Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101415 - 101415
Опубликована: Июнь 1, 2025
Язык: Английский
The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 3447 - 3453
Опубликована: Март 28, 2025
Although noble metals Ag and Au have similar chemical reactivities, their catalytic selectivity for NO electroreduction is significantly different. Namely, hydroxylamine often considerably produced on while not observed the electrode. In this study, first-principles calculations electric field controlling constant potential (EFC-CP) method are adopted to unveil underlying reasons. We first reveal a distinct NO* adsorption configuration, vertical inclined Au, leading different reduction pathways NOH* HNO*, respectively. Via complete electrochemical barrier detailed kinetic analysis, we find difference between mainly induced by strength of NH2OH*. On Ag, obtained NH2OH* prefers desorb produce hydroxylamine, bonded strongly favors further ammonia. The study advances our understanding factors regulating product selectivity, providing crucial insights designing catalysts toward production.
Язык: Английский
Процитировано
0
Advanced Materials, Год журнала: 2025, Номер unknown
Опубликована: Апрель 3, 2025
Glycine plays a crucial role in various industrial and daily applications. However, traditional synthesis methods are often associated with high toxicity, energy intensity, inefficiency. This study introduces an efficient eco-friendly method for synthesizing glycine via the reductive coupling of oxalic acid nitrate using Bi metal catalyst, enhanced by lattice strain from oxide composites undergoing electrochemical transformation. At applied potential -0.76 V versus reversible hydrogen electrode (RHE), catalyst achieves impressive Faradaic efficiency (FE) 79.1%, yielding record concentration 0.17 m, substantially higher than conventional Bi-based systems. Furthermore, introduction glycolaldehyde hydroxylamine as reactants raise FE to 91.3% production rate 2433.3 µmol h-1 under identical conditions. Electrochemical analysis theoretical calculations demonstrate that expansion notably boosts facilitating NH2OH formation promoting reduction oxime intermediates. These results underscore significance engineering enhancing active site performance accelerating reaction kinetics, offering sustainable alternative methods.
Язык: Английский
Процитировано
0
JACS Au, Год журнала: 2025, Номер 5(4), С. 2015 - 2026
Опубликована: Апрель 5, 2025
Amino acids are widely used in food, pharmaceuticals, and agrochemicals, presenting significant societal demand, the artificial synthesis of amino is an important yet challenging task. Through electrocatalytic C-N coupling, from biomass α-keto waste nitrate under mild aqueous conditions has become a green alternative strategy. Rare-earth-based materials, due to their unique 4f orbitals tunable crystal facets, often serve as potential resource-rich catalysts. However, structure-performance relationship coupling for remains unclear. Therefore, eight rare-earth-based catalysts were screened this work CeO2 was chosen appropriate model catalyst mechanism investigation on electrosynthesis alanine. Four nanomaterials with distinct morphologies facets synthesized, among which nanorods (CeO2-NRs) exposing (110) facet exhibited highest oxygen vacancy (Ov) concentration optimal electrosynthetic performance A series control experiments, electrochemical characterizations, situ attenuated total reflection Fourier transform infrared spectroscopy (in ATR-FTIR), online differential mass spectrometry (DEMS), quasi electron paramagnetic resonance (quasi EPR) combined density functional theory (DFT) calculations indicated that pathway alanine involved reduction NO3 - produce *NH2OH situ, nucleophilically attacked carbonyl group pyruvate form key intermediate species, oxime, then underwent further amination generate The step responsible difference four nanocrystals lay oxime (PO), confirming more Ov exposure facilitated cleavage N-O bond (*OOC(H3C)C=N-OH→*OOC(H3C)C=N), while also lowering energy consumption hydrogenation C=N (*OOC(H3C)C=NH→*OOC(H3C)CNH2). This innovative strategy not only provides new route valorization but offers valuable guidance design efficient field.
Язык: Английский
Процитировано
0
Journal of the American Chemical Society, Год журнала: 2025, Номер unknown
Опубликована: Май 16, 2025
Tuning the surface strain is a powerful strategy to enhance catalytic activity of metal nanocatalysts, yet an atomically precise catalyst with intramolecular unlock atomic-level strain-structure-activity relationship still highly desired. Herein, we report synthesis, structural anatomy, and performance toward cyclohexanone oxime electrosynthesis Ag16Cu18(C≡C-C6H11)24 (Ag16Cu18) nanocluster, which has Cu6 ring in center. The Cu-Cu distance only 1.616 Å single crystal, shortest bond Cu nanomaterials date. Furthermore, once Ag16Cu18 was loaded onto carbon paper, ultrashort elongated ∼2.40 Å, showing strong compressive strain. exhibited excellent electrosynthesis, manifested by maximal Faradaic efficiency, yield, yield rate reaching 47.4%, 95.4%, 2.66 mmol·h-1·cm-2 at -0.35 V, respectively. In-situ attenuated total reflection surface-enhanced infrared spectroscopy revealed that sites adjacent Ag atoms primarily reduce NO stabilize it *NH2OH stage, while provide H* for reduction adsorb react *NH2OH, forming simultaneously. Density functional theory calculations confirmed presence ring, facilitates formation adsorption, hence significantly contributing generation. This study not reports case clusters but also provides understanding employing bimetallic nanocluster-based catalysts valuable organic molecules.
Язык: Английский
Процитировано
0
Chem Catalysis, Год журнала: 2025, Номер unknown, С. 101415 - 101415
Опубликована: Июнь 1, 2025
Язык: Английский
Процитировано
0