing material that has the potential to replace Cd-based sensitizers for eco-friendly applications.

A highly efficient light capturing 2D (nanosheet)-1D (nanorod) combined hierarchical ZnO nanostructure for efficient quantum dot sensitized solar cells.

A novel hierarchical ZnO nanostructure array composed of nanosheet branched (NB) ZnO nanorods (NRs) has been fabricated using a two-step solution reaction. The obtained nanosheet branched (NB) ZnO nanorods (NRs) exhibited considerably enhanced light capturing compared with ZnO thin films and ZnO nanorods. This combined 2D (nanosheet) and 1D (nanorod) hierarchical structure has significant potential as an efficient photoanode for quantum dot-sensitized solar cells (QDSSCs) because the nanosheets provide a large surface area for quantum dot loading and the nanorods present pathways for fast charge transfer. The CdSe/CdS co-sensitized QDSSCs using these nanosheet branched (NB) ZnO nanorods (NRs) as a photoanode exhibit a highly enhanced solar-energy conversion efficiency of 4.4% under conditions of 1 sun illumination.

Spatial Separation of Cocatalysts on Z-Scheme Organic/Inorganic Heterostructure Hollow Spheres for Enhanced Photocatalytic H2 Evolution and In-Depth Analysis of the Charge-Transfer Mechanism.

A Z-scheme heterojunction with spatially separated cocatalysts is proposed for overcoming fundamental issues in photocatalytic water splitting, such as inefficient light absorption, charge recombination, and sluggish reaction kinetics. For efficient light absorption and interfacial charge separation, Z-scheme organic/inorganic heterojunction photocatalysts are synthesized by firmly immobilizing ultrathin g-C3 N4 on the surface of TiO2 hollow spheres via electrostatic interactions. Additionally, two cocatalysts, Pt and IrOx , are spatially separated along the Z-scheme charge-transfer pathway to enhance surface charge separation and reaction kinetics. The as-prepared Pt/g-C3 N4 /TiO2 /IrOx (PCTI) hollow sphere photocatalyst exhibits an exceptional H2 evolution rate of 8.15 mmol h-1 g-1 and a remarkable apparent quantum yield of 24.3% at 330 nm in the presence of 0.5 wt% Pt and 1.2 wt% IrOx cocatalysts on g-C3 N4 and TiO2 , respectively. Photoassisted Kelvin probe force microscopy is used to systematically analyze the Z-scheme charge-transfer mechanism within PCTI. Furthermore, the benefits of spatially separating cocatalysts in the PCTI system are methodically investigated in comparison to randomly depositing them. This work adequately demonstrates that the combination of a Z-scheme heterojunction and spatially separated cocatalysts can be a promising strategy for designing high-performance photocatalytic platforms for solar fuel production.

Highly efficient visible light photocatalysis of novel CuS/ZnO heterostructure nanowire arrays.

Here, a facile approach for the fabrication of CuS nanoparticle (NP)/ZnO nanowire (NW) heterostructures on a mesh substrate through a simple two-step solution method is demonstrated. Successive ionic layer adsorption and reaction (SILAR) was employed to uniformly deposit CuS NPs on the hydrothermally grown ZnO NW array. The synthesized CuS/ZnO heterostructure NWs exhibited superior photocatalytic activity under visible light compared to bare ZnO NWs. This strong photocatalytic activity under visible light is due to the interfacial charge transfer (IFCT) from the valence band of the ZnO NW to the CuS NP, which reduces CuS to Cu(2)S. After repeated cycles of photodecolorization of Acid Orange 7 (AO7), the photocatalytic behavior of CuS/ZnO heterostructure NWs exhibited no significant loss of activity. Furthermore, our CuS/ZnO NWs/mesh photocatalyst floats in solution via partial superhydrophobic modification of the NWs.

Photo-stimulated resistive switching of ZnO nanorods.

Resistive switching memory devices are promising candidates for emerging memory technologies because they yield outstanding device performance. Storage mechanisms for achieving high-density memory applications have been developed; however, so far many of them exhibit typical resistive switching behavior from the limited controlling conditions. In this study, we introduce photons as an unconventional stimulus for activating resistive switching behaviors. First, we compare the resistive switching behavior in light and dark conditions to describe how resistive switching memories can benefit from photons. Second, we drive the switching of resistance not by the electrical stimulus but only by the modulation of photon. ZnO nanorods were employed as a model system to demonstrate photo-stimulated resistive switching in high-surface-area nanomaterials, in which photo-driven surface states strongly affect their photoconductivity and resistance states.

Fabrication and characterization of flower-like CuO-ZnO heterostructure nanowire arrays by photochemical deposition.

A simple two step solution-based method was applied to fabricate CuO-ZnO heterostructured nanowire (NW) arrays. First, ZnO nanowires were grown on a Si substrate using the ammonia solution hydrothermal reaction. Afterwards, flower-like CuO crystals were photochemically deposited on the tip of the ZnO NWs, using ultraviolet (UV) light (312 nm wavelength) irradiation at room temperature. The morphology of the CuO was controlled by reaction time, density of ZnO NWs, and concentration of the solution. Because the deposited CuO is p-type and has narrow band gap properties, CuO-ZnO heterostructured NWs exhibited a stable p-n junction property and good ability to absorb visible light. Through investigation of UV light-triggered reaction phenomena, we found that the production of OH(-) from the photocatalytic process on the surface of ZnO NWs plays a critical role in the CuO deposition mechanism.

Multifunctional transparent ZnO nanorod films.

Transparent ZnO nanorod (NR) films that exhibit extreme wetting states (either superhydrophilicity or superhydrophobicity through surface chemical modification), high transmittance, UV protection and antireflection have been prepared via the facile ammonia hydrothermal method. The periodic 1D ZnO NR arrays showed extreme wetting states as well as antireflection properties due to their unique surface structure and prevented the UVA region from penetrating the substrate due to the unique material property of ZnO. Because of the simple, time-efficient and low temperature preparation process, ZnO NR films with useful functionalities are promising for fabrication of highly light transmissive, antireflective, UV protective, antifogging and self-cleaning optical materials to be used for optical devices and photovoltaic energy devices.

Triple-Channel Charge Transfer over W18O49/Au/g-C3N4 Z-Scheme Photocatalysts for Achieving Broad-Spectrum Solar Hydrogen Production.

Z-scheme heterojunctions are fundamentally promising yet practically appealing for photocatalytic hydrogen (H2) production owing to the enhanced redox power, spatial separation of charge carriers, and broad-spectrum solar light harvesting. The charge-transfer dynamics at Z-scheme heterojunctions can be accelerated by inserting charge-transfer mediators at the heterojunction interfaces. In this study, we introduce Au nanoparticle mediators in the Z-scheme W18O49/g-C3N4 heterostructure, which enables an improved H2 production rate of 3465 µmol/g·h compared with the direct Z-scheme W18O49/g-C3N4 (1785 µmol/g·h) under 1 sun irradiation. The apparent quantum yields of H2 production with W18O49/Au/g-C3N4 are 3.9% and 9.3% at 420 and 1200 nm, respectively. The improved photocatalytic H2 production activity of W18O49/Au/g-C3N4 is attributable to the triple-channel charge-transfer mechanism: channel I─Z-scheme charge transfer facilitates charge separation and increased redox power of the photoexcited electrons; channels II and III─the localized surface plasmon resonances from Au (channel II) and W18O49 (channel III) enable light harvesting extension from visible to near-infrared wavelengths.

Yolk-shell nanostructures: synthesis, photocatalysis and interfacial charge dynamics.

Solar energy has long been regarded as a promising alternative and sustainable energy source. In this regard, photocatalysts emerge as a versatile paradigm that can practically transform solar energy into chemical energy. At present, unsatisfactory conversion efficiency is a major obstacle to the widespread deployment of photocatalysis technology. Many structural engineering strategies have been proposed to address the issue of insufficient activity for semiconductor photocatalysts. Among them, creation of yolk-shell nanostructures which possess many beneficial features, such as large surface area, efficient light harvesting, homogeneous catalytic environment and enhanced molecular diffusion kinetics, has attracted particular attention. This review summarizes the developments that have been made for the preparation and photocatalytic applications of yolk-shell nanostructures. Additional focus is placed on the realization of interfacial charge dynamics and the possibility of achieving spatial separation of charge carriers for this unique nanoarchitecture as charge transfer is the most critical factor determining the overall photocatalytic efficiency. A future perspective that can facilitate the advancement of using yolk-shell nanostructures in sophisticated photocatalytic systems is also presented.

Wettability control and water droplet dynamics on SiC-SiO2 core-shell nanowires.

We present a simple method for fabricating superhydrophobic SiC-SiO(2) core-shell nanowire surfaces via the facile dip-coating of alkyltrichlorosilanes. Water droplets displayed a variety of shapes with varying surface energies on the nanowire surfaces, which could be modified through chemisorption of alkyltrichlorosilanes with variable carbon chain length. The effects of UV irradiation on the superhydrophobic nanowire arrays were also investigated. UV light efficiently decomposed the chemisorbed molecules, and the superhydrophobic surface gradually converted into a hydrophilic surface with increasing UV exposure. The water droplet impact behavior on the modified surfaces was studied to test the stability of the superhydrophobicity under dynamic conditions.

Chemically modified superhydrophobic WO(x) nanowire arrays and UV photopatterning.

A facile route is reported for the fabrication of superhydrophobic tungsten oxide (WO(x)) nanowire surfaces through the chemical adsorption of alkyltrichlorosilane with a static water contact angle (CA) of 163.5 degrees. It is confirmed that CAs on the superhydrophobic surface decreased gradually under UV illumination because of the UV-assisted decomposition of alkyltrichlorosilane chemically adsorbed onto the surface. Superhydrophobic-superhydrophilic switching is also demonstrated by alternating self-assembled monolayer deposition and UV irradiation on the photopatterned nanowire surfaces. Furthermore, the superhydrophobic surface could be transformed selectively into a hydrophilic state by simply exposing the surface to UV through a shadow mask. These studies provide a relatively simple strategy for the design of superhydrophobic surfaces.

The fabrication of highly uniform ZnO/CdS core/shell structures using a spin-coating-based successive ion layer adsorption and reaction method.

We developed a successive ion layer adsorption and reaction method based on spin-coating (spin-SILAR) and applied the method to the fabrication of highly uniform ZnO/CdS core/shell nanowire arrays. Because the adsorption, reaction, and rinsing steps occur simultaneously during spin-coating, the spin-SILAR method does not require rinsing steps between the alternating ion adsorption steps, making the growth process simpler and faster than conventional SILAR methods based on dip-coating (dip-SILAR). The ZnO/CdS core/shell nanowire arrays prepared by spin-SILAR had a denser and more uniform structure than those prepared by dip-SILAR, resulting in the higher power efficiency for use in photoelectrochemical cells.

Three-Dimensional Nanoporous Metal Structures from Poly(2-vinylpyridine)-block-Poly(4-vinylpyridine) Copolymer Thin Film.

We fabricated 3D nanoporous metal structures from poly(2-vinylpyridine)-block-poly(4-vinylpyridine) copolymer (P24VP) thin film with vertically oriented lamellar nanodomains by coordinating corresponding metal precursors followed by reduction to metals. Although metal precursors are coordinated with both P2VP and P4VP blocks, the metal coordination power toward P4VP block is much greater than that toward P2VP block. Thus, most of the metal precursors are located in the P4VP block, while a few exist in the P2VP block. After the metal precursors were reduced to corresponding metals by reactive ion etching, metals located in P4VP regions became continuous main frames. However, metals in P2VP regions could not be continuous because of smaller amounts, resulting in nanoporous structures. Using these 3D nanoporous structures, we measured the electrocatalytic activity for hydrogen evolution reaction. 3D nanoporous platinum (Pt) showed enhanced catalytic activity compared with Pt flat film due to the large surface area. Moreover, 3D nanoporous Pt/cobalt bimetallic structures showed better catalytic activity than 3D nanoporous Pt structures.

Growth of hierarchical gold clusters for use in superomniphobic electrodes.

We developed a method to fabricate a superomniphobic gold electrode by synthesizing hierarchical gold clusters on a gold substrate and treating the surface with low surface energy materials. The reduction of gold ions was repeated several times, causing the gold microparticles to grow in random directions and form hierarchical gold clusters. Treatment of the gold structures with perfluorothiol resulted in a superhydrophobic surface that also exhibited superoleophobicity for oils and liquids with surface tensions as low as 25.6 mN. The resulting electrode was not contaminated by hydrophilic and hydrophobic liquids, and by analyzing the current-voltage characteristics of the electrode with a PEDOT:PSS solution droplet, the electrode was found to be waterproof.

Combinational Biomimicking of Lotus Leaf, Mussel, and Sandcastle Worm for Robust Superhydrophobic Surfaces with Biomedical Multifunctionality: Antithrombotic, Antibiofouling, and Tissue Closure Capabilities.

Surface wetting occurring in daily life causes undesired contaminations, which are critical issues in various fields. To solve these problems, the nonwetting property of a superhydrophobic (SH) surface has proven its utility by preventing contaminant infiltration, serious infections, or malfunction. However, the application of SH surfaces in the biomedical field has been limited due to the weak durability and toxicity of the related components. To overcome these limitations, we developed a robust and biocompatible SH surface through combinational biomimicking of three natural organisms, lotus leaf, mussel, and sandcastle worm, for the first time. Using the water-immiscible and polycationic characteristics of mussel adhesive protein (iMglue), an SH iMglue-SiO2(TiO2/SiO2)2 coating was fabricated by solution-based electrical charge-controlled layer-by-layer growth of nanoparticles (NPs). The fabricated iMglue-SiO2(TiO2/SiO2)2 SH surface showed excellent durable nonwetting properties and was applied to an intracatheter tube coating to develop antithrombotic catheters under blood flow. Furthermore, we developed a iMglue-employed SH patch for a tissue closure bandage by spraying hydrophobic SiO2 NPs on the iMglue-covered cotton pads. The prepared iMglue-employing SH patch showed perfect bifunctionality with excellent antibiofouling and tissue closure capabilities. Our work presents a novel, useful strategy for fabricating a biomedically multifunctional, robust SH surface through combinational mimicking of natural organisms.