Design of NiCoP nanorod loaded on cocoon carbon substrate and its non-metal doping for efficient hydrogen evolution.

The quest for effective and sustainable electrocatalysts for hydrogen evolution is crucial in advancing the widespread use of H2. In this study, we utilized silkworm cocoons as the source material to produce porous N-doped carbon (PNCC) substrates through a process involving degumming and annealing. Subsequently, NiCoP nanorod (NiCoP@PNCC) is deposited onto the substrates via a simple impregnation and calcination method to enhance the catalytic performance for the hydrogen evolution reaction (HER). The optimal spacing between the silk fibers of PNCC facilitates longitudinal growth, increases the active surface area, and balances the adsorption and desorption of reaction intermediates, thereby accelerating HER kinetics. Consequently, NiCoP@PNCC demonstrates impressive performance, with 44 mV overpotential to achieve a current density of 10 mA cm-2. Additionally, density functional theory (DFT) calculations reveal that the electronic structure and energy band of NiCoP@PNCC can be modified through the doping of elements such as B, C, N, O, F, and S. In addition, with the electronegativity enhancement of the doping elements, the interaction between Co atoms in NiCoP@PNCC and O atoms in adsorbed H2O molecules gradually enhanced, which is conducive to the dissociation of water in alkaline solution. This research introduces a novel approach for fine-tuning the catalytic activity of transition metal phosphides.

Photodegradation of Microplastics through Nanomaterials: Insights into Photocatalysts Modification and Detailed Mechanisms.

Microplastics (MPs) pose a profound environmental challenge, impacting ecosystems and human health through mechanisms such as bioaccumulation and ecosystem contamination. While traditional water treatment methods can partially remove microplastics, their limitations highlight the need for innovative green approaches like photodegradation to ensure more effective and sustainable removal. This review explores the potential of nanomaterial-enhanced photocatalysts in addressing this issue. Utilizing their unique properties like large surface area and tunable bandgap, nanomaterials significantly improve degradation efficiency. Different strategies for photocatalyst modification to improve photocatalytic performance are thoroughly summarized, with a particular emphasis on element doping and heterojunction construction. Furthermore, this review thoroughly summarizes the possible fundamental mechanisms driving the photodegradation of microplastics facilitated by nanomaterials, with a focus on processes like free radical formation and singlet oxygen oxidation. This review not only synthesizes critical findings from existing studies but also identifies gaps in the current research landscape, suggesting that further development of these photocatalytic techniques could lead to substantial advancements in environmental remediation practices. By delineating these novel approaches and their mechanisms, this work underscores the significant environmental implications and contributes to the ongoing development of sustainable solutions to mitigate microplastic pollution.

Inhibiting the Jahn-Teller Effect of Manganese Hexacyanoferrate via Ni and Cu Codoping for Advanced Sodium-Ion Batteries.

Manganese (Mn)-based Prussian blue analogs (PBAs) are of great interest as a prospective cathode material for sodium-ion batteries (SIBs) due to their high redox potential, easy synthesis, and low cost. However, the Jahn-Teller effect and low electrical conductivity of Mn-based PBA cause poor structure stability and unsatisfactory performance during the cycling. Herein, a novel nickel- and copper-codoped K2Mn[Fe(CN)6] cathode is developed via a simple coprecipitation strategy. The doping elements improve the electrical conductivity of Mn-based PBA by reducing the bandgap, as well as suppress the Jahn-Teller effect by stabilizing the framework, as verified by the density functional theory calculations. Simultaneously, the substitution of sodium with potassium in the lattice is beneficial for filling vacancies in the PBA framework, leading to higher average operating voltages and superior structural stability. As a result, the as-prepared Mn-based cathode exhibits excellent reversible capacity (116.0 mAh g-1 at 0.01 A g-1) and superior cycling stability (81.8% capacity retention over 500 cycles at 0.1 A g-1). This work provides a profitable doping strategy to inhibit the Jahn-Teller structural deformation for designing stable cathode material of SIBs.

Performance of Nitrogen-Doped Carbon Nanoparticles Carrying FeNiCu as Bifunctional Electrocatalyst for Rechargeable Zinc-Air Battery.

Catalysts for zinc-air batteries (ZABs) must be stable over long-term charging-discharging cycles and exhibit bifunctional catalytic activity. In this study, by doping nitrogen-doped carbon (NC) materials with three metal atoms (Fe, Ni, and Cu), a single-atom-distributed FeNiCu-NC bifunctional catalyst is prepared. The catalyst includes Fe(Ni-doped)-N4 for the oxygen evolution reaction (OER), Fe(Cu-doped)-N4 for the oxygen reduction reaction (ORR), and the NiCu-NC catalytic structure for the oxygen reduction reaction (ORR) in the nitrogen-doped carbon nanoparticles. This single-atom distribution catalyst structure enhances the bifunctional catalytic activity. If a trimetallic single-atom catalyst is designed, it will surpass the typical bimetallic single-atom catcalyst. FeNiCu-NC exhibits outstanding performance as an electrocatalyst, with a half-wave potential (E1/2) of 0.876 V versus RHE, overpotential (Ej = 10) of 253 mV versus RHE at 10 mA cm-2, and a small potential gap (ΔE = 0.61 V). As the anode in a ZAB, FeNiCu-NC can undergo continuous charge-discharged cycles for 575 h without significant attenuation. This study presents a new method for achieving high-performance, low-cost ZABs via trimetallic single-atom doping.

Influences of Composite Electrodeposition Parameters on the Properties of Ni-Doped Co-Mn Composite Spinel Coatings.

To enhance the comprehensive performance of solid oxide fuel cells (SOFCs) ferritic stainless steel (FSS) interconnectors, a novel approach involving composite electrodeposition and thermal conversion is proposed to prepare Ni-doped Co-Mn composite spinel protective coatings on FSS surfaces. The process involves the composite electrodeposition of a Ni-doped Co-Mn precursor coating, followed by thermal conversion to obtain the Co-Mn-Ni composite spinel coating. Crofer 22H was used as the substrate and orthogonal experiments were designed to investigate the influences of deposition solution pH, stirring rate, cathode current density, and the element content of Mn and Ni on the surface morphology and properties of the composite coatings, respectively. The characterization of the prepared coatings was conducted through macroscopic and microscopic morphology observations of the component surface, energy dispersive spectroscopy (EDS) analysis, and area specific resistance (ASR) testing, etc. Finally, the optimized composite electrodeposition parameters and the Mn-Ni content ratio in the solution were obtained. Experimental results indicated that the composite spinel coating prepared with the optimized process parameters exhibited excellent adhesion to the substrate, and the diffusion and migration of Cr element has been effectively inhibited. Compared with the substrate, the ASR of the coated components has also been decreased simultaneously, which provided an effective method for the surface modification of SOFC FSS interconnectors.

Sm, Nd doped BiFeO3epitaxial film for photodetector with extremely large on-off current ratio.

BiFeO3is one of the star materials in the field of ferroelectric photovoltaic for its relatively narrow bandgap (2.2-2.7 eV) and better visible light absorption. However, a high temperature over 600 °C is indispensable in the usual BiFeO3growth process, which may lead to impure phase, interdiffusion of components near the interface, oxygen vacancy and ferrous iron ions, which will result in large leakage current and greatly aggravate the ferroelectricity and photoelectric response. Here we prepared Sm, Nd doped epitaxial BiFeO3film via a rapid microwave assisted hydrothermal process at low temperature. The Bi0.9Sm0.5Nd0.5FeO3film exhibits narrow bandgap (1.35 eV) and photo response to red light, the on-off current ratio reaches over 105. The decrease in band gap and +2/+3 variable element doping are responsible for the excellent photo response. The excellent photo response performances are much better than any previously reported BiFeO3films, which has great potential for applications in photodetection, ferroelectric photovoltaic and optoelectronic devices.

Emerging Amorphous to Crystalline Conversion Chemistry in Ca-Doped VO2 Cathodes for High-Capacity and Long-Term Wearable Aqueous Zinc-Ion Batteries.

Amorphous transition metal oxides have attracted significant attention in energy storage devices owing to their potentially desirable electrochemical properties caused by abundant unsaturated dangling bonds. However, the amorphization further amplifies the shortcoming of the poor intrinsic electronic conductivity of the metal oxides, resulting in unsatisfying rate capability and power density. Herein, freestanding amorphous Ca-doped V2 O5 (a-Ca-V2 O5 ) cathodes are successfully prepared via in situ electrochemical oxidation of Ca-doped VO2 nanoarrays for wearable aqueous zinc-ion batteries. The doping of Ca and construction of freestanding structure effectively uncover the potential of amorphous V2 O5 , which can make full use of the abundant active sites for high volumetric capacity and simultaneously achieve fast reaction kinetics for excellent rate performance. More importantly, the introduction of Ca can notably reduce the formation energy of VO2 according to theoretical calculation results and realizes amorphous to crystalline reversible conversion chemistry in the charge/discharge procedure, thereby facilitating the reversible capacity of the newly developed a-Ca-V2 O5 . This work provides an innovative design strategy to construct high-rate capacity amorphous metal oxides as freestanding electrodes for low-cost and high-safe wearable energy-storage technology.

Progress, Challenge, and Prospect of LiMnO2 : An Adventure toward High-Energy and Low-Cost Li-Ion Batteries.

Lithium manganese oxides are considered as promising cathodes for lithium-ion batteries due to their low cost and available resources. Layered LiMnO2 with orthorhombic or monoclinic structure has attracted tremendous interest thanks to its ultrahigh theoretical capacity (285 mAh g-1 ) that almost doubles that of commercialized spinel LiMn2 O4 (148 mAh g-1 ). However, LiMnO2 undergoes phase transition to spinel upon cycling cause by the Jahn-Teller effect of the high-spin Mn3+ . In addition, soluble Mn2+ generates from the disproportionation of Mn3+ and oxygen release during electrochemical processes may cause poor cycle performance. To address the critical issues, tremendous efforts have been made. This paper provides a general review of layered LiMnO2 materials including their crystal structures, synthesis methods, structural/elemental modifications, and electrochemical performance. In brief, first the crystal structures of LiMnO2 and synthetic methods have been summarized. Subsequently, modification strategies for improving electrochemical performance are comprehensively reviewed, including element doping to suppress its phase transition, surface coating to resist manganese dissolution into the electrolyte and impede surface reactions, designing LiMnO2 composites to improve electronic conductivity and Li+ diffusion, and finding compatible electrolytes to enhance safety. At last, future efforts on the research frontier and practical application of LiMnO2 have been discussed.

2D Atomic Layers for CO2 Photoreduction.

Artificial photosynthesis can convert carbon dioxide into high value-added chemicals. However, due to the poor charge separation efficiency and CO2 activation ability, the conversion efficiency of photocatalytic CO2 reduction is greatly restricted. Ultrathin 2D photocatalyst emerges as an alternative to realize the higher CO2 reduction performance. In this review, the basic principle of CO2 photoreduction is introduced, and the types, advantages, and advances of 2D photocatalysts are reviewed in detail including metal oxides, metal chalcogenides, bismuth-based materials, MXene, metal-organic framework, and metal-free materials. Subsequently, the tactics for improving the performance of 2D photocatalysts are introduced in detail via the surface atomic configuration and electronic state tuning such as component tuning, crystal facet control, defect engineering, element doping, cocatalyst modification, polarization, and strain engineering. Finally, the concluding remarks and future development of 2D photocatalysts in CO2 reduction are prospected.

Highly Efficient and Stable Mo-CoP3 @FeOOH Electrocatalysts for Alkaline Seawater Splitting.

The introduction of high-valence state elements and highly active species is promisingly desired to design superior electrocatalysts for water electrolysis. Exploring scalable synthetic strategies is necessary for an in-depth understanding of the mechanism of improving electrocatalytic performance. But it remains challenging. Herein, several electrocatalysts through element doping are prepared. The obtained Mo-CoP3 -2@FeOOH samples show the overpotentials (OER) of 232 mV (alkaline seawater) and 262 mV (KOH electrolyte). As HER catalyst, it also presents an excellent electrocatalytic performance. The above electrocatalysts are utilized as anode/cathode to assemble devices for alkaline seawater/water electrolysis, which delivers a cell voltage of 1.58 V and durability of 350 h. Density functional theory calculations reveal that Mo ion doping and FeOOH significantly enhance the density states of the Fermi level and tune the position of the d-band center. It expedites the charge transfer and decreases the adsorption energy of intermediates. It demonstrates that transition-metal phosphides coated with highly active FeOOH offer an effective route to fabricate high-performance and durable catalysts for seawater/water electrolysis.

Preparation of NiS/Ti3C2Tx co-doped with N and P at the covalent interface and its electromagnetic wave absorption properties.

The harm of electromagnetic waves on human daily life has gradually received attention, and electromagnetic waves absorption materials have been used to address this issue. MXene, as a new type of 2D material, is a very promising electromagnetic wave absorption material. In this study, NiS nanoparticles were grown on the surface of S terminated Ti3C2Tx, and -S group acted as sulfur sources to construct Ti-S-Ni covalent interface directly in NiS/Ti3C2Tx composites. To further regulate the interface structure and electromagnetic properties, -P and -NH2 groups were also introduced onto the surface of MXene to achieve the N, P co-doping NiS/Ti3C2Tx composites with covalent interface. By investigating the electromagnetic wave absorption performance of the composites, it was found that N and P doping could effectively enhance the electron transfer rate at the interface and optimize the conduction loss, resulting in a significant improvement in performance. The minimum reflection loss was -50.6 dB at a frequency of 15.6 GHz, and the matching thickness was only 1.14 mm with an effective absorption bandwidth of 3.6 GHz. These results provide an important references and guidance for further research and development of high-performance electromagnetic wave absorption materials.

Preparation and Electromagnetic Wave Absorption Properties of N-Doped SiC Nanowires.

Enhancing the conductivity loss of SiC nanowires through doping is beneficial for improving their electromagnetic wave absorption performance. In this work, N-doped SiC nanowires were synthesized using three different methods. The results indicate that a large amount of Si2ON will be generated during the microwave synthesis of SiC nanowires in a nitrogen atmosphere. In addition, the secondary heat-treatment of the as-synthesized SiC nanowires under nitrogen atmosphere will significantly reduce their stacking fault density. When ammonium chloride is introduced as a doped nitrogen source in the reaction raw material, the N-doped SiC nanowires with high-density stacking faults can be synthesized by microwave heating. Therefore, the polarization loss induced by faults and the conductivity loss caused by doping will synergistically enhance the dielectric and EMW absorption properties of SiC nanowires in the range of 2-18 GHz. When the filling ratio of N-doped SiC nanowires is 20 wt.%, the composite shows a minimum reflection loss of -22.2 dB@17.92 GHz, and an effective absorption (RL ≤ -10 dB) bandwidth of 4.24 GHz at the absorber layer thickness of 2.2 mm. Further, the N-doped SiC nanowires also exhibit enhanced high-temperature EMW absorption properties with increasing temperature.

Alkaloid Precipitant Reaction Inspired Controllable Synthesis of Mesoporous Tungsten Oxide Spheres for Biomarker Sensing.

Highly porous sensitive materials with well-defined structures and morphologies are extremely desirable for developing high-performance chemiresistive gas sensors. Herein, inspired by the classical alkaloid precipitant reaction, a robust and reliable active mesoporous nitrogen polymer sphere-directed synthesis method was demonstrated for the controllable construction of heteroatom-doped mesoporous tungsten oxide spheres. In the typical synthesis, P-doped mesoporous WO3 monodisperse spheres with radially oriented channels (P-mWO3-R) were obtained with a diameter of ∼180 nm, high specific surface area, and crystalline skeleton. The in situ-introduced P atoms could effectively adjust the coordination environment of W atoms (Wδ+-Ov), giving rise to dramatically enhanced active surface-adsorbed oxygen species and unusual metastable ε-WO3 crystallites. The P-mWO3-R spheres were applied for the sensing of 3-hydroxy-2-butanone (3H2B), a biomarker of foodborne pathogenic bacteria Listeria monocytogenes (LM). The sensor exhibited high sensitivity (Ra/Rg = 29 to 3 ppm), fast response dynamics (26/7 s), outstanding selectivity, and good long-term stability. Furthermore, the device was integrated into a wireless sensing module to realize remote real-time and precise detection of LM in practical applications, making it possible to evaluate food quality using gas sensors conveniently.

Local Construction of Mn-Based Layered Cathodes through Covalency Modulation for Sodium-Ion Batteries.

P2-type Mn-based layered oxides are among the most prevalent cathodes for sodium-ion batteries (SIBs) owing to their low cost, resource abundance, and high theoretical specific capacity. However, they usually suffer from Jahn-Teller (J-T) distortion from high-spin Mn3+ and poor cycling stability, resulting in rapid degradation of their structural and electrochemical properties. Herein, a stable P2-type Mn-based layered oxide is realized through a local construction strategy by introducing high-valence Ru4+ to overcome these issues. It has been revealed that the Ru substitution in the as-constructed Na0.6Mg0.3Mn0.6Ru0.1O2 (NMMRO) renders the following favorable effects. First, the detrimental P2-OP4 phase transition is effectively inhibited owing to the robust Ru-O covalency bond. Second, the Mg/Mn ordering is disturbed and the out-of-plane displacement of Mg2+ and in-plane migration of Mn4+ are suppressed, leading to improved structural stability. Third, the redox ability of Mn is increased by weakening the covalence between Mn and O through the local Ru-O-Mn configurations, which contributes to the attenuated J-T distortion. Last, the strong Ru-O covalency bond also leads to enhanced electron delocalization between Ru and O, which decreases the oxidation of oxygen anion and thereby reduces the driving force of metal migration. Because of these advantages, the structural integrity and electrochemical properties of NMMRO are largely improved compared with the Ru-free counterpart. This work provides deeper insights into the effect of local modulation for cationic/anionic redox-active cathodes for high-performance SIBs.

Coupling Zn2+ doping and rich oxygen vacancies in MnO2 nanowire toward advanced aqueous zinc-ion batteries.

Easy collapse of structure and sluggish reaction kinetics restrict the practical application of MnO2 in the field of aqueous Zn-ion batteries (ZIBs). To circumvent these obstacles, Zn2+ doping MnO2 nanowire electrode material with rich oxygen vacancies is prepared by one-step hydrothermal method combined with plasma technology. The experimental results indicate that Zn2+ doping MnO2 nanowire not only stabilizes the interlayer structure of MnO2, but also provide additional specific capacity as electrolyte ions. Meanwhile, plasma treatment technology induces the oxygen-deficient Zn-MnO2 electrode optimizing the electronic structure to improve the electrochemical behavior of the cathode materials. Especially, the optimized Zn/Zn-MnO2 batteries obtain outstanding specific capacity (546 mAh g-1 at 1 A g-1) and superior cycling durability (94% over 1000 continuous discharge/charge tests at 3 A g-1). Greatly, the H+ and Zn2+ reversible co-insertion/extraction energy storage system of Zn//Zn-MnO2-4 battery is further revealed by the various characterization analyses during the cycling test process. Further, from the perspective of reaction kinetics, plasma treatment also optimizes the diffusion control behavior of electrode materials. This research proposes a synergistic strategy of element doping and plasma technology, which has enhanced the electrochemical behaviors of MnO2 cathode and shed light on the design of the high-performance manganese oxide-based cathodes for ZIBs.

Tuning 2D Magnetism in Cobalt Monoxide Nanosheets Via In Situ Nickel-Doping.

Element doping has become an effective strategy to engineer the magnetic properties of two-dimensional (2D) materials and is widely explored in van der Waals layered transition metal dichalcogenides. However, the high-concentration substitution doping of 2D nonlayered metal oxides, which can preserve the original crystal texture and guarantee the homogeneity of doping distribution, is still a critical challenge due to the isotropic bonding of closed-packed structures. In this work, the synthesis of high-quality 2D nonlayered nickel-doped cobalt monoxide nanosheets via in situ atmospheric pressure chemical vapor deposition method is reported. High-resolution transmission electron microscopy confirmed that nickel atoms are doped at the intrinsic cobalt atom sites. The nickel doping concentration is stable at ≈15%, superior to most magnetic dopants doping in 2D materials and metal oxides. Magnetic measurements showed that pristine cobalt monoxide is nonferromagnetic, whereas nickel-doped cobalt monoxide exhibits robust ferromagnetic behavior with a Curie temperature of ≈180 K. Density functional theory calculations reveal that nickel atoms can improve the internal ferromagnetic correlation, giving rise to significant ferromagnetic performance of cobalt monoxide nanosheets. These results provide a valuable case for tuning the competing correlated states and magnetic ordering by substitution doping in 2D nonlayered oxide semiconductors.

Electron Redistribution Enables Redox-Resistible Li6 PS5 Cl towards High-Performance All-Solid-State Lithium Batteries.

Sulfide electrolytes with high ionic conductivity hold great promise for all-solid-state lithium batteries. However, the parasitic redox reactions between sulfide electrolyte and Li metal result in interfacial instability and rapid decline of the battery performance. Herein, a redox-resistible Li6 PS5 Cl (LPSC) electrolyte is created by regulating the electron distribution in LPSC with Mg and F incorporation. The introduction of Mg triggers the electron agglomeration around S atom, inhibiting the electron acceptance from Li, and F generates the self-limiting interface, which hinders the redox reactions between LPSC and Li metal. This redox-resistible Li6 PS5 Cl-MgF2 electrolyte therefore presents a high critical current density (2.3 times that of pristine electrolyte). The LiCoO2 /Li6 PS5 Cl-MgF2 /Li cell shows an outstanding cycling stability (93.3 %@100 cycles at 0.2 C). This study highlights the electronic structure modulation to address redox issues on sulfide-based lithium batteries.

Ultrahigh-Voltage LiCoO2 at 4.7 V by Interface Stabilization and Band Structure Modification.

Lithium cobalt oxide (LCO) is widely used in Li-ion batteries due to its high volumetric energy density, which is generally charged to 4.3 V. Lifting the cut-off voltage of LCO from 4.3 V to 4.7 V will increase the specific capacity from 150 to 230 mAh g-1 with a significant improvement of 53%. However, LCO suffers serious problems of H1-3/O1 phase transformation, unstable interface between cathode and electrolyte, and irreversible oxygen redox reaction at 4.7 V. Herein, interface stabilization and band structure modification are proposed to strengthen the crystal structure of LCO for stable cycling of LCO at an ultrahigh voltage of 4.7 V. Gradient distribution of magnesium and uniform doping of nickel in Li layers inhibit the harmful phase transitions of LCO, while uniform LiMgx Ni1- x PO4 coating stabilizes the LCO-electrolyte interface during cycles. Moreover, the modified band structure improves the oxygen redox reaction reversibility and electrochemical performance of the modified LCO. As a result, the modified LCO has a high capacity retention of 78% after 200 cycles at 4.7 V in the half cell and 63% after 500 cycles at 4.6 V in the full cell. This work makes the capacity of LCO one step closer to its theoretical specific capacity.

Highly Efficient Photocatalytic Hydrogen Evolution over Mo-Doped ZnIn2S4 with Sulfur Vacancies.

The introduction of impure atoms or crystal defects is a promising strategy for enhancing the photocatalytic activity of semiconductors. However, the synergy of these two effects in 2D atomic layers remains unexplored. In this case, the preparation of molybdenum-doped thin ZnIn2S4-containing S vacancies (Mo-doped Sv-ZnIn2S4) is conducted using a one-pot solvothermal method. The coordination of Mo doping and S vacancies not only enhances visible light absorption and facilitates the separation of photogenerated carriers but also provides many active sites for photocatalytic reactions. Meanwhile, the Mo-S bonds play function as high-speed channels to rapidly transfer carriers to the active sites, which can directly promote hydrogen evolution. Consequently, Sv-ZnIn2S4 with an optimized amount of Mo doping exhibits a high hydrogen evolution rate of 5739 µmol g-1 h-1 with a corresponding apparent quantum yield (AQY) of 21.24% at 420 nm, which is approximately 5.4 times higher than the original ZnIn2S4. This work provides a new strategy for the development of highly efficient and sustainable 2D atomic photocatalysts for hydrogen evolution.

Rare earth Y doping induced lattice strain of mesoporous PtPd nanospheres for alkaline oxygen reduction electrocatalysis.

The synthesis of catalysts with controllable morphology and composition is important to enhance the catalytic performance for oxygen reduction reaction (ORR). Herein, trimetallic PtPdY mesoporous nanospheres (PtPdY MNs) are produced via a one-step chemical reduction method applying F127 as soft temple under acidic condition. The mesoporous structure provides a large contact area and also stimulates the diffusion and mass transfer of reactants and products. Besides, synergistic effect among Pt, Pd and Y elements effectively alters their electronic structure, enhancing the catalytic activity. Therefore, the PtPdY MNs show excellent ORR permanence to Pt/C under the alkaline solution. This study offers an effective channel for the preparation of mesoporous metals with rare earth metal doping towards promising electrocatalytic applications.