The reduction of CO2 to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy-dense liquid fuels such as methanol remains rare, particularly under low-temperature and low-pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, in this study, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO2 to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO2 reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl]+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H-PNP)Ir(H)3 (H-PNP=HN(C2H4PiPr2)2). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room-temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades.
Fernández, Sergio, et al. "Room-Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO<sub>2</sub>." Angewandte Chemie (International Edition), vol. 64, no. 4, Nov. 2024. https://doi.org/10.1002/anie.202416061
Fernández, Sergio, Assaf, Eric A., Ahmad, Shahbaz, Travis, Benjamin D., Curley, Julia B., Hazari, Nilay, Ertem, Mehmed Z., & Miller, Alexander J. M. (2024). Room-Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO<sub>2</sub>. Angewandte Chemie (International Edition), 64(4). https://doi.org/10.1002/anie.202416061
Fernández, Sergio, Assaf, Eric A., Ahmad, Shahbaz, et al., "Room-Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO<sub>2</sub>," Angewandte Chemie (International Edition) 64, no. 4 (2024), https://doi.org/10.1002/anie.202416061
@article{osti_2500295,
author = {Fernández, Sergio and Assaf, Eric A. and Ahmad, Shahbaz and Travis, Benjamin D. and Curley, Julia B. and Hazari, Nilay and Ertem, Mehmed Z. and Miller, Alexander J. M.},
title = {Room-Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO<sub>2</sub>},
annote = {The reduction of CO2 to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy-dense liquid fuels such as methanol remains rare, particularly under low-temperature and low-pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, in this study, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO2 to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO2 reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl]+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H-PNP)Ir(H)3 (H-PNP=HN(C2H4PiPr2)2). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room-temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades.},
doi = {10.1002/anie.202416061},
url = {https://www.osti.gov/biblio/2500295},
journal = {Angewandte Chemie (International Edition)},
issn = {ISSN 1433-7851},
number = {4},
volume = {64},
place = {United States},
publisher = {Wiley},
year = {2024},
month = {11}}
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)
Grant/Contract Number:
SC0012704; SC0021173
OSTI ID:
2500295
Report Number(s):
BNL--226464-2025-JAAM
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 4 Vol. 64; ISSN 1433-7851