Efficiency Of H2O2 Generation Research Articles

Pyridyl‐Imine‐Functionalized Donor–Acceptor Covalent Organic Frameworks for Optimal Photosynthesis of Hydrogen Peroxide

AbstractThe artificial photosynthesis of hydrogen peroxide (H2O2) using semiconductor photocatalysts is gaining attention as an eco‐friendly and energy‐efficient method. Covalent organic frameworks (COFs) show great promise in enhancing photocatalytic H2O2 production due to their tunable structures and functional diversity. However, the efficiency of H2O2 generation is close to the photoelectric properties of COFs and the microenvironment of their active sites. Herein, the synthesis of pyridyl‐imine‐functionalized COFs (PyIm‐COFs) featuring donor–acceptor (D–A) moieties to improve H2O2 production efficiency is reported. By employing benzothiadiazole (BT) units with varied fluorine substitutions, the electronic environment of the active sites, optimizing the selective two‐electron (2e−) oxygen reduction reaction (ORR), is tuned. Among the synthesized COFs, PyIm‐BT_F exhibits the highest photocatalytic activity, achieving a H2O2 production rate of 5342 µmol g−1 h−1. The importance of D–A moieties in the rational design of COF‐based photocatalysts, providing a novel strategy for sustainable H2O2 production through optimized active site environments, is underscored.

Alkali metal cation adsorption–induced surface polarization in polymeric carbon nitride for enhanced photocatalytic hydrogen peroxide production

Photocatalytic hydrogen peroxide (H2O2) generation on the catalyst surface from oxygen is an electron-demanding process, making the construction of an electron-rich surface highly advantageous. In this study, a localized electric field was observed on the surface of polymeric carbon nitride (g-C3N4) when alkali metal cations were adsorbed onto it. These fields effectively inhibited surface carrier recombination and extended their lifespan, thereby enhancing H2O2 production. As a result, g-C3N4 achieved a superior H2O2 yield of 2.25mM after 1h in a 0.25M K+ solution, which was 2.06 times greater than that (1.09 mM) achieved in a pure solvent. Notably, the increase in photocatalytic efficiency showed a remarkable dependence on ion species. At low concentrations, H2O2 generation efficiency was in the order of Li+<Na+<K+<Rb+<Cs+. However, after optimizing the ion concentration, the highest H2O2 production was achieved in a solution containing K+ instead of Cs+. Molecular dynamics simulations and temperature-dependent photocatalysis experiments revealed that the synergistic interaction between adsorption energy and adsorption distance was crucial in governing the extent to which alkali metal cation adsorption enhanced g-C3N4 photocatalytic H2O2 production. This study provides theoretical insights for the design of materials for electron-demanding photocatalysis and aids in understanding variations in photocatalytic behavior in natural waters.

Integrating Multipolar Structures and Carboxyl Groups in sp2-Carbon Conjugated Covalent Organic Frameworks for Overall Photocatalytic Hydrogen Peroxide Production.

The direct production of hydrogen peroxide (H2O2) through photocatalytic reaction via H2O and O2 is considered as an ideal approach. However, the efficiency of H2O2 generation is generally limited by insufficient charge and mass transfer. Covalent organic framework (COFs) offer a promising platform as metal-free photocatalyst for H2O2 production due to their potential for rational design at the molecular level. Herein, we integrated the multipolar structures and carboxyl groups into COFs to enhance the efficiency of photocatalytic H2O2 production in pure water without any sacrificial agents. The introduction of octupolar and quadrupolar structures, along with an increase of molecular planarity, created efficient oxygen reduction reaction (ORR) sites. Meanwhile, carboxyl groups could not only boost O2 and H2O2 movement via enhancement of pore hydrophilicity, but also promote proton conduction, enabling the conversion to H2O2 from ⋅O2 -, which is the crucial intermediate product in H2O2 photocatalysis. Overall, we demonstrate that TACOF-1-COOH, consisting of optimal octupolar and quadrupolar structures, along with enrichment sites (carboxyl groups), exhibited a H2O2 yield rate of 3542 μmol h- 1 g-1 and a solar-to-chemical (SCC) efficiency of 0.55 %. This work provides valuable insights for designing metal-free photocatalysts for efficient H2O2 production.

Integrating Multipolar Structures and Carboxyl Groups in sp2‐Carbon Conjugated Covalent Organic Frameworks for Overall Photocatalytic Hydrogen Peroxide Production

The direct production of hydrogen peroxide (H2O2) through photocatalytic reaction via H2O and O2 is considered as an ideal approach. However, the efficiency of H2O2 generation is generally limited by insufficient charge and mass transfer. Covalent organic framework (COFs) offer a promising platform as metal‐free photocatalyst for H2O2 production due to their potential for rational design at the molecular level. Herein, we integrated the multipolar structures and carboxyl groups into COFs to enhance the efficiency of photocatalytic H2O2 production in pure water without any sacrificial agents. The introduction of octupolar and quadrupolar structures, along with an increase of molecular planarity, created efficient oxygen reduction reaction (ORR) sites. Meanwhile, carboxyl groups could not only boost O2 and H2O2 movement via enhancement of pore hydrophilicity, but also promote proton conduction, enabling the conversion to H2O2 from ·O2‐, which is the crucial intermediate product in H2O2 photocatalysis. Overall, we demonstrate that TACOF‐1‐COOH, consisting of optimal octupolar and quadrupolar structures, along with enrichment sites (carboxyl groups), exhibited a H2O2 yield rate of 3542 μmol h‐1 g‐1 and a solar‐to‐chemical (SCC) efficiency of 0.55%. This work provides valuable insights for designing metal‐free photocatalysts for efficient H2O2 production.

Metal–Organic Framework Fe-BTC as Heterogeneous Catalyst for Electro-Fenton Treatment of Tetracycline

This study explores the use of the iron-containing metal–organic framework (MOF), Basolite®F300, as a heterogeneous catalyst for electrochemically-driven Fenton processes. Electrochemical advanced oxidation processes (EAOPs) have shown promise on the abatement of recalcitrant organic pollutants such as pharmaceuticals. Tetracyclines (TC) are a frequently used class of antibiotics that are now polluting surface water and groundwater sources worldwide. Acknowledging the fast capability of EAOPs to treat persistent pharmaceutical pollutants, we propose an electrochemical Fenton treatment process that is catalyzed by the use of a commercially available MOF material to degrade TC. The efficiency of H2O2 generation in the IrO2/carbon felt setup is highlighted. However, electrochemical oxidation with H2O2 production (ECO-H2O2) alone is not enough to achieve complete TC removal, attributed to the formation of weak oxidant species. Incorporating Basolite®F300 in the heterogeneous electro-Fenton (HEF) process results in complete TC removal within 40 min, showcasing its efficacy. Additionally, this study explores the effect of varying MOF concentrations, indicating optimal removal rates at 100 mg L−1 due to a balance of kinetics and limitation of active sites of the catalysts. Furthermore, the impact of the applied current on TC removal is investigated, revealing a proportional relationship between current and removal rates. The analysis of energy efficiency emphasizes 50 mA as the optimal current, however, balancing removal efficiency with electrical energy consumption. This work highlights the potential of Basolite®F300 as an effective catalyst in the HEF process for pollutant abatement, providing valuable insights into optimizing electrified water treatment applications with MOF nanomaterials to treat organic pollutants.

Catalysis of oxygen reduction reaction for H2O2 electrogeneration: The impact of different conductive carbon matrices and their physicochemical properties

Abstract Carbon-based catalysts are widely used in oxygen reduction reactions (ORR) via 2e- for H2O2 electrogeneration. The direct comparability of the structural proprieties of different carbon matrices applied on ORR, however, has never been tested. Here, we evaluate how the electrochemical and structural properties of different carbon-based materials, including carbon Printex XE2B (PXE2BC), Printex L6 (PL6C), carbon derived from lignin (LIGC), graphite (GRA) and glassy carbon (GC), affect on ORR. All the materials were characterized by Raman spectroscopy, X-ray photoelectron spectrometry (XPS), elementary analysis, field emission gun scanning electron microscopy, surface area measurements and electrochemical assays for the evaluation of ORR. Notably, the morphology, the size of the particles and the types of functional groups present in the structure of carbon materials were keys in the efficiency of ORR. The carbon materials PL6C and PXE2BC with high surface area and oxygenated functional groups in their structure displaced the ORR potential, facilitating the reaction. Carbon materials with less surface area, such as GRA, LIGC and GC, and whose main functional groups in their structures were non-oxygenated or nitrogenated, were less active in ORR. The displacement of the potential and the efficiency of H2O2 generation were directly dependent on the electrochemical and structural characteristics of the materials used as catalysts. These results are particularly relevant regarding a proper choice of carbon catalyst can increase the efficiency of ORR.