Engineering of Hybrid SiO2@{N-P-Fe} Catalysts with Double-Ligand for Efficient H2 Production from HCOOH

Energies, Год журнала: 2025, Номер 18(3), С. 514 - 514

Опубликована: Янв. 23, 2025

Two Fe-based hybrids, [SiO2@NP(Ph)2/FeII/PP3] and [SiO2@NP(t-Bu)2/FeII/PP3], were synthesized using the double-ligand approach by covalently grafting NP ligands onto surface of SiO2. Both catalytic systems evaluated for H2 production through formic acid dehydrogenation (FADH), revealing important efficiency without requiring additional additives and/or co-catalysts. During continuous addition FA, [SiO2@NP(t-Bu)2/FeII/PP3] demonstrated great stability, achieving total TONs = 20,636 20,854, respectively. FT-IR Raman spectroscopy provided insights into role ligands, such as NP(Ph)2 NP(t-Bu)2, on assembly structural configuration active hybrid Fe catalysts their ability to dehydrogenate acid. Additional studies, including in situ mapping solution potential (Eh) reaction an Arrhenius study activation energy (Ea), revealed a correlation between Ea rates: system with 29.4 KJ/mol shows rate 58 mL-H2/min, while 50.6 55 mL-H2/min. This is first example heterogeneous FADH where original strategy “double-ligand” has been homogeneous systems. Herein we demonstrate that can engineer decrease barrier via two synergistic steps: (i) ligand SiO2 (ii) PP3 double ligand. leads boost catalyst, which time shown be able outperform parental reference/homogenous catalyst [FeII/PP3].

Язык: Английский

Highly‐Efficient Reusable [Silica@Iminophosphine‐Fe^II] Hybrids for Hydrogen Production via Formic Acid and Formaldehyde Dehydrogenation

Chemistry - A European Journal, Год журнала: 2025, Номер unknown

Опубликована: Фев. 5, 2025

Abstract The use of hybrids, developed by grafting homogeneous catalysts onto supporting materials, has already demonstrated significant potential in various catalytic processes. These systems combine the advantages catalysts, such as high activity and selectivity, with those solid supports, including enhanced recyclability. Catalytic hydrogen (H 2 ) production via dehydrogenation C1 organic molecules targeting its fuel cells is a contemporary scientific issue directly connected climate crisis. Here, Iminophospine hybrid [SiO @benzNP] reduced analogue @benzNHP] were synthesized, covalently grafted on colloidal SiO , fully characterized (FT‐IR, RAMAN, TGA, ssNMR, BET), used for in‐situ synthesis @benzNP‐Fe II ] @benzNHP‐Fe complexes H from formic acid (HCOOH) formaldehyde (HCHO), at 80 °C. In HCOOH, both heterogenized exhibit producing CO 1 : ratio, without contamination, making them ideal cell applications. [SiO₂@benzNHP‐Fe catalyst superior performance substates. HCOOH dehydrogenation, over 82,000 turnover number (TONs) achieved retained efficiency five cycles, any further metal addition. HCHO it showed excellent well, achieving 1.3 L pure TONs exceeding 7,000, 3 consecutive uses. Advanced spectroscopic analysis confirmed stability structural integrity linking Schiff base reduction N−H groups to activity, durability reusability. This study demonstrates materials non‐noble metals cost‐effective sustainable production, paving way scalable renewable energy solutions.

Язык: Английский

Formic Acid Dehydrogenation over a Recyclable and Self-Reconstructing Fe/Activated Carbon Catalyst

Energy & Fuels, Год журнала: 2024, Номер unknown

Опубликована: Авг. 30, 2024

A novel catalyst, denoted as ACox@ImFe, was synthesized using matrix-activated oxidized carbon (ACox) featuring a [Fe2+-imidazole]-based complex covalently bonded to the surface through Si–O–C bonding. The catalytic system, distinguished by its innovative hybrid structure that includes Fe2+ and imidazole on an matrix in presence of polydentate phosphine, demonstrated remarkable turnover numbers (TONs), reaching 428,880 effectively decomposed 53 mL formic acid (FA) over 8 cycles. This sustained performance underscores effectiveness, stability, durability which further evidenced cumulative H2 production 22.1 L same period. Structural analysis Raman, Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), paramagnetic resonance (EPR) revealed structural changes used catalyst compared pristine material. Despite observed changes, such Fe-site aggregation restructuring, maintained high efficiency, with enhanced activity noted each reuse. stability carbon-based radicals from confirmed, is crucial for catalyst. Notably, upon repeated use, underwent self-reconstruction process, linked alterations hydrophobicity overall structure, resulting water improved performance, making ACox@ImFe robust effective system sustainable production.

Язык: Английский