Phase Engineering of Molybdenum Carbide-Cobalt Heterostructures for Long-Lasting Zn-Air Batteries.

Developing highly active and robust oxygen catalysts is of great significance for the commercialization of Zn-air batteries (ZABs) with long-life stability. Herein, heterostructured catalysts comprising molybdenum carbide and metallic Co are prepared by a simple dicyandiamide-assisted pyrolysis strategy. Importantly, the crystalline phase of molybdenum carbide in the catalysts can be carefully regulated by adjusting the CoMo-imidazole precursor and dicyandiamide ratio. The electronic configuration of Co and Mo centers as well as the phase-dependent oxygen reduction reaction performance of these heterostructures (ß-Mo2C/Co, ß-Mo2C/η-MoC/Co, and η-MoC/Co) was disclosed. A highly active η-MoC/Co cathode enables ZABs with outstanding long-term stability over 850 h with a low voltage decaying rate of 0.06 mV·h-1 and high peak power density of 162 mW·cm-2. This work provides a new idea for the rational design of efficient and stable cathode catalysts for ZABs.

Tunable Heterogeneous FeCo Alloy-Mo0.82N Bifunctional Electrocatalysts for Temperature-Adapted Zn-Air Batteries.

The practical applications of temperature-tolerant Zn-air batteries (ZABs) rely on highly active and stable bifunctional catalysts that accelerate cathodic oxygen reduction (ORR) and oxygen evolution (OER) reactions. Herein, we successfully integrated fascinating transition metal nitrides and FeCo alloys through a simple coordination assembly and pyrolysis process. Importantly, the alloy-to-nitride ratio in the heterogeneous catalyst can be carefully regulated through the subsequent etching process. Moreover, the composition-dependent ORR/OER performance of the FeCo-Mo0.82N catalysts was revealed. Aqueous ZABs using the optimized FeCo-Mo0.82N-60 as a cathode exhibit a high peak power density of 149.7 mW cm-2 and an impressive stability of 600 h with a low charge-discharge voltage gap decay rate of 0.025 mV h-1, which exceeds those of most of recent reports. Furthermore, the FeCo-Mo0.82N-60-based flexible ZABs display a small specific capacity degradation (3%) from 40 to -10 °C, demonstrating excellent temperature tolerance.

Unlocking active metal site of Ti-MOF for boosted heterogeneous catalysis via a facile coordinative reconstruction.

Constructing sophisticated hollow structure and exposing more metal sites in metal-organic frameworks (MOFs) can not only enhance their catalytic performance but also endow them with new functions. Herein, we present a facile coordinative reconstruction strategy to transform Ti-MOF polyhedron into nanosheet-assembled hollow structure with a large amount of exposed metal sites. Importantly, the reconstruction process relies on the esterification reaction between the organic solvent, i.e. ethanol and the carboxylic acid ligand, allowing the conversion of MOF without the addition of any other modulators and/or surfactants. Moreover, the surface and internal structure of the reconstructed MOF can be well tuned via altering the conversion time. Impressively, the reconstructed MOF exhibits ∼5.1-fold rate constant compared to the pristine one in an important desulfurization reaction for clean fuels production, i.e. the oxidation of dibenzothiophene.

Bismuth Nanoparticle-Embedded Porous Carbon Frameworks as a High-Rate Chloride Storage Electrode for Water Desalination.

Capacitive deionization (CDI) is a promising cost-effective and low energy consumption technology for water desalination. However, most of the previous works focus on only one side of the CDI system, i.e., Na+ ion capture, while the other side that stores chloride ions, which is equally important, receives very little attention. This is attributed to the limited Cl- storage materials as well as their sluggish kinetics and poor stability. In this article, we demonstrate that a N-doped porous carbon framework is capable of suppressing the phase-transformation-induced performance decay of bismuth, affording an excellent Cl- storage and showing potential for water desalination. The obtained Bi-carbon composite (Bi/N-PC) shows a capacity of up to 410.4 mAh g-1 at 250 mA g-1 and a high rate performance. As a demonstration for water desalination, a superior desalination capacity of 113.4 mg g-1 is achieved at 100 mA g-1 with excellent durability. Impressively, the CDI system exhibits fast ion capturing with a desalination rate as high as 0.392 mg g-1 s-1, outperforming most of the recently reported Cl- capturing electrodes. This strategy is applicable to other Cl- storage materials for next-generation capacitive deionization.

Non-3d Metal Modulation of a 2D Ni-Co Heterostructure Array as Multifunctional Electrocatalyst for Portable Overall Water Splitting.

Portable water splitting devices driven by rechargeable metal-air batteries or solar cells are promising, however, their scalable usages are still hindered by lack of suitable multifunctional electrocatalysts. Here, a highly efficient multifunctional electrocatalyst is demonstrated, i.e., 2D nanosheet array of Mo-doped NiCo2 O4 /Co5.47 N heterostructure deposited on nickel foam (Mo-NiCo2 O4 /Co5.47 N/NF). The successful doping of non-3d high-valence metal into a heterostructured nanosheet array, which is directly grown on a conductive substrate endows the resultant catalyst with balanced electronic structure, highly exposed active sites, and binder-free electrode architecture. As a result, the Mo-NiCo2 O4 /Co5.47 N/NF exhibits remarkable catalytic activity toward the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), affording high current densities of 50 mA cm-2 at low overpotentials of 310 mV for OER, and 170 mV for HER, respectively. Moreover, a low voltage of 1.56 V is achieved for the Mo-NiCo2 O4 /Co5.47 N/NF-based water splitting cell to reach 10 mA cm-2 . More importantly, a portable overall water splitting device is demonstrated through the integration of a water-splitting cell and two Zn-air batteries (open-circuit voltage of 1.43 V), which are all fabricated based on Mo-NiCo2 O4 /Co5.47 N/NF, demonstrating a low-cost way to generate fuel energy. This work offers an effective strategy to develop high-performance metal-doped heterostructured electrode.