mA Cm-2 Current Density Research Articles

Synergistic Catalytic Sites in High-Entropy Metal Hydroxide Organic Framework for Oxygen Evolution Reaction.

The integration of multiple elements in a high-entropy state is crucial in the design of high-performance, durable electrocatalysts. High-entropy metal hydroxide organic frameworks (HE-MHOFs) are synthesized under mild solvothermal conditions. This novel crystalline metal-organic framework (MOF) features a random, homogeneous distribution of cations within high-entropy hydroxide layers. HE-MHOF exhibits excellent electrocatalytic performance for the oxygen evolution reaction (OER), reaching a current density of 100mA cm-2 at ≈1.64 VRHE, and demonstrates remarkable durability, maintaining a current density of 10mA cm-2 for over 100 h. Notably, HE-MHOF outperforms precious metal-based electrocatalysts despite containing only ≈60% OER active metals. Ab initio calculations and operando X-ray absorption spectroscopy (XAS) demonstrate that the high-entropy catalyst contains active sites that facilitate a multifaceted OER mechanism. This study highlights the benefits of high-entropy MOFs in developing noble metal-free electrocatalysts, reducing reliance on precious metals, lowering metal loading (especially for Ni, Co, and Mn), and ultimately reducing costs for sustainable water electrolysis technologies.

Magnetic CuFe2O4 Spinel-Polypyrrole Pseudocapacitive Composites for Energy Storage.

This investigation focused on the fabrication of ceramic ferrimagnetic CuFe2O4-conductive polypyrrole (PPy) composites for energy storage. CuFe2O4 with a crystal size of 20-30 nm and saturation magnetization of 31.4 emu g-1 was prepared by hydrothermal synthesis, and PPy was prepared by chemical polymerization. High-active-mass composite electrodes were fabricated for energy storage in supercapacitors for operation in a sodium sulfate electrolyte. The addition of PPy to CuFe2O4 resulted in a decrease in charge transfer resistance and an increase in capacitance in the range from 1.20 F cm-2 (31 F g-1) to 4.52 F cm-2 (117.4 F g-1) at a 1 mV s-1 sweep rate and from 1.17 F cm-2 (29.9 F g-1) to 4.60 F cm-2 (120.1 F g-1) at a 3 mA cm-2 current density. The composites showed higher capacitance than other magnetic ceramic composites of the same mass containing PPy in the same potential range and exhibited improved cyclic stability. The magnetic behavior of the composites was influenced by the magnetic properties of ferrimagnetic CuFe2O4 and paramagnetic PPy. The composites showed a valuable combination of capacitive and magnetic properties and enriched materials science of magnetic supercapacitors for novel applications based on magnetoelectric and magnetocapacitive properties.

Coupling CoIr Nanoalloys with MXene by Lewis Acidic Molten Salt Etching for Wide-pH-Environment Hydrogen Evolution Reaction.

Metal/MXene-based materials show broad prospects in energy conversation through the strong metal-support interaction (SMSI). However, the difficulty and harshness of synthesis heavily limit their further application. Herein, using Lewis acidic molten salt to etch MAX as a precursor of MXene, a more convenient and safer strategy is designed to in situ construct the MXene-supported CoIr nanoalloy (CoIr/MXene) catalyst through Ti─O─M bond. The special layered structure and oxygen-containing functional group of MXene regulate the SMSI upon CoIr nanoalloys. Moreover, the contact angle and in situ Raman test results exhibit good interface hydrophilicity of MXene, enhancing the water adsorption on interfaces, and accelerating the mass transfer process. As a result, CoIr/MXene shows high hydrogen evolution reaction (HER) performance, which only needs overpotentials of 34 and 50mV to drive a current density of 10mA cm-2 in alkaline and acidic media, respectively, with excellent stability. Especially, in alkaline media, CoIr/MXene possesses 6 times higher HER mass activity (4.297 A mgIr -1) than commercial Pt/C catalysts (0.686 A mgPt -1) at the potential of 50mV, indicating larger active site density and intrinsic activity for CoIr/MXene. This work expands the application of the molten salt assist etching strategy and provides new insight for the development of metal/MXene-based catalysts.

Different FeS Concentrations for Encapsulating ZIF-67 Nanomaterials toward the Enhanced Oxidation Evolution Reaction.

Due to the slow kinetic nature of the oxygen evolution reaction (OER), the development of electrocatalysts with high efficiency, stability, and economy for oxygen production using metal-organic framework (MOF) materials is still a challenging research topic. In this work, we chose the different concentrations of FeS adsorption to encapsulate metal cobalt-based ZIF-67 MOF for preparing a series of electrocatalysts (ZIF1FeSx, x = 0.2, 0.5, 0.75, and 1), which were mainly explored for the electrocatalytic OER. Among them, ZIF1FeS0.5 has excellent electrocatalytic activity for OER, which can be driven by low overpotentials of 276 and 349 mV at 10 and 50 mA cm-2 current densities, and more than 92% of the initial overpotential can be maintained after 100 h of continuous OER at 10 mA cm-2 current density. This is mainly due to the electronic interactions between the cobalt-based MOF and the FeS, which shift the electronic state of the active metal center to a higher valence state for increasing the number of active sites and enhancing the efficiency of electron transfer to facilitate the OER course. This work may contribute to the design of effective catalysts for the OER during the electrolysis of alkaline solutions.

Zincophilic Nanospheres Assembled as Solid-Electrolyte Interphase on Zn Metal Anodes for Reversible High-rate Zn-Ion Storage.

Aqueous Zn-ion batteries (ZIBs) are considered to be one of the most promising energy storage devices in the post-lithium-ion era with fast ionic conductivity, safety, and low cost. However, excessive accumulation of zinc dendrites will fracture and produce dead zinc, resulting in the unsatisfied utilization rate of Zn anodes, which greatly restricts the lifespan of the battery and reduces the reversibility. In this paper, by constructing a protective layer of ZnSnO3 hollow nanospheres in situ growth on the surface of the Zn anode, more zincophilic sites are established on the electrode surface. It demonstrates that uniform deposition of Zn ions by deepening the binding energy with Zn ion and its unique hollow structure shortens the diffusion distance of Zn ions and enhances the reaction kinetics. The assembled Zn-ion hybrid supercapacitor (ZHSC) of ZnSnO3@Zn//AC achieved a long-term lifespan with 4000 cycles at a current density of 10mAcm-2 with a Coulombic efficiency of 99.31% and capacity retention of 79.6%. This work offers a new path for advanced Zn anodes interphase supporting the long cycle life with large capacities and improving electrochemical reversibility.

Pd@CuInP2S6 Core-Shell Nanospheres with Exceptional Hydrogen Evolution Capability and Stability in Both Alkaline and Acidic Media under Large Current Density Exceeding 1000mAcm-2.

By combining Pd with 2D layered crystal CuInP2S6 (CIPS) via laser irradiation in liquids, low-loading Pd@CIPS core-shell nanospheres are fabricated as an efficient and robust electrocatalysts for HER in both alkaline and acidic media under large current density (⩾1000mAcm-2). Pd@CIPS core-shell nanosphere has two structural features, i) the out-shell is the nanocomposite of PdHx and PdInHx, and ii) there is a kind of dendritic structure on the surface of nanospheres, while the dendritic structure porvides good gas desorption pathway and cause the Pd@CIPS system to maintain higher HER activity and stability than that of commercial Pt/C under large current densities. Pd@CIPS exhibits very low overpotentials of -218 and -313mV for the large current density of 1000mAcm-2, and has a small Tafel slope of 29 and 63mVdec-1 in 0.5mH2SO4 and 1mKOH condition, respectively. Meanwhile, Pd@CIPS has an excellent stability under -10 and -500mAcm-2 current densities and 50000 cycles cyclic voltammetry tests in 0.5mH2SO4 and 1mKOH, respectively, which being much superior to that of commercial Pt/C. Density functional theory (DFT) reveals that engineering electronic structure of PdHx and PdInHx nanostructure can strongly weaken the Pd─H bonding.

Modulating Interfacial Zn2+ Desolvation and Transport Kinetics through Coordination Interaction toward Stable Anodes in Aqueous Zn-Ion Batteries.

Aqueous Zn-ion batteries (AZIBs) are promising candidates for grid-scale energy-storage applications, but uneven Zn2+ flux distribution and undesirable water-related interfacial side reactions seriously hinder their practical application. Herein, a strategy of regulating the coordination interaction between Zn2+ and artificial interphase layers (AILs) to modulate the interfacial Zn2+ desolvation/transport behaviors and relieve side reactions for building stable Zn anodes is proposed. By selectively choosing appropriate polymers with different functional groups, it is shown that compared with the strong interaction offered by aryl groups in polystyrene-based AILs, cyano groups in polyacrylonitrile (PAN)-based AILs provide a moderate coordination interaction with Zn2+, which not only accelerates interfacial Zn2+desolvation kinetics but also enables efficient Zn2+ transport within AILs. Moreover, the Zn2+ transport kinetics of PAN-based AILs can be further enhanced with the incorporation of an ionic conductor, zinc phosphate (ZP). Because of these advantages, the Zn anodes decorated with the hybrid AILs composed of PAN and ZP can steadily operate for >2000h at 0.2mA cm-2 and >350h at a high current density of 10mA cm-2. This work provides a valuable guideline for selective design of AILs at the molecular level for durable AZIBs.

Plasma-Induced Oxygen Defect Engineering in Perovskite Oxide for Boosting Oxygen Evolution Reaction.

Perovskite oxides are considered highly promising candidates for oxygen evolution reaction (OER) catalysts due to their low cost and adaptable electronic structure. However, modulating the electronic structure of catalysts without altering their nanomorphology is crucial for understanding the structure-property relationship. In this study, a simple plasma bombardment strategy is developed to optimize the catalytic activity of perovskite oxides. Experimental characterization of plasma-treated LaCo0.9Fe0.1O3 (P-LCFO) reveals abundant oxygen vacancies, which expose numerous active sites. Additionally, X-ray photoelectron spectroscopy and X-ray absorption fine structure analyses indicate a low Co valence state in P-LCFO, likely due to the presence of these oxygen vacancies, which contributes to an optimized electronic structure that enhances OER performance. Consequently, P-LCFO exhibits significantly improved OER catalytic activity, with a low overpotential of 294mV at a current density of 10mAcm-2, outperforming commercial RuO2. This work underscores the benefits of plasma engineering for studying structure-property relationships and developing highly active perovskite oxide catalysts for water splitting.

Rare-Earth (R) In-Plane Ordering in Novel (Mo, R, Nb)4AlC3 Quinary o-MAX Nanolaminates and their 2D Derivatives.

Nanolamellar transition metal carbides are gaining increasing attentions because of the promising application in energy storage of their 2D derivatives. There are in-plane and out-of-plane atomic ordered occupations, which is thought to only be formed in separated systems due to totally different origins and crystallographic structure. In present work, starting from (Mo, Nb)4AlC3 o-MAX phase where out-of-plane ordered occupation is experimentally and theoretically proved for Mo/Nb atoms, rare-earth elements (R = Y, Gd-Tm, Lu) are introduced, and the novel Mo3.33- xR0.67NbxAlC3 (x = 1, 1.25, 1.5, 1.75, 2, 2.25, and 2.5) super-ordered (s-) MAX phase is synthesized, where R is ordered at the outer layer in the strict stoichiometry meanwhile Mo/Nb maintains the out-of-plane ordered occupation. By R introduction, s-MAX is easier to be delaminated to obtain the s-MXene with the topochemical ordered vacancies, leading into the enhanced supercapacitance of 114.9 F g-1 in Mo1.33Nb2C3 s-MXene compared with 95.1 F g-1 in Mo2Nb2C3 o-MXene. By Pt anchoring, very low overpotential of 22mV at a current density of 10mA cm-2 is achieved for HER applications. This study demonstrates a novel variety of s-MAX phase and seeks to inspire further exploration of the ordered MAX and MXene families.

Nanoarchitectonics of few-layer Ni3Fe nanosheets embedded porous nitrogen-doped carbon derived from asphalt waste: An efficient electrocatalyst for oxygen evolution reaction

The design and fabrication of stable, high-performance, and affordable oxygen evolution reaction (OER) electrocatalysts is essential for performing practical water electrolysis and generating green hydrogen energy. Here, we report that 2D few layer Ni3Fe nanosheets embedded with 2D porous nitrogen doped carbon (N-NixFe@CF) from asphalt waste and then convolved and assembled into 1D hollow nanotube structures by Lewis acid molten salt etching method, which were used as electrocatalysts for OER. Benefiting from the integrate of 1D hollow nanotube structure and 2D porous nanosheets, the close contact between catalysts and support, and the increased conductivity, the resultant N-Ni3Fe@CF catalysts exhibited high catalytic activities in the OER with low overpotential at a current density of 10 mA cm−2 (114 mV), low Tafel slope (166.6 mV dec−1), and excellent electrochemical stability. This work provides a new concept for expanding the use of asphalt wastes and by-products, as well as a straightforward synthesis method for producing economical, efficient, and long-lasting alkaline OER electrocatalysts.

Ultrafast Hole Trapping in Te-MoTe2-MoSe2/ZnO S-Scheme Heterojunctions for Photochemical and Photo-/Electrochemical Hydrogen Production.

Te-MoTe2-MoSe2/ZnO S-scheme heterojunctions are engineered to ascertain the advanced redox ability in sustainable HER operations. Photo-physical studies have established the steady state transfer of photo-induced charge carriers whereas an improved transfer dynamics realized by state-of-art ultrafast transient absorption and irradiated-XPS analysis of optimized 5wt% Te-MoTe2-MoSe2/ZnO heterostructure. 2.5, 5, and 7.5wt% Te-MoTe2-MoSe2/ZnO photocatalysts (2.5MTMZ, 5MTMZ and 7.5MTMZ) exhibited 2.8, 3.3, and 3.1-fold higher HER performance than pristine ZnO with marvelous apparent quantum efficiency of 35.09%, 41.42% and 38.79% at HER rate of 4.45, 5.25, and 4.92 mmol/gcat/h, respectively. Electrochemical water splitting experiments manifest subdued 583 and 566 mV overpotential values of 2.5MTMZ and 5MTMZ heterostructures to achieve 10 mAcm-2 current density for HER, and 961 and 793 mV for OER, respectively. For optimized 5MTMZ photocatalyst, lifetime kinetic decay of interfacial charge transfer step is evaluated to be 138.67 ps as compared to 52.92 ps for bare ZnO.

Multicomponent Interface and Electronic Structure Engineering in Ir-Doped CoMO4-Co(OH)2 (M = W and Mo) Enable Promoted Oxygen Evolution Reaction.

The core principles of multicomponent interface and electronic structure engineering are essential in designing high-performance catalysts for the oxygen evolution reaction (OER). However, combining these aspects within a catalyst is a significant challenge. In this investigation, a novel approach involving the development of hybrid Ir-doped CoMO4-Co(OH)2 (M = W and Mo) hollow nanoboxes was introduced, enabling remarkably efficient water oxidation electrocatalysis. Constructed from ultrathin nanosheet-assembled hollow nanoboxes, these structures boast a wealth of active centers for intermediate species, which in turn enhance both charge transfer and mass transport capabilities. Moreover, the compelling electronic and synergistic effects arising from the interaction between CoMO4 and Co(OH)2 significantly bolster OER electrocatalysis by facilitating efficient electron transfer. The introduction of Ir atoms serves to strategically adjust the electronic structure, fine-tune its electronic state, and operate as active centers to enhance OER electrocatalysis, thus diminishing the overpotential. This configuration results in Ir-CoWO4-Co(OH)2 and Ir-CoMoO4-Co(OH)2 exhibiting impressively low overpotentials of 252 and 261 mV, respectively, to 10 mA cm-2. Utilized in conjunction with the Pt/C catalyst in a two-electrode system for overall water splitting, a mere 1.53 V cell potential is needed to achieve the desired 10 mA cm-2 current density.

Unlocking Fe(III) Ions Improving Oxygen Evolution Reaction Activity and Dynamic Stability of Anodized Nickel Foam.

Fe has been reported to play a crucial role in improving the catalytic activity and stability of Ni/Co-based electrocatalysts for the oxygen evolution reaction (OER), while the Fe effect remains intangible. Here, we design several experiments to identify the activity and stability improvement using porous anodized nickel foam (ANF) as the electrode and 1.0 M KOH containing 1000 μM Fe(III) ions as the electrolyte. Systematic investigations reveal that Ni sites serve as hosts to capture Fe ions to create active FeNi-based intermediates on the surface of ANF to improve the OER activity significantly, and Fe ions regulate catalytic equilibrium and maintain the stability for a long time. The system exhibits 242 and 343 mV overpotentials to reach 10 and 1000 mA cm-2 current densities and a robust stability of 360 h at an industrially suitable current density (1000 mA cm-2). This work expands insights into the Fe(III) catalysis effect on the OER efficiency of Ni-based catalysts and provides an economical and practical way to commercial application.

Bimetallic NiCo Metal-Organic Frameworks with High Stability and Performance Toward Electrocatalytic Oxidation of Urea in Seawater.

The urea oxidation reaction (UOR) is an alternative anodic reaction for hydrogen generation via water splitting. The significance of UOR lies in both H2 production and the decontamination of urea-containing wastewater. Commercial electrocatalysts in this field are generally based on noble metals and show several limitations. Bimetal-organic frameworks (BMOFs) can be excellent candidates for the replacement of noble-metal-based catalysts beacuse of their promising features, such as a tunable structure, high surface area, and abundant sites for electrocatalysis. In this study, a series of nickel-cobalt BMOFs (Nix-Coy-BMOFs: x and y refer to a molar fraction of Ni and Co) were synthesized and applied as electrocatalysts in UOR. In particular, a Ni0.15Co0.85-MOF material with a structure similar to that of its parent Co-MOF, revealed exceptional electrocatalytic performance, as evidenced by low values of overpotential (1.33 V vs RHE at 10 mA cm-2), TOF (0.47 s-1), and Tafel slope (125 mV dec-1). At a 40 mA cm-2 current density, Ni0.15Co0.85-MOF also showed excellent stability during the 72 h tests. This performance of NiCo-BMOF can be assigned to the synergistic effect between Co and Ni, abundant active sites, porosity, and a tunable structure, all of which result in an increased reaction rate due to the acceleration of charge and mass transfers. Thus, the present work introduces an efficient noble-metal-free UOR for energy generation from urea-based wastewater.

Ameliorating Ion-Transport Resistances in Membrane Capacitive Deionization Using Patterned Ion-Exchange Membranes and Ionomer Infiltrated Electrodes

Currently, 2 billion people live in water scarce regions and 4 billion people experience water scarcity for at least 1 month per year [1]. Besides implications to the broad masses, the U.S. Marine Corps also face enormous challenges of generating potable water during squad level field missions. Reverse osmosis is the most reliable and economical process for desalinating water, but it requires piping that can tolerate large pressures and is not conducive for portable missions. Membrane capacitive deionization (MCDI) is a modular and electrified water desalination platform that does not generate significant acoustic, thermal, or electromagnetic signatures nor does it require high pressure piping. Flow-by MCDI, which is commercialized, uses electrical energy to remove ions from water. The system architecture feature two porous electrodes covered by ion-exchange membranes – the latter material is used to prevent co-ion adsorption and greater Coulombic efficiency than the variant that does not utilize ion-exchange membranes.Our previous research improved the energy efficiency of MCDI by using IEMs with lower area-specific resistance (ASR) values and porous ionic conductors in the spacer channel that augmented solution conductivity and curtailed ohmic losses. Reducing these resistances enabled the MCDI to operate at 700 mV lower cell voltage at 2 mA cm-2 current density. This is important for shrinking the size of the MCDI unit and lowering the overall capital costs.This talk presents our recent work examining ionic charge transport resistance at patterned and non-patterned ion-exchange membrane interfaces in MCDI. Membrane surface patterning increased the interfacial area between the membrane and aqueous stream promoting greater salt removal fluxes. Soft-lithography methods were used to micropattern poly(phenylene alkylene) cation exchange membranes and anion exchange membranes with systematically varied topographies (e.g., cylindrical well and line structures that vary from 9 to 20 mm). We can reduce the MCDI cell voltage by 1 V when utilizing micropatterned ion-exchange membranes and ionomer infiltrated electrodes (operating at 2 mA cm-2 with a 2000 ppm NaCl feed). This translated to a 2.4x greater energy normalized adsorbed salt (ENAS) value - a metric used to assess the energy consumption for MCDI. Our future work examines electrode materials deposited at pattern membrane interfaces to reduce interfacial transport resistances from the membrane to the electrode. This strategy has been shown to be effective in reducing charge-transfer resistances in both proton exchange membrane (PEM) and AEM fuel cells and reducing the water dissociation kinetics resistance in bipolar membranes [2-5]. References Somini Sengupta, Weiyi Cai, A Quarter of Humanity Faces Looming Water Crises, in The New York Times. 2019: United States of America.Kole, S., et al., Bipolar membrane polarization behavior with systematically varied interfacial areas in the junction region. Journal of Materials Chemistry A, 2021. 9(4): p. 2223-2238.Breitwieser, M., et al., Tailoring the Membrane-Electrode Interface in PEM Fuel Cells: A Review and Perspective on Novel Engineering Approaches. Advanced Energy Materials, 2018. 8(4).Hee-Tak Kim, T.V.R., Ho-Jin Kweon, Microstructured Membrane Electrode Assembly for direct methanol fuel cell. Journal of The Electrochemical Society, 2007. 154(10).Tomizawa, M., et al., Heterogeneous pore-scale model analysis of micro-patterned PEMFC cathodes. Journal of Power Sources, 2023. 556. Figure 1

Sulfur-Phosphorus Doped Metal Composites As Superior Catalyst for Electrolytic Hydrogen Production in Real Seawater

In the face of the increasingly severe global energy crisis and challenges posed by climate change, promoting energy transition has become an international consensus. Among various renewable energy sources, hydrogen is considered an ideal energy carrier due to its clean and efficient characteristics. The electrolysis of seawater for hydrogen production has garnered widespread attention for its ability to fully utilize abundant seawater resources and the advantage of zero carbon dioxide emissions. However, achieving efficient, stable, and economically viable hydrogen production in seawater still faces many challenges, with catalyst design and optimization being recognized as key issues.Firstly, NiFe-LDH was synthesized using a simple one-pot solvothermal method. Subsequently, phosphorization, sulfurization, and sulfur-phosphorus co-doping were conducted to obtain samples namely NiFe-P, NiFe-S and NiFe-SP, respectively. Various electrochemical tests, including hydrogen evolution reaction (HER), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were firstly performed in simulated seawater to evaluate the electrochemical performance of the synthesized catalysts. The overall seawater splitting reaction was conducted with the same catalysts for both anode and cathode sides.After comparing the electrochemical activity of four different catalysts, it was found that NiFe-SP performs superior HER activity in alkaline simulated seawater. NiFe-SP required merely -0.143 V to deliver 100 mA cm-2 current density, which was 95 mV lower than NiFe-LDH to achieve the same current density. In EIS tests, NiFe-SP exhibited a smaller charge transfer resistance than NiFe-LDH, and NiFe-SP had the largest double-layer capacitance (Cdl) value in ECSA measurements, indicating that NiFe-SP possessed and lowest reaction resistance and the maximum electrochemically active surface area.X-ray Diffraction (XRD) and Raman spectroscopy analyses indicate that the catalyst, after sulfur-phosphorus doping, does not exhibit a pure-phase LDH structure but transforms into a heterogeneous structure of Ni3S2 and FeS2. Scanning Electron Microscopy (SEM) observations suggest that sulfur-phosphorus co-doping causes the original spherical structure of NiFe-LDH to aggregate, with the appearance of some lamellar structures on the surface. Energy Dispersive Spectroscopy (EDS) also confirms the successful doping of sulfur and phosphorus elements into NiFe-LDH, with uniform distribution on the material's surface.Finally, the catalyst underwent a 2000-hours continuous stability test at a constant current of 100 mA cm-² in real seawater. The results indicate that the potential of NiFe-SP increased by only 5%, demonstrating that the doping of sulfur and phosphorus not only reduces the catalytic overpotential but also significantly sustains potential retention. This suggests that the metal composite structure obtained after sulfur-phosphorus co-doping is well-formed and stable. The systematic electrochemical tests and stability evaluation in this study highlights the potential of sulfur-phosphorus co-doped metal composite NiFe-SP as an efficient and stable catalyst for real seawater electrolysis. This not only contributes to a deeper understanding of the fundamental principles governing catalyst behavior but also opens new possibilities for the practical application of hydrogen production technology. Figure 1

Unique Multi-Hetero-Interface Engineering of Fe-Doped Co-LDH@MoS2-Ni3S2 Nanoflower-Based Electrocatalyst for Overall Water-Splitting: An Experimental and Theoretical Investigation.

Herein, a self-supported, robust, and noble-metal-free 3D hierarchical interface-rich Fe-doped Co-LDH@MoS2-Ni3S2/NF heterostructure electrocatalyst has been prepared through a controllable two-step hydrothermal process. The resultant electrode shows low overpotential of ~95 mV for hydrogen evolution reaction (HER), ~220 mV for the oxygen evolution reaction (OER),and the two-electrode system requires only a cell voltage of ~1.54 V at 10 mA cm-2 current density, respectively. Extensive ab initio calculations were carried out to find out the overpotential for HER, orbital interaction through the determination of electron density of states and quantification of charge transfer by Bader charge analysis. The computed overpotential matched closely with the experimental data. The superior HER performance of the tri-layer is enhanced due to the charge transfer (1.7444 e) to Fe-doped Co-LDH from Ni3S2-MoS2 hybrid. This research strategy paves an effective pathway for affordable green H2 production and future efficient non-precious bifunctional electrocatalyst design for overall water electrolysis.

Hydrothermally Synthesized rGO/MnO2/MoS2 Nanohybrids as Superior Bifunctional Electrocatalysts for Oxygen and Hydrogen Evolution Reactions.

This investigation delved into the field of bifunctional electrocatalyst water splitting, aimed at advancing sustainable energy by addressing the scarcity of efficient nonprecious electrocatalysts capable of facilitating both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). This study focused on nanohybrids consisting of hydrothermally synthesized rGO/MnO2/MoS2 composites and highlighted their efficacy as bifunctional electrocatalysts. The synergistic integration of rGO/MnO2/MoS2 enhanced the surface area, magnified electroactive sites, established a customized conductive arrangement, and provoked the efficiency in splitting of water. The nanohybrid displayed exceptional catalytic performance for the OER and HER, with significantly reduced overpotentials of 208 and 205 mV in 1 M KOH at 10 mA cm-2 current density, respectively. The findings underscore the potential of these cost-effective and environmentally friendly rGO/MnO2/MoS2 nanohybrids in advancing the field of electrocatalysis for renewable energy applications.

In Situ Synthesis of High-Entropy (Oxy)Hydroxides Via Electrochemical Reconfiguration As Catalysts For Efficient Water Oxidation.

Surface reconstruction plays a pivotal role in enhancing the activity of the oxygen evolution reaction (OER), particularly in terms of the structural transformation from metal oxides to (oxy)hydroxides. Herein, a novel (oxy)hydroxide (FeCoNiCuMoOOH) with high entropy is developed by the electrochemical reconstitution of corresponding oxide (FeCoNiCuMoOx). Significantly, the FeCoNiCuMoOOH exhibits much higher OER electrocatalytic activity and durability with an overpotential as low as 201mV at a current density of 10mA cm-2, and with a Tafel slope of 39.4mV dec-1. The FeCoNiCuMoOOH/NF presents high stability when testing under a constant current at 100mA cm-2 within 1000h. The surface reconstruction is a process of dissolution-reprecipitation of Cu and Mo species and co-hydroxylation of five metal species, which ultimately leads to the formation of FeCoNiCuMoOOH from FeCoNiCuMoOx. This study holds great significance in the realm of designing high-entropy (oxy)hydroxides catalysts with exceptional activity and stability for OER.

Multi-Component and Nanoporous Design toward RuO2-Based Electrocatalyst with Enhanced Performance for Acidic Water Splitting.

Developing electrocatalysts with excellent activity and stability for water splitting in acidic media remains a formidable challenge due to the sluggish kinetics and severe dissolution. As a solution, a multi-component doped RuO2 prepared through a process of dealloying-annealing is presented. The resulting multi-doped RuO2 possesses a nanoporous structure, ensuring a high utilization efficiency of Ru. Furthermore, the dopants can regulate the electronic structure, causing electron aggregation around unsaturated Ru sites, which mitigates Ru dissolution and significantly enhances the catalytic stability/activity. The representative catalyst (FeCoNiCrTi-RuO2) shows an overpotential of 167 mV at 10 mAcm-2 for oxygen evolution reaction (OER) in 0.5 m H2SO4 solution with a Tafel slope of 53.1mVdec-1, which is among the highest performance reported. Moreover, it remains stable for over 200 h at a current density of 10mAcm-2. This work presents a promising approach for improving RuO2-based electrocatalysts, offering a crucial advancement for electrochemical water splitting.