High Areal Capacity Cation and Anionic Redox Solid-State Batteries Enabled by Transition Metal Sulfide Conversion.

Pure sulfur (S8 and Li2S) all solid-state batteries inherently suffer from low electronic conductivities, requiring the use of carbon additives, resulting in decreased active material loading at the expense of increased loading of the passive components. In this work, a transition metal sulfide in combination with lithium disulfide is employed as a dual cation-anion redox conversion composite cathode system. The transition metal sulfide undergoes cation redox, enhancing the electronic conductivity, whereas the lithium disulfide undergoes anion redox, enabling high-voltage redox conducive to achieving high energy densities. Carbon-free cathode composites with active material loadings above 6.0 mg cm-2 attaining areal capacities of ∼4 mAh cm-2 are demonstrated with the possibility to further increase the active mass loading above 10 mg cm-2 achieving cathode areal capacities above 6 mAh cm-2, albeit with less cycle stability. In addition, the effective partial transport and thermal properties of the composites are investigated to better understand FeS:Li2S cathode properties at the composite level. The work introduced here provides an alternative route and blueprint toward designing new dual conversion cathode systems, which can operate without carbon additives enabling higher active material loadings and areal capacities.

Research Progress in the Preparation of Transition Metal Sulfide Materials and Their Supercapacitor Performance.

Transition metal sulfides are widely used in supercapacitor electrode materials and exhibit excellent performance because of their rich variety, low price, and high theoretical specific capacity. At present, the main methods to prepare transition metal sulfides include the hydrothermal method and the electrochemical method. In order to further improve their electrochemical performance, two aspects can be addressed. Firstly, by controllable synthesis of nanomaterials, porous structures and large surface areas can be achieved, thereby improving ion transport efficiency. Secondly, by combining transition metal sulfides with other energy storage materials, such as carbon materials and metal oxides, the synergy between different materials can be fully utilized. However, future research still needs to address some challenges. In order to guide further in-depth research, it is necessary to combine the current research-derived knowledge and propose a direction for future development of transition metal sulfide electrode materials.

Fe7S8 coupled with VS4 heterogeneous interface engineering driven by FeV bimetallic MOFs: An efficient all-pH and durable hydrogen evolution.

Rational design and preparation of a multiphase electrocatalyst for hydrogen evolution reaction (HER) has become a hot research topic, while applicable and pH versatility of vanadium tetrasulfide (VS4) and heptairon octasulfide (Fe7S8) composites have rarely been reported. Here, the facile topological sulfide self-template sacrifice method using FeV bimetallic MOFs is designed to obtain Fe7S8 coupled with VS4 heterostructures, enhancing the electron precipitation in the catalysts and attracts electrons to migrate. According to DFT simulations, the electronic coupling at the atomic orbital level and the modulation of interfacial electrons among various interfaces play a crucial role in enhancing the intermediate state process of the hydrogen evolution reaction (HER) across the entire pH range, promoting the optimal d-band centroid value (εd). Reassuringly, the prepared 3D Fe7S8/VS4 electrodes possessed excellent performances of η10 = 53 mV, η10 = 135 mV and η10 = 38 mV in a conventional three-electrode configuration in a 1 M KOH, 1 M Na2SO4, and 0.5 M H2SO4, and the stabilized currents can all be maintained for 48 h. This innovative design of in situ heterostructured materials constructed from dual transition metal sulfides provides inspiring ideas for the preparation of all-pH catalysts.

Synergistic enhancement of Zn-air battery performance via integration of Ni-doped cobalt sulfide nanoparticles within N, S-doped carbon matrix.

Exploring precious metal-free bifunctional electrocatalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is essential for the practical application of rechargeable Zn-air battery (ZAB). Herein, Ni-doped Co9S8 nanoparticles embedded in a defect-rich N, S co-doped carbon matrix (d-NixCo9-xS8@NSC) are synthesized via a facile pyrolysis and acid treatment process. The introduction of abundant defects in both the carbon matrix and metal sulfide provides numerous active sites and significantly enhances the electrocatalytic performances for both the ORR and OER. d-NixCo9-xS8@NSC exhibits a superior half-wave potential of 0.841 V vs. RHE for the ORR and delivers a low overpotential of 0.329 V at 10 mA cm-2 for the OER. Additionally, Zn-air secondary battery using d-NixCo9-xS8@NSC as the air cathode displays a higher specific capacity of 734 mAh gZn-1 and a peak power density of 148.03 mW cm-2 compared to those of state-of-the-art Pt/C-RuO2 (673 mAh gZn-1 and 136.9 mW cm-2, respectively). These findings underscore the potential of d-NixCo9-xS8@NSC as a high-performance electrocatalyst for secondary ZABs, offering new perspectives on the design of efficient noble metal-free electrocatalysts for future energy storage and conversion applications.

A Class of Sodium Transition-Metal Sulfide Cathodes With Anion Redox.

Sodium-ion batteries (SIBs) are entering commercial relevance as a sustainable and low-cost alternative to lithium-ion batteries. Improving the energy density of SIBs is critical to enable their widespread adoption. Here, a new class of cathode materials Na6MS4 (M = Co, Mn, Fe, and Zn) that exhibit high charge-storage capacity is reported. Using Na6CoS4 as a prototypical example, a six-electron conversion reaction dominated by anion redox is observed, confirmed through various electrochemical and spectroscopic techniques. After the initial cycle, Na6CoS4 delivers a high capacity of 392 mA h g-1 with a long lifespan of over 500 cycles. The reaction involves, initially, the transformation of crystalline Na6CoS4 to a nearly amorphous structure consisting of mainly CoS and sulfur nanoparticles, which then reversibly cycles between nearly amorphous a-CoS/S and a-Na6CoS4. Such anion-redox-driven conversion-type cathodes hold the potential to enable energy-dense, stable SIBs.

Tungsten sulfide highly boosted Fe(III)/peroxymonosulfate system for rapid degradation of cyclohexanecarboxylic acid: Performance, mechanisms, and applications.

In this study, the Fe(III)/WS2/peroxymonosulfate (PMS) system was found to remove up to 97% of cyclohexanecarboxylic acid (CHA) within 10 min. CHA is a model compound for naphthenic acids (NAs), which are prevalent in petroleum industrial wastewater. The addition of WS2 effectively activated the Fe(III)/PMS system, significantly enhancing its ability to produce reactive oxidative species (ROS) for the oxidation of CHA. Further experimental results and characterization analyses demonstrated that the metallic element W(IV) in WS2 could provide electrons for the direct reduction of Fe(III) to Fe(II), thus rapidly activating PMS and initiating a chain redox process to produce ROS (SO4•-, •OH, and 1O2). Repeated tests and practical exploratory experiments indicated that WS2 exhibited excellent catalytic performance, reusability and anti-interference capacity, achieving efficient degradation of commercial NAs mixtures. Therefore, applying WS2 to catalyze the Fe(III)/PMS system can overcome speed limitations and facilitate simple, economical engineering applications.

Synergistic dual built-in electric fields in 1T-MoS2/Ni3S2/LDH for efficient electrocatalytic overall water splitting reactions.

Designing cost-effective electrocatalysts for water decomposition is crucial for achieving environmental-friendly hydrogen production. A transition metal sulfide/hydroxide electrocatalyst (1T-MoS2/Ni3S2/LDH) with double heterogeneous interfaces was developed through a two-step hydrothermal assisted electrodeposition method. The presence of the two built-in electric fields not only accelerated the charge transfer at the interface, but also enhanced the adsorption of the reactants and intermediate groups, and therefore improved the reaction rate and overall catalytic performance. The results suggest that the 1T-MoS2/Ni3S2/LDH catalysts display exceptional electrocatalytic reactivity. Under alkaline conditions, the overpotential of the electrocatalyst was 187 (η50) mV for OER and 104 (η10) mV for HER. Furthermore, the two-electrode system assembled by the electrocatalyst needs only a voltage of 1.55 V to deliver a current density of 10 mA cm-2. Our result provides a simple and effective methodical approach to the design of dual heterogeneous interfacial electrocatalysts.

Hybrid supercapacitors using metal-organic framework derived nickel-sulfur compounds.

HYPOTHESIS: Metal-organic frameworks (MOFs) are highly suitable precursors for supercapacitor electrode materials owing to their high porosity and stable backbone structures that offer several advantages for redox reactions and rapid ion transport. EXPERIMENTS: In this study, a carbon-coated Ni9S8 composite (Ni9S8@C-5) was prepared via sulfuration at 500 ℃ using a spherical Ni-MOF as the sacrificial template. FINDING: The stable carbon skeleton derived from Ni-MOF and positive structure-activity relationship due to the multinuclear Ni9S8 components resulted in a specific capacity of 278.06 mAh·g-1 at 1 A·g-1. Additionally, the hybrid supercapacitor (HSC) constructed using Ni9S8@C-5 as the positive electrode and the laboratory-prepared coal pitch-based activated carbon (CTP-AC) as the negative electrode achieved an energy density of 69.32 Wh·kg-1 at a power density of 800.06 W·kg-1, and capacity retention of 83.06 % after 5000 cycles of charging and discharging at 5 A·g-1. The Ni-MOF sacrificial template method proposed in this study effectively addresses the challenges associated with structural collapse and agglomeration of Ni9S8 during electrochemical reactions, thus improving its electrochemical performance. Hence, a simple preparation method is demonstrated, with broad application prospects in supercapacitor electrodes.

Effects of Lithium Halides on Electrode-Electrolyte Bifunctional Materials for High-Capacity All-Solid-State Batteries.

All-solid-state batteries have attracted attention because of their high energy density, safety, and long cycle life. Sulfide active materials exhibit high capacities and enable an enhanced energy density in all-solid-state batteries. In this study, we synthesized electrode-electrolyte bifunctional materials in the system Li2S-V2S3-LiX (X = F, Cl, Br, or I) through a mechanochemical process. In addition, the effects of the addition of lithium halides on the electrochemical properties were investigated. All-solid-state batteries with the Li2S-V2S3-LiI electrode showed the highest capacity of 400 mAh g-1 among all the cells, even though their electronic and ionic conductivities were the same. From the point of view of the ionic conductivity and structure of the electrodes during cycling, it was clarified that a high reversible capacity was achieved not only by high ionic and electronic conductivities before cycling but also by maintaining the ionic conductivity even at the deep state of charge. Furthermore, high-loading all-solid-state cells were fabricated using the Li2S-V2S3-LiI materials with a mass loading of 37.3 mg cm-2, exhibiting a high areal capacity of approximately 11.5 mAh cm-2 at 60 °C and good cycle performance.

Catalytic chemistry inspired hollow carbon nanofibers loaded with NiS/Ni as high-performance and safe Li+ reservoir.

Transition metal sulfides (TMSs) based anodes hold a very broad application prospect in lithium ion batteries (LIBs). In this work, the catalytic effect of metallic nickel at high temperature was used to generate hollow carbon nanofibers loaded with NiS and Ni (denoted as NiS/Ni@HCNF). The heteroatoms doped carbon fibers buffer the huge volumetric change of NiS during the discharge/charge process, and enhance the ion transport efficiency and electrical conductivity. In addition, the high specific surface area brought by the hollow carbon nanofibers can accelerate the electrolyte penetration and speed up the transport of ions as well as electrons. When used as anode of half cell, this electrode gives 958.5 and 612.9 mAh/g after running 1000 cycles under 1 and 2 A/g, showing the extremely-low attenuation rates of 0.0483 % per cycle and 0.0643 % per cycle, respectively. Impressively, NCM//NiS/Ni@HCNF battery shows the discharge capacity of 187.6 mAh/g at 1st cycle. Regarding the next 100 cycles, the relatively-high discharge capacities (>110 mAh/g) and coulombic efficiency (CE) values (>96 %) are discerned. It is noted that the usage of NiS/Ni@HCNF electrode improves the activation energy for thermal runaway, corroborating the elevated thermal safety of battery.

Composite of CoS1.97 nanoparticles decorated CuS hollow cubes with rGO as thin film electrode for high-performance all solid flexible supercapacitors.

Stretchable flexible thin-film electrodes are extensively explored for developing new wearable energy storage devices. However, traditional carbon-based materials used in such independent electrodes have limited practical applications owing to their low energy storage capacity and energy density. To address this, a unique structure and remarkable mechanical stability thin-film flexible positive electrode comprising CoS1.97 nanoparticles decorated hollow CuS cubes and reduced graphene oxide (rGO), hereinafter referred to as CCSrGO, is prepared. Transition metal sulfide CoS1.97 and CuS shows high energy density owing to the synergistic effects of its active components. The electrode can simultaneously meet the high-energy density and safety requirements of new wearable energy storage devices. The electrode has excellent electrochemical performance (1380 F/g at 1 A/g) and ideal capacitance retention (93.8 % after 10,000 cycles) owing to its unique three-dimensional hollow structure and polymetallic synergies between copper and cobalt elements, which are attributed to their different energy storage mechanisms. Furthermore, a flexible asymmetric supercapacitor (FASC) was constructed using CCSrGO as the positive electrode and rGO as the negative electrode (CCSrGO//rGO), which delivers an energy density of 100 Wh kg-1 and a corresponding power density of 2663 W kg-1 within a voltage window of 0-1.5 V. The resulting FASC can power a light-emitting diode (LED) at different bending and twisting angles, exerting little effect on the capacitance. Therefore, the prepared CCSrGO//rGO FASC devices show great application prospects in energy storage.

Strong Carbon Layer-Encapsulated Cobalt Tin Sulfide-Based Nanoporous Material as a Bifunctional Electrocatalyst for Zinc-Air Batteries.

Global demands for cost-effective, durable, highly active, and bifunctional catalysts for metal-air batteries are tremendously increasing in scientific research fields. In this work, a strategy for the rational fabrication of carbon layer-encapsulated cobalt tin sulfide nanopores (CoSnOH/S@C NPs) material as a bifunctional electrocatalyst for rechargeable zinc (Zn)-air batteries by a cost-effective and facile two-step hydrothermal method is reported. Moreover, the effect of metal elements on the morphology of CoSnOH nanodisks material via the hydrothermal method is investigated. Owing to its excellent nanostructure, exclusive porous network, and high specific surface area, the optimized CoSnOH/S@C NPs material reveals superior catalytic properties. The as-prepared CoSnOH/S@C NPs electrocatalyst reveals better properties of oxygen reduction reaction (half-wave potential of -0.88 V vs reversible hydrogen electrode) and oxygen evolution reaction (overpotential of 137 mV at 10 mA cm-2) when compared with commercial Pt/C and IrO2 catalyst materials. Most significantly, the CoSnO/S@C NPs-based Zn-air battery exhibits more excellent cycling stability than the Pt/C+IrO2 catalyst-based one. Consequently, the proposed material provides a new route for fabricating more active and stable multifunctional catalyst materials for energy conversion and storage systems.

Effect of in-plane Mott-Schottky on the hydroxyl deprotonation in MoS2@Co3S4/NC heterostructure for efficient overall water splitting.

The development of clean energy sources such as hydrogen is indispensable for achieving the long-term goal of carbon neutrality by the mid-century. The utilization of renewable energy for power generation to electrolyze water for hydrogen production is one of the most desirable green hydrogen production methods. The cathode side of the decomposing water undergoes the oxygen precipitation reaction, and the oxygen precipitation mechanism can be divided into the adsorbed evolution mechanism (AEM) and lattice oxygen oxidation mechanism (LOM). Based on the adsorbed evolution mechanism (AEM), the deprotonation (DeP) process involving multiple electron transfers is central to determining the oxygen release. DeP is essentially a proton-transfer process that allows for the establishment of a bifunctional catalyst system with both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Consequently, an all-transition-metal-based MoS2@Co3S4/NC heterostructure was designed and constructed in this study for the efficient total decomposition of water. The MoS2@Co3S4/NC catalyst achieved the HER and OER current densities of 10 mA cm-2 at the low overpotential (56 mV, 243 mV) and showed excellent long-term durability among all samples. The Mott-Schottky effect is considered the driving force for the HER and DeP in the OER. This study proposes a rational design for bifunctionalized non-precious metal electrolytic water catalysts using the Mott-Schottky effect as a criterion.

Preparation of Cu7.2S4@N, S co-doped carbon honeycomb-like composite structure for high-rate and high-stability sodium-ion storage.

Sodium ion batteries (SIBs) attract most of the attention as alterative secondary battery systems for future large-scale energy storage and power batteries due to abundance resource and low cost. However, the lack of anode materials with high-rate performance and high cycling-stability has limited the commercial application of SIBs. In this paper, Cu7.2S4@N, S co-doped carbon (Cu7.2S4@NSC) honeycomb-like composite structure was designed and prepared by a one-step high-temperature chemical blowing process. As an anode material for SIBs, Cu7.2S4@NSC electrode exhibited an ultra-high initial Coulomb efficiency (94.9%) and an excellent electrochemical property including a high reversible capacity of 441.3 mAh g-1 after 100 cycles at 0.2 A g-1, an excellent rate performance of 380.4 mAh g-1 even at 5 A g-1, and a superior long-cycle stability with a capacity retention rate of approximately 100% after 700 cycles at 1A g-1.

A Review of Transition Metal Sulfides as Counter Electrodes for Dye-Sensitized and Quantum Dot-Sensitized Solar Cells.

Third-generation solar cells, including dye-sensitized solar cells (DSSCs) and quantum dot-sensitized solar cells (QDSSCs), have been associated with low-cost material requirements, simple fabrication processes, and mechanical robustness. Hence, counter electrodes (CEs) are a critical component for the functionality of these solar cells. Although platinum (Pt)-based CEs have been dominant in CE fabrication, they are costly and have limited market availability. Therefore, it is important to find alternative materials to overcome these issues. Transition metal chalcogenides (TMCs) and transition metal dichalcogenides (TMDs) have demonstrated capabilities as a more cost-effective alternative to Pt materials. This advantage has been attributed to their strong electrocatalytic activity, excellent thermal stability, tunability of bandgap energies, and variable crystalline morphologies. In this study, a comprehensive review of the major components and working principles of the DSSC and QDSSC are presented. In developing CEs for DSSCs and QDSSCs, various TMS materials synthesized through several techniques are thoroughly reviewed. The performance efficiencies of DSSCs and QDSSCs resulting from TMS-based CEs are subjected to in-depth comparative analysis with Pt-based CEs. Thus, the power conversion efficiency (PCE), fill factor (FF), short circuit current density (Jsc) and open circuit voltage (Voc) are investigated. Based on this review, the PCEs for DSSCs and QDSSCs are found to range from 5.37 to 9.80% (I-/I3- redox couple electrolyte) and 1.62 to 6.70% (S-2/Sx- electrolyte). This review seeks to navigate the future direction of TMS-based CEs towards the performance efficiency improvement of DSSCs and QDSSCs in the most cost-effective and environmentally friendly manner.

Designing of trimetallic-phase ternary metal sulfides coupled with N/S doped carbon protector for superior and safe Li/Na storage.

Traditional transition metal sulfides (TMSs) have shown favorable potentials in energy storage. Nevertheless, its further usage is plagued by the issues of particle breakage and large volume change. In this work, the nanostructured ternary TMSs coupled with N/S doped carbon protector (NiCoFe-S@NSC) is delicately designed via compositional regulation and spatial structure protection strategies. As lithium ion batteries anode, this electrode gives an impressive capacity of 995.7 mAh/g after running 1000 cycles at 1 A/g. More importantly, NiCoFe-S@NSC electrode still shows a discharge capacity of 221.94 mAh/g after running 20,000 cycles at 10 A/g, reflecting an extremely-low capacity decay rate of 0.0377 ‰ per cycle. As sodium ion batteries anode, a high initial discharge capacity of 896.4 mA h g-1 can be found. Even after running 400 cycles at 5 A/g, the electrode still displays a reversible capacity of 334.5 mAh/g with outstanding coulombic efficiency above 98.0 %. Impressively, LiNixCoyMn1-x-yO2//NiCoFe-S@NSC full cell gives incipient discharge/charge capacities of 186.89/240.18 mAh/g. Moreover, the discharge capacities for the following 100 cycles remain above 150 mAh/g. Thermal runaway tests also demonstrate the higher thermal safety of cells with NiCoFe-S@NSC electrode, accompanying with the promoted activation energy.

Activity and mechanism of vanadium sulfide for organic contaminants oxidation with peroxymonosulfate.

Transition metal sulfides have been demonstrated to be effective for peroxymonosulfate (PMS) activation towards wastewater treatment. However, the activity of vanadium sulfide (VS4) and the role of the chemical state of V have not been revealed. Here, three types of VS4 with various morphologies and chemical states of V were synthesized by using methanol (M-VS4, nanosphere composed of nanosheets), ethanol (E-VS4, sea urchin like nanosphere) and ultrapure water (U-VS4, compact nanosphere) as hydrothermal solvent, respectively, and used as heterogeneous catalysts to activate PMS for the degradation of refractory organic pollutants. The effects of PMS concentration, temperature, pH, inorganic ions, and humic acid (HA) on the degradation efficiency of VS4/PMS system were investigated systematically. The results indicated that the highest specific surface area and lowest ratio of V5+ enable E-VS4/PMS system possessed the highest performance in degrading tetracycline hydrochloride (TCH), in which 100% TCH was removed after operating 10 min (0.805 min-1) under a relatively low concentration of PMS (1 mM) and catalyst (100 mg/L). It also revealed that the system exhibited a typical radical process in TCH degradation, which could be attributed to the redox cycles between V5+, V4+ and V3+ in the presence of PMS to generate various radicals. This radical process enabled the E-VS4/PMS system with a high activity in wide reaction conditions and high mineralization ratios in degrading various refractory organic pollutants within 10 min. In addition, the E-VS4/PMS system exhibited favorable reusability and stability with very less V and S ions leaching, and showed excellent performance in real water purification.

Interface Engineering on Amorphous/Crystalline Hydroxides/Sulfides Heterostructure Nanoarrays for Enhanced Solar Water Splitting.

Developing highly efficient and stable noble-metal-free electrocatalysts for water splitting is critical for producing clean and sustainable energy. Here, we design a hierarchical transition metal hydroxide/sulfide (NiFe(OH)x-Ni3S2/NF) electrode with dual heterointerface coexistence using a cation exchange-induced surface reconfiguration strategy. The electrode exhibits superior electrocatalytic activities, achieving low overpotentials of 55 mV for hydrogen evolution and 182 mV for oxygen evolution at 10 mA cm-2. Furthermore, the assembled two-electrode system requires voltages as low as 1.55 and 1.62 V to deliver industrially relevant current densities of 500 and 1000 mA cm-2, respectively, with excellent durability for over 200 h, which is comparable to commercial electrolysis. Theoretical calculations reveal that the hierarchical heterostructure increases the electronic delocalization of the Fe and Ni catalytic centers, lowering the energy barrier of the rate-limiting step and promoting O2 desorption. Finally, by implementing the catalysts in a solar-driven water electrolysis system, we demonstrate a record and durable solar-to-hydrogen (STH) conversion efficiency of up to 20.05%. This work provides a promising strategy for developing low-cost and high-efficiency bifunctional catalysts for a large-scale solar-to-hydrogen generation.

Sensitive fluorescent detection and micromechanism of Mn-doped CuS probe for oxytetracycline hydrochloride.

The novel CuMnS nanoflower fluorescent probe based on Mn-doped CuS was developed to achieve the fluorescence detection of oxytetracycline hydrochloride (OTC), the fluorescent sensor has good selectivity and stability. The doping of Mn significantly increased the fluorescence intensity of CuS, which was above 10 times that of CuS. When the predominant species of OTC molecule was zwitterionic OTC+/-at the solution pH of about 5.00, the fluorescence quenching efficiency of CuMnS by OTC reached the highest. Through fluorescence lifetime and UV absorption, the sensing mechanism between CuMnS and OTC was found to be static quenching. Moreover, Multiwfn wavefunction analysis program based on density function theory (DFT) calculation was applied to compare the interactions between different OTC species and CuMnS at different pH, to reveal the micromechanism of fluorescence quenching of CuMnS by OTC from the views of atoms. The molecular surface quantitative analysis and basin analysis of different OTC species demonstrated that the N atom and O atoms of tricarbonylamide moiety of zwitterionic OTC+/- can provide lone pair electrons to form a non-fluorescent ground state complex with CuMnS. Meanwhile, the electrostatic attraction of OTC+/- with negatively charged CuMnS was also beneficial to the interaction, resulting in the effective fluorescence quenching of CuMnS. This work offers a convenient method for sensitively detecting OTC and broadens the application of CuMnS in the field of fluorescence detection.

Designing nitrogen-enriched heterogeneous NiS@CoNi2S4 embedded in nitrogen-doped carbon with hierarchical 2D/3D nanocage structure for efficient alkaline hydrogen evolution and triiodide reduction.

Fabrication of efficient non-precious electrocatalysts with hierarchical nanostructures and the desired compositions is highly desirable to enhance the catalytic activity and stability for hydrogen evolution reaction (HER) and triiodide reduction reaction (IRR). This work proposes a zeolitic imidazolate framework (ZIF) template-based strategy to generate sulfide embedded in nitrogen-doped carbon with a hierarchical 2D/3D nanocage structure. ZIF-67, as a sacrificial template, is first etched to form 2D/3D NiCo layered double hydroxide/2-Methylimidazole (NiCo LDH/MeIm) and then converted to CoNi2S4 nanoparticles embedded in nitrogen-doped carbon (CoNi2S4/NC) through one-step sulfurization and pyrolysis. When a core-shell ZIF-8@ZIF-67 is designed as a template for the generation of Ni@NiCo LDH/MeIm, the obtained NiS@CoNi2S4/NC not only retains the unique 2D/3D nanostructure but also has a high N content, abundant active sites, larger specific surface area, and hierarchical pore distribution. NiS@CoNi2S4/NC mediates an overpotential of 126 mV at 10 mA cm-2 and a Tafel slope of 47.2 mV dec-1 in the alkaline HER. The solar cell equipped with NiS@CoNi2S4/NC as the IRR catalyst achieves a high cell efficiency of 7.96 %. NiS@CoNi2S4/NC shows durably high HER and IRR activity. This controllable synthetic strategy provides a valuable support for developing efficient catalysts in electrocatalytic energy conversion systems.