Solar-Powered AEM Electrolyzer via PGM-Free (Oxy)hydroxide Anode with Solar to Hydrogen Conversion Efficiency of 12.44.

Water electrolyzers powered by renewable energy are emerging as clean and sustainable technology for producing hydrogen without carbon emissions. Specifically, anion exchange membrane (AEM) electrolyzers utilizing non-platinum group metal (non-PGM) catalysts have garnered attention as a cost-effective method for hydrogen production, especially when integrated with solar cells. Nonetheless, the progress of such integrated systems is hindered by inadequate water electrolysis efficiency, primarily caused by poor oxygen evolution reaction (OER) electrodes. To address this issue, a NiFeCo─OOH has developed as an OER electrocatalyst and successfully demonstrated its efficacy in an AEM electrolyzer, which is powered by renewable electricity and integrated with a silicon solar cell.

Synergistic Effects in LaNiO3 Perovskites between Nickel and Iron Heterostructures for Improving Durability in Oxygen Evolution Reaction for AEMWE.

Perovskite materials that aren't stable during the oxygen evolution reaction (OER) are unsuitable for anion-exchange membrane water electrolyzers (AEMWE). But through manipulating their electronic structures, their performance can further increase. Among the first-row transition metals, nickel and iron are widely recognized as prominent electrocatalysts; thus, the researchers are looking into how combining them can improve the OER. Recent research has actively explored the design and study of heterostructures in this field, showcasing the dynamic exploration of innovative catalyst configurations. In this study, a heterostructure is used to manipulate the electronic structure of LaNiO3 (LNO) to improve both OER properties and durability. Through adsorbing iron onto the LNO (LNO@Fe) as γ iron oxyhydroxide (γ-FeOOH), the binding energy of nickel in the LNO exhibited negative shifts, inferring nickel movement toward the metallic state. Consequently, the electrochemical properties of LNO@Fe are further improved. LNO@Fe showed excellent performance (1.98 A cm-2, 1 m KOH, 50 °C at 1.85 V) with 84.1% cell efficiency in AEMWE single cells, demonstrating great improvement relative to LNO. The degradation for the 850 h durability analysis of LNO@Fe is ≈68 mV kh-1, which is ≈58 times less than that of LNO.

Longevous Cycling of Rechargeable Zn-Air Battery Enabled by "Raisin-Bread" Cobalt Oxynitride/Porous Carbon Hybrid Electrocatalysts.

Developing commercially viable electrocatalyst lies at the research hotspot of rechargeable Zn-air batteries, but it is still challenging to meet the requirements of energy efficiency and durability in realistic applications. Strategic material design is critical to addressing its drawbacks in terms of sluggish kinetics of oxygen reactions and limited battery lifespan. Herein, a "raisin-bread" architecture is designed for a hybrid catalyst constituting cobalt nitride as the core nanoparticle with thin oxidized coverings, which is further deposited within porous carbon aerogel. Based on synchrotron-based characterizations, this hybrid provides oxygen vacancies and Co-Nx -C sites as the active sites, resulting from a strong coupling between CoOx Ny nanoparticles and 3D conductive carbon scaffolds. Compared to the oxide reference, it performs enhanced stability in harsh electrocatalytic environments, highlighting the benefits of the oxynitride. Furthermore, the 3D conductive scaffolds improve charge/mass transportation and boost durability of these active sites. Density functional theory calculations reveal that the introduced N species into hybrid can synergistically tune the d-band center of cobalt and improve its bifunctional activity. As a result, the obtained air cathode exhibits bifunctional overpotential of 0.65 V and a battery lifetime exceeding 1350 h, which sets a new record for rechargeable Zn-air battery reported so far.

How to Change the Reaction Chemistry on Nonprecious Metal Oxide Nanostructure Materials for Electrocatalytic Oxidation of Biomass-Derived Glycerol to Renewable Chemicals.

Au and Pt are well-known catalysts for electrocatalytic oxidation of biomass-derived glycerol. Although some nonprecious-metal-based materials to replace the costly Au and Pt are used for this reaction, the fundamental question of how the nonprecious catalysts affect the reaction chemistry and mechanism compared to Au and Pt catalysts is still unanswered. In this work, both experimental and computational methods are used to understand how and why the reaction performance and chemistry for the electrocatalytic glycerol oxidation reaction (EGOR) change with electrochemically-synthesized CuCo-oxide, Cu-oxide, and Co-oxide catalysts compared to conventional Au and Pt catalysts. The Au and Pt catalysts generate major glyceric acid and glycolic acid products from the EGOR. Interestingly, the prepared Cu-based oxides produce glycolic acid and formic acid with high selectivity of about 90.0%. This different reaction chemistry is related to the enhanced ability of CC bond cleavage on the Cu-based oxide materials. The density functional theory calculations demonstrate that the formic acids are mainly formed on the Cu-based oxide surfaces rather than in the process of glycolic acid formation in the free energy diagram. This study provides critical scientific insights into developing future nonprecious-based materials for electrochemical biomass conversions.

3D-printed NiFe-layered double hydroxide pyramid electrodes for enhanced electrocatalytic oxygen evolution reaction.

Electrochemical water splitting has been considered one of the most promising methods of hydrogen production, which does not cause environmental pollution or greenhouse gas emissions. Oxygen evolution reaction (OER) is a significant step for highly efficient water splitting because OER involves the four electron transfer, overcoming the associated energy barrier that demands a potential greater than that required by hydrogen evolution reaction. Therefore, an OER electrocatalyst with large surface area and high conductivity is needed to increase the OER activity. In this work, we demonstrated an effective strategy to produce a highly active three-dimensional (3D)-printed NiFe-layered double hydroxide (LDH) pyramid electrode for OER using a three-step method, which involves direct-ink-writing of a graphene pyramid array and electrodeposition of a copper conducive layer and NiFe-LDH electrocatalyst layer on printed pyramids. The 3D pyramid structures with NiFe-LDH electrocatalyst layers increased the surface area and the active sites of the electrode and improved the OER activity. The overpotential (η) and exchange current density (i0) of the NiFe-LDH pyramid electrode were further improved compared to that of the NiFe-LDH deposited Cu (NiFe-LDH/Cu) foil electrode with the same base area. The 3D-printed NiFe-LDH electrode also exhibited excellent durability without potential decay for 60 h. Our 3D printing strategy provides an effective approach for the fabrication of highly active, stable, and low-cost OER electrocatalyst electrodes.

Fluorine-Decorated Graphene Nanoribbons for an Anticorrosive Polymer Electrolyte Membrane Fuel Cell.

Pt-supported carbon material-based electrocatalysts are formidably suffering from carbon corrosion when H2O and O2 molecules are present at high voltages in polymer electrolyte membrane fuel cells (PEMFCs). In this study, we discovered that the edge site of a fluorine-doped graphene nanoribbon (F-GNR) was slightly adsorbed with H2O and was thermodynamically unfavorable with O atoms after defining the thermodynamically stable structure of the F-GNR from DFT calculations. Based on computational predictions, the physicochemical and electrochemical properties of F-GNRs with/without Pt nanoparticles derived from a modified Hummer's method and the polyol process were investigated as support materials for electrocatalysts and additives in the cathode of a PEMFC, respectively. The Pt/F-GNR showed the lowest degradation rate in carbon corrosion and was effective in the cathode as additives, resulting from the enhanced carbon corrosion durability owing to the improved structural stability and water management. Notably, the F-GNR with highly stable carbon corrosion contributed to achieving a more durable PEMFC for long-term operation.

High-Efficiency Anion-Exchange Membrane Water Electrolyzer Enabled by Ternary Layered Double Hydroxide Anode.

Developing high-efficiency and low-cost oxygen-evolving electrodes in anion exchange membrane (AEM) water electrolysis technology is one of the major challenges. Herein, it is demonstrated that the surface corrosion of a conventional Ni foam electrode in the presence of Fe3+ and V3+ cations can transform it into an electrode with a high catalytic performance for oxygen evolution reaction (OER). The corroded electrode consists of a ternary NiFeV layered double hydroxide (LDH) nanosheet array supported on the Ni foam surface. This NiFeV LDH electrode achieves an OER current density of 100 mA cm-2 at an overpotential of 272 mV in 1 m KOH, outperforming the IrO2 catalyst by 180 mV. Density functional theory calculations reveal that the unique structure and the presence of vanadium in NiFeV LDH play a key role in achieving improved OER activity. When coupled with a commercial Pt/C cathode catalyst, the resulting AEM water electrolyzer achieves a cell current density as high as 2.1 A cm-2 at a voltage of only 1.8 Vcell in 1 m KOH, which is similar to the performance of the proton exchange membrane water electrolyzer obtained from the IrO2 and Pt/C catalysts pair.

Effects of Annealing Temperature on the Oxygen Evolution Reaction Activity of Copper-Cobalt Oxide Nanosheets.

Developing high performance, highly stable, and low-cost electrodes for the oxygen evolution reaction (OER) is challenging in water electrolysis technology. However, Ir- and Ru-based OER catalysts with high OER efficiency are difficult to commercialize as precious metal-based catalysts. Therefore, the study of OER catalysts, which are replaced by non-precious metals and have high activity and stability, are necessary. In this study, a copper-cobalt oxide nanosheet (CCO) electrode was synthesized by the electrodeposition of copper-cobalt hydroxide (CCOH) on Ni foam followed by annealing. The CCOH was annealed at various temperatures, and the structure changed to that of CCO at temperatures above 250 °C. In addition, it was observed that the nanosheets agglomerated when annealed at 300 °C. The CCO electrode annealed at 250 °C had a high surface area and efficient electron conduction pathways as a result of the direct growth on the Ni foam. Thus, the prepared CCO electrode exhibited enhanced OER activity (1.6 V at 261 mA/cm2) compared to those of CCOH (1.6 V at 144 mA/cm2), Co3O4 (1.6 V at 39 mA/cm2), and commercial IrO2 (1.6 V at 14 mA/cm2) electrodes. The optimized catalyst also showed high activity and stability under high pH conditions, demonstrating its potential as a low cost, highly efficient OER electrode material.

Effect of Copper Cobalt Oxide Composition on Oxygen Evolution Electrocatalysts for Anion Exchange Membrane Water Electrolysis.

Copper cobalt oxide nanoparticles (CCO NPs) were synthesized as an oxygen evolution electrocatalyst via a simple co-precipitation method, with the composition being controlled by altering the precursor ratio to 1:1, 1:2, and 1:3 (Cu:Co) to investigate the effects of composition changes. The effect of the ratio of Cu2+/Co3+ and the degree of oxidation during the co-precipitation and annealing steps on the crystal structure, morphology, and electrocatalytic properties of the produced CCO NPs were studied. The CCO1:2 electrode exhibited an outstanding performance and high stability owing to the suitable electrochemical kinetics, which was provided by the presence of sufficient Co3+ as active sites for oxygen evolution and the uniform sizes of the NPs in the half cell. Furthermore, single cell tests were performed to confirm the possibility of using the synthesized electrocatalyst in a practical water splitting system. The CCO1:2 electrocatalyst was used as an anode to develop an anion exchange membrane water electrolyzer (AEMWE) cell. The full cell showed stable hydrogen production for 100 h with an energetic efficiency of >71%. In addition, it was possible to mass produce the uniform, highly active electrocatalyst for such applications through the co-precipitation method.

Electrodeposition of High-Surface-Area IrO2 Films on Ti Felt as an Efficient Catalyst for the Oxygen Evolution Reaction.

Under acidic conditions, IrO2 exhibits high catalytic activity with respect to the oxygen evolution reaction (OER). However, the practical application of Ir-based catalysts is significantly limited owing to their high cost in addition to the scarcity of the metal. Therefore, it is necessary to improve the efficiency of the utilization of such catalysts. In this study, IrO2-coated Ti felt (IrO2/Ti) electrodes were prepared as high-efficiency catalysts for the OER under acidic conditions. By controlling the surface roughness of the Ti substrate via wet etching, the optimum Ti substrate surface area for application in the IrO2/Ti electrode was determined. Additionally, the IrO2 film that was electrodeposited on the 30 min etched Ti felt had a large surface area and a uniform morphology. Furthermore, there were no micro-cracks and the electrode obtained (IrO2/Ti-30) exhibited superior catalytic performance with respect to the OER, with a mass activity of 362.3 A g Ir - 1 at a potential of 2.0 V (vs. RHE) despite the low Ir loading (0.2 mg cm-2). Therefore, this proposed strategy for the development of IrO2/Ti electrodes with substrate surface control via wet etching has potential for application in the improvement of the efficiency of catalyst utilization with respect to the OER.

Improvement of the Bias Stress Stability in 2D MoS2 and WS2 Transistors with a TiO2 Interfacial Layer.

The fermi-level pinning phenomenon, which occurs at the metal-semiconductor interface, not only obstructs the achievement of high-performance field effect transistors (FETs) but also results in poor long-term stability. This paper reports on the improvement in gate-bias stress stability in two-dimensional (2D) transition metal dichalcogenide (TMD) FETs with a titanium dioxide (TiO2) interfacial layer inserted between the 2D TMDs (MoS2 or WS2) and metal electrodes. Compared to the control MoS2, the device without the TiO2 layer, the TiO2 interfacial layer deposited on 2D TMDs could lead to more effective carrier modulation by simply changing the contact metal, thereby improving the performance of the Schottky-barrier-modulated FET device. The TiO2 layer could also suppress the Fermi-level pinning phenomenon usually fixed to the metal-semiconductor interface, resulting in an improvement in transistor performance. Especially, the introduction of the TiO2 layer contributed to achieving stable device performance. Threshold voltage variation of MoS2 and WS2 FETs with the TiO2 interfacial layer was ~2 V and ~3.6 V, respectively. The theoretical result of the density function theory validated that mid-gap energy states created within the bandgap of 2D MoS2 can cause a doping effect. The simple approach of introducing a thin interfacial oxide layer offers a promising way toward the implementation of high-performance 2D TMD-based logic circuits.

Noble-Metal-Free Electrocatalysts for Oxygen Evolution.

Oxygen evolution reaction (OER) plays a vital role in many energy conversion and storage processes including electrochemical water splitting for the production of hydrogen and carbon dioxide reduction to value-added chemicals. IrO2 and RuO2 , known as the state-of-the-art OER electrocatalysts, are severely limited by the high cost and low earth abundance of these noble metals. Developing noble-metal-free OER electrocatalysts with high performance has been in great demand. In this review, recent advances in the design and synthesis of noble-metal-free OER electrocatalysts including Ni, Co, Fe, Mn-based hydroxides/oxyhydroxides, oxides, chalcogenides, nitrides, phosphides, and metal-free compounds in alkaline, neutral as well as acidic electrolytes are summarized. Perspectives are also provided on the fabrication, evaluation of OER electrocatalysts and correlations between the structures of the electrocatalysts and their OER activities.

Three-Dimensional Honeycomb-Like Cu0.81Co2.19O4 Nanosheet Arrays Supported by Ni Foam and Their High Efficiency as Oxygen Evolution Electrodes.

We prepare three-dimensional honeycomb-like Cu0.81Co2.19O4 nanosheet arrays supported by Ni foam via electrochemical codeposition of cobalt and copper hydroxides on Ni foam followed by thermal oxidation. The codeposition with Cu changes the morphology of the cobalt hydroxide deposit to form honeycomb-like nanostructures, significantly decreasing the onset potential for oxygen evolution. The Cu0.81Co2.19O4 anode displays an exceptionally low overpotential of 290 mV at a current density of 10 mA cm-2 in 1 M KOH, and an anion-exchange membrane water electrolysis cell employing the above anode achieves a current density of 100 mA cm-2 at 1.68 V in 0.1 M KOH.

Spontaneous and applied potential driven indium recovery on carbon electrode and crystallization using a bioelectrochemical system.

Indium removal and recovery on a carbon electrode under a microbial fuel cell (MFC)-based oxidation/reduction reaction were examined using synthetic wastewater. More than 90% of In3+ ions were removed after continuous operation of the MFC for 14 days with an average current generation of ∼50 µA. During operation, indium particulates formed on the cathode carbon electrode. Scanning electron microscopy equipped with X-ray energy dispersive spectroscopy showed that they were composed of amorphous and crystalline indium hydroxides (In(OH)3 and In(OH)·H2O). When the current flow was reversed to drive the oxidation of the particles to recover the indium from indium hydroxides, a few indium oxide (In2O3) nanocrystals with a rectangular platelet shape formed on the electrode, while the majority of the amorphous and crystalline indium hydroxides re-dissolved into the aqueous environment. Overall, these results demonstrate a feasible route towards the MFC-based recovery of indium with the simultaneous generation of bioelectricity.

Synthesis of hierarchical MoO2/MoS2 nanofibers for electrocatalytic hydrogen evolution.

Perpendicularly attached MoS2 nanosheets on MoO2 conductive nanofibers were synthesized by combining electrospinning, calcination, and sulfurization processes. Compared to randomly stacked MoS2 nanosheets on MoO2 nanofiber, they show greater hydrogen evolution reaction (HER) performance (i.e., onset potential of -180 mV versus normal hydrogen electrode with the Tafel slope of 59 mV dec-1). HER performance decreases with increasing MoS2 nanocrystal size.

Alloyed 2D Metal-Semiconductor Heterojunctions: Origin of Interface States Reduction and Schottky Barrier Lowering.

The long-term stability and superior device reliability through the use of delicately designed metal contacts with two-dimensional (2D) atomic-scale semiconductors are considered one of the critical issues related to practical 2D-based electronic components. Here, we investigate the origin of the improved contact properties of alloyed 2D metal-semiconductor heterojunctions. 2D WSe2-based transistors with mixed transition layers containing van der Waals (M-vdW, NbSe2/WxNb1-xSe2/WSe2) junctions realize atomically sharp interfaces, exhibiting long hot-carrier lifetimes of approximately 75,296 s (78 times longer than that of metal-semiconductor, Pd/WSe2 junctions). Such dramatic lifetime enhancement in M-vdW-junctioned devices is attributed to the synergistic effects arising from the significant reduction in the number of defects and the Schottky barrier lowering at the interface. Formation of a controllable mixed-composition alloyed layer on the 2D active channel would be a breakthrough approach to maximize the electrical reliability of 2D nanomaterial-based electronic applications.

Alloyed 2D Metal-Semiconductor Atomic Layer Junctions.

Heterostructures of compositionally and electronically variant two-dimensional (2D) atomic layers are viable building blocks for ultrathin optoelectronic devices. We show that the composition of interfacial transition region between semiconducting WSe2 atomic layer channels and metallic NbSe2 contact layers can be engineered through interfacial doping with Nb atoms. WxNb1-xSe2 interfacial regions considerably lower the potential barrier height of the junction, significantly improving the performance of the corresponding WSe2-based field-effect transistor devices. The creation of such alloyed 2D junctions between dissimilar atomic layer domains could be the most important factor in controlling the electronic properties of 2D junctions and the design and fabrication of 2D atomic layer devices.

Exploring the effects of the size of reduced graphene oxide nanosheets for Pt-catalyzed electrode reactions.

Pt-supported reduced graphene oxide (Pt/RGO) catalysts were prepared over the RGO sheets with different sizes for methanol oxidation and oxygen reduction reactions in acidic media. The Pt on the smaller RGO presented higher catalytic activities than the Pt on the larger RGO and the commercial Pt/C catalyst.

Toward new fuel cell support materials: a theoretical and experimental study of nitrogen-doped graphene.

Nano-scale Pt particles are often reported to be more electrochemically active and stable in a fuel cell if properly displaced on support materials; however, the factors that affect their activity and stability are not well understood. We applied first-principles calculations and experimental measurements to well-defined model systems of N-doped graphene supports (N-GNS) to reveal the fundamental mechanisms that control the catalytic properties and structural integrity of nano-scale Pt particles. DFT calculations predict thermodynamic and electrochemical interactions between N-GNS and Pt nanoparticles in the methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). Moreover, the dissolution potentials of the Pt nanoparticles supported on GNS and N-GNS catalysts are calculated under acidic conditions. Our results provide insight into the design of new support materials for enhanced catalytic efficiency and long-term stability.

Transfer printing of metal nanoring and nanodot arrays for use in catalytic reactions.

Nanoscale metal ring and dot catalyst arrays are printed over large substrate areas using vertically aligned carbon-based stamps with the ring- and dot-shaped tips. The fundamental nature of these ring and dot catalysts is successfully compared by applying them in diverse electrocatalytic reactions in acidic and alkaline media.