Contact-Electro-Catalysis for Direct Oxidation of Methane under Ambient Conditions.

The conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo- and electro- chemical processes, challenges such as complex catalyst design, costly oxidants, and unwanted byproducts remain. This study exploits the concept of contact-electro-catalysis, initiating chemical reactions through charge exchange at a solid-liquid interface, to report a novel process for directly converting methane under ambient conditions. Utilizing the electrification of commercially available Fluorinated Ethylene Propylene (FEP) with water under ultrasound, we demonstrate how this interaction promote the activation of methane and oxygen molecules. Our results show that the yield of HCHO and CH3OH can reach 467.5 and 151.2 µmol ⋅ gcat -1, respectively. We utilized electron paramagnetic resonance (EPR) to confirm the evolution of hydroxyl radicals (⋅OH) and superoxide radicals (⋅OOH). Isotope mass spectrometry (MS) was employed to analyze the elemental origin of CH3OH, which can be further oxidized to HCHO. Additionally, we conducted density functional theory (DFT) simulations to assess the reaction energies of FEP with H2O, O2, and CH4 under these conditions. The implications of this methodology, with its potential applicability to a wider array of gas-phase catalytic reactions, underscore a significant advance in catalysis.

Revealing the Photophysical and Photochemical Reaction Processes of Carprofen in Different Solutions via Ultrafast Femtosecond to Nanosecond Transient Absorption.

Carprofen (CP), one kind of a nonsteroidal anti-inflammatory drug, exhibits phototoxic side effects in physiology, while its phototoxic mechanism is ambiguous. To uncover CP's photophysical and photochemical reaction processes, femtosecond to nanosecond transient absorption spectroscopies were employed to directly detect excited states and transient intermediates of CP upon UV irradiation in pure acetonitrile (MeCN), MeCN/water 1:1, and acid/alkaline buffer solutions. The transient absorption data together with DFT calculations were integrated to elucidate mechanisms for photochemical reactions of CP in different solutions. The associated photophysical and photochemical reaction pathways are dependent on various solution environments. In a pure MeCN solvent, CP is excited to a singlet state (S1) and rapidly interacts with the solvent to proceed solvent rearrangement (SR). It then undergoes vibrational cooling (VC) and proceeds intersystem crossing (ISC) to produce the lowest triplet state (3CP). 3CP finally decays to the ground state. While in a MeCN/water 1:1 solution, deprotonated S1 of CP experiences SR and VC processes, and then it is promoted to a deprotonated triplet state (3CP-). 3CP- undergoes the parallel reactions: dechlorination to a phenyl radical (2CP-) and decarboxylation to a T1 anion (3CP-(de-CO2)). Finally, both intermediates produce the radical anion species 2CP-(de-CO2). In a pH = 7.4 (MeCN/PBS 1:1) solution, 3CP- can be converted into 2CP-(de-CO2) more quickly. Interestingly, we found that the dechlorination step can be promoted in an alkaline solution. Phenyl and chlorine radicals produced in an aqueous solution may be the root cause of the drug's harmful side effects on the human body. This may be useful to guide the design of related CP drugs with minimal phototoxicity in the pharmaceutical process.

Rapid synthesis of high-purity molybdenum carbide with controlled crystal phases.

The synthesis of phase-pure carbide nanomaterials is crucial for understanding their structure-performance relationships, and for advancing their application in catalysis. Molybdenum carbides, in particular, have garnered increasing interest due to their Pt-like surface electronic properties and high catalytic activity. Traditional methods for synthesizing molybdenum carbide are often lengthy and energy-intensive, leading to an uncontrolled phase, low purity, and excessive carbon coverage, which hinder their catalytic performance improvement. This work introduces a novel pulsed Joule heating (PJH) technique that overcomes these limitations, enabling the controlled synthesis of high-purity molybdenum carbides (ß-Mo2C, η-MoC1-x, and α-MoC1-x) within seconds by using MoOx/4-Cl-o-phenylenediamine as the hybrid precursor. The PJH method allows precise control over the diffusion of carbon species in the Mo-C system, resulting in a significantly improved phase purity of up to 96.89 wt%. Moreover, the electronic structure of platinum catalysts on molybdenum carbide was modulated through electron metal-support interaction (EMSI) between Pt and MoxC, and contributed to enhanced catalytic performance compared to carbon-supported Pt catalysts during the hydrogen evolution reaction. Overall, this work paves the way for efficient production of high-quality molybdenum carbide nanomaterials, and thus is expected to accelerate their industrial deployments in practical catalytic reactions.