Non‐Metallic Phosphorus Corrole as Efficient Electrocatalyst in Hydrogen Evolution Reaction

Abstract

The economical consideration of using an electrocatalyst in energy-related field, composed of non-precious/sustainable elements is quite noteworthy. In this work, the phosphorus(V) complex of tris-(pentafluorophenyl)corrole [(TPFC)P V (OH) 2 ] was reported as electrocatalyst for the hydrogen evolution reaction (HER). The electrochemical studies revealed that the HER experienced a ECEC pathway (E: electron transfer step, C: chemical step), and the possible intermediate [P V ]À H species was suggested. (TPFC)P V (OH) 2 displayed excellent HER activity in dimethylformamide (DMF) with trifluoroacetic acid (TFA) as the proton source, and the turnover frequency (TOF) reached 31.75 s À 1 at an overpotential of 900 mV. Interestingly, the HER electrocatalytic performance remained extraordinary even applying water as a proton source in acetonitrile/water (v/v = 2 : 3), with a TOF of 18.40 mol H 2 mol cat À 1 h À 1 at an overpotential of 900 mV.

Substituent Effect on Ligand‐Centered Electrocatalytic Hydrogen Evolution of Phosphorus Corroles

“…All studied corroles 1P-5P (Synthetic details and characterization see Supporting Information) were well characterized by nuclear magnetic resonance (NMR), high-resolution mass spectroscopy (HRMS) (Figures S1-S13 in the Supporting Information) (4P has been characterized in our previous work). [16] We firstly examined the photophysical properties of 1P-5P via obtaining spectra of ultraviolet-visible spectroscopy (UV/Vis) and fluorescence emission (Figure 1b, c, e). All data are summarized in Table S1.…”

“…[15] More recently, our group had probed the HER catalytic efficacy of non-metallic phosphorus corrole and it turned out that phosphorous corrole is a new kind of promising HER molecular catalyst. [16] To explore the effect of peripheral substituents on the electrocatalytic HER activity of phosphorous corrole, we here have prepared a series of phosphorus corroles 1P-5P with different electron structure. The complexes 1P-4P were prepared according to the methods reported previously.…”

“…Jiang and co‐workers reported a PEGylated (PEG, polyethylene glycol) porphyrin tin complex as an effective molecular electrocatalyst for HER and provided new mechanistic insights into proton reduction [15] . More recently, our group had probed the HER catalytic efficacy of non‐metallic phosphorus corrole and it turned out that phosphorous corrole is a new kind of promising HER molecular catalyst [16] …”

Milestones and Most Recent Advances in Corrole’s Science and Technology

“…Adsorbed on a graphite electrode, this complex catalyzed the HER from aqueous acidic solution at low overpotential (−0.3 V vs NHE), high catalytic turnover numbers (TON ≫ 10 7 ), and a turnover frequency (TOF) of 600 s –1 . Many other transition (such as Mn, Fe, Ni, Cu, Mo, Au) and post-transition (such as P) metallocorroles and even free-base corroles were since examined as HER electrocatalysts under homogeneous and heterogeneous conditions. ,− In one recent study published by Mizrahi et al, the authors showed that a corrole-fused binuclear iron corrole is a better electrocatalyst than the analogues mononuclear complex . Another development is the 2021 report by Kumar et al, who took advantage of the just disclosed substituent-free corrole (the parent corrole) and its metal complexes .…”

Electrocatalytic Hydrogen Evolution of the Cobalt Triaryl Corroles Bearing Hydroxyl Groups

“…Previously, we have reported the catalytic activity of pentafluorophenyl and amino, [19] nitro, [15a] cyano, [20] and ethoxycarbonyl [21] substituted cobalt corroles and nonmetallic phosphorus corroles [22] in the electrocatalytic HER. To test whether hydroxyl at meso‐ phenyl substituent can act as a proton relay group in the electrocatalytic HER.…”