Evaluating the Intrinsic Zinc Storage Capacity of Cation-Preintercalated Cathode with Electrochemically Active Surface Area.

The guest cation preintercalation strategy has been widely adopted to improve the performance of zinc-vanadium batteries. However, existing studies always ignore the deintercalation of guest cations. This work focuses on the severe and universal deintercalation phenomenon and confirms the unaltered capacity after deintercalation, indicating that the capacity improvement mechanism cannot be attributed to the role of guest cations. Therefore, after excluding all of the previously researched factors for capacity improvement, the decisive factor is identified as the morphology (surface area). Based on the electrochemically active surface area (ECSA), a quantitative relationship with intrinsic capacity is established for the first time. This guides us to enhance battery capacity via enhancing ECSA through liquid-phase ultrasonic crushing to achieve the highest capacity of cation-preintercalated V2O5·nH2O (333.7 mAh g-1 at 10 A g-1). We believe that the enhanced ECSA is a plausible explanation for the improved performance of hydrated vanadium oxides.

Enabling Uniform and Stable Lithium-Ion Diffusion at the Ultrathin Artificial Solid-Electrolyte Interface in Siloxene Anodes.

Constructing a stable and robust solid electrolyte interphase (SEI) has a decisive influence on the charge/discharge kinetics of lithium-ion batteries (LIBs), especially for silicon-based anodes which generate repeated destruction and regeneration of unstable SEI films. Herein, a facile way is proposed to fabricate an artificial SEI layer composed of lithiophilic chitosan on the surface of two-dimensional siloxene, which has aroused wide attention as an advanced anode for LIBs due to its special characteristics. The optimized chitosan-modified siloxene anode exhibits an excellent reversible cyclic stability of about 672.6 mAh g-1 at a current density of 1000 mA g-1 after 200 cycles and 139.9 mAh g-1 at 6000 mA g-1 for 1200 cycles. Further investigation shows that a stable and LiF-rich SEI film is formed and can effectively adhere to the surface during cycling, redistribute lithium-ion flux, and enable a relatively homogenous lithium-ion diffusion. This work provides constructive guidance for interface engineering strategy of nano-structured silicon anodes.

N-Terminalized Ti3 C2 Tx MXene for Supercapacitor with Extraordinary Pseudocapacitance Performance.

MXenes have demonstrated significant potential in electrochemical energy storage, particularly in supercapacitors, owing to their exceptional properties. The surface terminal groups of MXene play a pivotal role in pseudocapacitive mechanism. Considering the hindered electrolyte ion transport caused by -F terminal groups and the limited ion binding sites associated with -O terminal groups, this study proposes a novel strategy of replacing -F with -N terminal groups. The modulated MXene-N electrode, featuring a substantial number of -N terminal groups, demonstrates an exceptionally high gravimetric capacitance of 566 F g-1 (at a scan rate of 2 mV s-1 ) or 588 F g-1 (at a discharge rate of 1 A g-1 ) in 1 м H2 SO4 electrolyte, and the potential window is significantly increased. Furthermore, subsequent spectra analysis and density functional theory calculations are employed to investigate the mechanism associated with -N terminal groups. This work exemplifies the significance of terminal modulation in the context of electrochemical energy storage.

Advances in Aqueous Zinc Ion Batteries based on Conversion Mechanism: Challenges, Strategies, and Prospects.

Recently, aqueous zinc-ion batteries with conversion mechanisms have received wide attention in energy storage systems on account of excellent specific capacity, high power density, and energy density. Unfortunately, some characteristics of cathode material, zinc anode, and electrolyte still limit the development of aqueous zinc-ion batteries possessing conversion mechanism. Consequently, this paper provides a detailed summary of the development for numerous aqueous zinc-based batteries: zinc-sulfur (Zn-S) batteries, zinc-selenium (Zn-Se) batteries, zinc-tellurium (Zn-Te) batteries, zinc-iodine (Zn-I2) batteries, and zinc-bromine (Zn-Br2) batteries. Meanwhile, the reaction conversion mechanism of zinc-based batteries with conversion mechanism and the research progress in the investigation of composite cathode, zinc anode materials, and selection of electrolytes are systematically introduced. Finally, this review comprehensively describes the prospects and outlook of aqueous zinc-ion batteries with conversion mechanism, aiming to promote the rapid development of aqueous zinc-based batteries.

MoO2 Nanoclusters Embedded in Hierarchical Nitrogen Doped Carbon Nanoflower as Electrocatalytic Mediators in Aqueous Zinc-Tellurium Batteries: Enhancing Electrochemical Kinetics of Tellurium Redox Reaction.

Aqueous zinc-ion batteries (AZIBs) are considered to be one of the most promising devices for large-scale energy storage systems owing to their high theoretical capacity, environmental friendliness, and safety. However, the ionic intercalation or surface redox mechanisms in conventional cathode materials generally result in unsatisfactory capacities. Conversion-type aqueous zinc-tellurium (Zn-Te) batteries have recently gained widespread attention owing to their high theoretical specific capacities. However, it remains an enormous challenge to improve the slow kinetics of the aqueous Zn-Te batteries. Here, MoO2 nanoclusters embedded in hierarchical nitrogen-doped carbon nanoflower (MoO2 /NC) hosts are successfully synthesized and loaded with Te in aqueous Zn-Te batteries. Benefitting from the highly dispersed MoO2 nanoclusters and hierarchical nanoflower structure with a large specific surface area, the electrochemical kinetics of the Te redox reaction are significantly improved. As a result, the Te-MoO2 /NC electrode exhibits superior cycling stability and a high specific capacity of 493 mAh g-1 at 0.1 A g-1 . Meanwhile, the conversion mechanism is systematically explored using a variety of ex situ characterization methods. Therefore, this study provides a novel approach for enhancing the kinetics of the Te redox reaction in aqueous Zn-Te batteries.

Surface Phase Engineering Modulated Iron-Nickel Nitrides/Alloy Nanospheres with Tailored d-Band Center for Efficient Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) plays a key role in many electrochemical energy conversion systems, but it is a kinetically sluggish reaction and requires a large overpotential to deliver appreciable current, especially for the non-noble metal electrocatalysts. In this study, the authors report a surface phase engineering strategy to improve the OER performance of transition metal nitrides (TMNs). The iron-nickel nitrides/alloy nanospheres (FeNi3 -N) wrapped in carbon are synthesized, and the optimized FeNi3 -N catalyst displays dual-phase nitrides on the surface induced by atom migration phenomenon, resulting from the different migration rates of metal atoms during the nitridation process. It shows excellent OER performance in alkaline media with an overpotential of 222 mV at 10 mA cm-2 , a small Tafel slope of 41.53 mV dec-1 , and long-term durability under high current density (>0.5 A cm-2 ) for at least 36 h. Density functional theory (DFT) calculations further reveal that the dual-phase nitrides are favorable to decrease the energy barrier, modulate the d-band center to balance the absorption and desorption of the intermediates, and thus promote the OER electrochemical performance. This strategy may shed light on designing OER and other catalysts based on surface phase engineering.

Preparation of Hollow Cobalt-Iron Phosphides Nanospheres by Controllable Atom Migration for Enhanced Water Oxidation and Splitting.

Transition metal phosphides (TMPs), especially the dual-metal TMPs, are highly active non-precious metal oxygen evolution reaction (OER) electrocatalysts. Herein, an interesting atom migration phenomenon induced by Kirkendall effect is reported for the preparation of cobalt-iron (Co-Fe) phosphides by the direct phosphorization of Co-Fe alloys. The compositions and distributions of the Co and Fe phosphides phases on the surfaces of the electrocatalysts can be readily controlled by Cox Fey alloys precursors and the phosphorization process with interesting atom migration phenomenon. The optimized Co7 Fe3 phosphides exhibit a low overpotential of 225 mV at 10 mA cm-2 in 1 m KOH alkaline media, with a small Tafel slope of 37.88 mV dec-1 and excellent durability. It only requires a voltage of 1.56 V to drive the current density of 10 mA cm-2 when used as both anode and cathode for overall water splitting. This work opens a new strategy to controllable preparation of dual-metal TMPs with designed phosphides active sites for enhanced OER and overall water splitting.

Protective Strategy to Boost the Stability of Aminated Graphene in Fenton-like Reactions.

Improving the stability of aminated metal-free catalysts is a big challenge in Fenton-like reactions. Herein, trinuclear iron cluster (Fe3 cluster)-protected aminated graphene (Fe3-NH2-GR) is designed by a protective strategy. By protecting with the Fe3 cluster, the lone pair electrons of amino groups are protected and the N content of Fe3-NH2-GR can be fixed steadily. In peroxymonosulfate (PMS)-based Fenton-like reactions with a fixed-bed reactor, the lifetime of Fe3-NH2-GR is two times longer than that of aminated graphene (NH2-GR) under the same conditions. The deactivation kinetics shows that both Fe3-NH2-GR and NH2-GR follow zero-order kinetics and the deactivation rate constants of Fe3-NH2-GR are lower than that of NH2-GR at every period. Moreover, Fe3-NH2-GR still maintains 50% phenol degradation after 40 h rather than being constantly deactivated as NH2-GR. This stable activity is attributed to the formation of -O-NO2, while the N content will be lost in NH2-GR. This protective strategy by the Fe3 cluster provides a reliable method to enhance the efficiency and stability of carbon catalysts in Fenton-like reactions.

Surfactant-Free Synthesis of Ultrafine Pt Nanoparticles on MoS2 Nanosheets as Bifunctional Catalysts for the Hydrodeoxygenation of Bio-Oil.

Hydrodeoxygenation (HDO) of bio-oil is a crucial step for improving the bio-fuel quality, but developing highly dispersed Pt-based catalysts with high selectivity for target alkanes remains a great challenge. This study presents a fast surfactant-free method to prepare the MoS2-supported Pt catalyst for HDO. Ultrafine Pt nanoparticles with sizes of <5 nm can be readily grown on chemically exfoliated MoS2 nanosheets (NSs) via the direct microwave-assisted thermal reduction. The obtained Pt NPs/MoS2 composites show excellent catalytic performance in the conversion of palmitic acid, and the best selectivity (also the yield) of hexadecane and pentadecane is 80.56 and 19.43%, respectively.

Polyaniline Derived N-Doped Carbon-Coated Cobalt Phosphide Nanoparticles Deposited on N-Doped Graphene as an Efficient Electrocatalyst for Hydrogen Evolution Reaction.

The development of highly efficient and durable non-noble metal electrocatalysts for the hydrogen evolution reaction (HER) is significant for clean and renewable energy research. This work reports the synthesis of N-doped graphene nanosheets supported N-doped carbon coated cobalt phosphide (CoP) nanoparticles via a pyrolysis and a subsequent phosphating process by using polyaniline. The obtained electrocatalyst exhibits excellent electrochemical activity for HER with a small overpotential of -135 mV at 10 mA cm-2 and a low Tafel slope of 59.3 mV dec-1 in 0.5 m H2 SO4 . Additionally, the encapsulation of N-doped carbon shell prevents CoP nanoparticles from corrosion, exhibiting good stability after 14 h operation. Moreover, the as-prepared electrocatalyst also shows outstanding activity and stability in basic and neutral electrolytes.

Decoration of Cu2O photocathode with protective TiO2 and active WS2 layers for enhanced photoelectrochemical hydrogen evolution.

A Cu2O based multi-layered photocathode was fabricated with a layer-by-layer assembly method for enhanced photoelectrochemical (PEC) hydrogen evolution. Au was first electrodeposited on the fluorine-doped tin oxide glass to decrease the electrochemical impedance of the Cu2O photocathode. A layer of TiO2 was then coated to increase the light-to-electricity energy conversion efficiency and the chemical stability by forming a p-n junction with Cu2O. Exfoliated WS2 nanosheets obtained from lithium insertion were then coated as the electron acceptor to facilitate the hydrogen evolution. This photocathode is effective for PEC hydrogen evolution, and a photocurrent of -10 mA cm-2 can be obtained at -0.33 V versus RHE in a phosphorus buffer (pH = 6.0) under visible light (λ ≥ 420 nm, 100 mW cm-2) on the optimized photocathode.

Synthesis of MoS2/graphene hybrid supported Au and Ag nanoparticles with multi-functional catalytic properties.

The detection and removal of nitroaromatic compounds is an important issue for environmental protection. In this study, a hybrid of molybdenum disulfide (MoS2) and graphene (GR) was first synthesized using a facile hydrothermal method. Au and Ag nanoparticles were then deposited onto the surface of the MoS2/GR hybrid with sodium citrate as the stabilizer and reductant. Compared to using pure MoS2 as the support, the obtained Au (Ag)-MoS2/GR composites showed improved activity for electrochemical detection and chemical reduction of 4-nitrophenol. The activity enhancement appears to be due to the addition of GR, which could improve the conductivity as well as provide more active sites. The successful synthesis of Au (Ag)-MoS2/GR composites could provide new multi-function catalysts for environmental protection.

[ARM-based Embedded Detection System of Cardiovascular Function Parameters].

A cardiovascular function testing system was designed in platform which was built with ARM microprocessor s3c2440 and Linux system, to achieve pulse wave acquisition, feature extraction, index calculation and so on. This article mainly describes the hardware circuit, and describes the touchscreen driver, external ADC driver, and visualization QT-based applications in detail. The system is easy to use, with real-time, low power consumption. Compared with common cardiovascular function test instrument, the results shows that the system can better assess the cardiovascular function, expecially in several key indicators like subendocardial myocardial viability rate and augmentation index, the indicators show good correlations.

Microwave-assisted 1T to 2H phase reversion of MoS2 in solution: a fast route to processable dispersions of 2H-MoS2 nanosheets and nanocomposites.

Exfoliated molybdenum disulfide (MoS2) has unique 2H phase and semiconductor properties and potential applications across a wide range of fields. However, the chemically exfoliated MoS2 nanosheets from Li x MoS2 have a 1T phase, and searching for a fast route to get processable 2H-MoS2 nanosheets and its nanocomposites is still an urgent task. This study reports on a simple, fast and efficient microwave strategy to achieve the 1T to 2H phase conversion of MoS2 and the successful preparation of processable 2H-MoS2 nanosheets and their nanocomposites. The method here may be easily changed to achieve the phase change of other exfoliated TMDs.

Template-Assisted in situ synthesis of superaerophobic bimetallic MOF composites with tunable morphology for boosted oxygen evolution reaction.

CoFe bimetallic organic frameworks (CoFe-MOFs) with tunable morphology and electronic structure are synthesized in situ utilizing cobalt hydroxide (Co(OH)2) as a semi-sacrificial template and different anionic iron salts as modifying factors in a non-calcined synthesis method. This work defines the impact of three different anionic metallic iron salts (FeCl3, Fe(NO3)3, and Fe2(SO4)3) on the morphology of MOF materials and their resulting oxygen evolution reaction (OER) catalytic activity. Employing ferric chloride (FeCl3) as the metallic iron source, heterostructured electrocatalysts (BN-CoFe-MOF) with nanoparticles decorated nanoneedle tips are obtained, exhibiting a low overpotential (230 mV at 10 mA cm-2) and a Tafel slope of 105.6 mV dec-1 in 1.0 M KOH. It also demonstrates long time stability for at least 50 h at a current density of 10 mA cm-2. The investigation uncovers that the splendid OER activity and stability of the BN-CoFe-MOF heterojunction can be attributed to its large specific surface area, desirable mesoporous structure, superaerophobic characteristic, and high exposure of active centers. This work not only provides an efficient and cost-effective MOF based OER electrocatalyst but also serves as a valuable reference for future research on morphology control and strategies to enhance the OER activity of MOF catalysts.

N-Doping-Induced Amorphization for Achieving Ultrastable Aqueous Zinc-Ion Batteries.

Vanadium-based oxides, known for their high capacity and low cost, have garnered significant attention as promising cathode candidates in aqueous zinc-ion batteries. Nonetheless, their poor rate performance and limited durability in aqueous electrolytes present a challenge to the realistic implementation of vanadium-based aqueous zinc-ion batteries. Here, we synthesized nitrogen-doped V2O3@C (N-V2O3@N-C) via ammonia treatment of V2O3@C derived from vanadium-based metal-organic framework (V-MOF), aiming to achieve outstanding rate and cycling performance. The N-V2O3@N-C electrode exhibits notable in situ self-transformation into an amorphous state. Density functional theory calculations reveal that the distorted N-V2O3 structure and uneven charge distribution result in the creation of an amorphous state. As expected, Zn/N-V2O3@N-C aqueous zinc-ion batteries can achieve remarkable specific capacity (349.0 mAh g-1 at 0.1 A g-1), along with impressive rate performance, showcasing a capacity of 253.5 mAh g-1 at 5 A g-1 and exceptional durability at 5 A g-1 (96.4% after 1350 cycles). The employed induced amorphization approach offers novel perspectives for designing high-performance cathodes that exhibit both sturdy structures and extended cycling lifespans.

Facilely tuning the coating layers of Fe nanoparticles from iron carbide to iron nitride for different performance in Fenton-like reactions.

In this study, a series of Fe-based materials are facilely synthesized using MIL-88A and melamine as precursors. Changing the mass ratio of melamine and MIL-88A could tune the coating layers of generated zero-valent iron (Fe0) particles from Fe3C to Fe3N facilely. Compared to Fe/Fe3N@NC sample, Fe/Fe3C@NC exhibits better catalytic activity and stability to degrade carbamazepine (CBZ) with peroxymonosulfate (PMS) as oxidant. Free radical quenching tests, open-circuit potential (OCP) test and electron paramagnetic resonance spectra (EPR) prove that hydroxyl radicals (OH) and superoxide radical (O2-) are dominant reactive oxygen species (ROSs) with Fe/Fe3C@NC sample. For Fe/Fe3N@NC sample, the main ROSs are changed into sulfate radicals (SO4-) and high valent iron-oxo (Fe (IV)=O) species. In addition, the better conductivity of Fe3C is beneficial for the electron transfer from Fe0 to the Fe3C, thus could keep the activity of the surface sites and obtain better stability. DFT calculation reveals the better adsorption and activation ability of Fe3C than Fe3N. Moreover, PMS can also be adsorbed on the Fe sites of Fe3N with shorter FeO bonds and longer SO bonds than on Fe3C, the Fe (IV)=O is thus present in the Fe/Fe3N@NC/PMS system. This study provides a novel strategy for the development of highly active Fe-based materials for Fenton-like reactions and thus could promote their real application.

Accelerated screening of active sites on biochar for catalysis and adsorption via multidimensional fingerprint factor descriptors.

Highly active biochar has great application potential in heterogeneous catalysis and adsorptive processes. The complexity of carbonization process makes it difficult to construct target active sites. This work put forward a reactive descriptor based on pyrolysis parameters and intrinsic composition of biomass. Results show that the model showed better predictive performance for C-C/C=C (R2 = 0.85), C=O (R2 = 0.85) and defect (R2 = 0.91) sites. The SHapley Additive exPlanation analysis shows that the pyrolysis parameters and the higher heating values are equally important for the active sites. The predictive performance and guiding role of the descriptor were validated by experiments. The descriptors proposed in this study integrated significant advantages of simplicity and easy accessibility, which would break the bottleneck of accurate construction of active sites and provide a theoretical basis for high-value resource utilization of biomass.

Boosting Suzuki coupling reaction via pore expanding and palladium-zinc alloying.

A palladium-zinc alloy nanoparticles decorated nitrogen-doped porous carbon catalyst (PdZn30-NC) was synthesized and utilized for Suzuki coupling reaction. The alloying palladium (Pd) with zinc (Zn) and pore expanding are realized simultaneously. Density functional theory (DFT) calculations and experimental studies reveal that the alloying Pd with Zn can lower the energy barrier in Suzuki coupling reaction. Nitrogen adsorption-desorption measurements uncover that pore expansion caused by the zinc nitrate hexahydrate assisted calcination gives rise to the multiplication of mesopore with a pore diameter of 6 nm, which facilitates mass transfer during the reaction. As a result, the alloying Pd with Zn and pore expanding together endow PdZn30-NC with excellent catalytic activity. PdZn30-NC demonstrates exceptional catalytic activity and stability in Suzuki coupling reaction. A high biphenyl yield of 97.7 % within 40 min and stable reusability of 93.3 % yield after five reuse cycles can be achieved. This work not only offers a viable method for Suzuki coupling reaction, but also provides insights for designing new catalysts toward Suzuki coupling reaction.

Facile synthesis of pyrite FeS2 on carbon spheres for high-efficiency Fenton-like reaction.

Designing iron-based catalysts for Fenton-like reactions with peroxymonosulfate (PMS) as oxidants have attracted growing attentions. Herein, pyrite FeS2 supported on carbon spheres (FeS2@C) is synthesized by a facile low-temperature method. The FeS2@C/PMS system can degrade carbamazepine (CBZ) effectively in a wide pH range. Sulfate radicals (SO4·-), hydroxyl radicals (·OH), superoxide radical (O2·-), and singlet oxygen (1O2) are the responsible reactive oxygen species (ROSs) for CBZ degradation. Moreover, in the simulated fixed-bed reactor, the FeS2@C/PMS system can maintain a high CBZ removal ratio of >95% for than 8 h, exhibiting its excellent stability. The outstanding performance of FeS2@C/PMS system is attributed to the presence of carbon spheres and lattice S2-, which together promote the Fe(III)/Fe(II) redox cycle. The FeS2@C is a promising catalyst due to its facile synthesis, low cost, high efficiency, and excellent stability to activate PMS for organics degradation.