Reductive Formylation of Nitroarenes using HCOOH over Bimetallic C−N Framework Derived from the Integration of MOF and COF

Abstract

CoZn embedded CÀ N framework is prepared by the carbonization of CoZn containing MOF integrated with COF porous architecture in Ar atmosphere. The graphitic nature of porous carbon is confirmed from Raman analysis. The porosity and nanostructure information are retrieved from N 2 -sorption and transmission electron microscopic analysis, respectively. The incorporation of different metals and their oxidation states and types of nitrogen present in the CÀ N framework are confirmed from X-ray photoelectron spectroscopy. The basicity of the materials is determined from a CO 2 -temperature programmed desorption. ZnCo embedded CÀ N framework exhibits excellent activity in the selective reductive formylation using HCOOH. For comparison, more than 15 materials are prepared, and their activities are compared. Several control experiments are performed to establish a structure-activity relation. The recycling experiment, hot-filtration test, and poisoning experiment demonstrate the metal embedded porous CÀ N framework's recyclability and stability. A reaction mechanism for the reductive N-formylation of nitroaromatics is presented based on structure-activity relationship, control reactions, and physicochemical characterizations. The development of interesting MOF-COF-derived metal nanoclusters embedded CÀ N framework for selective reductive formylation of nitroaromatics using formic acid will be highly attractive to catalysis researchers and industrialists.

Oxygen Vacancy-Mediated Z-Scheme Charge Transfer in a 2D/1D B-Doped g-C3N4/rGO/TiO2 Heterojunction Visible Light-Driven Photocatalyst for Simultaneous/Efficient Oxygen Reduction Reaction and Alcohol Oxidation

“…It signifies that TBCN@3%rGO contains moderate and strong basic sites, where CO 2 chemisorption takes place. 57,58 This basicity distribution arises due to the "N" surroundings in the triazine moieties of TBCN@3%rGO, which are effectively involved in the deprotonation of alcohols and promote their complexation on the surface of TBCN@3% rGO. 59 Moreover, the NH 3 -TPD profile in Figure 6b shows a weak desorption signal around 150 °C and a broad NH 3 desorption signal from 300 to 550 °C.…”

A CoPd nanoalloy embedded N-doped porous carbon catalyst for the selective reduction and reductive amination of levulinic acid using formic acid in water

“…† The Co 2p 3/2 of Co@N-C was deconvoluted into three peaks that appeared at 778.3 eV, 780.4 eV, and 784.5 eV corresponding to metallic Co, Co-N, and a satellite peak, respectively. 38 Similarly, Co 2p 1/2 can be deconvoluted at 794.1 eV attributed to the Co 0 (Fig. 2a).…”

“…The carbonized catalysts exhibited the graphitic band (G band) at 1585.2 cm −1 , corresponding to the in-plane vibration of sp 2 carbon atoms, and a disorder band (D band) at 1324.3 cm −1 representing the nonperfect crystalline structure of the material due to the N doping in the framework. 38 The intensity ratio of the D band and G band (I D /I G ) for Co 1−x -Pd x @N-C catalysts was higher than that of Co@N-C and Pd@N-C (Fig. S1 †).…”

Visible-light-induced photocatalytic reductive carbonylation of nitroarenes using formic acid as a hydrogen source over a water-dispersible CTF-based palladium catalyst

“…11,12 Thus far, several studies have been reported on the one-pot synthesis of N-formamides from nitroarenes using HCOOH or its derivatives. 5,[13][14][15][16] Given the fact that a selective decomposition of HCOOH to H 2 + CO 2 and the use of CO 2 as a formylation source thermodynamically are feasible (ΔG 298K = −35 kJ mol −1 ), it requires activation energy, which is generally provided through thermal energy and a suitable catalyst. 17,18 However, using light energy as an energy source is a much more sustainable process and can answer the energy crisis and mitigate environmental threats.…”

“…11,12 Thus far, several studies have been reported on the one-pot synthesis of N -formamides from nitroarenes using HCOOH or its derivatives. 5,13–16…”