Spontaneous Process Research Articles

Simulation of Neutron Multiplicity Counting Based on Monte Carlo Code RMC

Neutron multiplicity pertains to the probability distribution of the quantity of neutrons released during induced or spontaneous fission processes within fissile materials. The technology for neutron multiplicity measurement leverages temporal correlations in the emission of fission neutrons from nuclear materials. It employs mathematical tools to elucidate the processes of neutron generation, multiplication within the nuclear material, and detection of outside nuclear materials. In this paper, two multiplicity counting methods are devised building on the RMC (Reactor Monte Carlo) code. The results obtained from both methods, including singles, doubles, and triples counting rates, exhibit good agreement with MCNP. Additionally, parameters associated with the detection efficiency and decay time of the apparatus are computed. By amalgamating the acquired singles, doubles, and triples counting rates, the mass of fissile material within the sample is inversely determined using a passive method with the point model equation. Notably, the point model equation reveals that spontaneous fission neutrons and induced neutrons possess distinct energy spectra, challenging the validity of the assumption that the probability of neutrons being captured without causing fission can be disregarded. In light of these considerations, the neutron multiplicity counting equation was rederived. The accuracy of the Monte Carlo simulation results is improved using the new method.

In-Depth Investigation of Role of -BCO2 in the Degradation of Sulfamethazine by Metal-Free Biochar/Persulfate: The Mechanism of Occurrence of Nonradical Process.

The remediation of organic wastewater through advanced oxidation processes (AOPs) based on metal-free biochar/persulfate systems has been extensively researched. In this work, boron-doped alkali lignin biochar (BKC1:3) was utilized to activate peroxymonosulfate (PMS) for the removal of sulfamethazine (SMZ). The porous structure and substantial specific surface area of BKC1:3 facilitated the adsorption and thus degradation of SMZ. The XPS characterization and density functional theory (DFT) calculations demonstrated that -BCO2 was the main active site of BKC1:3, which dominated the occurrence of nonradical pathways. Neither quenching experiments nor EPR characterization revealed the generation of free radical signals. Compared with KC, BKC1:3 possessed more electron-rich regions. The narrow energy gap (ΔEgap = 1.87 eV) of BKC (-BCO2) promoted the electron transfer to the substable complex (BKC@PMS*) on SMZ, driving the electron transfer mechanism. In addition, the adsorption energy of BKC(-BCO2)@PMS was lower (-0.75 eV → -5.12 eV), implying a more spontaneous adsorption process. The O-O (PMS) bond length in BKC(-BCO2)@PMS increased significantly (1.412 Å → 1.481 Å), which led to the easier decomposition of PMS during adsorption and facilitated the generation of 1O2. More importantly, a combination of Gaussian and LC-MS techniques was hypothesized regarding the attack sites and degradation intermediates of the active species in this system. The synergistic T.E.S.T software and toxicity tests predicted low or even no toxicity of the intermediates. Overall, this study proposed a strategy for the preparation of metal-free biochar, aiming to inspire ideas for the treatment of organic-polluted wastewater through advanced oxidation processes (AOPs).

Highly effective and selective recovery of germanium from coal acid leaching solution by trihydroxyl functionalized titanium dioxide

In this study, a novel trihydroxyl functionalized titanium dioxide (TiO2-NH2-3OH) was successfully synthesized by the Schiff base reaction method. TiO2-NH2-3OH was characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), x-ray Photoelectron Spectroscopy (XPS), x-ray diffraction techniques (XRD), and further applied to recover germanium (Ge(IV)) from coal acid leaching solution. TiO2-NH2-3OH exhibited superior capture performance on Ge(IV) at a pH of 3, and the optimal TiO2-NH2-3OH dosages were 0.8 g L−1. The distribution coefficients of germanium for coexisting metal ions (Zn2+, Co2+, Mn2+, Ni2+ and Al3+) were all greater than 1, indicating that TiO2-NH2-3OH had good selective adsorption performance for Ge(IV) in complex solution environments. Compared with other kinetic models, pseudo-second-order model was more suitable to reveal the absorption of Ge(IV). Moreover, the experiment data were fitted better with Langmuir model at 298 K than the other isothermal models, and the maximum adsorption capacity was up to 72.94 mg g−1. Thermodynamic data suggesting that the capture of Ge(IV) on TiO2-NH2-3OH was a spontaneous endothermic process, increasing the temperature was beneficial for the adsorption reaction to proceed. TiO2-NH2-3OH with saturated adsorption still maintained a high removal rate of 80.55 % of Ge(IV) after five cycles, indicating good stability and recyclability of TiO2-NH2-3OH. XPS analysis indicated that the capture of germanium by TiO2-NH2-3OH may be due to the ion exchange interaction between -OH and Ge(OH)4 on the adsorbent surface. This work indicated that TiO2-NH2-3OH had great advantages and potential for the recovery of Ge(IV) from coal acid leaching solution.

Stage development characteristics of oxygen-lean combustion of coal in fire zone: Leap-migration mechanism, kinetic transition mechanism, and critical oxygen concentration

Effectively preventing the re-ignition of fire zones and safely unsealing enclosed fire zones are challenging. To address these issues, a thermogravimetric analysis technique was used to explore the leap-migration mechanism of the characteristic parameters (burnout index (H), comprehensive combustion performance parameters (Cb, S, and HF), and maximum combustion mass loss rate (dWmax))/temperatures (maximum pyrolysis mass loss rate point temperature (TVmax), pyrolysis endpoint temperature (Td), thermal polycondensation endpoint temperature (Tp), maximum combustion mass loss rate point temperature (TWmax), burnout temperature (Th), and combustion half-peak width (ΔT1/2)) of low-rank coal oxygen-lean combustion under different time-scale effects (TSEs). The sensitivity of characteristic parameters/temperatures to changes in oxygen concentration under coal rank transition was analyzed. Simultaneously, the kinetic real-time transformation mechanism during the oxygen-lean combustion stage progression was investigated. The results revealed that because of the competition between oxidation and pyrolysis, the leap-migration interval of characteristic parameters/temperatures for oxygen-lean combustion of low-rank coals is in the range of 5 %–3% oxygen concentration. This feature was less affected by the coal rank but is not affected by the TSE. In the low oxygen-lean range (5 %-1%), a change of oxygen concentration was more sensitive to the coal rank, and the high sensitivity of the oxygen concentration change reduced the influence of the coal rank on coal combustion performance. In addition, the apparent activation energy (Eα) curves during the early stage of combustion were relatively concentrated with the change of oxygen concentration, but relatively dispersed during the late stage of combustion. At 3 % oxygen concentration, the Eα values of different coals began to continuously decrease with increasing conversion rate, approaching the spontaneous reaction activation energy value of 40 kJ/mol. At oxygen concentration of 1 % reflected the complete limitation of the oxidation consumption reaction. Therefore, the critical oxygen concentration of typical low-rank coal oxygen-lean combustion was determined below 3 % oxygen concentration. The results of this study can provide scientific guidance for the unsealing of fire zones, and the effective prevention and control of the formation of new fire zone disasters.

Garnet-Based Solid Li-Metal Batteries Operable under High External Pressure with HCOOH-Induced Electron-Blocking and Lithiophilic Interlayer.

Despite good compatibility with Li metal, garnet solid electrolytes suffer from severe electron-attack-induced Li-metal penetration and large interfacial resistance. Here, a formic acid (HCOOH)-induced electron-blocking and lithiophilic interlayer is created via a spontaneous reaction with surface Li2CO3 contamination on the garnet electrolyte (LLZTO) pellet. Unlike previous methods that involved immersing LLZTO in acidic solutions, this study employs a volatile small-molecule organic acid that is easily removable, condensed, and recyclable, thus circumventing the environmental drawbacks associated with acid waste. The Li symmetric cell assembled with HCOOH-treated LLZTO exhibits a low interfacial impedance (3 Ω cm2) and a high critical current density (1.7 mA cm-2) at room temperature, enabling the cell to cycle continuously for over 1000 h at 0.2 mA cm-2. Furthermore, under a stacking pressure of 2 MPa, stable lithium plating/stripping was achieved at a current density of 0.3 mA cm-2 with the assistance of HCOOH treatment. Additionally, the battery paired with a LiFePO4 cathode delivers a high capacity of 151.7 mAh g-1 at 1 C and maintains 88.5% of the initial capacity after 500 cycles, suggesting the feasibility of this interfacial engineering strategy for garnet-based solid Li-metal batteries.

Efficient adsorption of methyl red, methyl orange and bromothymol blue by polyamine resin: Role of linearity and size of carboxylate in enhanced encapsulation and molecular matching

Dyes constitute the major contribution to the environmental organic pollutants. Besides being hazardous to aquatic life, dyes are highly toxic and injurious to human health. Herein, we disclose the synthesis of a novel hyper cross-linked, dubbed as BPA-PEA, for the adsorptive removal of methyl red (MR), methyl orange (MO) and bromothymol blue (BTB). BPA-PEA displayed maximum adsorption capacities (qmax) for the adsorptive removal of these ionic dyes as 230.6 mg/g, 117.7 mg/g, and 80.42 mg/g for MR, MO and BTB, respectively. Density Functional Theory (DFT) simulations indicate a spontaneous binding process, with binding order closely aligns with the experimentally observed order (MR > MO > BTB). Moreover, the higher interaction in the resin-MR complex was believed due to the linearity and smaller size of the carboxylate group in the MR. Response Surface Methodology (RSM) optimization shows excellent suitability from their statistical parameter as well as low SSE value with the experimental values. The kinetic and isothermal data suggest that the adsorption process followed a chemisorption pathway and adsorption equilibrium was achieved within 2, 6, and 18 h for BTB, MR, and MO, respectively. A significant influence of pH was also observed in the adsorption of MO (5.5), MR (6.1), and BTB (5.3). The BPA-PEA was found to be thermally stable (Td = 348 °C) and mesoporous in nature, having a high surface area (78.3 m2 g−1). The adsorption mechanism is mainly governed by electrostatic interaction between the dyes and adsorbent, however, other adsorptive mechanism such as H-bonding interactions, hydrophobic interactions or π-π interactions were also involved. In addition, the adsorption efficiency of BPA-PEA was maintained for consecutive 5 cycles, with slightly decline (less than 5 mg/g for MR, MO, and BTB) in the adsorption capacity. Given the high adsorption capacity, short adsorption time, and reusability, BPA-PEA can serve as a promising adsorbent for the removal of anionic dyes from wastewater.

Development of an in-situ forming collagen-based hydrogel as a regenerative bioadhesive for corneal perforations

Corneal injuries play a significant role in global visual impairment, underscoring the demand for innovative biomaterials with specific attributes such as adhesion, cohesion, and regenerative potential. In this study, we have developed a biocompatible bioadhesive for corneal reconstruction. Derived from Collagen type I, naturally present in human corneal stromal tissue, the bioadhesive was cross-linked with modified polyethylene glycol diacrylate (PEGDA-DOPA), rendering it curable through visible light exposure and exhibiting superior adhesion to biological tissues even in wet conditions. The physicochemical characteristics of the proposed bioadhesive were customized by manipulating the concentration of its precursor polymers and adjusting the duration of photocrosslinking. To identify the optimal sample with maximum adhesion, mechanical strength, and biocompatibility, characterization tests were conducted. The optimal specimen, consisting of 30 % (w/v) PEGDA-DOPA and cured with visible light for 5 min, exhibited commendable adhesive strength of 783.6 kPa and shear strength of 53.7 kPa, surpassing that of commercialized eye adhesives.Additionally, biocompatibility test results indicated a notably high survival rate (>100 %) of keratocytes seeded on the hydrogel adhesive after 7 days of incubation. Consequently, this designed bioadhesive, characterized by high adhesion strength, robust mechanical strength, and excellent biocompatibility, is anticipated to enhance the spontaneous repair process of damaged corneal stromal tissue.

Petroleum residue-based ultrathin-wall graphitized mesoporous carbon and its high-efficiency adsorption mechanism

Creating petroleum residue-based new functional materials are vital for the sustainable development of petroleum residues. This study developed a method to prepare a petroleum residue-based ultrathin-wall graphitized mesoporous carbon (PGMC) with high specific surface area by the carbonization of a composite of the petroleum residue uniformly mixed with aluminium isopropoxide. Results show that the PGMC possesses a highly fluffy ultrathin-wall mesoporous structure with a high degree of graphitization. It had a high specific surface area of 1174 m2 g−1 with a high pore volume of 4.57 cm3 g−1 and a narrow pore size distribution at 8.09 nm. These unique features endow the PGMC with excellent adsorption properties for Congo red, Malachite green, and Methylene blue removal. The experimental data were better described with Freundlich isotherm and Quasi-second-order kinetic models. Thermodynamic analysis indicated a spontaneous and endothermic adsorption process. The adsorption mechanisms proposed that pore-filling effect, π-π conjugation, and electrostatic interaction were the main interactions between the PGMC and dyestuff, followed by functional groups and hydrogen bonding. Moreover, the PGMC could maintain good adsorption rates after five cycles, proving that it is an effective adsorbent with good adsorption ability and cycling stability.

“Stick–slip” fluctuations in local electrical conductivity maps on graphite surfaces: A revisit

Electrical conductivity images of graphite surfaces are routinely obtained using scanning probe microscopy. Although the acquired conductivity maps often display a trigonal pattern with smooth variations, a “stick–slip” type of fluctuation has also been reported, where the local conductivity inversely correlates with the friction force during probe scanning. In this work, we revisit the lattice-resolved variations in local conductivity on graphite surfaces and reveal a new series of behaviors. Unlike previous observations, we demonstrate that local conductivity can exhibit in-phase, out-of-phase, or mixed-mode correlations with “stick–slip” lateral force signals. These behaviors are attributed to the cross-talk effect between interface contact conductivity and lateral force, induced by the inhomogeneous conductivity of the tip apex. This mechanism is experimentally validated, showing that local conductivity variations can switch within a single scan due to spontaneous changes in the conductivity of the tip. Our findings enhance the understanding of lattice-resolved electrical conductivity data on graphite surfaces and suggest a novel approach to amplify small lateral forces using inhomogeneous probe tips.

Surface Enhanced Nonlinear Raman Processes for Advanced Vibrational Probing.

Surface enhanced Raman scattering (SERS) is not restricted to the well-known one-photon excited spontaneous Raman process that gives information on molecular composition, structure, and interaction through vibrational probing with high sensitivity. The enhancement mainly originates in high local fields, specifically those provided by localized surface plasmon resonances of metal nanostructures. High local fields can particularly support nonlinear Raman scattering, as it depends on the fields to higher powers. By revealing plasmon-molecule interactions, nonlinear Raman processes provide a very sensitive access to the properties of metal nanomaterials and their interfaces with molecules and other materials. This Perspective discusses plasmon-enhanced spontaneous and coherent nonlinear Raman scattering with the aim of identifying advantages that lead to an advanced vibrational characterization of such systems. The discussion will highlight the aspects of vibrational information that can be gained based on specific advantages of different incoherent and coherent Raman scattering and their surface enhancement. While the incoherent process of surface enhanced hyper Raman scattering (SEHRS) gives highly selective and spectral information complementary to SERS, the incoherent process of surface enhanced pumped anti-Stokes Raman scattering (SEPARS) can help to infer effective nonresonant SERS cross sections and allows to see "hot" vibrational transitions. Surface enhanced coherent anti-Stokes Raman scattering (SECARS) and surface enhanced stimulated Raman scattering (SESRS) combine the advantages of high local fields and coherence, which gives rise to high detection sensitivity and offers possibilities to explore molecule-plasmon interactions for a comprehensive characterization of composite and hybrid structures in materials research, catalysis, and nanobiophotonics.

Chemically-Driven Autonomous Janus Electromagnets as Magnetotactic Swimmers.

An electromagnet is a particular device that takes advantage of electrical currents to produce concentrated magnetic fields. The most well-known example is a conventional solenoid, having the form of an elongated coil and creating a strong magnetic field through its center when it is connected to a current source. Spontaneous redox reactions located at opposite ends of an anisotropic Janus swimmer can effectively mimic a standard power source, due to their ability to wirelessly generate a local electric current. Herein, we propose the coupling of thermodynamically spontaneous redox reactions occurring at the extremities of a hybrid Mg/Pt Janus swimmer with a solenoidal geometry to generate significant magnetic fields. These chemically driven electromagnets spontaneously transform the redox-induced electric current into a magnetic field with a strength in the range of μT upon contact with an acidic medium. Such on-board magnetization allows them to perform compass-like rotational motion and magnetotactic displacement in the presence of external magnetic field gradients, without the need of using ferromagnetic materials for the swimmer design. The torque force experienced by the swimmer is proportional to the internal redox current, and by varying the composition of the solution, it is possible to fine-tune its angular velocity.

Chemically‐Driven Autonomous Janus Electromagnets as Magnetotactic Swimmers

AbstractAn electromagnet is a particular device that takes advantage of electrical currents to produce concentrated magnetic fields. The most well‐known example is a conventional solenoid, having the form of an elongated coil and creating a strong magnetic field through its center when it is connected to a current source. Spontaneous redox reactions located at opposite ends of an anisotropic Janus swimmer can effectively mimic a standard power source, due to their ability to wirelessly generate a local electric current. Herein, we propose the coupling of thermodynamically spontaneous redox reactions occurring at the extremities of a hybrid Mg/Pt Janus swimmer with a solenoidal geometry to generate significant magnetic fields. These chemically driven electromagnets spontaneously transform the redox‐induced electric current into a magnetic field with a strength in the range of μT upon contact with an acidic medium. Such on‐board magnetization allows them to perform compass‐like rotational motion and magnetotactic displacement in the presence of external magnetic field gradients, without the need of using ferromagnetic materials for the swimmer design. The torque force experienced by the swimmer is proportional to the internal redox current, and by varying the composition of the solution, it is possible to fine‐tune its angular velocity.

Ni-Zn/CeO2 nanocomposites for enhanced adsorptive removal of 4-chlorophenol.

Chlorophenols are one of the major organic pollutants responsible for the contamination of water bodies. This study explores the application of Ni-Zn/CeO2 nanocomposites, synthesized via the aqueous co-precipitation method, as effective adsorbents for the 4-chlorophenol removal from aqueous solutions. The nanocomposites' chemical and structural characteristics were assessed using different physical characterization methods, viz. X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, zeta potential, using a Box-Behnken design within response surface methodology, optimal conditions of pH 3, temperature 20 °C, contact time 120 min, adsorbent dosage 0.05 g, and 4-chlorophenol concentration 50 ppm are identified. Among the nanocomposites tested, NZC 20:10:70, with 20% Ni and 10% Zn, achieves enhanced performance, removing 99.1% of 4-chlorophenol within 2 h. Adsorption kinetics follow the pseudo-second-order model and equilibrium data fit the Freundlich isotherm. Thermodynamic analysis indicates an exothermic and spontaneous process. The adsorption capacity of NZC 20:10:70 shows significant enhancement, growing from 19.85 mg/g at 10 ppm to 96.33 mg/g at 50 ppm initial concentration. Physical characterization confirms NZC 20:10:70's superior properties, including a high surface area of 118.471 m2/g. Evaluating economic viability, NZC 20:10:70 demonstrates robust reusability, retaining 85% efficiency over eight regeneration cycles. These results highlight NZC 20:10:70 as a promising adsorbent for effective and sustainable chlorophenol removal in water treatment.

The inhibitory effects of free and bound phenolics from Phyllanthus emblica Linn. on α-amylase: a comparison study.

Phyllanthus emblica Linn. (PE) is rich in polyphenols, which can be categorized into free and bound phenolics (PEFP and PEBP). This study evaluated the inhibitory effect of PEFB and PEBP on α-amylase for the first time. The mechanism of the inhibition effect of PEFP and PEBP on α-amylase was investigated by enzyme inhibition kinetics, multispectral analysis, thermodynamics, and molecular docking. Free and bound phenolics inhibited α-amylase activity effectively in a mixed type of inhibition. Fluorescence quenching and thermodynamic analyses showed that the binding of PEFP and PEBP to α-amylase occurred through a static quenching process (Kq = 6.94 × 10¹² and 5.74 × 10¹² L mol-1 s-1), which was accompanied by a redshift (λem from 343 to 347 nm), leading to a change in the microenvironment. This process was found to be a spontaneous exothermic reaction (ΔG < 0). Circular dichroism (CD) analysis confirms that the secondary structure of α-amylase was altered, in particular a decrease in α-helixes and an increase in random coils. Molecular docking studies showed that PEFP and PEBP interacted with α-amylase through hydrogen bonding and hydrophobic interactions. The present study provides valuable insights into the mechanism of action of PEFP and PEBP on α-amylase, which will provide a theoretical basis for their possible use as novel natural α-amylase inhibitors. © 2024 Society of Chemical Industry.

Green adsorbents for pharmaceutics removal from urine: Analysis of isotherms, kinetics, adsorption interactions, cost estimation, and environmental impact

Husks of rice (RH), coffee (CH), and cholupa (CLH) were used to produce natural adsorbents. The natural adsorbents were used to remove pharmaceuticals such as diclofenac, ciprofloxacin, and acetaminophen in a mixture of distilled water. However, CH stood out for its efficiency in removing ciprofloxacin (74%) due to the higher concentration of acidic groups, as indicated by the Boehm method. In addition, CH removed 86% of ciprofloxacin individually. Therefore, CH was selected and used to remove other fluoroquinolones, such as levofloxacin and Norfloxacin. Although electrostatic interactions favored removals, better removal was observed for ciprofloxacin due to its smaller molecular volume. Then, ciprofloxacin was selected, and the effect of pH, matrix, and adsorbent doses were evaluated. In this way, using a pH of 6.2 in urine with a dose of 1.5 g L−1, it is possible to adsorb CIP concentrations in the range (0.0050–0.42 mmol L−1). Subsequently, the high R2 values and low percentages of APE and Δq indicated better fits for pseudo-second-order kinetics, suggesting a two-stage adsorption. At the same time, the Langmuir isotherm recommends a monolayer adsorption with a Qm of 25.2 mg g−1. In addition, a cost of 0.373 USD/g CIP was estimated for the process, where the material can be reused up to 4 times with a CIP removal in the urine of 51%. Consequently, thermodynamics analysis showed an exothermic and spontaneous process with high disorder. Furthermore, changes in FTIR analysis after adsorption suggest that CH in removing CIP in urine involves electrostatic attractions, hydrogen bonds and π-π interactions. In addition, the life cycle analysis presents, for the 11 categories evaluated, a lower environmental impact of the CIP removal in urine with CH than for the preparation of adsorbent, confirming that the adsorption process is more environmentally friendly than materials synthesis or other alternatives of treatments. Furthermore, future directions of the study based on real applications were proposed.

Ag/Nico LDH Heterogeneous Structure for Efficient Alkaline Oxygen Evolution

Hydrogen is regarded as an ideal energy carrier owing to the highest energy density, presenting the possibility of substituting for traditional fossil fuels. Nowadays, water splitting is significant in producing large-scale hydrogen. However, the sluggish reaction kinetics during anodic OER, caused by the four-electron transfer, has hindered this energy conversion strategy. Although IrO2 and RuO2 are currently the representative OER electrocatalysts, their high cost and unsatisfactory performance limit their commercial application.Numerous electrocatalysts, including oxides, hydroxides, high-entropy alloy, metal organic frameworks, and their hybrids, have been developed to address this issue. Among them, layered double hydroxides (LDH) have demonstrated outstanding performance due to their highly adjustable structure, powerful host-guest interaction, and single-atomic-like active sites. NiCo LDH has attracted significant attention because of its appropriate atomic and electronic structure, intrinsic active sites and defects, compared with single-type Ni-based or Co-based catalysts. However, to meet the requirements of industrial production, a simple and scalable method to synthesize electrocatalysts with favorable OER activity and stability is imperative.We propose a facile and scalable strategy to synthesize Ag-decorated NiCo LDH (Ag/NiCo LDH) by electrodeposition and subsequent spontaneous redox reaction. A spontaneous redox reaction driven by the difference in standard redox potential of reactants can be applied to prepare heterogeneous catalysts in consequence of the facile process, tight combination between substrate and decorated materials, and no supplementary energy input. Silver metal, with its appropriate standard redox potential, good conductivity, and low cost compared to Iridium and Ruthenium, serves as a suitable decorated material. This strategy provides several advantages, for example, Ⅰ) optimizing the electronic structure of Ni and Co by the charge transfer from Ni, Co to Ag; Ⅱ) exposing more active surface area because of the heterogeneous structure, Ⅲ) improving the charge transfer capacity owing to the excellent conductivity of Ag nanoparticles, Ⅳ) increasing the stability of NiCo LDH due to the tight combination of Ag and NiCo LDH, Ⅴ) lowering the catalysts' price compared with Iridium and Ruthenium.The synthesized Ag/NiCo LDH exhibits enhanced OER performance in 1M KOH electrolyte, achieving an overpotential of 440 mV at a current density of 1000 mA cm-2 geo, surpassing that of NiCo LDH (722 mV at 1000 mA cm-2 geo). Surprisingly, Ag/NiCo LDH demonstrates exceptional durability, lasting over 425 h at 1000 mA cm-2 geo, an improvement of nearly eight-fold compared to NiCo LDH (50 h). This study provides a promising approach for developing efficient and stable electrocatalysts for alkaline oxygen evolution.

Ni-Pt Core-Shell Formation via Spontaneous Galvanic Displacement Reaction at Boron Doped Diamond Electrodes for Ammonia Oxidation Reaction

Ammonia is a major environmental pollutant that is highly toxic and may cause unfavourable effects to the human body, even in low concentrations. As a result, the monitoring and elimination of NH3 has been an important topic worth exploring in depth. Moreover, ammonia can be a suitable fuel cell source because its theoretical electrical charge density is relatively high and it’s possible to take this advantage by converting ammonia to nitrogen and electrical energy via the ammonia oxidation reaction (AOR). This reaction requires a catalyst to decrease the energy barrier that prevents the molecule from reacting and transforming into nitrogen.Ammonia electro-oxidation reaction has been paid much attention in recent years because it is widely used in various fields. However, the electro-oxidation of ammonia is a complex process, especially the reaction intermediate has a slow toxic effect on the electrode. To reduce the catalyst poisoning by the absorption of intermediate, the constituent and structure of the catalysts must be deeply researched.Herein, a bimetallic Pt–Ni catalyst-modified boron-doped diamond (BDD) electrode was done via spontaneous galvanic displacement reaction for the ammonia oxidation reaction. The synergistic properties may include the promotion of low-temperature oxidation, improvement of the oxidation resistance, and increased catalytic efficiency. BDD was used as the electrode substrate in this work due to its excellent resistance to corrosion and good stability over time in a highly corrosive environment. First, nickel was electro-deposited through chronoamperometry on the BDD electrode surface at a potential of -1.1V vs Ag/AgCl in 0.1M KClO4 & 5mM Ni (NO3)2.6H2O aqueous solution. Second, platinum was deposited on the nickel particles on the BDD electrode surface through a spontaneous galvanic displacement reaction by a redox process which involves the nickel oxidation and Pt2+ reduction, using a K2PtCl4 precursor on the BDD surface while forming a core shell structure. Lastly, the Pt-Ni deposited on the BDD surface was then characterized through different techniques such as XPS, SEM, EDS, and Raman before and after the ammonia oxidation reaction.Preliminary studies of the behaviour of BDD electrodes in the presence of Ni and Pt have been carried out to determine the electrochemical conditions at which the substrate works with these metal salts. The results found with these studies will show how Pt-Ni catalyst will improve AOR in alkaline media.

A Sustainable Process for Rare Earth Electrowinning in Chloride Based Molten Salts

Neodymium production has become increasingly important due to use of neodymium–iron–boron (NdFeB) magnets in green energy, consumer technology and defense applications. The state-of-the-art practice features a neodymium fluoride and lithium fluoride molten salt with a consumable carbon anode converting dissolved neodymium oxide and carbon to neodymium metal and CO2.1-2 The anode effect results in PFCs and CO emissions, which make the current neodymium electrowinning process unsustainable.3-4 Some attempts have been made to electrolyze the chloride salt of neodymium to produce chlorine at the anode. Chlorine is a value-added product which neither consumes the anode nor produces other deleterious GHGs. Additionally, the chloride of neodymium can be non-carbothermically produced through a spontaneous reaction with hydrochloric acid, producing only water as a side product. However, a common problem in chloride rare earth electrowinning is the low Coulombic efficiency (10-50%) obtained in lab-scale and pilot-scale efforts.5 The neodymium chloride electrolysis process notoriously encounters a two-step reduction producing an intermediate divalent (Nd2+) oxidation state which is stable in the chloride media.6-7 The intermediate neodymium species diffuses away from the cathode leading to Coulombic efficiency loss. Additionally, the kinetics of the chlorine evolution reaction (CER) in chloride molten salts are known to be relatively sluggish, causing significant anodic overpotentials which elevate the specific energy consumption during electrowinning. Furthermore, electrowinning from molten salts often produces spongy or dendritic deposits of metal requiring energy-intensive purification. In this talk, we will address all aforementioned technical hurdles and report on our efforts achieving high Coulombic efficiency (~85%), and compact deposits with superior as-electrowon neodymium metal purity (>99 wt.%). Furthermore, we will report the development of a new anode which catalyzes chlorine evolution, lowering the anodic overpotential considerably during electrolysis at high current densities of practical interest for electrowinning. Specific energy consumption is calculated for some example cases and found to be between 2.1 and 3.5 kWh/kg representing a significant improvement over the conventional oxyfluoride process. Figure 1

Aqueous Polysulfide-Based Redox Flow Battery with Soluble Molecular Catalysts

Aqueous polysulfide-based redox flow batteries (RFBs) are promising for large-scale energy storage applications due to their low cost and high safety1. However, polysulfide negolyte suffers from poor kinetics, resulting in low operating current density and low energy efficiency2-5. Herein, we proposed a molecular catalyst strategy to transfer the sluggish electrochemical polysulfide reduction reaction to a fast chemical reaction via homogeneous catalysis. Inspired by the electron transport chain in the respiratory process, we selected riboflavin sodium phosphate (FMN-Na) as the molecular catalyst to transfer electrons from electrode to polysulfide with the disulfide bond cleavage6. The reaction rate (or turnover frequency) kobs is determined to be 33 s–1 at 1 M K2S4 solution, and this spontaneous chemical electron transfer process is verified by ultraviolet-visible light spectroscopy. In the polysulfide-ferrocyanide (S-Fe) RFB, the overpotential is dramatically decreased from over 800 mV to 241 mV at 30 mA cm–2 with the assistance of FMN-Na as the molecular catalysts. The catalyzed S-Fe RFB and polysulfide-iodide RFB showed stable operation for over 1,000 cycles at 40 mA cm–2. This work offers a simple but effective method to resolve the bottleneck for aqueous polysulfide-based RFBs, and such a homogeneous catalysis strategy may shed light on other flow battery systems with poor kinetics. We will combine operando spectroscopic techniques and theoretical calculation to discuss the possible reaction mechanism and intermediate.AcknowledgmentThis work is supported by two grants from the Research Grants Council (RGC) T23-713/22-R and RFS2223-4S03. Reference Y. Yao, J. Lei, Y. Shi, F. Ai and Y.-C. Lu, Nat. Energy, 2021, 6, 582-588. Z. Li and Y.-C. Lu, Nat. Energy, 2021, 6, 517-528. X. Wei, G.-G. Xia, B. Kirby, E. Thomsen, B. Li, Z. Nie, G. G. Graff, J. Liu, V. Sprenkle and W. Wang, J. Electrochem. Soc., 2015, 163, A5150. Z. Li, M. S. Pan, L. Su, P.-C. Tsai, A. F. Badel, J. M. Valle, S. L. Eiler, K. Xiang, F. R. Brushett and Y.-M. Chiang, Joule, 2017, 1, 306-327. J. Lei, Y. Yao, Y. Huang and Y.-C. Lu, ACS Energy Lett., 2023, 8, 429-435. J. Lei, Y. Zhang, Y. Yao, Y. Shi, K. L. Leung, J. Fan and Y.-C. Lu, Nat. Energy, 2023, DOI: 10.1038/s41560-023-01370-0.

Advanced Hybrid Polymer/Ceramic PEO-SnF2 Protective Mechanism for Sodium Metal Anodes

In the face of mounting global energy requirements and pressing environmental issues, the scientific community turned to lithium-metal batteries, celebrated for their superior capacity and efficiency. However, challenges arising from the scarcity and increasing costs of lithium have redirected research efforts towards sodium batteries. Sodium metal anodes, with their remarkable theoretical specific capacity of ~1166 mAh/g, low anode potential of -2.714 V vs standard hydrogen electrode, and cost benefits, are increasingly recognized as promising candidates for conventional energy storage systems. Notwithstanding their advantages, the unstable and fragile solid electrolyte interphase (SEI) due to the spontaneous reaction between metallic Na and a liquid electrolyte remains a significant limitation. As this SEI layer expands, it hinders ion transport, causing increased polarization and diminishing the battery's energy efficiency. Specifically, during the plating process, Na ions are deposited beneath the SEI layer, causing significant expansion. This expansion fractures the fragile SEI, allowing dendrites to grow through these defects. As these dendrites grow, they can pierce the separator, posing a risk of short-circuiting the battery. While numerous studies have proposed designs for protecting sodium metal interphase, to overcome these challenges, this study amalgamates mechano-electrochemical protective strategies to enhance sodium metal anode stability, offering groundbreaking solutions to these challenges.Central to our exploration were tin fluoride (SnF2) and silicon nitride (Si3N4), both established as effective in generating robust artificial SEI layers on the sodium metal surface. These layers, rich in NaF and NaxN respectively, demonstrated a notable improvement in cycling performance, effectively suppressing dendrite growth and enhancing the battery's cycling stability by nearly 3.5 times compared to bare sodium anodes.Building upon these foundational insights, a novel approach was conceptualized: a hybrid protective mechanism combining polyethylene oxide (PEO) with the presence of SnF2 as an additive, is particularly efficacious. This combination was specifically chosen to provide chemical stability, morphological conformality, and mechanical flexibility to accommodate the mechano-electrochemical instability upon sodiation/desodiation processes. Through this novel strategy, we aimed to amalgamate the strengths of both components, ensuring optimal outcomes. This composite artificial SEI under a 0.25 mA/cm2 current density, delivers a cycling performance 10 times superior to bare sodium metal and survived up to 1800 hours of cycling. Impressively, at a high current density of 0.5 mA/cm2, the hybrid system still performed much better than its untreated counterpart and continued cycling for up to 800 hours of cycling. The synergy of PEO and SnF2 remarkably minimized electrolyte decomposition, inhibited dendrite formation, and stabilized Na plating/stripping processes, all of which consolidated its promise for sodium metal battery technology.