Mesoporous carbon nitrides (MCNs) with large surface areas and uniform pore diameters are unique semiconducting materials and exhibit highly versatile structural and excellent physicochemical properties, which promote their application in diverse fields such as metal free catalysis, photocatalytic water splitting, energy storage and conversion, gas adsorption, separation, and even sensing. These fascinating MCN materials can be obtained through the polymerization of different aromatic and/or aliphatic carbons and high nitrogen containing molecular precursors via hard and/or soft templating approaches. One of the unique characteristics of these materials is that they exhibit both semiconducting and basic properties, which make them excellent platforms for the photoelectrochemical conversion and sensing of molecules such as CO, and the selective sensing of toxic organic acids. The semiconducting features of these materials are finely controlled by varying the nitrogen content or local electronic structure of the MCNs. The incorporation of different functionalities including metal nanoparticles or organic molecules is further achieved in various ways to develop new electronic, semiconducting, catalytic, and energy harvesting materials. Dual functionalities including acidic and basic groups are also introduced in the wall structure of MCNs through simple UV-light irradiation, which offers enzyme-like properties in a single MCN system. In this review article, we summarize and highlight the existing literature covering every aspect of MCNs including their templating synthesis, modification and functionalization, and potential applications of these MCN materials with an overview of the key and relevant results. A special emphasis is given on the catalytic applications of MCNs including hydrogenation, oxidation, photocatalysis, and CO activation.
Sodium-ion batteries (SIBs) are an attractive prospect for energy storage in applications ranging from portable devices to large-scale energy storage grids. However, practical application of SIBs is hindered by their large size and concomitant sluggish kinetics. The hybridization strategy has been widely utilized as one of the effective ways to facilitate the enhancement of battery performance of the SIB electrodes. A combination of transition metal compounds and carbonaceous species is a popular hybrid that could offer a wide range of possibilities for fabricating high-performance and long-lasting SIB anodes. This Review specifically highlights hybridization strategies of transition metal compounds, including metal oxides, metal sulfides, metal phosphides, and metal carbides with different carbon species. Systematic discussion of the Na + -ion storage mechanism in these hybrids has been given special importance. The effect of the hybridization on SIB performance is comprehensively covered in this Review to gauge the full impact of these materials as promising SIB anodic materials for the future.
Heteropoly acids (HPAs) are unique materials with interesting properties, including high acidity and proton conductivity. However, their low specific surface area and high solubility in polar solvents make them unattractive for catalytic or energy applications. This obstacle can be overcome by creating nanoporosity within the HPA. We synthesized mesoporous phosphotungstic acid (mPTA) with a spherical morphology through the self‐assembly of phosphotungstic acid (PTA) with a polymeric surfactant as stabilized by KCl and hydrothermal treatment. The mPTA nanostructures had a surface area of 93 m2 g−1 and a pore size of 4 nm. Their high thermal stability (ca. 450 °C) and lack of solubility in ethylene carbonate/diethyl carbonate (EC/DEC) electrolyte are beneficial for lithium‐ion batteries (LIBs). Optimized mPTA showed a reversible capacity of 872 mAh g−1 at 0.1 A g−1 even after 100 cycles for LIBs, as attributed to a super‐reduced state of HPA and the storage of Li ions within the mesochannels of mPTA.
Mesoporous carbon nitride (MCN) with well-ordered porous structures is a promising anode material for secondary ion batteries owing to their unique physico-and electrochemical properties. However, the practical application of these MCNs in sodium-ion batteries (SIBs) is still limited because of their confined interlayer distance, which results in restricted accommodation of Na ions inside the lattice. Here, we report on the synthesis of highly ordered sulfur-doped MCN (S-MCN) through a hard template approach by employing dithiooxamide (DTO) as a single molecular precursor containing carbon, nitrogen, and sulfur elements. The interlayer distance of carbon nitride is significantly expanded upon the introduction of larger S ions on the MCN lattice, which enables high capability of Na ion accommodation. We also demonstrate through the first-principles density functional theory calculation that the present S-MCN is highly optimized not only for the chemical structure but also for uptaking abundant Na ions with high adsorption energy. The specific discharge capacity of SIBs appears to be remarkably enhanced for S-MCN (304.2 mA h g −1 ) compared to the nonporous S-CN (167.9 mA h g −1 ) and g-C 3 N 4 (5.4 mA h g −1 ), highlighting the pivotal roles of the highly ordered mesoporous structure and S-doping in enhancing the electrochemical functionality of carbon nitride as an anode material for SIBs.
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