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Updated: Jan 15, 2026
Hydrogen Production and Utilization in a Membrane Reactor
Published on: March 10, 2023
Thermochemical heterolytic hydrogenation catalysis proceeds through polarization-driven hydride transfer
Hai-Xu Wang1,2, Yogesh Surendranath3
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA, USA.
This study reveals a new mechanism for heterolytic hydrogenation reactions, showing how catalyst polarization drives hydride transfer. This finding impacts carbon dioxide hydrogenation and NAD+ regeneration for sustainable chemistry.
Area of Science:
- Catalysis
- Electrochemistry
- Chemical Reaction Mechanisms
Background:
- Heterolytic hydrogenation is crucial for CO2 conversion and NADH regeneration.
- Existing models overlook interfacial charge separation's role in these reactions.
Purpose of the Study:
- To investigate the electrochemical potential of catalysts during heterolytic hydrogenation.
- To uncover evidence for an interfacial electrochemical hydride transfer mechanism.
Main Methods:
- Quantifying catalyst electrochemical potential during turnover.
- Analyzing the influence of proton acceptors on catalyst polarization.
Main Results:
- Proton acceptors induce catalyst surface polarization.
- This polarization controls M-H intermediate hydricity, driving hydride transfer.
- An interfacial electrochemical hydride transfer mechanism was supported.
Conclusions:
- The proposed mechanism applies to diverse media and reactions like CO2 hydrogenation and NAD+ regeneration.
- This framework allows intrinsic kinetics determination and guides sustainable catalyst design.
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