Electrocatalytic hydrogen evolution with a copper porphyrin bearing meso-(o-carborane) substituents

Abstract

A newly designed copper complex of 5,15-bis(pentafluorophenyl)-10,20-bis(o-carborane)porphyrin (1) was synthesized and tested for electrocatalytic hydrogen evolution reaction (HER). In acetonitrile, 1 was much more efficient than Cu 5,15-bis(pentafluorophenyl)-10,20-diphenylporphyrin (2) for...

Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins

“…Cu porphyrins have recently been shown to be highly active and stable for electrocatalytic HER. [42,45,49,50] We showed recently that Cu porphyrins outperformed other transition metal porphyrin analogues for HER under the same conditions. [51] Through controllable β-oxidation using oxone as the oxidant, we made analogue 2 with one β-lactone group as well as analogues 3 and 4 with two β-lactone groups in a cis and trans configuration, respectively.…”

“…[43][44][45] It is shown that with the introduction of electron-withdrawing substituents, metal porphyrins will become easier to be reduced to generate catalytically active species for proton reduction. [10,38,42] This effect will in general lead to the anodic shift of electrocatalytic HER waves. In addition to the benefits of studying structure-activity relationships, metal porphyrins have very rich and characteristic spectroscopic features, [46][47][48] which are also beneficial for reaction mechanism studies.…”

“…Metal porphyrins have been shown to be active and robust electrocatalysts for HER. [33][34][35][36][37][38][39] Importantly, because (1) porphyrin macrocycles can capture a metal ion to provide a rigid and stable M-N 4 coordination environment, [10,[34][35][36][37] and (2) metal porphyrin electronic structures can be systematically modified through the introduction of various meso-and β-substituents with different numbers and positions at the macrocycle, [40][41][42] metal porphyrins are considered as appealing models to study the dependence of catalyst activities on their electronic structures. [43][44][45] It is shown that with the introduction of electron-withdrawing substituents, metal porphyrins will become easier to be reduced to generate catalytically active species for proton reduction.…”

Benzene-fused porphyrin(2.1.2.1) array: synthesis, structure, and electrocatalytic hydrogen evolution

“…9 c They were first loaded onto CNTs to obtain BPD/CNT and BP/CNT using the method reported. 12 The morphologies of BPD/CNT and BP/CNT were then evaluated using scanning electron microscopy (SEM) (Fig. S6, ESI†), which showed no clear aggregation of BPD/CNT and BP/CNT .…”

“…The high-resolution XPS spectra of Cu 2p 1/2 and Cu 2p 3/2 showed peaks at 935.1 and 955.2 eV, respectively, corresponding to Cu( ii ), which is similar to the XPS result of a hybrid of a porphyrin(1.1.1.1) copper complex and CNTs. 12…”