Polyoxometallate Cluster Induced High-Entropy Oxide Sub-1 nm Nanosheets as Photoelectrocatalysts for Zn-Air Batteries.

The lack of highly efficient and inexpensive catalysts severely hinders the large-scale application of Zn-air batteries (ZABs). High-entropy oxides (HEOs) exhibit unique structures and attractive properties; thus, they are promising to be used in ZABs. However, conventional high-temperature synthesis methods tend to obtain microscale HEOs with a lower exposure rate of active sites. Here, we report a facile solvothermal strategy for preparing two-dimensional (2D) HEO sub-1 nm nanosheets (SNSs) induced by polyoxometalate (POM) clusters. Taking advantage of the special 2D sub-1 nm structure and precise element regulation, these 2D HEOs-POM SNSs exhibit enhanced bifunctional oxygen evolution and oxygen reduction reaction activity under light irradiation. Further applying these 2D HEOs-POM SNSs to ZABs as cathode catalysts, the CoFeNiMnCuZnOx-phosphomolybdic acid SNSs-based ZABs deliver a low charge/discharge voltage gap of 0.25 V at 2 mA cm-2 under light irradiation. Meanwhile, it could maintain an ultralong-term stability for 1600 h at 2 mA cm-2 and 930 h at 10 mA cm-2. The 2D sub-1 nm structure and fine element control in HEOs provide opportunities to solve the problems of low intrinsic activity, limited active sites, and instability of air cathodes in ZABs.

Hybrid Sub-1 nm Nanosheets of Co-assembled MnZnCuOx and Polyoxometalate Clusters as Anodes for Li-ion Batteries.

Transition metal oxide (TMO) anode materials in lithium-ion batteries (LIBs) usually suffer from serious volume expansion leading to the pulverization of structures, further giving rise to lower specific capacity and worse cycling stability. Herein, by introducing polyoxometalate (POM) clusters into TMOs and precisely controlling the amount of POMs, the MnZnCuOx -phosphomolybdic acid hybrid sub-1 nm nanosheets (MZC-PMA HSNSs) anode is successfully fabricated, where the special electron rich structure of POMs is conducive to accelerating the migration of lithium ions on the anode to obtain higher specific capacity, and the non-covalent interactions between POMs and TMOs make the HSNSs possess excellent structural and chemical stability, thus exhibiting outstanding electrochemical performance in LIBs, achieving a high reversible capacity (1157 mAh g-1 at 100 mA g-1 ) and an admirable long-term cycling stability at low and high current densities.

Highly Active PdO/Mn3 O4 /CeO2 Nanocomposites Supported on One Dimensional Halloysite Nanotubes for Photoassisted Thermal Catalytic Methane Combustion.

In this work, we have successfully triggered the aqueous auto-redox reactions between reductive Ce(OH)3 and oxidative MnO4 - /Pd2+ ions to form PdO/Mn3 O4 /CeO2 (PMC) nanocomposites. PMC could spontaneously self-assemble into compact encapsulation on the surface of halloysite nanotubes (HNTs) to form the final one dimensional HNTs supported PMCs (HPMC). It is identified that there exists strong synergistic effects among the components of PdO, Mn3 O4 , and CeO2 , and hence HPMC could show excellent performance on photoassisted thermal catalytic CH4 combustion that its light-off temperature was sharply reduced to be 180 °C under visible light irradiation. Based on detailed studies, it is found that the catalytic reaction process well follows the classic MVK mechanism, and adsorption/activation of O2 into active oxygen species (O*) should be the rate-determining step for CH4 conversion.

Solvation Effect on the Improved Sodium Storage Performance of N-Heteropentacenequinone for Sodium-Ion Batteries.

The performance of electrode material is correlated with the choice of electrolyte, however, how the solvation has significant impact on electrochemical behavior is underdeveloped. Herein, N-heteropentacenequinone (TAPQ) is investigated to reveal the solvation effect on the performance of sodium-ion batteries in different electrolyte environment. TAPQ cycled in diglyme-based electrolyte exhibits superior electrochemical performance, but experiences a rapid capacity fading in carbonate-based electrolyte. The function of solvation effect is mainly embodied in two aspects: one is the stabilization of anion intermediate via the compatibility of electrode and electrolyte, the other is the interfacial electrochemical characteristics influenced by solvation sheath structure. By revealing the failure mechanism, this work presents an avenue for better understanding electrochemical behavior and enhancing performance from the angle of solvation effect.

In Situ Fabrication of Porous Cox P Hierarchical Nanostructures on Carbon Fiber Cloth with Exceptional Performance for Sodium Storage.

Superior high-rate performance and ultralong cycling life have been constantly pursued for rechargeable sodium-ion batteries (SIBs). In this work, a facile strategy is employed to successfully synthesize porous Cox P hierarchical nanostructures supported on a flexible carbon fiber cloth (Cox P@CFC), constructing a robust architecture of ordered nanoarrays. Via such a unique design, porous and bare structures can thoroughly expose the electroactive surfaces to the electrolyte, which is favorable for ultrafast sodium-ion storage. In addition, the CFC provides an interconnected 3D conductive network to ensure firm electrical connection of the electrode materials. Besides the inherent flexibility of the CFC, the integration of the hierarchical structures of Cox P with the CFC, as well as the strong synergistic effect between them, effectively help to buffer the mechanical stress caused by repeated sodiation/desodiation, thereby guaranteeing the structural integrity of the overall electrode. Consequently, Cox P@CFC as an anode shows a record-high capacity of 279 mAh g-1 at 5.0 A g-1 with almost no capacity attenuation after 9000 cycles.

3D Carbon Networks: Design and Applications in Sodium Ion Batteries.

As the key component of a new generation for low-cost energy storage systems, sodium-ion batteries (SIBs) have attracted enormous attention and research due to its promising potentiality in large-scale electrochemical energy storage. For practical application of SIBs, carbonaceous materials have been considered to be one of the best choices for electrodes in virtue of their abundant reserves, low cost, easy availability, and environmental friendliness. 3D carbon network (3D-carbon) is of particular interests, which has displayed outstanding features, including abundant active sites, interconnected multi-level pore structures, high electronic conductivity, and excellent mechanical stability. Herein, we review the structural advantages of 3D-carbon and its preparation methods, and then discuss recent progress in 3D carbon materials and their composites for SIBs. The superior functionalities of 3D-carbon are emphasized as support templates or encapsulation shell membranes. Finally, we summarize and outline the challenges and future prospects of 3D-carbon in SIBs.