Research progress on layered metal oxide electrocatalysts for an efficient oxygen evolution reaction.

Hydrogen, highly valued for its pristine cleanliness and remarkable efficiency as an emerging energy source, is anticipated to ascend to a preeminent status within the forthcoming energy landscape. Electrocatalytic water splitting is considered a pivotal, eco-friendly, and sustainable strategy for hydrogen production. The substantial energy consumption stemming from oxygen evolution side reactions significantly impedes the commercial viability of water electrolysis. Consequently, the pursuit of a cost-effective and efficacious oxygen evolution reaction (OER) catalyst stands as an imperative strategy for realizing hydrogen production via water electrolysis. Layered metal oxides, owing to their robust anisotropic properties, versatile adjustability, and extensive surface area, have emerged as suitable candidates for OER catalysts. However, owing to the distinctive attributes of layered metal oxides, ongoing investigations into these materials are slightly fragmented, lacking universal consensus. This article comprehensively surveys the recent advancements in layered metal oxide-based OER catalysts, categorized into single metal oxides, alkali cobalt oxides, perovskites, and miscellaneous metal oxides. Initially, the main OER intermediate reaction steps of layered metal oxides are scrutinized. Subsequently, the design, mechanism, and application of several pivotal layered metal oxides in the OER are systematically delineated. Finally, a summary is provided, alongside the proposal of future research trajectories and challenges encountered by layered metal oxides, with the aspiration that this paper may serve as a valuable reference for scholars in the field.

Janus electronic state of supported iridium nanoclusters for sustainable alkaline water electrolysis.

Metal-support electronic interactions play crucial roles in triggering the hydrogen spillover (HSo) to boost hydrogen evolution reaction (HER). It requires the supported metal of electron-rich state to facilitate the proton adsorption/spillover. However, this electron-rich metal state contradicts the traditional metal→support electron transfer protocol and is not compatible with the electron-donating oxygen evolution reaction (OER), especially in proton-poor alkaline conditions. Here we profile an Ir/NiPS3 support structure to study the Ir electronic states and performances in HSo/OER-integrated alkaline water electrolysis. The supported Ir is evidenced with Janus electron-rich and electron-poor states at the tip and interface regions to respectively facilitate the HSo and OER processes. Resultantly, the water electrolysis (WE) is efficiently implemented with 1.51 V at 10 mA cm-2 for 1000 h in 1 M KOH and 1.44 V in urea-KOH electrolyte. This research clarifies the Janus electronic state as fundamental in rationalizing efficient metal-support WE catalysts.

Covalently Bonded Ni Sites in Black Phosphorene with Electron Redistribution for Efficient Metal-Lightweighted Water Electrolysis.

The metal-lightweighted electrocatalysts for water splitting are highly desired for sustainable and economic hydrogen energy deployments, but challengeable. In this work, a low-content Ni-functionalized approach triggers the high capability of black phosphorene (BP) with hydrogen and oxygen evolution reaction (HER/OER) bifunctionality. Through a facile in situ electro-exfoliation route, the ionized Ni sites are covalently functionalized in BP nanosheets with electron redistribution and controllable metal contents. It is found that the as-fabricated Ni-BP electrocatalysts can drive the water splitting with much enhanced HER and OER activities. In 1.0 M KOH electrolyte, the optimized 1.5 wt% Ni-functionalized BP nanosheets have readily achieved low overpotentials of 136 mV for HER and 230 mV for OER at 10 mA cm-2. Moreover, the covalently bonding between Ni and P has also strengthened the catalytic stability of the Ni-functionalized BP electrocatalyst, stably delivering the overall water splitting for 50 h at 20 mA cm-2. Theoretical calculations have revealed that Ni-P covalent binding can regulate the electronic structure and optimize the reaction energy barrier to improve the catalytic activity effectively. This work confirms that Ni-functionalized BP is a suitable candidate for electrocatalytic overall water splitting, and provides effective strategies for constructing metal-lightweighted economic electrocatalysts.

Recent Advancements of Graphene-Based Materials for Zinc-Based Batteries: Beyond Lithium-Ion Batteries.

Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodine batteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this great potential research field.

Enlarging the Ni-O Bond Polarizability in a Phosphorene-Hosted Metal-Organic Framework for Boosted Water Oxidation Electrocatalysis.

The emerging lattice-oxygen oxidation mechanism (LOM) presents attractive opportunities for breaking the scaling relationship to boost oxygen evolution reaction (OER) with the direct OLattice-*O interaction. However, currently the LOM-triggering rationales are still debated, and a streamlined physicochemical paradigm is extremely desirable for the design of LOM-defined OER catalysts. Herein, a Ni metal-organic framework/black phosphorene (NiMOF/BP) heterostructure is theoretically profiled and constructed as a catalytic platform for the LOM-derived OER studies. It is found that the p-type BP host can enlarge the Ni-O bond polarizability of NiMOF through the Ni-O bond stretching and Ni valence declining synergically. Such an enlarged bond polarizability will in principle alleviate the lattice oxygen confinement to benefit the LOM pathway and OER performance. As a result, the optimized NiMOF/BP catalyst exhibits promising OER performance with a low overpotential of 260 mV at 10 mA cm-2 and long-term stability in 1 M KOH electrolyte. Both experiment and calculation results suggest the activated LOM pathway with a more balanced step barrier in the NiMOF/BP OER catalyst. This research puts forward Ni-O bond polarizability as the criterion to design LOM-scaled electrocatalysts for water oxidation.

Macroporous SnO2/MoS2 inverse opal hierarchitecture for highly efficient trace NO2 gas sensing.

The innovation of NO2 gas sensors is highly desirable in environmental monitoring and human safety. Herein, a macroporous SnO2/MoS2 inverse opal hierarchitecture has been constructed with substantial interface charge transfer, which realizes the efficient and stable detection of NO2 with an enhanced response, fast kinetics, and high selectivity at low temperatures.

Two-Dimensional Iron Phosphorus Trisulfide as a High-Capacity Cathode for Lithium Primary Battery.

Metal phosphorus trichalcogenide (MPX3) materials have aroused substantial curiosity in the evolution of electrochemical storage devices due to their environment-friendliness and advantageous X-P synergic effects. The interesting intercalation properties generated due to the presence of wide van der Waals gaps along with high theoretical specific capacity pose MPX3 as a potential host electrode in lithium batteries. Herein, we synthesized two-dimensional iron thio-phosphate (FePS3) nanoflakes via a salt-template synthesis method, using low-temperature time synthesis conditions in single step. The electrochemical application of FePS3 has been explored through the construction of a high-capacity lithium primary battery (LPB) coin cell with FePS3 nanoflakes as the cathode. The galvanostatic discharge studies on the assembled LPB exhibit a high specific capacity of ~1791 mAh g-1 and high energy density of ~2500 Wh Kg-1 along with a power density of ~5226 W Kg-1, some of the highest reported values, indicating FePS3's potential in low-cost primary batteries. A mechanistic insight into the observed three-staged discharge mechanism of the FePS3-based primary cell resulting in the high capacity is provided, and the findings are supported via post-mortem analyses at the electrode scale, using both electrochemical- as well as photoelectron spectroscopy-based studies.

Gel Electrolytes for Electrochemical Actuators and Sensors Applications.

Advanced functional materials, especially gel electrolytes, play a very important role in the preparation of electrochemical actuators and sensors, and have received extensive attention. In this review, a general classification of gel electrolytes is firstly introduced according to the type of medium. Then, the research progress of gel electrolytes with different types used to fabricate electrochemical actuators is summarized. Next, the current research progress of gel electrolytes used in different types of electrochemical sensors, including strain sensors, stress sensors, and gas sensors is introduced. Finally, the future challenges and development prospects of electrochemical actuators and sensors based on gel electrolytes are discussed. The huge application prospects of gel electrolyte are worthy of further focusing by researchers, which will have an indispensable impact on human life and development.

Synergizing Hydrogen Spillover and Deprotonation by the Internal Polarization Field in a MoS2 /NiPS3 Vertical Heterostructure for Boosted Water Electrolysis.

Hydrogen spillover (HSo) has emerged to upgrade the hydrogen evolution reaction (HER) activity of Pt-support electrocatalysts, but it is not applicable to the deprotonated oxygen evolution reaction (OER). Non-precious catalysts that can perform well in both HSo and deprotonation (DeP) are extremely desirable for a sustainable hydrogen economy. Herein, an affordable MoS2 /NiPS3 vertical heterostructure catalyst is presented to synergize HSo and DeP for efficient water electrolysis. The internal polarization field (IPF) is clarified as the driving force of HSo in HER electrocatalysis. The HSo from the MoS2 edge to NiPS3 can activate the NiPS3 basal plane to boost the HER activity of the MoS2 /NiPS3 heterostructure (112 mV vs reversible hydrogen electrode (RHE) at 10 mA cm-2 ), while for OER, the IPF in the heterostructure can facilitate the hydroxyl diffusion and render MoS2 -to-NiPS3 /P-to-S dual-pathways for DeP. As a result, the stacking of OER-inactive MoS2 on the NiPS3 surface still brings intriguing OER enhancements. With them serving as electrode couples, the overall water splitting is attested stably with a cell voltage of 1.64 V at 10 mA cm-2 . This research puts forward the IPF as the criterion in the rational design of HSo/DeP-unified non-precious catalysts for efficient water electrolysis.

Elemental Two-Dimensional Materials for Li/Na-Ion Battery Anode Applications.

Two-dimensional (2D) nanostructure is currently the subject in the fields of new energy storage and devices. During the past years, a broad range of 2D materials represented by graphene have been developed and endow with excellent electrochemical properties. Among them, elemental 2D materials (Xenes) are an emerged material family for Li/Na-ion battery (LIB/SIB) anodes. Compared with other 2D materials and bulk materials, Xenes may exhibit some great superiorities for Li/Na storage, including excellent conductivity, fast ion diffusion and large active sites exposure. In this review, we provide a systematic summary of the recent progress and achievements of Xenes as well as their applications in LIBs/SIBs. The broad categorization of Xenes from group IIIA to VIA has been concisely outlined, and the related details in syntheses, structures and Li/Na-ion storage properties are reviewed. Further, the latest research progress of Xenes in Li/Na ion batteries are summarized, together with mechanism discussions. Finally, the challenges and prospects of Xenes applied to Li/Na ion battery are proposed based on its current developments.

Shining Light on Anion-Mixed Nanocatalysts for Efficient Water Electrolysis: Fundamentals, Progress, and Perspectives.

HIGHLIGHTS: This review introduces recent advances of various anion-mixed transition metal compounds (e.g., nitrides, halides, phosphides, chalcogenides, (oxy)hydroxides, and borides) for efficient water electrolysis applications in detail. The challenges and future perspectives are proposed and analyzed for the anion-mixed water dissociation catalysts, including polyanion-mixed and metal-free catalyst, progressive synthesis strategies, advanced in situ characterizations, and atomic level structure-activity relationship. Hydrogen with high energy density and zero carbon emission is widely acknowledged as the most promising candidate toward world's carbon neutrality and future sustainable eco-society. Water-splitting is a constructive technology for unpolluted and high-purity H2 production, and a series of non-precious electrocatalysts have been developed over the past decade. To further improve the catalytic activities, metal doping is always adopted to modulate the 3d-electronic configuration and electron-donating/accepting (e-DA) properties, while for anion doping, the electronegativity variations among different non-metal elements would also bring some potential in the modulations of e-DA and metal valence for tuning the performances. In this review, we summarize the recent developments of the many different anion-mixed transition metal compounds (e.g., nitrides, halides, phosphides, chalcogenides, oxyhydroxides, and borides/borates) for efficient water electrolysis applications. First, we have introduced the general information of water-splitting and the description of anion-mixed electrocatalysts and highlighted their complementary functions of mixed anions. Furthermore, some latest advances of anion-mixed compounds are also categorized for hydrogen and oxygen evolution electrocatalysis. The rationales behind their enhanced electrochemical performances are discussed. Last but not least, the challenges and future perspectives are briefly proposed for the anion-mixed water dissociation catalysts.

Amorphous materials for elementary-gas-involved electrocatalysis: an overview.

Given the critical demands on energy conversion, storage, and transportation, tremendous interest has been devoted to the field of material development related to energy harvesting, recently. As the only route towards energy utilization, the carriers with the characteristics of low carbon are regarded as the future choice, e.g., hydrogen and ammonia. To this end, electrocatalysis provides a green way to access these substances. However, the unfulfilled conversion efficiency is the bottleneck for practical application. In this review, the promising characteristics of amorphous materials and the amorphous-induced electrocatalytic enhancement (AIEE) were emphasized. In the beginning, the characteristics of amorphous materials are briefly summarized. The basic mechanism of heterogeneous electrocatalytic reactions is illustrated, including the hydrogen/oxygen evolution and oxygen/nitrogen reduction. In the third part, the electrocatalytic performance of amorphous materials is discussed in detail, and the mechanism of AIEE is highlighted. In the last section of this review, the challenges and outlook for the development of amorphous enhanced electrocatalysis are presented.

Suppression of Sn2+ and Lewis acidity in SnS2/black phosphorus heterostructure for ppb-level room temperature NO2 gas sensor.

The selective detection of harmful gases is of great significance to human health and air quality, triggering the need for special customizations of sensing material structure. In this study, we prepared a novel SnS2/black phosphorus (BP) two-dimensional (2D)-2D heterostructure via the in situ hydrothermal growth of SnS2 nanosheets on exfoliated BP lamellae for NO2 sensing applications. In the SnS2/BP composite, the holes with high oxidizability in p-type BP could oxidize Sn2+ into Sn4+, thus inhibiting the formation of Lewis acidic S vacancies. This Sn2+/Lewis acidity suppression of the composite was further confirmed by X-ray photoelectron spectroscopy and acidic double-layer capacitance analyses, and promoted the adsorption and detection of acidic NO2. Owing to its valence and Lewis acidity engineering, the SnS2/BP heterostructure sensor could detect trace levels of NO2 as low as 100 ppb (parts per billion) with high response, fast response/recovery, good stability, and selectivity at room temperature. The high absorption energy of NO2 (-0.74 eV), as indicated by the density functional theory calculations, suggests that NO2 was chemically adsorbed on the SnS2/BP surface, which was also evidenced by the in situ Raman spectroscopy results. This work opens up interesting opportunities for the rational design of highly efficient NO2 gas sensors through Lewis acidity modification and interface engineering.

Atomic Layer Deposition of TiO2 Thin Films on the Inner Walls of Steel Tubes Increases Anti-coking Properties.

To suppress catalytic coking, TiO2 passivation films were deposited on the inner walls of SS316 stainless steel tubes by atomic layer deposition (ALD). Indentation test results showed a platform on the indentation curve of TiO2 films grown over 2000 ALD cycles due to internal stress-induced microcracks. In coking experiments, the TiO2-coated tubes exhibited a higher heat flux and lower pressure difference than bare ones. Analysis of the coking surface revealed that TiO2 thin film passivation can reduce the size and number of particulate deposits. At the same time, passivation treatment inhibits the formation of filamentous carbon and improves anti-coking performance by reducing the ability of the tube to adsorb amorphous deposition products. The coking surfaces of TiO2-coated tubes had less graphitization, indicating that the coking products had fewer defects and lower activated carbon contents.

Boosting Transport Kinetics of Cobalt Sulfides Yolk-Shell Spheres by Anion Doping for Advanced Lithium and Sodium Storage.

Cobalt sulfides have been popularly used in energy storage because of their high theoretical capacity and abundant redox reactions. However, poor reaction kinetics, rapid capacity decay, and severe polarization owing to volume changes during electrochemical reaction are still huge challenges for cobalt sulfides in practical applications. Herein, cobalt sulfide yolk-shell spheres were synthesized by phosphorus doping (P-CoS) to stabilize the structure of cobalt sulfides and improve their electronic/ion conductivity. Kinetic tests and density functional theory calculations confirm that the introduction of phosphorus into cobalt sulfides greatly reduces the diffusion barrier of Li+ in the intrinsic structure, thereby improving the reaction kinetics of electrode materials during the Li+ insertion/extraction process. In consequence, the P-CoS electrode delivers a high lithium storage capacity (781 mAh g-1 after 100 cycles at 0.2 A g-1 ), excellent rate capability (489 mAh g-1 at 10 A g-1 ), and outstanding cycling stability (no significant capacity decay over 4000 cycles at 5 A g-1 ). Especially for sodium-ion battery application, the P-CoS electrode expresses a striking capacity of approximately 260 mAh g-1 at 2 A g-1 after 900 cycles.

Gas sensors using ordered macroporous oxide nanostructures.

Detection and monitoring of harmful and toxic gases have gained increased interest in relation to worldwide environmental issues. Semiconducting metal oxide gas sensors have been considered promising for the facile remote detection of gases and vapors over the past decades. However, their sensing performance is still a challenge to meet the demands for practical applications where excellent sensitivity, selectivity, stability, and response/recovery rate are imperative. Therefore, sensing materials with novel architectures and fabrication processes have been pursued with a flurry of research activity. In particular, the preparation of ordered macroporous metal oxide nanostructures is regarded as an intriguing candidate wherein ordered aperture sizes in the range from 50 nm to 1.5 µm can increase the chemical diffusion rate and considerably strengthen the performance stability and repeatability. This review highlights the recent advances in the fabrication of ordered macroporous nanostructures with different dimensions and compositions, discusses the sensing behavior evolution governed by structural layouts, hierarchy, doping, and heterojunctions, as well as considering their general principles and future prospects. This would provide a clear scale for others to tune the sensing performance of porous materials in terms of specific components and structural designs.

Lithiation-Induced Non-Noble Metal Nanoparticles for Li-O2 Batteries.

Low-cost and highly active electrocatalysts are attractive for Li-O2 applications. Herein, a 3D interconnected plate architecture consisting of ultrasmall Co-Ni grains embedded in lithium hydroxide nanoplates (Co2Ni@LiOH) is designed and prepared by a lithiation strategy at room temperature. This catalyst exhibits a remarkably reduced charge potential of ∼3.4 V at 50 µA cm-2, which leads to the high roundtrip efficiency of ∼79%, among the best levels reported and a cycle life of up to 40 cycles. The well-aligned network facilitates the oxygen diffusion and the electrolyte penetration into the electrode. The enhanced electrical conductivity network improves the charge transport kinetics and more active sites are exposed, which facilitate the adsorption and dissociation of oxygen during the oxygen reduction reaction and the oxygen evolution reaction. This new catalyst design inspires the development of an effective non-noble metal catalyst for Li-O2 batteries.

Constructing Multifunctional Heterostructure of Fe2 O3 @Ni3 Se4 Nanotubes.

Heterostructures have attracted increasing attention due to their amazing synergetic effects, which may improve the electrochemical properties, such as good electrical/ionic conductivity, electrochemical activity, and mechanical stability. Herein, novel hierarchical Fe2 O3 @Ni3 Se4 nanotubes are successfully fabricated by a multistep strategy. The nanotubes show length sizes of ≈250-500 nm, diameter sizes of ≈100-150 nm, and wall thicknesses of ≈10 nm. The as-prepared Fe2 O3 @Ni3 Se4 nanotubes with INi:Fe = 1:10 show excellent Li storage properties (897 mAh g-1 high reversible charge capacity at 0.1 A g-1 ), good rate performance (440 mAh g-1 at 5 A g-1 ), and outstanding long-term cycling performance (440 mAh g-1 at 5 A g-1 during the 300th cycle) as an anode material for lithium ion batteries. In addition, the Fe2 O3 @Ni3 Se4 nanotubes with INi:Fe = 1:10 (the atomic ratio between Ni and Fe) show superior electrocatalytic performance toward the oxygen evolution reaction with an overpotential of only 246 mV at 10 mA cm-2 and a low Tafel slope of 51 mV dec-1 in 1 m KOH solution.

Few-layer NiPS3 nanosheets as bifunctional materials for Li-ion storage and oxygen evolution reaction.

The construction of two-dimensional (2D) ultrathin nanosheets is considered as a promising strategy for enhancing electrochemical performance, owing to their large surface area and fast electron transport. In this study, ultrathin few-layer NiPS3 nanosheets are obtained and systematically investigated by high-yield liquid phase exfoliation from their bulk layered crystals, and are exploited as anodes for lithium ion batteries (LIBs) and electrocatalysts for oxygen evolution reaction (OER). When evaluated as an anode for LIBs, NiPS3 nanosheets show excellent electrochemical properties in terms of stable cycling performance and rate capabilities. A stable reversible capacity of 796.2 mA h g-1 is delivered after the 150th cycle at a current density of 100 mA g-1. As for the OER, the exfoliated few-layer NiPS3 nanosheets have demonstrated excellent electrocatalytic performance, such as a low overpotential of 301 mV at a current density of 10 mA cm-2, a small Tafel slope of 43 mV dec-1, and an outstanding long-term durability. This work is expected to make a contribution to develop next generation high-performance electrochemically active materials for catalysts and batteries.

Ultrathin Porous NiFeV Ternary Layer Hydroxide Nanosheets as a Highly Efficient Bifunctional Electrocatalyst for Overall Water Splitting.

Herein, the hydrothermal synthesis of porous ultrathin ternary NiFeV layer double hydroxides (LDHs) nanosheets grown on Nickel foam (NF) substrate as a highly efficient electrode toward overall water splitting in alkaline media is reported. The lateral size of the nanosheets is about a few hundreds of nanometers with the thickness of ≈10 nm. Among all molar ratios investigated, the Ni0.75 Fe0.125 V0.125 -LDHs/NF electrode depicts the optimized performance. It displays an excellent catalytic activity with a modest overpotential of 231 mV for the oxygen evolution reaction (OER) and 125 mV for the hydrogen evolution reaction (HER) in 1.0 m KOH electrolyte. Its exceptional activity is further shown in its small Tafel slope of 39.4 and 62.0 mV dec-1 for OER and HER, respectively. More importantly, remarkable durability and stability are also observed. When used for overall water splitting, the Ni0.75 Fe0.125 V0.125 -LDHs/NF electrodes require a voltage of only 1.591 V to reach 10 mA cm-2 in alkaline solution. These outstanding performances are mainly attributed to the synergistic effect of the ternary metal system that boosts the intrinsic catalytic activity and active surface area. This work explores a promising way to achieve the optimal inexpensive Ni-based hydroxide electrocatalyst for overall water splitting.