Enhanced Piezocatalytic Performance of BaTiO₃ Nanosheets with Highly Exposed {001} Facets

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 32(35)

Published: June 23, 2022

Abstract Piezocatalysis has gradually come into the limelight due to its great potential for solving energy shortages and environmental pollution problems. However, limited piezocatalytic efficiency is a severe bottleneck practical applications. Here, well‐defined BaTiO 3 nanosheets with highly exposed {001} polar facets are successfully synthesized enhance activity. The [001] piezoelectric polarization can drive carriers migrate surface along out‐of‐plane direction. provides abundant active sites reaction. As result, superior degradation ratio of organic pollutants obtained high first‐order rate constant k 0.0835 min −1 , which 2.7 times higher than nanoparticles. Furthermore, display an outstanding H 2 production capability, 305 µmol g h –1 almost two that This work thus novel comprehensive strategy designing high‐performance piezocatalysts polarization, also insights optimization activity by regulating facet piezocatalysts.

Language: Английский

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Salient Achievements in Synthetic Organic Chemistry Enabled by Mechanochemical Activation

Synthesis, Journal Year: 2023, Volume and Issue: 55(16), P. 2439 - 2459

Published: May 3, 2023

Abstract Although known for millennia, it is only recently that mechanochemistry has received serious attention by chemists. Indeed, during the past 15 years an extraordinary number of reports concerning solid-state chemical transformations through grinding and milling techniques have been recorded. This short review discusses circumstances led this renaissance, highlighting present intense interest in so-called green chemistry, enabling capacity to handle insoluble substrates, identification profound influence additives can on mechanochemically activated reactions. The core account focuses salient developments synthetic organic especially amino acid peptide­ mechanosynthesis, successful employment mechanochemical activation combination with asymmetric organocatalysis, promising enzymatic whole cell biocatalysis, remarkable achievement multicomponent selective reactions via complex, multistep reaction pathways, mechanosynthesis representative heterocycles. final section comments some pending tasks area, such as scaling-up processes be practical use industry, requirement easier more efficient control parameters monitoring devices, consequently careful analysis additional procedures a proper understanding phenomena. 1 Introduction 2 Brief History Mechanochemistry 3 Milling Equipment Reaction Parameters 4 Attributes That Propelled Its Present Renaissance 4.1 Enormous Attention Being Presently Paid Sustainable Chemistry 4.2 Reduced Energy Consumption 4.3 Additive-Based 4.4 Handling Insoluble Reactants 4.5 ‘Impossible’ Reactions Are Successful 4.6 Air- Water-Sensitive Reagents Ball 5 Salient Developments Mechanochemical Activation Synthetic Organic 5.1 Amino Acid Peptide Mechanosynthesis 5.2 Asymmetric Synthesis Organocatalysis under Ball-Milling Conditions 5.3 Mechanoenzymology 5.4 Multicomponent Activated 5.5 Heterocycles Modification 6 Future Directions 6.1 Scaling-Up Protocols 6.2 Temperature-Controlled 6.3 Understanding Transformations 6.4 Emerging Techniques 7 Conclusions

Language: Английский

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Mechanochemistry-Directed Ligand Design: Development of a High-Performance Phosphine Ligand for Palladium-Catalyzed Mechanochemical Organoboron Cross-Coupling

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 6823 - 6837

Published: March 9, 2023

Mechanochemical synthesis that uses transition-metal catalysts has attracted significant attention due to its numerous advantages, including low solvent waste, short reaction times, and the avoidance of problems associated with solubility starting materials. However, even though mechanochemical environment is largely different from homogeneous solution systems, catalysts, which were originally developed for use in solution, have been used directly reactions without any molecular-level modifications ensure their suitability mechanochemistry. Alas, this limited development more efficient cross-coupling processes. Here, we report a conceptually distinct approach, whereby mechanochemistry-directed design develop ligands Suzuki-Miyaura reactions. The ligand was guided by experimental observation catalyst deactivation via aggregation palladium species, problem particularly prominent solid-state By embedding into poly(ethylene glycol) (PEG) polymer, found phosphine-ligated palladium(0) species could be immobilized fluid phase created PEG chains, preventing physical mixing crystalline solid thus undesired deactivation. This catalytic system showed high activity polyaromatic substrates close room temperature. These usually require elevated temperatures reactive presence systems conventional such as SPhos. present study hence provides important insights high-performance potential inspire industrially attractive, almost solvent-free technologies.

Language: Английский

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Tinkering with Mechanochemical Tools for Scale Up

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: April 28, 2023

Mechanochemistry provides an environmentally benign platform to develop more sustainable chemical processes by limiting raw materials, energy use, and waste generation while using physically smaller equipment. A continuously growing research community has steadily showcased examples of beneficial mechanochemistry applications at both the laboratory preparative scale. In contrast solution-based chemistry, mechanochemical have not yet been standardized, thus scaling up is still a nascent discipline. The purpose this Minireview highlight similarities, differences challenges various approaches that successfully applied for range scales. We hope provide discussion starting point those interested in further developing commercial use and/or industrialisation.

Language: Английский

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Mechanosynthesized electroactive materials for sustainable energy and environmental applications: A critical review

Progress in Materials Science, Journal Year: 2024, Volume and Issue: 145, P. 101299 - 101299

Published: April 16, 2024

Electrochemistry-driven techniques for advanced energy storage/conversion and environmental protection play a crucial role in achieving sustainable development goals. As an indispensable component diverse electrochemical systems, electroactive materials gain soaring interest terms of rational design synthesis. Notably, mechanochemistry-based green powerful synthesis has been widely employed to fabricate materials, given their scalability tunability. Recently, mechanochemically synthesized have applied various fields, leading significant progress. However, systematic analysis these advancements is still missing. Herein, we comprehensively discuss recent achievements mechanosynthesized applications. The mechanochemical introduced, along with different types materials. Subsequently, the review delves into applications conversion/storage systems remediation. structure-performance correlation are illustrated by discussing effects process on internal external properties performance. Lastly, key perspectives this field discussed, including monitoring, field-assisted synthesis, material performance optimization, practical applications, mechanochemistry-driven fuels/chemicals By illustrating current advances related aims shed some light upcoming research synthesis-driven sustainability.

Language: Английский

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Mechanochemical Organocatalysis: Do High Enantioselectivities Contradict What We Might Expect?

ChemSusChem, Journal Year: 2021, Volume and Issue: 15(2)

Published: Nov. 12, 2021

Ball mills input energy to samples by pulverising the contents of jar. Each impact on sample or wall jar results in an instantaneous transmission form a temperature and pressure increase (volume reduction). Conversely, enantioselective organocatalytic reactions proceed through perceived delicate well-organised transition states. Does there exist dichotomy idea mechanochemical organocatalysis? This Review provides survey literature reporting combination with ball milling conditions. Where possible, direct comparisons stirred solution, neat milled processes are drawn particular focus control stereoselectivity.

Language: Английский

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Mechanochemical techniques for the activation and use of zero-valent metals in synthesis

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(10), P. 763 - 775

Published: July 21, 2022

Language: Английский

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Mechanically activated solid state radical polymerization and cross‐linking via piezocatalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(20)

Published: March 15, 2023

Abstract Piezocatalysis offers a means to transduce mechanical energy into chemical potential, harnessing physical force drive redox reactions. Working in the solid state, we show here that piezoelectric BaTiO 3 nanoparticles can load flux of reactive radical species capable initiating state free polymerization. Activation powder by ball milling, striking with hammer, or repeated compressive loading generates highly hydroxyl radicals (⋅OH), which readily initiate chain growth and crosslinking acrylamide, acrylate, methacrylate styrenic monomers. Control experiments indicate critical role for chemisorbed water on nanoparticle surface, is oxidized ⋅OH via mechanoredox catalysis. The force‐induced production compressing dry materials represents promising new route harness synthesis.

Language: Английский

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Mechanochemical Synthesis of Aryl Fluorides by Using Ball Milling and a Piezoelectric Material as the Redox Catalyst

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(39)

Published: July 31, 2023

Abstract Aryl fluorides are important structural motifs in many pharmaceuticals. Although the Balz–Schiemann reaction provides an entry to aryl from aryldiazonium tetrafluoroborates, it suffers drawbacks such as long time, high temperature, toxic solvent, gas release, and low functional group tolerance. Here, we describe a general method for synthesis of tetrafluoroborates using piezoelectric material redox catalyst under ball milling conditions presence Selectfluor. This approach effectively addresses aforementioned limitations. Furthermore, can be recycled multiple times. Mechanistic investigations indicate that this fluorination may proceed via radical pathway, Selectfluor plays dual role both source fluorine terminal reductant.

Language: Английский

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Dual Nickel(II)/Mechanoredox Catalysis: Mechanical‐Force‐Driven Aryl‐Amination Reactions Using Ball Milling and Piezoelectric Materials

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(42)

Published: Aug. 28, 2023

Abstract The combination of a nickel(II) catalyst and mechanoredox under ball‐milling conditions promotes mechanical‐force‐driven C−N cross‐coupling reactions. In this nickel(II)/mechanoredox cocatalyst system, the modulation oxidation state nickel center, induced by piezoelectricity, is used to facilitate highly efficient aryl‐amination reaction, which characterized broad substrate scope, an inexpensive catalysts (NiBr 2 BaTiO 3 ), short reaction times, almost negligible quantity solvents. Moreover, can be readily up‐scaled multi‐gram scale, all synthetic operations carried out atmospheric without need for complicated setups. Furthermore, force‐induced system suitable excitation‐energy‐accepting molecules poorly soluble polyaromatic substrates that are incompatible with solution‐based nickel(II)/photoredox cocatalysts.

Language: Английский

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