A Metal–Organic Frameworks Derived 1T-MoS2 with Expanded Layer Spacing for Enhanced Electrocatalytic Hydrogen Evolution

Metal phase molybdenum disulfide (1T-MoS₂) is considered a promising electrocatalyst for hydrogen evolution reaction (HER) due to its activated basal and superior electrical conductivity. Here, a one-step solvothermal route is developed to prepare 1T-MoS₂ with expanded layer spacing through the derivatization of a Mo-based organic framework (Mo-MOFs). Benefiting from N,N-dimethylformamide oxide as external stress, the interplanar spacing of (002) of the MoS₂ catalyst is extended to 10.87 Å, which represents the largest one for the 1T-MoS₂ catalyst prepared by the bottom-up approach. Theoretical calculations reveal that the expanded crystal planes alter the electronic structure of 1T-MoS₂, lower the adsorption–desorption potentials of protons, and thus, trigger efficient catalytic activity for HER. The optimal 1T-MoS₂ catalyst exhibits an overpotential of 98 mV at 10 mA cm⁻² for HER, corresponding to a Tafel slope of 52 mV dec⁻¹. This Mo-MOFs-derived strategy provides a potential way to design high-performance catalysts by adjusting the layer spacing of 2D materials.     

Dandelion-Like Bi2S3/rGO hierarchical microspheres as high-performance anodes for potassium-ion and half/full sodium-ion batteries

Sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) have been considered as attractive alternatives for next-generation battery systems, which have promising application potential due to their earth abundance of potassium and sodium, high capacity and suitable working potential, however, the design and application of bi-functional high-performance anode still remain a great challenge up to date. Bismuth sulfide is suitable as anode owing to its unique laminar structure with relatively large interlayer distance to accommodate larger radius ions, high theoretical capacity and high volumetric capacity etc. In this study, dandelion-like Bi₂S₃/rGO hierarchical microspheres as anode material for PIBs displayed reversible capacity, and 206.91 mAh·g⁻¹ could be remained after 1,200 cycles at a current density of 100 mA·g⁻¹. When applied as anode materials for SIBs, 300 mAh·g⁻¹ could be retained after 300 cycles at 2 A·g⁻¹ and its initial Coulombic efficiency is as high as 97.43%. Even at high current density of 10 A·g⁻¹, 120.3 mAh·g⁻¹ could be preserved after 3,400 cycles. The Na₃V₂(PO₄)₃@rGO//Bi₂S₃/rGO sodium ion full cells were successfully assembled which displays stable performance after 60 cycles at 100 mA·g⁻¹. The above results demonstrate that Bi₂S₃/rGO has application potential as high performance bi-functional anode for PIBs and SIBs.

     

Fe-Regulated Amorphous-Crystal Ni(Fe)P2 Nanosheets Coupled with Ru Powerfully Drive Seawater Splitting at Large Current Density

Water electrolysis is an ideal method for industrial green hydrogen production. However, due to increasing scarcity of freshwater, it is inevitable to develop advanced catalysts for electrolyzing seawater especially at large current density. This work reports a unique Ru nanocrystal coupled amorphous-crystal Ni(Fe)P₂ nanosheet bifunctional catalyst (Ru-Ni(Fe)P₂/NF), caused by partial substitution of Fe to Ni atoms in Ni(Fe)P₂, and explores its electrocatalytic mechanism by density functional theory (DFT) calculations. Owing to high electrical conductivity of crystalline phases, unsaturated coordination of amorphous phases, and couple of Ru species, Ru-Ni(Fe)P₂/NF only requires overpotentials of 375/295 and 520/361 mV to drive a large current density of 1 A cm⁻² for oxygen/hydrogen evolution reaction (OER/HER) in alkaline water/seawater, respectively, significantly outperforming commercial Pt/C/NF and RuO₂/NF catalysts. In addition, it maintains stable performance at large current density of 1 A cm⁻² and 600 mA cm⁻² for 50 h in alkaline water and seawater, respectively. This work provides a new way for design of catalysts toward industrial-level seawater splitting.     

NiCo2S4 nanoparticles grown on reduced graphene oxides for high-performance asymmetric supercapacitors

The nanostructures of reduced graphene oxide (rGO)/NiCo₂S₄ are prepared using the simple hydrothermal method and the thermal treatment process, which could provide good conductivity and ideal specific surface area. The rGO/NiCo₂S₄ electrode shows a maximum specific capacitance of 1059 F g⁻¹, excellent rate capability, and good cycle life. Furthermore, the three dimensional structures of rGO/MnO (3D rGO/MnO) are also synthesized by the hydrothermal method and the thermal treatment process, which have the high specific surface area and good conductivity. The rGO/MnO electrode exhibits a maximum specific capacitance of 469 F g⁻¹. A rGO/MnO//rGO/NiCo₂S₄ asymmetric supercapacitors (ASC) is assembled using 2 M KOH solution as electrolyte, rGO/NiCo₂S₄ as positive electrode and rGO/MnO as negative electrode. The rGO/MnO//rGO/NiCo₂S₄ ASC shows an energy density of 38.8 Wh kg⁻¹ at a power density of 0.4 kW kg⁻¹ and a good cycle life, which provides a possibility toward actual application in energy-storage systems.     

IrPd Nanoalloy-Structured Bifunctional Electrocatalyst for Efficient and pH-Universal Water Splitting

The lack of high efficiency and pH-universal bifunctional electrocatalysts for water splitting to hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) hinders the large-scale production of green hydrogen. Here, an IrPd electrocatalyst supported on ketjenblack that exhibits outstanding bifunctional performance for both HER and OER at wide pH conditions is presented. The optimized IrPd catalyst exhibits a specific activity of 4.46 and 3.98 A mg_Ir⁻¹ in the overpotential of 100 and 370 mV for HER and OER, respectively, in alkaline conditions. When applied to the anion exchange membrane electrolyzer, the Ir₄₄Pd₅₆/KB catalyst shows a stability of >20 h at a current of 250 mA cm⁻² for water decomposition, indicating promising prospects for practical applications. Beyond offering an advanced electrocatalyst, this work also guides the rational design of desirable bifunctional electrocatalysts for HER and OER by regulating the microenvironments and electronic structures of metal catalytic sites for diverse catalysis.     

Ultra-Low Pt Doping and Pt–Ni Pair Sites in Amorphous/Crystalline Interfacial Electrocatalyst Enable Efficient Alkaline Hydrogen Evolution

Noble metal doping can achieve an increase in mass activity (MA) without sacrificing catalysis efficiency and stability, so that alkaline hydrogen evolution reaction (HER) performance of the catalyst can be optimized to the maximum degree. However, its excessively large ionic radius makes it difficult to achieve either interstitial doping or substitutional doping under mild conditions. Herein, a hierarchical nanostructured electrocatalyst with enriched amorphous/crystalline interfaces for high-efficiency alkaline HER is reported, which is composed of amorphous/crystalline (Co, Ni)₁₁(HPO₃)₈(OH)₆ homogeneous hierarchical structure with an ultra-low doped Pt (Pt-a/c-NiHPi). Benefiting from the structural flexibility of the amorphous component, extremely low Pt (0.21 wt.%, totally 3.31 µg Pt on 1 cm⁻² NF) are stably doped on it via a simple two-phase hydrothermal method. The DFT calculations show that due to the strongly electron transfer between the crystalline/amorphous components at the interfaces, electrons finally concentrate toward Pt and Ni in the amorphous components, thus the electrocatalyst has near-optimal energy barriers and adsorption energy for H₂O^* and H^*. With the above benefits, the obtained catalyst exhibits an exceptionally high MA (39.1 mA µg⁻¹_Pt) at 70 mV, which is almost the highest level among the reported Pt-based electrocatalysts for alkaline HER.     

High-Performance Bifunctional Porous Iron-Rich Phosphide/Nickel Nitride Heterostructures for Alkaline Seawater Splitting

Seawater is the most abundant natural water resource in the world, which is an inexhaustible and low-cost feedstock for hydrogen production by alkaline water electrolysis. It is appearling to develop robust and stable electrocatalysts for alkaline seawater electrolysis. However, the development of seawater electrolysis is seriously impeded by anodic chloride corrosion and chlorine evolution reaction, and few non-noble electrocatalysts show prominent catalytic performance and excellent durability. Here, a heterogeneous electrocatalyst constructed by in situ growing highly dispersed iron-rich bimetallic phosphide nanoparticles on metallic Ni₃N (Fe_2−2xCo_2xP/Ni₃N), which exhibits outstanding bifunctional catalytic activities for alkaline seawater splitting, is reported. The optimal (Fe_0.74Co_0.26)₂P/Ni₃N and Fe₂P/Ni₃N electrocatalysts demand only 113 and 212 mV to afford 100 mA cm⁻² for hydrogen and oxygen evolution reactions (HER and OER) in 1 m KOH, respectively, thus substantially expediting overall water/seawater electrolysis at 100 mA cm⁻² with 1.592/1.645 V. Particularly, Fe₂P/Ni₃N displays an unprecedented overpotential of 302 mV at 500 mA cm⁻², which represents the best alkaline seawater oxygen evolution activity among the ever-reported non-noble electrocatalysts; and thus substantially expedites overall water/seawater splitting at 500 mA cm⁻² with 1.701/1.768 V, surpassing most of the reported non-noble lectrocatalysts. This work provides a new approach for developing high-performance electrocatalysts for seawater splitting.     

Multifunctional Nanocrystalline-Assembled Porous Hierarchical Material and Device for Integrating Microwave Absorption,Electromagnetic Interference Shielding,and Energy Storage

Multifunctional applications including efficient microwave absorption and electromagnetic interference (EMI) shielding as well as excellent Li-ion storage are rarely achieved in a single material. Herein, a multifunctional nanocrystalline-assembled porous hierarchical NiO@NiFe₂O₄/reduced graphene oxide (rGO) heterostructure integrating microwave absorption, EMI shielding, and Li-ion storage functions is fabricated and tailored to develop high-performance energy conversion and storage devices. Owing to its structural and compositional advantages, the optimized NiO@NiFe₂O₄/15rGO achieves a minimum reflection loss of −55 dB with a matching thickness of 2.3 mm, and the effective absorption bandwidth is up to 6.4 GHz. The EMI shielding effectiveness reaches 8.69 dB. NiO@NiFe₂O₄/15rGO exhibits a high initial discharge specific capacity of 1813.92 mAh g⁻¹, which reaches 1218.6 mAh g⁻¹ after 289 cycles and remains at 784.32 mAh g⁻¹ after 500 cycles at 0.1 A g⁻¹. In addition, NiO@NiFe₂O₄/15rGO demonstrates a long cycling stability at high current densities. This study provides an insight into the design of advanced multifunctional materials and devices and provides an innovative method of solving current environmental and energy problems.     

Rational Synthesis of Core-Shell-Structured Nickel Sulfide-Based Nanostructures for Efficient Seawater Electrolysis

Versatile electrocatalysis at higher current densities for natural seawater splitting to produce hydrogen demands active and robust catalysts to overcome the severe chloride corrosion, competing chlorine evolution, and catalyst poisoning. Hereto, the core-shell-structured heterostructures composed of amorphous NiFe hydroxide layer capped Ni₃S₂ nanopyramids which are directly grown on nickel foam skeleton (NiS@LDH/NF) are rationally prepared to regulate cooperatively electronic structure and mass transport for boosting oxygen evolution reaction (OER) performance at larger current densities. The prepared NiS@LDH/NF delivers the anodic current density of 1000 mA cm⁻² at the overpotential of 341 mV in 1.0 m KOH seawater. The feasible surface reconstruction of Ni₃S₂-FeNi LDH interfaces improves the chemical stability and corrosion resistance, ensuring the robust electrocatalytic activity in seawater electrolytes for continuous and stable oxygen evolution without any hypochlorite production. Meanwhile, the designed Ni₃S₂ nanopyramids coated with FeNi₂P layer (NiS@FeNiP/NF) still exhibit the improved hydrogen evolution reaction (HER) activity in 1.0 m KOH seawater. Furthermore, the NiS@FeNiP/NF||NiS@LDH/NF pair requires cell voltage of 1.636 V to attain 100 mA cm⁻² with a 100% Faradaic efficiency, exhibiting tremendous potential for hydrogen production from seawater.     

Metallic Metastable Hybrid 1T′/1T Phase Triggered Co,P?SnS2 Nanosheets for High Efficiency Trifunctional Electrocatalyst

The development of trifunctional electrocatalyst for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) with deeply understanding the mechanism to enhance the electrochemical performance is still a challenging task. In this work, the distorted metastable hybrid-phase induced 1T′/1T Co,P SnS₂ nanosheets on carbon cloth (1T′/1T Co,P SnS₂@CC) is prepared and examined. The density functional theoretical (DFT) calculation suggests that the distorted 1T′/1T Co,P SnS₂ can provide excellent conductivity and strong hydrogen adsorption ability. The electronic structure tuning and enhancement mechanism of electrochemical performance are investigated and discussed. The optimal 1T′/1T Co,P SnS₂@CC catalyst exhibits low overpotential of ≈94 and 219.7 mV at 10 mA cm⁻² for HER and OER, respectively. Remarkably, the catalyst exhibits exceptional ORR activity with small onset potential value (≈0.94 V) and half-wave potential (≈0.87 V). Most significantly, the 1T′/1T Co,P SnS₂||Co,P SnS₂ electrolyzer required small cell voltages of ≈1.53, 1.70, and 1.82 V at 10, 100, and 400 mA cm⁻², respectively, which are better than those of state-of-the-art Pt-C||RuO₂ (≈1.56 and 1.84 V at 10 and 100 mA cm⁻²). The present study suggests a new approach for the preparation of large-scalable, high performance hierarchical 3D next-generation trifunctional electrocatalysts.     

Rational Engineering of p-n Heterogeneous ZnS/SnO2 Quantum Dots with Fast Ion Kinetics for Superior Li/Na-Ion Battery

Constructing heterogeneous nanostructures is an efficient strategy to improve the electrical and ionic conductivity of metal chalcogenide-based anodes. Herein, ZnS/SnO₂ quantum dots (QDs) as p-n heterojunctions that are uniformly anchored to reduced graphene oxides (ZnS-SnO₂@rGO) are designed and engineered. Combining the merits of fast electron transport via the internal electric field and a greatly shortened Li/Na ion diffusion pathway in the ZnS/SnO₂ QDs (3–5 nm), along with the excellent electrical conductivity and good structural stability provided by the rGO matrix, the ZnS-SnO₂@rGO anode exhibits enhanced electronic and ionic conductivity, which can be proved by both experiments and theoretical calculations. Consequently, the ZnS-SnO₂@rGO anode shows a significantly improved rate performance that simple counterpart composite anodes cannot achieve. Specifically, high reversible specific capacities are achieved for both lithium-ion battery (551 mA h g⁻¹ at 5.0 A g⁻¹, 670 mA h g⁻¹ at 3.0 A g⁻¹ after 1400 cycles) and sodium-ion battery (334 mA h g⁻¹ at 5.0 A g⁻¹, 313 mA h g⁻¹ at 1.0 A g⁻¹ after 400 cycles). Thus, this strategy to build semiconductor metal sulfides/metal oxide heterostructures at the atomic scale may inspire the rational design of metal compounds for high-performance battery applications.     

Cooperative Boron and Vanadium Doping of Nickel Phosphides for Hydrogen Evolution in Alkaline and Anion Exchange Membrane Water/Seawater Electrolyzers

Developing low-cost and high-performance transition metal-based electrocatalysts is crucial for realizing sustainable hydrogen evolution reaction (HER) in alkaline media. Here, a cooperative boron and vanadium co-doped nickel phosphide electrode (B, V-Ni₂P) is developed to regulate the intrinsic electronic configuration of Ni₂P and promote HER processes. Experimental and theoretical results reveal that V dopants in B, V-Ni₂P greatly facilitate the dissociation of water, and the synergistic effect of B and V dopants promotes the subsequent desorption of the adsorbed hydrogen intermediates. Benefiting from the cooperativity of both dopants, the B, V-Ni₂P electrocatalyst requires a low overpotential of 148 mV to attain a current density of −100 mA cm⁻² with excellent durability. The B, V-Ni₂P is applied as the cathode in both alkaline water electrolyzers (AWEs) and anion exchange membrane water electrolyzers (AEMWEs). Remarkably, the AEMWE delivers a stable performance to achieve 500 and 1000 mA cm⁻² current densities at a cell voltage of 1.78 and 1.92 V, respectively. Furthermore, the developed AWEs and AEMWEs also demonstrate excellent performance for overall seawater electrolysis.     

P and Se Binary Vacancies and Heterostructures Modulated MoP/MoSe2 Electrocatalysts for Improving Hydrogen Evolution and Coupling Electricity Generation

It is not enough to develop an ideal hydrogen evolution reaction (HER) electrocatalysts by single strategy. Here, the HER performances are significantly improved by the combined strategies of P and Se binary vacancies and heterostructure engineering, which is rarely explored and remain unclear. As a result, the overpotentials of MoP/MoSe₂-H heterostructures rich in P and Se binary vacancies are 47 and 110 mV at 10 mA cm⁻² in 1 m KOH and 0.5 m H₂SO₄ electrolytes, respectively. Especially, in 1 m KOH, the overpotential of MoP/MoSe₂-H is very close to commercial Pt/C at the beginning and even better than Pt/C when current density is over 70 mA cm⁻². The strong interactions between MoSe₂ and MoP facilitate electrons transfer from P to Se. Thus, MoP/MoSe₂-H possesses more electrochemically active sites and faster charge transfer capability, which are all in favor of high HER activities. Additionally, Zn-H₂O battery with MoP/MoSe₂-H as cathode is fabricated for simultaneous generation of hydrogen and electricity, which displays the maximum power density of up to 28.1 mW cm⁻² and stable discharging performance for 125 h. Overall, this work validates a vigorous strategy and provides guidance for the development of efficient HER electrocatalysts.     

An Ion-Crosslinked Supramolecular Hydrogel for Ultrahigh and Fast Uranium Recovery from Seawater

Large-scale uranium extraction from seawater is a crucial but challenging part of nuclear power generation. In this study, a new ion-crosslinked supramolecular Zn²⁺–poly(amidoxime) (PAO) hydrogel that can super-efficiently adsorb uranium from seawater is explored. By simply mixing two solutions of zinc chloride and PAO, a supramolecular Zn²⁺–PAO hydrogel is achieved via the interaction between zinc cations and amidoxime anions. In contrast with existing amidoxime-functionalized hydrogel-based adsorbents having low PAO contents and fiber-based adsorbents with weak hydrophilicity, the PAOs can be directly crosslinked using a small quantity of superhydrophilic zinc ion. Thus, a supramolecular hydrogel is formed, having both a high content of well-dispersed PAOs and good hydrophilicity. Relative to reported adsorbents, this low-cost hydrogel membrane exhibits outstanding uranium adsorption performance, reaching 1188 mg g^-1 of M_U/M_{dry gel} in 32 ppm uranium-spiked water. More importantly, after immersion in natural seawater for only 4 weeks, the uranium extraction capacity of the Zn²⁺–PAO hydrogel membrane reaches 9.23 mg g^-1 of M_U/M_{dry gel}. This work can provide a general strategy for designing a new type of supramolecular hydrogel, crosslinked by various bivalent/multivalent cation-crosslinkers and even many other superhydrophilic supramolecular crosslinkers, for the high-efficient and massive extraction of uranium from seawater.     

Flexible Graphene‐Wrapped Carbon Nanotube/Graphene@MnO2 3D Multilevel Porous Film for High‐Performance Lithium‐Ion Batteries

The ingenious design of a freestanding flexible electrode brings the possibility for power sources in emerging wearable electronic devices. Here, reduced graphene oxide (rGO) wraps carbon nanotubes (CNTs) and rGO tightly surrounded by MnO₂ nanosheets, forming a 3D multilevel porous conductive structure via vacuum freeze‐drying. The sandwich‐like architecture possesses multiple functions as a flexible anode for lithium‐ion batteries. Micrometer‐sized pores among the continuously waved rGO layers could extraordinarily improve ion diffusion. Nano‐sized pores among the MnO₂ nanosheets and CNT/rGO@MnO₂ particles could provide vast accessible active sites and alleviate volume change. The tight connection between MnO₂ and carbon skeleton could facilitate electron transportation and enhance structural stability. Due to the special structure, the rGO‐wrapped CNT/rGO@MnO₂ porous film as an anode shows a high capacity, excellent rate performance, and superior cycling stability (1344.2 mAh g⁻¹ over 630 cycles at 2 A g⁻¹, 608.5 mAh g⁻¹ over 1000 cycles at 7.5 A g⁻¹). Furthermore, the evolutions of microstructure and chemical valence occurring inside the electrode after cycling are investigated to illuminate the structural superiority for energy storage. The excellent electrochemical performance of this freestanding flexible electrode makes it an attractive candidate for practical application in flexible energy storage.     

Piezoelectricity regulated ohmic contact in M/BaTiO3 (M = Ru,Pd, Pt) for charge collision and hydrogen free radical production in ammonia electrosynthesis

Electrochemical nitrate reduction reaction (NO₃RR) is a promising alternative technique for NH₃ generation toward the energy-consuming Haber-Bosch process. Nevertheless, it remains hindered by the competitive hydrogen evolution reaction (HER). Herein, the piezoelectric effect of electron-rich BaTiO₃ with oxygen vacancies is introduced to promote NO₃RR performance. Combining with metal particles (Ru, Pd and Pt), the catalyst achieves a maximal Faradaic efficiency of 95.3% and NH₃ yield rate of 6.87 mg h⁻¹ mg_cat.⁻¹. Upon piezoelectricity, the interface between metal nanoparticles and BaTiO₃ is effectively modulated from Schottky contact to ohmic contact, which leads to unobstructed electron transfer. Abundant hydrogen radicals (·H) can be then produced from the collision between plentiful electrons and polar water molecules adsorbed on the polar surface. Such ·H can significantly facilitate the hydrogenation of reaction intermediates in NO₃RR. Meanwhile, this process suppresses the Volmer-Heyrovsky step, therefore inhibiting the HER within a wide range of external potential. This work suggests a new strategy for promoting the performance of multi-electron-involved catalytic reactions.     

Hydroxyapatite-Derived Heterogeneous Ru-Ru2P Electrocatalyst and Environmentally-Friendly Membrane Electrode toward Efficient Alkaline Electrolyzer

Alkaline membrane water electrolysis is a promising production technology, and advanced electrocatalyst and membrane electrode design have always been the core technology. Herein, an ion-exchange method and an environmentally friendly in situ green phosphating strategy are successively employed to fabricate Ru-Ru₂P heterogeneous nanoparticles by using hydroxyapatite (HAP) as a phosphorus source, which is an exceptionally active electrocatalyst for hydrogen evolution reaction (HER). Density functional theory calculation results reveal that strong electronic redistribution occurs at the heterointerface of Ru-Ru₂P, which modulates the electronic structure to achieve an optimized hydrogen adsorption strength. The obtained Ru-Ru₂P possesses excellent HER performance (24 mV at 10 mA cm⁻²) and robust stability (1000 mA cm⁻² for 120 h) in alkaline media. Furthermore, an environmentally friendly membrane electrode with a sandwich structure is assembled by HAP nanowires as an alkaline membrane, Ru-Ru₂P as a cathodic catalyst, and NiFe-LDH as an anodic catalyst, respectively. The voltage of (−) Ru-Ru₂P || NiFe-LDH/CNTs (+) (1.53 V at 10 mA cm⁻²) is lower than that of (−) 20 wt% Pt/C || RuO₂ (+) (1.60 V at 10 mA cm⁻²) for overall water splitting. Overall, the studies not only design an efficient catalyst but also provide a new route to achieve a high-stability electrolyzer for industrial H₂ production.     

Design of XS2 (X = W or Mo)-Decorated VS2 Hybrid Nano-Architectures with Abundant Active Edge Sites for High-Rate Asymmetric Supercapacitors and Hydrogen Evolution Reactions

Two-dimensional layered transition metal dichalcogenides have emerged as promising materials for supercapacitors and hydrogen evolution reaction (HER) applications. Herein, the molybdenum sulfide (MoS₂)@vanadium sulfide (VS₂) and tungsten sulfide (WS₂)@VS₂ hybrid nano-architectures prepared via a facile one-step hydrothermal approach is reported. Hierarchical hybrids lead to rich exposed active edge sites, tuned porous nanopetals-decorated morphologies, and high intrinsic activity owing to the strong interfacial interaction between the two materials. Fabricated supercapacitors using MoS₂@VS₂ and WS₂@VS₂ electrodes exhibit high specific capacitances of 513 and 615 F g⁻¹, respectively, at an applied current of 2.5 A g⁻¹ by the three-electrode configuration. The asymmetric device fabricated using WS₂@VS₂ electrode exhibits a high specific capacitance of 222 F g⁻¹ at an applied current of 2.5 A g⁻¹ with the specific energy of 52 Wh kg⁻¹ at a specific power of 1 kW kg⁻¹. For HER, the WS₂@VS₂ catalyst shows noble characteristics with an overpotential of 56 mV to yield 10 mA cm⁻², a Tafel slope of 39 mV dec⁻¹, and an exchange current density of 1.73 mA cm⁻². In addition, density functional theory calculations are used to evaluate the durable heterostructure formation and adsorption of hydrogen atom on the various accessible sites of MoS₂@VS₂ and WS₂@VS₂ heterostructures.     

Utilizing Metal-Thiocatecholate Functionalized UiO-66 Framework for Photocatalytic Hydrogen Evolution Reaction

Exploiting clean energy is essential for sustainable development and sunlight-driven photocatalytic water splitting represents one of the most promising approaches toward this goal. Metal-organic frameworks (MOFs) are competent photocatalysts owing to their tailorable functionality, well-defined structure, and high porosity. Yet, the introduction of the unambiguous metal-centered active site into MOFs is still challenging since framework motifs capable of anchoring metal ions firmly are lacking. Herein, the assembly using 1,4-dicarboxylbenzene-2,3-dithiol (H₂ dcbdt ) and Zr-Oxo clusters to give a thiol-functionalized UiO-66 type framework,  UiO-66-dcbdt, is reported. The thiocatechols on the struts are allowed to capture transition metal (TM) ions to generate  UiO-66-dcbdt-M  ( M   = Fe, Ni, Cu) with unambiguous metal-thiocatecholate moieties for photocatalytic hydrogen evolution reaction (HER).  UiO-66-dcbdt-Cu  is found the best catalyst exhibiting an HER rate of 4.18 mmol g⁻¹ h⁻¹ upon irradiation with photosensitizing Ru-polypyridyl complex. To skip the use of the external sensitizer,  UiO-66-dcbdt-Cu  is heterojunctioned with titanium dioxide (TiO₂) and achieves an HER rate of 12.63 mmol g⁻¹ h⁻¹ (32.3 times that of primitive TiO₂). This work represents the first example of MOF assembly employing H₂ dcbdt  as the mere linker followed by chelation with TM ions and undoubtedly fuels the rational design of MOF photocatalysts bearing well-defined active sites.     

Two-Dimensional Interlayer Space Induced Horizontal Transformation of Metal–Organic Framework Nanosheets for Highly Permeable Nanofiltration Membranes

Laminar membranes comprising graphene oxide (GO) and metal–organic framework (MOF) nanosheets benefit from the regular in-plane pores of MOF nanosheets and thus can support rapid water transport. However, the restacking and agglomeration of MOF nanosheets during typical vacuum filtration disturb the stacking of GO sheets, thus deteriorating the membrane selectivity. Therefore, to fabricate highly permeable MOF nanosheets/reduced GO (rGO) membranes, a two-step method is applied. First, using a facile solvothermal method, ZnO nanoparticles are introduced into the rGO laminate to stabilize and enlarge the interlayer spacing. Subsequently, the ZnO/rGO membrane is immersed in a solution of tetrakis(4-carboxyphenyl)porphyrin (H₂TCPP) to realize in situ transformation of ZnO into Zn-TCPP in the confined interlayer space of rGO. By optimizing the transformation time and mass loading of ZnO, the obtained Zn-TCPP/rGO laminar membrane exhibits preferential orientation of Zn-TCPP, which reduces the pathway tortuosity for small molecules. As a result, the composite membrane achieves a high water permeance of 19.0 L m⁻² h⁻¹ bar⁻¹ and high anionic dye rejection (>99% for methyl blue).