KOH Solution Research Articles

Early Strength and Microscopic Mechanisms of Alkali-Metal Hydroxide-Activated Tungsten Tailings

The excellent mechanical properties of alkaline-activated tailings are essential for their increased use in building materials. While numerous studies have been conducted on activated tailings, the strength of alkaline-activated tungsten slag has not been extensively explored due to the low reactivity of silicon and aluminum in these tailings. This research delves into the early unconfined compressive strength of tungsten tailings activated by two alkali solutions (NaOH and KOH) at three different alkali concentrations (mass ratio of alkali to tungsten tailings), cured at 80 °C over periods of one day, three days, and seven days. The study finds significant improvements in the stability of tungsten tailings when forming (C, N)-A-S-H or (C, K)-A-S-H gels with both alkalis. Scanning Electron Microscope (SEM) results show that the morphology of the (C, N)-A-S-H gels transitions from membranous to flocculated and then to a three-dimensional network as the NaOH content and curing time increase. Conversely, the (C, K)-A-S-H gels primarily exhibit thin-film morphology with some three-dimensional network structures. The presence of flocculation and three-dimensional mesh in the gels fosters the formation of a robust skeletal structure, enhancing the strength of the samples. Furthermore, specimens treated with NaOH solution exhibit a higher gel content compared to those treated with KOH solution. These factors contribute to the superior efficacy of sodium hydroxide in enhancing the strength of tungsten tailings compared to potassium hydroxide. X-ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) results identify the formation of new phases such as pirssonite, buetschliite, potassium bicarbonate, and potassium carbonate. The first new phase results from the carbonization of excess NaOH solution, while the latter phases arise from the carbonization of excess KOH solution. These carbonization processes negatively impact the strength of the materials.

Methods to characterize microplastics: case study on freshwater fishes from a tropical lagoon in Colombia.

Aquatic ecosystems face multiple anthropogenic pressures, and recently plastic pollution is one of the main problems. The Luruaco lagoon receives discharges from streams with high levels of microplastics (MPs) from urban areas that impact the resident ichthyofauna. We studied the prevalence, abundance and physical and chemical characteristics of MPs in fishes in the Luruaco Lagoon, Colombia. Four samplings were carried out where fish were captured with trawl nets. Each individual was assessed for total weight, total and standard length, and then a uroventral cut was made to extract stomach and intestine (GIT). Each structure was weighed, measured, and deposited in glass jars with filtered KOH solution. The abundance of MPs and frequency of occurrence were assessed. A principal component analysis (PCA) was used to describe the variation of the species dataset (%FO, proportion of MPs and their diet). Seven species were recorded and 271 individuals examined: Microplastics were identified in all species, and 1157 particles were found in their GIT, with a prevalence of 87.5% of MPs. Mugil liza and Andinoacara latifrons had a high proportion of MPs. The highest %FO was found in cichlid species. Four typologies and 13 colors of MPs were analyzed; fibers and color blue were predominant. A direct relationship was observed between the type of diet and the proportion and %FO of MPs.

Hydrothermal-Induced Cationic Vacancies in NiAl Hydroxide for Enhanced Oxygen Evolution Activities through Optimization of eg* Band Broadening.

Nickel-based hydroxides [Ni(OH)2] have attracted significant attention as effective oxygen evolution reaction (OER) catalysts. In recent years, defect engineering has been extensively utilized in Ni(OH)2 modification research. Numerous studies have confirmed that the generation of defects can expose more active sites and regulate electronic states, particularly through the introduction of Al cationic vacancies, which enhance conductivity and thereby improve the catalytic performance. The traditional method for producing cationic vacancies is electrochemical etching. However, this method generates a limited number of vacancies in the catalysts and has the complex etching process. Herein, we found that when NiAl layered double hydroxides were treated using a hydrothermal process at 100 °C in a KOH solution, more Al cationic vacancies were generated. Compared to the traditional method with an Al leaching efficiency of 24%, our proposed method achieved an Al leaching efficiency of 44%. Meanwhile, the electrochemical results showed that the overpotential was reduced by 110 mV at 10 A/g. Further experiments showed that the enhanced OER activities resulting from an increased number of cationic defects lead to structural distortions, which broaden the eg* band, significantly affecting the rate of electron transfer between the electrocatalyst and external circuitry, thereby enhancing the OER activity. This work presents a promising approach to creating cationic defects in Ni(OH)2 for high-performance electrocatalysts.

Stabilization of High‐Valent Molecular Cobalt Sites through Oxidized Phosphorus in Reduced Graphene Oxide for Enhanced Oxygen Evolution Catalysis

AbstractHeterogeneous molecular cobalt (Co) sites represent one type of classical catalytic sites for electrochemical oxygen evolution reaction (OER) in alkaline solutions. There are dynamic equilibriums between Co2+, Co3+ and Co4+ states coupling with OH−/H+ interaction before and during the OER event. Since the emergence of Co2+ sites is detrimental to the OER cycle, the stabilization of high‐valent Co sites to shift away from the equilibrium becomes critical and is proposed as a new strategy to enhance OER. Herein, phosphorus (P) atoms were doped into reduced graphene oxide to link molecular Co2+ acetylacetonate toward synthesizing a novel heterogeneous molecular catalyst. By increasing the oxidation states of P heteroatoms, the linked Co sites were spontaneously oxidized from 2+ to 3+ states in a KOH solution through OH− ions coupling at an open circuit condition. With excluding the Co2+ sites, the as‐derived Co sites with 3+ initial states exhibited intrinsically high OER activity, validating the effectiveness of the strategy of stabilizing high valence Co sites.

High-Entropy Prussian Blue Analogue Derived Heterostructure Nanoparticles as Bifunctional Oxygen Conversion Electrocatalysts for the Rechargeable Zinc-Air Battery.

In response to energy challenges, rechargeable zinc-air batteries (RZABs) serve as an ideal platform for energy storage with a high energy density and safety. Nevertheless, addressing the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in RZAB requires highly active and robust electrocatalysts. High-entropy Prussian blue analogues (HEPBAs), formed by mixing diverse metals within a single lattice, exhibit enhanced stability due to their increased mixing entropy, which lowers the Gibbs free energy. HEPBAs innately enable sacrificial templating, an effective way to synthesize complex structures. Impressively, in this study, we successfully transform HEPBAs into exquisite multiphase (multimetallic alloy, metal carbide, and metal oxide) heterostructure nanoparticles through a controlled synthesis process. The elusive multiphase heterostructure nanoparticles manifested two active sites for selective ORR and OER. By integrating CNT into HEPBA-derived nanoparticles (HEPBA/CNT-800), the HEPBA/CNT-800 demonstrates superior activity toward both ORR (E1/2 = 0.77 V) in a 0.1 M KOH solution and the OER (η = 330 mV at 50 mA cm-2) in a 1 M KOH solution. The RZAB with a HEPBA/CNT-based air electrode demonstrated an open-circuit voltage of 1.39 V and provided a significant energy density of 71 mW cm-2. Moreover, the charge and discharge cycles lasting up to 40 h at a current density of 5 mA cm-2 demonstrate its excellent stability. This work provides an alternative avenue for the rational design of HEPBA's derivative for a sustainable rechargeable metal-air battery platform.

Wet sulfuration of molybdate and reconstruction regulation of trace Fe doping for oxygen evolution

There is a growing interest in the development of active, durable, and cost-effective electrocatalysts for oxygen evolution reactions (OER). In this study, we synthesized a self-reconstruction iron-doped sulfide-regulated nickel molybdate catalyst using wet chemical sulfuration and electrodeposition techniques. The core-shell nanorods (SC@NMO) were produced through rapid sulfuration. We investigated the effects of sulfur leaching on rapid and extensive electrochemical self-reconstruction. Our approach utilized the phase change of Fe3+ and electrodeposition-induced restructuring to enhance the catalyst's OER activity and stability in an alkaline electrolyte. Notably, iron ions establish a precipitation-dissolution dynamic equilibrium at the interface between the catalyst surface and the electrolyte, which minimizes iron loss and results in a more efficient and stable catalyst. The prepared sample, SC-Fe(Ni)OOH@NMO, demonstrated exceptional oxygen evolution performance and long-term stability in a 1 M KOH solution, achieving an overpotential of only 279 mV at a current density of 100 mA cm−2. It maintained stable operation for 200 h in a high-concentration 6 M KOH solution. The above data prove that this work provides a feasible strategy to enhance the OER catalytic capacity of metal oxides by the two modification methods of co-doping of metal and non-metal and reconstruction.

Hydroxide-ion induced complete mineralization of poly(tetrafluoroethylene-co-hexafluoropropylene) copolymer (FEP) in subcritical water

Decomposition of poly(tetrafluoroethylene-co-hexafluoropropylene) copolymer (FEP) in supercritical and subcritical water was investigated with the aim of waste treatment. The efficiency of such decomposition was examined by using either oxidizing agents (O2, H2O2) or an alkaline reagent (KOH). When O2 was chosen, the highest F– and CO2 yields, 75 % and 64 %, respectively, were obtained from a reaction of FEP in supercritical water at 384 °C for 24 h. Under these conditions, traces of CHF3 were detected in the gas phase, the amount of which decreased with increasing the reaction time·H2O2 gave slightly higher reactivity than O2. In contrast, reactions with KOH induced efficient fluorine mineralization. When FEP reacted in 3.0 M KOH solution at 360 °C for 18 h, the F– yield reached 98 %. Hence, complete fluorine mineralization was achieved, where very little CO2 (∼0% yield) and no CHF3 were generated in the gas phase. Furthermore,19F NMR spectroscopy and combustion-ion chromatography revealed that the reaction solutions did not contain any organofluorine compounds during the reactions. FEP decomposed, releasing F– into the reaction solution, resulting in the formation of amorphous carbon in the residue.

Construction of Co-Ni3B/GDY heterostructured electrocatalyst for boosting oxygen evolution in alkaline media

Water splitting as the clean technology for hydrogen production garnered the widespread attention. The high overpotential required for oxygen evolution reaction (OER) is the central dilemma. Herein, Co-Ni3B/graphdiyne heterostructure on copper foam (Co-Ni3B/GDY/CF) was constructed for boosting alkaline OER. Detailed electrochemical analysis showed that Co-Ni3B/GDY/CF was an exceptional OER electrocatalyst with the low overpotentials of 270 and 335mV at 20 and 100mAcm−2 in 1.0M KOH solution, respectively, as well as high turnover frequency of 0.80s−1 at 400mV. Moreover, its catalytic performance outperformed the benchmarked RuO2/CF when the current density exceeded 200mAcm−2. Importantly, the equipped electrolyser Pt/C/CF||Co-Ni3B/GDY/CF showed low cell voltage (1.53V@10mAcm−2) and long-term durability. These results demonstrated that a synergistic effect at the heterointerface between GDY and Co-Ni3B was achieved, which regulated the electronic configuration, accelerated the charge transfer and increased the active surface areas. Furthermore, the density functional theory calculations revealed that Co-Ni3B/GDY with incomplete charge transfer lowered the energy barrier of the rate-determining step and optimized adsorption/desorption behavior of the intermediates, thereby effectively promoting O2 evolution.

One-Pot Fast Electrochemical Synthesis of Ternary Ni-Cu-Fe Particles for Improved Urea Oxidation

The climate crisis has become the most serious concern of human beings and environments worldwide in the 21st century. Global concerns about cancer epidemiology mainly originate from anthropogenic activities, particularly fossil-based operations. A key solution to this problem is the use of fuel cells—devices—capable of the direct conversion of fuel chemical energies like urea into electricity. To make their commercialization reasonable, one of the problems that needs to be solved is the development of anodic materials. The majority of investigations on urea oxidation are based on nickel, but its inadequate activity limits the efficiency of these devices. In this work, we propose and synthesize a Ni-Cu-Fe ternary electrocatalyst for urea oxidation through a fast and facile electrodeposition method. The properties of the synthesized material are examined by Scanning Electron Microscopy (SEM) conjugated with Energy Dispersive X-ray Spectroscopy (EDS), Transmission Electron Microscopy (TEM), and X-ray Diffraction (XRD). Its electrochemical properties were also examined in a 1 M KOH solution with and without 0.15 M urea. We found that the prepared powder is active in the electro-oxidation of urea, with 1.65 Vvs RHE required for a current density of 10 mA cm−2 and a stable potential of 2.38 Vvs RHE required for 3 h of polarization at 10 mA cm−2.

Confined pyrolysis synthesis of N-doped carbon-supported FePr nanoparticles for efficient oxygen reduction based on 3d–4f orbital coupling

To meet the growing demand for new energy storage and conversion technologies, there is an urgent need to prepare highly efficient, economical and durable oxygen reduction catalysts that can replace those based on precious. Herein, N-doped porous carbon supported FePr nanoparticles (FePr/NC) were prepared by confined adsorption and pyrolysis. The characterizations and electrocatalytic properties of the FePr/NC were investigated in details. The prepared FePr/NC catalyst showed excellent oxygen reduction reaction (ORR) catalytic performance with a half-wave potential (E1/2) of 0.87 V in a 0.1 M KOH solution, outperforming commercial Pt/C catalyst (E1/2 = 0.82 V) under the identical conditions. Besides, its onset potential (Eonset) was up to 1.002 V, exceeding the Pt/C (Eonset = 0.92 V). Moreover, the E1/2 only exhibited a negative shift of 7 mV after 2000 cycles, reflecting its significant stability. To understand their exceptional preference for the ORR, the electronic structure of Fe influenced by the doped Pr and the synergistic effect of the FePr nanoparticles with N-doped carbon were investigated. The coupling of Fe's 3d orbitals with Pr's 4 f orbitals in the FePr significantly enhanced the electrocatalytic activity. This work provides a promising strategy for preparation of high-quality transition metal-based carbon catalysts for green energy devices.

Exploring Alkali Hydroxide Influence on Calcium Titanate Formation for Application in Biodiesel Catalysts

Biodiesel has been recognized as the most widely utilized biofuel around the world due to its significant role in reducing the consumption of crude oil and lowering environmental pollution levels. By serving as a renewable alternative to fossil fuels, bioethanol helps decrease greenhouse gas emissions and contributes to a more sustainable energy future. Traditionally, alkali hydroxides like NaOH and KOH have been mainstays in biodiesel synthesis. However, their overuse can lead to unwanted byproducts and operational complexities. Since calcium titanate can occur at a strong base condition, it presents an alternative avenue worth exploring. In this study, we investigate the influence of alkali hydroxides, namely LiOH, NaOH, and KOH, on the formation of calcium titanate through hydrothermal methods, with varying heating times. We aim to understand how different hydroxides affect the synthesis process and the resultant properties of calcium titanate. We delve into the vibrational properties of Ca‒O‒Ti and Ti‒O bonds using Fourier transform infrared spectroscopy (FTIR), confirming the presence of calcium titanate (JCPDS No.42-0423) through X-ray diffractometry (XRD). This thorough characterization provides insight into the structural integrity and composition of the synthesized materials. Moreover, scanning electron microscopy (SEM) reveals the intriguing cube-like morphology of calcium titanate, offering visual evidence of its unique structure. The fatty acid methyl ester Iimpressively, our results show that calcium titanate synthesized in 7 M NaOH and KOH solutions, heated for 24 hours, emerges as a promising biodiesel catalyst. We observe fatty acid methyl ester provides the percentages of 63.67% and 90.02%, respectively, indicating the catalytic efficacy of these materials in biodiesel production. These findings not only contribute to the understanding of calcium titanate synthesis but also pave the way for a sustainable future in biodiesel production by introducing efficient and eco-friendly catalysts.

Interface Engineering of Flower-like Co 2 P/WO 3-x /Carbon Cloth Catalysts with Oxygen Vacancies for Efficient Oxygen Evolution Reaction.

The Constructing an efficient and low-cost oxygen evolution reaction (OER) electrocatalyst is critical for improving the performance of electrolysis in alkaline water. In this study, a self-supported electrocatalyst of flower-like cobalt phosphide and tungsten oxide (Co2P/WO3-x/CC) was prepared on carbon cloth (CC)surface by hydrothermal reaction with solution immersion etching and phosphorization annealing under H2/Ar atmosphere. This strategy can generate oxygen vacancies (OV), improving the speed of charge transfer between cobalt phosphide (Co2P) and tungsten oxide (WO3-x) components. The catalyst greatly increases the electrochemical active surface area, which is beneficial for efficient oxygen evolution. Electrochemical testing studies show that in 1.0 M KOH solution, Co2P-WO3-x/CC catalyst exhibits good OER activity, with a low overpotential of 254 mV at 10 mA cm-2, a small Tafel slope of 58.32 mV dec-1. The synergistic effect of oxygen vacancies and Co2P with WO3-xcan regulate electronic structures, expose more active sites, and cooperatively enhancing the OER activity. This study provides a workable strategy for preparing efficient non-noble metal OER electrocatalysts on engineered interfaces and OV.

Atomic orbitals modulated dual functional bimetallic phosphides derived from MOF on MOF structure for boosting high efficient overall water splitting

The electronic modulation characteristics of efficient metal phosphide electrocatalysts can be utilized to tune the performance of oxygen evolution reaction (OER). However, improving the overall water splitting performance remains a challenging task. By building metal organic framework (MOF) on MOF heterostructures, an efficient strategy for controlling the electrical structure of MOFs was presented in this study. ZIF-67 was in-situ synthesized on MIL-88 (Fe) using a two-step self-assembly method, followed by low-temperature phosphorization to ultimately synthesize FeP-CoP3 bimetallic phosphides. By combining atomic orbital theory and theoretical calculations (density functional theory), the results reveal the successful modulation of electronic orbitals in FeP-CoP3 bimetallic phosphides, which are synthesized from MOF on MOF structure. The synergistic impact of the metal center Co species and the phase conjugation of both kinds of MOFs are responsible for this regulatory phenomenon. Therefore, the catalyst demonstrates excellent properties, demonstrating HER 81 mV (η10) in a 1.0 mol L−1 KOH solution and OER 239 mV (η50) low overpotentials. The FeP-CoP3 linked dual electrode alkaline batteries, which are bifunctional electrocatalysts, have a good electrocatalytic ability and may last for 50 h. They require just 1.49 V (η50) for total water breakdown. Through this technique, the electrical structure of electrocatalysts may be altered to increase catalytic activity.

Redox-mediated synthesis of Cu2O/CuO/Mn3O4/C quaternary nanocomposites as an efficient electrode material for oxygen reduction reaction and supercapacitor application

Earth-abundant transition metal oxides (TMOs) hold significant promise as electroactive materials in various electrochemical energy conversion and storage applications, offering economic and environmental advantages over their less abundant counterparts. In this work, a simple and cost-effective redox-mediated reaction strategy under hydrothermal conditions has been adopted to synthesize the quaternary nanocomposites Cu2O/CuO/Mn3O4/C with variable amounts of carbon. The synthesized nanocomposites have been characterized using various analysis techniques, including powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Brunauer–Emmett–Teller (BET). The synthesized COM5 nanocomposite (Cu2O/CuO/Mn3O4/C-50), when used as an electrocatalyst for the oxygen reduction reaction (ORR), demonstrates a good limiting current density (JL), half-wave potential (E1/2), and onset potential (Eonset) of −5.50 mA/cm2, 0.75 V, and 0.95 V, respectively, as per the polarization curve. The COM5 nanocomposite exhibits a four-electron transfer mechanism, calculated using the Koutecky-Levich (K-L) equation. In an O2-saturated 0.1M KOH solution, the COM5 nanocomposite has shown a superior relative current durability of 84.46% over 14,000 s compared to the commercially available 10 wt% Pt/C, indicating its potential application in the ORR. However, for supercapacitor applications, the COM3 nanocomposite (Cu2O/CuO/Mn3O4/C-20) as active electrode material in galvanic charge-discharge (GCD) study shows superior performance (201 F/g at 1 A/g) compared to the COM2 nanocomposite (117 F/g at 1 A/g) in neutral aqueous electrolyte, possibly due to the lower charge transfer resistance (Rct) of 24.04 Ω compared to COM2 (34.63 Ω). In two-electrode studies, the COM3 nanocomposite exhibits a good energy density of 24.19 Wh/kg at 1 A/g and a 4.7 kW/kg power density at 5 A/g. Additionally, the COM3 nanocomposite shows excellent long-term durability (74% capacitance retention) at the current density of 5 A/g for 8000 cycles. The electrochemical findings indicate that the COM3 nanocomposite stands out as a superior electrode material for supercapacitors, while the COM5 nanocomposite proves to be an effective electrocatalyst for the oxygen reduction reaction.

ZnS-zeolitic imidazolate framework nanostructure anchored on Ni nanowires as a bifunctional electrocatalyst for high-efficiency overall water splitting

The design and construction of stable and inexpensive bifunctional catalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) present a challenge in electrocatalytic water splitting. In this study, we utilized zeolitic imidazolate frameworks-8 (ZIF-8) as the precursor to fabricate ZnS-ZIF-8 via facile sulfidation processes. The ZnS-ZIF-8 nanostructures were anchored on the surface of the nickel nanowire (denoted as Ni NWs@ ZnS-ZIF-8 nanocomposite) and their catalytic activity for HER, OER, and overall water splitting were studied. The prepared Ni NWs@ ZnS-ZIF-8 revealed a low overpotentials value of 90 and 260 mV at 10 mA cm−2 for HER and OER in 1.0 M KOH solution, respectively. The alkaline electrolyzer assembled by Ni NWs@ ZnS-ZIF-8 provides a low cell voltage of 1.61 V at 10 mA cm−2 current density to boost the overall water splitting and robust stability for 15 h. The superior electrocatalytic activity of Ni NWs@ ZnS-ZIF-8 is owing to the facile and effective electron transport of Ni NWs, accessible active sites of ZnS-ZIF-8, and as well as the synergistic effect of the nanocomposite structures. This finding presents a viable methodology for synthesizing a proficient noble-metal-free catalyst for energy conversion and storage.

Exploring Platinum Thin Films as Electrodes for High‐Temperature and ‐Pressure Electrochemical Studies in Aqueous Systems

ABSTRACTThis work reports a methodology for the fabrication of Pt thin‐film electrodes for electrochemical studies in hydrothermal systems. The research process was meticulous, with particular attention paid to the multilayer Ti/Pt/Ti/Al2O3 film structure and annealing conditions that are expected to impact the morphology of the films, surface composition and electrochemical response. The findings of this study are significant, as they provide valuable insights into the behaviour of Pt thin‐film electrodes in various media and conditions. Two different approaches were adopted for the preparation of the electrodes: in one case, the Ti/Pt/Ti/Al2O3 films deposited on sapphire wafers were exposed to rapid thermal annealing at 900°C under argon for 5 min, followed by argon ion milling to etch the final electrode pattern (Pt‐RA(900)), while in the other case, uncapped Pt films were annealed, after etching, in a tubular oven under argon at specific temperatures between 200°C and 900°C (Pt‐TO). Rapid annealing at 900°C on capped films resulted in the formation of a Pt3Ti intermetallic alloy with remarkable mechanical and chemical stability even after 10 h of immersion in deionised water, acid (0.1 M H2SO4) and alkaline media (0.1 M KOH) conditions at temperatures up to 150°C, despite the dissolution of the Al2O3 top layer at 150°C and long immersion times (> 10 h). In the case of uncapped Pt films, diffusion and oxidation of Ti through the Pt film at high temperature resulted in the formation of TiO2 on the surface of Pt. The results were confirmed by using a comprehensive suite of ex‐situ characterisation techniques to follow changes in the Pt electrode surface morphology and composition before and after immersion in H2O, 0.1 M H2SO4 and 0.1 M KOH solutions under argon. Ex‐situ electrochemical characterisation studies were also conducted to correlate the changes in the electrode surface properties, including the electrochemical surface area, with different annealing conditions and after various hydrothermal treatments in neutral, alkaline and acidic media.

Durability of epoxy and vinyl ester polymers in wet, seawater, and seawater sea sand concrete environments: Molecular dynamics simulations

Epoxy and vinyl ester (VE) deteriorate under harsh environmental conditions typical of marine and offshore applications. Enhancing their performance requires a deeper understanding of their molecular-level interactions with these environments. This study uses molecular dynamics simulations to investigate the behavior of epoxy and VE under dry, wet, Na2SO4, NaCl, NaOH, KOH, and simulated seawater sea sand concrete (SWSSC) pore solution environments. The effect of temperatures ranging from 300 K to 368 K was also explored. Key parameters, such as radial distribution function, hydrogen bond dynamics, diffusion coefficients of water molecules and ions, swelling ratio, and glass transition temperature (Tg), were analyzed. Results show that epoxy is more sensitive to environmental effects than VE. In the dry state, three types of hydrogen bonds (H-bonds) were identified, with 64 % of the hydroxyl (OH) group involved in epoxy and 34 % in VE. As temperature increases, polymer chain interactions weaken, leading to a decrease in H-bonds, with epoxy showing a faster decline. Absorbed water molecules accumulate near the polymer polar sites, particularly at the OH groups, breaking some polymer-polymer H-bonds and forming new ones with the polymer polar sites. The hydrogen atoms of most absorbed water molecules orient away from the OH group, creating binding sites for water clustering through water-water H-bonds, leading to plasticization and potential hydrolytic degradation. Ions increase the number of polymer-water H-bonds, significantly decreasing polymer-polymer H-bonds (by 59.22 % for epoxy and 51.52 % for VE in SWSSC), thus accelerating material deterioration. Free volume distribution and dynamics, the transition between bound and free water, hydrogen bond dynamics, as well as ion hydration and dehydration collectively influence the water diffusion process in the polymer networks. Ion species diffuse much slower than water molecules, with epoxy showing higher permeability to Cl- and OH- compared to VE. Glass transition temperature (Tg) of both polymers is sensitive to environmental exposure, with epoxy being more affected. The detrimental effect on Tg is ranked as SWSSC > KOH > NaOH > NaCl > Na2SO4 > Wet. These findings provide new nanoscale insights into the interactions between polymers and SWSSC environments, offering a foundation for accurately predicting the durability of polymer-reinforced SWSSC.

Iron phosphide nanoparticles anchored on 3D nitrogen-doped graphene as an efficient electrocatalysts for hydrogen evolution reaction in alkaline media

Electrocatalysts play a crucial role in hydrogen evolution reaction (HER), facilitating a clean and sustainable generation of hydrogen energy. To promote the HER process, it is imperative to employ highly efficient, stable, and cost-effective electrocatalysts. This research focuses on the design of iron phosphide nanoparticles anchored onto a porous three-dimensional nitrogen-doped graphene (FeP@3DNG). The porous framework of 3DNG serves a multifaceted purpose: it prevents the aggregation of FeP nanoparticles during phosphidation, safeguards the FeP electrocatalyst from oxidation during the HER, and simultaneously enhances electrical conductivity and stability. Notably, the FeP@3DNG nanocomposite demonstrated the efficient activity and highest HER activity with an overpotential of 76 mV to achieve 10 mA cm−2 and a small Tafel slope of 40.2 mV dec−1 as well as good long-term durability for 20 h in 1.0 M KOH solution. The high performance of the FeP@3DNG nanocomposite can be primarily corresponded to the synergistic effects of the highly active of FeP nanoparticles and advantages of porous three-dimensional graphene with excellent electrocatalytic activity, high specific surface area, and chemical stability, thus, resulting in the improvement the overall electrocatalytic activity.

Improving the Electrocatalytic Activity of a Core/Shell NiCo-ZIF@PBA Catalyst by Co-O-Fe Bridge Bonds for Water Oxidation.

In response to the limitations of slow reaction kinetics and elevated overpotentials in the OER, a novel core-shell structured electrocatalyst, termed NiCo-ZIF-67@Fe-Co-Ni-PBA or NiCo-ZIF@PBA, has been developed. This material demonstrates exceptional catalytic performance, exhibiting a minimal overpotential of approximately 188 mV at 10 mA cm-2, alongside a Tafel slope of 109 mV dec-1. Its robust stability in a 1 M KOH solution during the OER operations is noteworthy. Theoretical insights from DFT calculations reveal that a Co-O-Fe bridging configuration within NiCo-ZIF@PBA lowers the energy barrier for the reaction to 1.79 eV, a significant reduction from 2.67 eV observed with NiCo-ZIF-67. The improvement in electrochemical performance is primarily due to the emergence of Co3+ ions, which results from the efficient charge transfer occurring at the interface of the PBA and NiCo-ZIF core-shell structure. These findings suggest a promising strategy for designing advanced core-shell materials for electrocatalytic applications.

Simple solution immersion for realizing bifunctional catalyzation of water splitting in various electrolytes

Developing cost-effective, highly efficient and scalable bifunctional electrocatalysts for hydrogen production is crucial for advancing hydrogen energy systems. However, current methods are hindered by high energy consumption and material limitations. This work introduces a bifunctional electrocatalyst (NiFe-OH@Co2P@NF), by simply immersing a hierarchical cobalt phosphide electrode in mixed Ni/Fe solution, followed by forming layered nickel-iron hydroxides on the surface. Electrochemical tests reveal that this catalyst enhances active site exposure, accelerates electron transfer, and significantly lowers the overpotential for water electrolysis. It requires minimal overpotentials (79 mV at 10 mA cm−2, 175 mV at 150 mA cm−2) in 1 M KOH solution. In a dual-electrode electrolytic cell system, the catalyst enables efficient hydrogen production at a current density of 10 mA cm−2 with just 1.52 V, demonstrating robust stability during prolonged alkaline water splitting tests. Moreover, the bifunctional electrodes display good performance and durability in simulated alkaline seawater and 1 M KOH + seawater.