Synthesis Strategies for High Entropy Nanoparticles.

Nanoparticles (NPs) of high entropy materials (HEMs) have attracted significant attention due to their versatility and wide range of applications. HEM NPs can be synthesized by fragmenting bulk HEMs or disintegrating and recrystallizing them. Alternatively, directly producing HEMs in NP form from atomic/ionic/molecular precursors presents a significant challenge. A widely adopted strategy involves thermodynamically driving HEM NP formation by leveraging the entropic contribution but incorporating strategies to limit NP growth at the elevated temperatures used for maximizing entropy. A second approach is to kinetically drive HEM NP formation by promoting rapid reactions of homogeneous reactant mixtures or using highly diluted precursor dissolutions. Additionally, experimental evidence suggests that enthalpy plays a significant role in driving HEM NP formation processes at moderate temperatures, with the high energy cost of generating additional surfaces and interfaces at the nanoscale stabilizing the HEM phase. This review critically assesses the various synthesis strategies developed for HEM NP preparation, highlighting key illustrative examples and offering insights into the underlying formation mechanisms. Such insights are critical for fine-tuning experimental conditions to achieve specific outcomes, ultimately enabling the effective synthesis of optimized generations of these advanced materials for both current and emerging applications across various scientific and technological fields.

Covalent Organic Framework-Based Materials for Advanced Lithium Metal Batteries.

Lithium metal batteries (LMBs), with high energy densities, are strong contenders for the next generation of energy storage systems. Nevertheless, the unregulated growth of lithium dendrites and the unstable solid electrolyte interphase (SEI) significantly hamper their cycling efficiency and raise serious safety concerns, rendering LMBs unfeasible for real-world implementation. Covalent organic frameworks (COFs) and their derivatives have emerged as multifunctional materials with significant potential for addressing the inherent problems of the anode electrode of the lithium metal. This potential stems from their abundant metal-affine functional groups, internal channels, and widely tunable architecture. The original COFs, their derivatives, and COF-based composites can effectively guide the uniform deposition of lithium ions by enhancing conductivity, transport efficiency, and mechanical strength, thereby mitigating the issue of lithium dendrite growth. This review provides a comprehensive analysis of COF-based and derived materials employed for mitigating the challenges posed by lithium dendrites in LMB. Additionally, we present prospects and recommendations for the design and engineering of materials and architectures that can render LMBs feasible for practical applications.

Covalent Organic Frameworks: Their Composites and Derivatives for Rechargeable Metal-Ion Batteries.

Covalent organic frameworks (COFs) have attracted considerable interest in the field of rechargeable batteries owing to their three-dimensional (3D) varied pore sizes, inerratic porous structures, abundant redox-active sites, and customizable structure-adjustable frameworks. In the context of metal-ion batteries, these materials play a vital role in electrode materials, effectively addressing critical issues such as low ionic conductivity, limited specific capacity, and unstable structural integrity. However, the electrochemical characteristics of the developed COFs still fall short of practical battery requirements due to inherent issues such as low electronic conductivity, the tradeoff between capacity and redox potential, and unfavorable micromorphology. This review provides a comprehensive overview of the recent advancements in the application of COFs, COF-based composites, and their derivatives in rechargeable metal-ion batteries, including lithium-ion, lithium-sulfur, sodium-ion, sodium-sulfur, potassium-ion, zinc-ion, and other multivalent metal-ion batteries. The operational mechanisms of COFs, COF-based composites, and their derivatives in rechargeable batteries are elucidated, along with the strategies implemented to enhance the electrochemical properties and broaden the range of their applications.

Optimizing Pt-Based Alloy Electrocatalysts for Improved Hydrogen Evolution Performance in Alkaline Electrolytes: A Comprehensive Review.

The splitting of water through electrocatalysis offers a sustainable method for the production of hydrogen. In alkaline electrolytes, the lack of protons forces water dissociation to occur before the hydrogen evolution reaction (HER). While pure Pt is the gold standard electrocatalyst in acidic electrolytes, since the 5d orbital in Pt is nearly fully occupied, when it overlaps with the molecular orbital of water, it generates a Pauli repulsion. As a result, the formation of a Pt-H* bond in an alkaline environment is difficult, which slows the HER and negates the benefits of using a pure Pt catalyst. To overcome this limitation, Pt can be alloyed with transition metals, such as Fe, Co, and Ni. This approach has the potential not only to enhance the performance but also to increase the Pt dispersion and decrease its usage, thus overall improving the catalyst's cost-effectiveness. The excellent water adsorption and dissociation ability of transition metals contributes to the generation of a proton-rich local environment near the Pt-based alloy that promotes HER. Significant progress has been achieved in comprehending the alkaline HER mechanism through the manipulation of the structure and composition of electrocatalysts based on the Pt alloy. The objective of this review is to analyze and condense the latest developments in the production of Pt-based alloy electrocatalysts for alkaline HER. It focuses on the modified performance of Pt-based alloys and clarifies the design principles and catalytic mechanism of the catalysts from both an experimental and theoretical perspective. This review also highlights some of the difficulties encountered during the HER and the opportunities for increasing the HER performance. Finally, guidance for the development of more efficient Pt-based alloy electrocatalysts is provided.

Two-Dimensional Palladium Phosphoronitride for Oxygen Reduction.

Two-dimensional (2D) catalysts often show extraordinary activity at low mass loading since almost all their atoms are exposed to electrolyte. Palladium (Pd) holds great promise for catalyzing oxygen reduction reaction (ORR) but 2D Pd-based ORR catalyst has rarely been reported. Herein, 2D ternary palladium phosphoronitride (Pd3P2Nx) is synthesized, for the first time, for ORR catalysis. The synthesis is guided by a rational design using first-principles density functional theory calculations, and then realized via a postsynthesis substitutional doping of ternary palladium thiophosphate (Pd3P2S8), which almost completely replaces sulfur atoms by nitrogen atoms without destroying the 2D morphology. The doping process exposes the interlocked Pd atoms of Pd3P2S8 and introduces ligands that improve the affinity of oxygen intermediates, resulting in greater kinetics and lower activation energy for ORR. The mass activity of the pristine Pd3P2S8 is dramatically increased as much as 5-fold (from 0.03 to 0.151 mA µg-1 Pd in Pd3P2Nx). The ORR diffusion-limited current density of Pd3P2Nx (6.2 mA cm-2) exceeds that of commercial Pt/C, and it shows fast kinetics and robust long-term stability. Our theoretical calculations not only guide the experimental doping process, but also provides insights into the underlying mechanism of the outstanding ORR activity and stability.

Mechanistic Investigation of Electrostatic Field-Enhanced Water Evaporation.

Investigations on external electrostatic field (EEF)-enhanced liquid water evaporation have been reported decades ago, which suggest that molecular alignment and polarization tuned by EEF accelerating the phase change process could be responsible for EEF-enhanced water evaporation. However, a detailed study revealing the role of EEF in altering the intermolecular and intramolecular water structure is lacking. Herein, an EEF is proved to tune water state by accelerating the thermal movement of water molecules, lowering the molecular escaping energy, and loosening the hydrogen bond structure. The detailed mechanisms and field interactions (heat and electrostatic) are investigated by in situ Raman characterizations and molecular dynamic simulations, which reveal that an EEF can effectively reduce the free energy barrier of water evaporation and then increase the evaporated water molecule flux. As a proof of concept, an EEF is integrated into an interfacial two-dimentional solar steam generator, enhancing the efficiency by up to 15.6%. Similar to a catalyst lowing activation energy and enhancing kinetics of a chemical reaction, the EEF enhances water state tuning, lowers evaporation enthalpy, and then boosts steam generation rate with negligible additional energy consumption, which can serve as a generic method for water evaporation enhancement in water harvesting, purification, and beyond.

Facial Synthesis of Three-Dimensional Cross-Linked Cage for High-Performance Lithium Storage.

Silicon/C composite is a promising anode material for high-energy Li-ion batteries. However, synthesizing high-performance Si-based materials at large scale and low cost remains a huge challenge. Here, we for the first time report the preparation of an interconnected three-dimensional (3D) porous Si-hybrid architecture by using a spray drying method. In this unique structure, the highly robust C-CNT-RGO cages not only can improve the conductivity of the electrode and buffer the volume expansion but also suppress the Si nanoparticles aggregation. As a result, the 3D Si@po-C/CNT/RGO electrode achieves long-life cycling stability at high rates (a reversible capacity of 854.9 mA h g(-1) at 2 A g(-1) after 500 cycles and capacity decay less than 0.013% per cycle) and good rate capability (1454.7, 1198.8, 949.2, 597.8, and 150 mA h g(-1) at current densities of 1, 2, 4, 10, and 20 A g(-1), respectively). Moreover, this novel electrode could deliver high reversible capacities and long-life stabilities even with high mass loading density (764.9 mA h g(-1) at 1.0 mg cm(-2) after 500 cycles and 472.2 mA h g(-1) at 1.5 mg cm(-2) after 400 cycles, respectively). This cheap and scalable strategy can be extended to fabricate other materials with large volume expansion (Sn, Ge, transition-metal oxides) and 3D porous carbon for other potential applications.

Hollow silica-copper-carbon anodes using copper metal-organic frameworks as skeletons.

Hollow silica-copper-carbon (H-SCC) nanocomposites are first synthesized using copper metal-organic frameworks as skeletons to form Cu-MOF@SiO(2) and then subjected to heat treatment. In the composites, the hollow structure and the void space from the collapse of the MOF skeleton can accommodate the huge volume change, buffer the mechanical stress caused by lithium ion insertion/extraction and maintain the structural integrity of the electrode and a long cycling stability. The ultrafine copper with a uniform size of around 5 nm and carbon with homogeneous distribution from the decomposition of the MOF skeleton can not only enhance the electrical conductivity of the composite and preserve the structural and interfacial stabilization, but also suppress the aggregation of silica nanoparticles and cushion the volume change. In consequence, the resulting material as an anode for lithium-ion batteries (LIBs) delivers a reversible capacity of 495 mA h g(-1) after 400 cycles at a current density of 500 mA g(-1). The synthetic method presented in this paper provides a facile and low-cost strategy for the large-scale production of hollow silica/copper/carbon nanocomposites as an anode in LIBs.