Amorphous FeSnOx Nanosheets with Hierarchical Vacancies for Room-Temperature Sodium-Sulfur Batteries.

Room-temperature sodium-sulfur (RT Na-S) batteries, noted for their low material costs and high energy density, are emerging as a promising alternative to lithium-ion batteries (LIBs) in various applications including power grids and standalone renewable energy systems. These batteries are commonly assembled with glass fiber membranes, which face significant challenges like the dissolution of polysulfides, sluggish sulfur conversion kinetics, and the growth of Na dendrites. Here, we develop an amorphous two-dimensional (2D) iron tin oxide (A-FeSnOx) nanosheet with hierarchical vacancies, including abundant oxygen vacancies (Ovs) and nano-sized perforations, that can be assembled into a multifunctional layer overlaying commercial separators for RT Na-S batteries. The Ovs offer strong adsorption and abundant catalytic sites for polysulfides, while the defect concentration is finely tuned to elucidate the polysulfides conversion mechanisms. The nano-sized perforations aid in regulating Na ions transport, resulting in uniform Na deposition. Moreover, the strategic addition of trace amounts of Ti3C2 (MXene) forms an amorphous/crystalline (A/C) interface that significantly improves the mechanical properties of the separator and suppresses dendrite growth. As a result, the task-specific layer achieves ultra-light (~0.1 mg cm-2), ultra-thin (~200 nm), and ultra-robust (modulus=4.9 GPa) characteristics. Consequently, the RT Na-S battery maintained a high capacity of 610.3 mAh g-1 and an average Coulombic efficiency of 99.9 % after 400 cycles at 0.5 C.

Boron-Nitrogen-Edged Biomass-Derived Carbon: A Multifunctional Approach for Colorimetric Detection of H2O2, Flame Retardancy, and Triboelectric Nanogenerator.

Enhancing the concentration and type of nitrogen (N) dopants within the Sp2-carbon domain of carbon recycled from biomass sources is an efficient approach to mimic CNT, GO, and rGO to activate oxidants such as H2O2, excluding toxic chemicals and limiting reaction steps. However, monitoring the kind and concentration of N species in the Sp2-C domain is unlikely with thermal treatments only. A high temperature for graphitization reduces N moieties, leading to low electron density. This inhibits H2O2 adsorption and activation on catalyst surfaces. In this study, coffee waste (CW) is converted into B, N-doped biochar (BXNbY) using boric acid-assisted pyrolysis (H3BO3 mass = X and carbonization temperature = Y) under N2 to overcome the challenge. The B dopant regulates the concentration and type of N, provides Lewis's acid sites, and converts graphitic-N to pyridine-N in BXNbY. The optimized B3Nb900 exhibits excellent colorimetric sensing performance toward H2O2 with a low detection limit (36.9 nM) and high selectivity in the presence of many interferences and milk samples due to high pyridinic-N and Sp2 domain sizes. Interestingly, B enhances other properties of N-containing CW-derived carbon and introduces self-extinguishing and tribopositive properties. Hence, BXNbY-coated polyurethane foam shows excellent flame retardancy and energy harvesting performance.

Engineering FeOOH/Fe2O3@Carbon Interfaces with Biomass-Derived Carbon Nanodot/Iron Colloids for Efficient Redox-Modulated Dopamine Voltammetric Detection.

The Fe2+/Fe3+ redox couple is effective for voltammetric detection of trace dopamine (DA). However, achieving adequate concentrations with high electroactive surface area (ECSA), DA affinity, and fast interfacial charge transfer is challenging. Consequently, most reported Fe-based sensors have a high nanomolar range detection limit (LOD). Herein, we address these limitations by manipulating the phase and morphology of FeOOH/Fe2O3 heterojunctions anchored on sp2-carbon. FeOOH/Fe2O3 is synthesized by variable temperature aging of unique Fe5H9O15/Fe2O3@sp2-carbon colloidal nanoparticles, which form via chelation between biomass-derived carbon nanodots (CNDs) and Fe2+ ions. At 27°C and 120°C, Fe5H9O15/Fe2O3@sp2-carbon transforms into ß-FeOOH/Fe2O3 nanoparticles and α-FeOOH/Fe2O3 nanosheet, respectively. The ß-FeOOH/Fe2O3 interface exhibits higher eg orbital electron occupancy than α-FeOOH/Fe2O3, thereby facilitating oxygen adsorption and the generation of Fe2+/Fe3+ sites near the polarization potential of DA. This facilitates interfacial electron transfer between Fe3+ and DA. Moreover, its nanoparticle morphology enhances ECSA and DA adsorption compared to α-FeOOH/Fe2O3 nanosheets. With a LOD of ~3.11 nM, ß-FeOOH/Fe2O3 surpasses the lower threshold in humans (~10 nM) and matches noble-metal sensors. Furthermore, it exhibits selective detection of DA over 10 biochemicals in urine. Therefore, the ß-FeOOH/Fe2O3@sp2-C platform holds promise as a low-cost, easy-to-synthesize, and practical voltammetric DA monitor.

Enhancing electrochemical carbon dioxide reduction efficiency through heat-induced metamorphosis of copper nanowires into copper oxide/copper nanotubes with tunable surface.

Electrochemical CO2 reduction reaction (CO2RR) presents a unique opportunity to convert carbon dioxide (CO2) to value-added products while simultaneously storing renewable energy in the form of chemical energy. However, particle applications of this technology are limited due to the poor efficiency and product selectivity of the existing catalyst. In this study, we demonstrate a facile method for the heat-induced transformation of copper nanowires into CuOx/Cu nanotubes with defect-enriched surfaces. During this transformation, the outward migration of copper results in the formation of tubular structures encased within nanosized oxide grains. Notably, the hydrogen faradaic efficiency (FE) decreases with extended heat treatment, while carbon monoxide (CO) FE increases. As compared to Cu NWs, Cu NTs exhibit lower selectivity towards H2 and single-carbon (C1) products and favor the formation of multi-carbon (C2+) products. Consequently, a 2-fold increase in the single pass CO2 conversion (SPCC) and C2+ half-cell energy efficiency (EEhalf cell) was noted after heat treatment. The Cu NT-4 variant, synthesized under optimized conditions, exhibits the highest FE of 72.1 % for C2+ products at an operating current density (ID) of 500 mA cm-2.

Leveraging Direct Pyrolysis for the Synthesis of 10†nm Monodispersed Fe3O4/Fe3C NPS@Carbon to Improve SupercapacitANCE in Acidic Electrolyte.

The prevailing practice advocates pre-oxidation of electrospun Fe-salt/polymer nanofibers (Fe-salt/polymer Nf) before pyrolysis as advantageous in the production of high-performance FeOx@carbon nanofibers supercapacitors (FeOx@C). However, our study systematically challenges this notion by demonstrating that pre-oxidation facilitates the formation of polydispersed and large FeOx nanoparticles (FeOx@CI-DA) through "external" Fe3+ Kirkendall diffusion from carbon, resulting in subpar electrochemical properties. To address this, direct pyrolysis of Fe-salt/polymer Nf is proposed, promoting "internal" Fe3+ Kirkendall diffusion within carbon and providing substantial physical confinement, leading to the formation of monodispersed and small FeOx nanoparticles (FeOx@CDA). In 1 M H2SO4, FeOx@CDA demonstrates ~2.60× and 1.26× faster SO4 2- diffusivity, and electron transfer kinetics, respectively, compared to FeOx@CI-DA, with a correspondingly ~1.50× greater effective surface area. Consequently, FeOx@CDA exhibits a specific capacity of 161.92 mAhg-1, ~2× higher than FeOx@CI-DA, with a rate capability ~19 % greater. Moreover, FeOx@CDA retains 94 % of its capacitance after 5000 GCD cycles, delivering an energy density of 26.68 Whkg-1 in a FeOx@CDA//FeOx@CDA device, rivaling state-of-the-art FeOx/carbon electrodes in less Fe-corrosive electrolytes. However, it is worth noting that the effectiveness of direct pyrolysis is contingent upon hydrated Fe-salt. These findings reveal a straightforward approach to enhancing the supercapacitance of FeOx@C materials.

1-D Carbon Nano-Coils Derived from Almond Skin: Exhibiting Density of State, Diffusivity, Electron Transfer Rate, and Dopamine Redox Modulation Properties Akin to Graphene Oxide.

The quest to develop graphene-like biomass-carbon for advanced biomolecule redox modulation and sensing remains a challenge. The primary obstacle is the limited ability of biomass to undergo extensive graphitization during pyrolysis resulting in the formation of amorphous carbon materials with a small carbon-double-bond-carbon domain size (Lsp2 ), density of state (LDOS), ion diffusivity (D), and electron transfer rate constant (Ks). Herein, using almond skin (AS) the morphology of biomass is demonstrated as the key to overcoming these limitations. AS consists of 1D syringyl/guaiacyl lignin nano-coils which under H2 /H2 annealing transform into pyrolytic 1D carbon nano-coils (r-gC). Spectroscopy and microscopy analyses reveal that the sheet layering structure, crystallinity, LDOS, and Lsp2 of r-gC mimic those of graphene oxide (GO). Moreover, its unique 1D morphology and profound microstructure facilitate faster charge transfer and ion diffusion than GO's planar structure, leading to better redox modulation and sensing of the neurotransmitter dopamine (DA) in physiological fluids. r-gC's DA detection limit of 3.62 nM is below the lower threshold found in humans and on par with the state-of-the-art. r-gC is also DA-selective over 14 biochemicals. This study reveals that biomasses with well-defined and compact lignin structures are best suited for developing highly electroactive graphene-like biomass carbon.

FeCx-coated biochar nanosheets as efficient bifunctional catalyst for electrochemical detection and reduction of 4-nitrophenol.

Herein, we present the exceptional performance of FeCx-coated carbon sheets (FC) derived from the pyrolysis of waste biomass as a bifunctional catalyst for electrochemical detection and catalytic reduction of 4-nitrophenol (4-NP). Despite having a lower surface area, larger particle size, and lesser N content, the FC material prepared at a calcination temperature of 900 °C (FC900) outperforms the other samples. Deeper investigations revealed that the FC900 efficiently facilitates the charge transfer process and enhances the diffusion rate of 4-NP, leading to increased surface coverage of 4-NP on the surface of FC900. Additionally, relatively weaker interactions between 4-NP and FC900 allow the facile adsorption and desorption of reaction intermediates. Due to the synergetic interplay of these factors, FC900 exhibited a linear response to changes in 4-NP concentration from 1 µM to 100 µM with a low limit of detection (LOD) of 84 nM (S/N = 3) and high sensitivity of 12.15 µA µM-1 cm-2. Importantly, it selectively detects 4-NP in the presence of five times more concentrated 2-aminophenol, 4-aminophenol, catechol, resorcinol, and hydroquinone and ten times more concentrated metal salts such as Na2SO4. NaNO3, KCl, CuCl2, and CaCl2. Moreover, FC900 can accurately detect micromolar levels of 4-NP in river water with high recovery values (99.8-103.5 %). In addition, FC900 exhibited outstanding catalytic activity in reducing 4-NP to 4-aminophenol (4-AP), achieving complete conversion within 8 min with a high-rate constant of 0.42 min-1. FC900 also shows high recyclability in six consecutive catalytic reactions due to Fe magnetic property.

Modification of the electronic structure of g-C3N4 using urea to enhance the visible light-assisted degradation of organic pollutants.

Graphitic carbon nitride has been proven to be a good candidate for using solar energy for photo-induced pollutant degradation. However, the high photo-induced holes-electron recombination rate, unfavorable morphology, and textural properties limited their application. In this study, we present a novel g-C3N4 with a novel electronic structure and physiochemical properties by introducing a single nitrogen in the graphitic network of the g-C3N4 through a novel method involving step-by-step co-polycondensation of melamine and urea. Through extensive characterization using techniques such as XPS, UPS-XPS, Raman, XRD, FE-SEM, TEM, and N2 adsorption-desorption, we analyze the electronic and crystallographic properties, as well as the morphology and textural features of the newly prepared g-C3N4 (N-g-C3N4). This material exhibits a lower C/N ratio of 0.62 compared to conventional g-C3N4 and a reduced band gap of 2.63 eV. The newly prepared g-C3N4 demonstrates a distinct valance band maxima that enhances its photo-induced oxidation potential, improving photocatalytic activity in degrading various organic pollutants. We thoroughly investigate the photocatalytic degradation performance of N-g-C3N4 for Congo red (CR) and sulfamethoxazole (SMX), and removal of up to 90 and 86% was attained after 2 h at solution pH of 5.5 for CR and SMX. The influence of different parameters was examined to understand the degradation mechanism and the influence of reactive oxygenated species. The catalytic performance is also evaluated in the degradation of various organic pollutants, and it showed a good performance.

Theoretical verification on adsorptive removal of caffeine by carbon and nitrogen-based surfaces: Role of charge transfer, π electron occupancy, and temperature.

Eliminating an emerging water pollutant, caffeine molecules, from an aqueous solution using carbon and nitrogen-based adsorbents is of significant interest to public health. These adsorbents have been shown to have decent adsorption capacity toward caffeine due to their surface functionality. Therefore, screening various carbon and nitrogen-based surfaces can be a better option for high-performance adsorbents to remove caffeine efficiently from wastewater. Herein, we present combined first principles and molecular dynamics quantification of the adsorption enthalpies of caffeine molecules on the possible active sites of carbon and nitrogen-based adsorbents (graphene, phagraphene, graphdiyne, single-wall carbon nanotube, fullerene, and graphitic carbon nitride) with the incorporation of Van der Waals interactions. From the DFT calculations, N-doped carbon surfaces show the highest adsorption energies of single and dimer CAF compared to pristine carbon-based adsorbents. A charge density difference and Bader charge analysis display that high charge transfer occurs between the caffeine's oxygen and the surface's nitrogen atoms. An abundance of π-electrons from the nitrogen atoms, composed of large electron clouds of aromatic rings on the graphitic carbon surface, tends to favor extensive π-π interactions with the caffeine molecule. The high value of pz electron occupancy (1.445) of N in the hexagonal ring of the graphitic surface transfers additional charge transfer, which leads to strong adsorption energy of CAF than pristine surfaces. Also, the g-C3N4 surface adsorbs the CAF molecule with higher adsorption than other N-doped carbon surfaces due to the high pz_eo (1.5448) of N atoms on the surface. At 310 K, the water molecules' kinetics aids the single and dimer caffeine molecules to adsorb with the highest adsorption energies on the active sites of g-C3N4 surfaces than graphene adsorbent.

Electronic structure modulation of multi-walled carbon nanotubes using azo dye for inducing non-radical reaction: Effect of graphitic nitrogen and structural defect.

Multiwalled carbon nanotube (MWCNT) have a great potential for advanced oxidation process as a metal free catalyst. However, there catalytic activity is very low and needs to be appropriately tuned. Herein, we demonstrate a novel synthesis method for tuning the defect and surface functionality of MWCNT using azo dyes and the catalytic performance was tested for the degradation of different organic contaminates using PMS as an oxidant. The content, type of heteroatom functional groups, and the defect parameters were optimized by varying the pH and concentration of the organic dye. The quenching effect showed that singlet oxygen (1O2) is the primary reactive species generated by graphitic nitrogen, which can be boosted by the degree of graphitic structure disruption in MWCNT. The Linear sweep voltammetry (LSV) also confirmed that extrinsic doping enhanced the non-radical degradation by increasing the direct charge transfer rate from MB to PMS. Moreover, the designed catalyst showed a fast degradation performance with 35.1 kJ/mol activation energy and achieved the highest dye degradation rate and even surpassed some state-of-the-art metal-based and metal-free catalysts. The effect of inorganic anions study has also confirmed its industrial applicability.

In situ construction of Fe3O4@FeOOH for efficient electrocatalytic urea oxidation.

Substituting water oxidation half of water splitting with anodic oxidation of urea can reduce the cost of H2 production and provide an avenue for treating urea-rich wastewater. However, developing an efficient and stable electrocatalyst is necessary to overcome the indolent kinetics of the urea oxidation reaction (UOR). Accordingly, we have used the Schikorr reaction to deposit Fe3O4 particles on the nickel foam (Fe3O4/NF). Results from the various analysis indicated that under the operational conditions, Fe3O4 underwent surface reconstruction to produce a heterolayered structure wherein a catalytically active FeOOH layer encased a conducting Fe3O4. Fe3O4/NF outperformed RuO2 as a UOR catalyst and delivered a current density of 10 50 and 100 mA cm-2 at low applied potentials of 1.38 1.42 and 1.46 V, respectively, with a Tafel slope of 28 mV dec-1. At the applied potential of 1.4 V, Fe3O4/NF demonstrated a turnover frequency (TOF) of 2.8 × 10-3 s-1, highlighting its superior intrinsic activity. In addition, a symmetrical urea electrolyzer constructed using Fe3O4/NF produced the current density of 10 mA cm-2 at a cell voltage of 1.54 V.

Efficient imidazolium ionic liquid as a tri-functional robust catalyst for chemical fixation of CO2 into cyclic carbonates.

The recent increase in CO2 levels has had an extensive impact on the environment; hence an effective catalyst for chemical CO2 fixation into value-added products is demanded. This work demonstrates a simple approach towards the chemical fixation of CO2 to cyclic carbonates without solvent, metal and additives using one-pot synthesized tri-functional-imidazolium bromide ionic liquid. Herein, synthesized tri-functional-imidazolium-based ionic liquids, namely 3-(2-hydroxyethyl)-1-vinyl-1H-imidazole-3-ium bromide ([VIMEtOH][Br] (24 and 72 h)), 3-(2-hydroxyethyl)-1-vinyl-1H-imidazole-3-ium hydroxyl ([VIMEtOH][OH]) and poly 3-(2-hydroxyethyl)-1-vinyl-1H-imidazole-3-ium bromide (poly [VIMEtOH][Br]), were used for the comprehensive investigation of chemical fixation of CO2 into cyclic carbonates and their physiochemical properties. In case of [VIMEtOH][Br] ionic liquid, it displayed time-dependent synthesis dissolution in the reaction system. This study found that [VIMEtOH][Br]-72 ionic liquid is not dissolved in the reaction system. The effect on the catalytic efficiency of the presence of functional groups in ionic liquids such as N-vinyl (-CC-N), acidic proton of imidazolium (-C (2)-H) and hydroxyl (-OH) along with bromide anion and the reaction conditions are systematically investigated. For CO2 fixation, 99.6% conversion of propylene oxide with an excellent selectivity of propylene carbonate (≥99%) over [VIMEtOH][Br]-72 catalyst (at 120 °C, 2 MPa, 2 h) was observed without co-catalyst, metal and solvent. Also, it demonstrated an excellent wide substrates scope of epoxide and all reactions were performed on gram-scalable, which are potential prospects for industrial use.

Hydroxypicolinic acid tethered on magnetite core-silica shell (HPCA@SiO2@Fe3O4) as an effective and reusable adsorbent for practical Co(II) recovery.

The soaring demand and future supply risk for cobalt (Co) necessitate more efficient adsorbents for its recycling from electronic wastes, as a cheaper and less hazardous option for its production. Herein, a magnetic adsorbent covalently tethered with 5-hydroxypicolinic acid (HPCA) as Co(II) ligand was developed. The magnetic component (Fe3O4) was protected with silica (SiO2), then silanized with chloroalkyl linker and subsequently functionalized with HPCA via SN2 nucleophilic substitution (HPCA@SiO2@Fe3O4). Results from FTIR, TGA, EA, and XPS confirm the successful adsorbent preparation with high HPCA loading of 2.62 mmol g-1. TEM-EDS reveal its imperfect spherical morphology with ligands well-distributed on its surface. HPCA@SiO2@Fe3O4 is hydrophilic, water-dispersible and magnetically retrievable, which is highly convenient for its recovery. The Co(II) capture on HPCA@SiO2@Fe3O4 involves monodentate coordination with carboxylate (COO-) and lone pair acceptance from pyridine (aromatic -N = ) moiety of HPCA, with minor interaction from acidic silanols (Si-O-). The binding occurs at 2 HPCA: 1 Co(II) ratio, that follows the Sips isotherm model with competitive Qmax = 92.35 mg g-1 and pseudo-second order kinetics (k2 = 0.0042 g mg-1 min-1). In a simulated LIB liquid waste, HPCA@SiO2@Fe3O4 preferentially captures Co(II) over Li(I) with αLi(I)Co(II)=166 and Mn(II) with αMn(II)Co(II)=55, which highlights the importance of HPCA for Co(II) recovery. Silica protection of Fe3O4 rendered the adsorbent chemically stable in acidic thiourea solution for its regeneration by preventing the deterioration of the magnetic component. Covalent functionalization averted ligand loss, which allowed HPCA@SiO2@Fe3O4 to deliver consistent and reversible adsorption/desorption performance. Overall results demonstrate the potential of HPCA@SiO2@Fe3O4 as a competitive and practical adsorbent for Co(II) recovery in liquid waste sources.

Critical Review, Recent Updates on Zeolitic Imidazolate Framework-67 (ZIF-67) and Its Derivatives for Electrochemical Water Splitting.

Design and construction of low-cost electrocatalysts with high catalytic activity and long-term stability is a challenging task in the field of catalysis. Metal-organic frameworks (MOF) are promising candidates as precursor materials in the development of highly efficient electrocatalysts for energy conversion and storage applications. This review starts with a summary of basic concepts and key evaluation parameters involved in the electrochemical water-splitting reaction. Then, different synthesis approaches reported for the cobalt-based Zeolitic imidazolate framework (ZIF-67) and its derivatives are critically reviewed. Additionally, several strategies employed to enhance the electrocatalytic activity and stability of ZIF-67-based electrocatalysts are discussed in detail. The present review provides a succinct insight into the ZIF-67 and its derivatives (oxides, hydroxides, sulfides, selenides, phosphide, nitrides, telluride, heteroatom/metal-doped carbon, noble metal-supported ZIF-67 derivatives) reported for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting applications. Finally, this review concludes with the associated challenges and the perspectives on developing the best economic, durable electrocatalytic materials.

Electrochemically engineered zinc(iron)oxyhydroxide/zinc ferrite heterostructure with interfacial microstructure and hydrophilicity ideal for supercapacitors.

Zinc ferrite@nickel foam (ZF@Nf) is a potential commercial supercapacitor electrode due to its large theoretical capacity, abundant elemental composition, excellent conductivity, and stability. However, deficient active sites limit its specific capacitance (SC). Herein, we demonstrate that engineering ZF's interfacial microstructure and hydrophilicity mitigate this limitation. ZF@Nf is used as the working electrode in a 3-electrode cell and subjected to multiple oxygen evolution reaction cycles in potassium hydroxide. Systematic changes in ZF's porosity, crystallinity, hydrophilicity, and composition after each cycle were characterised using spectroscopy, sorption isotherm, microscopy and photography techniques. During cycling, the edges of ZF partially phase-transform into a dense polycrystalline zinc(iron)oxyhydroxide film via semi-reversible oxidation resulting in zinc(iron)oxyhydroxide/ZF interface formation. The maximum ion-accessible zinc(iron)oxyhydroxide film density is obtained after 1000 cycles. Strong ionic interaction at the interface induces high hydrophilicity, this together with the 3-dimensional diffusion channels of the zinc(iron)oxyhydroxide significantly increase electroactive surface area and decrease ion diffusion resistance. Consequently, the SC, energy density, and rate-capability of the interface compare favourably with state-of-the-art electrodes. The strong interfacial interaction and polycrystallinity also ensure long-term electrochemical stability. This study proves the direct correlation between interfacial microstructure and hydrophilicity, and SC which provides a blueprint for future energy-storage electrode design.

Methylcellulose/tannic acid complex particles coated on alginate hydrogel scaffold via Pickering for removal of methylene blue from aqueous and quinoline from non-aqueous media.

Adsorbents reported for liquid phase decontamination under both aqueous and non-aqueous media are all dispersed phase sorbents that further require a tedious separation step post adsorption. Herein, a monolith, highly porous, and mechanically robust scaffold was synthesized for the adsorption of pollutants from both aqueous and non-aqueous media with facile separation and regeneration. Methylcellulose-tannic acid complex particles were prepared and systematically decorated on the surface of interpenetrating polymer network (IPN) scaffold via Pickering emulsion. Due to the surface coating of the particles, plausible amphiphilic adsorption of quinoline (QUI) and methylene blue (MB) was achieved from fuel and water, respectively. The hydroxyl (OH-) and carboxyl (COOH-) groups of tannic acid, alginate, and polyacrylic acid created hydrogen bonding, electrostatic interaction, acid-base interaction, and π-π stacking. Maximum adsorption capacity of 791.17 mg/g MB and 460.92 mg/g QUI was recorded with facile separation, excellent adsorbent regeneration, and reusability. Although both followed the pseudo-second-order adsorption kinetic model, a different mechanism was identified to govern the adsorption under aqueous and non-aqueous environment i.e. only the surface particles were active for QUI adsorption while the scaffold was also involved for MB adsorption.

Hyper-crosslinked tetraphenylborate as a regenerable sorbent for Cs+ sequestration in aqueous media through cation-π interactions.

Practical adsorbents that could efficiently collect radioactive Cesium (Cs+) are critically important in achieving proper management and treatment measures for nuclear wastes. Herein, a hyper-crosslinked tetraphenylborate-based adsorbent (TPB-X) was prepared by reacting TPB anions as Cs+ binding sites with dimethoxymethane (DMM) as crosslinker. The most efficient TPB-X synthesis was attained at 1:4 TPB/DMM mole ratio with sorbent yield of 81.75%. Various techniques such as FTIR, TGA-DTG, N2 adsorption/desorption and SEM-EDS reveal that TPB-X is a water-insoluble, thermally stable and highly porous granular sorbent. Its hierarchical pore structure explains its very high BET surface area (1030 m2 g-1). Sequestration of Cs+ by TPB-X involves its exchange with H+ followed by its binding with the phenyl rings of TPB through cation-π interactions. The Cs+ adsorption in TPB-X is endothermic and spontaneous, which adheres to the Hill isotherm model (qm = 140.58 mg g-1) and follows pseudo-second order kinetics (k2 = 0.063 g mg-1 h-1). Calculations from the density functional theory reveal that the binding of TPB anion is strongest for Cs+. Thus, TPB-X was able to selectively capture Cs+ in simulated surface water containing Na+, K+, Mg2+, and Ca2+ and in HLLW containing Na+, Rb+, Sr2+, and Ba2+. Hyper-crosslinking was found beneficial in rendering TPB-X reusable as the sorbent was easily retrieved from the feed after Cs+ capture and was able to withstand the acid treatment for its regeneration. TPB-X exhibited consistent performance with no sign of chemical or physical deterioration. TPB-X offers a practical approach in handling Cs+ contaminated streams as it can be repeatedly used to enrich Cs+ in smaller volume of media, which can then be purified for Cs+ reuse or stored for long-term natural Cs+ decay process.

Ground coffee waste-derived carbon for adsorptive removal of caffeine: Effect of surface chemistry and porous structure.

Carbon-based adsorbents show high adsorption capacity towards caffeine due to their porosity and surface functionality. However, the main limiting factor for high performance has not been addressed; furthermore, the adsorption interaction with different active sites needs to be explored. In this study, we synthesized a hierarchical porous nitrogen-doped carbon with unique surface functionality by single-step calcination of coffee waste with KOH under N2. The porous structure, nitrogen content, and types are optimized by varying calcination temperature and KOH concentration. The result of the adsorption experiments shows that both the nitrogen type and the pore size distribution are the limiting factors to adsorption. In addition, the effect of acidic and basic functional groups is studied in detail. The adsorption of caffeine on CW-C is dominantly governed by EDA interaction between the resonance structure of pyridonic-N and the electron-withdrawing group of the caffeine, and the dispersive force caused by the oxidized-N and delocalized π electron of caffeine. Furthermore, we demonstrate that the surface of CW-C is not suitable for the formation of electrostatic and non-electrostatic interaction with caffeine. The maximum adsorption capacity of caffeine at 25 °C is 274.2 mg/g. Moreover, we demonstrate that the unique physio-chemical properties of CW-C are capable of adsorbing other emerging contaminants such as diclofenac, where maximum adsorption capacity of 242.3 mg/g diclofenac is recorded.

Synergetic effect of ZnCo2O4/inorganic salt as a sustainable catalyst system for CO2 utilization.

Currently, it is essential to consider the rapidly increasing emission of CO2 into the atmosphere, causing major environmental issues such as climate change and global warming. In this work, we have developed the binary catalyst system (ZnCo2O4/inorganic salt) for chemical fixation of CO2 with epoxides into cyclic carbonates without solvent, and all reactions were performed on a large scale using a 100 ml batch reactor. Two mesoporous catalysts of ZnCo2O4 with different architecture, such as flakes (ZnCo-F) and spheres (ZnCo-S) were synthesized and utilized as a heterogeneous catalyst for cycloaddition reaction. The bifunctional property of catalysts is mainly attributed to strong acidic and basic properties confirmed by TPD (NH3 & CO2) analysis. The ZnCo-F catalyst exhibited excellent conversion of propylene oxide (99.9%) with good corresponding selectivity of propylene carbonate (≥99%) in the presence of inorganic salt (KI) at 120 °C, 2 MPa, 3 h. In addition, ZnCo-F catalyst demonstrated good catalytic applicability towards the various substrates scope of the epoxide. Furthermore, the catalytic properties were examined by evaluating the reaction parameter such as catalyst loading, pressure, temperature and time. The proposed catalyst exhibited good reusability for cycloaddition reaction without significant change in its catalytic activity and proposed a possible reaction mechanism for chemical fixation of CO2 with epoxide into cyclic carbonate over ZnCo-F/KI.

Synthesis and performance evaluation of plastic waste aerogel as sustainable and reusable oil absorbent.

Direct utilization of waste polyethylene terephthalate (PET) from the environment to form highly porous aerogel technology for oil absorption is an attractive approach from the view point of green chemistry. However, the oil absorption reaction is limited by low oil absorption capacity and less stability. For now, silica aerogel are used to solve these problem. Our goal is to substitute to these silica aerogel with PET aerogel technology. Herein, we have prepared an environmental waste PET based aerogel with 1.0:0.5 wt% PET, polyvinyl alcohol (PVA), and glutaraldehyde (GA) 0.2% v/v were dispersed in 10 mL DI water, followed by homogenization (30 min), sonication (10 min), and ageing (2 h) at 70 °C. To escape macroscopic cracking, cooling (8 h) at 4 °C was followed by freezing (6 h), freeze drying at -80 °C, and 5 mTorr for 18 h. The hybrid PET aerogel displays excellent performance towards oil absorption. Notably it showed high absorption capacity towards the different oils about 21-40 times its own weight, depending on the viscosity and density of the oil and solvents within 15-35 s, 25 °C, and 2 × 2 cm aerogel size. In addition, the aerogel shows there is no change in structure after several recycles due to high mechanical strength. Furthermore, because of the PET aerogel's high porosity (99.74%) and low density (0.0311 g/cm3), close bonding between PET-PVA occurs. Therefore, aerogel shows hydrophobic nature, good mechanical strength, high thermal stability, arrangement of the interconnected fibrillar pore network offers a high surface to volume ratio, low surface energy, high surface roughness, and more reusability. All these parameters are responsible for high oil absorption.