Search Results (281)

Some of nuclear power’s primary detractors are the unique environmental challenges and impacts of radioactive wastes generated during fuel cycle operations. Key benefits of spent fuel reprocessing (SFR) are reductions in primary high active waste (HAW) masses, volumes, and lengths of radiotoxicity at the expense of secondary waste generation and high capital and operational costs. By employing advanced waste management and resource recovery concepts in SFR beyond the existing standard PUREX process, such as minor actinide and fission product partitioning, these challenges could be mitigated, alongside further reductions in HAW volumes, masses, and duration of radiotoxicity. This work assesses various current and proposed SFR and fuel cycle options as base cases, with further options for fission product partitioning of the high heat radionuclides (HHRs), rare earths, and platinum group metals investigated. A focus on primary waste outputs and the additional energy that could be generated by the reprocessing of high-burnup PWR fuel from Gen III(+) reactors using a simple fuel cycle model is used; the effects of 5- and 10-year spent fuel cooling times before reprocessing are explored. We demonstrate that longer cooling times are preferable in all cases except where short-lived isotope recovery may be desired, and that the partitioning of high-heat fission products (Cs and Sr) could allow for the reclassification of traditional raffinates to intermediate level waste. Highly active waste volume reductions approaching 50% vs. PUREX raffinate could be achieved in single-target partitioning of the inactive and low-activity rare earth elements, and the need for geological disposal could potentially be mitigated completely if HHRs are separated and utilised. Full article

An anion exchange-assisted technique was used for the synthesis of platinum-decorated SnO₂ supports, providing nanocatalysts with enhanced activity for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). In this study, a series of SnO₂ supports, namely SnA (synthesized almost at room temperature), SnB (hydrothermally treated at 180 °C), and SnC (annealed at 600 °C), are systematically investigated, all loaded with 1 mol% Pt from H₂PtCl₆ under identical mild conditions. The chloride ions from the SnCl₄ precursors were efficiently removed via a strong-base anion exchange reaction, resulting in highly dispersed, crystalline ~5 nm cassiterite SnO₂ particles. All Pt/SnO₂ composites displayed mesoporous structures with type IVa isotherms and H₂-type hysteresis, with SP1a (Pt on SnA) exhibiting the largest surface area (122.6 m²/g) and the smallest pores (~3.5 nm). STEM-HAADF imaging revealed well-dispersed PtOx domains (~0.85 nm), while XPS confirmed the dominant Pt⁴⁺ and Pt²⁺ species, with ~25% Pt⁰ likely resulting from photoreduction and/or interactions with Sn–OH surface groups. Raman spectroscopy revealed three new bands (260–360 cm⁻¹) that were clearly visible in the sample with 10 mol% Pt and were due to the vibrational modes of the PtOx species and Pt-Cl bonds introduced due the addition and hydrolysis of H₂PtCl₆ precursor. TGA/DSC analysis revealed the highest mass loss for SP1a (~7.3%), confirming the strong hydration of the PtOx domains. Despite the predominance of oxidized PtOx species, SP1a exhibited the highest catalytic activity (k_app = 1.27 × 10⁻² s⁻¹) and retained 84.5% activity for the reduction of 4-NP to 4-AP after 10 cycles. This chloride-free low-temperature synthesis route offers a promising and generalizable strategy for the preparation of noble metal-based nanocatalysts on oxide supports with high catalytic activity and reusability. Full article

Against the backdrop of global energy transition and strict environmental regulations, supercritical carbon dioxide (scCO₂) fracturing and oil displacement technologies have emerged as pivotal green approaches in shale gas exploitation, offering the dual advantages of zero water consumption and carbon sequestration. However, the inherent low viscosity of scCO₂ severely restricts its sand-carrying capacity, fracture propagation efficiency, and oil recovery rate, necessitating the urgent development of high-performance thickeners. The current research on scCO₂ thickeners faces a critical trade-off: traditional fluorinated polymers exhibit excellent philicity CO₂, but suffer from high costs and environmental hazards, while non-fluorinated systems often struggle to balance solubility and thickening performance. The development of new thickeners primarily involves two directions. On one hand, efforts focus on modifying non-fluorinated polymers, driven by environmental protection needs—traditional fluorinated thickeners may cause environmental pollution, and improving non-fluorinated polymers can maintain good thickening performance while reducing environmental impacts. On the other hand, there is a commitment to developing non-noble metal-catalyzed siloxane modification and synthesis processes, aiming to enhance the technical and economic feasibility of scCO₂ thickeners. Compared with noble metal catalysts like platinum, non-noble metal catalysts can reduce production costs, making the synthesis process more economically viable for large-scale industrial applications. These studies are crucial for promoting the practical application of scCO₂ technology in unconventional oil and gas development, including improving fracturing efficiency and oil displacement efficiency, and providing new technical support for the sustainable development of the energy industry. This study innovatively designed an amphiphilic modified amino silicone oil polymer (MA-co-MPEGA-AS) by combining maleic anhydride (MA), methoxy polyethylene glycol acrylate (MPEGA), and amino silicone oil (AS) through a molecular bridge strategy. The synthesis process involved three key steps: radical polymerization of MA and MPEGA, amidation with AS, and in situ network formation. Fourier transform infrared spectroscopy (FT-IR) confirmed the successful introduction of ether-based CO₂-philic groups. Rheological tests conducted under scCO₂ conditions demonstrated a 114-fold increase in viscosity for MA-co-MPEGA-AS. Mechanistic studies revealed that the ether oxygen atoms (Lewis base) in MPEGA formed dipole–quadrupole interactions with CO₂ (Lewis acid), enhancing solubility by 47%. Simultaneously, the self-assembly of siloxane chains into a three-dimensional network suppressed interlayer sliding in scCO₂ and maintained over 90% viscosity retention at 80 °C. This fluorine-free design eliminates the need for platinum-based catalysts and reduces production costs compared to fluorinated polymers. The hierarchical interactions (coordination bonds and hydrogen bonds) within the system provide a novel synthetic paradigm for scCO₂ thickeners. This research lays the foundation for green CO₂-based energy extraction technologies. Full article

To ensure the sustainable use of limited resources, it is essential to establish selective and efficient recycling technologies for platinum group metals (PGMs). This study focused on the selective precipitation-based separation of Pt(IV) from hydrochloric acid (HCl) solutions in the presence of various metal ions, using trans-1,4-bis(aminomethyl)cyclohexane (BACT) as a precipitating agent. By using BACT, we succeeded in the selective separation of Pt(IV) by precipitation from HCl solutions containing Pd(II) and Rh(III). Notably, selective and efficient recovery of Pt(IV) was accomplished across various HCl concentrations, with a small amount of BACT and within a short shaking time. To evaluate the practical applicability of the method, Pt(IV) was recovered and purified from the HCl leachate of spent automotive exhaust gas purification catalysts using BACT. As a result, a high Pt recovery of 95.6% and a high purity of 99.3% were achieved. Although Pt(IV) was recovered as a precipitate containing BACT, it was found that Pt black could be readily obtained by dissolving the precipitate in HCl solution followed by reduction with sodium borohydride. Detailed structural analysis of the Pt(IV)-containing precipitate revealed that it is an ionic crystal composed of [PtCl₆]²⁻ and protonated BACT. The selective formation of this ionic crystal in HCl solution, along with its stability under such conditions, is the key to the selective recovery of Pt(IV) using BACT. Full article

Mineralogical variability exerts a profound influence on the flotation performance of Platinum Group Metal (PGM) ores, particularly those from the Platreef deposit, where complex associations and textures influence recovery, grade, and kinetics. This study integrates the Mode of Occurrence (MOC) and mineral associations into a modified Kelsall flotation kinetics model, optimized using a Particle Swarm Optimization (PSO) algorithm, to improve prediction accuracy. Batch flotation tests were conducted on eight samples from two lithologies—Pegmatoidal Feldspathic Pyroxenite (P-FPX) and Feldspathic Pyroxenite (FPX)—with mineralogical characterization performed using MLA, QEMSCAN, and XRD. PGMs in liberated (L) and sulfide-associated (SL) forms accounted for up to 90.6% (FPX1), exhibiting high fast-floating fractions (θ_f = 0.77–0.84) and fast flotation rate constants (K_f = 1.45–1.78 min⁻¹). In contrast, PGMs locked in silicates (G class) showed suppressed kinetics (K_f < 0.09 min⁻¹, K_s anomalies up to 8.67 min⁻¹) and were associated with lower recovery (P-FPX3 = 83.25%) and increased model error (P-FPX4 = 57.3). FPX lithologies achieved the highest cumulative recovery (FPX4 = 90.35%) and the best concentrate grades (FPX3 = 116.5 g/t at 1 min), while P-FPX1 had the highest gold content (10.45%) and peak recovery (94.37%). Grade-recovery profiles showed steep declines after 7 min, particularly in slow-floating types (e.g., P-FPX2, FPX2), with fast-floating lithologies stabilizing above 85% recovery at 20 min. The model yielded R² values above 0.97 across all samples. This validates the predictive power of MOC-integrated flotation kinetics for complex PGM ores and supports its application in geometallurgical plant design. Model limitations in capturing complex locked ore textures (SAG, G classes) highlight the need for reclassification based on floatability indices and further integration of machine learning methods. Full article

The development of efficient platinum group metal-free (PGM-free) catalysts for the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR) is essential for advancing hydrogen-based energy technologies. In this study, Ni_xMo_100−x composites supported on Carbon Ketjenblack EC-300J (CK) were synthesized via thermal reduction under a controlled Ar/H₂ (95:5) atmosphere to investigate the effect of the Ni/Mo molar ratio on electrocatalytic performance. Structural and morphological analyses by XRD and TEM confirmed the formation of the NiMo alloys and carbide phases with controlled particle size distributions (~18 nm), while BET measurements revealed specific surface areas up to 124.69 m² g⁻¹ for the Pt-loaded samples. Notably, the 3% Pt/Ni₉₀Mo₁₀-CK catalyst exhibited outstanding bifunctional activity in a half-cell configuration, achieving an overpotential of 65.2 mV and a Tafel slope of 41.6 mV dec⁻¹ for the HER, and a Tafel slope of 32.9 mV dec⁻¹ with an exchange current density of 1.03 mA cm⁻² for the HOR. These results demonstrate that compositional tuning and minimal Pt incorporation synergistically enhance the catalytic efficiency, providing a promising platform for next-generation hydrogen electrocatalysts. Full article

In a dynamic global market, platinum-group metals (PGMs), particularly palladium, are in high demand across various industries due to their unique properties. Palladium plays a crucial role in environmentally friendly technologies, such as catalytic converters, which mitigate harmful automotive emissions. Additionally, it is essential for clean energy production, particularly in hydrogen generation, which makes palladium a critical resource for building a sustainable and secure supply chain. This study evaluates the prospects of the palladium market through strategic analysis, focusing on the Russian mining and metals company PJSC MMC Norilsk Nickel. The research employs strategic and industry analysis methods to examine palladium production, market dynamics, and technological advancements, as well as emerging applications in the context of a green economy. The article analyzes the economics of palladium production, including price volatility driven by stringent environmental regulations and the rising adoption of electric vehicles. The palladium market faces challenges such as a constrained resource base, supply disruptions due to sanctions, price instability, and growing demand from key sectors, particularly the automotive industry. Nevertheless, innovation-driven trends offer promising opportunities for market growth, aligning with sustainable development principles and the transition toward a green, low-carbon economy in both established and emerging markets. As a key scientific contribution, this study proposes a modified methodological approach to industry analysis, enabling the assessment of a mining and metals company’s competitive sustainability in the palladium market over the medium and long term. Furthermore, the research models the life cycle of palladium as a commodity, considering evolving market trends and the rapid development of new industries within the green economy. Full article

Although platinum-based catalysts are highly effective for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs), their high cost and scarcity limit large-scale commercialization. As a result, platinum group metal-free catalysts—particularly Fe-N-C materials—have received increasing attention as promising alternatives. Despite significant progress, no platinum-group metal-free (PGM-free) catalyst has yet matched the performance and durability of commercial Pt/C in acidic media. Recent advances in synthesis strategies, however, have led to notable improvements in the activity, stability, and active site density of Fe-N-C catalysts. This review highlights key synthesis approaches, including pyrolysis, MOF-derived templates, and cascade anchoring, and discusses how these methods contribute to improved nitrogen coordination, electronic structure modulation, and active site engineering. The continued refinement of these strategies, alongside improved catalyst screening techniques, is essential for closing the performance gap and enabling the practical deployment of non-PGM catalysts in PEMFC technologies. Full article

An efficient protocol was developed for the microwave-mediated metallation of 5-(4-methoxycarbonylphenyl)-10,15,20-tris(pentafluorophenyl)porphyrin (P1) with bis(benzonitrile)platinum dichloride salt and subsequent 1,3-dipolar cycloaddition of the resulting PtP1 with an azomethine ylide to give two isomeric metallochlorins: PtC1 (main isomer) and PtC3. The methyl ester group of metalloporphyrin PtP1 and metallochlorin PtC1 was successfully hydrolysed in an alkaline medium to yield the corresponding derivatives PtP2 and PtC2 in moderate-to-good yields. As a proof of concept of the reactivity of the carboxy group in PtP2 and PtC2, these compounds were conjugated with a hydroxylated derivative of indomethacin, a known potent non-steroidal anti-inflammatory, obtaining the conjugates PtP2-Ind and PtC2-Ind. The obtained platinum(II) porphyrins and chlorins were characterized by UV-Vis, NMR spectroscopy and mass spectrometry. The structure of PtP1 was also confirmed by X-ray crystallography. Singlet oxygen generation studies were carried out, as well as theoretical calculations, which demonstrated that the prepared Pt(II) complexes can be considered potential photosensitizers for PDT. Full article

The effective management of High-Level Liquid Waste (HLLW) is critical for environmental and human health protection. The presence of platinum group metals (PGMs) in HLLW, particularly their refractory nature due to their high melting points, complicates vitrification processes. This study presents a targeted adsorption strategy using COF-42 for Pd²⁺ sequestration in HLLW systems. The comprehensive characterization of COF-42 and its Pd-loaded counterpart (Pd@COF-42) via PXRD, FT-IR, TGA, XPS, and SEM confirms structural robustness and successful Pd²⁺ incorporation. Kinetic and thermodynamic analyses reveal pseudo-second-order adsorption behavior with a maximum capacity of 170.6 mg/g, highlighting the exceptional Pd²⁺ affinity. Systematic optimization identifies HNO₃ concentration (≤3 M) and adsorbent dosage (≤30 mg) as critical parameters governing adsorption efficiency through protonation–deprotonation equilibria. Furthermore, COF-42 exhibits superior selectivity for Pd²⁺ over 13 competing metal ions and maintains ~80% adsorption efficiency after four regeneration cycles. These performance metrics originate from the synergistic interplay of (1) framework flexibility enabling adaptive Pd²⁺ coordination, (2) hierarchical porosity facilitating ion diffusion, and (3) dense –NH/–NH₂ groups acting as electron-rich chelation sites. Full article

Noble metals are widely recognized for their ability to catalyze the electro-oxidation of organic compounds, with smaller particle sizes significantly enhancing electrocatalytic activity. In this study, catalytic electrodes decorated with atomic-level platinum and Pt-Au clusters were fabricated using cyclic atomic-metal electrodeposition. The interactions between the iminium (protonated imine) groups in emeraldine salt polyaniline (PANI) and metal chloride complexes in the electrolyte enabled precise control over the cluster size and composition. The electrocatalytic activity of these electrodes for propanol oxidation was systematically evaluated using cyclic voltammetry (CV). Notably, PANI electrodes decorated with odd-numbered atomic-level Pt clusters exhibited higher peak oxidation currents compared to even-numbered clusters, revealing a unique even–odd effect. For atomic-level Pt-Au clusters, the catalytic activity was significantly influenced by the sequence of Pt and Au deposition, with PANI-Au₁Pt₃ achieving the highest catalytic activity (35.34 mA/cm²). Bi-metallic clusters consistently outperformed mono-metallic clusters, and clusters containing only one Pt atom demonstrated superior catalytic activity. These findings provide valuable insights into the design of high-performance catalytic electrodes by leveraging atomic-level control of the cluster size, composition, and deposition sequence, paving the way for advanced applications in electrochemical sensors. Full article

Direct methanol fuel cells (DMFCs) represent a promising pathway for energy conversion, yet their reliance on platinum-group metal (PGM)-based anode catalysts poses critical sustainability challenges, which stem from finite mineral reserves, environmentally detrimental extraction processes, and prohibitive lifecycle costs. Current anode catalysts for DMFCs are dominated by platinum materials; therefore, this review systematically evaluates the following three emerging eco-efficient design paradigms using platinum materials as a starting point: (1) the atomic-level optimization of low-Pt alloy surfaces to maximize catalytic efficiency per metal atom, (2) Earth-abundant transition metal compounds (e.g., nitrides and sulfides) and coordination-tunable metal–organic frameworks as viable PGM-free alternatives, and (3) mechanically robust carbon architectures with engineered topological defects that enhance catalyst stability through covalent metal–carbon interactions. Through comparative analysis with pure Pt benchmarks, we critically examine how these strategic material innovations collectively mitigate CO intermediate poisoning risks and improve electrochemical durability. Such fundamental advances in catalyst design not only address immediate technical barriers, but also establish essential material foundations for the development of DMFC technologies compatible with circular economy frameworks and United Nations Sustainable Development Goal 7 targets. Full article

Adsorbents derived from Merrifield’s resin and a reaction with three functionalizing ligands namely 1,2-ethanedithiol (M-EDT), 1,2-benzenedithiol (M-BDT), and 2-benzimidazolylmethylthio acetic acid (M-BITAA) were synthesized for the recovery and separation of PGMs from simulated solutions. M-EDT, M-BDT and M-BITAA resins were characterized by the FTIR, UV-Vis, TGA, CHNS and SEM techniques, which confirmed significant structural modifications in these resins. A batch adsorption study revealed that M-BITAA exhibited the highest capacity for Pd(II), with about 0.244 mmol·g⁻¹, while that of both M-EDT and M-BDT resins was below 0.094 mmol·g⁻¹. The adsorbents obeyed the Langmuir isotherm in 0.8 M HCl solution. Batch adsorption further showed, in a competitive study, that M-BITAA was not selective for Pd(II) but an attractive sorbent for other PGMs such as Pt(IV), which may be advantageous for solutions containing these PGMs. Full article

The rational development of single-atom catalysts (SACs) for selective formic acid dehydrogenation (FAD) requires an atomic-scale understanding of metal–support interactions and electronic modulation. In this study, spin-polarized density functional theory (DFT) calculations were performed to systematically examine platinum-group SACs anchored on graphitic carbon nitride (g-C₃N₄). The findings reveal that Pd and Au SACs exhibit superior selectivity toward the dehydrogenation pathway, lowering the free energy barrier by 1.42 eV and 1.39 eV, respectively, compared to the competing dehydration route. Conversely, Rh SACs demonstrate limited selectivity due to nearly equivalent energy barriers for both reaction pathways. Stability assessments indicate robust metal–support interactions driven by d–p orbital hybridization, while a linear correlation is established between the d-band center position relative to the Fermi level and catalytic selectivity. Additionally, charge transfer (ranging from 0.029 to 0.467 e) substantially modulates the electronic structure of the active sites. These insights define a key electronic descriptor for SAC design and offer a mechanistic framework for optimizing selective hydrogen production. Full article

In our research aimed at replacing precious transition metals like platinum with abundant base metals such as nickel for efficient triplet emitters, we synthesized and studied Ni(II) complexes [Ni(L^NHR)Cl]. These complexes containing the N^C^N cyclometalating dipyridyl-phenide ligand, equipped with pending H-bonding amine groups (NH(C₆H₅) (L^NHPh) and NH(C₆H₅CH₂), ClL^NHBn). Molecular structures determined from experimental X-ray diffractometry and density functional theory (DFT) calculations in the ground state showed marked deviation of the Cl⁻ coligand (ancillary ligand) from the ideal planar coordination, with τ₄ values of 0.35 and 0.33, respectively, along with hydrogen bonding interactions of the ligand NH function with the Cl⁻ coligand. The complexes exhibit long-wavelength absorption bands at approximately 425 nm in solution, with the experimental spectra being accurately reproduced through time-dependent density functional theory (TD-DFT) calculations. Vibrationally structured emission profiles and steady-state photoluminescence quantum yields of 30% for [Ni(L^NHPh)Cl] and 40% for [Ni(L^NHBn)Cl] (along with dual excited state lifetimes in the ns and in the ms range) were found in frozen 2-methyl-tetrahydrofuran (2MeTHF) glassy matrices at 77 K. Furthermore, within a poly(methyl methacrylate) matrix, the complexes showed emission bands centered at around 550 nm within a temperature range from 6 K to 300 K with lifetimes similar to 77 K. Based on TD-DFT potential scans along the metal–ligand (Ni–N) coordinate, we found that in a rigid environment that restricts the geometry to the Franck-Condon region, either the triplet T₅ or the singlet S₄ state could contribute to the photoluminescence. Full article