Electrolyte Solvation Chemistry for Stabilizing the Zn Anode via Functionalized Organic Agents.

As a potential candidate for grid-scale energy storage technology, aqueous Zn-ion batteries (ZIBs) have attracted considerable attention due to their intrinsic safety, environmental friendliness, and ease of fabrication. Nevertheless, the road to industry for this technique is hindered by serious issues, including undesired side reactions, random growth of the Zn dendrites, electrode passivation, and anode corrosion, which are associated with the high reactivity of water molecules during the electrochemical reactions. These challenges are strongly dependent on electrolyte solvation chemistry (ESC), which subsequently determines the electrochemical behavior of the metal ions and water molecules on the electrode surface. In this work, a comprehensive understanding of optimized ESC with specified functional groups on the mixing agents to stabilize the Zn anode is provided. First, the challenges facing the ZIBs and their chemical principles are outlined. Specific attention is paid to the working principles of the mixing agents with different functional groups. Then the recent progress is summarized and compared. Finally, perspectives on future research for the aqueous Zn batteries are presented from the point of view.

Wet-chemistry synthesis of two-dimensional Pt- and Pd-based intermetallic electrocatalysts for fuel cells.

Two-dimensional (2D) noble-metal-based nanomaterials have attracted tremendous attention and have widespread promising applications as a result of their unique physical, chemical, and electronic properties. Especially, 2D Pt- and Pd-based intermetallic nanoplates (IMNPs) and nanosheets (IMNSs) are widely studied for fuel cell (FC)-related reactions, including the cathodic oxygen reduction reaction (ORR) and anodic formic acid, methanol and ethanol oxidation reactions (FAOR, MOR and EOR). Wet-chemistry synthesis is a powerful strategy to prepare metallic nanocrystals with well-controlled dispersity, size, and composition. In this review, a fundamental understanding of the FC-related reactions is firstly elaborated. Subsequently, the current wet-chemistry synthesis pathways for 2D Pt- and Pd-based IMNPs and IMNSs are briefly summarized, as well as their electrocatalytic applications including in the ORR, FAOR, MOR, and EOR. Finally, we provide an overview of the opportunities and current challenges and give our perspectives on the development of high-performance 2D Pt- and Pd-based intermetallic electrocatalysts towards FCs. We hope this review offers timely information on the synthesis of 2D Pt- and Pd-based IMNPs and IMNSs and provides guidance for the efficient synthesis and application of them.

Highly Anisotropic Second-Order Nonlinear Optical Effects in the Chiral Lead-Free Perovskite Spiral Microplates.

Chiral metal halide perovskites with intrinsic asymmetric structures have drawn increased research interest for the application of second-order nonlinear optics (NLO). However, designing chiral perovskites with the features of a large NLO coefficient, high laser-induced damage thresholds (LDT), and environmental friendliness remains a major challenge. Herein, we have synthesized two chiral hybrid bismuth halides: (R/S-MBA)4Bi2Br10 spiral structure microplates, templated by chiral (R/S)-methylbenzylamine (R/S-MBA). The as-grown chiral lead-free perovskite spiral microplates exhibit a recorded second harmonic generation (SHG) effect with a large effective second-order NLO coefficient (deff) of 11.9 pm V-1 and a high LDT of up to 59.2 mJ cm-2. More importantly, the twisted screw structures show competitive circular polarization sensitivity at 1200 nm with an anisotropy factor (gSHG-CD) of 0.58, which is about 3 times higher than that of reported Pb-based chiral perovskites. These findings provide a new platform to design multifunctional lead-free chiral perovskites for nonlinear photonic applications.

Intermetallic Nanocrystals: Seed-Mediated Synthesis and Applications in Electrocatalytic Reduction Reactions.

In recent years, intermetallic nanocrystals (IMNCs) have attracted extensive attention in the field of electrocatalysis. However, precise control over the size, shape, composition, structure, and exposed crystal facet of IMNCs seems to be a challenge to the traditional method of high-temperature annealing although these parameters have a significant effect on the electrocatalytic performance. Controllable synthesis of IMNCs by the wet chemistry method in the liquid phase shows great potential compared with the traditional high-temperature annealing method. In this Review, we attempt to summarize the preparation of IMNCs by the seed-mediated synthesis in the liquid phase, as well as their applications in electrocatalytic reduction reactions. Several representative examples are purposely selected for highlighting the huge potential of the seed-mediated synthesis approach in chemical synthesis. Specifically, we personally perceive the seed-mediated synthesis approach as a promising tool in the future for precise control over the size, shape, composition, structure, and exposed crystal facet of IMNCs.

Challenges and advances of organic electrode materials for sustainable secondary batteries.

Organic electrode materials (OEMs) emerge as one of the most promising candidates for the next-generation rechargeable batteries, mainly owing to their advantages of bountiful resources, high theoretical capacity, structural designability, and sustainability. However, OEMs usually suffer from poor electronic conductivity and unsatisfied stability in common organic electrolytes, ultimately leading to their deteriorating output capacity and inferior rate capability. Making clear of the issues from microscale to macroscale level is of great importance for the exploration of novel OEMs. Herein, the challenges and advanced strategies to boost the electrochemical performance of redox-active OEMs for sustainable secondary batteries are systematically summarized. Particularly, the characterization technologies and computational methods to elucidate the complex redox reaction mechanisms and confirm the organic radical intermediates of OEMs have been introduced. Moreover, the structural design of OEMs-based full cells and the outlook for OEMs are further presented. This review will shed light on the in-depth understanding and development of OEMs for sustainable secondary batteries.

Large-Scale Growth of Ultrathin Low-Dimensional Perovskite Nanosheets for High-Detectivity Photodetectors.

Low-dimensional organic-inorganic hybrid perovskites have demonstrated to be promising semiconductor materials due to their unique optoelectronic properties, however, the controllable growth of high-quality ultrathin 2D perovskites with large lateral dimension still faces great challenges. Herein, we report the controllable growth of large-scale ultrathin 2D (C6H5(CH2)3NH3)3Pb2I7 ((PPA)3Pb2I7) perovskite nanosheets (NSs) using a facile antisolvent-assisted crystallization approach under mild condition. As a result, the well-defined regular-shaped (PPA)3Pb2I7 NSs, with the largest lateral size over 100 µm, have been successfully synthesized, which is more than several ten times larger than that of other 2D perovskite NSs previously reported. Moreover, the thickness of the achieved 2D perovskite NSs can be well-tuned by altering the concentration of the precursor solution, with the smallest thickness down to ∼4.7 nm. More importantly, the photodetectors based on the high-quality (PPA)3Pb2I7 perovskites exhibit fascinating performance, including an extremely low dark current (∼1.5 pA), fast response/recovery rate (∼850/780 µs), and high detectivity (∼1.2 × 1010 Jones). This work provides a simple and promising strategy to controllably grow large-scale and ultrathin 2D perovskite NSs for low-cost and high-performance optoelectronic devices.

Accelerating oxygen evolution electrocatalysis of two-dimensional NiFe layered double hydroxide nanosheets via space-confined amorphization.

NiFe layered double hydroxides (LDHs) have received widespread attention due to their unique structures and inherent electrocatalytic activity towards the oxygen evolution reaction (OER). Extensive studies have been reported to further improve the electrocatalytic activity of NiFe-LDHs via various strategies. However, controlling the degree of amorphization and stabilizing the amorphous zone during the electrocatalytic process are still challenging. Here, we report a facile method to synthesize a space-confined amorphous NiFe-LDH (SCA-NiFe-LDH) by selectively etching the surfaces of electrocatalysts. Due to the successful anchoring of amorphous zones onto the basal planes of the two-dimensional NiFe-LDH, the optimized SCA-NiFe-LDH exhibits high electrocatalytic activity with a low overpotential of 190 mV at 10 mA cm-2, a Tafel slope of 31 mV dec-1 and excellent long-term stability. The substantially enhanced OER performance is attributed to the increased amount of active sites and the modified electronic structure of NiFe-LDH after amorphization.

Sn-Doped Rutile TiO2 Hollow Nanocrystals with Enhanced Lithium-Ion Batteries Performance.

Hollow structures and doping of rutile TiO2 are generally believed to be effective ways to enhance the performance of lithium-ion batteries. Herein, uniformly distributed Sn-doped rutile TiO2 hollow nanocrystals have been synthesized by a simple template-free hydrothermal method. A topotactic transformation mechanism of solid TiOF2 precursor is proposed to illustrate the formation of rutile TiO2 hollow nanocrystals. Then, the Sn-doped rutile TiO2 hollow nanocrystals are calcined and tested as anode in the lithium-ion battery. They deliver a highly reversible specific capacity of 251.3 mA h g-1 at 0.1 A g-1 and retain ∼110 mA h g-1 after 500 cycles at a high current rate 5 A g-1 (30 C), which is much higher than most of the reported work.

Ultrafast Molecular Stitching of Graphene Films at the Ethanol/Water Interface for High Volumetric Capacitance.

Compact graphene film electrodes with a high ion-accessible surface area have the promising potential to realize high-density electrochemical energy storage (or high volumetric capacitance), which is vital for the development of flexible, portable, and wearable energy storage devices. Here, a novel, ultrafast strategy for stitching graphene sheets into films, in which p-phenylenediamine (PPD) molecules are uniformly intercalated between the graphene sheets, is simply constructed at the ethanol/water interface. Due to uniformly interlayer spacing (∼1.1 nm), good wettability, and an interconnected ion transport channel, the binder-free PPD-graphene film with a high packing density (1.55 g cm-3) delivers an ultrahigh volumetric capacitance (711 F cm-3 at a current density of 0.5 A g-1), high rate performance, high power and energy densities, and excellent cycling stability in aqueous electrolytes. This interfacial stitching strategy holds new promise for the future design of enhanced electrochemical energy-storage devices.