Search Results (7)

In this study, an electrochemical system for methane conversion was developed, employing Ni- and Ce-doped LaCoO₃ perovskite as the anode catalyst in an Na₂CO₃ electrolyte. Structural characterization revealed that the La_1−yCe_yCo_1−xNi_xO₃ (x = 0–0.5, y = 0–0.12) synthesized by the sol–gel method maintains the perovskite structure, but is rich in oxygen vacancies. Electrochemical studies revealed that the performance of methane activation is related to the presence of Ni(III) in the catalyst, and reactive oxygen species (•OH and HOO⁻) are provided through water oxidation reactions (WOR) in the Na₂CO₃ electrolyte. The electrocatalytic performance of the synthesized La_0.92Ce_0.08Co_0.5Ni_0.5O₃ during methane conversion was verified in an electrolysis cell, and ethanol and acetic acid were identified as the methane conversion oxygenates. Under ambient conditions, the formation rate of ethanol reached 577.0 μmol g_cat⁻¹ h⁻¹ at 0.90 V (vs. Ag/AgCl) in 0.5 mol L⁻¹ Na₂CO₃. The catalyst was found to retain structural integrity and sustain catalytic activity over multiple reaction cycles. Full article

Developing high-efficiency photoelectrodes plays an important role in the photoelectrocatalytic generation of hydrogen peroxide (H₂O₂) in the photoelectrochemical (PEC) water splitting field. In this work, an innovative strategy was proposed, the synergistic photocatalytic production of H₂O₂ using a bidirectional photoanode–photocathode coupling system under visible-light irradiation. Fe₂O₃-Ti, as the photoanode, which was built by way of Fe₂O₃ loaded on Ti-mesh using the hydrothermal-calcination method, was investigated in terms of the suitability of its properties for PEC H₂O₂ production after optimization of the bias voltage, the type of electrolyte solution, and the concentration of the electrolyte. Afterwards, a H-type double-electrode coupling system with an Fe₂O₃-Ti photoanode and a WO₃@Co₂SnO₄ photocathode was established for the bidirectional synergistic production of H₂O₂ under visible-light irradiation. The yield of H₂O₂ reached 919.56 μmol·L⁻¹·h⁻¹ in 2 h over −0.7 V with 1 mol·L⁻¹ of KHCO₃ as the anolyte and 0.1 mol·L⁻¹ Na₂SO₄ as the catholyte (pH = 3). It was inferred that H₂O₂ production on the WO₃@Co₂SnO₄ photocathode was in line with the 2e^- oxygen reduction reaction (ORR) principle, and on the Fe₂O₃-Ti photoanode was in line with the 2e^- water oxidation reaction (WOR) rule, or it was indirectly promoted by the electrolyte solution KHCO₃. This work provides an innovative idea and a reference for anode–cathode double coupling systems for the bidirectional production of H₂O₂. Full article

The visible-light-driven photocatalytic production of hydrogen peroxide (H₂O₂) is currently an emerging approach for transforming solar energy into chemical energy. In general, the photocatalytic process for producing H₂O₂ includes two pathways: the water oxidation reaction (WOR) and the oxygen reduction reaction (ORR). However, the utilization efficiency of ORR surpasses that of WOR, leading to a discrepancy with the low oxygen levels in natural water and thereby impeding their practical application. Herein, we report a novel donor–bridge–acceptor (D-B-A) organic polymer conjugated by the Sonogashira–Hagihara coupling reaction with tetraphenylethene (TPE) units as the electron donors, acetylene (A) as the connectors and pyrene (P) moieties as the electron acceptors. Notably, the resulting TPE-A-P exhibits a remarkable solar-to-chemical conversion of 1.65% and a high BET-specific surface area (1132 m²·g⁻¹). Furthermore, even under anaerobic conditions, it demonstrates an impressive H₂O₂ photosynthetic efficiency of 1770 μmol g⁻¹ h⁻¹, exceeding the vast majority of previously reported photosynthetic systems of H₂O₂. The outstanding performance is attributed to the effective separation of electrons and holes, along with the presence of sufficient reaction sites facilitated by the incorporation of alkynyl electronic bridges. This protocol presents a successful method for generating H₂O₂ via a water oxidation reaction, signifying a significant advancement towards practical applications in the natural environment. Full article

Electrosynthesis of H₂O₂ via both pathways of anodic two-electron water oxidation reaction (2e-WOR) and cathodic two-electron oxygen reduction reaction (2e-ORR) in a diaphragm-free bath can not only improve the generation rate and Faraday efficiency (FE), but also simplify the structure of the electrolysis bath and reduce the energy consumption. The factors that may affect the efficiency of H₂O₂ generation in coupled electrolytic systems have been systematically investigated. A piece of fluorine-doped tin oxide (FTO) electrode was used as the anode, and in this study, its catalytic performance for 2e-WOR in Na₂CO₃/NaHCO₃ and NaOH solutions was compared. Based on kinetic views, the generation rate of H₂O₂ via 2e-WOR, the self-decomposition, and the oxidative decomposition rate of the generated H₂O₂ during electrolysis in carbonate electrolytes were investigated. Furthermore, by choosing polyethylene oxide-modified carbon nanotubes (PEO-CNTs) as the catalyst for 2e-ORR and using its loaded electrode as the cathode, the coupled electrolytic systems for H₂O₂ generation were set up in a diaphragm bath and in a diaphragm-free bath. It was found that the generated H₂O₂ in the electrolyte diffuses and causes oxidative decomposition on the anode, which is the main influent factor on the accumulated concentration in H₂O₂ in a diaphragm-free bath. Full article

Hexanary high-entropy oxides (HEOs) were synthesized through the mechanochemical sol-gel method for electrocatalytic water oxidation reaction (WOR). As-synthesized catalysts were subjected to characterization, including X-ray diffraction (XRD), Fourier transforms infrared (FTIR) analysis, and scanning electron microscopy (SEM). All the oxide systems exhibited sharp diffraction peaks in XRD patterns indicating the defined crystal structure. Strong absorption between 400–700 cm⁻¹ in FTIR indicated the formation of metal-oxide bonds in all HEO systems. WOR was investigated via cyclic voltammetry using HEOs as electrode platforms, 1M KOH as the basic medium, and 1M methanol (CH₃OH) as the facilitator. Voltammetric profiles for both equiatomic (EHEOs) and non-equiatomic (NEHEOs) were investigated, and NEHEOs exhibited the maximum current output for WOR. Moreover, methanol addition improved the current profiles, thus leading to the electrode utility in direct methanol fuel cells as a sequential increase in methanol concentration from 1M to 2M enhanced the OER current density from 61.4 to 94.3 mA cm⁻² using NEHEO. The NEHEOs comprising a greater percentage of Al, ([Al_0.35(Mg, Fe, Cu, Ni, Co)_0.65]₃O₄) displayed high WOR catalytic performance with the maximum diffusion coefficient, D° (10.90 cm² s⁻¹) and heterogeneous rate constant, k° (7.98 cm s⁻¹) values. These primary findings from the EC processes for WOR provide the foundation for their applications in high-energy devices. Conclusively, HEOs are proven as novel and efficient catalytic platforms for electrochemical water oxidation. Full article

Photocatalytic water splitting is one of the promising approaches to solving environmental problems and energy crises. However, the sluggish 4e⁻ transfer kinetics in water oxidation half-reaction restricts the 2e⁻ reduction efficiency in photocatalytic water splitting. Herein, cobalt vanadate-decorated polymeric carbon nitride (named CoVO/PCN) was constructed to mediate the carrier kinetic process in a photocatalytic water oxidation reaction (WOR). The photocatalysts were well-characterized by various physicochemical techniques such as XRD, FT-IR, TEM, and XPS. Under UV and visible light irradiation, the O₂ evolution rate of optimized 3 wt% CoVO/PCN reached 467 and 200 μmol h⁻¹ g⁻¹, which were about 6.5 and 5.9 times higher than that of PCN, respectively. Electrochemical tests and PL results reveal that the recombination of photogenerated carriers on PCN is effectively suppressed and the kinetics of WOR is significantly enhanced after CoVO introduction. This work highlights key features of the tuning carrier kinetics of PCN using charge-conducting materials, which should be the basis for the further development of photocatalytic O₂ reactions. Full article

Lignin is a unique renewable aromatic resource in nature. In the past decades, researchers have attempted to breakdown the linkage bonds in lignin to provide aromatic platform chemicals that used to come from the petrochemical industry. In recent years, electrochemical lignin degradation under mild conditions has drawn much attention from the scientific community owing to its potential to scale up and its environmental friendliness. Sustainable electrochemical degradation of lignin consumes less energy and usually requires mild conditions, but low degradation efficiency and insufficient product selectivity are still significant challenges. The method for lignin degradation by reactive oxygen species (ROS) generated through the water oxidation reaction (WOR) at the anode and oxygen reduction reaction (ORR) at the cathode are more attractive for sustainable electrochemical degradation. The present contribution aims to review advancements in electrochemical degradation of lignin in aqueous or non-aqueous supporting electrolytes, focusing on the regulation of ROS in situ generated on the electrode. Full article