Slow Reaction Research Articles

Toward Practical Li–S Batteries: On the Road to a New Electrolyte

AbstractThe lithium–sulfur (Li–S) battery system has attracted considerable attention due to its ultrahigh theoretical energy density and promising applications. However, with the increasing demands on S loading and electrolyte content, practical Li–S batteries still face several serious challenges, such as slow reaction kinetics at the cathode interface, unstable anode interface reactions, and undesirable crosstalk effects between the cathode and anode. Traditional electrolyte systems often struggle to address these challenges under practical conditions, thereby rendering it imperative to establish a new electrolyte system for practical Li–S batteries. This review first discusses the necessity of establishing a new electrolyte and propose specific parameter requirements, such as the electrolyte‐to‐sulfur mass ratio (Em/S). Subsequently, some electrolyte modification strategies proposed by researchers are summarized to address the different challenges associated with practical Li–S batteries. Finally, the combination of different strategies is reviewed, aiming to reveal more effective design approaches that simultaneously address multiple challenges, while providing guidance for establishing a new balanced electrolyte for practical Li–S batteries. This article promotes the development of new electrolytes for practical Li–S batteries and can act as a reference for the development of electrolytes for other secondary batteries.

Anion Doping and Dual-Carbon Confinement Strategies to Synergistically Boost the Sodium Storage Performance of Cobalt-Based Sulfides.

Cobalt-based sulfides (CSs) are generally regarded as potentially valuable anode materials for sodium-ion batteries (SIBs) due to their excellent theoretical capacity and natural abundance. Nevertheless, their slow reaction kinetics and poor structural stability restrict the practical application of the materials. In this study, the dual-carbon-confined Se-CoS2@NC@C hollow nanocubes with anion doping are synthesized using ZIF-67 as the substrate by resorcin-formaldehyde (RF) encapsulation and subsequent carbonization and sulfurization/selenization. RF- and ZIF-67-derived dual-carbon skeleton hollow structures with a robust carbon skeleton and abundant internal space minimize cyclic stress, mitigate volume changes and maintain the structural integrity of the material. More importantly, Se doping increases the lattice spacing of CoS2, weakens the strength of Co-S bonds, and modulates the electronic structure around Co atoms, thereby optimizing the adsorption energy of the material. As a result, the hollow nanocubes of Se-CoS2@NC@C demonstrates excellent electrochemical performance as the anode for SIBs, delivering a high reversible capacity of 549.4 mAh g-1 at 0.5 A g-1 after 100 cycles and a superb rate performance (541.1 mAh g-1 at 0.2 A g-1, and 393.3 mAh g-1 at 5 A g-1). This study proposes a neoteric strategy for synthesizing advanced anodes for SIBs through the synergy of anion doping engineering and dual-carbon confinement strategy.

On-Site Multiply Stimulated Self-Confinement of an Integrated DNA Cascade Circuit for Highly Reliable Intracellular Imaging of miRNA and In Situ Interrogation of the Relevant Regulatory Pathway.

Artificial DNA circuits represent a versatile yet promising toolbox for in situ monitoring and concomitant regulation of diverse biological events within live cells. Nonetheless, their performance is significantly impeded by the diffusion-dominated slow reaction kinetics and the uncontrollable off-target activation. Herein, a self-localized cascade (SLC) circuit is reported for the robust and efficient microRNA (miRNA) analysis in living cells. The SLC circuit consists of the cell-specific localization module and the analyte-specific signal amplification module. By integrating the reaction probes of these two modules, the complexity of the system is reduced to realize the responsive co-localization of circuitry probes and the simultaneous cascade signal amplification. Taking advantage of the specifically activated, self-localized, and cascade design, the SLC circuit successfully achieves the robust miRNA-21 (miR-21) imaging and the accurate cells differentiation. Moreover, the reverse regulation mechanism is successfully explored between messenger RNA (mRNA) and miRNA through the engineered SLC circuit and further elucidates the underlying signaling pathways between them. Therefore, the SLC circuit provides a powerful tool for the sensitive detection of intracellular biomolecules and the study of the corresponding cell regulatory mechanisms.

Electrical-Modulated Flexible Acoustic Metamaterial: Enhancing Low-Frequency Absorption via an Ionic Electroactive Polymer.

The growing concern over low-frequency noise pollution resulting from global industrialization has posed substantial challenges in noise attenuation. However, conventional acoustic metamaterials, with fixed geometries, offer limited flexibility in the frequency range adjustment once constructed. This research unveiled the promising potential of ionic electroactive polymers, particularly ionic polymer-metal composites (IPMCs), as a superior candidate to design tunable acoustic metamaterial due to its bidirectional energy conversion capabilities. The previously perceived limitations of the IPMC, including slow reaction and high energy expenditure, owning to its inherent sluggish intermediary ionic mass transport process, were astutely leveraged to expedite the attenuation of low-frequency sound energy. Both our experimental and simulation results elucidated that the IPMC can generate voltage potentials in response to acoustic pressure at frequencies significantly higher than those previously established. In addition, the peak absorption frequency can be effectively shifted by up to 45.7% with the application of a 4 V voltage. By further integration with a microperforated panel (MPP) structure, the developed metamaterial absorbers can achieve complete sound absorption, which was continuously tunable under minimal voltage stimulation across a wide frequency spectrum. In addition, a microslit structure IPMC metamaterial absorber was designed to realize modulation of the perforation rate, and the absorption peak can be shifted by up to 79.2%. These findings signify a pioneering application of ionic intelligent materials and may pave the way for further innovations of tunable low-frequency acoustic structures, ultimately advancing the pragmatic deployment of both soft intelligent materials and acoustic metamaterials.

Click catalysis and DNA conjugation using a nanoscale DNA/silver cluster pair.

DNA-bound silver clusters are most readily recognized by their strong fluorescence that spans the visible and near-infrared regions. From this suite of chromophores, we chose a green-emitting Ag106+ bound to C4AC4TC3GT4 and describe how this DNA/cluster pair is also a catalyst. A DNA-tethered alkyne conjugates with an azide via cycloaddition, an inherently slow reaction that is facilitated through the joint efforts of the cluster and DNA. The Ag106+ structure is the catalytic core in this complex, and it has three distinguishing characteristics. It facilitates cycloaddition while preserving its stoichiometry, charge, and spectra. It also acidifies its nearby alkyne to promote H/D exchange, suggesting a silver-alkyne complex. Finally, it is markedly more efficient when compared with related multinuclear DNA-silver complexes. The Ag106+ is trapped within its C4AC4TC3GT4 host, which governs the catalytic activity in two ways. The DNA has orthogonal functional groups for both the alkyne and cluster, and these can be systematically separated to quench the click reaction. It is also a polydentate ligand that imprints an elongated shape on its cluster adduct. This extended structure suggests that DNA may pry apart the cluster to open coordination sites for the alkyne and azide reactants. These studies indicate that this DNA/silver cluster pair work together with catalysis directly driven by the silver cluster and indirectly guided by the DNA host.

Manipulating Orbital Hybridization of CoSe2 by S Doping for the Highly Active Catalytic Effect of Lithium-Sulfur Batteries.

In recent years, various transition metal compounds have been extensively studied to deal with the problems of slow reaction kinetics and the shuttle effect of lithium-sulfur (Li-S) batteries. Nevertheless, their catalytic performance still needs to be further improved by enhancing intrinsic catalytic activity and enriching active sites. Doping is an effective means to boost the catalytic performance through adjusting the electron structure of the catalysts. Herein, the electron structure of CoSe2 is adjusted by doping P, S with different p electron numbers and electronegativity. After S doping (S-CoSe2), the content of Co2+ increases, and charge is redistributed. Furthermore, more electrons are transferred between Li2S4/Li2S and S-CoSe2, and optimal Co-S bonds are formed between them with optimized d-p orbital hybridization, making the bonds of Li2S4/Li2S the longest and easy to break and decompose. Consequently, the Li-S batteries with the S-CoSe2-modified separator achieve improved rate performance and cycling performance, benefiting from the better bidirectional catalytic activity. This work will provide reference for the selection of the anion doping element to enhance the catalytic effect of transition metal compounds.

N, S, Se-Codoped dual carbon encapsulation and Se substitution in pyrite-type FeS2 for high-rate and long-life sodium-ion batteries

The use of metal sulfides as anodes in sodium-ion batteries (SIBs) faces significant challenges due to slow reaction kinetics and extensive shuttling of sodium polysulfides (NaPSs). In response, a selenium-substituted iron disulfide encapsulated in a nitrogen-sulfur-selenium-codoped dual carbon framework (Se-FeS2@NSSC) has been engineered for high-performance SIBs. Selenium substitution within the FeS2 lattice improves electrical conductivity, facilitates favorable redox kinetics that reducing the possibility of NaPSs generation. Moreover, the dual NSSC encapsulation promotes Na+/electron transport and efficiently manages volume expansion during electrochemical processes. Strong interfacial interaction (Fe-S-C bonding) between Se-FeS2 and NSSC further suppress NaPSs shuttling, significantly alleviating the cell failure and thus prolonging its lifespan. Consequently, Se-FeS2@NSSC demonstrates a top-notch performance, achieving a notable capacity of 725 mAh g-1 at 0.5 A g-1, unparalleled rate capability (355.1 mAh g-1 at 30 A g-1), and sustained cyclic stability (89.6 % capacity is retained after 1250 cycles). Theoretical analyses underscore the critical role of selenium in diminishing bulk stress–strain energies, lowering energy barriers for Na+ diffusion, and decreasing Gibbs free energy for conversion reactions, thereby markedly bolstering electrochemical kinetics and overall performance of Se-FeS2@NSSC. The insights gleaned from this research foster advancements in developing next-generation anodes with high capacity and durability, representing a promising response to the existing hurdles in SIBs technology.

Effect of thermochemical treatment of sewage sludge on its phosphorus leaching efficiency: Insights into leaching behavior and mechanism

Thermochemical conversion, including hydrothermal processing, pyrolysis and incineration, has become a promising technology for sewage sludge (SS) treatment and disposal. Furthermore, acid leaching is considered as an effective method to recover phosphorus (P) from SS and its thermochemical treatment products. This study has investigated the potential of P reclamation from SS and its thermochemical derivatives, including hydrochar (HC), biochar (BC), and SS incinerated ash (SA). Comparative analyses of physicochemical properties of these derivatives revealed a decrease in hydroxyl and aromatic groups and an increase in aliphatic and oxygen-containing functional groups in HC and BC. Leaching experiments using 1 M sulfuric acid (H2SO4) and 1 M oxalic acid (C2H2O4) suggested that H2SO4 slightly outperformed C2H2O4 in terms of P leaching efficiency. HC achieved 79.1 % optimal leaching efficiency in 60 min using H2SO4, while BC, SS, and SA required 360 min to achieve comparable efficiency. SS and BC reached optimal leaching efficiency at 74.1 % and 76.2 % in H2SO4, while SA achieved 80.9 % in C2H2O4. Importantly, HC and SA are more favorable for P extraction using acid leaching, whereas BC tends to be a potential P carrier. Time-dependent kinetics revealed a two-stage leaching process, i.e., fast and slow reaction stages. Shrinking core model indicates product layer diffusion as the primary rate-limiting step in both stages. Overall, these fundamental insights play an important role in practical P recovery through acid leaching of SS derived residues after thermochemical treatment.

Thermodynamics and kinetics of cation partitioning between plagioclase and trachybasaltic melt in static and dynamic systems: A reassessment of the lattice strain and electrostatic energies of substitution

Most of the solidification history of magmas beneath active volcanoes takes place in chemically and physically perturbed plumbing systems where the growth of crystals is collectively governed by a range of kinetic processes related to the dynamics of crustal reservoirs and eruptive conduits. In this context, we have experimentally investigated the partitioning of major, minor, and trace cations between plagioclase and trachybasaltic melt under conventional static (no physical perturbation) and dynamic (melt stirring) crystallization regimes. Slow interface reaction kinetics are established between the advancing crystal surface and the adjacent melt, as the result of the combined control of a small degree of effective undercooling, prolonged diffusive relaxation, and convective homogenization. The kinetic aspects of plagioclase growth influence the partitioning of trace cations during transport of structural units across the crystal-melt interface, with consequent departure from macroscopic equilibrium in the system. The type and number of charge–balanced and −imbalanced configurations produced by the accommodation of trace cations into the coordination polyhedron can be thermodynamically rationalized in terms of lattice strain and electrostatic partitioning energetics. However, the overall solution energy accompanying trace cation kinetic substitutions cannot be entirely deconvoluted from major component activities in both melt and plagioclase phases. The emerging view that slow interface kinetic processes may lead to strong compositional dependence for the partition coefficient in dynamic subvolcanic environments contrasts markedly with the conventional idea that the energetics of cation partitioning are dominantly controlled by the effect of isothermal changes in the bulk system.

Programming Fast DNA Amplifier Circuits with Versatile Toehold Exchange Pathway.

DNA amplifier circuits establish powerful tools to dynamically control molecular assembly for computation, sensing, and biological applications. However, the slow reaction speed remains a major barrier to their practical utility. Here, diverse fast DNA amplifier circuits termed toehold exchange polymerization (TEP) and toehold exchange catalysis (TEC) using toehold exchange-mediated assembly as a fundamental mechanism are built. Both TEP and TEC with a duplex and a hairpin can respond within minutes to diverse nucleic acid inputs with high fidelity. In addition, the circuits can amplify live-cell signals for fluorescence imaging target RNA dynamics and discriminating different cell lines. Compared with existing DNA circuits that involve time scales of hours for transducing small signals, TEP and TEC exhibit much faster dynamics, simpler design, and comparable sensitivity. These features make TEP and TEC promising platforms to develop programmable nucleic acid tools and devices and to create fast sensing and processing systems, amenable to wide practical applications.

Efficient Co-ZrO2 electrocatalyst achieves high-performance solid-state lithium-sulfur batteries

Abstract Li-S batteries are recognized as a promising secondary battery system because of their high energy density, low cost, and environmental friendliness. However, the development of Li-S batteries is mainly limited by issues such as electrode volume expansion, lithium polysulfide (LiPSs) shuttle, and slow redox reaction kinetics of sulfur. Here, a kind of solid-state Li-S battery with in situ solidified solid-state electrolytes (SSEs) is reported, which dramatically reduces the electrode/electrolyte interfacial impedance. In addition, electrospinning is used to fabricate a macroporous carbon nanofibers film (MP-CNFs) loaded with dispersed Co-ZrO2 nanodot electrocatalyst as the cathode host. The in-situ gel electrolyte can be easily infiltrated into the porous carbon nanofibers and contact the Co-ZrO2 catalyst, thus fully exerting its catalytic and conversion effects on LiPSs. The results indicate that solid-state Li-S batteries exhibit a high initial capacity of 795.5 mA h·g−1 and a capacity retention rate of ∼100% after 200 cycles at 1 C.

Rational Design of Er2O3/ZnS as Highly Competent Electrocatalyst for OER Application

The fabrication of an extremely productive, inexpensive and prominent electrocatalyst is required to improve the slow oxygen evolution reaction (OER). Here, a hydrothermal approach was utilized to fabricate Er2O3/ZnS composite as a competent electrode material for the purpose of efficient water splitting. The various analytical tools were used to evaluate morphology, crystallinity, functionality, surface area, elemental composition and thermal stability of the reported materials. The large surface area of the Er2O3/ZnS composite (61.06 m2 g-1), makes it a suitable candidate for carrying out the OER process. Moreover, the electrochemical study for Er2O3/ZnS composite was conducted on nickel foam (NF) as a substrate to determine the electrolytic nature. The electrochemical study showed that the synthesized composite responds to an impressive overpotential (260 mV) and low Tafel value (40 mV dec-1) at an ideal current density (j) of 10 mA cm-2. The Er2O3/ZnS composite exhibits a reduced onset potential of approximately 1.31 V and exceptional durability of about 30 h. The electrochemical observation suggests that incorporating Er2O3 into ZnS resulted in an enlarged surface area and enhanced active regions which reduce the resistance and promote the rapid binding of electrolyte ions. The composite (Er2O3/ZnS) developed by this approach can be utilized in various energy conversion and storage applications.

Efficient Photocatalytic H2O2 Production and Green Oxidation of Glycerol over a SrCoO3-Incorporated Catalyst

Photocatalysis for H2O2 production suffers from low carrier utilization and slow reaction kinetics. Herein, a photocatalytic system supported by a SrCoO3-MoS2 (SCOS) heterojunction, which possessed a unique S-O electron transport channel, was proposed to facilitate H2O2 production under condition where glycerol served as a sacrificial agent. The SCOS heterojunction achieved a remarkable yield of 15.90mmolg−1 h−1 H2O2 production, 3.7 times higher than the base component SCO. The construction of the heterojunction enriched the oxygen vacancies on the catalyst surface, facilitated photogenerated charge separation, and promoted the adsorption of O2, reducing the oxygen reduction reaction (ORR) energy barrier. Besides, glycerol served as a unique proton donor, efficiently captured holes to enhance H2O2 production, and generated valuable by-products including glyceric acid and dihydroxyacetone. Furthermore, SCOS exhibited excellent stability over repeated cycles with consistent H2O2 yields. This study offers an efficient photocatalytic system and demonstrates glycerol’s potential in green oxidation processes.

Stabilization effect of nano-SiO2@iron-phosphorus on ferrallisols, calcareous soil and organic soil heavily polluted by heavy metals: A fast reaction curing stabilization process

The remediation of soil pollution by heavy metals (HMs) presents a significant challenge in environmental restoration. Stabilization remediation technology has proven effective in treating HMs contaminated soil. However, its development is constrained by drawbacks such as slow reaction kinetics and low adsorption capacity. This research synthesized a nano-SiO2@iron‑phosphorus (FPOH) material by SiO32− encapsulating the iron-phosphate precipitate obtained from Fe ion and phosphate. In addition, this research applied this material to ferrallisols, calcareous soils and organic soils with three different levels of high pollution by Cd, Pb, Cu and Zn. The experimental results indicate that all experimental soils stabilized rapidly within 1 day and met the requirements of remediation engineering standards (ChinaMEE HJ 1282-2023). Analysis of the possible mechanisms suggests that the FPOH material effectively fills voids with phosphate mineral formation, preventing the secondary release of HMs. During the stabilization process, FPOH involves the adsorption of free ions and small organic molecules in the soil, which does not affect its high reactivity. The development and utilization of FPOH offer valuable insights for soil stabilization remediation.

Study on multi-field coupling characteristics of underground coal combustion and nitrogen injection parameter optimization

Underground coal fires, which are widely distributed and cause serious resource waste and environmental hazards, have become a common concern of the international community. This paper aims to reveal the mechanism of coal spontaneous combustion and the expansion law of underground coal fires. A void rate model from the goaf to the ground surface and a multi-field coupling model for underground coal fires were established. Based on which, the combustion process from the beginning of oxidation to the formation of large-scale fire of the remaining coal in goaf was analyzed. Furthermore, the evolution law of underground coal fire after nitrogen injection and the influence of different nitrogen injection parameters were analyzed. The results show that the coal spontaneous combustion can be divided into three stages: slow reaction stage (stage Ⅰ), violent combustion stage (stage Ⅱ), and stable combustion stage (stage Ⅲ), and the transformation of different stages is mainly controlled by the oxidation reaction rate of coal. To obtain the optimal parameters for nitrogen injection for fire suppression, the fire extinguishing efficiency concerning nitrogen injection time, nitrogen injection amount and nitrogen injection position, as well as the distribution law of nitrogen in rock strata were analyzed. Through range analysis, it is determined that the most effective fire extinguishing occurs with the injection rate of 0.15 m3/s in stage I, and the injection position has little influence on the fire extinguishing effect. This understanding contributes to a deeper understanding of the multi-field coupling mechanism of underground coal fires and provides a guidance for extinguishing and preventing underground coal fires.

Preparation of MoS2 nanosheets/nitrogen-doped carbon nanotubes/MoS2 nanoparticles and their electrochemical energy storage properties

Inferior electrical conductivity, huge volume swell, shuttle effect and slow redox reactions in Li-S batteries restrict their practical applications. In this study, molybdenum disulfide nanosheets anchored on nitrogen-doped carbon nanotubes encapsulating molybdenum disulfide nanoparticles (MoS2/NC/MoS2 NTs) were prepared by heat treatment, ammonia etching, high-temperature sulfurization, and solvent-thermal in-situ growth using polypyrrole-coated molybdenum trioxide nanorods (MoO3 NRs) as templates. The hollow structure of nitrogen-doped carbon nanotubes and the high specific surface area are conducive to increasing sulfur loading, increasing the contact area of electrolyte, accelerating the electron transport, and shortening the lithium ion transport route. The MoS2 nanosheets on the outer layer of the nitrogen-doped carbon tubes and the MoS2 particles wrapped inside can anchor polysulfides by chemisorption, slowing down the shuttle effect and enhancing the energy storage performance of lithium-sulfur batteries. The MoS2/NC/MoS2/S nanotubes (MoS2/NC/MoS2/S NTs) maintain a capacity of 498.9 mAh g−1 over 500 cycles at 1.0 A g−1, with an average single-cycle capacity decay rate of 0.061 %. The density functional theory calculations, the adsorption experiments, and the X-ray photoelectron spectroscopy results all confirm that the MoS2/NC/MoS2 NTs are able to anchor lithium polysulfides through strong adsorption, thus effectively mitigating the shuttle effect of polysulfides. The synthesis of MoS2/NC/MoS2/S NTs in this study is of important significance for the development of advanced lithium-sulfur batteries.

Constructing p-n heterojunction in CoO@TiO2 photocatalytic material to enhance the performance of catalytic degradation of Rhodamine B

Traditional Fenton reactions suffer from slow reaction rates and energy wastage degrade dye contaminant. By constructing a heterojunction interface between quantum dots and titanium dioxide, a CoO@TiO2 photocatalyst is prepared to extend the photoresponse range to longer wavelengths. Under infrared light irradiation, RhB is degraded by over 97 % after 120 min. CoO@TiO2 possesses a large surface area, loaded with a substantial amount of quantum dots, forming a p-n heterojunction, significantly enhancing the photocatalytic rate. This study provides a new approach for the efficient preparation of photocatalysts for the degradation of organic dye pollutants.

Progresses and Perspectives of Carbon-Free Metal Compounds-Modified Separators for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur batteries (LSBs) have the advantages of high theoretical specific capacity, excellent energy density, abundant elemental sulfur reserves. However, the LSBs is mainly limited by shuttling of lithium polysulfides (LiPSs), slow reaction kinetics of sulfur cathode. For solving the above problems, by developing high-performance battery separators, the reversible capacity, Coulombic efficiency (CE) and cycle life of LSBs can be effectively enhanced. Carbon-free based metal compounds are expected to be highly efficient separator modifiers for a new generation of high-performance LSBs by virtue of superior chemical adsorption capacity, strong catalytic properties and excellent lithophilicity to a certain extent. They can give play to the synergistic effect of their "adsorption-catalysis" sites to accelerate the redox kinetics of LiPSs, and their good lithophilicity can accelerate the Li+ transport kinetics, thus showing more remarkable electrochemical performances. However, a comprehensive summary of carbon-free metal compounds-modified separators for LSBs is still lacking. Here, this review systematically summarizes the researching progresses and performance characteristics of carbon-free-based metal compounds modified materials for separators of LSBs, and summarizes the corresponding mechanisms of using carbon-based separators to enhance the performance of LSBs. Finally, the review also looks forward to the prospects of LSBs using carbon-free metal compounds separators.

Hydrogen-bonded organic framework-sulfur composite for high performance lithium–sulfur batteries

With the rapid development of energy storage devices, lithium–sulfur batteries are considered as one of the promising candidates due to their high energy density (2600 Wh Kg−1) and low cost of sulfur. Despite these advantages, the application of lithium–sulfur batteries is limited by many issues, such as the shuttle effect of polysulfide and slow redox reactions. In this paper, hydrogen-bonded organic frameworks (HOFs) materials are chosen for the first time to improve the performance of sulfur cathodes by exploiting their unique properties. Thanks to the abundant hydrogen bond of HOFs materials, which can interact with lithium polysulfide, this S-HOF composite can inhibit the shuttle of polysulfide and enhance the transformation of polysulfide. As a result, the HOF-S composite has a high initial capacity of 1100 mAh g−1 at 0.1 C and 530 mAh g−1 at 1 C. In this paper, hydrogen-bonded organic frameworks (HOFs) materials are chosen for the first time to improve the performance of sulfur cathodes. In the S-HOF, abundant hydrogen bond sites can interact with lithium polysulfide to inhibit the shuttle of polysulfide and accelerate the redox conversion of polysulfide. Therefore, the S-HOF composite has higher capacity and cycle stability. The initial capacity of the S-HOF composite is 1100 mAh g–1 at 0.1 C and 530 mAh g–1 at 1 C.

Interface Engineering of VOx/Ni/Ni3N Heterostructures for Electrochemical Urea-Assisted Hydrogen Production.

Electrocatalytic hydrogen generation driven by renewable energy sources is severely limited by the slow oxygen evolution reaction (OER). Urea-assisted alkaline hydrogen production offers a perspective approach. However, the construction of efficient and robust anode catalysts is still challenging. Herein, an amorphous/crystalline VOx/Ni/Ni3N-heterostructured catalyst grown on carbon cloth was synthesized and used as a bifunctional electrocatalyst for the hydrogen evolution reaction (HER) and urea electrooxidation reaction (UOR). Benefiting from the electronic modification of intercomponents and abundant active sites, VOx/Ni/Ni3N exhibits an excellent electrochemical performance toward the HER and UOR. Theoretical calculations confirmed that the crystalline/amorphous VOx/Ni/Ni3N heterostructure has a suitable water dissociation energy and H* adsorption energy, thereby promoting the HER process. When the UOR and HER are integrated into an electrolytic device, VOx/Ni/Ni3N requires a potential of 1.40 V to achieve a current density of 10 mA cm-2.