Mechanistic and kinetic relevance of hydrogen and water in CO2 hydrogenation on Cu-based catalysts

Lin, Ting C.; Nolen, Michelle A.; Farberow, Carrie A.; Kwon, Stephanie; Bhan, Aditya

doi:10.1016/j.jcat.2024.115936

Title: Mechanistic and kinetic relevance of hydrogen and water in CO₂ hydrogenation on Cu-based catalysts

Journal Article · Thu Jan 02 00:00:00 UTC 2025 · Journal of Catalysis

DOI: https://doi.org/10.1016/j.jcat.2024.115936 · OSTI ID:2522823

Lin, Ting C. ^[1];

^[2]; Farberow, Carrie A. ^[3]; Kwon, Stephanie ^[4];

^[1]

University of Minnesota, Minneapolis, MN (United States)
Colorado School of Mines, Golden, CO (United States); National Renewable Energy Laboratory (NREL), Golden, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)

Here, we ally steady-state kinetics, kinetic isotope effects, and density functional theory (DFT) calculations to illustrate that Cu-based catalysts remain saturated by H-adatoms (H*) and molecular formic acid (HCOOH**) during CO₂ hydrogenation. High H* coverage under methanol synthesis conditions is evidenced by reverse water-gas shift (RWGS) rates that exhibit positive H₂ reaction orders only at P_H2 ≲ 0.5 bar, above which methanol synthesis and RWGS rates exhibit first and zeroth order dependence on P_H2, respectively. HCOOH** also accumulates on the surface with increasing P_CO2 as informed by the Langmuir-type dependence on P_CO2 (0.25-23 bar) for both methanol synthesis and RWGS. As both HCOOH** and H* have one H-atom per site occupied, the two species share the same P_H2 dependence and give rise to CO₂ reaction orders that are independent of P_H2. Surface coverages determined based on kinetic analyses are further corroborated with DFT-derived adsorption energies that show favorable HCOOH** adsorbate-adsorbate interactions as well as repulsive interactions for bidentate formate (HCOO**) on H*-saturated surfaces. Methanol selectivity remains invariant with P_CO2 and P_CO despite CO inhibiting reaction rates, thereby demonstrating methanol synthesis and RWGS occur on the same active site. In contrast, water preferentially inhibits methanol synthesis rates, increases methanol synthesis H₂ reaction order from 1.0 to 1.5, and alters the methanol synthesis H₂/D₂ kinetic isotope effect; the inhibitory effect of H₂O thus cannot be attributed to competitive adsorption alone and instead reflects a change in the rate-determining step for methanol synthesis. The disparate kinetics of methanol synthesis and RWGS evince a branching pathway where methanol is formed from formates and CO is formed from carboxylates. The presented work thus identifies the relevant surface species, underscores the distinct catalytic role of water in branching methanol synthesis and RWGS pathways, and, in doing so, details a mechanistic picture that yields predictable rates and reaction orders for both methanol synthesis and RWGS on Cu-based CO₂ hydrogenation catalysts.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC36-08GO28308; SC0025321

OSTI ID:: 2522823

Report Number(s):: NREL/JA--5100-92648; MainId:94429; UUID:fde91c30-9fb4-443c-9a92-8b7f853b15a3; MainAdminId:76162

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Vol. 443; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Mechanistic and kinetic relevance of hydrogen and water in CO2 hydrogenation on Cu-based catalysts

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Title: Mechanistic and kinetic relevance of hydrogen and water in CO₂ hydrogenation on Cu-based catalysts