Biomimetic Design of a Dynamic M-O-V Pyramid Electron Bridge for Enhanced Nitrogen Electroreduction.

Electrochemical nitrogen reduction reaction (eNRR) offers a sustainable route for ammonia synthesis; however, current electrocatalysts are limited in achieving optimal performance within narrow potential windows. Herein, inspired by the heliotropism of sunflowers, we present a biomimetic design of Ru-VOH electrocatalyst, featuring a dynamic Ru-O-V pyramid electron bridge for eNRR within a wide potential range. In situ spectroscopy and theoretical investigations unravel the fact that the electrons are donated from Ru to V at lower overpotentials and retrieved at higher overpotentials, maintaining a delicate balance between N2 activation and proton hydrogenation. Moreover, N2 adsorption and activation were found to be enhanced by the Ru-O-V moiety. The catalyst showcases an outstanding Faradaic efficiency of 51.48% at -0.2 V (vs RHE) with an NH3 yield rate exceeding 115 µg h-1 mg-1 across the range of -0.2 to -0.4 V (vs RHE), along with impressive durability of over 100 cycles. This dynamic M-O-V pyramid electron bridge is also applicable to other metals (M = Pt, Rh, and Pd).

A novel design of Cu(I) active site on the metal-organic framework for exploring the structural transformation of Fenton-like catalysts through in situ "capturing" OH.

The mutual transformation of reactive oxygen species may affect the structural transformation of catalysts during the Fenton-like processes. Its in-depth understanding is essential to achieve high catalytic activity and stability. In this study, a novel design of Cu(I) active sites based on the metal-organic framework (MOF) is proposed to "capture" OH- produced via Fenton-like processes and re-coordinate the oxidized Cu sites. The Cu(I)-MOF presents an excellent removal efficiency for sulfamethoxazole (SMX), with a high removal kinetic constant of 7.146 min-1. Combing DFT calculations with experimental observations, we have revealed that the Cu of Cu(I)-MOF exhibits a lower d-band center, enabling efficient activation of H2O2 and spontaneous "capturing" of OH- to form Cu-MOF, which can be reorganized into the Cu(I)-MOF through molecular regulation for recycle. This research demonstrates a promising Fenton-like approach for solving the trade-off between catalytic activity and stability and provides new insights into the design and synthesis of efficient MOF-based catalysts for water treatment.

H2O2 activation by two-dimensional metal-organic frameworks with different metal nodes for micropollutants degradation: Metal dependence of boosting reactive oxygen species generation.

The existence of organic micropollutants (OPMs) in water poses a considerable threat to the environment. A centralized approach towards pollutants abatement has dominated over the recent decades wherein heterogeneous Fenton-like based advanced oxidation processes can be a promising technology. The application of engineered nanomaterials offers more opportunities to enhance their catalyst properties. This study synthesizes a series of ultrathin two-dimensional (2D) Metal-organic frameworks (MOFs) nanosheets with tunable metal clusters. The formation of reactive oxygen species (•OH and 1O2) can be significantly boosted via transferring the adsorbed H2O2 onto the solid-liquid interface by systematically tuning the metal species. The Co-MOF nanosheets exhibited an ultrafast degradation kinetic for BPA with a rate of 2.23 min-1 (4.98 times higher than that of the bulk MOF) and TOF (turnover frequency) value of 9.99 min-1, which are observably greater than that of the existing materials reported to date. Density functional theory simulation and experimental results unravel the mechanism for ROS formation, which is strongly metal-depend. We further loaded the powder onto a flow-through poly (vinylidene fluoride) (PVDF) microfiltration membrane and observed that the representative OPMs could be rapidly degraded, indicating promising properties for practical application.

Electrocatalytical oxidation of arsenite by reduced graphene oxide via in-situ electrocatalytic generation of H2O2.

Preoxidation of As(III) to As(V) is required for the efficient removal of total arsenic in the treatment of wastewater. In this work, the electro-Fenton oxidation of As(III) with a high efficiency was successfully achieved by using the system of the stainless steel net (SSN) coating with reduced graphene oxide (RGO@SSN) as the cathode and stainless steel net (SSN) as the sacrificial anode. The RGO@SSN was synthesized by electrophoretic deposition-annealing method. The carbon disorder and defects of RGO resulted from the remained oxygen-containing functional groups facilitated the electrocatalytically active sites for two-electron oxygen reduction reaction (ORR). A high concentration (up to 1000 µmol/L) of H2O2 was in-situ produced through two-electron oxygen reduction reaction of electro-catalysis, and then served as the electro-Fenton reagent for the oxidation of As(III). HO generated by H2O2 participating the electro-Fenton reaction or decomposed at the surface of RGO@SSN cathode at acid condition endowed the strong oxidizing ability for As(III). The electro-Fenton equipped with RGO@SSN cathode has a promising application in the oxidation and removal of organic or inorganic pollutants in wastewater.