Large‐Area, Free‐Standing, Two‐Dimensional Supramolecular Polymer Single‐Layer Sheets for Highly Efficient Electrocatalytic Hydrogen Evolution

Abstract

The rational construction of covalent or noncovalent organic two-dimensional nanosheets is a fascinating target because of their promising applications in electronics, membrane technology, catalysis, sensing, and energy technologies. Herein, a large-area (square millimeters) and free-standing 2D supramolecular polymer (2DSP) single-layer sheet (0.7-0.9 nm in thickness), comprising triphenylene-fused nickel bis(dithiolene) complexes has been readily prepared by using the Langmuir-Blodgett method. Such 2DSPs exhibit excellent electrocatalytic activities for hydrogen generation from water with a Tafel slope of 80.5 mV decade(-1) and an overpotential of 333 mV at 10 mA cm(-2) , which are superior to that of recently reported carbon nanotube supported molecular catalysts and heteroatom-doped graphene catalysts. This work is promising for the development of novel free-standing organic 2D materials for energy technologies.

Structural Engineering of Low‐Dimensional Metal–Organic Frameworks: Synthesis, Properties, and Applications

“…[179][180][181][182][183][184] In the following paragraphs, we will briefly introduce the synthesis of MOF nanosheets at various interfaces, including air-liquid, liquid-liquid, and solid-liquid interfaces. [179][180][181][182][183][184] In the following paragraphs, we will briefly introduce the synthesis of MOF nanosheets at various interfaces, including air-liquid, liquid-liquid, and solid-liquid interfaces.…”

[Cu3(C6Se6)]n: The First Highly Conductive 2D π–d Conjugated Coordination Polymer Based on Benzenehexaselenolate

“…[1,2] Recently, there are growing interests in design and synthesis of 2D covalent or noncovalent organic materials with in-plane π-conjugation structure. [17][18][19][20][21][22][23][24][25][26][27][28][29] The planar structure of these graphene analogues facilitates the synthesis of benzene-and triphenylene-polyselenols and CPs containing these ligands (relevant results are in preparation). [17][18][19][20][21][22][23][24][25][26][27][28][29] The planar structure of these graphene analogues facilitates the synthesis of benzene-and triphenylene-polyselenols and CPs containing these ligands (relevant results are in preparation).…”

“…The synthesis of protected BHS hexakis(tertbutylseleno)benzene (t-Bu 6 BHS) was reported by Turner and Vaid in 2012. [17][18][19][20][21][22][23][24][25][26][27][28][29] The planar structure of these graphene analogues facilitates the [33] An alternative approach is Lewis acid promoted deprotection protocol.…”

Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order

“…1,9−11 For example, free-standing monolayers of covalent organic frameworks (COFs), 6,7,12,13 as well as metal–organic frameworks (MOFs), 14−18 have recently been reported as 2D polymers and supramolecular polymers with applicability in templating, 12 photoelectric conversion, 14 and electrocatalytic hydrogen evolution. 15 Although promising results have been achieved with the networks comprising covalent bonds, 2D supramolecular polymers represent a promising approach toward molecularly precise structures over large areas. 9 Apart from the more sophisticated 2D MOFs with coordination bonds, 2D supramolecular organic frameworks (SOFs) built with other noncovalent bonds represent an incipient type of 2D supramolecular polymer.…”