Subnanometric Nickel Phosphide Heteroclusters with Highly Active Ni^δ+–P^δ− Pairs for Nitrate Reduction toward Ammonia

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 26, 2025

The development of efficient electrocatalysts for the neutral nitrate reduction reaction (NO3–RR) toward ammonia (NH3) is essential to address environmental issues caused by NO3– but remains considerably challenging owing sluggish kinetics NO3–RR in media. Herein, we report subnanometric heteroclusters with strongly coupled nickel–phosphorus (Ni–P) dual-active sites as boost NO3–RR. Experimental and theoretical results reveal that feature Ni–P promotes electron transfer from Ni P, generating Niδ+–Pδ− active pairs, which Niδ+ species are highly Pδ− tunes interfacial water hydrogen bonding network promote dissociation step accelerate proton during Consequently, NO3–RR, exhibit a large NH3 yield rate 0.61 mmol h–1 cm–2 at −0.8 V versus reversible electrode, 2.8- 3.3-fold larger than those on nanoparticles clusters, respectively, generated exists NH4+ electrolytes. This study offers an approach boosting electrocatalytic reactions multiple intermediates designing sites.

Язык: Английский

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Dissecting the hydrogen bond network of water: Charge transfer and nuclear quantum effects

Science, Год журнала: 2024, Номер 386(6726)

Опубликована: Окт. 24, 2024

The molecular structure of water is dynamic, with intermolecular hydrogen (H) bond interactions being modified by both electronic charge transfer and nuclear quantum effects (NQEs). Electronic NQEs potentially change under acidic or basic conditions, but such details have not been measured. In this work, we developed correlated vibrational spectroscopy, a symmetry-based method that separates interacting from noninteracting molecules in self- cross-correlation spectra, giving access to previously inaccessible information. We found hydroxide (OH − ) donated ~8% more negative the H network water, hydronium (H 3 O + accepted ~4% less water. Deuterium oxide (D 2 O) had ~9% bonds compared O), solutions displayed dominant than ones.

Язык: Английский

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Bimetallic Phthalocyanine Catalyst for Ammonia Electrosynthesis from Nitrate Reduction across All pH Ranges

Applied Catalysis B Environment and Energy, Год журнала: 2025, Номер 366, С. 125027 - 125027

Опубликована: Янв. 5, 2025

Язык: Английский

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pK_a Matching Enables Quantum Proton Delocalization in Acid-1-Methylimidazole Binary Mixtures

Journal of Chemical Information and Modeling, Год журнала: 2025, Номер unknown

Опубликована: Янв. 7, 2025

Short hydrogen bonds (SHBs), characterized by donor–acceptor heteroatom separations below 2.7 Å, are prevalent in condensed-phase systems. Recently, we identified SHBs nonaqueous binary mixtures of acetic acid and 1-methylimidazole (MIm), where electronic nuclear quantum effects facilitate extensive proton delocalization. In this work, explore the conditions favoring SHB formation acid–base propose that difference pKa values between base, measured a nonaqueous, aprotic solvent like DMSO, is key determinant. Using MIm as model perform structure calculations to systematically analyze matching across 97 acid-MIm pairs DMSO solutions. Through combination first-principles simulations infrared spectroscopy, confirm delocalization protons benzoic salicylic mixtures. Our results demonstrate can significantly alter behavior systems, transforming interactions from conventional transfer mechanical This work establishes valuable alternative water for assessing highlights importance bond networks modulating these conditions. By elucidating impact effects, our provides insights designing organic leverage advanced material applications.

Язык: Английский

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Selective separation of arsenic and antimony enabled by desolvation effect during distillation process: chlorine/oxygen affinity mechanism

Separation and Purification Technology, Год журнала: 2025, Номер unknown, С. 131829 - 131829

Опубликована: Янв. 1, 2025

Язык: Английский

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Hydrogen Bonds under Electric Fields with Quantum Accuracy

The Journal of Physical Chemistry A, Год журнала: 2025, Номер unknown

Опубликована: Апрель 29, 2025

Hydrogen bonds (H-bonds) are pivotal in various chemical and biological systems exhibit complex behavior under external perturbations. This study investigates the structural, vibrational, energetic properties of prototypical H-bonded dimers, water (H2O)2, hydrogen fluoride (HF)2, sulfide (H2S)2, ammonia (NH3)2 - respective monomers static homogeneous electric fields (EFs) using accurate explicitly correlated singles doubles coupled cluster method (CCSD) for equilibrium geometries harmonic vibrational frequencies perturbative triples CCSD(T) energies. As response H2O, HF, H2S, NH3 monomers, it turns out that dipole derivatives primarily govern geometry relaxation. Perturbation theory including cubic anharmonicity can reproduce CCSD results on Stark effect, except NH3, where deviations arise due to its floppiness. The field-induced modifications H-bond lengths, effects, binding energies, charge-transfer mechanisms dimers elucidated. Symmetry-adapted perturbation (SAPT) analysis reveals electrostatics dominates stabilization H-bonds across all field strengths, while induction contributions increase significantly with stronger fields, particularly more polarizable atoms. Our reveal a universal strengthening intermolecular interactions at moderate strong intensities significant variability among inherent differences molecular polarizability charge distribution. Notably, direct correlation is observed between energies effect stretching mode donor molecule, both relation energy term, investigated dimers. All these findings provide insights into EF-driven modulation H-bonds, highlighting implications catalysis, hydrogen-based technologies, processes.

Язык: Английский

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Quantum Delocalization Enables Water Dissociation on Ru(0001)

Physical Review Letters, Год журнала: 2025, Номер 134(17)

Опубликована: Апрель 30, 2025

Язык: Английский

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Water’s hydrogen bonds are seen like never before

Physics Today, Год журнала: 2025, Номер 2025(02)

Опубликована: Фев. 12, 2025

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Passively Q-Switched 2.79-Μm Er, Cr: Ysgg Laser Based on Pure Water Saturable Absorber

Опубликована: Янв. 1, 2025

Язык: Английский

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•OH Dominates the Dark Oxidation of Elemental Mercury at the Liquid–Ice Interface during Environmentally Relevant Freeze–Thaw Cycles

Environmental Science & Technology Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 3, 2025

Язык: Английский

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