Cu7 S4 Research Articles

Phase Engineered CuxS-Ag2S with Photothermoelectric Activity for Enhanced Multienzyme Activity and Dynamic Therapy.

The insufficient exposure sites and active site competition of multienzyme are the two main factors to hinder its therapeutic effect. Here, a phase-junction nanomaterial (amorphous-crystalline CuxS-Ag2S) is designed and prepared through a simple room temperature ion-exchange process. A small amount of Ag+ is added into Cu7S4 nanocrystals, which transforms Cu7S4 into amorphous phased CuxS and produces crystalline Ag2S simultaneously. In this structure, the overhanging bonds on the amorphous CuxS surface provide abundant active sites for optimizing the therapeutic activity. Meanwhile, the amorphous state enhances the photothermal effect through non-radiative relaxation, and due to its low thermal resistance, phase-junction CuxS-Ag2S forms a significant temperature gradient to unlock the optimized thermo-electrodynamic therapy. Furthermore, benefiting from the high asymmetry of the amorphous state, the material forms a spin-polarized state that can effectively inhibit electron-hole recombination. In this way, the thermoelectric effect can facilitate the enzyme-catalyzed cycle by providing electrons and holes, enabling an enhanced coupling of thermoelectric therapy with multienzyme activity, which induces excellent anti-tumor performance. More importantly, the catalytic process simulated by density-functional theory proves that Ag+ alleviates the burden on the Cu sites through favorable adsorption of O2 and prevents active site competition.

Revealing the Dynamic Lithiation Process of Copper Disulfide by in Situ TEM.

Transition metal oxides, fluorides, and sulfides are extensively studied as candidate electrode materials for lithium-ion batteries driven by the urgency of developing next-generation higher energy density lithium batteries. These conversion-type electrode materials often require nanosized active materials to enable a "smooth" lithiation and de-lithiation process during charge/discharge cycles, determined by their size, structure, and phase. Herein, the structural and chemical changes of Copper Disulfide (CuS2) hollow nanoparticles during the lithiation process through an in situ transmission electron microscopy (TEM) method are investigated. The study finds the hollow structure of CuS2 facilitates the quick formation of fluidic Li2S "drops," accompanied by a de-sulfurization to the Cu7S4 phase. Meanwhile, the metallic Cu phase emerges as fine nanoparticles and grows into nano-strips, which are embedded in the Li2S/Cu7S4 matrix. These complex nanostructured phases and their spatial distribution can lead to a low de-lithiation barrier, enabling fast reaction kinetics.

Copper Activation Enabling Reversible Aqueous Cu-ZnS Battery Chemistry.

The aqueous metal-sulfide batteries (AMSBs) have attracted research interest due to their high capacity, environmentally friendly qualities, and the accessibility of raw materials. However, the design strategies for metal-sulfide cathode have rarely been reported. Here, the copper-activated sphalerite in which Zn2+ is substituted by Cu2+ through ion exchange has been introduced for the first time as cathode for aqueous Cu/ZnS batteries. After sphalerite transformed to CuS, a two-step conversion of CuS→Cu7 S4 →Cu2 S storage mechanism has been proposed. At 0.7 A g-1 current density, the capacity can reach 532.4 mAh g-1 after 100 cycles. When cycled once at a current density of 35 mA g-1 , the initial reversible capacity can reach 461 mAh g-1 under 1 A g-1 . Furthermore, the assembled Zn//ZnS hybrid ion cell delivers an energy of up to 460 Wh kg-1 , which is better than for many AMSBs.

Construction of Cu7 S4 @CuCo2 O4 Yolk-Shell Microspheres Composite and Elucidation of Its Enhanced Photocatalytic Activity, Mechanism, and Pathway for Carbamazepine Degradation.

Water pollution caused by the massive use of medicines has caused significant environmental problems. This work first reports the synthesis and characterization of the Cu7 S4 /CuCo2 O4 (CS/CCO) yolk-shell microspheres via hydrothermal and annealing methods, and then investigates their photocatalytic performance in removing organic water pollutants. The 10-CS/CCO composite with yolk-shell microspheres exhibits the highest photodegradation rate of carbamazepine (CBZ), reaching 96.3% within 2h. The 10-CS/CCO also demonstrates more than two times higher photodegradation rates than the pure (Cu7 S4 ) CS and (CuCo2 O4 ) CCO. This outstanding photocatalytic performance can be attributed to the unique yolk-shell structure and the Z-scheme charge transfer pathway, reducing multiple reflections of the acting light. These factors enhance the light absorption efficiency and efficiently transfer photoexcited charge carriers. In-depth, photocatalytic degradation pathways of CBZ are systematically evaluated via the identification of degradation intermediates with Fukui index calculation. The insights gained from this work can serve as a guideline for developing low-cost and efficient Z-scheme photocatalyst composites with the yolk-shell structure.

Elucidating the Origin of Enhanced Photocatalytic Hydrogen Production on Tuned Cu7 S4 /CdS Heterostructures.

Direct Z-scheme Cu7 S4 /CdS Janus photocatalysts are successfully prepared by cation exchange method. Extensive studies containing single-nanoparticle impact electrochemistry are performed and reveal that optimizing the Cu7 S4 /CdS ratio can decrease the accumulation of holes on valence band of CdS for inhibiting photo-corrosion and promote the accumulation of electrons on the conduction band of Cu7 S4 for boosting the electron reducibility. With the optimized heterostructures, hydrogen evolution is remarkable promoted up to 21.62 mmol/g/h and quantum efficiency is up to 14.37% using polylactic acid plastic waste as feedstock.

Self-Assembled Supercrystals Enhance the Photothermal Conversion for Solar Evaporation and Water Purification.

Photothermal materials can convert renewable solar energy into thermal energy and have great potential for solar water evaporation. Copper sulfide (Cu2- x S) is an easily available and inexpensive plasmonic material with a high photothermal conversion efficiency and can be applied to solar evaporation and water purification. Monodispersed Cu7 S4 nanoparticles (NPs) and supercrystalline self-assembled superparticles are obtained via wet chemical synthesis and micelle self-assembly. The photothermal properties of the superstructures are investigated using the finite difference time domain method and laser radiation photothermography. The results show that the electromagnetic field intensity and photothermal efficiency of the self-assembly are significantly higher than those of isolated NPs, which is due to the plasmonic coupling of the NPs. The evaporation efficiency of the superstructure is significantly higher than that of isolated NPs, the metal salt ion and total organic carbon concentrations in the waterbody significantly decrease after evaporation, and the water polluted by high salt and organic dye concentrations is purified. The water quality significantly improves after the lake water from Fuxian Lake in the Yunnan-Guizhou Plateau of China is used for solar evaporation. The color changes from pale yellow to colorless and the ion and total organic carbon contents significantly decrease.

High-Performance Memristors Based on Ultrathin 2D Copper Chalcogenides.

Copper chalcogenides represent a class of materials with unique crystal structures, high electrical conductivity, and earth abundance, and are recognized as promising candidates for next-generation green electronics. However, their 2D structures and the corresponding electronic properties have rarely been touched. Herein, a series of ultrathin copper chalcogenide nanosheets with thicknesses down to two unit cells are successfully synthesized, including layered Cu2 Te, as well as nonlayered CuSe and Cu9 S5 , via van der Waals epitaxy, and their nonvolatile memristive behavior is investigated for the first time. Benefiting from the highly active Cu ions with low migration barriers, the memristors based on ultrathin 2D copper chalcogenide crystals exhibit relatively small switching voltage (≈0.4V), fast switching speed, high switching uniformity, and wide operating temperature range (from 80 to 420 K), as well as stable retention and good cyclic endurance. These results demonstrate their tangible applications in future low-power, cryogenic, and high temperature harsh electronics.

2D Cu9 S5 /PtS2 /WSe2 Double Heterojunction Bipolar Transistor with High Current Gain.

Bipolar junction transistor (BJT) as one important circuit element is now widely used in high-speed computation and communication for its capability of high-power signal amplification. 2D materials and their heterostructures are promising in building high-amplification and high-frequency BJTs because they can be naturally thin and highly designable in tailoring components properties. However, currently the low emitter injection efficiency results in only moderate current gain achieved in the pioneer researches, severely restraining its future development. Herein, it is shown that an elaborately designed double heterojunction bipolar transistor (DHBT) can greatly promote the injection efficiency, improving the current gain by order of magnitude. In this DHBT high-doping-density wide-bandgap 2D Cu9 S5 is used as emitter and narrow-bandgap PtS2 as base. This heterostructure efficiently suppresses the reverse electron flux from base and increase the injection efficiency. Consequently, the DHBT achieves an excellent current gain (β ≈ 910). This work systematically explores the electrical behavior of 2D materials based DHBT, and provides deep insight of the architecture design for building high gain DHBT, which may promote the applications of 2Dheterojunctions in the fields of integrated circuits.

Pd@Au Bimetallic Nanoplates Decorated Mesoporous MnO2 for Synergistic Nucleus-Targeted NIR-II Photothermal and Hypoxia-Relieved Photodynamic Therapy.

Bimetallic nanoparticles have received considerable attention owing to synergistic effect and their multifunctionality. Herein, new multifunctional Pd@Au bimetallic nanoplates decorated hollow mesoporous MnO2 nanoplates (H-MnO2 ) are demonstrated for achieving not only nucleus-targeted NIR-II photothermal therapy (PTT), but also tumor microenvironment (TME) hypoxia relief enhanced photodynamic therapy (PDT). The Pd@Au nanoplates present a photothermal conversion efficiency (PTCE) as high as 56.9%, superior to those PTAs activated in the NIR-II region such as Cu9 S5 nanoparticles (37%), Cu3 BiS3 nanorods (40.7%), and Au/Cu2-x S nanocrystals (43.2%). They further functionalize with transactivator of transcription (TAT) moiety for cell nuclear-targeting and biodegradable hollow mesoporous MnO2 (≈100 nm) loaded with photosensitizer Ce6 (TAT-Pd@Au/Ce6/PAH/H-MnO2 ) to construct a hierarchical targeting nanoplatform. The as-made TAT-Pd@Au/Ce6/PAH/H-MnO2 demonstrates good premature renal clearance escape ability and increased tumor tissue accumulation. It can be degraded in acidic TME and generate O2 by reacting to endogenous H2 O2 to relieve the hypoxia for enhanced PDT, while the released small TAT-Pd@Au nanoplates can effectively enter into the nucleus to mediate PTT. As a result, a remarkable therapeutic effect is achieved owing to the synergistic PTT/PDT therapy. This hierarchical targeting, TME-responsive, cytoplasm hypoxia relief PDT, and nuclear NIR-II PTT synergistic therapy can pave a new avenue for nanomaterials-based cancer therapy.

A Photochemical Route towards Metal Sulfide Nanosheets from Layered Metal Thiolate Complexes.

Synthesizing nanomaterials with anisotropic architectures, especially two-dimensional (2D) nanosheets (NSs), is a key focus of materials science research. Metal sulfide nanosheets (MSNSs) are typically obtained involving exfoliation of bulk metal sulfides with layered structures. The synthesis of NSs of intrinsically non-layered metal sulfides has received relatively less attention. Metal alkanethiolates with lamellar structures are now shown to serve as effective scaffolds for constructing NSs. A novel photochemical step was employed to transform 2D metal thiolates into MSNSs. By this strategy the 2D nature of metal thiolate precursors was preserved in the final products, resulting in the successful synthesis of NSs of binary PbS, CdS, and Cu9 S5 , as well as ternary wurtzite CuInS2 , Cu2 SnS3 . Results encourage the wider utilization of photochemical strategies in the synthesis of anisotropic MSNSs.

Bullet-like Cu9 S5 Hollow Particles Coated with Nitrogen-Doped Carbon for Sodium-Ion Batteries.

Metal sulfides with excellent redox reversibility and high capacity are very promising electrode materials for sodium-ion batteries. However, their practical application is still hindered by the poor rate capability and limited cycle life. Herein, a template-based strategy is developed to synthesize nitrogen-doped carbon-coated Cu9 S5 bullet-like hollow particles starting from bullet-like ZnO particles. With the structural and compositional advantages, these unique nitrogen-doped carbon-coated Cu9 S5 bullet-like hollow particles manifest excellent sodium storage properties with superior rate capability and ultra-stable cycling performance.

Natural Humic-Acid-Based Phototheranostic Agent.

Humic acids, a major constituent of natural organic carbon resources, are naturally formed through the microbial biodegradation of animal and plant residues. Due to numerous physiologically active groups (phenol, carboxyl, and quinone), the biomedical applications of humic acid have been already investigated across different cultures for several centuries or even longer. In this work, sodium humate, the sodium salt of humic acid, is explored as phototheranostic agent for light-induced photoacoustic imaging and photothermal therapy based on intrinsic absorption in the near-infrared region. The purified colloidal sodium humate exhibits a high photothermal conversion efficiency up to 76.3%, much higher than that of the majority of state-of-the-art photothermal agents including gold nanorods, Cu9 S5 nanoparticles, antimonene quantum dots, and black phosphorus quantum dots, leading to obvious photoacoustic enhancement in vitro and in vivo. Besides, highly effective photothermal ablation of HeLa tumor is achieved through intratumoral injection. Impressively, sodium humate reveals ultralow toxicity at the cellular and animal levels. This work promises the great potential of humic acids as light-mediated theranostic agents, thus expanding the application scope of traditional humic acids in biomedical field.

Noble-Metal-Free Janus-like Structures by Cation Exchange for Z-Scheme Photocatalytic Water Splitting under Broadband Light Irradiation.

Z-scheme water splitting is a promising approach based on high-performance photocatalysis by harvesting broadband solar energy. Its efficiency depends on the well-defined interfaces between two semiconductors for the charge kinetics and their exposed surfaces for chemical reactions. Herein, we report a facile cation-exchange approach to obtain compounds with both properties without the need for noble metals by forming Janus-like structures consisting of γ-MnS and Cu7 S4 with high-quality interfaces. The Janus-like γ-MnS/Cu7 S4 structures displayed dramatically enhanced photocatalytic hydrogen production rates of up to 718 μmol g-1 h-1 under full-spectrum irradiation. Upon further integration with an MnOx oxygen-evolution cocatalyst, overall water splitting was accomplished with the Janus structures. This work provides insight into the surface and interface design of hybrid photocatalysts, and offers a noble-metal-free approach to broadband photocatalytic hydrogen production.

Plasmon Enhanced Direct Bandgap Emissions in Cu7 S4 @Au2 S@Au Nanorings.

Nanostructured copper sulfides, promising earth-abundant p-type semiconductors, have found applications in a wide range of fields due to their versatility, tunable low bandgap, and environmental sustainability. The synthesis of hexagonal Cu7 S4 @Au2 S@Au nanorings exhibiting plasmon enhanced emissions at the direct bandgap is reported. The synthesized Cu7 S4 @Au2 S@Au nanorings show greatly enhanced absorption and emission by local plasmons compared to pure copper sulfide nanoparticles.

Shape-Controlled Synthesis of High-Quality Cu7S4Nanocrystals for Efficient Light-Induced Water Evaporation

Copper sulfides (Cu2-x S), are a novel kind of photothermal material exhibiting significant photothermal conversion efficiency, making them very attractive in various energy conversion related devices. Preparing high quality uniform Cu2-x S nanocrystals (NCs) is a top priority for further energy-and sustainability relevant nanodevices. Here, a shape-controlled high quality Cu7 S4 NCs synthesis strategy is reported using sulfur in 1-octadecene as precursor by varying the heating temperature, as well as its forming mechanism. The performance of the Cu7 S4 NCs is further explored for light-driven water evaporation without the need of heating the bulk liquid to the boiling point, and the results suggest that as-synthesized highly monodisperse NCs perform higher evaporation rate than polydisperse NCs under the identical morphology. Furthermore, disk-like NCs exhibit higher water evaporation rate than spherical NCs. The water evaporation rate can be further enhanced by assembling the organic phase Cu7 S4 NCs into a dense film on the aqueous solution surface. The maximum photothermal conversion efficiency is as high as 77.1%.

Ultrasmall Cu7 S4 @MoS2 Hetero-Nanoframes with Abundant Active Edge Sites for Ultrahigh-Performance Hydrogen Evolution.

Increasing the active edge sites of molybdenum disulfide (MoS2 ) is an efficient strategy to improve the overall activity of MoS2 for the hydrogen-evolution reaction (HER). Herein, we report a strategy to synthesize the ultrasmall donut-shaped Cu7 S4 @MoS2 hetero-nanoframes with abundant active MoS2 edge sites as alternatives to platinum (Pt) as efficient HER electrocatalysts. These nanoframes demonstrate an ultrahigh activity with 200 mA cm(-2) current density at only 206 mV overpotential using a carbon-rod counter electrode. The finding may provide guidelines for the design and synthesis of efficient and non-precious chalcogenide nanoframe catalysts.

Cu7 S4 Nanosuperlattices with Greatly Enhanced Photothermal Efficiency.

According to the simulation, the self-assembly of Cu7 S4 nanocrystals would enhance the photothermal conversion efficiency (PCE) because of the localized surface plasmon resonance effects, which is highly desirable for photothermal therapy (PTT). A new strategy to synthesize Cu7 S4 nanosuperlattices with greatly enhanced PCE up to 65.7% under irradiation of 808 nm near infrared light is reported here. By tuning the surface properties of Cu7 S4 nanocrystals during the synthesis via thermolysis of a new single precursor, dispersed nanoparticles (NPs), rod-like alignments, and nanosuperlattices are obtained, respectively. To explore their PTT applications, these hydrophobic nanostructures are transferred into water by coating with home-made amphiphilic polymer while maintaining their original structures. Under identical conditions, the PCE are 48.62% and 56.32% for dispersed NPs and rod-like alignments, respectively. As expected, when the nanoparticles are self-assembled into nanosuperlattices, the PCE is greatly enhanced up to 65.7%. This strong PCE, along with their excellent photothermal stability and good biocompatibility, renders these nanosuperlattices good candidates as PTT agents. In vitro photothermal ablation performances have undoubtedly proved the excellent PCE of our Cu7 S4 nanosuperlattices. This research offers a versatile and effective solution to get PTT agents with high photothermal efficiency.

Cube-in-cube hollow Cu9 S5 nanostructures with enhanced photocatalytic activities in solar H2 evolution.

Hydrogen produced from water under solar energy is an ideal clean energy source, and the efficiency of hydrogen production usually depends on the catalytic systems based on new compounds and/or a unique nanostructure. Herein, well-defined cube-in-cube hollow Cu9 S5 nanostructures have been successfully prepared with Cu2 O nanocubes and CS2 as precursors, and single-shell hollow Cu9 S5 nanocubes could be obtained by replacing CS2 with Na2 S. The formation mechanism of cube-in-cube hollow nanostructures has been proposed based on the Kirkendell effect and an outward self-assembly process. Further studies revealed that the cube-in-cube hollow Cu9 S5 nanostructures exhibited better photocatalytic activity toward solar H2 evolution and would be a promising photocatalyst in the solar hydrogen industry.

Controllable synthesis of wurtzite Cu(2)ZnSnS(4) nanocrystals by hot-injection approach and growth mechanism studies.

Wurtzite Cu2 ZnSnS4 (WZ-CZTS) has been controllably synthesized through a hot-injection route. The crystal-growth mechanism of WZ-CZTS has been investigated by using time-dependent XRD patterns, TEM images, and absorption spectra analysis, and revealed that WZ-CZTS nucleated and grew from monoclinic Cu7 S4 nanocrystals through phase transformation of Cu7 S4 to WZ-CZTS within 5 min. The synthesis processes are dependent on precursor concentration, reaction temperature, reaction time, organic ligand, and sulfur source and have been studied in detail. It was revealed that the width of the WZ-CZTS nanocrystals was mainly controlled by the precursor concentration, which determines the diameter of Cu7 S4 . The length could be regulated by the ratio of dodecanethiol (DDT) to oleylamine (OLA) and reaction time.