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Mechanistic insights to drive catalytic hydrogenation of formamide intermediates to methanol via deaminative hydrogenation

Journal Article · · Frontiers in Energy Research
 [1];  [2];  [1];  [1]
  1. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Washington State Univ., Pullman, WA (United States)
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Amine-promoted hydrogenation of CO2 to methanol typically proceeds via a formamide intermediate when amines are used as additives or if the hydrogenation is performed in carbon capture solvents. The catalysts used for the hydrogenation of the formamide intermediate dictate the selectivity of the products formed: 1) Deoxygenative hydrogenation (C–O bond cleavage) resulting in N-methylation of amine and deactivation of the solvent, 2) Deaminative hydrogenation (C–N bond cleavage) resulting in formation of methanol and regeneration of the solvent. To date, catalytic reductions of CO2 with amine promoters suffer from poor selectively for methanol which we attribute to the limiting formamide intermediate, though to date, the conditions that favor C–N cleavage have yet to be fully understood. To better understand the reactivity of the formamide intermediates, a range of heterogenous catalysts were used to study the hydrogenation of formamide. Well-known gas phase CO2 hydrogenation catalysts catalyze the hydrogenation of formamide to N-methyl product via C–O bond cleavage. However, the selectivity can be readily shifted to selective C–N bond cleavage by addition of an additive with sufficient basicity for both homogenous and heterogeneous catalytic systems. The base additive shifts the selectivity by deprotonating a hemiaminal intermediate formed in situ during the formamide hydrogenation. This prevents dehydration process leading to N-methylated product, which is a key capture solvent deactivation pathway that hinders amine use in carbon capture, utilization, and storage (CCUS). The findings from this study provide a roadmap on how to improve the selectivity of known heterogenous catalysts, enabling catalytic reduction of captured CO2 to methanol.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Fossil Energy and Carbon Management (FECM)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
2305513
Report Number(s):
PNNL-SA--181662
Journal Information:
Frontiers in Energy Research, Journal Name: Frontiers in Energy Research Vol. 11; ISSN 2296-598X
Publisher:
Frontiers Research FoundationCopyright Statement
Country of Publication:
United States
Language:
English

References (43)

Integrated Capture and Conversion of CO2 to Methanol in a Post‐Combustion Capture Solvent: Heterogeneous Catalysts for Selective CN Bond Cleavage journal October 2022
Highly Selective Monomethylation of Amines with CO2/H2 via Ag/Al2O3 as a Catalyst journal March 2023
CO 2 Capture and Conversion with a Multifunctional Polyethyleneimine-Tethered Iminophosphine Iridium Catalyst/Adsorbent journal March 2014
Integrated Capture and Conversion of CO 2 to Methane Using a Water‐lean, Post‐Combustion CO 2 Capture Solvent journal October 2021
Mechanistic Insights on the Ruthenium‐Catalyzed Hydrogenation of Amides – C–N vs. C–O Cleavage journal May 2011
Carbon Capture and Utilization Update journal March 2017
An insight of CO 2 hydrogenation to methanol synthesis: Thermodynamics, catalysts, operating parameters, and reaction mechanism journal December 2021
Comparative study of synthesis of methylamines from carbon oxides and ammonia over Cu/A12O3 journal May 1996
Reaction Path Analysis of CO2 Reduction to Methanol through Multisite Microkinetic Modelling over Cu/ZnO/Al2O3 Catalysts journal September 2021
A Bioinspired Multicomponent Catalytic System for Converting Carbon Dioxide into Methanol Autocatalytically journal July 2020
Multiscale modelling of CO2 reduction to methanol over industrial Cu/ZnO/Al2O3 heterogeneous catalyst: Linking ab initio surface reaction kinetics with reactor fluid dynamics journal December 2020
Advances in catalytic homogeneous hydrogenation of carbon dioxide to methanol journal January 2018
Chemical transformations of captured CO2 into cyclic and polymeric carbonates journal July 2019
Synthesis of methylamines from CO2, H2 and NH3. Catalytic behaviour of various metal-alumina catalysts journal November 1997
Synthesis of methylamines from CO2, H2 and NH3 over Cu–Mg–Al mixed oxides journal May 1999
Integrated CO 2 Capture and Conversion to Formate and Methanol: Connecting Two Threads journal September 2019
Bench-Scale Testing and Process Performance Projections of CO 2 Capture by CO 2 –Binding Organic Liquids (CO 2 BOLs) with and without Polarity-Swing-Assisted Regeneration journal February 2016
The Role of Carbon Capture and Utilization, Carbon Capture and Storage, and Biomass to Enable a Net-Zero-CO 2 Emissions Chemical Industry journal March 2020
Reactive Capture of CO2: Opportunities and Challenges journal December 2022
Hydrogen Autotransfer in the N -Alkylation of Amines and Related Compounds using Alcohols and Amines as Electrophiles journal November 2009
Tandem Amine and Ruthenium-Catalyzed Hydrogenation of CO 2 to Methanol journal January 2015
Conversion of CO 2 from Air into Methanol Using a Polyamine and a Homogeneous Ruthenium Catalyst journal January 2016
Hydroxide Based Integrated CO 2 Capture from Air and Conversion to Methanol journal February 2020
Homogeneous Carbon Capture and Catalytic Hydrogenation: Toward a Chemical Hydrogen Battery System journal April 2022
Catalytic Hydrogenation of Carboxylic Acid Esters, Amides, and Nitriles with Homogeneous Catalysts journal January 2014
Homogeneous and heterogeneous catalytic reduction of amides and related compounds using molecular hydrogen journal August 2020
Synthesis of methylamines from carbon dioxide and ammonia journal January 1995
In situ hydrogenation of captured CO2 to formate with polyethyleneimine and Rh/monophosphine system journal January 2013
Methylation of amines, nitrobenzenes and aromatic nitriles with carbon dioxide and molecular hydrogen journal January 2014
Development of GSK's acid and base selection guides journal January 2015
Catalytic reduction of CO 2 by H 2 for synthesis of CO, methanol and hydrocarbons: challenges and opportunities journal January 2016
Chemoselective reduction of carboxamides journal January 2016
CO 2 capture by amines in aqueous media and its subsequent conversion to formate with reusable ruthenium and iron catalysts journal January 2016
The steps of activating a prospective CO 2 hydrogenation catalyst with combined CO 2 capture and reduction journal January 2016
Highly productive CO 2 hydrogenation to methanol – a tandem catalytic approach via amide intermediates journal January 2017
Unravelling the mechanisms of CO2 hydrogenation to methanol on Cu-based catalysts using first-principles multiscale modelling and experiments journal January 2017
Carbon capture and storage (CCS): the way forward journal January 2018
Heterogeneously catalyzed selective hydrogenation of amides to alcohols and amines journal January 2018
Towards environmentally benign capture and conversion: heterogeneous metal catalyzed CO 2 hydrogenation in CO 2 capture solvents journal January 2020
Catalytic coproduction of methanol and glycol in one pot from epoxide, CO 2 , and H 2 journal January 2020
An amino acid based system for CO 2 capture and catalytic utilization to produce formates journal January 2021
Next steps for solvent-based CO2 capture; integration of capture, conversion, and mineralisation journal January 2022
Phosphate assisted integrated carbon dioxide capture and conversion to methane journal January 2023

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
C-N cleavage
Carbon capture and utilization
N-methylation
catalysis
hydrogenation
hydrogenation catalysis
methanol synthesis