Encapsulation of Silver Nanoparticles in an Amine‐Functionalized Porphyrin Metal–Organic Framework and Its Use as a Heterogeneous Catalyst for CO₂ Fixation under Atmospheric Pressure

Abstract

A new porphyrin-based compound, [Zn (C H N )(C H N O ) (DEF) ](DEF) (1; DEF=N,N-diethylformamide), has been synthesized by employing 5,10,15,20-tetrakis(4-pyridyl)porphyrin, 1,2-diamino-3,6-bis(4-carboxyphenyl)benzene, and Zn salt at 100 °C under solvothermal conditions. The structure, as determined by single-crystal XRD studies, is three-dimensional with threefold interpenetration. The usefulness of free -NH groups in the ligand was exploited for anchoring silver nanoparticles through a simple solution-based route. The silver-loaded sample, Ag@1, was characterized by powder XRD, energy-dispersive X-ray spectroscopy, high-resolution TEM, SEM, X-ray photoelectron spectroscopy, and inductively coupled plasma MS analysis, which clearly indicated that silver nanoparticles with a size of 3.83 nm were uniformly distributed within the metal-organic framework (MOF). The Ag@1 sample was evaluated for possible catalytic activity for the carboxylation of a terminal alkyne by employing CO under atmospheric pressure; this gave excellent results. The Ag@1 catalyst was found to be robust, active, and recyclable. The present studies suggest that porphyrin MOFs not only exhibit interesting structures, but also show good heterogeneous catalytic activity towards the fixation of CO .

Ordered Mesoporous CeO2‐supported Ag as an Effective Catalyst for Carboxylative Coupling Reaction Using CO2

“…On the basis of the experimental results, DFT calculations and previous reports, a plausible reaction mechanism for the carboxylative coupling reaction is proposed in Scheme . Firstly, Ag nanoparticles of Ag/M−CeO 2 can coordinate terminal alkynes with Cs 2 CO 3 to form silver acetylide intermediate A .…”

“…In the effort to develop sustainable processes, a few heterogeneous catalysts have been introduced in this reaction. For instance, CuBr loaded on activated carbon, CuCl 2 incorporated in polyvinyl imidazolium tri‐cationic ionic liquid, Cu nanoparticles supported on Al 2 O 3 , and Ag nanoparticles encapsulated in the porphyrin MOF displayed excellent catalytic activities for the carboxylative coupling reaction. However, due to the thermodynamic and kinetic stability of CO 2 , the transformation of CO 2 to functionalized 2‐alkynoates using heterogeneous catalysts under mild reaction condition remains a great challenge.…”

Silver Nanoparticles Architectured HMP as a Recyclable Catalyst for Tetramic Acid and Propiolic Acid Synthesis through CO2 Capture at Atmospheric Pressure

“…The spectra appeared in Figure , was a drop in stretching frequency for the N peak upon nanoparticle grafting, while all the other peaks remain almost unchanged. The coordination interaction within the nanocatalyst is favoured between N site of the chelating type polymer ligand and Ag NPs which may promote the suitable binding of Ag NPs on the HMP‐2 polymer surface …”

Formaldehyde Gas Adsorption in High‐Capacity Silver‐Nanoparticle‐Loaded ZIF‐8 and UiO‐66 Frameworks

“…The experimental results showed that the optimized Ag 2 O@Uio-66 composite exhibited a high chemical absorption rate of 1 ppm for H 2 S at room temperature. Gargi Dutta et al, [23] studied the application of silver nanoparticles encapsulation in aminogenatedporphyrin MOFs as co-stationary polyphase catalysts under atmospheric pressure. Silver nanoparticles were anchored to MOFs by simple solution method, and carboxylation catalytic activity of terminal alkynes was studied by inverting phase atmospheric pressure method.…”