Design Principles and Mechanistic Understandings of Non-Noble-Metal Bifunctional Electrocatalysts for Zinc-Air Batteries.

Zinc-air batteries (ZABs) are promising energy storage systems because of high theoretical energy density, safety, low cost, and abundance of zinc. However, the slow multi-step reaction of oxygen and heavy reliance on noble-metal catalysts hinder the practical applications of ZABs. Therefore, feasible and advanced non-noble-metal electrocatalysts for air cathodes need to be identified to promote the oxygen catalytic reaction. In this review, we initially introduced the advancement of ZABs in the past two decades and provided an overview of key developments in this field. Then, we discussed the working mechanism and the design of bifunctional electrocatalysts from the perspective of morphology design, crystal structure tuning, interface strategy, and atomic engineering. We also included theoretical studies, machine learning, and advanced characterization technologies to provide a comprehensive understanding of the structure-performance relationship of electrocatalysts and the reaction pathways of the oxygen redox reactions. Finally, we discussed the challenges and prospects related to designing advanced non-noble-metal bifunctional electrocatalysts for ZABs.

Supercritical diethylamine facilitated loading of ultrafine Ru particles on few-layer graphene for solvent-free hydrogenation of levulinic acid to γ-valerolactone.

We demonstrate a facile and versatile method to grow Ru particles uniformly on pristine few-layer graphene (FLG) in supercritical diethylamine. In particular, a large number of Ru subnanometer clusters less than 1.0 nm were observed. The particle size can be tuned by manipulating the loading content of Ru and controlling the reaction temperature. The resulting Ru/FLG showed remarkably high activity, selectivity, and reusability towards the hydrogenation of levulinic acid to γ-valerolactone. This method is flexible, and can be extended to the synthesis of a variety of other ultrafine metal particles supported on FLG.

Heterogeneous electrochemical CO2 reduction using nonmetallic carbon-based catalysts: current status and future challenges.

Electrochemical CO2 reduction (ECR) offers an important pathway for renewable energy storage and fuels production. It still remains a challenge in designing highly selective, energy-efficient, robust, and cost-effective electrocatalysts to facilitate this kinetically slow process. Metal-free carbon-based materials have features of low cost, good electrical conductivity, renewability, diverse structure, and tunability in surface chemistry. In particular, surface functionalization of carbon materials, for example by doping with heteroatoms, enables access to unique active site architectures for CO2 adsorption and activation, leading to interesting catalytic performances in ECR. We aim to provide a comprehensive review of this category of metal-free catalysts for ECR, providing discussions and/or comparisons among different nonmetallic catalysts, and also possible origin of catalytic activity. Fundamentals and some future challenges are also described.

N-Doping of graphene oxide at low temperature for the oxygen reduction reaction.

Nitrogen doping of graphene oxide was demonstrated for the first time at a temperature as low as 5 °C in ammonia solution with the aid of ultrasonication. Controlling the ultrasonication time and bath temperature permitted tuning of the N doping level. The resulting N doped graphene oxide showed high activity towards the oxygen reduction reaction.

Scalable exfoliation and dispersion of two-dimensional materials - an update.

The preparation of dispersions of single- and few-sheet 2D materials in various solvents, as well as the characterization methods applied to such dispersions, is critically reviewed. Motivating factors for producing single- and few-sheet dispersions of 2D materials in liquids are briefly discussed. Many practical applications are expected for such materials that do not require high purity formulations and tight control of donor and acceptor concentrations, as required in conventional Fab processing of semiconductor chips. Approaches and challenges encountered in exfoliating 2D materials in liquids are reviewed. Ultrasonication, mechanical shearing, and electrochemical processing approaches are discussed, and their respective limitations and promising features are critiqued. Supercritical and more conventional liquid and solvent processing are then discussed in detail. The effects of various types of stabilizers, including surfactants and other amphiphiles, as well as polymers, including homopolymeric electrolytes, nonionic polymers, and nanolatexes, are discussed. Consideration of apparent successes of stabilizer-free dispersions indicates that extensive exfoliation in the absence of dispersing aids results from processing-induced surface modifications that promote stabilization of 2D material/solvent interactions. Also apparent paradoxes in "pristineness" and optical extinctions in dispersions suggest that there is much we do not yet quantitatively understand about the surface chemistry of these materials. Another paradox, emanating from modeling dilute solvent-only exfoliation by sonication using polar components of solubility parameters and surface tension for pristine graphene with no polar structural component, is addressed. This apparent paradox appears to be resolved by realizing that the reactivity of graphene to addition reactions of solvent radicals produced by sonolysis is accompanied by unintended polar surface modifications that promote attractive interactions with solvent. This hypothesis serves to define important theoretical and experimental studies that are needed. We conclude that the greatest promise for high volume and high concentration processing lies in applying methods that have not yet been extensively reported, particularly wet comminution processing using small grinding media of various types.