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.

Experimental and Theoretical Insights of Anion Regulation in MOF-Derived Ni-Co-Based Nanosheets for Supercapacitors and Anion Exchange Membrane Water Electrolyzers.

The anionic components have a significant role in regulating the electrochemical properties of mixed transition-metal (MTM)-based materials. However, the relationship between the anionic components and their inherent electrochemical properties in MTM-based materials is still unclear. Herein, we report the anion-dependent supercapacitive and oxygen evolution reaction (OER) properties of in situ grown binary Ni-Co-selenide (Se)/sulfide (S)/phosphide (P) nanosheet arrays (NAs) over nickel foam starting from MOF-derived Ni-Co layered double hydroxide precursors. Among them, the Ni-Co-Se NAs exhibited the best specific capacity (289.6 mA h g-1 at 4 mA cm-2). Furthermore, a hybrid device constructed with Ni-Co-Se NAs delivered an excellent energy density (74 W h kg-1 at 525 W kg-1) and an ultra-high power density (10 832 W kg-1 at 46 W h kg-1) with outstanding durability (∼94%) for 10 000 cycles. Meanwhile, the Ni-Co-Se NAs showed superior electrocatalytic OER outputs with the lowest overpotential (235 mV at 10 mA cm-2) and Tafel slope. In addition, Ni-Co-Se NAs outperformed IrO2 as an anode in an anion exchange membrane water electrolyzer at a high current density (>1.0 A cm-2) and exhibited a stable performance up to 48 h with a 99% Faraday efficiency. Theoretical analyses validate that the Se promotes OH adsorption and improves the electrochemical activity of the Ni-Co-Se through a strong electronic redistribution/hybridization with an active metal center due to its valence 4p and inner 3d orbital participations. This study will provide in-depth knowledge of bifunctional activities in MTM-based materials with different anionic substitutions.

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.

Enhanced CO2 Methanation Activity of Sm0.25Ce0.75O2-δ-Ni by Modulating the Chelating Agents-to-Metal Cation Ratio and Tuning Metal-Support Interactions.

Highly active and selective CO2 methanation catalysts are critical to CO2 upgrading, synthetic natural gas production, and CO2 emission reduction. Wet impregnation is widely used to synthesize oxide-supported metallic nanoparticles as the catalyst for CO2 methanation. However, as the reagents cannot be homogeneously mixed at an atomic level, it is challenging to modulate the microstructure, crystal structure, chemical composition, and electronic structure of catalysts via wet impregnation. Herein, a scalable and straightforward catalyst fabrication approach has been designed and validated to produce Sm0.25Ce0.75O2-δ-supported Ni (SDC-Ni) as the CO2 methanation catalyst. By varying the chelating agents-to-total metal cations ratio (C/I ratio) during the catalyst synthesis, we can readily and simultaneously modulate the microstructure, metallic surface area, crystal structure, chemical composition, and electronic structure of SDC-Ni, consequently fine-tuning the oxide-support interactions and CO2 methanation activity. The optimal C/I ratio (0.1) leads to an SDC-Ni catalyst that facilitates C-O bond cleavage and significantly improves CO2 conversion at 250 °C. A CO2-to-CH4 yield of >73% has been achieved at 250 °C. Furthermore, a stable operation of >1500 hours has been demonstrated, and no degradation is observed. Extensive characterizations were performed to fundamentally understand how to tune and enhance CO2 methanation activity of SDC-Ni by modulating the C/I ratio. The correlation of physical, chemical, and catalytic properties of SDC-Ni with the C/I ratio is established and thoroughly elaborated in this work. This study could be applied to tune the oxide-support interactions of various catalysts for enhancing the catalytic activity.

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.

Cobalt-Iron-Phosphate Hydrogen Evolution Reaction Electrocatalyst for Solar-Driven Alkaline Seawater Electrolyzer.

Seawater splitting represents an inexpensive and attractive route for producing hydrogen, which does not require a desalination process. Highly active and durable electrocatalysts are required to sustain seawater splitting. Herein we report the phosphidation-based synthesis of a cobalt-iron-phosphate ((Co,Fe)PO4) electrocatalyst for hydrogen evolution reaction (HER) toward alkaline seawater splitting. (Co,Fe)PO4 demonstrates high HER activity and durability in alkaline natural seawater (1 M KOH + seawater), delivering a current density of 10 mA/cm2 at an overpotential of 137 mV. Furthermore, the measured potential of the electrocatalyst ((Co,Fe)PO4) at a constant current density of -100 mA/cm2 remains very stable without noticeable degradation for 72 h during the continuous operation in alkaline natural seawater, demonstrating its suitability for seawater applications. Furthermore, an alkaline seawater electrolyzer employing the non-precious-metal catalysts demonstrates better performance (1.625 V at 10 mA/cm2) than one employing precious metal ones (1.653 V at 10 mA/cm2). The non-precious-metal-based alkaline seawater electrolyzer exhibits a high solar-to-hydrogen (STH) efficiency (12.8%) in a commercial silicon solar cell.

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.

Promoting electrocatalytic overall water splitting by sulfur incorporation into CoFe-(oxy)hydroxide.

The design and fabrication of highly cost-effective electrocatalysts with high activity, and stability to enhance the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has been considered to be one of the most promising approaches toward overall water splitting. In this study, sulfur-incorporated cobalt-iron (oxy)hydroxide (S-(Co,Fe)OOH) nanosheets were directly grown on commercial iron foam via galvanic corrosion and hydrothermal methods. The incorporation of sulfur into (Co,Fe)OOH results in superior catalytic performance and high stability in both the HER and OER conducted in 1 M KOH. The incorporation of sulfur enhanced the electrocatalytic activity by modifying the electronic structure and chemical states of (Co,Fe)OOH. An alkaline water electrolyzer for overall water splitting was fabricated using a two-electrode configuration utilizing the S-(Co,Fe)OOH bifunctional electrocatalyst in both the HER and OER. The fabricated electrolyzer outperformed a precious metal-based electrolyzer using Pt/C as the HER electrocatalyst and IrO2 as the OER electrocatalyst, which are the benchmark catalysts. This electrolyzer provides a lower potential of 1.641 V at 10 mA cm-2 and maintains 98.4% of its performance after 50 h of durability testing. In addition, the S-(Co,Fe)OOH-based electrolyzer successfully generated hydrogen under natural illumination upon its combination with a commercial silicon solar cell and exhibited a solar to hydrogen (STH) efficiency of up to 13.0%. This study shows that S-(Co,Fe)OOH is a promising candidate for application in the future renewable energy industry due to its high cost-effectiveness, activity, and stability during overall water splitting. In addition, the combination of a commercial silicon solar cell with an alkaline water electrolyzer has great potential for the production of hydrogen.

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.

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.