Ions In Sites Research Articles

Enhanced and Efficient Predictions of Dynamic Ionization through Constant-pH Adiabatic Free Energy Dynamics.

Dynamic or structurally induced ionization is a critical aspect of many physical, chemical, and biological processes. Molecular dynamics (MD) based simulation approaches, specifically constant pH MD methods, have been developed to simulate ionization states of molecules or proteins under experimentally or physiologically relevant conditions. While such approaches are now widely utilized to predict ionization sites of macromolecules or to study physical or biological phenomena, they are often computationally expensive and require long simulation times to converge. In this article, using the principles of adiabatic free energy dynamics, we introduce an efficient technique for performing constant pH MD simulations within the framework of the adiabatic free energy dynamics (AFED) approach. We call the new approach pH-AFED. We show that pH-AFED provides highly accurate predictions of protein residue pKa values, with a MUE of 0.5 pKa units when coupled with driven adiabatic free energy dynamics (d-AFED), while reducing the required simulation times by more than an order of magnitude. In addition, pH-AFED can be easily integrated into most constant pH MD codes or implementations and flexibly adapted to work in conjunction with enhanced sampling algorithms that target collective variables. We demonstrate that our approaches, with both pH-AFED standalone as well as pH-AFED combined with collective variable based enhanced sampling, provide promising predictive accuracy, with a MUE of 0.6 and 0.5 pKa units respectively, on a diverse range of proteins and enzymes, ranging up to 186 residues and 21 titratable sites. Lastly, we demonstrate how this approach can be utilized to understand the in vivo performance engineered antibodies for immunotherapy.

Magnetic bentonite with organic modification highly efficient for adsorption of Ce(III) and Y(III)

A simple organic magnetic adsorbent (PAA-MBent) was synthesized using 2-hydroxyphosphonylacetic acid and applied to the adsorption of Ce(III) and Y(III). It was confirmed that the phosphoryl groups could effectively regulate the homogeneous loading of magnetic particles on the bentonite during the synthesis process, and the hydroxyl and phosphoryl groups can be sufficiently used on the surface of bentonite to increase the abundance of adsorption sites, which have favorable coordination with Ce(III) and Y(III). The experimental results showed that the maximal adsorption capacity was increased to 99.11 mg/g and 65.65 mg/g for Ce(III) and Y(III), respectively, which was 2.52 and 2.91 times higher than magnetic bentonite. The adsorption behavior conformed to the Langmuir isothermal adsorption model and the pseudo-second-order kinetic model, and the adsorption of Ce(III) by PAA-MBent performed better than that of Y(III). The adsorption efficiency was affected by ionic strength and site inhibition of coexisting cations, and its adsorption selectivity was mainly disturbed by the competition of Al ions. The results after adsorption identified the key adsorption mechanisms as ion exchange, electrostatic attraction, functional group complexation, and hole filling. After five cycles, the adsorbent still exhibited good adsorption and magnetic recovery performance. These results reveal that PAA-MBent is promised to be a novel, inexpensive and effective adsorbent for the removal of Ce(III) and Y(III) from contaminated water.

Investigating the Effect of GLU283 Protonation State on the Conformational Heterogeneity of CCR5 by Molecular Dynamics Simulations.

CCR5 is a class A GPCR and serves as one of the coreceptors facilitating HIV-1 entry into host cells. This receptor has vital roles in the immune system and is involved in the pathogenesis of different diseases. Various studies were conducted to understand its activation mechanism, including structural studies in which inactive and active states of the receptor were determined in complex with various binding partners. These determined structures provided opportunities to perform molecular dynamics (MD) simulations and to analyze conformational changes observed in the protein structures. The atomic-level dynamic studies allow us to explore the effects of ionizable residues on the receptor. Here, our aim was to investigate the conformational changes in CCR5 when it forms a complex with either the inhibitor maraviroc (MRV), an approved anti-HIV drug, or HIV-1 envelope protein GP120, and compare these changes to the receptor's apo form. In our simulations, we considered both ionized and protonated states of ionizable binding site residue GLU2837.39 in CCR5 as the protonation state of this residue was considered ambiguously in previous studies. Our molecular simulations results suggested that in fact, the change in the protonation state of GLU2837.39 caused interaction profiles to be different between CCR5 and its binding partners, GP120 or MRV. We observed that when the protonated state of GLU2837.39 was considered in complex with the envelope protein GP120, there were substantial structural changes in CCR5, indicating that it adopts a more active-like conformation. On the other hand, CCR5 in complex with MRV always adopted an inactive conformation regardless of the protonation state. Hence, the CCR5 coreceptor displays conformational heterogeneity not only depending on its binding partner but also influenced by the protonation state of the binding site binding site residue GLU2837.39. This outcome is also in accordance with some studies showing that GP120 binding could activate signaling pathways. This outcome could also have significant implications for discovering novel CCR5 inhibitors as anti-HIV drugs using in silico methods such as molecular docking, as it may be necessary to consider the protonated state of GLU2837.39.

Zwitterionic covalent organic nanosheets for selective analysis of domoic acid in marine environment

BackgroundDomoic acid (DA) is a neurotoxic compound causing amnesic shellfish poisoning, secreted by red algae and diatoms. As a glutamate analogue, DA accumulates in filter-feeding marine organisms, posing significant health risks to humans upon consumption. Detecting DA in marine environments remains challenging due to its low concentration and interference from complex matrices. Effective detection and removal require materials with high efficiency and selectivity, which traditional inorganic ionic materials lack due to their limited adsorption capacity and selectivity. Ionic covalent organic frameworks (iCOFs) expected to become highly efficient DA adsorbents due to tunable ionic sites. ResultsThus, a zwitterionic covalent organic nanosheet (TGDB-iCONs) was synthesized to selectively capture DA. TGDB-iCONs was prepared by one-step Schiff-base reaction of the charged monomer triaminoguanidine hydrochloride. It uniformly distributed positively charged guanidinium and negatively charged chloride ions on the surface, forming zwitterionic binding sites. The self-peeling of TGDB-iCONs facilitated the exposure of active sites and improved the adsorption efficiency. Several binding forces were generated between TGDB-iCONs and DA, including complementary electrostatic hydrophilic interactions, which were verified by density functional theory (DFT) calculation. TGDB-iCONs exhibited ultra-fast adsorption kinetics (7 min) and relatively high adsorption capacity (66.48 mg/g) for DA. Furthermore, TGDB-iCONs exhibit strong salt resistance, which is attributed to the charge “shielding” effect of the zwitterionic ions present in TGDB-iCONs. TGDB-iCONs could highly selectively enrich DA and detect trace DA from marine environment including seawater, algae and marine organisms and the limit of detection as low as 0.3 ng/kg. Significance and noveltyThis comprehensive study not only sheds light on the vast potential of ionic covalent organic frameworks nanosheets (iCONs) in supporting early warning, control, and traceability of DA, but also lays a solid foundation for future research endeavors aimed at designing and harnessing the unique properties of iCONs.

Construction of VO2@V2C MXene heterostructure toward superior-rate rechargeable aqueous zinc batteries

V2C MXene delivers excellent metallic properties and robust mechanical stability. However, its low capacity, easy volume expansion during charge/discharge and relatively short cycle life limits its further development. It is an effective strategy to build Van der Waals heterostructures that can shield the monolithic materials from defects and integrate the advantages of the monolithic materials. Herein, via a one-step hydrothermal method, a VO2@V2C heterostructure is successfully constructed by the controllable oxidation of V2C, which allows for shorter ion diffusion distances, faster ion transport and enhancement of hydrophilic properties of the material. The VO2@V2C heterostructures have incredible reversibility (440.9 mAh/g at 0.2 A/g), remarkable cycling stability (142.7 mAh/g at 1.0 A/g after 900 cycles) and superior-rate capacity (255.3 mAh/g at 6.0 A/g). Density functional theory (DFT) calculations revealed that VO2@V2C possesses excellent adsorption capacity for zinc ions and outstanding electrical conductivity. The heterogeneous interface between the two materials is conducive to the increase of the embedding sites of zinc ions, which promotes the homogeneous distribution and rapid diffusion of zinc ions in the materials, and consequently enhances the capacity and cycling reliability of the electrodes. It provides a new idea for the selection of cathode electrodes for aqueous zinc ion batteries (ZIBs) in present study.

The embedding of 1,8-diazabicyclo[5.4.0]undec-7-ene into hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure

The preparation of cyclic carbonates via CO2 cycloaddition reaction was crucial for the lithium industry. Herein, a series of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) based hyper-crosslinked ionic polymers with different ionic site densities were prepared by simultaneously Friedel-Crafts alkylation and quaternization reactions. The obtained P[DBU]DCX(1:1) with a high ionic site density (1.45 mmol g−1), prepared by the equimolar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene and α,α′-dichloro-p-xylene, exhibiting excellent catalytic performance with a chloropropylene carbonate (CPC) yield of 98.8 % and selectivity of 99.3 % at atmospheric pressure. Meanwhile, the conversion capacity was comparable with other catalysts. Moreover, the CO2 cycloaddition reaction over P[DBU]DCX(1:1) catalyst followed pseudo-first-order kinetics, and the activation energy (Ea) was obtained to be 28.7 kJ/mol by performing kinetic experiments at different temperatures. In addition, it also had a good reusability and universality for different epoxides. The synergistic effects of abundant quaternary nitrogen cations derived from DBU and chlorine anions on the activation of CO2 and epoxide were explored based on density functional theory calculation. This study offers a new approach for the design and application of hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure.

An extensive inquisition on the impact of modifier oxides over the luminescent properties of Eu3+ embedded Li-Al tri-former glasses for photonic applications

A novel, tri-former glasses with the composition 45B2O3+12P2O5+8SiO2+3Al2O3+10LiF+20MO+1Eu2O3 with varying metal oxides have been fabricated following the melt-quenching technique. The absorption, luminescence and radiative decay measurements were carried out, and the specific colour emitted by the glass sample was determined employing the CIE chromaticity diagram. While monitoring the excitation at 393 nm, luminescence spectra of all the glass samples exhibit red emission pertaining to the 5D0→7F2 transition at around 615 nm. The local geometry around the Eu3+ ions site and the nature of the Rare Earth ion-ligand bond have been analyzed employing Judd-Ofelt theory and the R/O ratio spectral parameter. The intensity parameters follows the trend as Ω2 > Ω4 > Ω6 and the results are co-related well with the R/O ratio spectral parameter values. Radiative properties such as σPE, βR and AR of every glass in the present series possess higher values, and the FWHM exhibits lower value, indicating the potentiality of the BPSAEu:M glasses for lasing applications. Among the prepared samples, BPSAEu:Ba glass exhibit higher values for σPE and AR as 42.3 × 10−22 cm2 and 641.71 s−1 respectively which are apt for laser applications. The quantum yield pertaining to the 5D0→7F2 transition exhibit more than 65 % for all the samples and particularly Barium oxide incorporated glass BPSAEu:Ba exhibits 84 %. The present study suggests that BPASEu:Ba glass is a promising luminescent material for photonic/LED applications.

Facile synthesis of mesoporous Co3O4 anchoring on the g-C3N4 nanosheets for high performance supercapacitor

The rational design of the hybrid supercapacitor is the proficient way to confront the problem addressed in the supercapacitor through the collective advantage of each material and even shows laudable electrochemical properties from intertwined effects. A hydrothermal technique was used to effectively incorporate cobalt oxide into layered g-C3N4 nanosheets for a high-performance-based hybrid supercapacitor. The nanocomposite of Co3O4/g-C3N4 (with 0.01 M Co3O4) achieved a maximum specific capacitance of approximately 455 F/g at a current density of 1 A/g. It exhibited 95 % cyclic stability over 10,000 cycles, without sacrificing its coulombic efficiency in a three-electrode configuration. The enhanced charge storage contribution arises from the effective incorporation of cobalt oxide into the layered carbon nitride, increasing the number of electrochemically active sites for electrolytic ions. A symmetric device was fabricated using a KOH gel-based electrolyte, delivering high energy and power density of 28.13 Wh/kg and 1.68 kW/kg, respectively, with a maximum cell operating voltage of 1.2 V. Furthermore, the device demonstrated excellent cyclic stability of 95 % with constant coulombic efficiency.

Influence of Dy3+ doping on Mössbauer, magnetic and microwave absorption properties of M-type Ba0.5Ca0.5DyxFe12-xO19 hexaferrites

The present research paper reports a systematic study of the magnetic, and structural properties of Ba0.5Ca0.5DyxFe12-xO19 M-type hexaferrite. The dysprosium was doped @ x = 0 − 0.2, keeping Δx = 0.05, in BCDF by the sol–gel self-ignition technique. The sintering of the synthesized samples was performed for 4 h at 1050°C. The crystallographic analysis of the samples was made from the X-ray diffractograms (XRD), while the morphological and elemental analysis was made from field emission scanning electron microscopy (FESEM), and energy-dispersive X-ray spectroscopy (EDAX) profiles. The structural results revealed the formation of the M-type hexaferrite having P63/mmc as a space group along with the co-existence of a secondary Fe2O3 phase. FESEM micrographs exhibit the hexagonal platelets randomly arranged with agglomerations at some places giving rise to the random variations in particle size with varying ’x’. Magnetic measurements (VSM) show that the saturation magnetization (MS) and coercivity (HC) increase with the increasing Dy3+ doping pointing towards the fact that the Dy doping in Ba-Ca ferrite can be used to fabricate the hard ferrites with good saturation magnetization. The Mössbauer spectrum recorded at room temperature reveals five superimposed sextets representing the five Fe3+ ion sites. Investigating the Microwave absorption (MWA) characteristics in the frequency range 8 − 12 GHz (X-band), reveals that the sample with x = 0.1 having 3 mm thickness possesses good MWA power. Its minimum RL value for matching frequency 10.06 GHz is approximately −26.96 dB, indicating that more than 90 % of microwaves are absorbed. The current work offers the Dysprosium-doped BCDF hexaferrites, as promising candidatesfor microwave absorption applications.

Porous Organic Cage as an Efficient Platform for Industrial Radioactive Iodine Capture

AbstractHerein, we firstly develop porous organic cage (POC) as an efficient platform for highly effective radioactive iodine capture under industrial operating conditions (typically ≥150 °C), ≤150 ppmv of I2). Due to the highly dispersed and readily accessible binding sites as well as sufficient accommodating space, the constructed NKPOC‐DT‐(I−) (NKPOC=Nankai porous organic cage) demonstrates a record‐high I2 uptake capacity of 48.35 wt % and extraordinary adsorption capacity of unit ionic site (~1.62) at 150 °C and 150 ppmv of I2. The I2 capacity is 3.5, 1.6, and 1.3 times higher than industrial silver‐based adsorbents Ag@MOR and benchmark materials of TGDM and 4F‐iCOF‐TpBpy‐I− under the same conditions. Furthermore, NKPOC‐DT‐(I−)Me exhibits remarkable adsorption kinetics (k1=0.013 min−1), which is 1.2 and 1.6 times higher than TGDM and 4F‐iCOF‐TpBpy‐I− under the identical conditions. NKPOC‐DT‐(I−)Me thus sets a new benchmark for industrial radioactive I2 adsorbents. This work not only provides a new insight for effectively enhancing the adsorption capacity of unit functional sites, but also advances POC as an efficient platform for radioiodine capture in industry.

Metal-Organic Framework Nanofluidic Synapse.

Chemical synapse completes the signaling through neurotransmitter-mediated ion flux, the emulation of which has been a long-standing obstacle in neuromorphic exploration. Here, we report metal-organic framework (MOF) nanofluidic synapses in which conjugated MOFs with abundant ionic storage sites underlie the ionic hysteresis and simultaneously serve as catalase mimetics that sensitively respond to neurotransmitter glutamate (Glu). Various neurosynaptic patterns with adaptable weights are realized via Glu-mediated chemical/ionic coupling. In particular, nonlinear Hebbian and anti-Hebbian learning in millisecond time ranges are achieved, akin to those of chemical synapses. Reversible biochemical in-memory encoding via enzymatic Glu clearance is also accomplished. Such results are prerequisites for highly bionic electrolytic computers.

A sustainable one-pot synthesis of 2,5-diformylfuran from carbohydrates using tetracationic ionic liquid

A plausible solution to the current energy crisis is the development of cost-effective and inherently secure methods for accelerating the sustainable production of value-added compounds from biomass. In this study, we have developed a highly efficient catalytic system for the conversion of fructose into 2,5-diformylfuran (DFF) using tetracationic ionic liquids with dual Brønsted acid sites and four bromide ion sites. The presence of Brønsted acid sites promotes the production of 5-hydroxymethylfurfural (HMF), while the bromide anions react to form a DFF, which undergoes further transformation via the Kornblum mechanism. Under optimized conditions, a remarkable DFF yield of 99.6 % was attained in dimethyl sulfoxide (DMSO) at 140 °C for 6 h. Moreover, the catalyst exhibited excellent stability and reusability, indicating its potential for industrial application in the synthesis of DFF from fructose. With the help of this effort, Br- anion may be able to throw some light on the oxidation of HMF to DFF. Overall, this study highlights the promising application of tetracationic ionic liquid catalyst systems, showcasing the potential for the efficient utilization of renewable biomass resources and the synthesis of high-value-added compounds.

Preparation of Polymeric Aluminum Chloride-Loaded Porous Carbon and Evaluation of Its Pb2+ Immobilization Mechanisms in Soil

In recent years, the remediation of heavy metal-contaminated soils has attracted great attention worldwide. Previous research on the removal of toxic heavy metals from wastewater effluents through adsorption by typical solid wastes (e.g., fly ash and coal gangue) has mainly focused on the control of wastewater pollutants. In this study, a coal gangue (CG) by-product from Hancheng City was used as a raw material to prepare polymeric aluminum chloride-loaded coal gangue-based porous carbon (PAC-CGPC) by hydrothermal synthesis. This material was subsequently employed to assess its performance in mitigating Pb2+ in soils. In addition, the effects of the pore structure of the prepared material on the adsorption rates, adsorption mechanisms, and plant root uptakes of soil Pb2+ were investigated in this study. The raw CG and prepared PAC-CGPC materials exhibited specific surface areas of 1.8997 and 152.7892 m2/g, respectively. The results of adsorption kinetics and isotherms indicate that the adsorption of Pb2+ based on PAC-CGPC mainly follows a pseudo-second-order kinetic model, suggesting that chemisorption may be the dominant process. In addition, the adsorption isotherm results showed that the Freundlich model explained better the adsorption process of Pb2+, suggests that the adsorption sites of lead ions on APC-CGPC are not uniformly distributed and tend to be enriched in APC, and also shows the ion exchange between aluminum and lead ions. The thermodynamic model fitting results demonstrated the occurrence of spontaneous and exothermic PAC-CGPC-based adsorption of Pb2+, involving ion exchange and surface complexation. The effects of the PAC-CGPC addition on soybean plants were further explored through pot experiments. The results revealed substantial decreases in the Pb2+ contents in the soybean organs (roots, stems, and leaves) following the addition of the PAC-CGPC material at a dose of 3% compared with the control and raw CG groups. Furthermore, the addition of the PAC-CGPC material at a dose of 3% effectively reduced the bioavailable Pb2+ content in the soil by 82.11 and enhanced soybean growth by 15.3%. These findings demonstrated the inhibition effect of the PAC-CGPC material on the translocation of Pb2+ in the soybean seedlings. The modified CG adsorbent has highly pore structure and good hydrophilicity, making it prone to migration in unsaturated soils and, consequently, enhancing Pb2+ immobilization. This research provides theoretical support for the development of CG-based materials capable of immobilizing soil pollutants.

Application of waste gypsum as novel selective depressant in the flotation separation of apatite from dolomite

The accumulation of gypsum slag not only causes resource wastage, but also poses serious environmental hazards, therefore, utilizing the resources of the main components in gypsum slag is an imperative task. In this study, gypsum was used as an inorganic depressant for the flotation separation of apatite from dolomite through the selective adsorption of gypsum on the surface of dolomite. Micro-flotation experiments showed that sodium oleate exhibited a good ability to collect apatite and dolomite, but poor ability to collect gypsum. At pH 9.5, when 3.75 g/L gypsum was added to the slurry, the recovery of dolomite decreased from 76.77 % to 18.34 %, whereas that of apatite was 86.45 %. Atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy were employed to elucidate the adsorption characteristics of gypsum on the apatite and dolomite surfaces. The results showed that gypsum was selectively adsorbed on the raised particles on the dolomite surface and combined with the active sites of Ca and Mg metal ions. However, the adsorption of gypsum on the surface of apatite was weak and had little effect on the flotation performance. Density functional theory calculations showed that the O in gypsum reacted easily with Ca and Mg metal ions on the mineral surface. The adsorption energies of gypsum at the Ca and Mg sites on the dolomite surface were −81.97 and −86.18 kJ/mol, respectively, whereas the adsorption energy on the apatite surface was only −34.20 kJ/mol. Gypsum is the main component of gypsum slag, and this study provides a potential recycling method for gypsum slag resources.

Production of hydrochar from the hydrothermal carbonisation of food waste feedstock for use as an adsorbent in removal of heavy metals from water

AbstractIn this research, discarded butternut peels were converted into hydrochar products through hydrothermal carbonisation (HTC), with adjustments made to the temperature (ranging from 180 to 260℃) and residence time (spanning 45–180 min). The findings indicated that both the temperature and time of carbonisation significantly influenced the yield of hydrochar (HC), as well as its physiochemical and structural properties. Higher temperatures and prolonged residence time led to decreased yield, elevated fixed carbon content and an increased fuel ratio. Furthermore, raising the process conditions increased HHV and reduced the oxygen-containing functional groups. The HC yield dropped from 28.75 to 17.58% with increased carbonisation temperature and time. The findings of this study also suggest that modified hydrochar is a promising material for removing heavy metals from wastewater. It is a relatively low-cost and abundant material that can be produced from various biomass feedstocks, including food waste. In addition, it is a sustainable and environmentally friendly option for wastewater treatment. Hydrochar-based systems offer several advantages over traditional methods of heavy metal removal, such as chemical precipitation and ion exchange. The unique physicochemical characteristics of hydrochar, including its porous structure and oxygen-rich functional groups, offer a high surface area and more binding sites for heavy metal ions. By changing the physicochemical properties of hydrochar with chemicals like phosphoric acid, it is possible to increase its adsorption capacity. The Freundlich isotherm was the best fit for the adsorption data for all three metal ions (Pb2+, Cu2+ and Cd2+), indicating that the adsorption process is multilayer and heterogeneous.

Construction of ion/electron transfer multi-channels for the composite film electrode from GO and cellulose derived porous carbon in supercapacitor

Due to excellent flexibility and dispersibility, 2D graphene oxide (GO) is regarded as one of the prospective materials for preparing self-supporting electrode material. Nevertheless, the self-stacking characteristic of GO significantly restricts the ion transmission and accessibility in GO-based electrodes, especially in the direction perpendicular to the electrode surface. Herein, a novel composite film was fabricated from GO and 3D porous carbon (PC) through vacuum filtration combined with thermal reduction strategy. The combination of GO and PC not only avoids the self-stacking of GO, but also exposes more active sites for ions in the inner. A massive released nitrogen and oxygen-containing gases during the thermal reduction endows the reduced graphene oxide (RGO) with abundant porous and CC, which contributes to the energy storage in the direction perpendicular to the electrode surface. Besides, the high specific surface area of the prepared composite film is favorable for the storage and release of charge on the electrode surface. Benefiting from the above characteristics, the electrode assembled by the as-prepared film exhibits ultrahigh areal/volumetric specific capacitance in supercapacitor and ZIHCs (Zinc ion hybrid capacitors). This work provides a promising approach for the development of advanced self-supported electrode materials with desirable electrochemical properties.

Role of active redox sites and charge transport resistance at reaction potentials in spinel ferrites for improved oxygen evolution reaction

Fe and Ni oxide-based systems are often investigated as electrocatalysts for the oxygen evolution reaction (OER) in water electrolysis and the improvement in OER activity is explained by two main reasons, (i) improving bulk electrical conductivity and (ii) synergic effect between Ni and Fe. Among the two factors, the identification of the dominant factor for OER is very important for catalyst engineering in the right direction. In order to have a better understanding, spinel-structured ZnFe2O4 nanoparticles have been synthesized and its bulk conductivity is studied by progressively varying Ni doping. The conductivity of the synthesised compounds follows the order of ZnFe2O4 > Ni0.3Zn0.7Fe2O4 > Ni0.5Zn0.5Fe2O4 > Ni0.7Zn0.3Fe2O4 > NiFe2O4. The oxygen evolution studies reveal that NiFe2O4 is highly active with an onset potential of 1.57 V versus reversible hydrogen electrode (RHE) and Tafel slope of 102 mV/dec. With the increase in Ni doping, the structure changes from spinel to inverse spinel as confirmed by X-ray diffraction and Raman spectra. Further, the contribution from Ni redox sites in addition to Fe ion sites and FexNi1−xOOH species formation, causes improved OER performance. This study uniquely proves that the OER activity majorly relies on redox/active metal sites, FexNi1−xOOH species and charge transfer resistance at OER potential rather than the bulk electrical conductivity of spinel ferrites. This conclusion is supported by voltammetry and impedance studies of five different spinel ferrites.

Enhanced CO2 conversion through confinement of cross-linked ionic polymer within the pores of porous carbon materials

It is crucial to employ an integrated catalyst to avoid the complications of the recovery process. This work reports the fabrication of porous carbon@ionic liquid (PC@IL) composites with readily accessible active ion sites, achieved by confining cross-linked ionic liquid (IL) within the channels of porous carbon (PC). The incorporation of porous carbon not only confines the IL within its framework, creating microsites for CO2 adsorption and conversion, but also simplifies catalyst recovery. The results indicate that PC@IL composites exhibit excellent cycloaddition activity towards CO2 in a co-catalyst- and solvent-free environment. Notably, PC@IL(C)-24 demonstrates remarkable catalytic performance across various epoxides under 1 bar of CO2, with yields above 90 % at 90 °C for 12 h, and achieving a remarkable styrene carbonate yield of up to 92.8 % under a CO2 pressure of 1 bar (at 100 °C for 12 h). Control experiments confirm that the confinement effect exerted by N,S co-doped carbon on cross-linked IL plays a pivotal role in enhancing both stability and activity of PC@IL composites, thereby providing novel insights for designing functionalized porous carbon catalysts for CO2 cycloaddition conversion.

Highly Selective Recovery of Gold by In Situ Magnetic Field-Assisted Fe/Co-MOF@PDA/NdFeB Double Network Gel.

There are enormous economic benefits to conveniently increasing the selective recovery capacity of gold. Fe/Co-MOF@PDA/NdFeB double-network organogel (Fe/Co-MOF@PDA NH) is synthesized by aggregation assembly strategy. The package of PDA provides a large number of nitrogen-containing functional groups that can serve as adsorption sites for gold ions, resulting in a 21.8% increase in the ability of the material to recover gold. Fe/Co-MOF@PDA NH possesses high gold recovery capacity (1478.87mg g-1) and excellent gold selectivity (Kd = 5.71mL g-1). With the assistance of an in situ magnetic field, the gold recovery capacity of Fe/Co-MOF@PDA NH is increased from 1217.93 to 1478.87mg g-1, and the recovery rate increased by 24.7%. The above excellent performance is attributed to the efficient reduction of gold by FDC/FC+, Co2+/Co3+ double reducing couple, and the optimization of the reduction reaction by the magnetic field. After the samples are calcined, high-purity gold (95.6%, 22K gold) is recovered by magnetic separation. This study proposes a forward-looking in situ energy field-assisted strategy to enhance precious metal recovery, which has a guiding role in the development of low-carbon industries.

S‐Tetrazine‐Bridged 2,2′‐Bipyrimidine as Superior Atom‐Economic Multi‐Charge Cathode Material for Lithium‐Ion Batteries

AbstractNitrogen‐containing heterocyclic molecules feature metal resource‐independence, flexible conjugation structure and fast charge storage kinetics, making them promising to be used as the electrode material in lithium‐ion batteries. However, an insufficiently high capacity (<400 mAh g−1) seriously threatens their practical application. Herein, a novel molecule, viz. 3,6‐bis(2‐pyrimidinyl)‐1,2,4,5‐tetrazine (DPmT), is developed by inserting an electron‐withdrawing π‐bridge unit of s‐tetrazine between two pyrimidine rings, in which a dense assembly of multiple active sites is realized. The DTmP exhibits a remarkable atom economy of 40 g (mol e)−1, which refers to the molecule mass per unit of charge transferred. The cathode material of DPmT yields a high capacity of 653 mAh g−1 and an energy density of 1188 Wh kg−1 at 50 mA g−1 at 70 °C. And 80% capacity retention is achieved after 500 cycles at 500 mA g−1, confirming its superior cyclability. Spectroscopy studies and theoretical calculations are performed to investigate the charge storage process. First, the C═N and N═N are claimed as plausible binding sites for the lithium ions. Second, the introduction of s‐tetrazine significantly enhances molecular planarity, thereby promoting charge delocalization and molecular stability. This work provides a novel strategy for designing atom‐economic multi‐charge electrode materials with high capacity.