Recent Advances in Functionalized Biomass-Derived Porous Carbons and their Composites for Hybrid Ion Capacitors.

Hybrid ion capacitors (HICs) have aroused extreme interest due to their combined characteristics of energy and power densities. The performance of HICs lies hidden in the electrode materials used for the construction of battery and supercapacitor components. The hunt is always on to locate the best material in terms of cost-effectiveness and overall optimized performance characteristics. Functionalized biomass-derived porous carbons (FBPCs) possess exquisite features including easy synthesis, wide availability, high surface area, large pore volume, tunable pore size, surface functional groups, a wide range of morphologies, and high thermal and chemical stability. FBPCs have found immense use as cathode, anode and dual electrode materials for HICs in the recent literature. The current review is designed around two main concepts which include the synthesis and properties of FBPCs followed by their utilization in various types of HICs. Among monovalent HICs, lithium, sodium, and potassium, are given comprehensive attention, whereas zinc is the only multivalent HIC that is focused upon due to corresponding literature availability. Special attention is also provided to the critical factors that govern the performance of HICs. The review concludes by providing feasible directions for future research in various aspects of FBPCs and their utilization in HICs.

Multiple Heteroatom Doped Nanoporous Biocarbon for Supercapacitor and Zinc-ion Capacitor.

The use of nanoporous carbon for energy storage has seen a significant rise due to its exciting properties such as high surface area, hierarchical porosity and exceptional electrochemical properties. These unique advantages of exceptional surface and electrochemical properties of these porous carbon nanostructures can be coupled with the individual doping of heteroatoms such as S, N, O, and B for achieving high energy storage capacity and stability. Herein, we integrated the synthesis of carbon nitride (CN) and borocarbonitride (BCN) with solid state activation for introducing multiple heteroatoms (B, N, O, and S) onto the nanoporous carbon frameworks. The produced materials exhibit abundance of micro and mesoporosity, a high surface area of 2909 m2 g-1, and a pore volume of 0.87 cm3 g-1. Also, it offers an exceptional capacitance of 233.5 F g-1 at 0.5 A g-1 with 3 M KOH as electrolyte. Further, the optimised material was explored as cathode in zinc ion capacitor which delivers an energy and power density of 50.4 Wh kg-1 and 400 W kg-1 respectively in addition to high cyclability. Studies on the formation of the intermediate phases during charging/discharging of the cell through ex situ characterization result in some useful insights into the stability of ZIC.

Recent advances in food waste-derived nanoporous carbon for energy storage.

Affordable and environmentally friendly electrochemically active raw energy storage materials are in high demand to switch to mass-scale renewable energy. One particularly promising avenue is the feasibility of utilizing food waste-derived nanoporous carbon. This material holds significance due to its widespread availability, affordability, ease of processing, and, notably, its cost-free nature. Over the years, various strategies have been developed to convert different food wastes into nanoporous carbon materials with enhanced electrochemical properties. The electrochemical performance of these materials is influenced by both intrinsic factors, such as the composition of elements derived from the original food sources and recipes, and extrinsic factors, including the conditions during pyrolysis and activation. While current efforts are dedicated to optimizing process parameters to achieve superior performance in electrochemical energy storage devices, it is timely to take stock of the current state of research in this emerging field. This review provides a comprehensive overview of recent developments in the fabrication and surface characterisation of porous carbons from different food wastes. A special focus is given on the applications of these food waste derived porous carbons for energy storage applications including batteries and supercapacitors.

This review compiles very recent literature on the synthesis of porous carbon from food waste biomass and their efficient utilisation as electrode material for energy storage applications in supercapacitor devices.

The Rise of Xene Hybrids.

Xenes, mono-elemental atomic sheets, exhibit Dirac/Dirac-like quantum behavior. When interfaced with other 2D materials such as boron nitride, transition metal dichalcogenides, and metal carbides/nitrides/carbonitrides, it enables them with unique physicochemical properties, including structural stability, desirable bandgap, efficient charge carrier injection, flexibility/breaking stress, thermal conductivity, chemical reactivity, catalytic efficiency, molecular adsorption, and wettability. For example, BN acts as an anti-oxidative shield, MoS2 injects electrons upon laser excitation, and MXene provides mechanical flexibility. Beyond precise compositional modulations, stacking sequences, and inter-layer coupling controlled by parameters, achieving scalability and reproducibility in hybridization is crucial for implementing these quantum materials in consumer applications. However, realizing the full potential of these hybrid materials faces challenges such as air gaps, uneven interfaces, and the formation of defects and functional groups. Advanced synthesis techniques, a deep understanding of quantum behaviors, precise control over interfacial interactions, and awareness of cross-correlations among these factors are essential. Xene-based hybrids show immense promise for groundbreaking applications in quantum computing, flexible electronics, energy storage, and catalysis. In this timely perspective, recent discoveries of novel Xenes and their hybrids are highlighted, emphasizing correlations among synthetic parameters, structure, properties, and applications. It is anticipated that these insights will revolutionize diverse industries and technologies.

Nanohybrids of BCN-Fe1-xS for Sodium and Lithium Hybrid Ion Capacitors.

Hybrid ion capacitors (HIC) are receiving a lot of attention due to their potential to achieve high energy and power densities, but they remain insufficient. It is imperative to explore outstanding and environmentally benign electrode materials to achieve high-performing HIC systems. Here, a unique boron carbon nitride (BCN)-based HIC system that comprises a microporous BCN structure and Fe1-xS nanoparticle incorporated BCN nanosheets (BNF) as cathode and anode, respectively is reported. The BNF is prepared through a facile one-pot calcination process using dithiooxamide (DTO), boric acid, and iron source. In situ, crystal growth of Fe1-xS facilitates the formation of BCN structure through the creation of holes/defects in the polymeric structure. The first principle density functional (DFT) theory simulations demonstrate the structural and electronic properties of the hybrid of BCN and Fe1-xS as compelling anode materials for HIC applications. The DFT calculations reveal that both BCN and BNF structures have excellent metallic characters with Li+ storage capacities of 128.4 and 1021.38 mAh g-1 respectively. These findings are confirmed experimentally where the BCN-based HIC system delivers exceptional energy and power densities of 267.5 Wh kg-1/749.5 W kg-1 toward Li+ storage, which outweighs previous HIC performances and demonstrates favorable performance for Li+ and Na+ storages.

Incorporation of Bimetallic Sulfide with Carbon Nitride for Advanced Na-Ion Batteries.

Sodium-ion batteries (SIBs) have received tremendous attention owing to their low cost, high working voltages, and energy density. However, the design and development of highly efficient SIBs represent a great challenge. Here, a unique and reliable approach is reported to prepare carbon nitride (CN) hybridized with nickel iron sulfide (NFCN) using simple reaction between Ni-Fe layered double hydroxide and dithiooxamide. The characterization results demonstrate that the hybridization with optimal amount of CN induces local distortion in the crystal structure of the hybrid, which would benefit SIB performance. Systematic electrochemical studies with a half-cell configuration show that the present hybrid structure exhibits a promising reversible specific capacity of 348 mAh g-1 at 0.1 A g-1 after 100 cycles with good rate capability. Simulation result reveals that the iron atoms in nickel iron sulfide act as a primary active site to accommodate Na+ ions. At last, with a full cell configuration using NFCN and Na3 V2 (PO4 )2 O2 F as the anode and cathode, respectively, the specific capacity appears to be ≈95 mAh g-1 after 50 cycles at 0.1 A g-1 condition. This excellent performance of these hybrids can be attributed to the synergistic effect of the incorporated CN species and the high conductivity of nickel-iron sulfide.

Influence of PEGylation on WS2 Nanosheets and Its Application in Photothermal Therapy.

Photothermal therapy (PTT) is an alternative cancer therapy with minimal side effects and higher efficiency and selectivity. In this study, WS2 nanosheets were developed by ultrasonic exfoliation with different ratios of polyethylene glycol (PEG), and their effects on physicochemical properties were studied. The utilization of PEG during sonication significantly influenced the size and thickness of the resulting WS2 nanosheet layers, which was confirmed through scanning electron microscopy, atomic force microscopy, and dynamic light scattering analyses. PEG functionalization also improved the dispersibility of WS2 in aqueous solution by making its surface hydrophilic, which resulted in better biocompatibility. The intrinsic near-infrared absorbance of the nanosheets positions them as valuable agents for PTT. The study further explores the efficacy of these nanosheets as photothermal agents in the ablation of MDAMB-231 breast cancer cells. Although the use of PEG to demonstrate exfoliation and biocompatibility for WS2 has been reported previously, the effect of PEGylation on various physicochemical properties has not been studied in-depth until now. This study paves the way for the use of highly versatile PEG across a range of 2D material systems.

Multifunctional carbon nitride nanoarchitectures for catalysis.

Catalysis is at the heart of modern-day chemical and pharmaceutical industries, and there is an urgent demand to develop metal-free, high surface area, and efficient catalysts in a scalable, reproducible and economic manner. Amongst the ever-expanding two-dimensional materials family, carbon nitride (CN) has emerged as the most researched material for catalytic applications due to its unique molecular structure with tunable visible range band gap, surface defects, basic sites, and nitrogen functionalities. These properties also endow it with anchoring capability with a large number of catalytically active sites and provide opportunities for doping, hybridization, sensitization, etc. To make considerable progress in the use of CN as a highly effective catalyst for various applications, it is critical to have an in-depth understanding of its synthesis, structure and surface sites. The present review provides an overview of the recent advances in synthetic approaches of CN, its physicochemical properties, and band gap engineering, with a focus on its exclusive usage in a variety of catalytic reactions, including hydrogen evolution reactions, overall water splitting, water oxidation, CO2 reduction, nitrogen reduction reactions, pollutant degradation, and organocatalysis. While the structural design and band gap engineering of catalysts are elaborated, the surface chemistry is dealt with in detail to demonstrate efficient catalytic performances. Burning challenges in catalytic design and future outlook are elucidated.

Preclinical safety assessment of red emissive gold nanocluster conjugated crumpled MXene nanosheets: a dynamic duo for image-guided photothermal therapy.

Red emissive gold nanoclusters have potential as biological fluorescent probes, but lack sufficient light-to-heat conversion efficiency for photothermal therapy (PTT). MXene nanomaterials, on the other hand, have shown promise in PTT due to their strong near-infrared absorption abilities, but their instability caused by restacking of the sheets can decrease their available surface area. One approach to address this issue is to design sheets with wrinkles or folds. However, the crumpled or 3D MXene materials reported in the literature are actually aggregates of multiple nanosheets rather than a single sheet that is folded. In this study, a modified method for crumpling a single MXene sheet and further conjugating it with red emissive gold nanoclusters and folic acid was developed. A detailed in vitro toxicity study was performed in various cell lines and cellular uptake in cancer cells was studied using AFM to understand its interaction at the nano-bio interface. The material also demonstrated excellent utility as a bioimaging and PTT agent in vitro, with its high fluorescence allowing bioimaging at a lower concentration of 12 µg mL-1 and a photothermal conversion efficiency of 43.51%. In vitro analyses of the cell death mechanisms induced by PTT were conducted through studies of apoptosis, cell proliferation, and ROS production. In vivo acute toxicity tests were conducted on male and female Wistar rats through oral and intravenous administration (20 mg kg-1 dose), and toxicity was evaluated using various measures including body weight, hematology, serum biochemistry, and H&E staining. The findings from these studies suggest that the MXene gold nanoconjugate could be useful in a range of biomedical applications, with no observed toxicity following either oral or intravenous administration.

Synthesis and degradation mechanism of renally excretable gold core-shell nanoparticles for combined photothermal and photodynamic therapy.

Photothermal therapy (PTT) has emerged as a very potent therapeutic approach in the treatment of tumors. Gold nanoparticles have gained considerable scientific interest as a photosensitizer due to their absorbance in the near-infrared regions. However, their biodegradation and excretion from the body is a challenge. Various biodegradable systems consisting of liposomes and polymers have been synthesized, but their precise manufacturing and decomposition mechanisms have not yet been explored. Using zein nanoparticles as a template, we have fabricated a glutathione-functionalized gold core shell type of formulation. The scalability of the one-step seedless gold coating process is also reported. The synthesis procedure of these tunable nanoparticles is understood with TEM. The thermal degradation of the material under the physiological conditions is thoroughly examined using UV and TEM. In vitro PTT effectiveness on breast cancer cells is assessed after an extensive in vitro toxicity research. The mechanism of cell death is studied using ROS and cell cycle analysis. The material exhibited good efficacy as a PTT agent in mice and showed non-toxicity up to 14 days. The renal clearance study of the material in mice shows its disintegration into renal clearable minute gold seeds. All the findings suggest biodegradable glutathione-functionalized gold core-shell nanoparticles as potential photothermal cancer treatment agents.

Hydrothermal-Assisted Synthesis and Stability of Multifunctional MXene Nanobipyramids: Structural, Chemical, and Optical Evolution.

Recent advancements in two-dimensional materials have brought MXene (Ti3C2) into attention due to its exciting properties as a very promising material for various applications. In this work, we report a novel Ti3C2 nanobipyramid (Ti3C2 NB) structure obtained through a three-step process involving exfoliation, delamination, and subsequent hydrothermal treatment. The morphological and textural properties at each step of synthesis were studied using an array of experimental techniques such as transmission electron microscopy, scanning electron microscopy, and atomic force microscopy and the chemical properties through X-ray diffraction, Raman, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analysis. The Ti3C2 NBs exhibit fluorescence with an excitation-dependent emission. Further, the effect of temperature and pH on the fluorescence was also investigated, which opens up its scope in bioanalytical applications. Ti3C2 NBs showed a ∼43% increase in photoluminescence intensity from pH 3 to 11 while a ∼38% increase with the temperature from 20 to 80 °C. Usually, MXenes are highly susceptible to oxidation, but the Ti3C2 NBs were found to be chemically and optically stable even after 30 days. Bestowed with good hydrophilicity, the material exhibited high biocompatibility on the mouse fibroblast cell line L929. Further, L929 cells also showed good cellular adhesion on a Ti3C2 NB-modified glass substrate. These properties pave a way for its multifunctional ability as a sensor for pH and temperature as well as bioimaging.

Influence of Surface States on the Optical and Cellular Property of Thermally Stable Red Emissive Graphitic Carbon Dots.

Red emissive carbon dots from sucrose (SCD) were synthesized using a facile, isolation-free, one-pot method via microwave pyrolysis. Various passivation agents were used along with sucrose, and a relative change in the chemical and optical properties of the carbon dots was investigated. A detailed systematic study of the effect of various passivations, different solvents, pHs, and temperatures on optical properties was carried out. The influence of excitation wavelength and passivation on photoluminescence (PL) is discussed considering the functional groups associated with the passivating agents. The effect of different solvents on dispersibility and PL behavior has been understood in terms of the dielectric properties of the solvents. The decrease in PL intensity of SCD from pH 3 to 11 facilitates pH sensing. The PL of SCD was found to be essentially stable between the temperature range of 20 and 80 °C. Additionally, the effects of physicochemical properties with respect to passivation, such as charge and surface chemistry in determining the cellular uptake and cytotoxicity, are also addressed. Aside from sensors, the potential of SCDs as bioimaging agents has also been studied for mammalian cells. Moreover, SCD exhibits excellent PL stability investigated under different storage conditions for 15 days.

Emerging trends in porous materials for CO2 capture and conversion.

The presence of an excessive concentration of CO2 in the atmosphere needs to be curbed with suitable measures including the reduction of CO2 emissions at stationary point sources such as power plants through carbon capture technologies and subsequent conversion of the captured CO2 into non-polluting clean fuels/chemicals using photo and/or electrocatalytic pathways. Porous materials have attracted much attention for carbon capture and in the recent past; they have witnessed significant advancements in their design and implementation for CO2 capture and conversion. In this context, the emerging trends in major porous adsorbents such as MOFs, zeolites, POPs, porous carbons, and mesoporous materials for CO2 capture and conversion are discussed. Their surface texture and chemistry, and the influence of various other features on their efficiency, selectivity, and recyclability for CO2 capture and conversion are explained and compared thoroughly. The scientific and technical advances on the material structure versus CO2 capture and conversion provide deep insights into designing effective porous materials. The review concludes with a summary, which compiles the key challenges in the field, current trends and critical challenges in the development of porous materials, and future research directions combined with possible solutions for realising the deployment of porous materials in CO2 capture and conversion.

Preparation of graphene oxide-graphene quantum dots hybrid and its application in cancer theranostics.

Currently, an enormous amount of cancer research based on two-dimensional nano-graphene oxide (GO), as well as zero-dimensional graphene quantum dots (GQDs), is being carried out in the fields of therapeutics and diagnostics. However, the exploration of their hybrid "functional" nanomaterials in the theranostic system is still rare. In the current study, a stable complex of GO and GQDs was formed by an electrostatic layer-by-layer assembly via a polyethylene imine bridge (GO-PEI-GQDs). Furthermore, we compared separate mono-equivalents of the GO-PEI-GQDs complex - GO and GQDs, in terms of cell imaging (diagnostics), photothermal, and oxidative stress response in breast cancer cells (MDA-MB-231). GO-PEI-GQDs showed an excellent photothermal response (44-49 °C) upon 808 nm laser (0.5 W cm-2) exposure for 5 min at a concentration up to 50 µg/mL. We report new synergistic properties of GO-PEI-GQDs such as stable fluorescence imaging and enhanced photothermal and cytotoxic activities on cancer cells. Composite materials made up of GO and GQDs combining diverse properties help to study 2D-0D heterosystems and improve specific therapeutic systems in theranostics.

Plasmonic carbon nanohybrids for repetitive and highly localized photothermal cancer therapy.

Integrating metallic and non-metallic platform for cancer nanomedicine is a challenging task and bringing together multi-functionality of two interfaces is a major hurdle for biomaterial design. Herein, NIR light responsive advanced hybrid plasmonic carbon nanomaterials are synthesized, and their properties toward repetitive and highly localized photothermal cancer therapy are well understood. Graphene oxide nanosheets having thickness of ∼2 nm are synthesized using modified Hummers' method, thereafter functionalized with biodegradable NIR light responsive gold deposited plasmonic polylactic-co-glycolic acid nanoshells (AuPLGA NS, tuned at 808 nm) and NIR dye (IR780) to examine their repetitive and localized therapeutic efficacy as well resulting side effects to nearby healthy cells. It is observed that AuPLGA NS decorated graphene oxide nanosheets (GO-AuPLGA) and IR780 loaded graphene oxide nanosheets (GO-IR780) are capable in standalone complete photothermal ablation of cancer cells within 4 min. of 808 nm NIR laser irradiation and also without the aid of any anticancer drugs. However, GO-AuPLGA having the potential for repetitive photothermal treatment of a big tumor, ablate the cancer cells in highly localized fashion, without having side effects on neighboring healthy cells.