Dynamics of Water/Metal Interface for Aqueous-Phase Hydrogenation

The presence of water has been shown to enhance hydrogenation of polar chemical functional groups, such as C=O and N=O bonds, through proton shuttling. To demonstrate such rather sophisticated reaction pathways, explicit solvent models with dynamic change of local solvent structures should be considered. Beyond what we reported previously for water-promoted C=O hydrogenation in furfural,¹ in this presentation, we will highlight how the dynamics of the local water structures within the first solvation shell may affect the hydrogenation kinetics. Specifically, we find that the activation barriers correlate well with some collective variables that determine the local configuration and relative positions of surface hydrogen and water.² In addition, very recently we show that the proton shuttling can also be applied to C=C hydrogenation at solid-liquid interfaces in the presence of bifunctional metal-acid sites containing boric acid adsorbed on Ni.³ Our recent calculations show that the dynamic transformation of this metal-acid interface can promote hydrogenation of the C=C bond in cyclohexene. In experiments, a rate enhancement by more than 100 times has been observed when adding small amount of water into an organic solvent. According to our atomic models, dynamic formation of a B(OH)₃-H₂O complex is crucial for lowering the activation barrier of the first hydrogenation.⁴ Our findings thus provide fundamental insights of this dynamic transformation at the solid-liquid interface and its impact on catalytic activity and selectivity.

1. Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water, Z. Zhao, R. Bababrik, W.H. Xue, Y.P. Li, N. M. Briggs, D.-T. Nguyen, U. Nguyen, S. P. Crossley, S. W. Wang, B. Wang, D. E. Resasco, Nat. Catal. 2, 431-436 (2019)
2. Dynamic water-metal interface determines the hydrogenation kinetics, T. Le, S. Sun, D. E. Resasco, B. Wang, unpublished
3. Bifunctional metal-acid sites on nickel boride catalysts: Phenol Hydrodeoxygenation and water-promoted C=C hydrogenation, G. Li, T. Salas, S.-T. Sun, B. Wang, M. R. Komarneni, D. Resasco, J. Catal. 431, 115384 (2024)
4. Water-enhanced bifunctional metal-acid catalyst for C=C bond hydrogenation, S. Sun, T. Salas, G. Li, D. E. Resasco, B. Wang, unpublished

Bio:
Bin Wang is a Professor, Conoco-DuPont Professor at the School of Sustainable Chemical, Biological and Materials Engineering at the University of Oklahoma. He is also a visiting scientist at the Lawrence Livermore National Laboratory and Max Planck Institute for Sustainable Materials. Before joining OU in 2014, he was a postdoctoral researcher in Department of Physics and Astronomy at Vanderbilt University. He received his Ph.D. in Chemistry from Ecole Normale Supérieure de Lyon supported by a Marie Curie Fellowship in 2011. His research is focused on computational simulations of nanoscale materials and their applications in catalysis, optoelectronics, and batteries. He received a US Department of Energy Early Career award, an ACS COMP OpenEye Outstanding Junior Faculty Award, and a Bessel Research Award by the Alexander von Humboldt Foundation. He has also been included in “Influential Researchers” by ACS I&EC Research and “Emerging Investigators” by the RSC Catalysis Science & Technology.