Synchronous Regulation of D–Band Centers in Zn Substrates and Weakening Pauli Repulsion of Zn Ions Using the Ascorbic Acid Additive for Reversible Zinc Anodes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 11, 2024

Abstract The advanced aqueous zinc–ion batteries (AZIBs) are still challenging due to the harmful reactions including hydrogen evolution and corrosion. Here, a natural small molecule acid vitamin C (Vc) as an electrolyte additive has been selectively identified. Vc can adjust d band center of Zn substrate which fixes active H + so that reaction (HER) is restrained. Simultaneously, it could also fine–tune solvation structure ions enhanced electrostatics reduced Pauli repulsion verified by energy decomposition analysis (EDA). Hence, cell retains ultra–long cycle performance over 1300 cycles superior Coulombic efficiency (CE) 99.5 %. prepared full cells display increased rate capability, lifetime, self–discharge suppression. Our results shed light on mechanistic principle additives improvement ZIBs, anticipated render new round studies.

Язык: Английский

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Efficient Catalytic Upgrading of Ethanol to Higher Alcohols via Inhibiting C–C Cleavage and Promoting C–C Coupling over Biomass-Derived NiZn@NC Catalysts

ACS Catalysis, Год журнала: 2022, Номер 12(19), С. 11573 - 11585

Опубликована: Сен. 8, 2022

The conversion of renewable bioethanol into high-energy-density higher alcohols has become essential for meeting the increasing global demand to achieve carbon neutrality. In this study, Zn- and nitrogen-codoped Ni-based lignin-derived catalysts (NiZn@NC) were prepared by solvent volatile self-assembly in situ reductive carbonization using pulp paper waste stream alkali lignin as source. Lignin amphipathic derivatives with −COOH −NH2 groups would coordinate metal ions form a stable lignin–metal framework; thus, layer disperses NiZn bimetallic catalyst prevents from corroding. At an amination reagent/lignin mass ratio 1:2, ethanol 75.2% high alcohol yield 41.7% achieved over Ni20Zn1@NC catalyst. Experimental results density functional theory calculations showed that Zn doping improved electronic environment defect structures metallic Ni carrier, which effectively inhibited C–C cleavage suppressed byproduct formation, such methane. Thereby, synergetic effect between facilitated efficient aqueous Guerbet reaction. This work provides strategy pyrolytic stabilizing biomass macromolecules frameworks construction highly active cost-efficient upgrading.

Язык: Английский

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Mechanism of a cobalt-catalyzed hydroarylation reaction and origin of stereoselectivity

Catalysis Science & Technology, Год журнала: 2022, Номер 12(13), С. 4380 - 4387

Опубликована: Янв. 1, 2022

In the present study, mechanism of a cobalt-catalyzed hydroarylation reaction between N -pyridylindole and 1,6-enynes origin its stereoselectivity have been systematically investigated using DFT calculation method.

Язык: Английский

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Origin of asynchronicity in Diels–Alder reactions

Physical Chemistry Chemical Physics, Год журнала: 2021, Номер 23(36), С. 20095 - 20106

Опубликована: Янв. 1, 2021

Quantum chemical activation strain analyses reveal that asynchronicity in Diels–Alder reactions reduces both destabilizing Pauli repulsion as well stabilizing orbital interactions, and occurs if the former dominates.

Язык: Английский

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Role of Redox-Inactive Metal Ions in Modulating the Reduction Potential of Uranyl Schiff Base Complexes: Detailed Experimental and Theoretical Studies

Inorganic Chemistry, Год журнала: 2022, Номер 61(18), С. 7130 - 7142

Опубликована: Апрель 25, 2022

A mononuclear uranyl complex, [UO2L] (1), has been synthesized with the ligand N,N'-bis(3-methoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane (H2L). The complex showed a reversible U(VI)/U(V) redox couple in cyclic voltammetric measurements. reduction potential of this positive shift upon addition redox-inactive alkali- and alkaline-earth Lewis acidic metal ions (Li+, Na+, K+, Ca2+, Sr2+, Ba2+) to an acetonitrile solution 1. explained on basis acidity internal electric-field effect respective ions. bimetallic complexes [UO2LLi(NO3)] (2), [UO2LNa(BF4)]2 (3), [UO2LK(PF6)]2 (4), [(UO2L)2Ca]·(ClO4)2·CH3CN (5), [(UO2L)2Sr(H2O)2]·(ClO4)2·CH3CN (6), [(UO2L)2Ba(ClO4)]·(ClO4) (7) have also isolated solid state by reacting 1 corresponding characterized single-crystal X-ray diffraction. Density functional theory calculations optimized [UO2LM]n+ used rationalize experimental potentials imposed non-redox-active cations.

Язык: Английский

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Lewis Acid-Catalyzed Carbonyl-Ene Reaction: Interplay between Aromaticity, Synchronicity, and Pauli Repulsion

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(15), С. 11102 - 11110

Опубликована: Июль 24, 2023

The physical factors governing the catalysis in Lewis acid-promoted carbonyl-ene reactions have been explored detail quantum chemically. It is found that binding of a acid to carbonyl group directly involved transformation greatly accelerates reaction by decreasing corresponding activation barrier up 25 kcal/mol. makes process much more asynchronous and transition state less in-plane aromatic. remarkable acceleration induced catalyst ascribed, means strain model energy decomposition analysis methods, mainly significant reduction Pauli repulsion between key occupied π-molecular orbitals reactants not widely accepted stabilization LUMO enophile.

Язык: Английский

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Synchronous Regulation of D–Band Centers in Zn Substrates and Weakening Pauli Repulsion of Zn Ions Using the Ascorbic Acid Additive for Reversible Zinc Anodes

Angewandte Chemie, Год журнала: 2024, Номер 136(19)

Опубликована: Март 11, 2024

Abstract The advanced aqueous zinc–ion batteries (AZIBs) are still challenging due to the harmful reactions including hydrogen evolution and corrosion. Here, a natural small molecule acid vitamin C (Vc) as an electrolyte additive has been selectively identified. Vc can adjust d band center of Zn substrate which fixes active H + so that reaction (HER) is restrained. Simultaneously, it could also fine–tune solvation structure ions enhanced electrostatics reduced Pauli repulsion verified by energy decomposition analysis (EDA). Hence, cell retains ultra–long cycle performance over 1300 cycles superior Coulombic efficiency (CE) 99.5 %. prepared full cells display increased rate capability, lifetime, self–discharge suppression. Our results shed light on mechanistic principle additives improvement ZIBs, anticipated render new round studies.

Язык: Английский

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Thermochemical conversion of grape marc into carbon-negative syngas

Journal of Environmental Management, Год журнала: 2025, Номер 385, С. 125684 - 125684

Опубликована: Май 10, 2025

Язык: Английский

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Acetaldehyde Production via Photocatalytic Heterolytic Dehydrogenation of Ethanol Accelerated by Tuning Lewis Acid–Base Pairs over CsGeX₃3 (X = Cl, Br, I) Halide Perovskites

ACS Sustainable Chemistry & Engineering, Год журнала: 2025, Номер unknown

Опубликована: Май 29, 2025

Язык: Английский

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A simple and convenient strategy for the oxidation of C(sp³)–H bonds based on γ-valerolactone

Green Chemistry, Год журнала: 2023, Номер 26(1), С. 353 - 361

Опубликована: Ноя. 21, 2023

This work reports on a new carbon-centered radical based γ-valerolactone (GVL) that can activate C(sp 3 )–H bonds and has application potential in various radical-mediated reactions.

Язык: Английский

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