Formylation–decarbonylation relay strategy for the selective hydrogenation of CO2 to CO

James Luk; Luke Andrew; Garima Saini; Matthew J. Andrews; Emily Feeke; Aidan P. McKay; David B. Cordes; Michael Bühl; Amit Kumar

doi:10.1021/acscatal.5c07116

Formylation–decarbonylation relay strategy for the selective hydrogenation of CO₂ to CO

James Luk, Luke Andrew, Garima Saini, Matthew J. Andrews, Emily Feeke, Aidan P. McKay, David B. Cordes, Michael Bühl^*, Amit Kumar^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

Abstract

We report here an alternative approach to conducting the reverse water–gas shift (RWGS) reaction catalyzed by a ruthenium pincer complex and an amine. In this strategy, a secondary amine is first formylated by CO₂ and H₂ to make H₂O and formamide. The formamide then undergoes decarbonylation to produce CO with the concomitant regeneration of the amine. Both steps, formylation and decarbonylation, were independently investigated through catalytic optimization studies and DFT computations at the PBE0-D3(BJ)_PCM(THF)/def2-TZVP level. Using morpholine and Ru-MACHO pincer catalyst, a TON of 249 was achieved for the hydrogenation of CO₂ to CO (at 70 bar, 170 °C for 90 h) with 100% selectivity.

Original language	English
Number of pages	9
Journal	ACS Catalysis
Volume	ASAP
Early online date	23 Jan 2026
DOIs	https://doi.org/10.1021/acscatal.5c07116
Publication status	E-pub ahead of print - 23 Jan 2026

Keywords

Reverse water gas shift
Pincer
Carbon dioxide
Carbon monoxide
Hydrogenation

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10.1021/acscatal.5c07116Licence: CC BY

Luk_2026_ACSC_Formylation-decarbonylation-relay-strategy_CC
© 2026 The Authors. This publication is licensed under CC-BY 4.0 (https://creativecommons.org/licenses/by/4.0/).
Final published version, 2.67 MBLicence: CC BY

PolyCat: Mechanism and Machine Led Catalyst Discovery for a Circular Economy (NoWaste)
Kumar, A. (PI)
UKRI (EU)
1/08/23 → 31/07/28
Project: Standard
New Directions for the Sythesis: New Directions for the Synthesis and Degradation of Renewable and Recyclable Plastics Using Homogeneous Catalytic (De)hydrogenation
Kumar, A. (PI)
Medical Research Council
1/08/22 → 31/07/26
Project: Fellowship

Formylation–Decarbonylation Relay Strategy for the Selective Hydrogenation of CO2 to CO (dataset)
Luk, J. (Creator), Andrews, L. (Contributor), -, G. (Creator), Andrews, M. (Creator), Feeke, E. (Contributor), McKay, A. (Creator), Cordes, D. (Creator), Buehl, M. (Creator) & Kumar, A. (Creator), University of St Andrews, 26 Jan 2026
DOI: 10.17630/a2279782-f3d8-4f32-82ae-700b124b93b1
Dataset

File

Cite this

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title = "Formylation–decarbonylation relay strategy for the selective hydrogenation of CO2 to CO",

abstract = "We report here an alternative approach to conducting the reverse water–gas shift (RWGS) reaction catalyzed by a ruthenium pincer complex and an amine. In this strategy, a secondary amine is first formylated by CO2 and H2 to make H2O and formamide. The formamide then undergoes decarbonylation to produce CO with the concomitant regeneration of the amine. Both steps, formylation and decarbonylation, were independently investigated through catalytic optimization studies and DFT computations at the PBE0-D3(BJ)PCM(THF)/def2-TZVP level. Using morpholine and Ru-MACHO pincer catalyst, a TON of 249 was achieved for the hydrogenation of CO2 to CO (at 70 bar, 170 °C for 90 h) with 100\% selectivity.",

keywords = "Reverse water gas shift, Pincer, Carbon dioxide, Carbon monoxide, Hydrogenation",

author = "James Luk and Luke Andrew and Garima Saini and Andrews, \{Matthew J.\} and Emily Feeke and McKay, \{Aidan P.\} and Cordes, \{David B.\} and Michael B{\"u}hl and Amit Kumar",

note = "Funding: This research is funded by a UKRI Future Leaders Fellowship (MR/W007460/1) and an EPSRC grant (EP/Y005449/1; selected by ERC funded by EPSRC).",

year = "2026",

month = jan,

day = "23",

doi = "10.1021/acscatal.5c07116",

language = "English",

volume = "ASAP",

journal = "ACS Catalysis",

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TY - JOUR

T1 - Formylation–decarbonylation relay strategy for the selective hydrogenation of CO2 to CO

AU - Luk, James

AU - Andrew, Luke

AU - Saini, Garima

AU - Andrews, Matthew J.

AU - Feeke, Emily

AU - McKay, Aidan P.

AU - Cordes, David B.

AU - Bühl, Michael

AU - Kumar, Amit

N1 - Funding: This research is funded by a UKRI Future Leaders Fellowship (MR/W007460/1) and an EPSRC grant (EP/Y005449/1; selected by ERC funded by EPSRC).

PY - 2026/1/23

Y1 - 2026/1/23

N2 - We report here an alternative approach to conducting the reverse water–gas shift (RWGS) reaction catalyzed by a ruthenium pincer complex and an amine. In this strategy, a secondary amine is first formylated by CO2 and H2 to make H2O and formamide. The formamide then undergoes decarbonylation to produce CO with the concomitant regeneration of the amine. Both steps, formylation and decarbonylation, were independently investigated through catalytic optimization studies and DFT computations at the PBE0-D3(BJ)PCM(THF)/def2-TZVP level. Using morpholine and Ru-MACHO pincer catalyst, a TON of 249 was achieved for the hydrogenation of CO2 to CO (at 70 bar, 170 °C for 90 h) with 100% selectivity.

AB - We report here an alternative approach to conducting the reverse water–gas shift (RWGS) reaction catalyzed by a ruthenium pincer complex and an amine. In this strategy, a secondary amine is first formylated by CO2 and H2 to make H2O and formamide. The formamide then undergoes decarbonylation to produce CO with the concomitant regeneration of the amine. Both steps, formylation and decarbonylation, were independently investigated through catalytic optimization studies and DFT computations at the PBE0-D3(BJ)PCM(THF)/def2-TZVP level. Using morpholine and Ru-MACHO pincer catalyst, a TON of 249 was achieved for the hydrogenation of CO2 to CO (at 70 bar, 170 °C for 90 h) with 100% selectivity.

KW - Reverse water gas shift

KW - Pincer

KW - Carbon dioxide

KW - Carbon monoxide

KW - Hydrogenation

U2 - 10.1021/acscatal.5c07116

DO - 10.1021/acscatal.5c07116

M3 - Article

SN - 2155-5435

VL - ASAP

JO - ACS Catalysis

JF - ACS Catalysis

ER -

Formylation–decarbonylation relay strategy for the selective hydrogenation of CO2 to CO

Abstract

Keywords

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Projects

PolyCat: Mechanism and Machine Led Catalyst Discovery for a Circular Economy (NoWaste)

New Directions for the Sythesis: New Directions for the Synthesis and Degradation of Renewable and Recyclable Plastics Using Homogeneous Catalytic (De)hydrogenation

Datasets

Formylation–Decarbonylation Relay Strategy for the Selective Hydrogenation of CO2 to CO (dataset)

Cite this

Formylation–decarbonylation relay strategy for the selective hydrogenation of CO₂ to CO