RESUMEN

CdS quantum dots (CdS QDs) are regarded as a promising photocatalyst due to their remarkable response to visible light and suitable placement of conduction bands and valence bands. However, the problem of photocorrosion severely restricts their application. Herein, the CdS QDs-Co9S8 hollow nanotube composite photocatalyst has been successfully prepared by loading Co9S8 nanotubes onto CdS QDs through an electrostatic self-assembly method. The experimental results show that the introduction of Co9S8 cocatalyst can form a stable structure with CdS QDs, and can effectively avoid the photocorrosion of CdS QDs. Compared with blank CdS QDs, the CdS QDs-Co9S8 composite exhibits obviously better photocatalytic hydrogen evolution performance. In particular, CdS QDs loaded with 30% Co9S8 (CdS QDs-30%Co9S8) demonstrate the best photocatalytic performance, and the H2 production rate reaches 9642.7 µmol·g-1·h-1, which is 60.3 times that of the blank CdS QDs. A series of characterizations confirm that the growth of CdS QDs on Co9S8 nanotubes effectively facilitates the separation and migration of photogenerated carriers, thereby improving the photocatalytic hydrogen production properties of the composite. We expect that this work will facilitate the rational design of CdS-based photocatalysts, thereby enabling the development of more low-cost, high-efficiency and high-stability composites for photocatalysis.

RESUMEN

Efficient oxygen evolution reaction (OER) is vital for water electrolysis and advanced hydrogen energy production. However, the sluggish kinetics of this reaction require significant overpotentials, leading to high energy consumption. Therefore, developing OER electrocatalysts with exceptional performance and long-term durability is crucial for enhancing the energy efficiency and cost-effectiveness of the hydrogen production process. In this research, novel FeOOH/Co9S8 catalysts were prepared through a two-step hydrothermal reaction followed by one-step electrodeposition on nickel foam for an alkaline OER. The as-obtained catalysts possessed abundant non-homogeneous interfaces between FeOOH and Co9S8 nanosheets, conducive to optimized coordination environments of Fe and Co sites by redistributing interfacial charges. This synergy strengthened the chemisorption of oxygenated intermediates, leading to accelerated reaction kinetics, abundant active sites, and enhanced OER performance. The optimized electrocatalyst FeOOH/Co9S8-15 achieved a current density of 10 mA cm-2 at an overpotential of 248 mV and good stability for over 140 h. This study presents a novel approach for producing compelling and durable alkaline dielectric OER electrocatalysts, which will be helpful in the future manufacturing of advanced energy devices.

RESUMEN

Atomic doping is widely employed to fine-tune crystal structures, energy band structures, and the corresponding electrical properties. However, due to the difficulty in precisely regulating doping sites and concentrations, establishing a relationship between electricity properties and doping becomes a huge challenge. In this work, a modulation strategy on A-site cation dopant into spinel-phase metal sulfide Co9S8 lattice via Fe and Ni elements is developed to improve the microwave absorption (MA) properties. At the atomic scale, accurately controlling doped sites can introduce local lattice distortions and strain concentration. Tunned electron energy redistribution of the doped Co9S8 strengthens electron interactions, ultimately enhancing the high-frequency dielectric polarization (ɛ' from 10.5 to 12.5 at 12 GHz). For the Fe-doped Co9S8, the effective absorption bandwidth (EAB) at 1.7 mm increases by 5%, and the minimum reflection loss (RLmin) improves by 26% (EAB = 5.8 GHz, RLmin = -46 dB). The methodology of atomic-scale fixed-point doping presents a promising avenue for customizing the dielectric properties of nanomaterials, imparting invaluable insights for the design of cutting-edge high-performance microwave absorption materials.

RESUMEN

Developing an efficient and low-cost oxygen reduction electrocatalyst is essential for the application of aqueous zinc-air batteries (ZABs). Herein, we report a facile adsorption-confined pyrolysis strategy to fabricate the hybrid electrocatalyst (denoted as Co9S8/CoSA-PC) by embedding Co9S8 nanoparticles into Co single atoms (Co-SAs) anchored porous carbon sheets for boosting oxygen reduction reaction (ORR) durability. In this strategy, the Co2+ ions are first absorbed into oxygen-rich porous carbon nanosheets and further form the Co-SAs with the help of thiourea in the following pyrolysis procedure, which is believed to be able to confine the generated Co9S8 nanoparticles into carbon frameworks due to their interface interaction. Benefiting from the synergistic effect of different components, the obtained Co9S8/CoSA-PC electrocatalyst for ORR exhibits outstanding catalytic activity with a half-wave potential of 0.82 V and a distinguished long-term durability with a current retention of 80 % after cycling 80 h under alkaline conditions, which is superior to commercial Pt/C. Moreover, the assembled ZABs with Co9S8/CoSA-PC as cathodic catalyst deliver a high specific capacity of 764 mAh gZn-1 at 10 mA cm-2 and the outstanding peak power density of up to 221.4 mW cm-2. This work provides a novel structure design strategy to prepare transition metal sulfide-based electrocatalysts with superior durability for ORR.

RESUMEN

Co9S8 has been extensively studied as a promising catalyst for water electrolysis. Doping Co9S8 with Fe improves its oxygen evolution reaction (OER) performance by regulating the catalyst self-reconfigurability and enhancing the absorption capacity of OER intermediates. However, the poor alkaline hydrogen evolution reaction (HER) properties of Co9S8 limit its application in bifunctional water splitting. Herein, we combined Fe doping and sulfur vacancy engineering to synergistically enhance the bifunctional water-splitting performance of Co9S8. The as-synthesized Co6Fe3S8 catalyst exhibited excellent OER and HER characteristics with low overpotentials of 250 and 84 mV, respectively. It also resulted in the low Tafel slopes of 135 mV dec-1 for the OER and 114 mV dec-1 for the HER. A two-electrode electrolytic cell with Co6Fe3S8 used as both the cathode and anode produced a current density of 10 mA cm-2 at a low voltage of only 1.48 V, maintaining high stability for 100 h. The results of in/ex-situ experiments indicated that the OER process induced electrochemical reconfiguration, forming CoOOH/FeOOH active species on the catalyst surface to enhance its OER performance. Density functional theory (DFT) simulations revealed that Fe doping and the presence of unsaturated coordination metal sites in Co6Fe3S8 promoted H2O and H* adsorption for the HER. The findings of this study can help develop a strategy for designing highly efficient bifunctional water splitting electrocatalysts.

RESUMEN

The increase of reaction temperature of electrocatalysts and the construction of heterogeneous structures is regarded as an efficient method to improve the electrocatalytic water splitting activity. Here, we report an approach to enhance the local heat and active sites of the catalyst by building a heterostructure with Co9S8 to significantly improve its electrocatalytic performance. The as-fabricated Co9S8@Ce-NiCo LDH/NF electrode possesses a notable photothermal ability, as it effectively converts near-infrared (NIR) light into the local heat, owing to its significant optical absorption. Leveraging these favorable qualities, the prepared Co9S8@Ce-NiCo LDH/NF electrode showed impressive performance in both hydrogen evolution reaction (HER) (η100 = 144 mV) and oxygen evolution reaction (OER) (η100 = 229 mV) under NIR light. Compared to the absence of the NIR light, the presence of NIR irradiation leads to a 24.6 % increase in catalytic efficiency for HER and a 15.8 % increase for OER. Additionally, other dual-functional electrocatalysts like NiCo-P, NiFeMo, and NiFe(OH)x also demonstrated significantly enhanced photothermal effects and improved catalytic performance owing to the augmented photothermal conversion when combined with Co9S8. This work offers novel pathways for the development of photothermal-electrocatalytic systems that facilitate economically efficient and energy-conserving overall water splitting processes.

RESUMEN

Designing bifunctional low-cost photo-assisted electrocatalysts for converting solar and electric energy into hydrogen energy remains a huge challenge. Herein, a heterojunction (Fe cluster modified Co9 S8 loaded on carbon nanotubes, Co9 S8 -Fe@CNT) for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is demonstrated. Benefiting from the good electronic conductivity and spatial confinement of the carbon skeleton, as well as the electronic structure regulation of the Fe cluster, Co9 S8 -Fe@CNT exhibits excellent catalytic performance with a low overpotential of 150 mV for OER and 135 mV for HER at 10 mA cm-2 . Upon light irradiation, holes and electrons are generated in the valence band and conduction band of the Co9 S8 , respectively. Part of the charges are transferred to the interface to facilitate the catalytic reaction, while the remaining are transferred by the electrode. When working as a bifunctional catalyst for overall water splitting, the performance can reach 1.33 V at under light conditions, which is significantly better than 1.52 V in a dark environment. Theoretical calculations revealed lowered Gibbs free energy (∆GH *) of the heterojunction with the effect of Fe modification of Co9 S8 . This work sheds a new light in designing novel photoelectrochemical materials to convert solar and electric energy into chemical energy.

RESUMEN

Transition metal sulfides (TMSs) are considered as promising anodes for sodium-ion batteries (SIBs) due to their high theoretical capacity and low cost. However, TMSs suffer from massive volume expansion, slow sodium-ion diffusion kinetics, and poor electrical conductivity, which severely restrict their practical application. Herein, we design self-supporting Co9S8 nanoparticles embedded carbon nanosheets/carbon nanofibers (Co9S8@CNSs/CNFs) as anode materials for SIBs. The electrospun carbon nanofibers (CNFs) provide continuous conductive networks to accelerate the ion and electron diffusion/transport kinetics, while MOFs-derived carbon nanosheets (CNSs) buffer the volume variation of Co9S8, consequently improving the cycle stability. Benefitting from the unique design and pseudocapacitive features, Co9S8@CNSs/CNFs deliver a stable capacity of 516 mAh g-1 at 200 mA g-1 and a reversible capacity of 313 mAh g-1 after 1500 cycles at 2 A g-1. Note that, it also displays excellent sodium storage performance when assembled into a full cell. The rational design and excellent electrochemical properties endow Co9S8@CNSs/CNFs with the potential stepping into commercial SIBs.

RESUMEN

The development of highly active and stable earth-rich electrocatalysts remains a major challenge to release the reliance on noble metal catalysts in sustainable (electro)chemical processes. In this work, metal sulfides encapsulated with S/N co-doped carbon were synthesized with a one-step pyrolysis strategy, where S was introduced during the self-assembly process of sodium lignosulfonate. Due to the precise coordination of Ni and Co ions with lignosulfonate, an intense-interacted Co9S8-Ni3S2 heterojunction was formed inside the carbon shell, causing the redistribution of electrons. An overpotential as low as 200 mV was obtained over Co9S8-Ni3S2@SNC to reach a current density of 10 mA cm-2. Only a slight increase of 14.4 mV was observed in a 50 h chronoamperometric stability test. Density functional theory (DFT) calculations showed that Co9S8-Ni3S2 heterojunctions encapsulated with S/N co-doped carbon can optimize the electronic structure, lower the reaction energy barrier, and improve the OER reaction activity. This work provides a novel strategy for constructing highly efficient and sustainable metal sulfide heterojunction catalysts with the assistance of lignosulfonate biomass.

RESUMEN

Lithium-sulfur batteries (LSBs) are recognized as the prospective candidate in next-generation energy storage devices due to their gratifying theoretical energy density. Nonetheless, they still face the challenges of the practical application including low utilization of sulfur and poor cycling life derived from shuttle effect of lithium polysulfides (LiPSs). Herein, a hollow polyhedron with heterogeneous CoO/Co9 S8 /nitrogen-doped carbon (CoO/Co9 S8 /NC) is obtained through employing zeolitic imidazolate framework as precursor. The heterogeneous CoO/Co9 S8 /NC balances the redox kinetics of Co9 S8 with chemical adsorption of CoO toward LiPSs, effectively inhibiting the shuttle of LiPSs. The mechanisms are verified by both experiment and density functional theory calculation. Meanwhile, the hollow structure acts as a sulfur storage chamber, which mitigates the volumetric expansion of sulfur and maximizes the utilization of sulfur. Benefiting from the above advantages, lithium-sulfur battery with S-CoO/Co9 S8 /NC achieves a high initial discharge capacity (1470 mAh g-1 ) at 0.1 C and long cycle life (ultralow capacity attenuation of 0.033% per cycle after 1000 cycles at 1 C). Even under high sulfur loading of 3.0 mg cm-2 , lithium-sulfur battery still shows the satisfactory electrochemical performance. This work may provide an idea to elevate the electrochemical performance of LSBs by constructing a hollow metal oxide/sulfide/nitrogen-doped carbon heterogeneous structure.

RESUMEN

The electrocatalytic hydrogen evolution activity of transition metal sulfide heterojunctions are significantly increased when compared with that of a single component, but the mechanism behind the performance enhancement and the preparation of catalysts with specific morphologies still need to be explored. Here, we prepared a Co9S8/MoS2 heterojunction with microsphere morphology consisting of thin nanosheets using a facile two-step method. There is electron transfer between the Co9S8 and MoS2 of the heterojunction, thus realizing the redistribution of charge. After the formation of the heterojunction, the density of states near the Fermi surface increases, the d-band center of the transition metal moves downward, and the adsorption of both water molecules and hydrogen by the catalyst are optimized. As a result, the overpotential of Co9S8/MoS2 is superior to that of most relevant electrocatalysts reported in the literature. This work provides insight into the synergistic mechanisms of heterojunctions and their morphological regulation.

RESUMEN

A Z-scheme Cd0.85Zn0.15S/Co9S8(CZS-CS) photocatalyst was reasonably fabricated by a simple solvothermal method for the effective visible-light-driven H2evolution and organic pollutants degradation. The precise construction of the CZS-CS composites provided an efficient heterogeneous contact interface and abundant reaction sites for the proposed photocatalytic reaction. The homogeneous Co9S8nanocrystals were uniformly wrapped on the surface of Cd0.85Zn0.15S nanorods, forming an intimate-contact interface, markedly contributed to the light collection and effectively inhibited the charge-carrier recombination. The optimized CZS-CS-15 composites exhibited a special H2production rate reaching 19.15 mmol·h-1·g-1, roughly 1915 and 4.5 times of pure Co9S8and Cd0.85Zn0.15S samples and 85% of tetracycline (TC) molecule within 15 min was degraded. Furthermore, trapping experiments confirmed that h+was the main active species for TC photodegradation. Moreover, the obtained photocatalysts manifested stability without apparent activity declines during the proposed reactions. Finally, the Z-scheme photocatalytic mechanism was verified to illustrate the characteristics of efficient charge transfer and high redox ability. This study provided a rational and learnable strategy for designing dual-functional Z-scheme heterojunction photocatalysts.

RESUMEN

The development of nonprecious metal-based electrocatalysts with remarkable catalytic activity and long-cycling lifespan toward oxygen reduction reaction (ORR) and evolution reaction (OER) is especially important for rechargeable zinc-air batteries (ZABs). Herein, monodispersed Co9 S8 nanoparticles embedded in nitrogen-doped hierarchically porous hollow carbon spheres (Co9 S8 NPs/NHCS) are synthesized through a template-assisted strategy followed by a co-assembly, thermal annealing, and sulfurization process. Benefiting from larger specific surface area, hierarchically porous hollow structure, and carbon nanotubes self-growth, the obtained Co9 S8 NPs/NHCS-0.5 electrocatalyst exhibits decent performance for ORR (E1/2 =0.85 V) and OER (E10 =1.55 V). A rechargeable ZAB assembled using the Co9 S8 NPs/NHCS-0.5 as air cathode delivers a maximum power density of 116 mW cm-2 , high open circuit voltage of 1.47 V, and good durability (no obvious voltage decay after 1200 cycles (200 hours)). Such a hierarchically porous hollow structure of Co9 S8 NPs/NHCS-0.5 provides a confined space shell and an interconnected hollow core to achieve outstanding bifunctional catalytic activity and cycling stability, which surpass the benchmark Pt/C-RuO2 .

RESUMEN

Although lithium-sulfur batteries (LSBs) promise high theoretical energy density and potential cost effectiveness, their applications are severely impeded by the shuttling and sluggish redox kinetics of lithium polysulfides (LiPSs). In this context, a Co9 S8 @MoS2 heterostructure is sophisticatedly designed as an efficient catalytic host to boost the sulfur reduction reaction/evolution reaction (SRR/SER) kinetics and suppresses the LiPSs shuttling in LSBs. The results indicate that the electronic structure is manipulated in the Co9 S8 @MoS2 heterostructure, where the built-in electric fields (BIEFs) within the heterointerfaces enable the sufficient adsorption sites to accelerate the ionic diffusion/charge transfer kinetics for LiPSs redox, thus enhancing the sulfur conversion. By tuning the electronic structure, the metal d-band of Co9 S8 @MoS2 heterostructure plays an important role in adsorbing and catalyzing the conversion of LiPSs, thus promoting the reaction kinetics of the corresponding LSBs. This work unlocks the potential of heterostructures as promising catalysts to the design of high-energy and stabilized LSBs.

RESUMEN

Photocatalytic H2O2 production is an eco-friendly technique because only H2O, molecular O2 and light are involved. However, it still confronts the challenges of the unsatisfactory productivity of H2O2 and the dependence on organic electron donors or high purity O2, which restrict the practical application. Herein, we construct a type-II heterojunction of the protonated g-C3N4 coated Co9S8 semiconductor for photocatalytic H2O2 production. The ultrathin g-C3N4 uniformly spreads on the surface of the dispersed Co9S8 nanosheets by a two-step method of protonation and dip-coating, and exhibits improved photogenerated electrons transportability and e--h+ pairs separation ability. The photocatalytic system can achieve a considerable productivity of H2O2 to 2.17 mM for 5 h in alkaline medium in the absence of the organic electron donors and pure O2. The optimal photocatalyst also obtains the highest apparent quantum yield (AQY) of 18.10% under 450 nm of light irradiation, as well as a good reusability. The contribution of the type-II heterojunction is that the migrations of electrons and holes within the interface between g-C3N4 and Co9S8 matrix promote the separation of photocarriers, and another channel is also opened for H2O2 generation. The accumulated electrons in conduction band (CB) of Co9S8 contribute to the major channel of two-electron reduction of O2 for H2O2 production. Meanwhile, the electrons in CB of g-C3N4 participate in the single electron reduction of O2 as an auxiliary channel to enhance the H2O2 production.

RESUMEN

Accelerating phase transposition efficiency of lithium polysulfides (LiPSs) to L2S and hampering the solution of LiPSs are the keys to stabilizing lithium-sulfur (Li-S) batteries. Hence, the sulfiphilic ultrafine Co9S8 nanoparticles embedded lithiophilic N, S co-doping carbon nanofibers (Co9S8/NSCNF) are prepared via the dual-template method, which are then used as sulfur host in Li-S batteries. Particularly, the double active sites (Co9S8 and N, S) in Co9S8/NSCNF are prone to form "Co-S", "Li-O" or "Li-N" bonds, and then simultaneously improving the chemisorption and interface transposition capability of LiPSs. In case of the S@ Co9S8/NSCNF composites with high sulfur loading of 89% are employed as cathode, the cell possesses optimized "sulfiphilicity" and "lithiophilicity", which achieves remarkable sulfur electrochemistry, including outstanding reversibility of 816.8mAhg-1 over 500 cycles at 1.0C, excellent rate property of 742.2mAhg-1at 5.0C, and long-term cycling with a low attenuation of 0.011% per cycle over 1800 cycles at 3.0C. Impressively, a remarkable areal capacity of 11.51mAhcm-2 is retained under the sulfur loading of 15.3 mg cm-2 for 50 cycles. This research will deepen the understanding of the complex LiPSs interface transposition procedure and provide new ideas for the design of new host materials.

RESUMEN

We developed a molten salts process to prepare Co9 S8 nanoparticles (NPs) entrapped, S, N co-doped carbons. Cobalt chloride was used as the cobalt source. The melamine-formaldehyde (MF) resin provided the carbon source and nitrogen source, and thiourea provided sulfur source. In addition, common inorganic salts were added as templates to generate pores. The characterization results showed that the prepared materials contained high contents of N, S and Co, and were mesoporous composites. At the same time, the porosity of electrocatalyst depended on the type of salt and the mass ratio of precursor to salt, which further affected the electrocatalytic activity of hydrogen evolution reaction (HER). The best prepared catalyst showed excellent HER performance. The onset overpotential of the catalyst was low (33 mV) and had a small Tafel slope (61.1 mV dec-1 ), in addition to good stability in alkaline media.

Asunto(s)

RESUMEN

Sulfides are perceived as promising anode materials for potassium-ion batteries (PIBs) due to their high theoretical specific capacity and structural diversity. Nonetheless, the poor structural stability and sluggish kinetics of sulfides lead to unsatisfactory electrochemical performance. Herein, Ni3 S2 -Co9 S8 heterostructures with an open-ended nanocage structure wrapped by reduced graphene oxide (Ni-Co-S@rGO cages) are well designed as the anode for PIBs via a selective etching and one-step sulfuration approach. The hollow Ni-Co-S@rGO nanocages, with large surface area, abundant heterointerfaces, and unique open-ended nanocage structure, can reduce the K+ diffusion length and promote reaction kinetics. When used as the anode for PIBs, the Ni-Co-S@rGO exhibits high reversible capacity and low capacity degradation (0.0089% per cycle over 2000 cycles at 10 A g-1 ). A potassium-ion full battery with a Ni-Co-S@rGO anode and Prussian blue cathode can display a superior reversible capacity of 400 mAh g-1 after 300 cycles at 2 A g-1 . The unique structural advantages and electrochemical reaction mechanisms of the Ni-Co-S@rGO are revealed by finite-element-simulation in situ characterizations. The universal synthesis technology of bimetallic sulfide anodes for advanced PIBs may provide vital guidance to design high-performance energy-storage materials.

RESUMEN

Electrochemical water splitting for hydrogen production using cost-effective and high-efficiency electrocatalysts in alkaline electrolytes is of great significance for solving energy crisis and environmental pollution. Herein, we reported a superhydrophilic and underwater superaerophobic multistage layered micro-nano structure ofCo9S8-Ni3S2-CNTs/NF on nickel foam (NF) prepared by a simple one-step hydrothermal procedure. Particularly, the multistage layered micro-nano structure makes the electrode superhydrophilic and superaerophobic, which can facilitate the exposure of active sites, accelerate the tansfer of electrolyte and the release of gas bubbles. Consequently, the rough electrode demonstrated excellent catalytic performance in alkaline condition, which only need a low overpotential 127 mV for oxygen evolution reaction (OER) and 243 mV for hydrogen evolution reaction (HER) at 10 mA cm-2 and can keep a long durability for 10 h at 10 mA cm-2. In addition, the production of hydrogen in an electrolytic water device with Co9S8-Ni3S2-CNTs/NF as bifunctional electrode prowered by the electricity derived from solar and wind energy in laboratory condition was artificially simulated. This work represents a perspective in improving the electrocatalytic performance of water splitting by structure and wettability regulation and opens a new avenue for clean energy generation.

RESUMEN

Morphology optimization is an effective strategy to take full advantage of interface polarization for the improvement of electromagnetic wave attenuation capability. Herein, a general route was proposed to produce the flower-like core@shell structured MoS2-based nanocomposites through a simple hydrothermal process. Through the in-situ hydrothermal reaction between the Mo and S sources on the surface of CoNi nanoparticles, flower-like core@shell structured CoNi2S4/Co9S8@MoS2 nanocomposites could be successfully synthesized. By regulating the hydrothermal temperature, the flower-like geometrical morphology of samples could be effectively optimized, and the as-prepared sample (S2) synthesized at 200 °C displayed very excellent flower-like morphology compared to the samples (S1 and S3) obtained at 180 and 220 °C. Owing to the excellent interface polarization effect, the as-prepared S2 presented the evidently superior comprehensive microwave absorption properties in terms of strong aborption capability, wide absorption bandwidth and thin matching thicknesses compared to those of S1 and S3. The as-prepared core@shell structured CoNi2S4/Co9S8@MoS2 sample with very excellent flower-like morphology simultaneously displayed the minimal reflection loss of -50.61 dB with the matching thickness of 2.98 mm, and the effective absorption bandwidth of 8.40 GHz with the matching thickness of 2.36 mm. Therefore, we provided a general route for the production of flower-like core@shell structured MoS2-based nanocomposites, which could make the best of interface polarization to develop high-efficiency microwave absorbers.