Highly Crystalline Mesoporous Phosphotungstic Acid: A High-Performance Electrode Material for Energy-Storage Applications.

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 nitrides: synthesis, functionalization, and applications.

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 CO2, 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 CO2 activation.

Correction: Mesoporous carbon nitrides: synthesis, functionalization, and applications.

Correction for 'Mesoporous carbon nitrides: synthesis, functionalization, and applications' by Kripal S. Lakhi et al., Chem. Soc. Rev., 2017, DOI: .

Single-Step Synthesis of Mesoporous Carbon Nitride/Molybdenum Sulfide Nanohybrids for High-Performance Sodium-Ion Batteries.

Molybdenum disulfide (MoS2 ) is a promising candidate as a high-performing anode material for sodium-ion batteries (SIBs) due to its large interlayer spacing. However, it suffers from continued capacity fading. This problem could be overcome by hybridizing MoS2 with nanostructured carbon-based materials, but it is quite challenging. Herein, we demonstrate a single-step strategy for the preparation of MoS2 coupled with ordered mesoporous carbon nitride using a nanotemplating approach which involves the pyrolysis of phosphomolybdic acid hydrate (PMA), dithiooxamide (DTO) and 5-amino-1H-tetrazole (5-ATTZ) together in the porous channels of 3D mesoporous silica template. The sulfidation to MoS2 , polymerization to carbon nitride (CN) and their hybridization occur simultaneously within a mesoporous silica template during a calcination process. The CN/MoS2 hybrid prepared by this unique approach is highly pure and exhibits good crystallinity as well as delivers excellent performance for SIBs with specific capacities of 605 and 431 mAhg-1 at current densities of 100 and 1000 mAg-1 , respectively, for SIBs.

Carbon Nanoflakes and Nanotubes from Halloysite Nanoclays and their Superior Performance in CO2 Capture and Energy Storage.

Nanoporous carbon (HNC) with a flake and nanotubular morphology and a high specific surface area is prepared by using natural halloysite nanotubes (HNTs), a low-cost and naturally available clay material with a mixture of flaky and tubular morphology. A controlled pore-filling technique is used to selectively control the porosity, morphology, and the specific surface area of the HNC. Activated nanoporous carbon (AHNC) with a high specific surface area is also prepared by using HNT together with the activation process with zinc chloride (ZnCl2). HNC exhibits flakes and tubular morphologies, which offer a high specific surface area (837 m2/g). The specific surface area of AHNC is 1646 m2/g, 74 times greater than the specific surface area of pure HNT (22.5 m2/g). These data revealed that the single-step activation combined with the nanotemplating results in creating a huge impact on the specific surface area of the HNC. Both HNC and AHNC are employed as adsorbents for CO2 adsorption at different pressures and adsorption temperatures. The CO2 adsorption capacity of AHNC is 25.7 mmol/g at 0 °C, which is found to be significantly higher than that of activated carbon (AC), mesoporous carbon (CMK-3), mesoporous carbon nitride (MCN-1), and multiwalled carbon nanotube (MWCNT). AHNC is also tested as an electroactive material and demonstrates good supercapacitance, cyclic stability, and high capacitance retention. Specific capacitance of AHNC in the aqueous electrolyte is 197 F/g at 0.3 A/g, which is higher than that of AC, MWCNT, and CMK-3. The technique adopted for the preparation of both HNC and AHNC is quite unique and simple, has the potential to replace the existing highly expensive and sophisticated mesoporous silica-based nanotemplating strategy, and could also be applied for the fabrication of series of advanced nanostructures with unique functionalities.

Sulfur-Doped Mesoporous Carbon Nitride with an Ordered Porous Structure for Sodium-Ion Batteries.

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-C3N4 (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.