Carbon Layer Research Articles

Electron-Spin Regulation Driving Heterointerface Electron Distribution and Phase Transition toward Ultrafast and Durable Sodium Storage.

Phase engineering is an effective strategy for modulating the electronic structure and electron transfer mobility of cobalt selenide (CoSe2) with remarkable sodium storage. Nevertheless, it remains challenging to improve fast-charging and cycling performance. Herein, a heterointerface coupling induces phase transformation from cubic CoSe2 to orthorhombic CoSe2 accompanied by the formation of MoSe2 to construct a CoSe2/MoSe2 heterostructure decorated with N-doped carbon layer on a 3D graphene foam (CoSe2/MoSe2@NC/GF). The incorporated Mo cations in the bridged o-CoSe2/MoSe2 not only act an electron donor to regulate charge-spin configurations with more active electronic states but also trigger the upshift of d/p band centers and a decreased ∆d-p band center gap, which greatly enhances ion adsorption capability and lowers the ion diffusion barrier. As expected, the CoSe2/MoSe2@NC/GF anode demonstrates a high-rate capability of 447 mAh g-1 at 2 A g-1 and an excellent cyclability of 298 mAh g-1 at 1 A g-1 over 1000 cycles. The work deepens the understanding of the elaborate construction of heterostructured electrodes for high-performance SIBs.

Geothermal distribution and evolution of fault-controlled Linyi geothermal system: Constrained from hydrogeochemical composition and numerical simulation

This study explores the Linyi geothermal field, located in Shandong Province, China, characterized by its non-magmatic, active fault-controlled geothermal system. Utilizing a combination of geochemical analyses, temperature measurements, and numerical simulations, a detailed genetic model of the geothermal system has been developed. The analysis included extensive water geochemical and isotopic characterization to determine reservoir temperature, depth, and origin of the geothermal waters. The thermal-hydro coupling model was integrated with these data to refine the thermal distribution and assess the evolutionary dynamics of the geothermal system. Our findings indicate that the geothermal anomalies in the Linyi field are predominantly controlled by hydrothermal convection within the Ordovician and Cambrian carbonate layers, facilitated by the high permeability of the Yishu Fault. The fault acts as a crucial conduit for meteoric water recharge, which undergoes significant heating due to the geothermal gradient in deeper rock formations. Isotopic analyses of hydrogen and oxygen revealed the meteoric origin of the geothermal waters, with recharge likely originating from the nearby Yimeng Mountains. Furthermore, the study established a conceptual evolutionary model to understand the mechanisms driving the geothermal resource development in the area. It was determined that the geothermal resources are typically fault-controlled, with significant potential for further exploration due to the identified hydrothermal anomalies at the fault's footwall. The model predicts the preservation of heated meteoric water in the reservoir rock for periods ranging from 10 to 50 thousand years, providing a sustainable source of geothermal energy. This comprehensive approach not only enhances the understanding of the heat accumulation mechanism but also highlights the potential for optimizing geothermal exploration strategies within fault-controlled geothermal systems.

Nanosheet-interwoven structures and ion-electron decoupling storage enable Fe1-xS fast ion transport in Li+/Na+/K+ batteries

Fe1-xS, known for its high theoretical capacity, abundant resources, and intrinsic safety, has become a focal point as a universal anode for Li+/Na+/K+ batteries. However, its fast-charging capability is unsatisfactory due to sluggish ion transport rate and low electrical conductivity. Furthermore, its Li+/Na+/K+ storage mechanisms are still unclear. Here, we fabricate a single-crystal Fe1-xS/N-doped carbon composite nanosheet interwoven structure, in which N-doped carbon layers onto surface of Fe1-xS nanosheets ameliorate the electrical conduction and the interwoven nanosheets form open pore channels that favor permeation of electrolytes to boost ion transport. In-situ magnetometry reveals that ion-electron decoupling storage and transport occur in two-phase composites of Fe/Li2S, Fe/Na2S, and Fe/K2S, in which Fe phase stores and transports electrons and sulfide phase stores and transports ions in a space-charge form, resulting in extra ion storage and fast ion transport. Consequently, the nanosheet interwoven structure delivers high capacities (1320.1/652.2/350.6 mAh g−1), outstanding fast-charging performances (679.6/295.4/106.4 mAh g−1 at 20 A g−1), and long cycling life over 5000 cycles as Li+/Na+/K+ battery anodes, respectively

Revealing the regulation mechanism of Na3V2(PO4)2O2F crystal growth in sodium alginate solution for high-performance sodium ion batteries

Na3V2(PO4)2O2F (NVPFO) attracts tremendous attention as a cathode material for sodium-ion batteries (SIBs) because of its higher capacity and structural stability. However, its inherent poor conductivity affects rate performance and long cycle performance. Herein, a special lamellar NVPFO are successfully synthesized by sodium alginate (SA) assisted hydrothermal method. SA dissolves in water to form hydrogel, due to the specific cross-linking of SA and V4+, which restricts the crystal growth of nanoparticles. Meanwhile, a conductive carbon layer for sodium ion transport channels is constructed after carbonization. Based on multidimensional experiments and density functional theory (DFT) calculations, a mechanism for formation of special lamellar NVPFO in SA solution is proposed for the first time. The results show that special lamellar morphology shortens Na+ migration path and conductive coating facilitates electronic transmission. The optimized NVPFO@C-2 has better electrochemical performance with outstanding high rate capacity (106.8 mAh g–1 at 15 C) and long-term cyclability (99.8 mAh g−1 capacity retention of 87.1 % even after 1000 cycles at 5 C).

Insights into transition metal encapsulated inside carbon aerogel for accelerated electro-peroxone oxidation: Activity evaluation and reactive oxygen species generation

Transition metals have critical influences on the generation of reactive oxygen species in activating O3 and H2O2, as the binary oxidant sources in electro-peroxone (EP). To evaluate the catalytic activity of different metals and reveal the reactive oxygen species generation in heterogeneous EP, series of metals encapsulated inside carbon aerogel spheres (M@CS, M=Fe, Co, Ni, Zn) were fabricated for strengthening EP. Atrazine was used as model pollutant due to its low reactivity with O3, and the abatement trends followed Co@CS > Fe@CS > Ni@CS > Zn@CS. Co@CS exhibited the superior catalytic activity with maximum metal active site utilization (1.28 × 103 min-1 mol-1 per mole Co atom sites at pH 7) and minimum electric energy consumption (0.106 kWh/m3-log). The catalytic activity of M@CS was related to the adsorption energies for O3 and H2O2 (Fe@CS > Co@CS > Ni@CS > Zn@CS) and the graphitization degree (Co@CS > Fe@CS > Ni@CS > Zn@CS). Verified by theoretical calculation and in-situ Fourier transformed infrared, the metal effectively promoted the adsorption and decomposition of O3 and H2O2 into the surface oxygen intermediates, finally generating ·OH/·O2-/1O2. The carbon layer was conducive to the reduction of internal metal, ensuring catalyst durability. Electronic paramagnetic resonance and kinetic model revealed the occurrence, ratio and transient concentration of ·OH/·O2-/1O2 in M@CS/EP. M@CS/EP showed good performance for pollutant removal in coexistence of anions, humic acid and real water. This study provides guidance for selecting the metal–carbon catalyst in heterogeneous EP.

Quantum-Sized Co Nanoparticles with Rich Vacancies Enabled the Uniform Deposition of Lithium Metal and Fast Polysulfide Conversion.

The notorious polysulfide shuttling and uncontrollable Li-dendrite growth are the main obstacles to the marketization of Li-S batteries. Herein, a dual-functional material consisting of vacancy-rich quantum-sized Co nanodots anchored on a mesoporous carbon layer (v-Co/meso-C) is proposed. This material exposes more active sites to improve its reaction performance and simultaneously realizes excellent lithiophilicity and sulfiphilicity characteristics in Li-S electrochemistry. As Li metal deposition hosts, v-Co/meso-C shows small nucleation overpotential, low polarization, and ultra-long cycling stability in both half and symmetric cells, as confirmed by experimental studies. On the S cathode side, experimental and theoretical calculations demonstrate that v-Co/meso-C enhances the adsorption of polysulfides and boosts their catalytic conversion rate. This, in turn, suppresses the shuttle effect of polysulfides and improves sulfur utilization efficiency. Finally, a shuttle-free and dendrite-free v-Co/meso-C@Li//v-Co/meso-C@S full cell is fabricated, exhibiting excellent rate performance (739 mAhg-1 at 5.0 C) and good cyclability (capacity decay rate is 0.033% and 0.035% per cycle at 2.0 and 5.0 C, respectively). Even a pouch cell with high sulfur loading (5.5mgcm-2) and lean electrolyte/sulfur (4.8µLmg-1) can still work 50 cycles with 80% capacity retention rate. This study shows far-reaching implications in the design of dendrite-free, shuttle-free Li-S batteries.

Intercalation modified nano zirconium phosphate inhibitor for inhibiting coal spontaneous combustion

The synthesis and characterization of a modified zirconium phosphate (MZrP) nano-inhibitor for spontaneous coal combustion inhibition were explored through isooctylamine intercalation. Using oxidation experiment, FTIR and SEM, the variation rules of the characteristic parameters of the different coal samples were investigated. It was observed that MZrP exhibited enhanced dispersion within the coal matrix post-intercalation modification. As the MZrP concentration increased, there was a notable decrease in oxygen consumption rate, gas production concentration, and active group content in the coal, alongside a significant increase in apparent activation energy and inhibition efficacy. This enhanced inhibition is attributed to two primary mechanisms. Firstly, the hydrophilic nature of MZrP allows for its uniform distribution on the coal surface and within internal pores, creating a dense carbonized layer. This layer effectively retains moisture and isolates oxygen, enhancing physical inhibition. Secondly, MZrP inhibitor is thermally decomposed into phosphoric acid and its phosphoric acid derivatives, which can effectively capture the H- and -OH in the coal, and strengthens the inactivation of its reactive free radicals. The optimal inhibition was observed in coal samples treated with 6 wt% MZrP, exhibiting an average inhibition rate of 62.2 %, coupled with the lowest rates of gas production and oxygen consumption.

Constructing stress-release layer on Si nanoparticles for high-performance lithium storage

Tailing structures of silicon anode to alleviate the mechanical stress has an important significance in the development of lithium-ion batteries (LIBs). Herein, the stress-released layer of N-doped cubic carbon on the surface of Si nanoparticles (Si@NCC) is explored to stabilize the electrode. Endowed with the unique superiority, the Si@NCC electrode delivers an impressive lithium storage performance with high specific capacity of 630 mAh/g at 0.1 A/g, excellent cycling stability (72.0 % capacity retention after 100 cycles at 0.1 A/g) and good rate capability (375 mAh/g at 2 A/g). It has been demonstrated that the N-doped cubic carbon shell with high conductivity can effectively limit the expansion and agglomeration of Si nanoparticles. Besides, the COMSOL simulations of the stress distributions in materials confirm that the N-doped cubic carbon layer could remarkably decrease the stress originated from the volume expansion of Si nanoparticles during the lithiation. Therefore, this work provides ideas for the mechanical effect of Si-based anodes for lithium storage and sheds lights on the designing advanced materials toward high-performance energy storage devices.

Design and preparation of carbon-coated NaZnFe(MoO4)3 composite as novel anode materials for lithium/sodium-ion batteries

The investigation of new anode materials with novel crystal structure and high ionic conductivity is of great significance for potential applications in lithium/sodium-ion batteries. Herein, carbon-coated NaZnFe(MoO4)3 composite was produced by solid state method coupled with the mechanical ball milling technique. The crystal and morphology were accurately confirmed by XRD, XPS and SEM techniques. When tested with lithium-ion batteries, the charging capacity reached an impressive 1005 mA h g−1 during the initial cycle and 840 mA h g−1 after 50 cycles, resulting in a capacity retention of 84.2 %. This performance is 40 % higher than that of the sample without a carbon layer coating. When utilized as an anode for sodium-ion batteries, the carbon-coated NaZnFe(MoO4)3 composite electrode exhibited a remarkable specific capacity of 152 mA h g−1 and a high capacity retention of 74.9 % after 100 cycles at a rate of 100 mA g−1. Furthermore, the charge capacity was measured at 105 mA h g−1 after 500 cycles test conducted at 500 mA g−1, with a capacity retention of 86.0 %. The advantages of polyanionic molybdate NaZnFe(MoO4)3 combined with the simple carbon coating strategy make it possible to application in the next generation of Li/Na secondary batteries.

Cathode-Electrolyte Interphase Engineering toward Fast-Charging LiFePO4 Cathodes by Flash Carbon Coating.

Lithium iron phosphate (LiFePO4, LFP) batteries are widely used in electric vehicles and energy storage systems due to their excellent cycling stability, affordability and safety. However, the rate performance of LFP remains limited due to its low intrinsic electronic and ionic conductivities. In this work, an ex situ flash carbon coating method is developed to enhance the interfacial properties for fast charging. A continuous, amorphous carbon layer is achieved by rapidly decomposing the precursors and depositing carbon species in a confined space within 10 s. Simultaneously, different heteroatoms can be introduced into the surface carbon matrix, which regulates the irregular growth of cathode-electrolyte interphase (CEI) and selectively facilitates the inorganic region formation. The inorganic-rich, hybrid conductive CEI not only promotes electron and ion transport but also restricts parasitic side reactions. Consequently, LFP cathodes with fluorinated carbon coatings exhibited the highest capacity of 151 mAh g-1 at 0.2 C and 96mAhg-1 at 10 C, indicating their excellent rate capability over commercial LFP (58mAh g-1 at 10 C). This solvent-free, versatile surface modification is shown for other electrode materials, providing an efficient platform for electrode-electrolyte interphase engineering through a surface post-treatment.

Surface-Engineered Ni2P: An Efficient Oxygen Electrocatalyst for Zinc-Air Battery.

The surface engineering of electrocatalysts is one of the promising strategies to increase the intrinsic activity of electrocatalysts. It generates anion/cation vacancy defects and increases the electrochemically active surface area. We describethe surface engineering of Ni2P to favorably tune the bifunctional oxygen electrocatalytic activity and the development of a rechargeable zinc-air battery (ZAB). Ni2P encapsulated with N and P-dual doped carbon (Ni2P@NPC) is synthesized using a single-source precursor complex tris-(2,2'-bipyridine)nickel(II) bis(hexafluorophosphate). The surface engineering of the as-synthesized Ni2P@NPC is achieved by the controlled acid treatment at room temperature. The surface engineering removes carbon debris and opens the pores, exfoliates the encapsulating carbon layer, increases the P-vacancy in the crystal lattice, and boosts the electrochemically active surface area. Thesurface-engineered catalyst exhibits enhanced bifunctional activity towards oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). The electrocatalytically active sites of engineered catalysts are highly accessible for facilitated electron transfer kinetics. P-vacancy favors the facile formation of defect-rich OER active metal oxyhydroxide species. The rechargeable ZAB based on the engineered catalyst delivers a specific capacity of 770.25 mA h gZn-1, energy density of 692 Wh kgZn-1, and excellent charge-discharge cycling performance with negligible voltaic efficiency loss (0.6 %) after 100 h.

Effect of diammonium hydrogen phosphate coated with silica on flame retardancy of epoxy resin.

Epoxy resin has become one of the most widely used polymers owing to their excellent comprehensive properties. However, the inherent inflammability of epoxy resin (EP) has seriously limited its application in a range of fields with high fire safety requirements. Herein, a novel shell-core hierarchy architecture (DAP@SiO2) was prepared, composed of diammonium hydrogen phosphate (DAP) and in situ grown silica, and its structure and morphology were characterized by electron microscopy and infrared spectroscopy. The results indicated that silica particles were uniformly coated onto the surface of DAP. The modified DAP was used to reinforce the epoxy resin. The thermal stability of the EP blends was studied with the use of thermogravimetric analysis. The diammonium phosphate in DAP@SiO2 flame retardant produces pyrolysis gases such as NH3 and N2 during decomposition, diluting the concentration of oxygen and flammable volatile products around the flame. Secondly, silica migrates to the surface of epoxy resin to form a shielding layer, forming compounds containing Si-O-Si and O-Si-C structures, which can be cross-linked with other condensed phase products, greatly improving the thermal stability of the carbon layer. Fire behavior was evaluated using the limiting oxygen index (LOI), vertical burning test, and the cone calorimetry, and the flame retardancy mode of action was explained. With 12% of DAP@SiO2 involved, the EP blend passes UL-94 V-0 level, and its limiting oxygen index (LOI) reaches 33.2%. The incorporation of DAP@SiO2 in an EP matrix showed a slight reduction in the heat release and smoke production. The flame retardant mode of the EP polymer shows that its flame retardant and smoke suppression characteristics are related to the interaction of flame retardants in the gas phase and condensed phase. The mechanical properties test results illustrated that the tensile strength, elastic modulus and impact strength of EP/3%DAP@SiO2 are improved compared with pure EP. This is due to the crosslinking reaction between a large number of amino groups on the surface of DAP@SiO2 and the epoxy group on the epoxy resin, which significantly enhances the interfacial compatibility between DAP@SiO2 and epoxy resin, making the combination of DAP@SiO2 and epoxy resin closer.

Effects of liquid-phase carbon combining surfactant coatings on the performance of LiMn0.2Fe0.8PO4 cathode materials

Efforts to reduce the particle size of LiFexMn1-xPO4 materials and apply conductive carbon coatings have yielded substantial benefits in terms of obtaining lithium-ion batteries (LIBs) with enhanced electrochemical performance. However, LiFexMn1-xPO4 materials with small particle sizes and uniform carbon layers cannot be obtained by the conventional high-temperature solid-phase method, which is the most convenient and applicable method for the industrial-scale preparation of the cathode materials used in commercial LIBs. The present work addresses this issue by applying the cationic surfactant cetyltrimethylammonium bromide (CTAB) in conjunction with LiMn0.2Fe0.8PO4 (LMFP) particles, and obtaining a carbon layer by replacing the conventional in-situ solid-phase carbon coating process with a secondary liquid-phase coating process using sucrose as the carbon source. The CTAB surfactant is observed to be uniformly adsorbed on the surface of LMFP particles, and maintains small LMFP particle sizes by operating as a dispersant preventing their agglomeration. Additionally, the carbon network formed by CTAB pyrolysis acts as an intermediate medium ensuring that the conductive carbon layer is uniformly and firmly adhered to the LMFP particle surfaces at a high preparation temperature of 680°C. This composite carbon layer is demonstrated to enhance lithium-ion transport, while concurrently acting as a barrier interfering with manganese diffusion within the electrolyte during charge-discharge cycling. As a result, the optimal LMFP-based cathode material achieves reversible specific capacities of 160 mAh g−1 and 120 mAh g−1 at charge-discharge rates of 0.1 C and 5 C, respectively, and the capacity retention is 88 % after 500 cycles at 1 C. Hence, the results verify that the proposed surfactant-mediated liquid-phase carbon coating process is an effective method for enhancing the overall electrochemical performance of LMFP-based cathode materials.

Synthesis of MgAl-LDH from three alkali sources for boosting flame retardancy of EP with APP

Epoxy resin (EP) is used in construction materials due to its low curing shrinkage, excellent chemical stability, and mechanical properties. However, its flammability limits applications in the field of construction. Co-precipitation method with sodium hydroxide as the alkali source and hydrothermal method with urea as the alkali source are the common ways to prepare MgAl-LDH. In this study, MgAl-LDH1 (abbreviated as LDH1) was prepared by using NaOH as the alkali source at 65 ℃ for 12 h, MgAl-LDH2 (abbreviated as LDH2) by using urea as the alkali source at 120 ℃ for 12 h, and MgAl-LDH3 (abbreviated as LDH3) was prepared by using triethanolamine as the alkali source at 100 ℃ for 2 h. Then, LDH1, LDH2, LDH3 were compounded with ammonium polyphosphate (APP) to synergistically enhance the flame retardant properties of EP (Composite material abbreviated as LDH1-APP-EP, LDH2-APP-EP, LDH3-APP-EP). The results showed that the best flame retardant effect was achieved after compounding APP (5 wt%) with LDH3 (5 wt%) prepared with triethanolamine as the alkali source. Compared with Pure-EP, the peak exothermic rate and peak smoke production rate of LDH3-APP-EP prepared with triethanolamine as the alkali source decreased by 74.54 % and 67.44 %, respectively. Compared with LDH prepared with NaOH and urea as the alkali source, LDH prepared with triethanolamine as the alkali source has a larger layer spacing and a higher weight loss percentage which releases more gases, moisture, and carbon layers formed by triethanolamine during the combustion process to reduce the heat release from the fire. It’s evident that LDH3-APP-EP prepared with triethanolamine as the alkali source has higher residual carbon densities and the lowest residual carbon values based on SEM and Raman test results. This result proves that the LDH3 with triethanolamine as the alkali source has a good effect on EP flame retardation in this paper which provided a new way to design new efficient flame retardants.

Fluorine Doping Modulating Pore Structure and Adsorption Capability of Carbon Matrix Boosting Potassium Storage Performance of Red Phosphorus Anode

AbstractThe application of alloying‐typed red phosphorus (red P) anode in potassium‐ion batteries (KIBs) with ultra‐high theoretical capacity is hindered by the limited capacity and fast capacity decay due to poor electronic conductivity and huge volume change. Herein, a facile and efficient strategy of fluorine (F) doping is innovatively developed to modulate the pore structure of carbon matrix (F‐CNS) to encapsulate red P with enhanced potassium storage capability. Theoretical calculations reveal that F doping induces additional defects within the carbon layer, which facilitates P4 molecules embedding into the F‐doping‐induced micropores, enhances the adsorption ability toward K atoms and P4 molecules, and improves electrochemical kinetics assisted with more charge transfer obtained from the electron density difference, thus enabling robust potassium storage capability for such unique Red P@F‐CNS anode. Accordingly, the Red P@F‐CNS anode demonstrates outstanding cycling stability (90% capacity retention after 800 cycles at 2A g−1), and the potassium‐ion full cell (Red P@F‐CNS//KFeHCF) exhibits exceptional long‐term cycling performance (129 mAh g−1 after 2500 cycles at 5 A g−1 with only 0.014% decay per cycle). In situ characterizations confirm the superior structural integrity of the carbon‐based matrix. This study offers a rational design principle for engineering high‐performance carbon‐supported alloying‐typed anodes for KIBs.

Robust Nitrogen/Sulfur Co‐Doped Carbon Frameworks as Multifunctional Coating Layer on Si Anodes Toward Superior Lithium Storage

AbstractSilicon (Si)‐based anodes hold great potential for next‐generation lithium‐ion batteries (LIBs) due to their exceptional theoretical capacity. However, their practical application is hindered by the notably substantial volume expansion and unstable electrode/electrolyte interfaces during cycling, leading to rapid capacity degradation. To address these challenges, we have engineered a porous nitrogen/sulfur co‐doped carbon layer (CBPOD) to uniformly encapsulate Si, providing a multifunctional protective coating. This innovative design effectively passivates the electrode/electrolyte interface and mitigates the volumetric expansion of Si. The N/S co‐doping framework significantly enhances electronic and ionic conductivity. Furthermore, the carbonization process augments the elastic modulus of CBPOD and reconstructs the Si‐CBPOD interface, facilitating the formation of robust chemical bonds. These features collectively contribute to the high performance of the Si‐CBPOD anodes, which demonstrate a high reversible capacity of 1110.8 mAh g−1 after 1000 cycles at 4 A g−1 and an energy density of 574 Wh kg−1 with a capacity retention of over 75.6% after 300 cycles at 0.2 C. This study underscores the substantial potential of the CBPOD protective layer in enhancing the performance of Si anodes, providing a pathway for the development of composite materials with superior volumetric energy density and prolonged cyclic stability, thereby advancing high‐performance LIBs.

A one-stone-three-birds strategy to construct Mo-FeS2/Ni3S2@C electrocatalyst with strong interfacial coupling effect to achieve efficient oxygen evolution reaction

The development of high-performance oxygen evolution reaction (OER) electrocatalysts is quite pivotal to facilitate hydrogen production. In this work, we integrate the synergistic effects of heterogeneous interface engineering, multiscale engineering and doping engineering to greatly improve the catalytic activity of the electrocatalyst. Specifically, with a Anderson-type polymetallic oxonate (NH4)3[NiMo6O24H6]·7H2O as a precursor, the Mo-FeS2/Ni3S2@C nanowire arrays that uniformly grown on nickel foam (NF) surfaces were prepared by a simple hydrothermal process followed by calcination. The as-prepared Mo-FeS2/Ni3S2@C exhibits excellent alkaline OER performance with a low overpotential of 196 mV to achieve a current density of 10 mA cm−2 and maintain high stability for over 100 h at 100 mA cm−2. Theoretical calculations and experimental results indicate that the high activity of Mo-FeS2/Ni3S2@C is mainly attributed to the charge interaction at the multiple interfaces of FeS2, Ni3S2 and porous carbon layers. The Mo facilitates inducing the formation of high-valent Ni, Fe, thus forming of the Ni(Fe)OOH phase that contributes to the intrinsic OER active site of the Mo-FeS2/Ni3S2@C electrode. In addition, the surface of Mo-FeS2/Ni3S2@C nanowire is composed of ordered nanosheets, exhibiting a unique hierarchical multi-scale structure, which is conducive to exposing more active sites. This hierarchical structure gives it superhydrophilic and superoxyphobic properties, ensuring the stability during continuous electrolysis. This study showcases the importance of multi-engineering synergies and foresees the avenue of designing novel OER electrocatalysts.

S vacancies and heterojunction modulated MoS2/C@Fe3O4 towards improved full-spectrum photo-Fenton catalysis: Enhanced interfacial charge transfer and NIR absorption

Fe3O4-based core–shell/heterojunction composites exhibit favorable photothermal catalytic performance in environmental remediation, but limited by the weak interface electron transport efficiency and poor near infrared (NIR) absorption capacity. Herein, Sv-MoS2/C@Fe3O4 core–shell composites were prepared for the first time by coating S vacancies-bearing MoS2 (Sv-MoS2) on the surface of carbon-decorated Fe3O4 microspheres (C@Fe3O4) derived from copper slag-based polymer microspheres and was used as photothermal catalyst to activate H2O2 towards chlortethromycin hydrochloride (CTC) elimination from wastewater. By virtue of the synergistic effect of the petal-like Sv-MoS2, carbon-decorated layer and multi light reflection in porous microspheres, Sv-MoS2/C@Fe3O4 exhibited excellent full spectrum absorption and carrier migration efficiency, with catalytic activity of 0.149 min−1 and H2O2 utilization rate of 93.6 %. The degradation rate is 3.9 and 3.1 times of C@Fe3O4 and MoS2/C@Fe3O4 under full light irradiation which can heat the solution from room temperature to 72.4 °C. This excellent catalytic performance is mainly originated from that the S-type heterostructure promotes the charge separation, transfer and redox ability, and enhances catalytic oxidation by regulating electron density of the interfacial carbon and reducing the energy barrier of H2O2 activation through S vacancies. Moreover, the decorated carbon layer can serve as a hot core to provide heat to Sv-MoS2 and enhance the collision chance of photogenerated carriers, thus improving the catalytic performance of Sv-MoS2/C@Fe3O4. This work provides new strategies for constructing heterojunction materials with fast electron transport efficiency and using solar energy for environmental remediation.

Synergistic Regulation of Polyselenide Dissolution and Na‐Ion Diffusion of Se‐Vacancy‐Rich Bismuth Selenide toward Ultrafast and Durable Sodium‐Ion Batteries

AbstractMetal selenides (MSes) have great potential as candidate anode materials in high‐specific‐energy sodium‐ion batteries (SIBs) but are plagued by rapid capacity degradation and slow kinetics. Here, it is reveal that the Bi2Se3 anode discharge process involves multiple‐types of sodium polyselenides (Na‐pSex) which suffer from terrible dissolution and shuttling properties. Based on these observations, a nanoflower‐like composite of dual carbon‐confined Bi2Se3−x crystallites is designed via facile defect chemistry. The robust dual N‐doped carbon layer suppresses the precipitation and aggregation of Bi2Se3, significantly alleviating the dissolution and shuttle effect of Na‐pSex. Theoretical calculations indicate that the pyridine/pyrrole nitrogen sites exhibit strong van der Waals resistance and chemisorption properties against Na2Se4 and Na2Se2. Furthermore, the abundant Se vacancies improve the inherent conductivity of Bi2Se3, reduce the diffusion barrier of Na+, and accelerate the reaction kinetics. Consequently, the resulting Bi2Se3−x@DNC electrode exhibits extraordinary durability (over 2000 cycles at 10.0 A g−1) and high‐rate capability (354.4 mAh g−1 at 75.0 A g−1), propelling the battery performance to new heights. Encouragingly, the assembled hybrid capacitor displays competitive rate performance and an ultra‐long lifespan exceeding 40 000 cycles, making the Bi2Se3−x@DNC electrode a promising candidate for SIBs.

Enhanced mineralization of pharmaceutical residues at circumneutral pH by heterogeneous electro-Fenton-like process with Cu/C catalyst

Conventional electro-Fenton (EF) process at acidic pH ∼3 is recognized as a highly effective strategy to degrade organic pollutants; however, homogeneous metal catalysts cannot be employed in more alkaline media. To overcome this limitation, pyrolytic derivatives from metal-organic frameworks (MOFs) have emerged as promising heterogeneous catalysts. Cu-based MOFs were prepared using trimesic acid as the organic ligand and different pyrolysis conditions, yielding a set of nano-Cu/C catalysts that were analyzed by conventional methods. Among them, XPS revealed the surface of the Cu/C-A2-Ar/H2 catalyst was slightly oxidized to Cu(I) and, combined with XRD and HRTEM data, it can be concluded that the catalyst presents a core-shell structure where metallic copper is embedded in a carbon layer. The antihistamine diphenhydramine (DPH), spiked into either synthetic Na2SO4 solutions or actual urban wastewater, was treated in an undivided electrolytic cell equipped with a DSA-Cl2 anode and a commercial air-diffusion cathode able to electrogenerate H2O2. Using Cu/C as suspended catalyst, DPH was completely degraded in both media at pH 6–8, outperforming the EF process with Fe2+ catalyst at pH 3 in terms of degradation rate and mineralization degree thanks to the absence of refractory Fe(III)-carboxylate complexes that typically decelerate the TOC abatement. From the by-products detected by GC/MS, a reaction sequence for DPH mineralization is proposed.