Promoting hydrogen evolution reaction with a sulfonic proton relay

doi:10.1016/S1872-2067(22)64183-4

Abstract

Abstract:

Enzymes can activate otherwise unreactive substrates by using residues precisely located in the active sites. We herein report on a Ga porphyrin which bears a second-sphere sulfonic group (named as 1) and its high efficiency for the electrocatalytic hydrogen evolution reaction (HER). Complex 1 can achieve a large TOF value of 1.3 × 10⁵ s⁻¹ at low 295-mV overpotential with weak acetic acid (HOAc) as the proton source. Notably, 1 can catalyze H₂ generation at potentials close to the thermodynamic HER equilibrium, but the sulfonic-free analogues require >250 mV more cathodic potentials to initiate HER. Mechanistic studies showed that two-electron reduced Ga porphyrins were protonated to form Ga^III-H. For 1, its Ga^III-H underwent rapid protonolysis with HOAc to evolve H₂, but for sulfonic-free analogues, their Ga^III-H required further reduction at more cathodic potentials to trigger catalysis. This work presents a synthetic molecular catalyst to achieve high HER rates under low overpotentials by promoting the protonolysis of metal hydrides with otherwise unreactive weak acids.

Key words: Molecular electrocatalysis, Hydrogen evolution reaction, Ga porphyrin, Metal hydride, Second-coordination sphere, H-H bond formation

Ni Wang, Xue-Peng Zhang, Jinxiu Han, Haitao Lei, Qingxin Zhang, Hang Zhang, Wei Zhang, Ulf-Peter Apfel, Rui Cao. Promoting hydrogen evolution reaction with a sulfonic proton relay[J]. Chinese Journal of Catalysis, 2023, 45: 88-94.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64183-4

https://www.cjcatal.com/EN/Y2023/V45/I2/88

Figures/Tables 5

Fig. 1. (a) Representative proton relays in [FeFe] hydrogenases and synthetic HER catalysts. (b) Different reaction pathways of GaIII-H with strong and weak acids. (c) Molecular structures of Ga porphyrins 1, 2 and 3.

Fig. 2. (a) CVs of 0.5 mmol L-1 1 in acetonitrile with and without K2CO3. (b) CVs of 0.5 mmol L-1 1 in acetonitrile with and without 140 mmol L-1 HOAc. (c) CVs of 0.5 mmol L-1 3 in acetonitrile with and without 140 mmol L-1 HOAc. (d) LSVs of 140 mmol L-1 HOAc with and without 0.5 mmol L-1 1-3. Conditions: 0.1 mol L-1 Bu4NPF6, GC working electrode, 100 mV s-1 scan rate.

Fig. 3. (a) CVs of 0.5 mmol L-1 1 in acetonitrile with increasing HOAc. Inset: plot of catalytic current at ?1.84 V versus HOAc concentration. (b) Charge accumulated during the electrolysis of 140 mmol L-1 HOAc with 1 at ?1.65 V. (c) UV-vis spectra of 1 before and after electrolysis. (d) The FOWA of electrocatalytic HER with 1-3 and other reported molecular catalysts by using HOAc as the proton source.

Fig. 4. UV-vis (a) and EPR (b) spectra of 1, 1? and 12?. (c) UV-vis spectra of 1 and the reaction of 12? with HOAc. (d) UV-vis spectra of 3 and the reaction of 32? with HOAc.

Fig. 5. DFT-calculated HER mechanism with 1. The free energy barriers for the H-H bond formation steps in the conditions of appended sulfonic acid versus free acetic acid are provided.

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