Exploring Oxygen Vacancy Effect in 1D Structural SnIP for CO2 Electro-Reduction to Formate.

1D nanostructures exhibit a large surface area and a short network distance, facilitating electron and ion transport. In this study, a 1D van der Waals material, tin iodide phosphide (SnIP), is synthesized and used as an electrocatalyst for the conversion of CO2 to formate. The electrochemical treatment of SnIP reconstructs it into a web-like structure, dissolves the I and P components, and increases the number of oxygen vacancies. The resulting oxygen vacancies promote the activity of the CO2 reduction reaction (CO2RR), increasing the local pH of the electrode surface and maintaining the oxidative metal site of the catalyst despite the electrochemically reducing environment. This strategy, which stabilizes the oxidation state of the catalyst, also helps to improve the durability of CO2RR. In practice, 1D structured SnIP catalyst exhibits outstanding performance with >92% formate faradaic efficiency (FEformate) at 300 mA cm-2, a maximum partial current density for formate of 343 mA cm-2, and excellent long-term stability (>100 h at 100 mA cm-2 with >86% FEformate). This study introduced a method to easily generate oxygen vacancies on the catalyst surface by utilizing 1D materials and a strategy to improve the durability of CO2RR by stabilizing the oxidation state of the catalyst.

Electro-assisted methane oxidation to formic acid via in-situ cathodically generated H2O2 under ambient conditions.

Direct partial oxidation of methane to liquid oxygenates has been regarded as a potential route to valorize methane. However, CH4 activation usually requires a high temperature and pressure, which lowers the feasibility of the reaction. Here, we propose an electro-assisted approach for the partial oxidation of methane, using in-situ cathodically generated reactive oxygen species, at ambient temperature and pressure. Upon using acid-treated carbon as the electrocatalyst, the electro-assisted system enables the partial oxidation of methane in an acidic electrolyte to produce oxygenated liquid products. We also demonstrate a high production rate of oxygenates (18.9 µmol h-1) with selective HCOOH production. Mechanistic analysis reveals that reactive oxygen species such as ∙OH and ∙OOH radicals are produced and activate CH4 and CH3OH. In addition, unstable CH3OOH generated from methane partial oxidation can be additionally reduced to CH3OH on the cathode, and so-produced CH3OH is further oxidized to HCOOH, allowing selective methane partial oxidation.

Tailoring the Nanoporosity and Photoactivity of Metal-Organic Frameworks With Rigid Dye Modulators for Toluene Purification.

Facile synthesis of hierarchically porous metal-organic frameworks (MOFs) with adjustable porosity and high crystallinity attracts great attention yet remains challenging. Herein, a micromolar amount of dye-based modulator (Rhodamine B (RhB)) is employed to easily and controllably tailor the pore size of a Ti-based metal-organic framework (MIL-125-NH2 ). The RhB used in this method is easily removed by washing or photodegradation, avoiding secondary posttreatment. It is demonstrated that the carboxyl functional group and the steric effects of RhB are indispensable for enlarging the pore size of the MIL-125-NH2 . The resulting hierarchically porous MIL-125-NH2 (RH-MIL-125-NH2 ) exhibits optimized adsorption and photocatalytic activity because the newly formed mesopore with defects concurrently facilitates mass transport of guest molecules (toluene) and photogenerated charge separation. This work offers a meaningful basis for the construction of hierarchically porous MOFs and demonstrates the superiority of the hierarchical pore structure for adsorption and heterogeneous catalysis.

Catalytic Oxidation of Methane to Oxygenated Products: Recent Advancements and Prospects for Electrocatalytic and Photocatalytic Conversion at Low Temperatures.

Methane is an important fossil fuel and widely available on the earth's crust. It is a greenhouse gas that has more severe warming effect than CO2. Unfortunately, the emission of methane into the atmosphere has long been ignored and considered as a trivial matter. Therefore, emphatic effort must be put into decreasing the concentration of methane in the atmosphere of the earth. At the same time, the conversion of less valuable methane into value-added chemicals is of significant importance in the chemical and pharmaceutical industries. Although, the transformation of methane to valuable chemicals and fuels is considered the "holy grail," the low intrinsic reactivity of its C-H bonds is still a major challenge. This review discusses the advancements in the electrocatalytic and photocatalytic oxidation of methane at low temperatures with products containing oxygen atom(s). Additionally, the future research direction is noted that may be adopted for methane oxidation via electrocatalysis and photocatalysis at low temperatures.