2D Tungsten Borides Induced Interfacial Modulation Engineering Toward High-Rate Performance Zinc-Iodine Battery.

Aqueous zinc-iodine batteries are promising candidates for large-scale energy storage due to their high energy density and low cost. However, their development is hindered by several drawbacks, including zinc dendrites, anode corrosion, and the shuttle of polyiodides. Here, the design of 2D-shaped tungsten boride nanosheets with abundant borophene subunits-based active sites is reported to guide the (002) plane-dominated deposition of zinc while suppressing side reactions, which facilitates interfacial nucleation and uniform growth of zinc. Meanwhile, the interfacial d-band orbits of tungsten sites can further enhance the anchoring of polyiodides on the surface, to promote the electrocatalytic redox conversion of iodine. The resulting tungsten boride-based I2 cathodes in zinc-iodine cells exhibit impressive cyclic stability after 5000 cycles at 50 C, which accelerates the practical applications of zinc-iodine batteries.

Fundamentally Manipulating the Electronic Structure of Polar Bifunctional Catalysts for Lithium-Sulfur Batteries: Heterojunction Design versus Doping Engineering.

Heterogeneous structures and doping strategies have been intensively used to manipulate the catalytic conversion of polysulfides to enhance reaction kinetics and suppress the shuttle effect in lithium-sulfur (Li-S) batteries. However, understanding how to select suitable strategies for engineering the electronic structure of polar catalysts is lacking. Here, a comparative investigation between heterogeneous structures and doping strategies is conducted to assess their impact on the modulation of the electronic structures and their effectiveness in catalyzing the conversion of polysulfides. These findings reveal that Co0.125Zn0.875Se, with metal-cation dopants, exhibits superior performance compared to CoSe2/ZnSe heterogeneous structures. The incorporation of low Co2+ dopants induces the subtle lattice strain in Co0.125Zn0.875Se, resulting in the increased exposure of active sites. As a result, Co0.125Zn0.875Se demonstrates enhanced electron accumulation on surface Se sites, improved charge carrier mobility, and optimized both p-band and d-band centers. The Li-S cells employing Co0.125Zn0.875Se catalyst demonstrate significantly improved capacity (1261.3 mAh g-1 at 0.5 C) and cycle stability (0.048% capacity delay rate within 1000 cycles at 2 C). This study provides valuable guidance for the modulation of the electronic structure of typical polar catalysts, serving as a design directive to tailor the catalytic activity of advanced Li-S catalysts.

Interfacial "Double-Terminal Binding Sites" Catalysts Synergistically Boosting the Electrocatalytic Li2S Redox for Durable Lithium-Sulfur Batteries.

Catalytic conversion of polysulfides emerges as a promising approach to improve the kinetics and mitigate polysulfide shuttling in lithium-sulfur (Li-S) batteries, especially under conditions of high sulfur loading and lean electrolyte. Herein, we present a separator architecture that incorporates double-terminal binding (DTB) sites within a nitrogen-doped carbon framework, consisting of polar Co0.85Se and Co clusters (Co/Co0.85Se@NC), to enhance the durability of Li-S batteries. The uniformly dispersed clusters of polar Co0.85Se and Co offer abundant active sites for lithium polysulfides (LiPSs), enabling efficient LiPS conversion while also serving as anchors through a combination of chemical interactions. Density functional theory calculations, along with in situ Raman and X-ray diffraction characterizations, reveal that the DTB effect strengthens the binding energy to polysulfides and lowers the energy barriers of polysulfide redox reactions. Li-S batteries utilizing the Co/Co0.85Se@NC-modified separator demonstrate exceptional cycling stability (0.042% per cycle over 1000 cycles at 2 C) and rate capability (849 mAh g-1 at 3 C), as well as deliver an impressive areal capacity of 10.0 mAh cm-2 even in challenging conditions with a high sulfur loading (10.7 mg cm-2) and lean electrolyte environments (5.8 µL mg-1). The DTB site strategy offers valuable insights into the development of high-performance Li-S batteries.

Zinc-Doping Strategy on P2-Type Mn-Based Layered Oxide Cathode for High-Performance Potassium-ion Batteries.

Mn-based layered oxide is extensively investigated as a promising cathode material for potassium-ion batteries due to its high theoretical capacity and natural abundance of manganese. However, the Jahn-Teller distortion caused by high-spin Mn3+ (t2g 3 eg 1 ) destabilizes the host structure and reduces the cycling stability. Here, K0.02 Na0.55 Mn0.70 Ni0.25 Zn0.05 O2 (denoted as KNMNO-Z) is reported to inhibit the Jahn-Teller effect and reduce the irreversible phase transition. Through the implementation of a Zn-doping strategy, higher Mn valence is achieved in the KNMNO-Z electrode, resulting in a reduction of Mn3+ amount and subsequently leading to an improvement in cyclic stability. Specifically, after 1000 cycles, a high retention rate of 97% is observed. Density functional theory calculations reveals that low-valence Zn2+ ions substituting the transition metal position of Mn regulated the electronic structure around the MnO bonding, thereby alleviating the anisotropic coupling between oxidized O2- and Mn4+ and improving the structural stability. K0.02 Na0.55 Mn0.70 Ni0.25 Zn0.05 O2 provided an initial discharge capacity of 57 mAh g-1 at 100 mA g-1 and a decay rate of only 0.003% per cycle, indicating that the Zn-doped strategy is effective for developing high-performance Mn-based layered oxide cathode materials in PIBs.

Bimetallic alloy and semiconductor support synergistic interaction effects for superior electrochemical catalysis.

The design and fabrication of economically viable anode catalysts for the methanol oxidation reaction (MOR) have been challenging issues in direct methanol fuel cells (DMFCs) over the decades. In this work, a composite electrochemical catalyst of Pd-coupled Ag and ZnO for the possible replacement of expensive Pt catalysts in DMFCs is successfully prepared. The as-made Pd@Ag/ZnO exhibits specific activity, which is 1.8-fold, 2.8-fold, and 4.6-fold higher than that of a Pd/ZnO catalyst, 20% Pd/C catalyst and Pd black, respectively. The improvement of the catalytic mechanism is likely due to the synergistic interaction between Pd@Ag and ZnO. The density functional theory (DFT) calculation results confirm that Ag doped into Pd weakens the adsorption of CO, dramatically improving the capability to resist CO poisoning.

Synergistic Enhancement Effect for Boosting Raman Detection Sensitivity of Antibiotics.

In this paper, a two-step method is used to prepare a regenerative three-dimensional (3D) ZnO/Ag@Au substrate for developing a superior sensitive surface enhanced Raman scattering (SERS) method for detecting antibiotics. A great electromagnetic enhancement is observed from the as-prepared composite substrate, which is triggered by tuning the electron distribution of metals and semiconductor metal oxide. The strong interaction between target sample and the huge surface area of ZnO/Ag@Au composite promotes the charge transfer to produce promising chemical enhancement. The synergistic physical and chemical enhancement mechanisms are validated by density functional theory and finite difference time domain simulation. Additionally, the presence of light "echo effect" in the 3D structure of ZnO support could also amplify the efficiency of light excitation for Raman scattering. The above-stated merits benefit to boost the Raman scattering detection sensitivity for real samples. The ZnO/Ag@Au-based SERS substrate could detect rhodamine 6G molecules with an enhancement factor of up to 1.48 × 109 and the lowest detectable concentration of 10-10 M. As a real application, antibiotics sulfapyridine in milk is determined by using the proposed SERS protocol, and the limit of detection at 1 × 10-9 M could be reached. As a prospective, the ZnO/Ag@Au-based SERS method would be extended for food safety and biomedicine analysis.