Unveiling the role of dopants in boosting CuS supercapacitor performance: insights from first-principles calculations.

Transition metal sulfides have become famous in high energy density supercapacitor materials owing to their rich redox and high conductivity. While their development has achieved a breakthrough in terms of capacitance, there is little knowledge from the theoretical perspective on how dopants play a role in enhancing their capacitances. In this work, pseudocapacitance and quantum capacitance were evaluated through first-principles calculation to describe their role in transition metal sulfide, which here is represented by copper sulfide (CuS). The resulting quantum capacitance (CQ) was calculated in both the bulk and surface of CuS to determine which structure has a greater effect on the capacitance of the system. It was observed that the dopant increased CQ in the bulk system, which is different from the CQ of surface structures. Meanwhile, K+ ions were introduced on the surface structure to calculate transfer charge and work function shift, thus determining pseudocapacitance. All dopant types were able to increase the pseudocapacitance value, with Fe doping showing the highest capacitance of 111 F g-1, which is higher than that of the pristine structure (47 F g-1). The role of the dopant is discussed in detail in this work. Our results suggest that the increased capacitance of doped TMS materials was originated not only from the geometrical perspective but also from the higher pseudocapacitance value. Quantum capacitance, alternatively, could also contribute to the system when the dopant occurs in the bulk rather than only in the surface structure. This work may open a new perspective on how dopants play a role in increasing supercapacitor performance.

A Sustainable Approach for Preparing Porous Carbon Spheres Derived from Kraft Lignin and Sodium Hydroxide as Highly Packed Thin Film Electrode Materials.

A green synthetic strategy to design biomass-derived porous carbon electrode materials with precisely tailored structure and morphology has always been a challenging goal because these materials can fulfill the demands of next-generation supercapacitors and other electrochemical devices. Potassium hydroxide (KOH) is extensively utilized as an activator since it can produce porous carbon with high specific surface area and well-developed porous channels. The exploitation of sodium hydroxide (NaOH) as an activating agent is less referenced in the literature, although it offers some advantages over KOH in terms of low cost, less corrosiveness, and simple handling procedure, all of which are appealing particularly from an industrial viewpoint. The motivation for this present study is to fabricate porous carbon spheres in a sustainable manner via a spray drying approach followed by a carbonization process, using Kraft lignin as the carbon precursor and NaOH as an alternative activation agent instead of the high-cost and high-corrosive KOH for the first time. The structure of carbon particles can be accurately transitioned from a compact to hollow structure, and the surface textural properties can be easily tuned by altering the NaOH concentration. The obtained porous carbon spheres were applied as highly packed thin film electrode materials for supercapacitor devices. The specific capacitance value of porous carbon spheres with a highly compact structure (high packing density) is 66.5 F g-1, which is higher than that of commercial activated carbon and other biomass-derived carbon. This work provides a green processing for producing low-cost and environment-friendly porous carbon spheres from abundant Kraft lignin and important insight for selecting NaOH as an activator to tailor the morphology and structure, which represents an economical and sustainable approach for energy storage devices.

Revealing the synergetic interaction between amino and carbonyl functional groups and their effect on the electronic and optical properties of carbon dots.

Nitrogen and oxygen-based functionalized carbon dot (CDs) surfaces have attracted significant attention due to their ability to tailor the optical and electronic properties of CDs. However, the complex synthesis process and structure of the functionalized CDs hinder an in-depth understanding of their mechanism, limiting their potential applications. Herein, we report CDs functionalized with amino and carbonyl functional groups and reveal the mechanism of interaction between the amino and carbonyl groups and the CDs' optical and electronic properties. Both Time-dependent Density Functional Theory (TD-DFT) and experimental studies revealed that the synergetic effects between amino and carbonyl groups significantly shift the absorption peaks to the NIR region and strengthen their absorption intensity. Furthermore, their absorption and bandgap energy could be tuned by optimizing the amino to carbonyl ratio on CDs surfaces. This study suggests that amino and carbonyl groups synergistically tailor the CDs' optical and electronic properties through frontier orbital hybridization and high charge transfer. This knowledge opens a new avenue for tailoring the desired optical and electronic properties of CDs for any application.

Atomic and molecular adsorption on single platinum atom at the graphene edge: A density functional theory study.

We present a density functional theory study of atomic and molecular adsorption on a single Pt atom deposited at the edges of graphene. We investigate geometric and electronic structures of atoms (H, C, N, and O) and molecules (O2, CO, OH, NO, H2O, and OOH) on a variety of Pt deposited graphene edges and compare the adsorption states with those on a Pt(111) surface and on a Pt single atom. Furthermore, using the calculated adsorption energy and simple kinetic models, the catalytic activities of a Pt single-atom catalyst for the oxygen reduction reaction and CO oxidation are discussed.

Controlled morphology of electrospun nanofibers from waste expanded polystyrene for aerosol filtration.

This paper reports on the recycling of expanded polystyrene (EPS) waste to be repurposed as EPS nanofibrous mats for air filtration applications. The EPS nanofibrous mats were prepared via electrospinning technique. The EPS solutions for producing the mats were made by dissolving the EPS waste in dimethylformamide (DMF) and d-limonene solvents. The mixing ratio of DMF and d-limonene solvents were varied to obtain EPS solutions with different surface tension and viscosity. As a result, different fiber morphology (smooth fiber, wrinkled fiber, and beaded fiber) and diameter ranging from 314 nm to 3506 nm were obtained. The synthesized EPS nanofibrous mats were characterized by scanning electron microscope, Fourier-transform infrared spectroscopy, x-ray diffraction spectroscopy, differential scanning calorimetry, mechanical strength, porosity, and water contact angle measurement apparatus. The mechanical strength measurement exhibited that the beaded fiber had the highest tensile strength and the lowest elasticity compared to wrinkled and smooth fiber. The water contact angle measurement showed that the EPS nanofibrous mats were classified as ultra-hydrophobic, which was a good criterion for air filter media. Some filtration parameters of the EPS nanofibrous mats were measured, including particle collecting efficiency, pressured drop, and quality factor. The particle collecting efficiency of each EPS nanofibrous mats was measured using monodisperse polystyrene latex (PSL) particles and PM2.5 from burning incense as the test particles. The EPS nanofibrous mats had a high collecting efficiency (up to 99.99%) and had a low pressure drop (below 70 Pa) for the face velocity of 5.4 cm s-1. The quality factor of the EPS nanofibrous mats reached 0.10 for PSL filtration and 0.16 for PM2.5 filtration. Overall, the EPS nanofibrous mats with controlled morphology were suitable to be used as air filtration media with high mechanical strength, ultra-hydrophobic surface, and high quality factor.

Functionalized Phytochemicals-Embedded Carbon Dots Derived from Medicinal Plant for Bioimaging Application.

Precise visualization of biological processes necessitates reliable coloring technologies, and fluorescence imaging has emerged as a powerful method for capturing dynamic cellular events. Low emission intensity and solubility of intrinsic fluorescence are still challenging, hindering their application in the biomedical field. The nanostructurization and functionalization of the insoluble phytochemicals, such as chlorophyll and curcumin, into carbon dots (CDs) were conducted to address these challenges. Due to their unique fluorescence characteristics and biocompatibility, CDs derived from medicinal plants hold promise as bioimaging agents. Further, the nitrogen in situ functionalization of the as-synthesized CDs offered tunable optical properties and enhanced solubility. The surface modification aims to achieve a more positive zeta potential, facilitating penetration through biological membranes. This work provides valuable insights into utilizing functionalized phytochemical-embedded carbon dots for bioimaging applications. The doping of nitrogen by adding urea showed an alteration of surface charge, which is more positive based on zeta potential measurement. The more positive CD particles showed that Andrographis paniculata-urea-based CDs were the best particles to penetrate cells than others related to the alteration of the surface charge and the functional group of the CDs, with the optimum dose of 12.5 µg/mL for 3 h of treatment for bioimaging assay.

Trifunctional electrocatalysts based on a bimetallic nanoalloy and nitrogen-doped carbon with brush-like heterostructure.

Trifunctional ORR/OER/HER catalysts are emerging for various sustainable energy storage and conversion technologies. For this function, employing materials with 1D structures leads to catalysts having limited surface area and structural robustness. Instead of 1D catalysts, heterostructured catalysts (i.e., catalysts consisting of interfaces created by combining diverse structural components) have attracted much attention due to their high efficiency. We have fabricated a directly grown 1D-1D heterostructured bimetallic N-doped carbon trifunctional catalyst based on Fe/Co bimetallic-organic frameworks, forming nanobrushes (FeCoNC-NB) with improved resistance to collapsing and substantial numbers of exposed active sites. The secondary 1D structure of this design contributes to creating interparticle conductive networks. By combining the brush-like heterostructure, FeCo alloy active sites, and N-doped carbon as support and for encapsulation of the metal, the catalyst features a high ORR Eonset value (1.046 V), low OER overpotential (363 mV), and comparable HER overpotential (254 mV) in alkaline electrolyte. Zn-air batteries with FeCoNC-NB demonstrate a power density of 195 mW cm-2 and a superior battery life of up to 350 h. Self-powered FeCoNC-NB-based water electrolyzers as energy conversion devices are also demonstrated. This work drives the progress of trifunctional catalysts based on heterostructured nonprecious metal N-doped carbon for energy storage and conversion developments.

A High-Performance, Low Defected, and Binder-Free Graphene-Based Supercapacitor Obtained via Synergistic Electrochemical Exfoliation and Electrophoretic Deposition Process.

An integrated electrochemical exfoliation and electrophoretic deposition (EPD) method is developed to achieve a high-performance graphene supercapacitor. The electrochemical delamination of graphite sheet has obtained a low-defected few-layer graphene adorned with oxygen-containing functional groups. Then, the EPD process produced a binder-free electrode to alleviate the graphene restacking problem. The electrode prepared using a deposition voltage of 5 V exhibits the highest specific capacitance of 145.95 F/g at 0.5 A/g from three-electrode measurement. Moreover, this EPD-prepared electrode also demonstrates superior electrochemical properties compared to electrodes fabricated using PVDF binder. In the real symmetrical cell, the EPD-prepared electrode also shows excellent performance with a high rate capability of 82.31 % (from 0.5 A/g to 10 A/g), high cycling stability of 95.00 % (at 5 A/g) after 10,000 cycles, and rapid frequency response with short relaxation time ( τ 0 ${{\tau }_{0}}$ ) of 9.73 ms. These results indicate that this integration method is beneficial to construct a high performance binder-free supercapacitor electrode consisting of low-defected graphene materials, low electrode resistance, and less agglomeration of graphene sheets by utilizing an environmentally friendly process.

High Volumetric Energy Density Supercapacitor of Additive-Free Quantum Dot Hierarchical Nanopore Structure.

The high surface-area-to-volume ratio of colloidal quantum dots (QDs) positions them as promising materials for high-performance supercapacitor electrodes. However, the challenge lies in achieving a highly accessible surface area, while maintaining good electrical conductivity. An efficient supercapacitor demands a dense yet highly porous structure that facilitates efficient ion-surface interactions and supports fast charge mobility. Here we demonstrate the successful development of additive-free ultrahigh energy density electric double-layer capacitors based on quantum dot hierarchical nanopore (QDHN) structures. Lead sulfide QDs are assembled into QDHN structures that strike a balance between electrical conductivity and efficient ion diffusion by employing meticulous control over inter-QD distances without any additives. Using ionic liquid as the electrolyte, the high-voltage ultrathin-film microsupercapacitors achieve a remarkable combination of volumetric energy density (95.6 mWh cm-3) and power density (13.5 W cm-3). This achievement is attributed to the intrinsic capability of QDHN structures to accumulate charge carriers efficiently. These findings introduce innovative concepts for leveraging colloidal nanomaterials in the advancement of high-performance energy storage devices.

Theoretical Investigation of the Green-Synthesized Carbon-Based Nanomaterial Potential as Inhibitors of ACE2 for Blocking SARS-CoV-2 Binding.

Since the emergence of SARS-CoV-2 in 2020, the world has faced a global pandemic, emphasizing the urgent need for effective treatments to combat COVID-19. This study explores the use of green-synthesized carbon-based nanomaterials as potential inhibitors of ACE2, a critical receptor for SARS-CoV-2 entry into host cells. Specifically, the study examines four carbon-based nanomaterials, namely, CD1, CD2, CD3, and CD4 in amino, graphitic, pyridinic, and pyrrolic forms, respectively, synthesized from curcumin, to investigate their binding affinity with ACE2. Molecular docking studies revealed that CD3 (pyridinic form) exhibited the highest binding affinity with ACE2, surpassing that of the control compound, curcumin. Notably, CD3 formed hydrophobic interactions and hydrogen bonds with key ACE2 residues, suggesting its potential to block the binding of SARS-CoV-2 to human cells. Moreover, molecular dynamics simulations demonstrated the stability of these ligand-ACE2 complexes, further supporting the promise of CD3 as an inhibitor. Quantum chemical analyses, including frontier molecular orbitals, natural bond orbital analysis, and the quantum theory of atoms in molecules, unveiled valuable insights into the reactivity and interaction strengths of these ligands. CD3 exhibited desirable chemical properties, signifying its suitability for therapeutic development. The study's findings suggest that green-synthesized carbon-based nanomaterials, particularly CD3, have the potential to serve as effective inhibitors of ACE2, offering a promising avenue for the development of treatments against COVID-19. Further experimental validation is warranted to advance these findings and establish new therapies for the ongoing global pandemic.

Interface Analysis of LiCl as a Protective Layer of Li1.3Al0.3Ti1.7(PO4)3 for Electrochemically Stabilized All-Solid-State Li-Metal Batteries.

Regardless of the superiorities of Li1.3Al0.3Ti1.7(PO4)3 (LATP), such as stability against oxygen and moisture, high ionic conductivity, and low activation energy, its practical application in all-solid-state lithium metal batteries is still impeded by the formation of ionic-resistance interphase layers. Upon contact with Li metal, electron migration from Li to LATP causes the reduction of Ti4+ in LATP. As a result, an ionic-resistance layer will be formed at the interface between the two materials. Applying a buffer layer between them is a potential measure to mitigate this problem. In this study, we analyzed the potential role of LiCl to protect the LATP solid electrolyte through a first-principle study-based density functional theory (DFT) calculation. Density-of-states (DOS) analysis on the Li/LiCl heterostructure reveals the insulating roles of LiCl in preventing electron flow to LATP. The insulating properties begin at depths of 4.3 and 5.0 Å for Li (001)/LiCl (111) and Li (001)/LiCl (001) heterostructures, respectively. These results indicate that LiCl (111) is highly potential to be applied as a protecting layer on LATP to avoid the formation of ionic resistance interphase caused by electron transfer from the Li metal anode.

Novel strategy for high-performance supercapacitors through the polyvinylpyrrolidone (PVP)-assisted in situ growth of FeS2.

Iron disulfide or pyrite (FeS2) has emerged as a promising transition metal sulfide-based supercapacitor owing to its abundance and superb electrochemical properties. However, FeS2 still faces major hurdles in realizing its full potential, such as a low energy density and poor conductivity. In this study, we report a high-performance FeS2 supercapacitor synthesized by a direct one-step process with the help of polyvinylpyrrolidone (PVP). The incorporation of PVP on the active materials prevented dendritic expansion and acted as a binding for solving the current FeS2 limitations, while facilitating a one-step synthesis process. Additionally, PVP could enhance the electrochemical performance by enabling faster ion movement. An FeS2/PVP nanocomposite was successfully synthesized, and used in an asymmetric supercapacitor, demonstrating a high specific capacity of 735 F g-1 (at 2 A g-1) and a high energy density of 69.74 W h kg-1 (at 911 W kg-1). The superior electrochemical properties of FeS2/PVP were enabled by the lower charge-carrier resistance and better surface passivation by PVP, as demonstrated by both electrochemical experiments and first-principles calculations. The high-performance supercapacitor of FeS2 presented in this study synthesized in situ by an efficient method provides a new insight into novel supercapacitor electrodes.

In Vitro and Silico Studies on the N-Doped Carbon Dots Potential in ACE2 Expression Modulation.

The alteration of ACE2 expression level, which has been studied in many diseases, makes the topic of ACE2 inducer potential crucial to be explored. The ACE2 inducer could further be designed to control the ACE2 expression level, which is appropriate to a specific case. An in vitro study of well-characterized carbon dots (CDs), made from citric acid and urea, was performed to determine their ability to modulate the ACE2 receptor. Gene expression of ACE2 was quantified using concentrations adjusted for IC50 results from CDs viability assays in HEK 293 and A549 cell lines. RT-qPCR was used to assess the expression of the ACE2 gene and its induction effect in normal cell lines (HEK-293A). According to the results of the tests, ACE2 is expressed in HEK-293A cell lines, and diminazene aceturate can increase ACE2 expression. The effect of CDs on ACE2 gene expression was further examined on the cell lines that had previously been induced with diminazene aceturate, which resulted in upregulation of the ACE2 expression level. An in silico study has been done by using a molecular docking approach. The molecular docking results show that CDs can make strong interactions with ACE2 amino acid residues through hydrophobic interaction, π-π interaction, π-cation interaction, and ionic interaction.

Recent Progress in Colloidal Quantum Dot Thermoelectrics.

Semiconducting colloidal quantum dots (CQDs) represent an emerging class of thermoelectric materials for use in a wide range of future applications. CQDs combine solution processability at low temperatures with the potential for upscalable manufacturing via printing techniques. Moreover, due to their low dimensionality, CQDs exhibit quantum confinement and a high density of grain boundaries, which can be independently exploited to tune the Seebeck coefficient and thermal conductivity, respectively. This unique combination of attractive attributes makes CQDs very promising for application in emerging thermoelectric generator (TEG) technologies operating near room temperature. Herein, recent progress in CQDs for application in emerging thin-film thermoelectrics is reviewed. First, the fundamental concepts of thermoelectricity in nanostructured materials are outlined, followed by an overview of the popular synthetic methods used to produce CQDs with controllable sizes and shapes. Recent strides in CQD-based thermoelectrics are then discussed with emphasis on their application in thin-film TEGs. Finally, the current challenges and future perspectives for further enhancing the performance of CQD-based thermoelectric materials for future applications are discussed.

Curcumin-derived carbon-dots as a potential COVID-19 antiviral drug.

Even entering the third year of the COVID-19 pandemic, only a small number of COVID-19 antiviral drugs are approved. Curcumin has previously shown antiviral activity against SARS-CoV-2 nucleocapsid, but its poor bioavailability limits its clinical uses. Utilizing nanotechnology structures, curcumin-derived carbon-dots (cur-CDs) were synthesized to increase low bioavailability of curcumin. In-silico analyses were performed using molecular docking, inhibition of SARS-CoV-2 nucleocapsid C-terminal domain (N-CTD) and antiviral activity were assessed in dimer-based screening system (DBSS) and in vitro respectively. Curcumin bound with the N-CTD at ΔG = -7.6 kcal/mol, however modifications into cur-CDs significantly improved the binding affinity and %interaction. Cur-CDs also significantly increased protection against SARS-CoV-2 in both DBSS and in vitro at MOI = 0.1. This study demonstrated the effect of post-infection treatment of curcumin and novel curcumin-derived carbon-dots on SARS-CoV-2 N-CTD dimerization. Further investigation on pre-infection and in-vivo treatment of curcumin and cur-CDs are required for a comprehensive understanding on the carbon-dots enhanced antiviral activity of curcumin against SARS-CoV-2.

Porphyrin-derived carbon dots for an enhanced antiviral activity targeting the CTD of SARS-CoV-2 nucleocapsid.

BACKGROUND: Since effective antiviral drugs for COVID-19 are still limited in number, the exploration of compounds that have antiviral activity against SARS-CoV-2 is in high demand. Porphyrin is potentially developed as a COVID-19 antiviral drug. However, its low solubility in water restricts its clinical application. Reconstruction of porphyrin into carbon dots is expected to possess better solubility and bioavailability as well as lower biotoxicity. METHODS AND RESULTS: In this study, we investigated the antiviral activity of porphyrin and porphyrin-derived carbon dots against SARS-CoV-2. Through the in silico analysis and assessment using a novel drug screening platform, namely dimer-based screening system, we demonstrated the capability of the antivirus candidates in inhibiting the dimerization of the C-terminal domain of SARS-CoV-2 Nucleocapsid. It was shown that porphyrin-derived carbon dots possessed lower cytotoxicity on Vero E6 cells than porphyrin. Furthermore, we also assessed their antiviral activity on the SARS-CoV-2-infected Vero E6 cells. The transformation of porphyrin into carbon dots substantially augmented its performance in disrupting SARS-CoV-2 propagation in vitro. CONCLUSIONS: Therefore, this study comprehensively demonstrated the potential of porphyrin-derived carbon dots to be developed further as a promisingly safe and effective COVID-19 antiviral drug.

Coke-Resistant Ni/CeZrO2 Catalysts for Dry Reforming of Methane to Produce Hydrogen-Rich Syngas.

Dry reforming of methane was studied over high-ratio zirconia in ceria-zirconia-mixed oxide-supported Ni catalysts. The catalyst was synthesized using co-precipitation and impregnation methods. The effects of the catalyst support and Ni composition on the physicochemical characteristics and performance of the catalysts were investigated. Characterization of the physicochemical properties was conducted using X-ray diffraction (XRD), N2-physisorption, H2-TPR, and CO2-TPD. The results of the activity and stability evaluations of the synthesized catalysts over a period of 240 min at a temperature of 700 °C, atmospheric pressure, and WHSV of 60,000 mL g−1 h−1 showed that the 10%Ni/CeZrO2 catalyst exhibited the highest catalytic performance, with conversions of CH4 and CO2 up to 74% and 55%, respectively, being reached. The H2/CO ratio in the product was 1.4, which is higher than the stoichiometric ratio of 1, indicating a higher formation of H2. The spent catalysts showed minimal carbon deposition based on the thermo-gravimetry analysis, which was <0.01 gC/gcat, so carbon deposition could be neglected.

Correction: Solid-state nitrogen-doped carbon nanoparticles with tunable emission prepared by a microwave-assisted method.

[This corrects the article DOI: 10.1039/D1RA07290K.].

A Free-Standing Polyaniline/Silicon Nanowire Forest as the Anode for Lithium-ion Batteries.

Despite its high theoretical capacity, silicon anode has limited intrinsic conductivity and experiences significant volume changes during charge-discharge. To overcome these issues, facile metal-assisted chemical etching and in-situ polymerization of aniline are employed to produce a dense 1D polyaniline/silicon nanowire forest without noticeable agglomeration as a free-standing anode for lithium-ion batteries. This hybrid electrode possesses high cycling performance, delivering a stable capacity capped at 2 mAh cm-2 for 346 cycles of charge-discharge. Maximum capacity of 2 mAh cm-2 is also achievable at high-rate cell testing of 2 mA cm-2 , which cannot be obtained by the anode with plain silicon wafer and silicon nanowire only. The introduction of polyaniline on the silicon nanowire is shown to reduce the solid electrolyte interface (SEI) resistance, stabilize the SEI layer, further alleviate the effect of volume changes, and boost the conductivity of the hybrid anode, resulting in the high electrochemical performance of the anode.

Role of Intrinsic Points Defects on the Electronic Structure of Metal-Insulator Transition h-FeS.

Hexagonal iron sulfide (h-FeS) offers huge potential in the development of metal-insulator transition devices. A stoichiometric h-FeS is hard to obtain from its natural iron deficiency. The effect of this iron deficiency on the electronic properties is still obscure. Here, we performed a charged point defect calculation in h-FeS. We found that the most favorable point defect in h-FeS can be tuned with a proper synthesis environment. The single iron vacancy could induce a midgap state with 0.05 eV energy gap, which explains the h-FeS low experimental band gap value. Furthermore, a semiconductor-to-metal transition is observed in h-FeS with higher iron vacancy concentration showing better conductivity from the excess charges. We also observe that iron vacancies will induce a magnetic moment on the antiferromagnetic h-FeS. The findings that the induced MIT behavior and magnetic moment can be tuned by defect concentration may benefit the development of spintronics devices.