Defective Metal Oxides: Lessons from CO2 RR and Applications in NOx RR.

Sluggish reaction kinetics and the undesired side reactions (hydrogen evolution reaction and self-reduction) are the main bottlenecks of electrochemical conversion reactions, such as the carbon dioxide and nitrate reduction reactions (CO2 RR and NO3 RR). To date, conventional strategies to overcome these challenges involve electronic structure modification and modulation of the charge-transfer behavior. Nonetheless, key aspects of surface modification, focused on boosting the intrinsic activity of active sites on the catalyst surface, are yet to be fully understood. Engingeering of oxygen vacancies (OVs) can tune surface/bulk electronic structure and improve surface active sites of electrocatalysts. The continuous breakthroughs and significant progress in the last decade position engineering of OVs as a potential technique for advancing electrocatalysis. Motivated by this, the state-of-the-art findings of the roles of OVs in both the CO2 RR and the NO3 RR are presented. The review starts with a description of approaches to constructing and techniques for characterizing OVs. This is followed by an overview of the mechanistic understanding of the CO2 RR and a detailed discussion on the roles of OVs in the CO2 RR. Then, insights into the NO3 RR mechanism and the potential of OVs on NO3 RR based on early findings are highlighted. Finally, the challenges in designing CO2 RR/NO3 RR electrocatalysts and perspectives in studying OV engineering are provided.

Superhydrophobic MS@CuO@SA sponge for oil/water separation with excellent durability and reusability.

We present a superhydrophobic material based on commercially melamine sponge (MS) with great durability, recyclability, and excellent sorption performance. The fabrication process of this sponge is facile without using toxic reagents or sophisticated equipment and therefore it is simple to scale up. The CuO layer utilized to give a rough surface of the substrate (MS) was successfully prepared in a commercial microwave to seed copper nucleuses in an alkaline medium. Stearic acid (SA) plays a role as the self-assembled monolayer on the surface of the sponge skeletons. Throughout this study, the properties of the modified sponge were fully characterized, and the changes in wettability were carefully examined. Water contact angle (WCA) measurements revealed the excellent superhydrophobicity of the material with high static WCA of 165.1° and low dynamic WCA of 8°. Furthermore, the as-prepared sponge demonstrated high efficiency in separation (over 99.0%) of different oils from water. Notably, several unique properties of as-modified material were found, consisting of ultrafast sorption capacities of up to 32-52 times of its own weight by using 80 mL of each oil, outstanding reusability with good sorption capacity even after 40 cycles. Even under various harsh environments, the novel materials proved its outstanding durability and ultrafast sorption capacity of oils. The durability, recyclability, and superhydrophobic properties of the novel superhydrophobic sponge provide it a solid basis for oil-water separation applications through an ultrafast sorption capacity of oils as well as quick recovery of the oil by easy squeezing process.

Solar-driven conversion of carbon dioxide over nanostructured metal-based catalysts in alternative approaches: Fundamental mechanisms and recent progress.

Solar-driven carbon dioxide (CO2) conversion has gained tremendous attention as a prominent strategy to simultaneously reduce the atmospheric CO2 concentration and convert solar energy into solar fuels in the form of chemical bonds. Numerous efforts have been devoted to diverse photo-driven processes for CO2 conversion, which utilized a multidisciplinary strategy. Among them, the architecture of nanostructured metal-based catalysts is emerging as an eminent solution for the design of catalysts of this field. In this work, we first provide fundamental mechanisms of photochemical, photoelectrochemical, photothermal, and photobio(electro)chemical CO2 reduction processes to achieve an in-deep understanding of vital aspects. Importantly, the recent progress in the catalyst design for each reaction system is discussed and highlighted. Based on these analyses, an overview of photo-driven CO2 reduction on metal-based catalysts for solar fuel production is also spotlighted. Finally, we analyze challenges and prospects for the strategic direction of developments in the field.