Rational design of selective metal catalysts for alcohol amination with ammonia

Abstract

The lack of selectivity for the direct amination of alcohols with ammonia (a modern and clean route for the synthesis of primary amines) is an unsolved problem. Here, we combine first-principles calculations, scaling relations, kinetic simulations and catalysis experiments to determine the key factors that govern the activity and selectivity of metal catalysts for this reaction. We show that the loss of selectivity towards primary amines is linked to a surface-mediated C–N bond coupling between two N-containing intermediates: CH3NH and CH2NH. The barrier for this step is low enough to compete with the main surface hydrogenation reactions and it can be used as a descriptor for selectivity. The activity and selectivity maps (using the C and O adsorption energies as descriptors) were combined for the computational screening of 348 dilute bimetallic catalysts. Among the best theoretical candidates, Co98.5Ag1.5 and Co98.5Ru1.5 (5 wt% Co) were identified experimentally to be the most promising catalysts.

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Fig. 1: A reaction scheme for the catalytic amination of primary alcohols by ammonia.
Fig. 2: The main reaction pathways considered in the DFT calculation for CH3OH amination with NH3.
Fig. 3: The calculated maps for activity and the selectivity controlling barrier.
Fig. 4: Four possible C–N coupling pathways catalysed by the metal surface.
Fig. 5: Transition state structures featuring C–N coupling between various N-containing intermediates on a Co(111) surface.
Fig. 6: The experimental TOF for amines in the amination of 1-octanol with NH3 on cobalt-based bimetallic catalysts.
Fig. 7: The experimental selectivity to the primary amine OA versus the total amine formation.

Data availability

The data that support the plots in this paper and the other findings of this study are available from the corresponding authors on reasonable request.

Code availability

The script used for the modified microkinetic simulations using the open source CatMAP code is given in Supplementary Data 2.

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Acknowledgements

This work received granted access to the HPC resources of CINES and IDRIS under allocation no. 2015-080609 made by GENCI. It also benefited from the computational resources of the PSMN. Financial support was provided by the ANR grant SHAPES (grant no. 13-CDII-0004-06). The authors express their gratitude to E. Leroy from ICMPE-CMTR (UMR 7182 CNRS) for measuring the STEM-EDS-SDD cartographies.

Author information

T.W. and M.S. conducted the DFT calculations and microkinetics simulations, K.W., L.F., S.P. and J.I. performed the experiments and P.S., C.M. and M.P.-T. designed the study and wrote the paper.

Correspondence to Marc Pera-Titus or Philippe Sautet.

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Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Figs. 1–30 and Supplementary references.

Supplementary Data 1

Atomic coordinates of the optimized computational models.

Supplementary Data 2

Script used for the modified microkinetic simulations using the open source CatMAP code.

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