Recent Progress of Amorphous Nanomaterials

Chemical Reviews, Год журнала: 2023, Номер 123(13), С. 8859 - 8941

Опубликована: Июнь 26, 2023

Amorphous materials are metastable solids with only short-range order at the atomic scale, which results from local intermolecular chemical bonding. The lack of long-range typical crystals endows amorphous nanomaterials unconventional and intriguing structural features, such as isotropic environments, abundant surface dangling bonds, highly unsaturated coordination, etc. Because these features ensuing modulation in electronic properties, display potential for practical applications different areas. Motivated by elements, here we provide an overview unique general synthetic methods, covered contemporary research nanomaterials. Furthermore, discussed possible theoretical mechanism nanomaterials, examining how properties configurations contribute to their exceptional performance. In particular, benefits well enhanced electrocatalytic, optical, mechanical thereby clarifying structure–function relationships, highlighted. Finally, a perspective on preparation utilization establish mature systems superior hierarchy various is introduced, outlook future challenges opportunities frontiers this rapidly advancing field proposed.

Язык: Английский

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Economically viable electrocatalytic ethylene production with high yield and selectivity

Nature Sustainability, Год журнала: 2023, Номер 6(7), С. 827 - 837

Опубликована: Март 9, 2023

Язык: Английский

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Dopant- and Surfactant-Tuned Electrode–Electrolyte Interface Enabling Efficient Alkynol Semi-Hydrogenation

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(11), С. 6516 - 6525

Опубликована: Март 13, 2023

Electrochemical alkynol semi-hydrogenation has emerged as a sustainable and environmentally benign route for the production of high-value alkenols, featuring water hydrogen source instead H2. It is highly challenging to design electrode-electrolyte interface with efficient electrocatalysts their matched electrolytes break selectivity-activity stereotype. Here, boron-doped Pd catalysts (PdB) surfactant-modified are proposed enable simultaneous increase in alkenol selectivity conversion. Typically, compared pure commercial Pd/C catalysts, PdB catalyst achieves both higher turnover frequency (139.8 h-1) specific (above 90%) 2-methyl-3-butyn-2-ol (MBY). Quaternary ammonium cationic surfactants that employed electrolyte additives assembled at electrified response applied bias potential, establishing an interfacial microenvironment can facilitate transfer hinder suitably. Eventually evolution reaction inhibited promoted, without inducing decrease selectivity. This work offers distinct perspective on creating suitable electrosynthesis.

Язык: Английский

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Boosting the Electrochemical 5‐Hydroxymethylfurfural Oxidation by Balancing the Competitive Adsorption of Organic and OH⁻ over Controllable Reconstructed Ni₃S₂/NiO_x

Advanced Materials, Год журнала: 2023, Номер 35(45)

Опубликована: Июль 20, 2023

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) is a promising method for the efficient production biomass-derived high-value-added chemicals. However, its practical application limited by: 1) low activity and selectivity caused by competitive adsorption HMF OH- 2) operational stability uncontrollable reconstruction catalyst. To overcome these limitations, series Ni3 S2 /NiOx -n catalysts with controllable compositions well-defined structures are synthesized using novel in situ controlled surface strategy. behavior can be continuously adjusted varying ratio NiOx to on surface, as indicated characterizations, contact angle analysis, theoretical simulations. Owing balanced , optimized -15 catalyst exhibited remarkable performance, current density reaching 366 mA cm-2 at 1.5 VRHE Faradaic efficiency product, 2,5-furanedicarboxylic acid, 98%. Moreover, exhibits excellent durability, structure remaining stable over 100 h operation. This study provides new route design construction value-added biomass conversion offers insights into enhancing catalytic performance balancing adsorption.

Язык: Английский

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Electrochemical hydrogenation and oxidation of organic species involving water

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(4), С. 277 - 293

Опубликована: Март 25, 2024

Язык: Английский

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Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source

Accounts of Chemical Research, Год журнала: 2023, Номер 56(13), С. 1872 - 1883

Опубликована: Июнь 14, 2023

ConspectusThe hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic by using water (H2O) as hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid use high-pressure flammable gas or other toxic/expensive donors, which usually cause environmental, safety, cost concerns. Interestingly, utilizing easily available heavy (D2O) for deuterated syntheses also attractive due widespread applications molecules synthesis pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, how electrodes dictate outcomes remains elusive. Therefore, rational design nanostructured driving electrocatalytic series organics via H2O electrolysis developed.In this Account, we review recent advances different types functional groups, including C≡C, C≡N, C═C, C═O, C-Br/I bonds, -NO2, N-heterocycles, with over cathodes. First, general steps (reactant/intermediate adsorption, active atomic (H*) formation, surface reaction, product desorption) are analyzed, key factors proposed optimize performance (e.g., selectivity, activity, Faradaic efficiency (FE), rate, productivity) inhibit side reactions. Then, ex situ spectroscopic tools study intermediates interpret mechanisms introduced. Third, based knowledge mechanisms, introduce catalyst principles detail adoption reactants intermediates, promote formation H* from electrolysis, evolution reactions, improve FEs, space-time productivity products. We then some typical examples. (i) P- S-modified Pd decrease C═C adsorption enabling semihydrogenation alkynes high selectivity FEs at lower potentials. creating high-curvature nanotips concentrate substrates further speeds up process. (ii) By introducing low-coordination sites into Fe combining fluorine modify Co facilitate nitriles N-heterocycles activity obtained. (iii) forming isolated induce specific σ-alkynyl steering S vacancies Co3S4-x preferentially adsorb reduced group-decorated nitroarenes chemoselectivity realized. (iv) For reactant participated designing hydrophobic diffusion layer-supported ultrasmall Cu nanoparticles enhance mass transfer, activation, H2 ethylene ampere-level production 97.7% FE accomplished. Finally, provide outlook current challenges promising opportunities area. believe that summarized here paradigm highly selective nanomaterials achieve fascinating performances.

Язык: Английский

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Unveiling the structural transformation and activity origin of heteroatom-doped carbons for hydrogen evolution

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(20)

Опубликована: Май 8, 2023

Heteroatom-doped carbon materials have been widely used in many electrocatalytic reduction reactions. Their structure-activity relationships are mainly explored based on the assumption that doped remain stable during electrocatalysis. However, structural evolution of heteroatom-doped is often ignored, and their active origins still unclear. Herein, taking N-doped graphite flake (N-GP) as research model, we present hydrogenation both N C atoms consequent reconstruction skeleton hydrogen reaction (HER), accompanied by a remarkable promotion HER activity. The dopants gradually hydrogenated almost completely dissolved form ammonia. Theoretical simulations demonstrate species leads to from hexagonal 5,7-topological rings (G5-7) with thermoneutral adsorption easy water dissociation. P-, S-, Se-doped graphites also show similar removal heteroatoms formation G5-7 rings. Our work unveils activity origin toward opens door rethinking structure-performance carbon-based for other

Язык: Английский

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Developing electrochemical hydrogenation towards industrial application

Chemical Society Reviews, Год журнала: 2023, Номер 52(21), С. 7305 - 7332

Опубликована: Янв. 1, 2023

Electrochemical hydrogenation reactions hold the promise of more sustainable production routes for towards bulk and fine chemicals. Their broad applicability, reactor concepts, achieved milestones future perspectives are described herein.

Язык: Английский

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Ethylene Electrooxidation to 2-Chloroethanol in Acidic Seawater with Natural Chloride Participation

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15565 - 15571

Опубликована: Июль 3, 2023

Ethylene oxidation to oxygenates via electrocatalysis is practically promising because of less energy input and CO2 output compared with traditional thermal catalysis. However, current ethylene electrooxidation reaction (EOR) limited alkaline neutral electrolytes produce acetaldehyde glycol, significantly limiting cell efficiency. Here, we report for the first time an EOR 2-chloroethanol product in a strongly acidic environment natural seawater as electrolyte. We demonstrate Faradaic efficiency (FE) ∼70% low electrical consumption ∼1.52 × 10-3 kWh g-1 over commercial Pd catalyst. establish mechanism evidence that produced at potentials direct interaction adsorbed chloride anions (*Cl) reactant high coverage *Cl during reaction. Importantly, this differs from accepted multiple step subsequent chlorine chlorination reactions potentials. With highly active Cl- participation, production rate 26.3 g m-2 h-1 1.6 V operation. Significantly, show 223 times greater than glycol generation freshwater. chloride-participated proton exchange membrane electrolyzer exhibits 68% FE 2.2 operation seawater. This new understanding can be used designing selective anode under mild conditions.

Язык: Английский

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Microenvironment regulation breaks the Faradaic efficiency-current density trade-off for electrocatalytic deuteration using D2O

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 19, 2024

Abstract The high Faradaic efficiency (FE) of the electrocatalytic deuteration organics with D 2 O at a large current density is significant for deuterated electrosynthesis. However, FE and are two ends seesaw because severe evolution side reaction nearly industrial densities. Herein, we report combined scenario nanotip-enhanced electric field surfactant-modified interface microenvironment to enable arylacetonitrile in an 80% −100 mA cm −2 . increased concentration low activation energy due along tips accelerated transfer suppressed by surfactant-created deuterophobic contribute breaking trade-off between density. Furthermore, application our strategy other reactions improved efficiencies rationalizes design concept.

Язык: Английский

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