Ultrafast-Loaded Nickel Sulfide on Vertical Graphene Enabled by Joule Heating for Enhanced Lithium Metal Batteries.

The design and fabrication of a lithiophilic skeleton are highly important for constructing advanced Li metal anodes. In this work, a new lithiophilic skeleton is reported by planting metal sulfides (e.g., Ni3S2) on vertical graphene (VG) via a facile ultrafast Joule heating (UJH) method, which facilitates the homogeneous distribution of lithiophilic sites on carbon cloth (CC) supported VG substrate with firm bonding. Ni3S2 nanoparticles are homogeneously anchored on the optimized skeleton as CC/VG@Ni3S2, which ensures high conductivity and uniform deposition of Li metal with non-dendrites. By means of systematic electrochemical characterizations, the symmetric cells coupled with CC/VG@Ni3S2 deliver a steady long-term cycle within 14 mV overpotential for 1800 h (900 cycles) at 1 mA cm-2 and 1 mAh cm-2. Meanwhile, the designed CC/VG@Ni3S2-Li||LFP full cell shows notable electrochemical performance with a capacity retention of 92.44% at 0.5 C after 500 cycles and exceptional rate performance. This novel synthesis strategy for metal sulfides on hierarchical carbon-based materials sheds new light on the development of high-performance lithium metal batteries (LMBs).

Two Birds with One Stone: Contemporaneously Enhancing OER Catalytic Activity and Stability for Dual-Phase Medium-Entropy Metal Sulfides.

Transition metal-based sulfides exhibit remarkable potential as electrocatalysts for oxygen evolution reaction (OER) due to the unique intrinsic structure and physicochemical characteristics. Nevertheless, currently available sulfide catalysts based on transition metals face a bottleneck in large-scale commercial applications owing to their unsatisfactory stability. Here, the first fabrication of (FeCoNiMn2 )S2 dual-phase medium-entropy metal sulfide (dp-MEMS) is successfully achieved, which demonstrated the expected optimization of stability in the OER process. Benefiting from the "cell wall" -like structure and the synergistic effect in medium-entropy systems, (FeCoNiMn2 )S2 dp-MEMS delivers an exceptionally low overpotential of 169 and 232 mV at current densities of 10 and 100 mA cm-2 , respectively. The enhancement mechanism of catalytic activity and stability is further validated by density functional theory (DFT) calculations. Additionally, the rechargeable Zn-air batteries integrated with FeCoNiMn2 )S2 dp-MEMS exhibit remarkable performance outperforming the commercial catalyst (Pt/C+RuO2 ). This work demonstrates that the dual-phase medium-entropy metal sulfide-based catalysts have the potential to provide a greater application value for OER and related energy conversion systems.

Metal-Organic Framework Templated Z-Scheme ZnIn2S4/Bi2S3 Hierarchical Heterojunction for Photocatalytic H2O2 Production from Wastewater.

Metal-organic framework derived materials received a lot of attention due to their significant benefits in photocatalytic reactions. In this work, a Z-scheme ZnIn2S4/Bi2S3 hierarchical heterojunction is first developed by a one-pot method using CAU-17 as a template. The specific preparation method endows an intimate interface contact between these two monomers, and CAU-17-derived Bi2S3 possesses a high surface area and porosity, resulting in an efficient charge separation and O2 capture. Thus, for photocatalytic H2O2 production from the O2 reduction reaction, the ZnIn2S4/Bi2S3 heterojunction can achieve an H2O2 yield of 995 µmol L-1 in pure water and ambient air under visible light, 4.5 and 4 times that of ZnIn2S4 and Bi2S3, respectively. In addition, in tetracycline solution, ZnIn2S4/Bi2S3 can degrade tetracycline with a degradation rate of 95% by photocatalysis, and at the same time, a final H2O2 production yield of 1223 µmol L-1 is reached. Similarly, high yields of H2O2 are also obtained from wastewater containing o-nitrophenol, acid golden yellow, or acid red, and these pollutants are effectively degraded. This work reveals the potential of metal-organic framework-derived materials in photocatalysis, as well as provides insights into H2O2 green synthesis and wastewater treatment.

Recycling the Spent LiNi1- x - yMnxCoyO2 Cathodes for High-Performance Electrocatalysts toward Both the Oxygen Catalytic and Methanol Oxidation Reactions.

The traditional recycling methods of the spent lithium ion batteries (LIBs) involve the intricate and cumbersome steps. This work proposes a facile method of acid leaching followed by the sulfurization treatment to achieve the high Li leaching efficiency, and obtain high-performance multi-function electrocatalysts for oxygen reduction (ORR), oxygen evolution (OER), and methanol oxidation reactions (MOR) from the spent LIB ternary cathodes. By this method, the Li leaching efficiency from the spent LIB ternary cathode can reach 98.3%, and the transition metal sulfide heterostructures (LNMCO-H-450S) consisting MnS, NiS2, and NiCo2S4 phases can be obtained. LNMCO-H-450S shows the superior bifunctional oxygen catalytic activities with ORR half-wave potential of 0.763 V and OER potential at 10 mA cm-2 of 1.561 V, surpassing most of the state-of-the-art electrocatalysts. LNMCO-H-450S also demonstrates the superior MOR catalytic activity with the potential at 100 mA cm-2 being 1.37 V. Using LNMCO-H-450S as the oxygen catalyst, this work can construct the aqueous and solid-state zinc-air batteries with high power density of 309 and 257 mW cm-2, respectively. This work provides a promising strategy for the efficient recovery of Li, and reutilization of Ni, Co, and Mn from the spent LIB ternary cathodes.

Interfacial Chemistry and Catalysis of Inorganic Materials.

Heterogeneous catalysis is essential to most industrial chemical processes. To achieve a better sustainability of these processes we need highly efficient and highly selective catalysts that are based on earth-abundant materials rather than the more conventional noble metals. Here, we discuss the potential of inorganic materials as catalysts for chemical transformations focusing in particular on the promising transition metal phosphides and sulfides. We describe our recent and current efforts to understand the interfacial chemistry of these materials that governs catalysis, and to tune catalytic reactivity by controlled chemical modification of the material surfaces and by use of interfacial electric fields.

Activating and Identifying the Active Site of RuS2 for Alkaline Hydrogen Oxidation Electrocatalysis.

Searching for highly efficient and economical electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is crucial for the development of alkaline polymer membrane fuel cells. Here, we report a valid strategy to active pyrite-type RuS2 for alkaline HOR electrocatalysis by introducing sulfur vacancies. The obtained S-vacancies modified RuS2-x exhibits outperformed HOR activity with a current density of 0.676 mA cm-2 and mass activity of 1.43 mA µg-1, which are 15-fold and 40-fold improvement than those of Ru catalyst. In situ Raman spectra demonstrate the formation of S-H bond during the HOR process, identifying the S atom of RuS2-x is the real active site for HOR catalysis. Density functional theory calculations and experimental results including in situ surface-enhanced infrared absorption spectroscopy suggest the introduction of S vacancies can rationally modify the p orbital of S atoms, leading to enhanced binding strength between the S sites and H atoms on the surface of RuS2-x, together with the promoted connectivity of hydrogen-bonding network and lowered water formation energy, contributes to the enhanced HOR performance.

Construction of Core-shell Sb2 s3 @Cds Nanorod with Enhanced Heterointerface Interaction for Chromium-Containing Wastewater Treatment.

How to collaboratively reduce Cr(VI) and break Cr(III) complexes is a technical challenge to solve chromium-containing wastewater (CCW) pollution. Solar photovoltaic (SPV) technology based on semiconductor materials is a potential strategy to solve this issue. Sb2 S3 is a typical semiconductor material with total visible-light harvesting capacity, but its large-sized structure highly aggravates disordered photoexciton migration, accelerating the recombination kinetics and resulting low-efficient photon utilization. Herein, the uniform mesoporous CdS shell is in situ formed on the surface of Sb2 S3 nanorods (NRs) to construct the core-shell Sb2 S3 @CdS heterojunction with high BET surface area and excellent near-infrared light harvesting capacity via a surface cationic displacement strategy, and density functional theory thermodynamically explains the breaking of SbS bonds and formation of CdS bonds according to the bond energy calculation. The SbSCd bonding interaction and van der Waals force significantly enhance the stability and synergy of Sb2 S3 /CdS heterointerface throughout the entire surface of Sb2 S3 NRs, promoting the Sb2 S3 -to-CdS electron transfer due to the formation of built-in electric field. Therefore, the optimized Sb2 S3 @CdS catalyst achieves highly enhanced simulated sunlight-driven Cr(VI) reduction (0.154 min-1 ) and decomplexation of complexed Cr(III) in weakly acidic condition, resulting effective CCW treatment under co-action of photoexcited electrons and active radicals. This study provides a high-performance heterostructured catalyst for effective CCW treatment by SPV technology.

Implanting CuS Quantum Dots into Carbon Nanorods for Efficient Magnesium-Ion Batteries.

Magnesium-ion batteries (MIBs) are emerging as potential next-generation energy storage systems due to high security and high theoretical energy density. Nevertheless, the development of MIBs is limited by the lack of cathode materials with high specific capacity and cyclic stability. Currently, transition metal sulfides are considered as a promising class of cathode materials for advanced MIBs. Herein, a template-based strategy is proposed to successfully fabricate metal-organic framework-derived in-situ porous carbon nanorod-encapsulated CuS quantum dots (CuS-QD@C nanorods) via a two-step method of sulfurization and cation exchange. CuS quantum dots have abundant electrochemically active sites, which facilitate the contact between the electrode and the electrolyte. In addition, the tight combination of CuS quantum dots and porous carbon nanorods increases the electronic conductivity while accelerating the transport speed of ions and electrons. With these architectural and compositional advantages, when used as a cathode material for MIBs, the CuS-QD@C nanorods exhibit remarkable performance in magnesium storage, including a high reversible capacity of 323.7 mAh g-1 at 100 mA g-1 after 100 cycles, excellent long-term cycling stability (98.5 mAh g-1 after 1000 cycles at 1.0 A g-1 ), and satisfying rate performance (111.8 mA g-1 at 1.0 A g-1 ).

Long-Cycling-Life Sodium-Ion Battery Using Binary Metal Sulfide Hybrid Nanocages as Anode.

Due to the relatively high capacity and lower cost, transition metal sulfides (TMS) as anode show promising potential in sodium-ion batteries (SIBs). Herein, a binary metal sulfide hybrid consisting of carbon encapsulated CoS/Cu2 S nanocages (CoS/Cu2 S@C-NC) is constructed. The interlocked hetero-architecture filled with conductive carbon accelerates the Na+ /e- transfer, thus leading to improved electrochemical kinetics. Also the protective carbon layer can provide better volume accommondation upon charging/discharging. As a result, the battery with CoS/Cu2 S@C-NC as anode displays a high capacity of 435.3 mAh g-1 after 1000 cycles at 2.0 A g-1 (≈3.4 C). Under a higher rate of 10.0 A g-1 (≈17 C), a capacity of as high as 347.2 mAh g-1 is still remained after long 2300 cycles. The capacity decay per cycle is only 0.017%. The battery also exhibits a better temperature tolerance at 50 and -5 °C. A low internal impedance analyzed by X-ray diffraction patterns and galvanostatic intermittent titration technique, narrow band gap, and high density of states obtained by first-principle calculations of the binary sulfides, ensure the rapid Na+ /e- transport. The long-cycling-life SIB using binary metal sulfide hybrid nanocages as anode shows promising applications in versatile electronic devices.

Binary Metallic CuCo5 S8 Anode for High Volumetric Sodium-Ion Storage.

With the rapid improvement of compact smart devices, fabricating anode materials with high volumetric capacity has gained substantial interest for future sodium-ion batteries (SIBs) applications. Herein, a novel bimetal sulfide CuCo5 S8 material is proposed with enhanced volumetric capacity due to the intrinsic metallic electronic conductivity of the material and multi-electron transfer during electrochemical procedures. Due to the intrinsic metallic behavior, the conducting additive (CA) could be removed from the electrode fabrication without scarifying the high rate capability. The CA-free CuCo5 S8 electrode can achieve a high volumetric capacity of 1436.4 mA h cm-3 at a current density of 0.2 A g-1 and 100 % capacity retention over 2000 cycles in SIBs, outperforming most metal chalcogenides, owing to the enhanced electrode density. Reversible conversion reactions are revealed by combined measurements for sodium systems. The proposed new strategy offers a viable approach for developing innovative anode materials with high-volumetric capacity.

Waxberry-Like MnS/Ni3 S4 as High-Efficiency Bi-Functional Catalyst for Zn-Air Batteries.

In this paper, a waxberry-like MnS/Ni3 S4 composite catalyst was designed and synthesized. In this coating structure, MnS is located inside and Ni3 S4 is wrapped on the surface to form a spherical structure. This structure makes the material show excellent stability in the electrocatalytic process. The diffusion staggered region structure formed at the two-phase interface greatly enhances the synergistic interaction between MnS and Ni3 S4 . At the same time, the defects and vacancies formed by the diffusion mechanism at the interface of the two phases increase the active site and improve the interfacial electron transfer kinetics. Therefore, MnS/Ni3 S4 composites showed good catalytic performance for ORR/OER. At 10 mA cm-2 , the overpotential of it is only 320 mV, and the half-wave potential can reach 0.81 V. The catalyst also exhibited extraordinary cycle stability and small voltage gap when used as cathode of Zn-air batteries. When the current density is 3 mA cm-2 , the cyclic discharge can be stable for 400 h and the voltage difference between the front and back does not increase more than. When the current density increases to 5 mA cm-2 , the cyclic charge and discharge can be stable for more than 300 h.

Asymmetric supercapacitors based on SnNiCoS ternary metal sulfide electrodes.

While metal sulfides have extensively investigated as electrode materials for supercapacitors, the further optimization of their material system is still necessary to achieve satisfied performance. In this work, we reported the synthesis of ternary metal sulfide SnNiCoS and its application as electrode material of asymmetric supercapacitors, in which active carbon is used as the other electrode. For control experiments, asymmetric supercapacitors based on single metal sulfide CoS and binary metal sulfide NiCoS are also fabricated and investigated. The results show that the nanospherical SnNiCoS achieves the best performance. Ternary sulphide materials offer more redox than corresponding single-metal sulphides due to the synergy among various transition metal elements. The specific capacitance is 18.6 F cm-2at current density of 5 mA·cm-2. An energy density of 937.2µWh cm-2is achieved at a power density of 4000µW·cm-2. After 8000 cycles, the capacity retention rate is 82.9%. Present work indicates that SnNiCoS ternary metal sulfide could be a promising composite for high performance supercapacitors.

ZnS/CoS@C Derived from ZIF-8/67 Rhombohedral Dodecahedron Dispersed on Graphene as High-Performance Anode for Sodium-Ion Batteries.

Metal sulfides are highly promising anode materials for sodium-ion batteries due to their high theoretical capacity and ease of designing morphology and structure. In this study, a metal-organic framework (ZIF-8/67 dodecahedron) was used as a precursor due to its large specific surface area, adjustable pore structure, morphology, composition, and multiple active sites in electrochemical reactions. The ZIF-8/67/GO was synthesized using a water bath method by introducing graphene; the dispersibility of ZIF-8/67 was improved, the conductivity increased, and the volume expansion phenomenon that occurs during the electrochemical deintercalation of sodium was prevented. Furthermore, vulcanization was carried out to obtain ZnS/CoS@C/rGO composite materials, which were tested for their electrochemical properties. The results showed that the ZnS/CoS@C/rGO composite was successfully synthesized, with dodecahedrons dispersed in large graphene layers. It maintained a capacity of 414.8 mAh g-1 after cycling at a current density of 200 mA g-1 for 70 times, exhibiting stable rate performance with a reversible capacity of 308.0 mAh g-1 at a high current of 2 A g-1. The excellent rate performance of the composite is attributed to its partial pseudocapacitive contribution. The calculation of the diffusion coefficient of Na+ indicates that the rapid sodium ion migration rate of this composite material is also one of the reasons for its excellent performance. This study highlights the broad application prospects of metal-organic framework-derived metal sulfides as anode materials for sodium-ion batteries.

Synthesis of Bandgap-tunable Transition Metal Sulfides through Gas-phase Cation Exchange-induced Topological Transformation.

Oriented synthesis of transition metal sulfides (TMSs) with controlled compositions and crystal structures has long been promising for electronic devices and energy applications. Liquid-phase cation exchange (LCE) is a well-studied route by varying the compositions. However, achieving crystal structure selectivity is still a great challenge. Here, we demonstrate gas-phase cation exchange (GCE), which can induce a specific topological transformation (TT), for the synthesis of versatile TMSs with identified cubic or hexagonal crystal structures. The parallel six-sided subunit (PSS), a new descriptor, is defined to describe the substitution of cations and the transition of the anion sublattice. Under this principle, the band gap of targeted TMSs can be tailored. Using the photocatalytic hydrogen evolution as an example, the optimal hydrogen evolution rate of a zinc-cadmium sulfide (ZCS4) is determined to be 11.59 mmol h-1 g-1 , showing a 36.2-fold improvement over CdS.

A Tandem Interfaced (Ni3 S2 -MoS2 )@TiO2 Composite Fabricated by Atomic Layer Deposition as Efficient HER Electrocatalyst.

Reported herein is a highly active and durable hydrogen evolution reaction (HER) electrocatalyst, which is constructed following a tandem interface strategy and functional in alkaline and even neutral medium (pH ≈ 7). The ternary composite material, consisting of conductive nickel foam (NF) substrate, Ni3 S2 -MoS2 heterostructure, and TiO2 coating, is synthesized by the hydrothermal method and atomic layer deposition (ALD) technique. Representative results include: (1) versatile characterizations confirm the proposed composite structure and strong electronic interactions among comprised sulfide and oxide species; (2) the material outperforms commercial Pt/C by recording an overpotential of 115 mV and a Tafel slope of 67 mV dec-1 under neutral conditions. A long-term stability in alkaline electrolytes up to 200 h and impressive overall water splitting behavior (1.56 V @ 10 mA cm-2 ) are documented; (3) implementation of ALD oxide tandem layer is crucial to realize the design concept with superior HER performance by modulating a variety of heterointerface and intermediates electronic structure.

All-Electrochemical Nanofabrication of Stacked Ternary Metal Sulfide/Graphene Electrodes for High-Performance Alkaline Batteries.

Energy-storage materials can be assembled directly on the electrodes of a battery using electrochemical methods, this allowing sequential deposition, high structural control, and low cost. Here, a two-step approach combining electrophoretic deposition (EPD) and cathodic electrodeposition (CED) is demonstrated to fabricate multilayer hierarchical electrodes of reduced graphene oxide (rGO) and mixed transition metal sulfides (NiCoMnSx ). The process is performed directly on conductive electrodes applying a small electric bias to electro-deposit rGO and NiCoMnSx in alternated cycles, yielding an ideal porous network and a continuous path for transport of ions and electrons. A fully rechargeable alkaline battery (RAB) assembled with such electrodes gives maximum energy density of 97.2 Wh kg-1 and maximum power density of 3.1 kW kg-1 , calculated on the total mass of active materials, and outstanding cycling stability (retention 72% after 7000 charge/discharge cycles at 10 A g-1 ). When the total electrode mass of the cell is considered, the authors achieve an unprecedented gravimetric energy density of 68.5 Wh kg-1 , sevenfold higher than that of typical commercial supercapacitors, higher than that of Ni/Cd or lead-acid Batteries and similar to Ni-MH Batteries. The approach can be used to assemble multilayer composite structures on arbitrary electrode shapes.

Tailoring MSx Quantum Dots (M = Co, Ni, Cu, Zn) for Advanced Energy Storage Materials with Strong Interfacial Engineering.

Metal sulfides, as vital members of electrodes materials, still suffer from serious volume expansion and polysulfides shuttling. Herein, through inexpensive and high efficiency chemical-bonding/hydrophobic-association methods, a series of metal-sulfides quantum dots (QDs) with large-scale synthesis (≈100 g) is successfully prepared, further forming low-dimensional composites with high redox activity. For the derived electrodes samples, with the increasing of outer electron numbers (Co2+ /Ni2+ /Cu2+ /Zn2+ ), interfacial coupling is significantly modified. Among them, nanoscale ZnS@double carbon with rich interfacial Zn-O/S-C bonds displays remarkable electrochemical activity, with the capacity of ≈1000 mAh g-1 after 100 loops. Through tailoring double carbons and interfacial merits, in situ sulfur formation is stabilized, and the cycling stability of Zn-based samples can increase up to 4000 cycles. Even at 5.0 A g-1 after 1500 cycles, the full-cells capacity can reach up to ≈380 mAh g-1 . Supported by detailed kinetic analysis and ex situ technologies, the enhanced interfacial capacitances and ions moving are confirmed for the improved electrochemical properties. Given this, the work is expected to boost future developments of mineral processing, and QDs preparation, whilst providing effective strategies for advanced electrode materials.

Self-Supporting Multicomponent Hierarchical Network Aerogel as Sulfur Anchoring-Catalytic Medium for Highly Stable Lithium-Sulfur Battery.

The low utilization rate of active materials, shuttle effect of lithium polysulfides (LiPSs), and slow reaction kinetics lead to the extremely low efficiency and poor high current cycle stability of lithium sulfur batteries (Li-S batteries). In this paper, a self-supporting multicomponent hierarchical network aerogel is proposed as the modified cathode (S/GO@MX@VS4 ). It consists of graphene (GO) and MXene nanosheets (MX) loaded with VS4 nanoparticles. The experimental results and first-principles calculations show that the GO@MX@VS4 aerogel has strong adsorption and reversible conversion effects on LiPSs. It can not only inhibit the shuttle effect and improve the utilization rate of active substances by keeping the chain crystal structure of VS4 , but also promote the reversibility and kinetics of the reaction by accelerating the liquid-solid transformation in the reduction process and the decomposition of insoluble Li2 S in the oxidation process. The GO@MX@VS4 aerogel modified cathode with a multicomponent synergy exhibits the capacity ratios (Q1 /Q2 ) at different discharge stages is close to the theoretical value (1:2.8), and the capacity decay per cycle is 0.019% in 1200 cycles at 5C. Also, a high areal capacity of 6.90 mAh cm-2 is provided even at high sulfur loading (7.39 mg cm-2 ) and low electrolyte/sulfur ratio (E/S, 8.0 µL mg-1 ).

Iron Sulfide Na2 FeS2 as Positive Electrode Material with High Capacity and Reversibility Derived from Anion-Cation Redox in All-Solid-State Sodium Batteries.

It is desirable for secondary batteries to have high capacities and long lifetimes. This paper reports the use of Na2 FeS2 with a specific structure consisting of edge-shared and chained FeS4 as the host structure and as a high-capacity active electrode material. An all-solid-state sodium cell that uses Na2 FeS2 exhibits a high capacity of 320 mAh g-1 , which is close to the theoretical two-electron reaction capacity of 323 mAh g-1 , and operates reversibly for 300 cycles. The excellent electrochemical properties of all-solid-state sodium cells are derived from the anion-cation redox and rigid host structure during charging/discharging. In addition to the initial one-electron reaction of Nax FeS2 (1 ≤ x ≤ 2) activated Fe2+ /Fe3+ redox as the main redox center, the reversible sulfur redox further contributes to the high capacity. Although the additional sulfur redox affects the irreversible crystallographic changes, stable and reversible redox reactions are observed without capacity fading, owing to the local maintenance of the chained FeS4 in the host structure. Sodium iron sulfide Na2 FeS2 , which combines low-cost elements, is one of the candidates that can meet the high requirements of practical applications.

High Performance Bifunctional Electrocatalysts Designed Based on Transition-Metal Sulfides for Rechargeable Zn-Air Batteries.

Due to the energy crisis by the excessive consumption of fossil fuels, Zinc-air batteries (ZABs) with high theoretical energy density have attracted people's attention. The overall performance of ZABs is largely determined by the air cathode catalyst. Therefore, it is necessary to develop high-efficiency and low-cost bifunctional catalysts to replace noble metal catalysts to promote the development of ZABs. Among a variety of cathode catalysts, TMS has become a research hotspot in recent years because of its better electrical conductivity than metal phosphides and metal oxides. In this work, we focus on the means of improving the electrocatalytic performance of transition-metal sulfides (TMS) providing ideas for us to rationally design high-performance catalysts. Furthermore, the performance improvement law between catalyst performance and ZABs is also discussed in this work. Finally, some challenges and opportunities faced in the research of TMS electrocatalysis are briefly proposed, and strategies for improving the performance of ZABs are prospected.