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1.
Small ; : e2404337, 2024 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-38958089

RESUMO

Monoelemental atomic sheets (Xenes) and other 2D materials offer record electronic mobility, high thermal conductivity, excellent Young's moduli, optical transparency, and flexural capability, revolutionizing ultrasensitive devices and enhancing performance. The ideal synthesis of these quantum materials should be facile, fast, scalable, reproducible, and green. Microwave expansion followed by cryoquenching (MECQ) leverages thermal stress in graphite to produce high-purity graphene within minutes. MECQ synthesis of graphene is reported at 640 and 800 W for 10 min, followed by liquid nitrogen quenching for 5 and 90 min of sonication. Microscopic and spectroscopic analyses confirmed the chemical identity and phase purity of monolayers and few-layered graphene sheets (200-12 µm). Higher microwave power yields thinner layers with enhanced purity. Molecular dynamics simulations and DFT calculations support the exfoliation under these conditions. Electrostatic droplet switching is demonstrated using MECQ-synthesized graphene, observing electrorolling of a mercury droplet on a BN/graphene interface at voltages above 20 V. This technique can inspire the synthesis of other 2D materials with high purity and enable new applications.

2.
ChemSusChem ; : e202400999, 2024 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-38973030

RESUMO

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 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 3M 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.

3.
Adv Mater ; : e2403881, 2024 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-38899836

RESUMO

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.

4.
Sci Technol Adv Mater ; 25(1): 2357062, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38835629

RESUMO

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.

6.
Small ; : e2307610, 2024 Feb 11.
Artigo em Inglês | MEDLINE | ID: mdl-38342695

RESUMO

Borophene, a 2D material exhibiting unique crystallographic phases like the anisotropic atomic lattices of ß12 and X3 phases, has attracted considerable attention due to its intriguing Dirac nature and metallic attributes. Despite surpassing graphene in electronic mobility, borophene's potential in energy storage and catalysis remains untapped due to its inherent electrochemical and catalytic limitations. Elemental doping emerges as a promising strategy to introduce charge carriers, enabling localized electrochemical and catalytic functionalities. However, effective doping of borophene has been a complex and underexplored challenge. Here, an innovative, one-pot microwave-assisted doping method, tailored for the ß12 phase of borophene is introduced. By subjecting dispersed ß12 borophene in dimethylformamide to controlled microwave exposure with sulfur powder and FeCl3 as doping precursors, S- and Fe doping in borophene can be controlled. Employing advanced techniques including high-resolution transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, confirm successful sulfur and iron dopant incorporation onto ß12 borophene is confirmed, achieving doping levels of up to 11 % and 13 %, respectively. Remarkably, S- and Fe-doped borophene exhibit exceptional supercapacitive behavior, with specific capacitances of 202 and 120 F g-1 , respectively, at a moderate current density of 0.25 A g-1 .

7.
Small ; 20(25): e2311945, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38196051

RESUMO

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.

8.
Small ; 20(13): e2308084, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38243883

RESUMO

Ammonia is an essential commodity in the food and chemical industry. Despite the energy-intensive nature, the Haber-Bosch process is the only player in ammonia production at large scales. Developing other strategies is highly desirable, as sustainable and decentralized ammonia production is crucial. Electrochemical ammonia production by directly reducing nitrogen and nitrogen-based moieties powered by renewable energy sources holds great potential. However, low ammonia production and selectivity rates hamper its utilization as a large-scale ammonia production process. Creating effective and selective catalysts for the electrochemical generation of ammonia is critical for long-term nitrogen fixation. Single-atom alloys (SAAs) have become a new class of materials with distinctive features that may be able to solve some of the problems with conventional heterogeneous catalysts. The design and optimization of SAAs for electrochemical ammonia generation have recently been significantly advanced. This comprehensive review discusses these advancements from theoretical and experimental research perspectives, offering a fundamental understanding of the development of SAAs for ammonia production.

9.
Nanoscale ; 16(9): 4352-4377, 2024 Feb 29.
Artigo em Inglês | MEDLINE | ID: mdl-38275275

RESUMO

Semiconductor-based photocatalysis has attracted significant interest due to its capacity to directly exploit solar energy and generate solar fuels, including water splitting, CO2 reduction, pollutant degradation, and bacterial inactivation. However, achieving the maximum efficiency in photocatalytic processes remains a challenge owing to the speedy recombination of electron-hole pairs and the limited use of light. Therefore, significant endeavours have been devoted to addressing these issues. Specifically, well-designed heterojunction photocatalysts have been demonstrated to exhibit enhanced photocatalytic activity through the physical distancing of electron-hole pairs generated during the photocatalytic process. In this review, we provide a systematic discussion ranging from fundamental mechanisms to material strategies, focusing on TiO2-based heterojunction photocatalysts. Current efforts are focused on developing heterojunction photocatalysts based on TiO2 for a variety of photocatalytic applications, and these projects are explained and assessed. Finally, we offer a concise summary of the main insights and challenges in the utilization of TiO2-based heterojunction photocatalysts for photocatalysis. We expect that this review will serve as a valuable resource to improve the efficiency of TiO2-based heterojunctions for energy generation and environmental remediation.

10.
Adv Mater ; 36(2): e2306895, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37699553

RESUMO

Fast production of hydrogen and oxygen in large amounts at an economic rate is the need of the hour to cater to the needs of the most awaited hydrogen energy, a futuristic renewable energy solution. Production of hydrogen through simple water splitting via visible light photocatalytic approach using sunlight is considered as one of the most promising and sustainable approaches for generating clean fuels. For this purpose, a variety of catalytic techniques and novel catalysts have been investigated. Among these catalysts, carbon nitride is presently deemed as one of the best candidates for the visible light photocatalysis due to its unique molecular structure and adequate visible-range bandgap. Its bandgap can be further engineered by structural and morphological manipulation or by doping/hybridization. Among numerous synthetic approaches for carbon nitrides, supramolecular self-assembly is one of the recently developed elegant bottom-up strategies as it is bio-inspired and provides a facile and eco-friendly route to synthesize high surface area carbon nitride with superior morphological features and other semiconducting and catalytic properties. The current review article broadly covers supramolecular self-assembly synthesis of carbon nitride nanostructures and their photocatalytic water-splitting applications and provides a comprehensive outlook on future directions.

11.
Sci Total Environ ; 914: 169585, 2024 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-38157897

RESUMO

Biochar can be used for multifunctional applications including the improvement of soil health and carbon storage, remediation of contaminated soil and water resources, mitigation of greenhouse gas emissions and odorous compounds, and feed supplementation to improve animal health. A healthy soil preserves microbial biodiversity that is effective in supressing plant pathogens and pests, recycling nutrients for plant growth, promoting positive symbiotic associations with plant roots, improving soil structure to supply water and nutrients, and ultimately enhancing soil productivity and plant growth. As a soil amendment, biochar assures soil biological health through different processes. First, biochar supports habitats for microorganisms due to its porous nature and by promoting the formation of stable soil micro-aggregates. Biochar also serves as a carbon and nutrient source. Biochar alters soil physical and chemical properties, creating optimum soil conditions for microbial diversity. Biochar can also immobilize soil pollutants and reduce their bioavailability that would otherwise inhibit microbial growth. However, depending on the pyrolysis settings and feedstock resources, biochar can be comprised of contaminants including polycyclic aromatic hydrocarbons and potentially toxic elements that can inhibit microbial activity, thereby impacting soil health.


Assuntos
Poluentes do Solo , Solo , Solo/química , Carvão Vegetal/química , Carbono , Poluição Ambiental , Poluentes do Solo/química
12.
Small ; : e2304587, 2023 Dec 10.
Artigo em Inglês | MEDLINE | ID: mdl-38072818

RESUMO

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.

13.
Adv Sci (Weinh) ; 10(36): e2304289, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37908147

RESUMO

As it is now established that global warming and climate change are a reality, international investments are pouring in and rightfully so for climate change mitigation. Carbon capture and separation (CCS) is therefore gaining paramount importance as it is considered one of the powerful solutions for global warming. Sorption on porous materials is a promising alternative to traditional carbon dioxide (CO2 ) capture technologies. Owing to their sustainable availability, economic viability, and important recyclability, natural products-derived porous carbons have emerged as favorable and competitive materials for CO2 sorption. Furthermore, the fabrication of high-quality value-added functional porous carbon-based materials using renewable precursors and waste materials is an environmentally friendly approach. This review provides crucial insights and analyses to enhance the understanding of the application of porous carbons in CO2 capture. Various methods for the synthesis of porous carbon, their structural characterization, and parameters that influence their sorption properties are discussed. The review also delves into the utilization of molecular dynamics (MD), Monte Carlo (MC), density functional theory (DFT), and machine learning techniques for simulating adsorption and validating experimental results. Lastly, the review provides future outlook and research directions for progressing the use of natural products-derived porous carbons for CO2 capture.

14.
Chem Soc Rev ; 52(21): 7602-7664, 2023 Oct 30.
Artigo em Inglês | MEDLINE | ID: mdl-37830178

RESUMO

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.

15.
Chemistry ; 29(69): e202302723, 2023 Dec 11.
Artigo em Inglês | MEDLINE | ID: mdl-37673789

RESUMO

Designing unique nanomaterials for the selective sensing of biomolecules is of significant interest in the field of nanobiotechnology. In this work, we demonstrated the synthesis of ordered Cu nanoparticle-functionalised mesoporous C3 N5 that has unique peroxidase-like nanozymatic activity for the ultrasensitive and selective detection of glucose and glutathione. A nano hard-templating technique together with the in-situ polymerisation and self-assembly of Cu and high N-containing CN precursor was adopted to introduce mesoporosity as well as high N and Cu content in mesoporous C3 N5 . Due to the ordered structure and highly dispersed Cu in the mesoporous C3 N5 , a large enhancement of the peroxidase mimetic activity in the oxidation of a redox dye in the presence of hydrogen peroxide could be obtained. Additionally, the optimised Cu-functionalised mesoporous C3 N5 exhibited excellent sensitivity to glutathione with a low detection limit of 2.0 ppm. The strong peroxidase activity of the Cu-functionalised mesoporous C3 N5 was also effectively used for the sensing of glucose with a detection limit of 0.4 mM through glucose oxidation with glucose oxidase. This unique Cu-functionalised mesoporous C3 N5 has the potential for detecting various molecules in the environment as well as for next-generation glucose and glutathione diagnostic devices.


Assuntos
Cobre , Nanopartículas , Cobre/química , Glucose/química , Nanopartículas/química , Peróxido de Hidrogênio/química , Peroxidases , Glutationa , Colorimetria
16.
Small ; : e2304369, 2023 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-37715070

RESUMO

High-magnetization materials play crucial roles in various applications. However, the past few decades have witnessed a stagnation in the discovery of new materials with high magnetization. In this work, Ni/NiO nanocomposites are fabricated by depositing Ni and NiO thin layers alternately, followed by annealing at specific temperatures. Both the as-deposited samples and those annealed at 373 K exhibit low magnetization. However, the samples annealed at 473 K exhibit a significantly enhanced saturation magnetization exceeding 607 emu cm-3 at room temperature, surpassing that of pure Ni (480 emu cm-3 ). Material characterizations indicate that the composite comprises NiO nanoclusters of size 1-2 nm embedded in the Ni matrix. This nanoclustered NiO is primarily responsible for the high magnetization, as confirmed by density functional theory calculations. The calculations also indicate that the NiO clusters are ferromagnetically coupled with Ni, resulting in enhanced magnetization. This work demonstrates a new route toward developing artificial high-magnetization materials using the high magnetic moments of nanoclustered antiferromagnetic materials.

17.
Small ; : e2303269, 2023 Jun 29.
Artigo em Inglês | MEDLINE | ID: mdl-37386787

RESUMO

In this work, the synthesis of core-shell ordered mesoporous silica nanoparticles (CSMS) with tunable particle size and shape through a dual surfactant-assisted approach is demonstrated. By varying the synthesis conditions, including the type of the solvent and the concentration of the surfactant, monodispersed and ordered mesoporous silica nanoparticles with tunable particle size (140-600 nm) and morphologies (hexagonal prism (HP), oblong, spherical, and hollow-core) can be realized. Comparative studies of the Cabazitaxel (CBZ)-loaded HP and spherical-shaped CSMS are conducted to evaluate their drug delivery efficiency to PC3 (prostate cancer) cell lines. These nanoparticles showed good biocompatibility and displayed a faster drug release at acidic pH than at basic pH. The cellular uptake of CSMS measured using confocal microscopy, flow cytometry, microplate reader, and ICP-MS (inductively coupled plasma mass spectrometry) techniques in PC3 cell lines revealed a better uptake of CSMS with HP morphology than its spherical counterparts. Cytotoxicity study showed that the anticancer activity of CBZ is improved with a higher free radical production when loaded onto CSMS. These unique materials with tunable morphology can serve as an excellent drug delivery system and will have potential applications for treating various cancers.

18.
Small ; 19(41): e2302875, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37309270

RESUMO

Due to the depletion of fossil fuels and their-related environmental issues, sustainable, clean, and renewable energy is urgently needed to replace fossil fuel as the primary energy resource. Hydrogen is considered as one of the cleanest energies. Among the approaches to hydrogen production, photocatalysis is the most sustainable and renewable solar energy technique. Considering the low cost of fabrication, earth abundance, appropriate bandgap, and high performance, carbon nitride has attracted extensive attention as the catalyst for photocatalytic hydrogen production in the last two decades. In this review, the carbon nitride-based photocatalytic hydrogen production system, including the catalytic mechanism and the strategies for improving the photocatalytic performance is discussed. According to the photocatalytic processes, the strengthened mechanism of carbon nitride-based catalysts is particularly described in terms of boosting the excitation of electrons and holes, suppressing carriers recombination, and enhancing the utilization efficiency of photon-excited electron-hole. Finally, the current trends related to the screening design of superior photocatalytic hydrogen production systems are outlined, and the development direction of carbon nitride for hydrogen production is clarified.

19.
Adv Sci (Weinh) ; 10(18): e2301045, 2023 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-37096838

RESUMO

Carbon-based nanomaterials, including graphene, fullerenes, and carbon nanotubes, are attracting significant attention as promising materials for next-generation energy storage and conversion applications. They possess unique physicochemical properties, such as structural stability and flexibility, high porosity, and tunable physicochemical features, which render them well suited in these hot research fields. Technological advances at atomic and electronic levels are crucial for developing more efficient and durable devices. This comprehensive review provides a state-of-the-art overview of these advanced carbon-based nanomaterials for various energy storage and conversion applications, focusing on supercapacitors, lithium as well as sodium-ion batteries, and hydrogen evolution reactions. Particular emphasis is placed on the strategies employed to enhance performance through nonmetallic elemental doping of N, B, S, and P in either individual doping or codoping, as well as structural modifications such as the creation of defect sites, edge functionalization, and inter-layer distance manipulation, aiming to provide the general guidelines for designing these devices by the above approaches to achieve optimal performance. Furthermore, this review delves into the challenges and future prospects for the advancement of carbon-based electrodes in energy storage and conversion.


Assuntos
Fontes de Energia Elétrica , Carbono/química , Eletrodos , Transferência de Energia , Nanotubos de Carbono/química , Pontos Quânticos , Grafite/química , Condutividade Elétrica , Lítio/química , Técnicas Eletroquímicas , Sódio/química , Catálise
20.
Sci Technol Adv Mater ; 24(1): 2188879, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37007670

RESUMO

Carbon nitrides, a distinguished class of metal-free catalytic materials, have presented a good potential for chemical transformations and are expected to become prominent materials for organocatalysis. This is largely possible due to their low cost, exceptional thermal and chemical stability, non-toxicity, ease of functionalization, porosity development, etc. Especially, the carbon nitrides with increased porosity and nitrogen contents are more versatile than their bulk counterparts for catalysis. These N-rich carbon nitrides are discussed in the earlier parts of the review. Later, the review highlights the role of such carbon nitride materials for the various organic catalytic reactions including Knoevenagel condensation, oxidation, hydrogenation, esterification, transesterification, cycloaddition, and hydrolysis. The recently emerging concepts in carbon nitride-based organocatalysis have been given special attention. In each of the sections, the structure-property relationship of the materials was discussed and related to their catalysis action. Relevant comparisons with other catalytic materials are also discussed to realize their real potential value. The perspective, challenges, and future directions are also discussed. The overall objective of this review is to provide up-to-date information on new developments in carbon nitride-based organic catalysis reactions that could see them rising as prominent catalytic materials in the future.

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