Hydrogen Bonds Induced Ultra-Long Stability of Conductive Π-d Conjugated FeCo3(DDA)2 with High OER Activity.

Conductive π-d conjugated metal-organic frameworks (MOFs) have attracted wide concerns in electrocatalysis due to their intrinsic high conductivity. However, the poor electrocatalytic stability is still a major problem that hinders the practical application of MOFs. Herein, we report a novel approach to enhancing the stability of MOF-based electrocatalyst, namely, the introduction of hydrogen bonds (H-bonds). Impressively, the π-d conjugated MOF FeCo3(DDA)2 exhibits ultra-high oxygen evolution reaction (OER) stability (up to 2000 h). The experimental studies demonstrate that the presence of H-bonds in FeCo3(DDA)2 is responsible for its ultra-high OER stability. Besides that, FeCo3(DDA)2 also displays a prominent OER activity (an overpotential of 260 mV versus RHE at a current density of 10 mA cm-2 and a Tafel slope of 46.86 mV dec-1). Density functional theory (DFT) calculations further indicate that the synergistic effect of the Fe and Co sites in FeCo3(DDA)2 contributes to its prominent OER performance. This work provides a new avenue of boosting the electrocatalytic stability of conductive π-d conjugated MOFs. This article is protected by copyright. All rights reserved.

A Conductive Two-dimensional Trimetallic FeCoNi-Benzenehexathiol π-d Conjugated Metal-organic Framework for Highly Efficient Oxygen Evolution Reaction.

The poor electrically conductivity of metal-organic frameworks (MOFs) is the main factor hinder their application in electrocatalysis field. In this work, we synthesize a conductive two-dimensional (2D) trimetallic π-d conjugated metal-organic framework (MOF) FeCoNi-BHT (BHT = 1,2,3,4,5,6-benzenehexathiol) through coordinating Co, Fe and Ni ions with 1,2,3,4,5,6-benzenehexathiol ligands. FeCoNi-BHT is demonstrated possessing homogeneously dispersed abundant Co-S4, Fe-S4, Ni-S4 single-atom active sites (14.26 wt% of the metal elements) and a large specific surface area (267.05 m2g-1). The room temperature conductivity of FeCoNi-BHT is measured to be 92 S m-1, indicating its metallic behavior. DFT theoretical calculation reveals that the π-d conjugation structure of FeCoNi-BHT is responsible for its metallic behavior. In addition, FeCoNi-BHT exhibits prominent oxygen evolution reaction (OER) activity (an overpotential of 266 mV vs. RHE at 10 mA cm-2 and a Tafel value of 58 mV dec-1) in alkaline media. The combined experimental and DFT studies reveal that the synergistic effect of Co, Fe, Ni sites of FeCoNi-BHT contribute to its prominent OER activity. This work paves a new avenue of developing 2D π-d conjugated MOFs with different metal centers as highly efficient eletrocatalysts.

A Conductive 3D Dual-Metal π-d Conjugated Metal-Organic Framework Fe3 (HITP)2 /bpm@Co for Highly Efficient Oxygen Evolution Reaction.

Although 2D π-d conjugated metal-organic frameworks (MOFs) exhibit high in-plane conductivity, the closely stacked layers result in low specific surface area and difficulty in mass transfer and diffusion. Hence, a conductive 3D MOF Fe3 (HITP)2 /bpm@Co (HITP = 2,3,6,7,10,11-hexaiminotriphenylene) is reported through inserting bpm (4,4'-bipyrimidine) ligands and Co2+ into the interlayers of 2D MOF Fe3 (HITP)2 . Compared to 2D Fe3 (HITP)2 (37.23 m2  g-1 ), 3D Fe3 (HITP)2 /bpm@Co displays a huge improvement in the specific surface area (373.82 m2  g-1 ). Furthermore, the combined experimental and density functional theory (DFT) theoretical calculations demonstrate the metallic behavior of Fe3 (HITP)2 /bpm@Co, which will benefit to the electrocatalytic activity of it. Impressively, Fe3 (HITP)2 /bpm@Co exhibits prominent and stable oxygen evolution reaction (OER) performance (an overpotential of 299 mV vs RHE at a current density of 10 mA cm-2 and a Tafel slope of 37.14 mV dec-1 ), which is superior to 2D Fe3 (HITP)2 and comparable to commercial IrO2 . DFT theoretical calculation reveals that the combined action of the Fe and Co sites in Fe3 (HITP)2 /bpm@Co is responsible for the enhanced electrocatalytic activity. This work provides an alternative approach to develop conductive 3D MOFs as efficient electrocatalysts.

Enhanced photocatalytic driven hydroxylation of phenylboric acid to phenol over pyrenetetrasulfonic acid intercalated ZnAl-LDHs.

Layered double hydroxides (LDHs) own admirable potential due to their controllable composition and exchangeable interlayer anions. Herein, pyrenetetrasulfonic acid (PTS) intercalated ZnAl-LDHs (denoted as ZnAl-xPTS, x represents the amount of NaPTS in the starting material) are synthesized by a co-precipitation method, which display enhanced photocatalytic activity towards the hydroxylation of phenylboric acid to phenol. Various characterizations suggest that PTS plays significant roles in improving the photocatalytic activity: (1) PTS extends the light absorption from ultraviolet to visible light region; (2) the introduction of PTS upshifts the conduction band, which is feasible for the formation of O2∙-; (3) ZnAl-xPTS produces more free electrons under light irradiation, which leads to greatly improved activity. This study develops an alternative LDHs based photocatalyst for the production of phenol, which also provides an efficient strategy to improve the photocatalytic activity of LDHs.