Catalytic Synthesis of Formamides by Integrating CO₂ Capture and Morpholine Formylation on Supported Iridium Catalyst

Abstract

Herein we report an efficient and recyclable catalytic system for tandem CO2 capture and N‐formylation to value‐added chemicals. CO2 is apt to be captured by morpholine solution, while a highly efficient heterogeneous catalyst, isolated iridium atoms supported over nanadiamond/graphene, is discovered to be highly reactive for the formylation of morpholine, leading to the formation of N‐formylmorpholine with excellent productivity (with a turnover number of 5 120 000 in a single batch reaction) and selectivity (>99 %). In addition, the CO2 captured by morpholine under atmospheric conditions can be converted to N‐formylmorpholine with decent conversion (51 %), which realizes the integration of CO2 capture and conversion to value‐added chemicals.

A Machine Learning Model To Predict CO2 Reduction Reactivity and Products Transferred from Metal-Zeolites

“…The descriptor of N d is significantly correlated with the reaction pathway and the free energy changes in CO 2 RR (Figure 1b). Early transition metal-zeolites (Sc: 3d 1 ; Ti: 3d 2 ; Mn: 3d 5 ; Y: 4d 1 ; Zr: 4d 2 ; Nb: 4d 4 ; Ta: 5d 3 ; W: 5d 4 ) and main group metal-based Pb-zeolites (6d 0 ) with less N d showed high selectivity for the formation of CH 3 OH (Figure 2a). The relative binding strength with carbon and oxygen atoms in CO 2 determines the branching of the reaction network.…”

“…The industrial revolution has produced and released dramatic amounts of carbon dioxide (CO 2 ) in the atmosphere; e.g., the concentration of CO 2 is up to 420.99 ppm in 2022 . Carbon capture, utilization, and storage (CCUS) from various industrial processes is one of the most important technologies to achieve a carbon-neutral energy cycle. − CO 2 molecules can be converted to fuels or high value-added chemicals through diverse chemical approaches, including chemical, radiochemical, biological, photochemical, and electrochemical transformations . Among these methods, CO 2 reduction reaction (CO 2 RR) by photocatalytic and electrocatalytic reactions has attracted considerable attention due to its high environmental compatibility and mild reaction conditions.…”

Metal hydroxide assisted integrated direct air capture and conversion to methane with Ni/Al2O3catalysts

“…ICCU of CO 2 leads to valueadded products such as methanol, formate, formamide, dimethyl ether, carbon monoxide and methane. [8][9][10][11][12][13][14] Methane in particular is the main component of natural gas that constitutes a large proportion of the energy consumed around the world, accounting for example for 34% of the primary energy consumption in the United States. 15 Thus, providing new pathways to synthesize methane from CO 2 and green hydrogen, where the CO 2 is captured from point sources and the atmosphere would lead to green methane, while allowing for the continued use of the vast infrastructure already in place for natural gas distribution.…”

“…However, current ICCU with heterogeneous catalysts more commonly utilize rare-earth catalysts, such as ruthenium and iridium. 10,16 The Direct Air Capture of carbon dioxide (DAC) utilizing a hydroxide salt and the subsequent conversion of the obtained metal carbonate salt to methane is a process of importance. It would circumvent the volatility problems of amine-based sorbents and could be designed in such a way to avoid base deactivation as the choice of solvent should be less constrained.…”

“…However, current ICCU with heterogeneous catalysts more commonly utilize rare-earth catalysts, such as ruthenium and iridium. 10,16…”