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Abstract Low-cost detection systems are needed for the identification of microplastics (MPs) in environmental samples. However, their rapid identification is hindered by the need for complex isolation and pre-treatment methods. This study describes a comprehensive sensing platform to identify MPs in environmental samples without requiring independent separation or pre-treatment protocols. It leverages the physicochemical properties of macroporous-mesoporous silver (Ag) substrates templated with self-assembled polymeric micelles to concurrently separate and analyze multiple MP targets using surface-enhanced Raman spectroscopy (SERS). The hydrophobic layer on Ag aids in stabilizing the nanostructures in the environment and mitigates biofouling. To monitor complex samples with multiple MPs and to demultiplex numerous overlapping patterns, we develop a neural network (NN) algorithm called SpecATNet that employs a self-attention mechanism to resolve the complex dependencies and patterns in SERS data to identify six common types of MPs: polystyrene, polyethylene, polymethylmethacrylate, polytetrafluoroethylene, nylon, and polyethylene terephthalate. SpecATNet uses multi-label classification to analyze multi-component mixtures even in the presence of various interference agents. The combination of macroporous-mesoporous Ag substrates and self-attention-based NN technology holds potential to enable field monitoring of MPs by generating rich datasets that machines can interpret and analyze.

The recognition of the importance of nanostructures is mainly due to the development of nanotechnology. For further developments in materials sciences, a concept that integrates nanotechnology with material chemistry to fabricate functional materials has to be proposed. Nanoarchitectonics will carry out this task. In nanoarchitectonics, we architect functional material systems from nano-units (atoms, molecules, nanomaterials). The methodology is not specific to any particular material or application. It covers a wide range. Therefore, nanoarchitectonics can be thought of as the method for everything in materials science. As typical demonstrations for usages of nanoarchitectonics, this review paper presents our work on nanoarchitectonics for supercapacitors. We divide it into two categories with different approaches. The first is the development of carbon materials as supercapacitor electrode materials from biomass. The second category is preparing carbon materials using structures created by supramolecular assembly of fullerenes such as C60 and C70. By presenting examples using opposite starting materials, a complex natural material, and an ultimately simple molecule, we will demonstrate the versatility and breadth of possibilities of this approach.

The impact of contaminants on Copepod sp. and its molecular response is least explored, despite their abundance and dominance among invertebrates in aquatic environments. In the present investigation, Dioithona rigida, a cyclopoid zooplankton, was treated with selenium nanoparticles (SeNPs) to highlight the associated biochemical changes, and the chronic exposure effects were recorded using transcriptomic analysis. It was found that, SeNPs were acutely toxic with a lethal dose 50% of 140.9 mg/L. The de novo assembled transcriptome of the copepod comprised of 81,814 transcripts, which underwent subsequent annotations to biological processes (23,378), cellular components (21,414), and molecular functions (31,015). Comparison of the expressed transcripts against the treated sample showed that a total of 186 transcript genes were differentially expressed among the D. rigida treatments (control and SeNPs). The significant downregulated genes are coding for DNA repair, DNA-templated DNA replication, DNA integration, oxidoreductase activity and transmembrane transport. Similarly, significant upregulations were observed in protein phosphatase binding and regulation of membrane repolarization. Understanding the impact of SeNPs on copepods is crucial not only for aquatic ecosystem health but also for human health, as these organisms play a key role in marine food webs, ultimately affecting the fish consumed by humans. By elucidating the molecular responses and potential toxicological effects of SeNPs, explored in this provides key insights on risk assessments and regulatory policies, ensuring the safety of seafood and protecting human health from the unintended consequences of nanoparticle pollution.

ABSTRACTA series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen (‘OxP’) has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)4) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g−1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents.

ABSTRACTThe interaction between diverse nanoarchitectured fullerenes and cells is crucial for biomedical applications. Here, we detailed the preparation of hydrophilic self-assembled fullerenes by the liquid-liquid interfacial precipitation (LLIP) method and hydrophilic coating of the materials as a possible vascularization strategy. The interactions of vascular endothelial cells (ECs) with hydrophilic fullerene nanotubes (FNT-P) and hydrophilic fullerene nanowhiskers (FNW-P) were investigated. The average length and diameter of FNT-P were 16 ± 2 μm and 3.4 ± 0.4 μm (i.e. aspect ratios of 4.6), respectively. The average length and diameter of FNW-P were 65 ± 8 μm and 1.2 ± 0.2 μm (i.e. aspect ratios of 53.9), respectively. For two-dimensional (2D) culture after 7 days, the ECs remained viable and proliferated up to ~ 420% and ~ 400% with FNT-P and FNW-P of 50 μg/mL, respectively. Furthermore, an optimized chitosan-based self-healing hydrogel with a modulus of ~400 Pa was developed and used to incorporate self-assembled fullerenes as in vitro three-dimensional (3D) platforms to investigate the impact of FNT-P and FNW-P on ECs within a 3D environment. The addition of FNW-P or FNT-P (50 μg/mL) in the hydrogel system led to proliferation rates of ECs up to ~323% and ~280%, respectively, after 7 days of culture. The ECs in FNW-P hydrogel displayed an elongated shape with aligned morphology, while those in FNT-P hydrogel exhibited a rounded and clustered distribution. Vascular-related gene expressions of ECs were significantly upregulated through interactions with these fullerenes. Thus, the combined use of different nanoarchitectured self-assembled fullerenes and self-healing hydrogels may offer environmental cues influencing EC development in a 3D biomimetic microenvironment, holding promise for advancing vascularization strategy in tissue engineering.

The authors make the following corrections to the published paper [...]

High-surface-area porous carbon materials with high porosity and well-defined pore structures are the preferred advanced supercapacitors electrode materials. Here, we report the electrochemical supercapacitive performance of novel high-porosity activated carbon materials prepared from biowaste Terminalia chebula (Harro) seed stones involving zinc chloride (ZnCl2) activation. Activation is achieved by mixing ZnCl2 with Harro seed powder (1:1 w/w) followed by carbonization at 400–700 °C under a nitrogen gas atmosphere. The amorphous carbon materials obtained exhibit excellent performance as electrical double-layer capacitor electrodes in aqueous electrolyte (1 M sulfuric acid) due to high specific surface areas (as high as 1382.6 m2 g−1) based on well-developed micropore and mesopore structures, and partial graphitic structure containing oxygenated surface functional groups. An electrode prepared using material having the optimal surface textural properties achieved a large specific capacitance of 328.6 F g−1 at 1 A g−1 in a three-electrode cell setup. The electrode achieved a good capacitance retention of 44.7% at a high 50 A g−1 current density and outstanding cycling performance of 98.2% even following 10,000 successive charge/discharge cycles. Electrochemical data indicate the significant potential of Terminalia chebula seed-derived porous carbons as high-performance electrode materials for high-energy-storage supercapacitor applications.

Many researchers working on the development of dye-sensitized solar cells (DSCs) continue to focus on the synthesis of photoanode materials with high surface area, along with high light scattering ability to enhance light harvesting efficiency (LHE). Meanwhile, dye packing density, which also impacts the LHE significantly, is often overlooked. Solvothermally synthesized anatase TiO2 nanoparticles (SANP) were obtained by a new and simple approach using a mixed solvent, ethanol and acetic acid. SANP were applied in photoanodes of DSCs using either metal-free organic dye (D149) or organometallic (N719) dyes. Dye loading (packing density) was correlated with the isoelectric point (IEP) in addition to light scattering effects were shown to determine the devices photovoltaic efficiency (PCE); specifically when compared with ones employing commercially available TiO2 nanoparticles. SANP photoanodes sensitized with D149 dye were found to be optimised at 10 µm, yielding a PCE of 6.9%, superior to for transparent or transparent + scattering films from the commercial source (5.6% and 5.9%, respectively). Furthermore, a 7.7% PCE was achieved using a SANP photoanode sensitized with N719 dye, with 7.2% seen for the transparent photoanode and 7.9% with a scattering layer. The high PCEs of of SANP devices are attributed to the high dye loading capability in addition to light scattering. A further point of interest is that even with the increased reactivity of the surface towards dye adsorption, we did not observe any significant increase in recombination with the redox mediator, presumably due to the increased dye loading providing better shielding.

The energy storage performances of supercapacitors are expected to be enhanced by the use of nanostructured hierarchically micro/mesoporous hollow carbon materials based on their ultra-high specific surface areas and rapid diffusion of electrolyte ions through the interconnected channels of their mesoporous structures. In this work, we report the electrochemical supercapacitance properties of hollow carbon spheres prepared by high-temperature carbonization of self-assembled fullerene-ethylenediamine hollow spheres (FE-HS). FE-HS, having an average external diameter of 290 nm, an internal diameter of 65 nm, and a wall thickness of 225 nm, were prepared by using the dynamic liquid-liquid interfacial precipitation (DLLIP) method at ambient conditions of temperature and pressure. High temperature carbonization (at 700, 900, and 1100 °C) of the FE-HS yielded nanoporous (micro/mesoporous) hollow carbon spheres with large surface areas (612 to 1616 m2 g−1) and large pore volumes (0.925 to 1.346 cm3 g−1) dependent on the temperature applied. The sample obtained by carbonization of FE-HS at 900 °C (FE-HS_900) displayed optimum surface area and exhibited remarkable electrochemical electrical double-layer capacitance properties in aq. 1 M sulfuric acid due to its well-developed porosity, interconnected pore structure, and large surface area. For a three-electrode cell setup, a specific capacitance of 293 F g−1 at a 1 A g−1 current density, which is approximately 4 times greater than the specific capacitance of the starting material, FE-HS. The symmetric supercapacitor cell was assembled using FE-HS_900 and attained 164 F g−1 at 1 A g−1 with sustained 50% capacitance at 10 A g−1 accompanied by 96% cycle life and 98% coulombic efficiency after 10,000 consecutive charge/discharge cycles. The results demonstrate the excellent potential of these fullerene assemblies in the fabrication of nanoporous carbon materials with the extensive surface areas required for high-performance energy storage supercapacitor applications.

The fabrication of various sensing devices and the ability to harmonize materials for a higher degree of organization is essential for effective sensing systems. Materials with hierarchically micro- and mesopore structures can enhance the sensitivity of sensors. Nanoarchitectonics allows for atomic/molecular level manipulations that create a higher area-to-volume ratio in nanoscale hierarchical structures for use in ideal sensing applications. Nanoarchitectonics also provides ample opportunities to fabricate materials by tuning pore size, increasing surface area, trapping molecules via host–guest interactions, and other mechanisms. Material characteristics and shape significantly enhance sensing capabilities via intramolecular interactions, molecular recognition, and localized surface plasmon resonance (LSPR). This review highlights the latest advancements in nanoarchitectonics approaches to tailor materials for various sensing applications, including biological micro/macro molecules, volatile organic compounds (VOC), microscopic recognition, and the selective discrimination of microparticles. Furthermore, different sensing devices that utilize the nanoarchitectonics concept to achieve atomic-molecular level discrimination are also discussed.

Abstract Ultrathin 2D nanoporous materials offer enhanced sensitivity and high spatial resolution in sensing applications making them important for the selective discrimination of guest molecules. Here bottom‐up fabrication is reported of a novel molecularly‐thin nitrogen‐doped 2D fullerphene. Thermal annealing at 700 °C of a bottom‐up assembled fullerene C60‐ethylenediamine (EDA) thin film results in formation of a nitrogen‐doped ultrathin carbon film, fullerphene, which exhibits a hierarchically micro/mesoporous structure at its surfaces. N‐doping of fullerphene is dominated by pyrrolic and quaternary nitrogen atoms, which allow selective and repetitive adsorption and desorption of low‐molecular‐weight carboxylic acid vapors through noncovalent interactions. The large surface area (655.2 m2 g–1) and pore volume (0.659 cc g–1) offered by the hierarchical micro/mesoporous architecture leads to superior sensitivity of fullerphene to formic acid over acetic acid in the vapor phase demonstrating that novel 2D fullerphene provides an attractive platform for the discrimination of carboxylic acids at the single‐carbon‐atom level.

The development of science and technology of advanced materials using nanoscale units can be conducted by a novel concept involving combination of nanotechnology methodology with various research disciplines, especially supramolecular chemistry. The novel concept is called ‘nanoarchitectonics’ where self-assembly processes are crucial in many cases involving a wide range of component materials. This review of self-assembly processes re-examines recent progress in materials nanoarchitectonics. It is composed of three main sections: (1) the first short section describes typical examples of self-assembly research to outline the matters discussed in this review; (2) the second section summarizes self-assemblies at interfaces from general viewpoints; and (3) the final section is focused on self-assembly processes at interfaces. The examples presented demonstrate the strikingly wide range of possibilities and future potential of self-assembly processes and their important contribution to materials nanoarchitectonics. The research examples described in this review cover variously structured objects including molecular machines, molecular receptors, molecular pliers, molecular rotors, nanoparticles, nanosheets, nanotubes, nanowires, nanoflakes, nanocubes, nanodisks, nanoring, block copolymers, hyperbranched polymers, supramolecular polymers, supramolecular gels, liquid crystals, Langmuir monolayers, Langmuir–Blodgett films, self-assembled monolayers, thin films, layer-by-layer structures, breath figure motif structures, two-dimensional molecular patterns, fullerene crystals, metal–organic frameworks, coordination polymers, coordination capsules, porous carbon spheres, mesoporous materials, polynuclear catalysts, DNA origamis, transmembrane channels, peptide conjugates, and vesicles, as well as functional materials for sensing, surface-enhanced Raman spectroscopy, photovoltaics, charge transport, excitation energy transfer, light-harvesting, photocatalysts, field effect transistors, logic gates, organic semiconductors, thin-film-based devices, drug delivery, cell culture, supramolecular differentiation, molecular recognition, molecular tuning, and hand-operating (hand-operated) nanotechnology.

The electrical double-layer supercapacitance performance of the nanoporous carbons prepared from the Phyllanthus emblica (Amala) seed by chemical activation using the potassium hydroxide (KOH) activator is reported. KOH activation was carried out at different temperatures (700–1000 °C) under nitrogen gas atmosphere, and in a three-electrode cell set-up the electrochemical measurements were performed in an aqueous 1 M sulfuric acid (H2SO4) solution. Because of the hierarchical pore structures with well-defined micro- and mesopores, Phyllanthus emblica seed-derived carbon materials exhibit high specific surface areas in the range of 1360 to 1946 m2 g−1, and the total pore volumes range from 0.664 to 1.328 cm3 g−1. The sample with the best surface area performed admirably as the supercapacitor electrode-material, achieving a high specific capacitance of 272 F g−1 at 1 A g−1. Furthermore, it sustained 60% capacitance at a high current density of 50 A g−1, followed by a remarkably long cycle-life of 98% after 10,000 subsequent charging/discharging cycles, demonstrating the electrode’s excellent rate-capability. These results show that the Phyllanthus emblica seed would have significant possibilities as a sustainable carbon-source for the preparing high-surface-area activated-carbons desired in high-energy-storage supercapacitors.

Much attention has been paid to the synthesis of low-dimensional materials from small units such as functional molecules. Bottom-up approaches to create new low-dimensional materials with various functional units can be realized with the emerging concept of nanoarchitectonics. In this review article, we overview recent research progresses on materials nanoarchitectonics at two-dimensional liquid interfaces, which are dimensionally restricted media with some freedoms of molecular motion. Specific characteristics of molecular interactions and functions at liquid interfaces are briefly explained in the first parts. The following sections overview several topics on materials nanoarchitectonics at liquid interfaces, such as the preparation of two-dimensional metal-organic frameworks and covalent organic frameworks, and the fabrication of low-dimensional and specifically structured nanocarbons and their assemblies at liquid–liquid interfaces. Finally, interfacial nanoarchitectonics of biomaterials including the regulation of orientation and differentiation of living cells are explained. In the recent examples described in this review, various materials such as molecular machines, molecular receptors, block-copolymer, DNA origami, nanocarbon, phages, and stem cells were assembled at liquid interfaces by using various useful techniques. This review overviews techniques such as conventional Langmuir–Blodgett method, vortex Langmuir–Blodgett method, liquid–liquid interfacial precipitation, instructed assembly, and layer-by-layer assembly to give low-dimensional materials including nanowires, nanowhiskers, nanosheets, cubic objects, molecular patterns, supramolecular polymers, metal-organic frameworks and covalent organic frameworks. The nanoarchitecture materials can be used for various applications such as molecular recognition, sensors, photodetectors, supercapacitors, supramolecular differentiation, enzyme reactors, cell differentiation control, and hemodialysis.

The simplicity of fullerenes as assembled components provides attractive opportunities for basic understanding in self-assembly research. We applied in situ reactive methods to the self-assembly process of C60 molecules with melamine/ethylenediamine components in solution, resulting in a novel type of fullerene assemblies, micron-sized two-dimensional, amorphous shape-regular objects, fullerene rosettes. ATR–FTIR spectra, XPS, and TGA results suggest that the melamine/ethylenediamine components strongly interact and/or are covalently linked with fullerenes in the fullerene rosettes. The broad peak for layer spacing in the XRD patterns of the fullerene rosettes corresponds roughly to the interdigitated fullerene bilayer or monolayer of modified fullerene molecules. The fullerene rosettes are made from the accumulation of bilayer/monolayer assemblies of hybridized fullerenes in low crystallinity. Prototype sensor systems were fabricated upon immobilization of the fullerene rosettes onto surfaces of a quartz crystal microbalance (QCM), and selective sensing of formic acid was demonstrated as preliminary results for social-demanded toxic material sensing. The QCM sensor with fullerene rosette is categorized as one of the large-response sensors among reported examples. In selectivity to formic acids against basic guests (formic acid/pyridine >30) or aromatic guests (formic acid/toluene >110), the fullerene rosette-based QCM sensor also showed superior performance.

For the sustainable developments of life and society, various problems such as environmental, energy, and biohealth issues must be solved by a wide range of scientific and technical efforts. Therefore, the fabrication of functional materials and systems with strategic intelligence is required. As seen in the evolution processes in nature, self‐assembling processes are capable of creating highly intelligent materials and systems. This task would be taken by an emerging concept, nanoarchitectonics, through the combination of nanotechnology concepts with other scientific disciplines such as materials science, supramolecular chemistry, organic chemistry, and bio‐related science and technology. Herein, several examples are presented to overview intelligent nanoarchitectonics for the creation of functional materials and systems mainly through self‐assembly in various scale ranges. These examples are classified into several sections according to atom‐level, molecular‐level, materials‐level, and life‐level intelligent assembly, where several key items such as atom switch devices, molecular switches, molecular machines, shape‐shifting and shape‐specified assemblies, and cell control at interfaces are included. Discussions on these examples show a high possibility of the nanoarchitectonics' approach in intelligent fabrication of functional materials.

Low-molecular-weight acid vapors cause aging and destruction in material processing. In this paper, facile fabrication of novel corn-husk-shaped fullerene C60 crystals (CHFCs) through the dynamic liquid–liquid interfacial precipitation method is reported. The CHFCs were grown at the liquid–liquid interface between isopropyl alcohol (IPA) and a saturated solution of C60 in mesitylene under ambient temperature and pressure conditions. The average length, outer diameter, and inner diameter of CHFCs were ca. 2.88 μm, 672 nm, and 473 nm, respectively. X-ray diffraction (XRD) analysis showed the CHFCs exhibit a mixed face-centered cubic (fcc) and hexagonal-close pack (hcp) crystal phases with lattice parameters a = 1.425 nm, V = 2.899 nm3 for fcc phase and a = 2.182 nm, c = 0.936 nm, a/c ratio = 2.33, and V = 3.859 nm3 for hcp phase. The CHFCs possess mesoporous structure as confirmed by transmission electron microscopy (TEM) and nitrogen sorption analysis. The specific surface area and the pore volume were ca. 57.3 m2 g−1 and 0.149 cm3 g−1, respectively, are higher than the nonporous pristine fullerene C60. Quartz crystal microbalance (QCM) sensing results show the excellent sensing performance CHFCs sensitive to acetic acid vapors due to the enhanced diffusion via mesoporous architecture and hollow structure of the CHFCs, demonstrating the potential of the material for the development of a new sensor system for aliphatic acid vapors sensing.

Nanoarchitectonics has been paid much attention as an emerging concept to architect functional materials from molecular and nanounits through the combination of nanotechnology-oriented strategies and supramolecular-chemistry-like methodologies. This perspective article aims to figure out important keys for materials nanoarchitectonics. In the initial part, recent trends in materials nanoarchitectonics upon supramolecular self-assembly are overviewed. The overview processes extract several key words including dynamic natures, dimensional controls, and interfacial processes according to the following sections: (i) preparation of assembled structures and conversion into nanostructured materials, (ii) dynamic structural transformation to hierarchic materials, and (iii) material preparation and functions with dynamic flows at interfacial media. Not limited to the material production, dynamic processes at the interface can be also connected with forefront functions such as tuning of molecular receptors and mechanical controls. This perspective article can conclude that fabrication of functional materials and controls of nanosystems would be well-considered on the basis of these three key terms.

Pure graphene in the form of few-layer graphene (FLG) – 1 to 6 layers – is biocompatible and non-cytotoxic. This makes FLG an ideal material to incorporate into dental polymers to increase their strength and durability. It is well known that graphene has high mechanical strength and has been shown to enhance the mechanical, physical and chemical properties of biomaterials. However, for commercial applicability, methods to produce larger than lab-scale quantities of graphene are required. Here, we present a simple method to make large quantities of FLG starting with commercially available multi-layer graphene (MLG). This FLG material was then used to fabricate graphene dental-polymer composites. The resultant graphene-modified composites show that low concentrations of graphene (ca. 0.2 wt %) lead to enhanced performance improvement in physio-mechanical properties – the mean compressive strength increased by 27% and the mean compressive modulus increased by 22%. Herein we report a new, cheap and simple method to make large quantities of few-layer graphene which was then incorporated into a common dental polymer to fabricate graphene-composites which shows very promising mechanical properties.

Nanoporous carbon materials from biomass exhibit a high surface area due to well-defined pore structures. Therefore, they have been extensively used in separation and purification technologies as efficient adsorbents. Here, we report the iodine and methylene blue adsorption properties of the hierarchically porous carbon materials prepared from Areca catechu nut. The preparation method involves the phosphoric acid (H3PO4) activation of the Areca catechu nut powder. The effects of carbonization conditions (mixing ratio with H3PO4, carbonization time, and carbonization temperature) on the textural properties and surface functional groups were studied. The optimum textural properties were obtained at a mixing ratio of 1:1, carbonized for 3 h at 400 °C, and the sample achieved a high specific surface area of 2132.1 m2 g−1 and a large pore volume of 3.426 cm3 g−1, respectively. The prepared materials have amorphous carbon structures and contain oxygenated surface functional groups. Due to the well-defined micro-and mesopore structures with the high surface area and large pore volume, the optimal sample showed excellent iodine and methylene blue adsorption. The iodine number and methylene blue values were ca. 888 mg g−1 and 369 mg g−1, respectively. The batch adsorption studies of methylene dye were affected by pH, adsorbent dose, contact time, and initial concentration. The optimum parameters for the methylene blue adsorption were in alkaline pH, adsorbent dose of 2.8 g L−1, and contact time of 180 min. Equilibrium data could be best represented by the Langmuir isotherm model with a monolayer adsorption capacity of 333.3 mg g−1. Thus, our results demonstrate that the Areca catechu nut has considerable potential as the novel precursor material for the scalable production of high surface area hierarchically porous carbon materials that are essential in removing organic dyes from water.

Biomass-derived activated carbon materials with hierarchically nanoporous structures containing nitrogen functionalities show excellent electrochemical performances and are explored extensively in energy storage and conversion applications. Here, we report the electrochemical supercapacitance performances of the nitrogen-doped activated carbon materials with an ultrahigh surface area prepared by the potassium hydroxide (KOH) activation of the Nelumbo nucifera (Lotus) seed in an aqueous electrolyte solution (1 M sulfuric acid: H2SO4) in a three-electrode cell. The specific surface areas and pore volumes of Lotus-seed–derived carbon materials carbonized at a different temperatures, from 600 to 1000 °C, are found in the range of 1059.6 to 2489.6 m2 g−1 and 0.819 to 2.384 cm3 g−1, respectively. The carbons are amorphous materials with a partial graphitic structure with a maximum of 3.28 atom% nitrogen content and possess hierarchically micro- and mesoporous structures. The supercapacitor electrode prepared from the best sample showed excellent electrical double-layer capacitor performance, and the electrode achieved a high specific capacitance of ca. 379.2 F g−1 at 1 A g−1 current density. Additionally, the electrode shows a high rate performance, sustaining 65.9% capacitance retention at a high current density of 50 A g−1, followed by an extraordinary long cycle life without any capacitance loss after 10,000 subsequent charging/discharging cycles. The electrochemical results demonstrate that Nelumbo nucifera seed–derived hierarchically porous carbon with nitrogen functionality would have a significant probability as an electrical double-layer capacitor electrode material for the high-performance supercapacitor applications.

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 μm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3–5 nm metal particles on the tubes; (2) inside the tube’s central lumen resulting in 10–12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube’s wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

Nanoarchitectonics has been recently proposed as a post-nanotechnology concept. It is the methodology to produce functional materials from nanoscale units. Carbon-based materials are actively used in nanoarchitectonics approaches. This review explains several recent examples of energy and related applications of carbon materials from the viewpoint of the nanoarchitectonics concept. Explanations and discussions are described according to the classification of carbon sources for nanostructured materials: (i) carbon nanoarchitectonics from molecules and supramolecular assemblies; (ii) carbon nanoarchitectonics from fullerenes; (iii) carbon nanoarchitectonics from biomass; and (iv) carbon nanoarchitectonics with composites and hybrids. Functional carbon materials can be nanoarchitected through various processes, including well-skilled organic synthesis with designed molecular sources; self-assembly of fullerenes under various conditions; practical, low-cost synthesis from biomass; and hybrid/composite formation with various carbon sources. These examples strikingly demonstrate the enormous potential of nanoarchitectonics approaches to produce functional carbon materials from various components such as small molecules, fullerene, other nanocarbons, and naturally abundant biomasses. While this review article only shows limited application aspects in energy-related usages such as supercapacitors, applications for more advanced cells and batteries, environmental monitoring and remediation, bio-medical usages, and advanced devices are also expected.

Nanoarchitectonics is a universal concept to fabricate functional materials from nanoscale building units. Based on this concept, fabrications of functional materials with hierarchical structural motifs from simple nano units of fullerenes (C60 and C70 molecules) are described in this review article. Because fullerenes can be regarded as simple and fundamental building blocks with mono-elemental and zero-dimensional natures, these demonstrations for hierarchical functional structures impress the high capability of the nanoarchitectonics approaches. In fact, various hierarchical structures such as cubes with nanorods, hole-in-cube assemblies, face-selectively etched assemblies, and microstructures with mesoporous frameworks are fabricated by easy fabrication protocols. The fabricated fullerene assemblies have been used for various applications including volatile organic compound sensing, microparticle catching, supercapacitors, and photoluminescence systems.

Nanoarchitectonics of two-dimensional materials from zero-dimensional fullerenes is mainly introduced in this short review. Fullerenes are simple objects with mono-elemental (carbon) composition and zero-dimensional structure. However, fullerenes and their derivatives can create various types of two-dimensional materials. The exemplified approaches demonstrated fabrications of various two-dimensional materials including size-tunable hexagonal fullerene nanosheet, two-dimensional fullerene nano-mesh, van der Waals two-dimensional fullerene solid, fullerene/ferrocene hybrid hexagonal nanosheet, fullerene/cobalt porphyrin hybrid nanosheet, two-dimensional fullerene array in the supramolecular template, two-dimensional van der Waals supramolecular framework, supramolecular fullerene liquid crystal, frustrated layered self-assembly from two-dimensional nanosheet, and hierarchical zero-to-one-to-two dimensional fullerene assembly for cell culture.

Of the available environmentally friendly energy storage devices, supercapacitors are the most promising because of their high energy density, ultra-fast charging-discharging rate, outstanding cycle life, cost-effectiveness, and safety. In this work, nanoporous carbon materials were prepared by applying zinc chloride activation of lotus seed powder from 600 °C to 1000 °C and the electrochemical energy storage (supercapacitance) of the resulting materials in aqueous electrolyte (1M H2SO4) are reported. Lotus seed-derived activated carbon materials display hierarchically porous structures comprised of micropore and mesopore architectures, and exhibited excellent supercapacitance performances. The specific surface areas and pore volumes were found in the ranges 1103.0–1316.7 m2 g−1 and 0.741–0.887 cm3 g−1, respectively. The specific capacitance of the optimum sample was ca. 317.5 F g−1 at 5 mV s−1 and 272.9 F g−1 at 1 A g−1 accompanied by high capacitance retention of 70.49% at a high potential sweep rate of 500 mV s−1. The electrode also showed good rate capability of 52.1% upon increasing current density from 1 to 50 A g−1 with exceptional cyclic stability of 99.2% after 10,000 cycles demonstrating the excellent prospects for agricultural waste stuffs, such as lotus seed, in the production of the high performance porous carbon materials required for supercapacitor applications.

Hierarchically porous activated carbon materials from agro-waste, Jackfruit seeds are prepared by a chemical activation method involving the treatment with zinc chloride (ZnCl2) at different temperatures (600–1000 °C). The electrochemical supercapacitance performances of the prepared materials were studied in an aqueous electrolyte (1 M sulfuric acid, H2SO4) in a three-electrode system. Jackfruit seed carbons display nanoporous structures consisting of both micro- and mesopore architectures and they are amorphous in nature and also contain oxygenated surface functional groups, as confirmed by powder X-ray diffraction (pXRD), Raman scattering, and Fourier-transformed infrared (FTIR) spectroscopy, respectively. The surface areas and pore volumes were found to be 1216.0 to 1340.4 m2·g−1 and 0.804 to 1.144 cm3·g−1, respectively, demonstrating the better surface textural properties compared to the commercial activated carbons. Due to the high surface area, large pore volume, and well developed hierarchical micro- and mesoporosity, the optimal sample achieved a high specific capacitance of 292.2 F·g−1 at 5 mV·s−1 and 261.3 F·g−1 at 1 A·g−1 followed by outstanding high rate capability. The electrode sustained 71.6% capacity retention at a high current density of 20 A·g−1. Furthermore, the electrode displayed exceptional cycling stability with small capacitance loss (0.6%) even after 10,000 charging–discharging cycles, suggesting that Jackfruit seed would have potential in low-cost and scalable production of nanoporous carbon materials for supercapacitors applications.

We have investigated the textural properties, electrochemical supercapacitances and vapor sensing performances of bamboo-derived nanoporous carbon materials (NCM). Bamboo, an abundant natural biomaterial, was chemically activated with phosphoric acid at 400 °C and the effect of impregnation ratio of phosphoric acid on the textural properties and electrochemical performances was systematically investigated. Fourier transform-infrared (FTIR) spectroscopy confirmed the presence of various oxygen-containing surface functional groups (i.e. carboxyl, carboxylate, carbonyl and phenolic groups) in NCM. The prepared NCM are amorphous in nature and contain hierarchical micropores and mesopores. Surface areas and pore volumes were found in the range 218–1431 m2 g−1 and 0.26–1.26 cm3 g−1, respectively, and could be controlled by adjusting the impregnation ratio of phosphoric acid and bamboo cane powder. NCM exhibited electrical double-layer supercapacitor behavior giving a high specific capacitance of c.256 F g−1 at a scan rate of 5 mV s−1 together with high cyclic stability with capacitance retention of about 92.6% after 1000 cycles. Furthermore, NCM exhibited excellent vapor sensing performance with high sensitivity for non-aromatic chemicals such as acetic acid. The system would be useful to discriminate C1 and C2 alcohol (methanol and ethanol).

A highly active hydrotalcite-supported Ag/Pd bimetallic nanocluster catalyst has been developed by a simple, easy and safe chemical reduction method. The catalyst was characterized by high-resolution transmission electron microscopy (HR-TEM), which revealed very small (3.2 ± 0.7 nm) nanoclusters with a narrow size distribution. The bimetallic Ag/Pd catalyst showed strong cooperation between Ag and Pd for the alcohol oxidation reaction. The developed catalyst provided an efficient and environmentally friendly method for alcohol oxidation and one-pot cross-aldol condensation in water. A broad scope of α,β-unsaturated ketones with good to excellent yields were obtained under very mild conditions. This catalytic system offers an easy preparation method with a simple recovery process, good activity and reusability of up to five cycles without significant loss in the catalytic activity.

This short review article introduces several examples of self-assembly-based structural formation and shape-shifting using very simple molecular units, fullerenes (C60, C70, and their derivatives), as fullerene nanoarchitectonics. Fullerene molecules are suitable units for the basic science of self-assembly because they are simple zero-dimensional objects with only a single elemental component, carbon, without any charged or interactive functional groups. In this review article, self-assembly of fullerene molecules and their shape-shifting are introduced as fullerene nanoarchitectonics. An outline and a background of fullerene nanoarchitectonics are first described, followed by various demonstrations, including fabrication of various fullerene nanostructures, such as rods on the cube, holes in the cube, interior channels in the cube, and fullerene micro-horns, and also a demonstration of a new concept, supramolecular differentiation.

Nanoporous activated carbons-derived from agro-waste have been useful as suitable and scalable low-cost electrode materials in supercapacitors applications because of their better surface area and porosity compared to the commercial activated carbons. In this paper, the production of nanoporous carbons by zinc chloride activation of Washnut seed at different temperatures (400–1000 °C) and their electrochemical supercapacitance performances in aqueous electrolyte (1 M H2SO4) are reported. The prepared nanoporous carbon materials exhibit hierarchical micro- and meso-pore architectures. The surface area and porosity increase with the carbonization temperature and achieved the highest values at 800 °C. The surface area was found in the range of 922–1309 m2 g−1. Similarly, pore volume was found in the range of 0.577–0.789 cm3 g−1. The optimal sample obtained at 800 °C showed excellent electrochemical energy storage supercapacitance performance. Specific capacitance of the electrode was calculated 225.1 F g−1 at a low current density of 1 A g−1. An observed 69.6% capacitance retention at 20 A g−1 indicates a high-rate capability of the electrode materials. The cycling stability test up to 10,000 cycles revealed the outstanding stability of 98%. The fascinating surface textural properties with outstanding electrochemical performance reveal that Washnut seed would be a feasible agro-waste precursor to prepare nanoporous carbon materials as a low-cost and scalable supercapacitor electrode.

Nanoporous activated carbon materials derived from agro-wastes could be suitable low-cost electrode materials for high-rate performance electrochemical supercapacitors. Here we report high surface area nanoporous carbon materials derived from Lapsi seed agro-waste prepared by zinc chloride (ZnCl2) activation at 700 °C. Powder X-ray diffraction (pXRD) and Raman scattering confirmed the amorphous structure of the resulting carboniferous materials, which also incorporate oxygen-containing functional groups as confirmed by Fourier transform infrared (FTIR) spectroscopy. Scanning and transmission electron microscopy (SEM and TEM) analyses revealed the granular, nanoporous structures of the materials. High-resolution TEM (HR-TEM) confirmed a graphitic carbon structure containing interconnected mesopores. Surface areas and pore volumes of the materials were found, respectively, in the ranges from 931 to 2272 m2 g−1 and 0.998 to 2.845 cm3 g−1, and are thus superior to commercially available activated carbons. High surface areas, large pore volumes and interconnected mesopore structures of these Lapsi seed-derived nanoporous carbon materials lead to their excellent electrochemical supercapacitance performance in aqueous electrolyte (1 M H2SO4) with a maximum specific capacitance of 284 F g−1 at a current density of 1 A g−1. Furthermore, the electrodes showed high-rate capability sustaining 67.7% capacity retention even at high current density of 20 A g−1 with excellent cycle stability achieving 99% capacitance retention even after 10,000 charge–discharge cycles demonstrating the potential of Lapsi seed derived nanoporous carbons as suitable electrode materials in high-performance supercapacitor devices.

High surface area and large pore volume carbon materials having hierarchical nanoporous structure are required in high performance supercapacitors. Such nanoporous carbon materials can be fabricated from organic precursors with high carbon content, such as synthetic biomass or agricultural wastes containing cellulose, hemicellulose, and lignin. Using recently developed unique concept of materials nanoarchitectonics, high performance porous carbons with controllable surface area, pore size distribution, and hierarchy in nanoporous structure can be fabricated. In this review, we will overview the recent trends and advancements on the synthetic methods for the production of hierarchical porous carbons with one- to three-dimensional network structure with superior performance in supercapacitors applications. We highlight the promising scope of accessing nanoporous graphitic carbon materials from: (i) direct conversion of single crystalline self-assembled fullerene nanomaterials and metal organic frameworks, (ii) hard- and soft-templating routes, and (iii) the direct carbonization and/or activation of biomass or agricultural wastes as non-templating routes. We discuss the appealing points of the different synthetic carbon sources and natural precursor raw−materials derived nanoporous carbon materials in supercapacitors applications.

Self-assembly has been recognised as a ubiquitous aspect of modern chemistry. Our understanding and applications of self-assembly are substantially based on what has been learned from biochemical systems. In this review, we describe various aspects of self-assembly commencing with an account of the soft structures that are available by assembly of surfactant amphiphiles, which are important scientific and industrial materials. Variation of molecular design using rules defined by surfactant self-assembly permits synthesis of functional nanostructures in solution and at surfaces while increasing the strength of intermolecular interactions through π-π stacking, metal cation coordination and/or hydrogen bonding leads to formation of highly complex bespoke nanostructured materials exemplified by DNA assemblies. We describe the origins of self-assembly involving aggregation of lipid amphiphiles and how this subject has been expanded to include other highly advanced chemical systems.

Iodine and methylene blue adsorption properties of the high surface area nanoporous carbon materials derived from agro-waste and rice husk is reported. Rice husk was pre-carbonized at 300 °C in air followed by leaching out the silica nanoparticles by extraction with sodium hydroxide solution. The silica-free rice husk char was mixed with chemical activating agents sodium hydroxide (NaOH), zinc chloride (ZnCl2), and potassium hydroxide (KOH) separately at a mixing ratio of 1:1 (wt%) and carbonized at 900 °C under a constant flow of nitrogen. The prepared carbon materials were characterized by scanning electron microscopy (SEM), Fourier transformed-infrared spectroscopy (FT-IR), powder X-ray diffraction (pXRD), and Raman scattering. Due to the presence of bimodal micro- and mesopore structures, KOH activated samples showed high specific surface area ca. 2342 m2/g and large pore volume ca. 2.94 cm3/g. Oxygenated surface functional groups (hydroxyl, carbonyl, and carboxyl) were commonly observed in all of the samples and were essentially non-crystalline porous particle size of different sizes (

Here we report the aromatic vapor sensing performance of bitter melon shaped nanoporous fullerene C60 crystals that are self-assembled at a liquid-liquid interface between isopropyl alcohol and C60 solution in dodecylbenzene at 25 °C. Average length and center diameter of the crystals were ca. 10 μm and ~2 μm, respectively. Powder X-ray diffraction pattern (pXRD) confirmed a face-centered cubic (fcc) structure with cell dimension ca. a = 1.4272 nm, and V = 2.907 nm3, which is similar to that of the pristine fullerene C60. Transmission electron microscopy (TEM) confirmed the presence of a nanoporous structure. Quartz crystal microbalance (QCM) results showed that the bitter melon shaped nanoporous C60 performs as an excellent sensing system, particularly for aromatic vapors, due to their easy diffusion through the porous architecture and strong π–π interactions with the sp2-carbon.

Herein we demonstrate a novel (Pb0.50Ba0.50)ZrO3 (PBZ50) ceramic that exhibits a reentrant relaxor ferroelectric phase transition in an antiferroelectric-based perovskite system. The dielectric measurement has confirmed that the imaginary part of the dielectric constant for the reentrant phase is nearly frequency independent below the freezing temperature. The reentrant behavior could be scaled to a phenomenological equation involving the Vogel–Fulcher relationship. These results were further complemented by the polarization measurements. The PBZ50 was fabricated using a semi-wet synthetic route involving a solid-state thermochemical reaction. We believe this unusual phase transition sequence in the PBZ50 material would be highly useful in high-density data storage devices.

In this paper, wool carpet dye adsorption properties of nanoporous activated carbon materials (NCMs) prepared from bamboo agro-product is reported. Bamboo cane powder was chemically activated with phosphoric acid at different temperatures (400, 500, and 600 °C) at an impregnation ratio of 1:1. We found that the specific surface area and the total pore volume of NCM increases with temperature giving the highest surface area and pore volume ca. 2130 m2·g−1 and 2.69 cc·g−1 at 600 °C. Owing to superior surface textural properties, bamboo-derived NCM showed excellent adsorption capacity for wool carpet dyes Lanasyn orange (LO) and Lanasyn gray (LG). The adsorption phenomena could be described by Langmuir/Freundlich adsorption isotherm models. The maximum adsorption capacity was ca. 2.60 × 103 and 3.04 × 103 mg·g−1 for LO and LG, respectively. The adsorption followed pseudo second order kinetics with the second order rate constant of 1.24 × 10−3 g·mg−1·min−1 (LO) and 7.69 × 10−4 g·mg−1·min−1 (LG), respectively. This study demonstrated that the high surface area NCMs prepared from agro-product can be used as efficient and cost-effective adsorbent materials for the removal of dyes from industrial effluent.