Direct Z-scheme Cu2O/WO3/TiO2 nanocomposite as a potential supercapacitor electrode and an effective visible-light-driven photocatalyst.

This paper presents the synthesis of visible light-responsive ternary nanocomposites composed of cuprous oxide (Cu2O), tungsten trioxide (WO3), and titanium dioxide (TiO2) with varying weight percentages (wt.%) of the Cu2O. The resulting Cu2O/WO3/TiO2 (CWT) nanocomposites exhibited band gap energy ranging from 2.35 to 2.90 eV. Electrochemical and photoelectrochemical (PEC) studies confirmed a reduced recombination rate of photoexcited charge carriers in the CWT nanocomposites, facilitated by a direct Z-scheme heterojunction. The 0.50CWT nanocomposite demonstrated superior photodegradation activity (2.29 × 10-2 min-1) against Reactive Black 5 (RB5) dye under visible light activation. Furthermore, the 0.50CWT nanocomposite exhibited excellent stability with 80.51% RB5 photodegradation retention after five cycles. The 0.50CWT electrode achieved a maximum specific capacitance of 66.32 F/g at 10 mA/g current density, with a capacitance retention of 95.17% after 1000 charge-discharge cycles, affirming its stable and efficient supercapacitor performance. This was supported by well-defined peaks in cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) curves, indicating pseudocapacitive properties.

Incorporation of Ag in Co9S8-Ni3S2 for Predominantly Enhanced Electrocatalytic Activities for Oxygen Evolution Reaction: A Combined Experimental and DFT Study.

Electrodeposition of abundant metals to fabricate efficient and durable electrodes play a viable role in advancing renewable electrochemical energy technologies. Herein, we deposit Co9S8-Ag-Ni3S2@NF onto nickel foam (NF) to form Co9S8-Ag-Ni3S2@NF as a highly efficient electrode for oxygen evolution reaction (OER). The electrochemical investigation verifies that the Co9S8-Ag-Ni3S2@NF electrode exhibits superior electrocatalytic activity toward OER because of its nanoflowers' open-pore morphology, reduced overpotential (η10 = 125 mV), smaller charge transfer resistance, long-term stability, and a synergistic effect between various components, which allows the reactants to be more easily absorbed and subsequently converted into gaseous products during the water electrolysis process. DFT calculation also reveals that the introduction of Ag (222) surface into the Co9S8 (440)-Ni3S2 (120) system increases the electronic density of states per unit cell of a system and significantly reduces the energy barriers of intermediates for OER, leading to enhanced electrocatalytic activity for OER. This study showcases the innovation of employing trimetallic nanomaterials immobilized on a conductive, continuous porous three-dimensional network formed on a nickel foam (NF) substrate as a highly efficient catalyst for OER.

Highly Selective Electroreduction of Nitrobenzene to Aniline by Co-Doped 1T-MoS2.

The selective electrocatalytic reduction of nitrobenzene (NB) to aniline demands a desirable cathodic catalyst to overcome the challenges of the competing hydrogen evolution reaction (HER), a higher overpotential, and a lower selectivity. Here, we deposit Co-doped 1T MoS2 on Ti mesh by the solvothermal method with different doping percentages of Co as x % Co-MoS2 (where x = 3, 5, 8, 10, and 12%). Because of the lowest overpotential, lower charge-transfer resistance, strong suppression of the competing HER, and higher electrochemical surface area, 8% Co-MoS2 achieves 94% selectivity of aniline with 54% faradaic efficiency. The reduction process follows first-order dynamics with a reaction coefficient of 0.5 h-1. Besides, 8% Co-MoS2 is highly stable and retains 81% selectivity even after 8 cycles. Mechanistic studies showed that the selective and exothermic adsorption of the nitro group at x % Co-MoS2 leads to a higher rate of NB reduction and higher selectivity of aniline. The aniline product is successfully removed from the solution by polymerization at FTO. This study signifies the impact of doping metal atoms in tuning the electronic arrangement of 1T-MoS2 for the facilitation of organic transformations.

Phase-Selective Synthesis of Cobalt Sulfide Heterostructure Catalysts as Efficient Counter Electrodes in Dye-Sensitized Solar Cells.

Developing a cost-saving, high-efficiency, and simple synthesis of counter electrode (CE) material to replace pricy Pt for dye-sensitized solar cells (DSSCs) has become a research hotspot. Owing to the electronic coupling effects between various components, semiconductor heterostructures can significantly enhance the catalytic performance and endurance of counter electrodes. However, the strategy to controllably synthesize the same element in several phase heterostructures used as the CE in DSSCs is still absent. Here, we fabricate well-defined CoS2 /CoS heterostructures and use them as CE catalysts in DSSCs. The as-designed CoS2 /CoS heterostructures display high catalytic performance and endurance for the triiodide reduction in DSSCs thanks to the combined and synergistic effects. As a result, a DSSC with CoS2 /CoS achieves a high energy conversion with an efficiency of 9.47 % under standard simulated solar radiation, surpassing that of pristine Pt-based CE (9.20 %). Besides, the CoS2 /CoS heterostructures possess a quick activity initiation process and extended stability, broadening their potential applications in various areas. Therefore, our proposed synthetic approach could offer new insights for synthesizing functional heterostructure materials with improved catalytic activities in DSSCs.

Rational design of hierarchically nanostructured NiTe@CoxSy composites for hybrid supercapacitors with impressive rate capability and robust cycling durableness.

The hierarchically nanostructured NiTe@CoxSy composites are constructed on a foamed nickel substrate by a two-step electrode preparation process. Structural characterization shows the dense growing of CoxSy nanosheets around NiTe nanorods forms a hierarchical nanostructure which possesses synergetic effects from both compositional and structural complementarity, more pathways for ion/electrolyte transport, richer redox active sites, and better conductivity. Thanks to the rational design of this hierarchical structure, NiTe@CoxSy delivers a high areal capacitance of 7.7F cm-2 at 3 mA cm-2 and achieves the improved capacitance retention of 97.9% after 10,000 cycles. Of particular importance is the successful fabrication of NiTe@CoxSy//activated carbon hybrid supercapacitors. This hybrid device has a wide operating voltage window, high areal energy density of 0.48 mWh cm-2 at 2.55 mW cm-2, impressive rate capability of 62.3% even after a 20-fold increase of the current density, and a 115.1% of initial capacitance retention after 15,000 cycles. Meanwhile, two tandem such hybrid devices can easily drive a pair of mini fans or light up a heart-like pattern assembled by 10 red LEDs. These experimental results not only demonstrate that the hierarchically nanostructured NiTe@CoxSy composites can serve as a prospective candidate electrode; but also develop a novel strategy about how to achieve high-performance stockpile equipment by rationale designing a desirable nanostructures.

Sn Anodes Protected by Intermetallic FeSn2 Layers for Long-lifespan Sodium-ion Batteries with High Initial Coulombic Efficiency of 93.8.

With a theoretical capacity of 847 mAh g-1 , Sn has emerged as promising anode material for sodium-ion batteries (SIBs). However, enormous volume expansion and agglomeration of nano Sn lead to low Coulombic efficiency and poor cycling stability. Herein, an intermetallic FeSn2 layer is designed via thermal reduction of polymer-Fe2 O3 coated hollow SnO2 spheres to construct a yolk-shell structured Sn/FeSn2 @C. The FeSn2 layer can relieve internal stress, avoid the agglomeration of Sn to accelerate the Na+ transport, and enable fast electronic conduction, which endows quick electrochemical dynamics and long-term stability. As a result, the Sn/FeSn2 @C anode exhibits high initial Coulombic efficiency (ICE=93.8 %) and a high reversible capacity of 409 mAh g-1 at 1 A g-1 after 1500 cycles, corresponding to an 80 % capacity retention. In addition, NVP//Sn/FeSn2 @C sodium-ion full cell shows outstanding cycle stability (capacity retaining rate of 89.7 % after 200 cycles at 1 C).

Asymmetric Activation of the Nitro Group over a Ag/Graphene Heterointerface to Boost Highly Selective Electrocatalytic Reduction of Nitrobenzene.

The electrocatalytic reduction of nitrobenzene to aniline normally faces high overpotential and poor selectivity because of its six-electron redox nature. Herein, a Ag nanoparticles/laser-induced-graphene (LIG) heterointerface was fabricated on polyimide films and employed as an electrode material for an efficient nitrobenzene reduction reaction (NBRR) via a one-step laser direct writing technology. The first-principles calculations reveal that Ag/LIG shows the lowest activation barriers for the NBRR, which could be attributed to the optimum adsorption of the H atom realized by the appropriate interaction between Ag/LIG heterointerfaces and nitrobenzene. As a result, the overpotential of the NBRR is reduced by 217 mV after silver loading, and Ag/LIG shows a high aniline selectivity of 93%. Furthermore, an electrochemical reduction of nitrobenzene in tandem with an electrochemical oxidative polymerization of aniline was designed to serve as an alternative method to remove nitrobenzene from the aqueous solution. This strategy highlights the significance of heterointerfaces for efficient electrocatalysts, which may stimulate the development of novel electrocatalysts to boost the electrocatalytic activity.

Photogenerated reactive oxygen species and hyperthermia by Cu3SnS4 nanoflakes for advanced photocatalytic and photothermal antibacterial therapy.

BACKGROUND: The rapid spread of infectious bacteria has brought great challenges to public health. It is imperative to explore effective and environment-friendly antibacterial modality to defeat antibiotic-resistant bacteria with high biosafety and broad-spectrum antibacterial property. RESULTS: Herein, biocompatible Cu3SnS4 nanoflakes (NFs) were prepared by a facile and low-cost fabrication procedure. These Cu3SnS4 NFs could be activated by visible light, leading to visible light-mediated photocatalytic generation of a myriad of reactive oxygen species (ROS). Besides, the plasmonic Cu3SnS4 NFs exhibit strong near infrared (NIR) absorption and a high photothermal conversion efficiency of 55.7%. The ROS mediated cellular oxidative damage and the NIR mediated photothermal disruption of bacterial membranes collaboratively contributed to the advanced antibacterial therapy, which has been validated by the efficient eradication of both Gram-negative Escherichia coli and Gram-positive methicillin-resistant Staphylococcus aureus strains in vitro and in vivo. Meanwhile, the exogenous copper ions metabolism from the Cu3SnS4 NFs facilitated the endothelial cell angiogenesis and collagen deposition, thus expediting the wound healing. Importantly, the inherent localized surface plasmon resonance effect of Cu3SnS4 NFs empowered them as an active substrate for surface-enhanced Raman scattering (SERS) imaging and SERS-labeled bacteria detection. CONCLUSIONS: The low cost and biocompatibility together with the solar-driven broad-spectrum photocatalytic/photothermal antibacterial property of Cu3SnS4 NFs make them a candidate for sensitive bacteria detection and effective antibacterial treatment.

Low cost, robust, environmentally friendly, wood supported 3D-hierarchical Cu3SnS4 for efficient solar powered steam generation.

Solar steam generation has great potential in alleviating freshwater crises, particularly in regions with accessible seawater and abundant insolation. Inexpensive, efficient, and eco-friendly photothermal materials are desired to fabricate sunlight-driven evaporation devices. Here, we have designed an economical strategy to fabricate a high-performance wood-based solar steam generation device. In current study, 3D-hierarchical Cu3SnS4 has been loaded on wood substrates of variable sizes via an in-situ solvothermal method. Considering the water transportation capacity and thermal insulation property of wood, an enhanced light absorption was achieved by a uniform coating of Cu3SnS4 on the inside and outside of the 3D porous structure of the wood. Thanks for the synergistic effect of Cu3SnS4 and wood substrate, the obtained composite endorsed high-performance solar steam generation with a steam generation efficiency of 90% and an evaporation rate as high as 1.35 kg m-2h-1 under one sun.

Selective Electrosynthesis of 2,5-Diformylfuran in a Continuous-Flow System.

The gram-scale selective oxidation of biomass-based chemicals, in particular 5-hydroxymethylfurfural (HMF), into value-added 2,5-diformylfuran (DFF) has a high application potential but suffers from high cost, low selectivity, and harsh reaction conditions. Besides, the electrooxidation strategy requires the usage of expensive electrodes and struggles with low selectivity and efficiency, which restricts its further scaled-up application. In this regard, a continuous-flow system was developed through redox mediator I- /I2 for the efficient synthesis of DFF, which could accelerate the mass transfer of I- (I2 ) to aqueous (organic) phase and avoid over-oxidation to achieve high selectivity. After the solvent system, iodine concentration, and reaction time were optimized, highly efficient DFF synthesis (selectivity >99 %) could be achieved in the electrochemical flow system using inexpensive graphite felt (GF) as electrode. Moreover, selective HMF oxidation was paired with the hydrogen evolution reaction with increased efficiency after using in-situ-loaded GF-CoS2 /CoS and GF-Pt electrodes. As a result, the required energy to achieve the gram-scale synthesis of DFF was significantly reduced, demonstrating outstanding potential for large-scale production of the target product.

Donor-π-Acceptor Heterosystem-Functionalized Porous Hollow Carbon Microsphere for High-Performance Li-S Cathode Materials with S up to 93 wt.

Lithium-sulfur (Li-S) batteries, as a prospective energy storage system, are still plagued by many problems that prevent them from their application, especially the low content of sulfur in the cathode. Herein, a cathode material with S up to 93 wt % is designed via a hollow donor-π-acceptor heterosystem, which combines catalytic sites, adsorption sites, and good conductivity together. Following this guidance, a hollow porous carbon sphere is prepared with CoO particles and single V atoms decorated on it (Co/V-HPCS), providing ultrahigh volumetric space for sulfur. Even the electrode made of sulfur-loaded Co/V-HPCS (Co/V-HPCS@S) has a high content of 90 wt % (sulfur content in the electrode is ∼83.5 wt %), and the cathode exhibits an excellent discharge capacity of 575.2 mAh g-1 under 0.2C after 100 cycles. With careful analysis by means of a high-resolution transmission electron microscope (HRTEM), the catalytic amounts of CoO particles and single V atoms loaded on the carbon shell are confirmed, which endows the material with outstanding catalytic ability to transfer sulfur and excellent adsorption of polysulfides. This concept of the cathode material increases the possibility of advanced long-life Li-S batteries with high tap density and high energy density.

Morphology genetic 3D hierarchical SnO2microstructures constructed by Sub 5 nm nanocrystals for highly sensitive ethanol-sensor.

SnO2is widely used for ethanol-sensing applications due to its excellent physicochemical properties, low toxicity and high sensitivity. However it is a challenge to construct 3D-hierarchical structures with sub 5 nm primary grain particle, which is the optimized size for ethanol sensor. Herein, genetic tri-level hierarchical SnO2microstructures are synthesised by the genetic conversion of 3D hierarchical SnS2flowers assembled by ultrathin nanosheets. The SnS2nanosheets are morphology genetic converted to porous nanosheets with sub 5 nm SnO2nanoparticles during the calcination process. When used for the detection of ethanol, the sensor exhibits a high sensitivity of 0.5 ppm (Ra/Rg = 6.8) and excellent gas-sensing response (Ra/Rg= 183 to 100 ppm) with short response/recovery time (12 s/11 s). The excellent gas sensing performance is much better than that of the previous reported SnO2-based sensors. The highly sensitivity is attributed to the large surface area derived from the recrystallization and volume changes, which offers more active sites during the morphology genetic conversion from SnS2to SnO2. Furthermore, the flower-like 3D structure enhances the stability of the materials and is beneficial for the mass diffusion dynamics of ethanol.

Chemical Coupled PEDOT:PSS/Si Electrode: Suppressed Electrolyte Consumption Enables Long-Term Stability.

Huge volume changes of Si during lithiation/delithiation lead to regeneration of solid-electrolyte interphase (SEI) and consume electrolyte. In this article, γ-glycidoxypropyl trimethoxysilane (GOPS) was incorporated in Si/PEDOT:PSS electrodes to construct a flexible and conductive artificial SEI, effectively suppressing the consumption of electrolyte. The optimized electrode can maintain 1000 mAh g-1 for nearly 800 cycles under limited electrolyte compared with 40 cycles of the electrodes without GOPS. Also, the optimized electrode exhibits excellent rate capability. The use of GOPS greatly improves the interface compatibility between Si and PEDOT:PSS. XPS Ar+ etching depth analysis proved that the addition of GOPS is conducive to forming a more stable SEI. A full battery assembled with NCM 523 cathode delivers a high energy density of 520 Wh kg-1, offering good stability.

Self-Supported NaTi2(PO4)3 Nanorod Arrays: Balancing Na+ and Electron Kinetics via Optimized Carbon Coating for High-Power Sodium-Ion Capacitor.

The NaTi2(PO4)3 (NTP) anode materials exhibit high Na+ diffusion dynamics; carbon-based materials can effectively improve its limited electronic conductivity. However, the low Na+ diffusion of NTP/C composite materials from inhomogeneous carbon mixing or uncontrollable carbon coating cannot keep up with fast electron transfer, leading to undesirable electrochemical performances. Herein, a uniform and controllable carbon layer is designed on the self-supported-coated NTP nanorod arrays with binder-free (NTP@C NR) to improve Na+ and electron kinetics simultaneously. As a result, the NTP@C NR electrodes possess initial coulombic efficiency (ICE = 97%), good rate capabilities (89.1 mA h g-1 at 100 C), and stability with ≈78.4% of capacity retention rate at even 30 C over 1200 cycles. The sodium-ion capacitors with NTP@C NR as an anode and commercially activated carbon as a cathode exhibit ∼9180.0 W kg-1 of power density at 10 A g-1 and super high retention of ≈94.5% at 1 A g-1 over 7000 cycles. This work will help balance transport kinetics between the ion and electron for materials applied in storage devices.

Glycerol-crosslinked PEDOT:PSS as bifunctional binder for Si anodes: Improved interfacial compatibility and conductivity.

Developing conductive polymer binders is a new way to enhance the electric connectivity and mechanical contact of Si based anode material. While the linear structure of commercial PEDOT:PSS cannot effectively alleviate the volume expansion of Si. Herein, glycerol was introduced as a cross-linker to PEDOT:PSS binder for Si anodes, which can further improve the interfacial compatibility between silicon and PEDOT:PSS. After crosslinking, the peel force increased 2 times. As a result, the Si nanoparticles anode with the glycerol-crosslinked binder exhibited a high reversible capacity of 1951.5 mAh g-1 after 200 cycles at 0.5 A g-1 and superior rate capability (804 mAh g-1 at a high current of 8.0 A g-1) for the inherent superior conductivity of PEDOT:PSS.

Catalyst-Free Decarboxylation of Carboxylic Acids and Deoxygenation of Alcohols by Electro-Induced Radical Formation.

Electro-induced reduction of redox active esters and N-phthalimidoyl oxalates derived from naturally abundant carboxylic acids and alcohols provides a sustainable and inexpensive approach to radical formation via undivided electrochemical cells. The resulting radicals are trapped by an electron-poor olefin or hydrogen atom source to furnish the Giese reaction or reductive decarboxylation products, respectively. A broad range of carboxylic acid (1°, 2°, and 3°) and alcohol (2° and 3°) derivatives are applicable in this catalyst-free reaction, which tolerated a diverse range of functional groups. This method features simple operation, is a sustainable platform, and has broad application.

Well-defined CoSe2@MoSe2 hollow heterostructured nanocubes with enhanced dissociation kinetics for overall water splitting.

Hollow heterostructures have tremendous advantages in electrochemical energy storage and conversion areas due to their unique structure and composition characteristics. Here, we report the controlled synthesis of hollow CoSe2 nanocubes decorated with ultrathin MoSe2 nanosheets (CoSe2@MoSe2) as an efficient and robust bifunctional electrocatalyst for overall water splitting in a wide pH range. It is found that integrating ultrathin MoS2 nanosheets with hollow CoSe2 nanocubes can provide abundant active sites, promote electron/mass transfer and bubble release and facilitate the migration of charge carriers. Additionally, the surface electron coupling in the heterostructures enables it to serve as a source of sites for H+ and/or OH- adsorption, thus reducing the activation barrier for water molecules adsorption and dissociation. As a result, the title compound, CoSe2@MoSe2 hollow heterostructures, exhibits an overpotential of 183 mV and 309 mV at a current density of 10 mA cm-2 toward hydrogen evolution reactions and oxygen evolution reactions in 1.0 M KOH, respectively. When applied as both cathode and anode for overall water splitting, a low battery voltage of 1.524 V is achieved along with excellent stability for at least 12 h. This work provides a new idea for the design and synthesis of high-performance catalysts for electrochemical energy storage and conversion.

Highly active nanostructured CoS2/CoS heterojunction electrocatalysts for aqueous polysulfide/iodide redox flow batteries.

Aqueous polysulfide/iodide redox flow batteries are attractive for scalable energy storage due to their high energy density and low cost. However, their energy efficiency and power density are usually limited by poor electrochemical kinetics of the redox reactions of polysulfide/iodide ions on graphite electrodes, which has become the main obstacle for their practical applications. Here, CoS2/CoS heterojunction nanoparticles with uneven charge distribution, which are synthesized in situ on graphite felt by a one-step solvothermal process, can significantly boost electrocatalytic activities of I-/I3- and S2-/Sx2- redox reactions by improving absorptivity of charged ions and promoting charge transfer. The polysulfide/iodide flow battery with the graphene felt-CoS2/CoS heterojunction can deliver a high energy efficiency of 84.5% at a current density of 10 mA cm-2, a power density of 86.2 mW cm-2 and a stable energy efficiency retention of 96% after approximately 1000 h of continuous operation.

Utilizing the Space-Charge Region of the FeNi-LDH/CoP p-n Junction to Promote Performance in Oxygen Evolution Electrocatalysis.

The modulation of electron density is an effective option for efficient alternative electrocatalysts. Here, p-n junctions are constructed in 3D free-standing FeNi-LDH/CoP/carbon cloth (CC) electrode (LDH=layered double hydroxide). The positively charged FeNi-LDH in the space-charge region can significantly boost oxygen evolution reaction. Therefore, the j at 1.485 V (vs. RHE) of FeNi-LDH/CoP/CC achieves ca. 10-fold and ca. 100-fold increases compared to those of FeNi-LDH/CC and CoP/CC, respectively. Density functional theory calculation reveals OH- has a stronger trend to adsorb on the surface of FeNi-LDH side in the p-n junction compared to individual FeNi-LDH further verifying the synergistic effect in the p-n junction. Additionally, it represents excellent activity toward water splitting. The utilization of heterojunctions would open up an entirely new possibility to purposefully regulate the electronic structure of active sites and promote their catalytic activities.

Electrochemical Semipinacol Rearrangements of Allylic Alcohols: Construction of All-Carbon Quaternary Stereocenters.

The first examples of electrochemical trifluoromethylation and sulfonylation/semipinacol rearrangements of allylic alcohols were developed using cheap and stable RSO2Na (R = CF3, Ph) as reagents. Various ß-trifluoromethyl and sulfonated ketones were obtained in moderate to excellent yields. This strategy provides a facile, direct, and complementary approach to construct all-carbon quaternary stereocenters. In addition, the reaction has the advantages of being chemical oxidant-free and metal-free and has safe and mild reaction conditions.