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Frustrated Lewis pairs oxidize H2 without metals

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A carbon Lewis acid, BArF18, and lutidine cleave H2 and oxidize it at carbon electrodes about 1 V milder, without CO poisoning.

Source

Metal-free electrocatalytic hydrogen oxidation using frustrated Lewis pairs and carbon-based Lewis acids

Lawrence EJ, Clark ER, Curless LD, et al. · Chemical science · 2016

doi.org/10.1039/c5sc04564aRead the full paper ↗17 citationscc by

What they did

Authors combined a carbon-based Lewis acid (1+), a boron hydride-shuttle (BArF18), and 2,6-lutidine, tracked H2 activation by NMR and CV, and cycled bulk electrolysis at carbon paper.

What they found

Pre-formed 1-H lowers the H2 oxidation potential by ~1 V (~197 kJ mol−1) and another 110 mV versus prior FLP electrochemistry. After 25 min at 20 °C, 30% of 1+ is hydrided; conversion is quantitative in 17 h. The system tolerates CO and avoids H2-evolution side reactions.

The limits

What it doesn't show

An operating H2/O2 fuel cell and a fully air-stable boron FLP are future goals; a fourth H2 charge failed until more lutidine was added.

Key terms

Frustrated Lewis pair (FLP)
Sterically prevented LA/LB pair that can heterolytically split H2.
Hydride shuttle
[(μ-H)(BArF18)2]− that moves hydride from the boron FLP to 1+.
1+ / 1-H
Carbon Lewis acid and its hydride, the electrocatalytic couple.
CO tolerance
No binding or inhibition when the mixture is sparged with CO.
BArF18
Fluorinated aryl borane used with lutidine to activate H2.

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The H2 oxidation potential drops by about:

Common questions

How much does the potential drop?

About 1 V at carbon electrodes (~197 kJ mol−1).

Is it metal-free?

Yes—catalytic in the carbon Lewis acid 1+.

Does CO poison it?

No—unlike Pt or many hydrogenase mimics.

How fast is hydriding?

30% in 25 min at 20 °C; full in 17 h.

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