Sufficient Hydrogen Research Articles

Electrochemical Synthesis of Metasequoia-Like Reduced Graphene Oxide Coated Cobalt-Silver Catalyst for Stable and Efficient Electrocatalytic Nitrate Reduction to Ammonia.

Electrocatalytic nitrate (NO3 -) reduction to ammonia (NH3) is a green and efficient NH3synthesis technology. Metallic silver (Ag) is one of the well-known electrocatalysts for NO3 - reduction. However, under alkaline conditions, its poor water-splitting ability fails to provide sufficient protonic hydrogen required for NH3 synthesis, resulting in low NH3 selectivity. Additionally, metal catalysts are prone to leaching and oxidation during electrocatalysis, resulting in poor stability. Herein, cobalt (Co) into Ag (CoAg) catalyst is doped, which not only increases the NH3 selectivity by 34.4%, but also reduces the reduction potential by 0.1V. Meanwhile, reduced graphene oxide (rGO) as a protective "armor" is used to encapsulate the CoAg catalyst (rGO2.92@CoAg). The rGO2.92@CoAg catalyst shows excellent stability for over 300 hours (h) of continuous reaction. The Co and Ag contents in the rGO2.92@CoAg catalyst after continuous tests decreases by only 4.3% and 3.1%, respectively, which are much lower than those of the CoAg catalyst without the rGO (90.8%, 52.6%). Moreover, the rGO2.92@CoAg catalyst shows high Faradaic efficiency (99.3%) and NH3 yield rate (1.47mmol h-1 cm-2). Therefore, a high performance and strong stability rGO2.92@CoAg catalyst is obtained by Co doping and rGO coating, which provides theoretical basis for practical industrial application.

Enrichment of Active Hydrogen at Amorphous CoO/Cu2O Heterojunction Interfaces Enhances Electrocatalytic Nitrate Reduction to Ammonia.

The reduction of nitrate into valuable ammonia via electrocatalysis offers a green and sustainable synthetic pathway for ammonia. The electrocatalytic nitrate reduction reaction (NO3RR) encompasses two crucial reaction steps: nitrate deoxygenation and nitrite hydrogenation. Notably, the nitrite hydrogenation reaction is regarded as the rate-determining step of the process. Herein, the amorphous CoO support introduced for the construction of the a-CoO/Cu2O tandem catalyst provides sufficient active hydrogen and synergistically catalyzes the NO3RR. The a-CoO/Cu2O catalyst showed excellent performance with a maximum NH3 Faradaic efficiency of 95.72% and a maximum yield rate of 0.96mmol h-1 mgcat -1 at -0.4V. In the flow cell, the maximum NH3 yield rate of 12.14mmol h-1 mgcat -1 is achieved at -800mA. The high NO3RR activity of a-CoO/Cu2O is attributed to the synergistic cascade effect of amorphous CoO and Cu2O at the heterojunction interface, where Cu2O serves as the adsorption site for NO3 -, while the accelerated active hydrogen generation of amorphous CoO promotes the nitrite hydrogenation reaction. This work provides a strategy for designing multi-site cascade catalysts centered on amorphous structures to achieve efficient NO3RR.

Thinking Outside the Energetic Box: Stabilizing and Greening High-Energy Materials with Reticular Chemistry.

ConspectusReticular chemistry has provided intriguing opportunities for systematically designing porous materials with different pores by adjusting the building blocks. Among them, framework materials have demonstrated outstanding performance for the design of new functional materials used in a broad range of fields, including energetic materials. Energetic materials are widely used for rockets, satellites, mining, and tunneling. In terms of energetic materials, explosophores and nitrogen-rich heterocycles are fundamental building blocks for high-energy compounds. However, the traditional strategy of synthesizing HEDMs (high energy density materials) at the molecular level has faced the long-term challenge of balancing energy and stability. Inspired by reticular chemistry, nitrogen-rich heterocycles offer diverse nitrogen sites for designing diversified coordination interactions. Ionic bond interactions exist in a wide range of energetic salts. Furthermore, most metastable explosophores, e.g., nitro, nitramino, and amino groups, can form strong hydrogen-bonding networks. Based on these noncovalent interactions (such as coordination, ionic, and/or hydrogen bonds (HBs)) and/or covalent interactions can determine intermolecular packing/linkage of the energetic fuel and oxidizer components, reticular chemistry provides a new platform evolving from single-molecular design to various energetic frameworks (E of the energetic frameworks with superior comprehensive properties. For example, to achieve coordination with metals or introduce sufficient hydrogen bond donor/acceptor structural units, the host structure of energetic framework materials usually contains less oxygen-rich substituents such as nitro, so the host molecules of the framework, F) at the crystal level, which can enhance the integrated stabilities of EFs.Along with growing concerns about the environment and safety issues, considerable effort has been devoted to pursuing environmentally friendly and insensitive energetic materials. The newly emerging EFs are conducive to introducing explosophores into a green chemical pathway. Benefiting from these cross-disciplinary achievements, taming metastable energetic molecules in specific porous frameworks is a green strategy to desensitize energetic materials while concomitantly retaining excellent energetic properties, which has become one of the most forward and promising investigations. In the past decade, EFs have achieved further results in stabilizing and greening energetic materials using HBs, covalent bonds, and alkaline earth metal-involving coordination bonds to avoid heavy metal toxicity and to employ halogen-free oxidizers. Because this field is still expanding rapidly, it is of great value for researchers and possible users of the work to be able to view all the progress.Through this Account, we intend that more readers will become knowledgeable about EFs, including their definition, history, synthesis, properties, and possible applications. The aim of this Account is to present the latest advances in EFs in recent years and to offer a perspective on the future direction of this field.

Effect of active site size in dispersed MoS2 nanocatalysts on slurry-phase hydrocracking of residue

This work investigates the influence of active site size in dispersed MoS2 on the slurry-phase hydrocracking of Merey residue (MRR). MoS2 nanocatalysts with varying morphologies were synthesized using the ligand sulfurization method, employing molybdenum oleate as the Mo precursor. The results demonstrate that mono-layered or double-layered MoS2 plates with slab sizes of 3 ∼ 10 nm can be synthesized at a sulfurization temperature of 400 °C and a sulfurization time of 0.5 h. Prolonged sulfurization time results in the growth and agglomeration of MoS2 plates, leading to multi-layered slabs with increased length and larger particle size, as well as a wider distribution range. The MoS2-0.5 (prepared with a sulfurization time of 0.5 h) exhibits superior hydrocracking activity, effectively converting resin and asphaltene into light fractions and significantly suppressing coke formation. Specifically, the conversion rates of resin and asphaltene are 51.3 wt% and 92.1 wt%, respectively, with the minimal coke yield of 0.6 wt% under conditions of 430 °C, 1 h, 7 MPa initial H2, and a catalyst dosage of 500 μg/g. The catalytic activity of the MoS2 nanocatalysts exhibits a strong correlation with their size and morphology obtained at different sulfurization times. Density functional theory (DFT) calculations reveal that MoS2 with smaller slab sizes are more beneficial for the adsorption and dissociation of H2, due to higher adsorption energy (Eads) and lower activation barrier (Ea). This facilitates the generation of sufficient active hydrogen to encourage the hydrocracking of residue and suppress coke formation.

High-Density Atomically Dispersed Metals Activate Adjacent Nitrogen/Carbon Sites for Efficient Ammonia Electrosynthesis from Nitrate.

While electrocatalytic reduction of nitrate to ammonia presents a sustainable solution for addressing both the environmental and energy issues within the nitrogen cycle, it remains a great challenge to achieve high selectivity and activity due to undesired side reactions and sluggish reaction kinetics. Here, we fabricate a series of metal-N-C catalysts that feature hierarchically ordered porous structure and high-density atomically dispersed metals (HD M1/PNC). Specifically, the as-prepared HD Fe1/PNC catalyst achieves an ammonia production rate of 21.55 mol gcat-1 h-1 that is at least 1 order of magnitude enhancement compared with that of the reported metal-N-C catalysts, while maintaining a 92.5% Faradaic efficiency when run at 500 mA cm-2 for 300 h. In addition to abundant active sites, such high performance benefits from the fact that the high-density Fe can more significantly activate the adjacent N/C sites through charge redistribution for improved water adsorption/dissociation, providing sufficient active hydrogen to Fe sites for nitrate ammoniation, compared with the low-density counterpart. This finding deepens the understanding of high-density metal-N-C materials at the atomic scale and may further be used for designing other catalysts.

Engineering CoO/B heterojunction electrocatalysts for boosting electrocatalytic nitrate reduction to ammonia

Electrocatalytic nitrate reduction to ammonia represents a one-stone-two-birds approach for mitigating nitrate pollution and large-scale ammonia production. However, due to its multiple-electron process, it faces challenges regarding unsatisfactory Faraday efficiency (FE) and ammonia yield rate. Herein, a novel heterojunction electrocatalyst with sub-nanometric cobaltous oxide (CoO) decorated boron (B) nanosheets for electrocatalytic nitrate reduction (NO3RR) is first presented as an efficient electrocatalyst. The CoO/B heterojunction electrocatalyst exhibits a noteworthy NO3RR performance with an ammonia FE and yield rate of 95.41 % and 29.42 mg h-1 mgcat-1, respectively, in alkaline media at −0.4 V vs. reversible hydrogen electrode (RHE), surpassing CoO and B catalysts. Results demonstrated that the synergistic effect of CoO and B enhances the adsorption and activation of NO3−, lowers the formation energy of *NOH and provides sufficient active hydrogen to facilitate hydrogenation, thereby enhancing NO3RR performance. This work presents a novel approach for constructing cost-effective and high-performance NO3RR heterojunction electrocatalysts.

Improved Lignin Conversion to High-Value Aromatic Monomers through Phase Junction CdS with Coexposed Hexagonal (100) and Cubic (220) Facets.

Photocatalysis has the potential for lignin valorization to generate functionalized aromatic monomers, but its application has been limited by the slow conversion rate and the low selectivity to desirable aromatic products. In this work, we designed the phase junction CdS with coexposed hexagonal (100) and cubic (220) facets to improve the photogenerated charge carriers' transfer efficiency from (100) facet to (220) facet and the hydrogen transfer efficiency for an enhanced conversion rate of lignin to aromatic monomers. Water is found as a sufficient external hydrogen supplier to increase the yields of aromatic monomers. These innovative designs in the reaction system promoted complete conversion of PP-ol to around 94% of aromatic monomers after 1 h of visible light irradiation, which shows the highest reaction rate and selectivity of target products in comparison with previous works. PP-one is a byproduct from the overoxidation of PP-ol and is usually difficult to be further cleaved to acetophenone and phenol as the desirable aromatic monomers. TEA was first identified in this study as a sacrificial electron donor, a hydrogen source, and a mediator to enhance the cleavage of the Cβ-O bonds in PP-one. With the assistance of TEA, PP-one can be completely cleaved to desirable aromatic monomer products, and the reaction time is reduced from several hours to 10 min of visible light irradiation.

Turbulent partially cracked ammonia/air premixed spherical flames

The combustion of ammonia requires, for most energy conversion systems, a combustion promoter such as hydrogen to guarantee the start-up, stability and combustion efficiency. Partially cracked ammonia (PCA) can provide sufficient hydrogen concentrations to enhance the burning velocity in comparison with pure ammonia. However, little work exists on the use of PCA blends operating under relevant turbulent conditions. To that end the outwardly propagating spherical flame configuration was employed to determine the laminar and turbulent flame propagation characteristics of PCA (NH3/(H2+N2)) and corresponding binary (NH3/H2) mixtures across various turbulent combustion regimes. First, PCA and ammonia-hydrogen blends exhibit similar flame propagation rates under various turbulent intensities, even for the laminar case. The highest turbulent burning velocity was observed at leanest conditions, as opposed to laminar flames which exhibited highest flame speed at conditions above stoichiometry. Under rich conditions, no substantial flame enhancement due to turbulence was measured irrespective of the hydrogen content. This lack of flame enhancement under turbulent conditions is attributed to the effect of preferential diffusion with good agreement observed with trends in measured Markstein numbers. The normalized turbulent flame speed is dominated by the enhanced molecular diffusivity afforded by the presence of hydrogen up to 15 % enrichment, prior to decreasing upon further hydrogen addition under lean and stoichiometric conditions. This ‘bending’ phenomenon may be the contribution of several factors including; the transitioning between combustion regimes associated with low Damköhler numbers (Da) and flame thickening; merging of flamelets due to the presence of ammonia enhancing wrinkling; and combined changes in laminar burning velocity and preferential diffusional behavior. Furthermore, good agreement for turbulent flame speed is observed with a correlation that includes the influence of turbulent stretch (Ka) and non-equidiffusion (Le), with the agreement reducing with decreasing chemical to turbulent time scale ratios (Da << 1).

Modeling and Control of Ejector-Based Hydrogen Circulation System for Proton Exchange Membrane Fuel Cell Systems

Ejector-based proton exchange membrane fuel cells (PEMFCs) are of great interest due to their simplicity and feasibility. Thus, proton exchange membrane fuel cells are considered the most suitable technology for in-vehicle systems, industrial applications, etc. Despite the passive characteristics of the ejector, active control of the hydrogen supply system is needed to ensure sufficient hydrogen, maintain the stack pressure, and ensure effective entrainment. In this research, a novel semi-empirical model is proposed to accurately predict the entrainment performance of the ejector with an 80 kW fuel cell system. According to the precise semi-empirical model, the hydrogen supply system and the anode channel are modeled. Then, a fuzzy logic controller (FLC) is developed to supply sufficient and adequate gas flow and maintain the rapid dynamic response. Compared to the conventional proportional–integral–derivative controller, the fuzzy logic controller could reduce the anode pressure variability by 5% during a stepped case and 2% during a dynamic case.

Assessment of the green hydrogen value chain in cases of the local industry in Chile applying an optimization model

This study assessed the feasibility of integrating a green hydrogen value chain into the local industry, examining two case studies by comparing four scenarios. The optimization focused on generating electricity from stationary renewable sources, such as solar or through Power Purchase Agreements, to produce sufficient hydrogen in electrolyzers. Current demand profiles, renewable participation targets, electricity supply sources, levelized costs of energy and hydrogen, and technology options were considered. The most cost-effective scenario showed a levelized cost of energy of 0.032 and 0.05 US$/kWh and a hydrogen cost below 1.0 US$/kgH2 for cases 1 and 2, respectively. A sensitivity analysis highlighted the critical influence of fuel cell technology on cost modification, underscoring the importance of focusing cost reduction strategies on these technologies to enhance the economic viability of the green hydrogen value chain. Specifically, a high sensitivity towards reducing the levelized costs of energy and hydrogen in the port sector with adjustments in fuel cell technology costs was identified, indicating the need for specific policies and supports to facilitate their adoption.

ReaxFF reactive molecular dynamic and density functional theory study on the co-pyrolysis mechanism of waste 1,1,1,2-tetrafluoroethane and waste plastics to produce high value-added chemicals and fuels

Pyrolysis is one of the potential way for the degradation of hydrofluorocarbons, but it is difficult to make effective use of the complex pyrolysis products. The addition of plastics can provide sufficient hydrogen source for the degradation of hydrofluorocarbons to generate the high value-added chemicals and fuels. Density functional theory calculation and reactive molecular dynamic simulation are employed to investigate the co-pyrolysis mechanism of 1,1,1,2-tetrafluoroethane and low-density polyethylene in this work. The results show that the H atoms provided by low-density polyethylene promote the defluorination reactions of 1,1,1,2-tetrafluoroethane to generate HF and short chain hydrocarbons, and the number of F atoms in HF molecules accounted for nearly 80 % of the whole reaction system, achieving a better defluorination effect. The defluorination rate of 1,1,1,2-tetrafluoroethane and plastics co-pyrolysis is more than 5 times that of pure 1,1,1,2-tetrafluoroethane pyrolysis. The main co-pyrolysis products of 1,1,1,2-tetrafluoroethane and low-density polyethylene are H2, HF and short chain hydrocarbons, the purpose of hydrofluorocarbons degradation into high value-added chemicals and fuels is realized in this study. This work provides a green, effective way for the conversion waste hydrofluorocarbons and waste plastics into high value-added chemicals and fuels, and achieves the conversion of waste hydrofluorocarbon refrigerants to more economical products.

Electrocatalytic Conversion of Nitrate Into Ammonia Through Heterogeneous Catalysis of NiMoO4 and Cu/Cu2O

AbstractFacilitating equilibrium in the nitrogen cycle, electrochemical nitrate reduction (NitRR) to ammonia stands as a carbon‐free method for ammonia synthesis. Copper‐based catalysts, renowned for NitRR, face a hurdle in supplying sufficient hydrogen radicals (*H) for efficient hydrogenation of NitRR intermediates. Addressing this, NiMoO4 is leveraged as an excellent *H donor, synergistically coupling it with a copper‐based catalyst. The work introduces a high‐performance NiMoO4/CuO nanowire (NW)/Copper foam (CF) catalyst for NitRR, achieving a remarkable Faraday efficiency (FE) of 98.8% and a yield of 0.8221 mmol cm−2 h−1. Operating at −0.2 V versus reversible hydrogen electrode (vs RHE) in an H‐type electrolytic cell, the catalyst demonstrates exceptional stability over 20 h. Additionally, coupling NitRR with an air stripping process enables efficient collection of NH4Cl products, offering a practical avenue for converting waste nitrates into valuable ammonia products. In‐depth in situ electrochemistry and density‐functional theory (DFT) calculations affirm the transformation of CuO into Cu/Cu2O during the electrocatalytic reduction process. Cu/Cu2O catalyzes nitrate conversion to nitrite, while NiMoO4, serving as a *H donor, facilitates deoxidation and hydrogenation of other N intermediates on the Cu/Cu2O surface, effectively driving the reduction of nitrate to ammonia.

Investigation into hydrogen induced fracture of cable bolts under deep stress corrosion coupling conditions

The coupling effects of geostress and multi-attribute corrosion environments are the major causes of damage and rupture of prestressed cable bolts in deep underground environments. To determine impacts of different environmental factors on stress corrosion cracking of cable bolts in underground conditions, the accelerated stress corrosion tests and finite element numerical simulations were carried out. By implementing the material diffusion theory and appreciating the hydrogen induced lattice expansion effects, the diffusion and aggregation behavior of hydrogen in cable bolts were simulated. The influences of stress intensity and hydrogen concentration on failure mechanisms of cable bolts were studied by considering the hydrogen induced expansion strain. The failure only occurred in the environments where sufficient hydrogen concentration existed. The hydrogen diffusion flux and distribution were consistent with stress concentration distribution. The prestress accelerated the hydrogen diffusion to stress concentrated position leading to a greater strain in the stressed areas, which consequently induced hydrogen expansion stress and decreased cohesion strength of lattice near crack tip. The fractographic features of failed specimen were analysed and hydrogen assisted fracture was confirmed to be one of the main failure mechanisms leading to stress corrosion failures. The methodologies proposed could be used to study the diffusion and distribution of hydrogen in metals and the obtained results improved the understanding failure mechanism of hydrogen assisted SCC.

A DFT study for physical properties and hydrogen storage capability of indium-based hydride perovskites XInH3 (X = Li, K) for hydrogen storage application

The physical properties and hydrogen storage capability of indium-based hydride perovskites XInH3 (X = Li, K) have been assessed in the present study. The HSE06 hybrid functional inside the CASTEP code based on DFT is used for the investigation of both materials. Both the compounds are found thermodynamically stable which is confirmed by the phonon dispersion curves. The negative values of the cohesive energy also show that both the materials are thermodynamically stable. Both the materials have zero band gap and possess metallic nature with the lattice constant values of 4.37 and 4.32 Å for LiInH3 and KInH3, respectively. The spin polarized band structure and density of states show that both the materials have antiferromagnetic nature. The optical properties show that both materials have a higher absorption and conductivity in the lower energy region. LiInH3 possesses higher values of static reflectivity and refractive index than KInH3. Both the materials are found mechanically stable, anisotropic, hard, and ductile in nature. The value of gravimetric ratio is found to be 2.42% and 1.92% for LiInH3 and KInH3, respectively. Both the materials can store sufficient hydrogen, however, LiInH3 is recommended as a preferred material for hydrogen storage application.

Frustrated Lewis Pairs on Zr Single Atoms Supported N‐Doped TiO2‐x Catalysts for Electrochemical Nitrate Reduction To Ammonia

AbstractThe electrochemical reduction of nitrates (NO3RR) for ammonia synthesis at room temperature holds immense potential. One key challenge is the adsorption and activation of NO3−, along with the provision of sufficient active hydrogen to accelerate the hydrogenation process. Here, the study prepares N‐doped TiO2‐x supported by Zr single atoms (Zr‐TiON) with rich oxygen vacancies (Ov), in which unsaturated Zr (Lewis acidic, LA) sites together with oxygen atoms around Ov (Lewis base, LB) form frustrated Lewis acid‐base pairs (FLPs). At −60 mA cm−2, NH3 Faradaic efficiency reaches 94.8%, corresponding to the production rate of 663.15 µmol h−1 mgcat−1. The yield rate is up to 26.16 mmol h−1mgcat−1 at −1 A cm−2 in flowing electrolyzer. Theoretical calculations and in situ spectroscopy analysis reveal that the interaction between LA and LB sites in FLPs plays a crucial role in facilitating adsorption and activation of electron‐rich NO3− and electron‐deficient *H. The presence of enhanced FLPs significantly reduces the energy barrier for H2O dissociation, lowering it to 0.20 eV, which facilitates subsequent hydrogenation reactions. The abundance of *H accelerates hydrogenation process, thereby enhancing the activity of NO3RR. This FLP design offers a promising approach for paving the way for the development of highly efficient NO3RR catalysts.

Nanoparticles loaded with β-Lapachone and Fe3+ exhibit enhanced chemodynamic therapy by producing H2O2 through cascaded amplification

The rapid, irreversible change of active Fe2+ to inactive Fe3+ after the Fenton reaction occurring reduces the chemodynamic therapeutic (CDT) effect. Therefore, manipulation of the tumor microenvironment to provide sufficient hydrogen peroxide (H2O2) while maintaining metal ion catalyst activity is critical for effective CDT. Here, β-Lapachone (LPC) was loaded by mesoporous silica nanoparticles (MSNs) and coated with polydopamine (PDA) to further chelate Fe3+ and link aptamer AS1411, and a pH-controlled released, chemotherapy-photothermal therapy (PTT)-enhanced CDT-small molecule therapy combination drug delivery system with passive and active tumor targeting was engineered (designated as β-LPC@MSN@PDA/Fe3+-AS1411, LMPFA). The results showed that LFMPA nanoparticles massively accumulated in tumor tissues to achieve tumor targeting through AS1411 mediating and enhanced permeability and retention (EPR) effect. Subsequently, PDA released Fe3+ and LPC through acid response to exhibited CDT and chemotherapeutic therapy. Meanwhile, the photothermal effect of PDA promoted the release of LPC from the pores of MSN. LPC exerted chemotherapy effect and cyclically producing of H2O2 by the catalysis of NQO1, which enhanced the CDT activated by Fe3+. In addition, while serving as a targeted ligand, AS1411 could also exhibit a small molecule therapeutic effect by binding to nucleoli of tumor cells. This unique nano delivery system achieved the combination of chemotherapy, PTT, enhanced CDT and small molecule therapy, and fought against malignant tumors synergistically through multi-target and multi-dimension.

Impact of acidity and surface-modulated acid dissociation on cloud response to organic aerosol

Abstract. Acid dissociation of the organic aerosol fraction has the potential to impact cloud-activating properties by altering aqueous-phase H+ concentrations and water activity but is currently overlooked in most atmospheric aerosol models. We implemented a simple representation of organic acid dissociation in the aerosol–chemistry–climate box model ECHAM6.3–HAM2.3 and investigated the impact on aerosol-forming aqueous sulfur chemistry, cloud droplet number concentrations, and the shortwave radiative effect. Many atmospheric organic acids are also surface-active and may be strongly adsorbed at the surface of small aqueous droplets. The degree of dissociation has recently been observed for several atmospheric surface-active organics with Brönsted acid character to be significantly shifted in the surface, compared to the bulk aqueous solution. In addition to the well-known bulk acidity, we therefore introduced an empirical account of this surface-modulated dissociation to further explore the potential impact on aerosol climate effects. Malonic acid and decanoic acid were used as proxies for atmospheric organic aerosols of different surface-active and acid strengths. Both acids were found to yield sufficient hydrogen ion concentrations from dissociation in an aqueous droplet population to strongly influence aqueous aerosol sulfur chemistry, leading to enhanced cloud droplet number concentrations and a cooling shortwave radiative effect. Further considering the surface modulation of organic acid dissociation, the impact on cloud microphysics was smaller than according to the well-known bulk solution acidity but still significant. Our results show that organic aerosol acid dissociation can significantly influence predictions of aerosol and cloud droplet formation and aerosol–cloud–climate effects and that, even for a well-known bulk solution phenomenon such as acidity, it may be important to also consider the specific influence of surface effects when surface-active acids comprise a significant fraction of the total organic aerosol mass.

Synergistic effects of polymaleic acid and di(dioctylpyrophosphato) ethylene titanate on B4C modification in highly filled polymer fibers for improved neutron protection safety and wear comfort of articles

Developing wearable articles with radiation protection safety and wear comfort is one of the urgent issues in that flourishing nuclear technologies are accompanied by increasing radiation threats. However, current wearable articles either display insufficient shielding performance or exhibit poor air and water vapor permeability, which are difficult to meet the growing demand of personal protection in nuclear environments. In this paper, polymaleic acid (PMA) and di(dioctylpyrophosphato) ethylene titanate (DPET) have been used to superficially modify boron carbide (B4C) particles for constructing sufficient hydrogen bonds with polyvinyl alcohol (PVA) matrix. Synergistic effects of PMA and DPET lead to enhanced interfacial interaction. As high as 55 wt% B4C/PVA fibers have been obtained with smooth wet spinning. Their multi-layered fabrics display excellent air and water vapor permeability meanwhile thermal neutron shielding. Three-layer B4C/PVA fabrics have 89.2 % thermal neutron (0.025 eV) shielding rate. In addition, 321.1 mm/s air and 2236.2 g/m2·24 h water vapor permeability have been measured. Besides, the fabrics still show great flexibility in spite of the fibers with extreme filling of inorganic particles. This work provides alternative wear articles to cope with the dilemma of radiation protection safety and wear comfort in neutron radiation environments.

Development of IrO2 Nanosheet–Pt/C Composite as Reversal Tolerant Anode Catalysts for Polymer Electrolyte Fuel Cell

Introduction: During the start-up and shutdown cycles of a polymer electrolyte fuel cell (PEFC), certain areas of the anode flow channel may not receive sufficient hydrogen due to water blockage or sluggish diffusion. This can lead to hydrogen starvation, which in turn causes a shortage of protons during cell reaction. The result is an increase in anode potential, which triggers the carbon oxidation reaction (COR) and damages the catalyst layer.Promoting the oxygen evolution reaction (OER) to alleviate the COR is a promising strategy to develop reversal-tolerant anodes (RTAs). Incorporating OER-active materials, such as IrO2, as a co-catalyst is an effective way to mitigate the rise in anode potential and prevent COR [1].In this study, a novel OER-active material, iridium oxide nanosheet (IrO2(ns)), was used as the co-catalysts and combined with commercial Pt/C in three different ways; mixing Pt/C with normal- and small-sized IrO2 nanosheets (IrO2(ns)/Pt/C), and Pt/C mixed with carbon supported IrO2 nanosheet (Pt/C+IrO2(ns)/KB). The OER activity and tolerance to cell reversal conditions were characterized using a 3-electrode rotating disk electrode (RDE) setup. Experiment: IrO2(ns)(250 nm) colloid was synthesized following literature [2]. The resulting IrO2(ns)(250 nm) colloid was subjected to ultrasonication to obtain small-sized nanosheets (IrO2(ns)(100 nm)) [3]. Nanosheet-carbon composite (IrO2(ns)(100 nm)/KB) was prepared by mixing IrO2(ns)(100 nm) colloid and KB (Ketjen black EC-300J) and physically mixed with Pt/C. Commercially available IrO2 nanoparticles (c-IrO2) were purchased from Tokuriki Honten Co., Ltd. and added to Pt/C (c-IrO2-Pt/C) and used as a reference sample.The composite catalyst was prepared by mixing Pt/C with different IrO2 nanomaterials and will be denoted as IrO2(ns)(x mass%)-Pt/C or c-IrO2 (x mass%)-Pt/C depending on the source of the IrO2 material used. RDE studies were conducted using a 3-electrode half-cell setup with 0.1 M HClO4 as the electrolyte. The counter electrode was carbon fiber, and a reversible hydrogen electrode (RHE) was used as the reference electrode.Except for the OER activity, the electrodes for all measurement were prepared with a Pt loading of 8.0 μg/cm2. For hydrogen oxidation reaction (HOR) activity measurements, the electrolyte was purged with H2. For chronopotentiometry (CP) and electrochemically active Pt surface area (ECSA) measurement, the electrolyte was purged with N2. For OER activity measurements, the electrolyte was purged with N2, and the working electrode was prepared with a Pt loading of 17.3 μg/cm2. Except for ECSA measurement, all data were accumulated at an electrolyte temperature of 60oC. Results and Discussion: Figure 1 shows the OER activity (10 mV/s) of Pt/C and composite catalysts prepared with c-IrO2(5 mass%), IrO2(ns)(250 nm, 5 mass%), IrO2(ns)(100 nm, 5 mass%), IrO2(ns)(100 nm, 2.5 mass%) and IrO2(ns)(100 nm, 1 mass%). At 1.5 V vs. RHE, IrO2(ns)(100 nm, 2.5 mass%)-Pt/C exhibited a 2-fold increase in OER activity compared to IrO2(ns)(250 nm, 5 mass%)-Pt/C and a 25 % increase compared to c-IrO2 (5 mass%)-Pt/C. All composite catalysts displayed significantly higher OER activity than the pristine Pt/C sample.To simulate the degradation behavior in the fuel cell anode, a series of CP tests were performed at 16, 48, 80, and 112 μA/cm2. The HOR mass activity was used as a quantitative factor to present the decay caused by cell reversal degradation. The HOR activity before and after CP was evaluated using linear sweep voltammetry (LSV) from -0.08 V to 0.5 V vs. RHE. The HOR mass activity at 20 mV vs. RHE was calculated based on the Koutecky-Levich equation. After CP, the Pt/C sample showed a decrease in HOR activity from 851 A/g to 621 A/g (72% retention). In contrast, IrO2(ns)(100 nm, 2.5 mass%)-Pt/C showed an initial HOR activity comparable to Pt/C (1420 A/g) and still retained a high HOR activity of 1400 A/g after CP (100% retention). The addition of IrO2(ns) as a co-catalyst effectively suppressed the carbon oxidation reaction under cell reversal conditions.

Securing Autonomy of Military Barracks Through Renewable Energy Solutions

Abstract This article presents a concept of establishing a network of energy self-sufficient nodes in Slovenia and the EU, within the Defence RESilience Hub Network in Europe project initiated by the Ministry of Defence of Slovenia (MORS). The goal is to reduce the energy dependence of military facilities on external suppliers. A mathematical model of a military site’s micro-grid incorporates multiple energy vectors and their conversion and storage, with a focus on hydrogen technologies. A case study of a military site in Belgium shows that an energy system with solar and wind power can provide sufficient hydrogen for transportation needs and operate the site autonomously for up to 30 days. Additionally, the carbon footprint of the military base as an energy system was calculated, indicating potential reductions in environmental impacts.