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Dry reforming of methane (DRM) is considered one of the most promising technologies for efficient greenhouse gas management thanks to the fact that through this reaction, it is possible to reduce CO2 and CH4 to obtain syngas, a mixture of H2 and CO, with a suitable ratio for the Fischer-Tropsch production of long-chain hydrocarbons. Two other main processes can yield H2 from CH4, i.e., Steam Reforming of Methane (SRM) and Partial Oxidation of Methane (POM), even though, not having CO2 as a reagent, they are considered less green. Recently, scientists' challenge is to overcome the many drawbacks of DRM reactions, i.e., the use of precious metal-based catalysts, the high temperatures of the process, metal particle sintering and carbon deposition on the catalysts' surfaces. To overcome these issues, one proposed solution is to implement photo-thermal dry reforming of methane in which irradiation with light is used in combination with heating to improve the efficiency of the process. In this paper, we review the work of several groups aiming to investigate the pivotal promoting role of light radiation in DRM. Focus is also placed on the catalysts' design and the progress needed for bringing DRM to an industrial scale.

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The paper investigated the possibility of extractive separation of palladium from platinum and rhodium with ionic liquid Cyphos IL 101. A technological solution obtained by dissolving waste materials was used as the test material. Based on the experiments performed, it was found that a 10% (v/v) solution of the Cyphos IL 101 ionic liquid in toluene allows the extraction of both Pd and Pt with an efficiency of 99% from the initial solution when extraction is carried out at the pH 0.5, vorg:vaq phase ratio 1:1 and contact time of 15 min. Moreover, the research proved that it is possible to separate Pd from Pt at the stripping stage using a 0.1 mol/dm3 thiourea solution while maintaining a high selectivity coefficient.

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The traditional pyrometallurgical recycling of nano-sized platinum group metals (PGMs) from spent automotive catalysts (SACs) is an energy-intensive process that requires the addition of large quantities of copper capture and slag-forming reagents. Similarly, pyro-recycling of valuable metals from waste printed circuit boards (WPCBs) is also an energy- and reagent-intensive process that and carries a risk of pollution emissions. Based on the complementarity of composition and similarity of recycling process, synergistic pyro-recycling of SACs and WPCBs allow copper in WPCBs to capture PGMs in SACs and oxides from two waste form slag jointly, which offers benefits of enhanced metal recovery, reduced reagent and energy consumption, and suppressed pollutant emissions. However, the mechanisms of PGMs capture and pollutant transformation in co-smelting remain unknown. Here, we investigated the sub-processes mechanisms of slag formation, brominates fixation, multi-metal distribution and kinetic settlement. Oxides in both wastes support SiO2-Al2O3-CaO slag formation with low melting point and viscosity, where CaO suppresses the emission of brominated pollutants. Copper (50-100 µm) from WPCBs facilitates nano-sized PGMs in SACs recovery through capture and settlement. The results of demonstration experiments indicated a recovery rate of 94.6 %, 96.8 %, 97.2 %, and 98.1 % for Cu, Pt, Pd, and Rh, respectively, with a debromination efficiency exceeding 98 %. The theoretical analysis provides support for the establishment of a synergistic pyro-recycling process for SACs and WPCBs and provides insights into the potential for a greener and more efficient co-recycling of multi urban mines.

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There is an increasing concern about the presence of various types of pharmaceuticals in drinking water, as long-term exposure of people to even low concentrations of drugs can lead to many problems, such as endocrine disorders or drug resistance. As the removal in sewage treatment plants is not effective enough, as indicated, among others, by the EC and OECD reports, it is justified to search for new materials that will allow for an effective and rapid reduction of these pollutants in water. Therefore, in our work, catalytically active nanomaterials containing platinum group metals (PGMs) were synthesized from model and real multicomponent solutions and examined in reactions of organic compounds. The nanoparticles (NPs) were obtained from real solutions from the hydrometallurgical processing of spent automotive converters (SACs), and to the best of our knowledge, the novelty of the proposed paper is the application of solutions from SAC processing as precursors for PGM-NPs. The synthesized PGM-NPs were deposited on a support (TiO2), characterized and, finally, examined as nanocatalysts in a degradation reaction of ibuprofen (IB) from model aqueous solutions. The degree of IB degradation reached more than 90%. The main products of IB degradation were p-isobutylphenol and CO2.

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The high-entropy-alloy (HEA) nanoparticles with four, five or more metals significantly can yield the developments of functional materials with excellent performances in various reactions. However, the underlying reaction mechanisms of heterogeneous catalysis for HEA have been rarely investigated, due to their diverse elements and complex compositions. In this study, we successfully synthesized the homogeneously dispersed Ru-Rh-Pd-Pt HEA with adjustable compositions, as the multiple-atom-site catalysts (MASC). In the NOx reduction performance tests, Ru0.4 (Rh0.33Pd0.33Pt0.33)0.6 MASC showed the highest activity, which was significantly improved compared to that of the best monometal Rh, with the light-off temperature decreasing by ca. 50 °C. The Fourier transform infrared measurements revealed that the outstanding activity of Ru-Rh-Pd-Pt MASC was attributable to the well-coupled elementary steps of the CO adsorption, NO adsorption, NO dissociation and O spillover on the Ru, Rh, Rh-Pd and Pt sites, respectively, which explained the first clear reaction mechanism in heterogeneous catalysis for HEA.

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Palladium (Pd) recycling from waste materials is an important approach in order to meet the growing demand for Pd originating from its broad range of applications including automotive industry, electronics and catalysis. In this article, we discuss the design principles of solid-sorbents for efficient recovery of Pd from waste sources with a particular emphasis on porous organic polymers (POPs), which emerged as promising porous materials for Pd recovery due to their tunable chemical functionality, stability and porosity. We discuss the critical role of binding sites and porosity in the Pd uptake capacity, adsorption kinetics and selectivity. We also highlight the use of captured Pd within the polymer networks as heterogeneous catalysts for cross-coupling reactions.

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This study explores an eco-friendly method for recovering platinum group metals from a synthetic automotive three-way catalyst (TWC). Bioleaching of palladium (Pd) using the thiosulfate-copper-ammonia leaching processes, with biogenic thiosulfate sourced from a bioreactor used for biogas biodesulfurization, is proposed as a sustainable alternative to conventional methods. Biogenic thiosulfate production was optimized in a gas-lift bioreactor by studying the pH (8-10) and operation modes (batch and continuous) under anoxic and microaerobic conditions for 35 d. The maximum concentration of 4.9 g S2O32- L-1 of biogenic thiosulfate was reached under optimal conditions (batch mode, pH = 10, and airflow rate 0.033 vvm). To optimize Pd bioleaching from a ground TWC, screening through a Plackett-Burman design determined that oxygen and temperature significantly affected the leaching yield negatively and positively, respectively. Based on these results, an optimization through an experimental design was performed, indicating the optimal conditions to be Na2S2O3 1.2 M, CuSO4 0.03 M, (NH4)2SO4 1.5 M, Na2SO3 0.2 M, pH 8, and 60 °C. A remarkable 96.2 and 93.2% of the total Pd was successfully extracted from the solid at 5% pulp density using both commercially available and biogenic thiosulfate, highlighting the method's versatility for Pd bioleaching from both thiosulfate sources.

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Advanced electrocatalysts can enable the widespread implementation of clean energy technologies. This paper reviews an emerging class of electrocatalytic materials comprising holey two-dimensional free-standing Pt-group metal (h-2D-PGM) nanosheets, which are categorically challenging to synthesize but inherently rich in all the qualities necessary to counter the kinetic and thermodynamic challenges of an electrochemical conversion process with high catalytic efficiency and stability. Although the 2D anisotropic growth of typical nonlayered metal crystals has succeeded and partly improved their atom-utilization efficiency, regularly distributed in-planar porosity can further optimize three critical factors that govern efficient electrocatalysis process: mass diffusion, electron transfer, and surface reactivity. However, producing such advanced morphological features within h-2D-PGMs is difficult unless they are specially engineered using approaches such as templating or kinetic ramification during 2D growth or controlled etching of preformed 2D-PGM solids. Therefore, this review highlighting the successful fabrication of various porous PGM nanosheets and their electrocatalytic benefits involving smart nanoscale features could inspire next-generation scientific and technological innovations toward securing a sustainable energy future.

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Spent automotive catalysts (SACs) and diamond-wire-saw silicon kerf (DWSSK) are classified as hazardous wastes. Currently, the two wastes are treated separately using unrelated approaches. More than two independent approaches are required to recover platinum group metals (PGMs), Zr and rare earth elements (REEs) from SACs, and recover Si from DWSSK, which is time-consuming and laborious. In this study, a new approach was proposed to co-treat the two wastes based on the concept of using waste treats waste: using DWSSK (∼89.85 wt% Si) as a new metal collector to extract PGMs, REEs, and Zr simultaneously from SACs to obtain a Si-VM alloy (VM: valuable metal); meanwhile, using the carrier of SACs to form molten slag to eliminate the main impurity, O, from DWSSK. The largest recovery ratios of Pd, Rh, Zr, Ce, La, and Nd from SACs were 99.50 ± 0.10%, 99.14 ± 0.14 %, 96.19 ± 0.76%, 67.18 ± 4.57%, 61.24 ± 4.93% and 47.65 ± 7.27%, respectively, and the largest removal ratio of O from DWSSK was 99.96%. After smelting, the Si-VM alloy was separated into high-purity Si and VM-containing acid solutions via acid leaching. The leaching ratios of Pd, Rh, Ce, La, Nd, and Zr were 99.78%, 98.15%, 99.93%, ∼100%, 99.76% and 99.98%, respectively. The purity of Si was upgraded from 89.85 wt% (in DWSSK) to 99.98 wt% after acid leaching. The new approach proposed in this study is considered more environmentally friendly and cost-effective than the regular approaches that treat the two wastes separately.

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Acid bioleaching of Al by Acidithiobacillus thiooxidans has been explored as an environmentally friendly pretreatment to facilitate the extraction of platinum group metals from spent three-way catalysts (TWC). Biogenic sulfur obtained from desulfurization bioreactors improved the production of acid by A. thiooxidans compared to commercially available elemental sulfur. The lixiviation abilities of bacteria-free biogenic acid and biogenic acid with exponential or stationary phase bacteria were compared against a control batch produced by commercial H2SO4. The maximum Al leaching percentage (54.5%) was achieved using biogenic acids with stationary-phase bacteria at a TWC pulp density of 5% w/v whereas bacteria-free biogenic acid (23.4%), biogenic acid with exponential phase bacteria (21.7%) and commercial H2SO4 (24.7%) showed lower leaching abilities. The effect of different pulp densities of ground TWC (5, 30, and 60% w/v) on Al leaching and bacterial growth was determined. While greater Al leaching yields were obtained at lower TWC pulp density solutions (54.5% at 5% w/v and 2.5% at 60% w/v), higher pulp densities enhanced microbial growth (2.3 × 109 cells/mL at 5% w/v and 9.5 × 1010 cells/mL at 60% w/v). The dissolution of the metal from the solid into the liquid phase triggered the production of biological polymeric substances that were able to absorb traces of both Al (up to 24.80% at 5% w/v) and Pt (up to 0.40% at 60% w/v).

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Life Cycle Assessment (LCA) and Environmental Life Cycle Costing (eLCC) are useful methods for evaluating the environmental, energy and economic performances of innovative energy storage technologies. By using these methods, the production process of a small Polymer Electrolyte Membrane Unitized Regenerative Fuel Cell (PEM-URFC) stack has been investigated, aiming to assess its environmental, energy and economic impacts at the early design stage and to identify the contributions of its various components on these impacts. Indeed, the PEM-URFC stack includes Critical Raw Materials that affect the product's sustainability. Results show that the highest contributions are associated with the platinum group metals used for the catalyst and, to a lesser degree, the materials and energy used for the bipolar plates and porous transport layers. However, considering that the datasets for representing the impacts of one of the electrocatalysts (Iridium Ruthenium Oxide) are still missing in LCA commercial databases and literature, a sensitivity analysis is performed assuming its impact to be similar to that of other Platinum Group Metals (PGMs) extracted with them (e.g., Platinum, Nickel, Palladium, etc.). The analysis shows a high difference in results due to data and methodological assumptions, making the assimilation of Iridium Ruthenium Oxide to Rhodium the worst scenario, increasing environmental impacts by 37.54 %, energy impacts by 40.48 % and environmental price by 45.08 %. Moreover, the study identified issues for applying life cycle thinking approaches on URFC devices that must be resolved in future studies (e.g., increase the reliability of catalyst inventory data or improve guidelines on energy storage technologies).

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This article presents studies on the precipitation of Pt, Pd, Rh, and Ru nanoparticles (NPs) from model and real multicomponent solutions using sodium borohydride, ascorbic acid, sodium formate, and formic acid as reducing agents and polyvinylpyrrolidone as a stabilizing agent. As was expected, apart from PGMs, non-precious metals were coprecipitated. The influence of the addition of non-precious metal ions into the feed solution on the precipitation yield and catalytic properties of the obtained precipitates was studied. A strong reducing agent, NaBH4 precipitates Pt, Pd, Rh, Fe and Cu NPs in most cases with an efficiency greater than 80% from three- and four-component model solutions. The morphology of the PGMs nanoparticles was analyzed via SEM-EDS and TEM. The size of a single nanoparticle of each precipitated metal was not larger than 5 nm. The catalytic properties of the obtained nanomaterials were confirmed via the reaction of the reduction of 4-nitrophenol (NPh) to 4-aminophenol (NAf). Nanocatalysts containing Pt/Pd/Fe NPs obtained from a real solution (produced as a result of the leaching of spent automotive catalysts) showed high catalytic activity (86% NPh conversion after 30 min of reaction at pH 11 with 3 mg of the nanocatalyst).

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Platinum group metals (PGMs) are a group of six metals with high market value and key importance to many industrial sectors. Due to their low prevalence in the Earth's crust and high demand, these metals have been recognized as critical materials for many years. Along with economic development, the natural resources of the platinum group metals are gradually depleting, which is accompanied by the need to recover PGMs from secondary sources. The solutions resulting from the processing of such materials are characterized by high content of impurities and low content of precious metals. For this reason, in order to obtain pure metals, it is extremely important to choose an effective, selective method for the recovery and separation of the platinum group metals. This review focuses on the most important aspects of the characteristics of the PGMs, including their properties and occurrence, the processing of natural and secondary raw materials and the role of liquid-liquid extraction in the selective separation of metals from this group, not only on a laboratory scale but, above all, on an industrial scale. In addition, this study collects information on the most commonly used, commercially available extractants, based on current reports, taken from the scientific literature.

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Efficient cathodes for the hydrogen evolution reaction (HER) in acidic water electrolysis rely on the use of expensive platinum group metals (PGMs). However, to achieve economically viable operation, both the content of PGMs must be reduced and their intrinsically strong H adsorption mitigated. Herein, we show that the surface effects of hydrogenated TiO2 nanotube (TNT) arrays can make osmium, a so far less-explored PGM, a highly active HER electrocatalyst. These defect-rich TiO2 nanostructures provide an interactive scaffold for the galvanic deposition of Os particles with modulated adsorption properties. Through systematic investigations, we identify the synthesis conditions (OsCl3 concentration/temperature/reaction time) that yield a progressive improvement in Os deposition rate and mass loading, thereby decreasing the HER overpotential. At the same time, the Os particles deposited by this procedure remain mainly sub-nanometric and entirely cover the inner tube walls. An optimally balanced Os@TNT composite prepared at 3 mM/55 °C/30 min exhibits a record low overpotential (η) of 61 mV at a current density of 100 mA cm-2, a high mass activity of 20.8 A mgOs-1 at 80 mV, and a stable performance in an acidic medium. Density functional theory calculations indicate the existence of strong interactions between the hydrogenated TiO2 surface and small Os clusters, which may weaken the Os-H* binding strength and thus boost the intrinsic HER activity of Os centers. The results presented in this study offer new directions for the fabrication of cost-effective PGM-based catalysts and a better understanding of the synergistic electronic interactions at the PGM|TiO2 interface.

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Fertilizers play a vital role in the food-energy-water nexus. The traditional method of artificial nitrogen fixation to produce ammonia is a high-energy intensive centralized process that has caused an imbalance of the N-cycle due to the release of N-species to water. Electrocatalytic nitrate reduction (ENR) to ammonia is a promising N-resource recovery alternative that can enable the circular reuse of ammonia in decentralized settings. However, the primary challenge is identifying selective and affordable electrocatalysts. Identifying electrodes that rely on something other than platinum-group metals is required to surpass barriers associated with using expensive and endangered elements. In this study, an earth-abundant bimetallic catalyst, Cu/Co(OH)x, prepared and optimized by electrodeposition, demonstrates superior ammonia production. Under environmentally relevant conditions of 30 mg NO3--N L-1, Cu/Co(OH)x showed higher ammonia production than pristine Cu foam with 0.7 and 0.3 mmol NH3 gcat-1 h-1, respectively. The experimental evaluation demonstrated direct reduction and catalytic hydrogenation mechanisms in Cu/Co(OH)x sites. Leaching analyses suggest that Cu/Co(OH)x has outstanding stability with negligible metal concentration below the maximum contaminant level for both Cu and Co. These results provide a framework for using earth-abundant materials in ENR with comparable efficiency and energy consumption to platinum-group materials.

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Halogenated platinum salts are known respiratory sensitizers in the workplace, and occupational exposure to platinum via the respiratory system and skin has been reported. The aim of this study was to compare the permeability and skin retention of potassium hexachloroplatinate to previously published data of potassium tetrachloroplatinate. Experiments were performed using female Caucasian skin and Franz diffusion cells with the application of 0.3 mg Pt/mL in the donor solution for 24-h. After 8-h of exposure, 1.87 ng/cm2 of Pt was detected in the receptor solution with exposure to potassium hexachloroplatinate, whereas 0.47 ng/cm2 was detected with exposure to potassium tetrachloroplatinate. After 24-h of exposure the Pt retention in the skin was 1861.60 ng/cm2 and 1486.32 ng/cm2 with exposure to potassium hexa- and tetrachloroplatinate respectively. The faster rate of Pt permeation from exposure to potassium hexachloroplatinate was confirmed by the flux and permeability coefficient values. The results indicate a higher permeability and skin retention of Pt when exposed to potassium hexachloroplatinate, confirming a higher risk associated with occupational exposure to this platinum compound relative to potassium tetrachloroplatinate.

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OBJECTIVES: Precious metals refinery workers are exposed to soluble platinum group metals (PGMs) during PGM-refining but may also be exposed to hazardous non-PGMs (Pb, Co, Ni, Cu, As and Ag) still present in the matte following base metals refining. The aim of this article was to report the skin and respiratory exposure of workers to soluble non-PGMs during PGM-refining. METHODS: Skin and respiratory exposure (of 40 workers at two precious metals refineries) were measured simultaneously over two consecutive shifts. Skin exposure was measured on the palm, wrist, neck and forehead using Ghostwipes™ and respiratory exposure was measured using the MDHS method 46/2 during which soluble metals were extracted using 0.07 M HCl and mechanical agitation, followed by ICP-MS analysis. RESULTS: The geometric means (GM) of average skin exposure to individual soluble metals on all anatomical areas was found in the order Cu (0.018 µg/cm2) > Ni (0.016 µg/cm2) > Pb (0.008 µg/cm2) > Ag (0.006 µg/cm2) > As (0.004 µg/cm2) > Co (0.0008 µg/cm2) with the palm being the highest exposed anatomical area. The order of the GM respiratory exposure was Pb (0.224 µg/m3) > Ag (0.201 µg/m3) > Cu (0.159 µg/m3) > As (0.079 µg/m3) > Ni (0.034 µg/m3) > Co (0.016 µg/m3) with exposure to As exceeding the South African occupational exposure limit (20 µg/m3) during concentrate handling (max 66.174 µg/m3). CONCLUSIONS: Workers were exposed to a mixture of toxic PGM and non-PGMs via the skin and inhalation. Exposure to these metals could lead to the development of diseases, such as contact dermatitis, occupational allergy, or occupational cancer. Non-PGMs must be included in hazardous chemical risk assessments and control strategies implemented at precious metals refineries.

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The study reported in this article has shown for the first time that strongly acidic solutions (pH < 0.5) obtained after hydrometallurgical treatment of spent automotive converters (SAC) may be valuable secondary sources of platinum group metal (PGM) nanoparticles (NPs). The PGM precipitation strongly depended on the solution pH; the yield of the precipitated PGM NPs increased considerably from 40% to almost 100% when the pH was adjusted to 7-8. To improve the NPs stability, commercial TiO2 was used as support to obtain efficient recyclable PGM@TiO2 catalysts. The size of the PGM NPs was smaller than 5 nm, while the diameter of the supported particles varied from 10 to 50 nm. The size and dispersion of PGM NPs on the support strongly depended on the pH of the medium: at pH < 0.5, the Pt and Pd NPs were significantly smaller than the NPs obtained at pH 7-8. Also, in the case of Pt@TiO2 and Rh@TiO2, the NPs were well dispersed on the support in contrast to the large agglomerates of Pd@TiO2. The PGM@TiO2 showed catalytic properties in the reduction of 4-nitrophenol to 4-aminophenol, particularly, at pH above 11. The highest conversion of 98% was obtained with 1% Pd@TiO2 at pH 14 after only 15 min. The catalyst was easily separated from the reaction mixture and reused in 7 consecutive cycles without significant loss of activity. The PGM@TiO2 synthesized from the real solution showed a similar catalytic activity (70% conversion at pH 14) as that obtained from model solution.

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A novel ionic liquid (IL) functionalized with thiodiglycol amic acid containing a soft S donor was synthesized for the effective and efficient extraction of platinum group metals (Ru, Rh, and Pd) from aqueous nitric acid solutions, such as high-level radioactive liquid waste (HLLW). The IL enabled rapid extraction of Pd(II) with an extraction ratio of approximately 100%. The extractions of Ru(III) and Rh(III) by the IL were slower than that of Pd(II), but the rates were accelerated by temperature elevation. The extractions of Ru(III) and Rh(III) at 50 °C reached equilibrium within 4 and 8 h, respectively, with the extraction ratios of over 90% without assisting agents or other methods for the extraction system. Furthermore, the IL could extract more than 90% of Ru(III), Rh(III), and Pd(II) from the simulated HLLW within 2 h at 50 °C.

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Complexes that incorporate both ligand(s) and metal(s) exhibiting cytotoxic activity can especially be interesting to develop multifunctional drug molecules with desired activities. In this review, the limited number of solution results collected in our laboratory on the complexes of Pd(II) and two other platinum group metals-the half-sandwich type, [(η6-p-cym)Ru(H2O)3]2+, and [(η5-Cp*)Rh(H2O)3]2+-with hydroxamic acid derivatives of three amino acids, two imidazole analogues, and four small peptides are summarized and evaluated. Unlike the limited number of coordination sites of these metal ions (four and three for Pd(II) and the organometallic cations, respectively), the ligands discussed here offer a relatively high number of donor atoms as well as variation in their position within the ligands, resulting in a large versatility of the likely coordination modes. The review, besides presenting the solution equilibrium results, also discusses the main factors, such as (N,N) versus (O,O) chelate; size of chelate; amino-N versus imidazole-N; primary versus secondary hydroxamic function; differences between hydrolytic ability of the metal ions studied; and hydrolysis of the coordinated peptide hydroxamic acids in their Pd(II) complexes, which all determine the coordination modes present in the complexes formed in measurable concentrations in these systems. The options for the quantitative evaluation of metal binding effectivity and selectivity of the various ligands and the comparison with each other by using solution equilibrium data are also discussed.

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