Recent Progress on Phase Engineering of Nanomaterials

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(23), P. 13489 - 13692

Published: Nov. 14, 2023

As a key structural parameter, phase depicts the arrangement of atoms in materials. Normally, nanomaterial exists its thermodynamically stable crystal phase. With development nanotechnology, nanomaterials with unconventional phases, which rarely exist their bulk counterparts, or amorphous have been prepared using carefully controlled reaction conditions. Together these methods are beginning to enable engineering (PEN), i.e., synthesis phases and transformation between different obtain desired properties functions. This Review summarizes research progress field PEN. First, we present representative strategies for direct modulation diverse kinds nanomaterials. We cover ranging from metal nanostructures such as Au, Ag, Cu, Pd, Ru, alloys; oxides, borides, carbides; transition dichalcogenides (TMDs) 2D layered review growth wet-chemical reduction seed-mediated epitaxial chemical vapor deposition (CVD), high pressure transformation, electron ion-beam irradiation. After that, summarize significant influence on various unconventional-phase also discuss potential applications developed areas including catalysis, electrochemical energy storage (batteries supercapacitors), solar cells, optoelectronics, sensing. Finally, existing challenges future directions

Language: Английский

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Macrocycle‐Based Covalent Organic Frameworks

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(16)

Published: Jan. 6, 2023

Macrocycles with well-defined cavities and the ability to undergo supramolecular interactions are classical materials that have played an essential role in science. However, one of most substantial barriers limiting utilization macrocycles is their aggregation, which blocks active regions. Among many attempted strategies prevent such installing into covalent organic frameworks (COFs), porous stable reticular networks, has emerged as ideal solution. The resulting macrocycle-based COFs (M-COFs) preserve macrocycles' unique activities, enabling applications various fields single-atom catalysis, adsorption/separation, optoelectronics, phototherapy, structural design forming single-layered or mechanically interlocked COFs. properties unmatchable by any combination other substrates, opening a new chapter advanced materials. This review focuses on latest progress concepts, synthesis, properties, M-COFs, presents in-depth outlook challenges opportunities this emerging field.

Language: Английский

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Tuning the Local Coordination of CoP_1–xS_x between NiAs- and MnP-Type Structures to Catalyze Lithium–Sulfur Batteries

ACS Nano, Journal Year: 2023, Volume and Issue: 17(3), P. 3143 - 3152

Published: Jan. 30, 2023

The slow conversion and rapid shuttling of polysulfides remain major challenges that hinder the practical application lithium-sulfur (Li-S) batteries. Efficient catalysts are needed to accelerate suppress shuttling. However, lack a rational understanding catalysis poses obstacles design catalysts, thereby limiting development Li-S Herein, we theoretically analyze modulation electronic structure CoP1-xSx caused by NiAs-to-MnP-type transition its influence on catalytic activity. We found interacting d-orbitals active metal sites play determining role in adsorption catalysis, optimal dz2-, dxz-, dyz-orbitals an appropriately distorted five-coordinate pyramid enable higher activity compared with their parent structures. Finally, rationally designed S were electrospun into carbonized nanofibers form nanoreactor chains for use as cathodes. resultant batteries exhibited superior properties over 1000 cycles only decay rate 0.031% per cycle demonstrated high capacity 887.4 mAh g-1 at loading 10 mg cm-2. structural bonding analyses this study provide powerful approach catalysts.

Language: Английский

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Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15473 - 15481

Published: July 8, 2023

Three-dimensional covalent organic frameworks (3D COFs), with interconnected pores and exposed functional groups, provide new opportunities for the design of advanced materials through postsynthetic modification. Herein, we demonstrate successful annulation 3D COFs to construct efficient CO2 reduction photocatalysts. Two COFs, NJU-318 NJU-319Fe, were initially constructed by connecting hexaphenyl-triphenylene units pyrene- or Fe-porphyrin-based linkers. Subsequently, moieties within postsynthetically transformed into π-conjugated hexabenzo-trinaphthylene (pNJU-318 pNJU-319Fe) enhance visible light absorption photoreduction activity. The optimized photocatalyst, pNJU-319Fe, shows a CO yield 688 μmol g-1, representing 2.5-fold increase compared that unmodified NJU-319Fe. Notably, direct synthesis hexabenzo-trinaphthylene-based COF catalysts was unsuccessful due low solubility conjugated This study not only provides an effective method photocatalysts but also highlights unlimited tunability structural

Language: Английский

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Enhanced Electron Delocalization within Coherent Nano‐Heterocrystal Ensembles for Optimizing Polysulfide Conversion in High‐Energy‐Density Li‐S Batteries

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(13)

Published: Dec. 25, 2023

Abstract Commercialization of high energy density Lithium‐Sulfur (Li‐S) batteries is impeded by challenges such as polysulfide shuttling, sluggish reaction kinetics, and limited Li + transport. Herein, a jigsaw‐inspired catalyst design strategy that involves in situ assembly coherent nano‐heterocrystal ensembles (CNEs) to stabilize high‐activity crystal facets, enhance electron delocalization, reduce associated barriers proposed. On the surface, stabilized facets induce aggregation. Simultaneously, surrounded surface with enhanced activity promote 2 S deposition diffusion, synergistically facilitating continuous efficient sulfur redox. Experimental DFT computations results reveal dual‐component hetero‐facet alters coordination Nb atoms, enabling redistribution 3D orbital electrons at center promoting d‐p hybridization sulfur. The CNE, based on level gradient lattice matching, endows maximum transfer catalysts establishes smooth pathways for ion diffusion. Encouragingly, NbN‐NbC‐based pouch battery delivers Weight 357 Wh kg −1 , thereby demonstrating practical application value CNEs. This work unveils novel paradigm designing high‐performance catalysts, which has potential shape future research electrocatalysts storage applications.

Language: Английский

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Single-atom platinum with asymmetric coordination environment on fully conjugated covalent organic framework for efficient electrocatalysis

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 22, 2024

Abstract Two-dimensional (2D) covalent organic frameworks (COFs) and their derivatives have been widely applied as electrocatalysts owing to unique nanoscale pore configurations, stable periodic structures, abundant coordination sites high surface area. This work aims construct a non-thermodynamically Pt-N 2 active site by electrochemically modifying platinum (Pt) single atoms into fully conjugated 2D COF conductive agent-free pyrolysis-free electrocatalyst for the hydrogen evolution reaction (HER). In addition maximizing atomic utilization, single-atom catalysts with definite structures can be used investigate catalytic mechanisms structure-activity relationships. this work, in-situ characterizations theoretical calculations reveal that nitrogen-rich graphene analogue not only exhibits favorable metal-support effect Pt, adjusting binding energy between Pt H* intermediates forming instead of typical 4 environment, but also enhances electron transport ability structural stability, showing both conductivity stability in acidic environments.

Language: Английский

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Advanced development of three-dimensional covalent organic frameworks: Valency design, functionalization, and applications

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 504, P. 215659 - 215659

Published: Jan. 16, 2024

Language: Английский

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Covalent Organic Framework-Based Materials for Advanced Lithium Metal Batteries

ACS Nano, Journal Year: 2024, Volume and Issue: 18(27), P. 17439 - 17468

Published: June 27, 2024

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

Language: Английский

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Unlocking Synthesis of Polyhedral Oligomeric Silsesquioxane-Based Three-Dimensional Polycubane Covalent Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3373 - 3382

Published: Jan. 25, 2024

Reticular chemistry effectively yields porous structures with distinct topological lattices for a broad range of applications. Polyhedral oligomeric silsesquioxane (POSS)-based octatopic building blocks rare Oh symmetric configuration and attracting inorganic features have great potential creating three-dimensional (3D) covalent organic frameworks (COFs) new topologies. However, the intrinsic flexibility intensive motion cubane-type POSS molecules make construction 3D regular challenging. Herein, by fastening three or four cores per aromatic rigid linker from rational steric directions, we successfully developed serial crystalline COFs unpresented "the" scu Both experimental theoretical results proved formation target POSS-based COFs. The resultant hybrid networks designable chemical skeletons high surface areas maintain superiorities both components, such as their compatibility salts, abundant periodic electroactive sites, excellent thermal stability, open multilevel nanochannels. Consequently, polycubane could serve outstanding solid electrolytes ionic conductivity 1.23 × 10–4 S cm–1 lithium-ion transference number 0.86 at room temperature. This work offers pathway to generate ordered multiconnected flexible cube motifs enrich topologies

Language: Английский

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Three-dimensional covalent organic frameworks with nia nets for efficient separation of benzene/cyclohexane mixtures

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 27, 2024

Abstract The synthesis of three-dimensional covalent organic frameworks with highly connected building blocks presents a significant challenge. In this study, we report two 3D COFs the nia topology, named JUC-641 and JUC-642, by introducing planar hexagonal triangular prism nodes. Notably, our adsorption studies breakthrough experiments reveal that both exhibit exceptional separation capabilities, surpassing previously reported most porous polymers, factor up to 2.02 for benzene cyclohexane. Additionally, dispersion-corrected density functional theory analysis suggests good performance these can be attributed incorporation aromatic presence extensive pore structures. Consequently, research not only expands diversity but also highlights potential COF materials as promising candidates environmentally-friendly applications.

Language: Английский

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