Group Metals Research Articles

Nitrogen Fixation by Manganese Complexes - Waiting for the Rush?

Manganese is currently experiencing a great deal of attention in homogeneous catalysis as a sustainable alternative to platinum group metals due to its abundance, affordable price and low toxicity. While homogeneous nitrogen fixation employing well-defined transition metal complexes has been an important area of research in coordination chemistry, manganese derivatives have been only sporadically used in this research area. In this contribution, the authors systematically cover manganese organometallic chemistry related to N2 activation spanning almost 60 years, identify apparent pitfalls and outline encouraging perspectives for its future development.

Tailored Porous Ferrocene-Based Metal-Organic Frameworks as High-Performance Proton Conductors.

Although crystalline metal-organic frameworks (MOFs) have gained a great deal of interest in the field of proton conduction in recent years, the low stability and poor proton conductivity (σ) of some MOFs have hindered their future applications. As a result, resolving the issues listed above must be prioritized. Due to their exceptional structural stability, MOFs with ferrocene groups that exhibit particular physical and chemical properties have drawn a lot of attention. This study describes the effective preparation of a set of three-dimensional ferrocene-based MOFs, MIL-53-FcDC-Al/Ga and CAU-43, containing both main group metals and 1,1'-ferrocene dicarboxylic acid (H2FcDC). Multiple measurements, including powder X-ray diffraction (PXRD), infrared (IR), and scanning electron microscopy (SEM), confirmed that the addition of ferrocene groups enhanced the thermal, water, and acid-base stabilities of the three MOFs. Consequently, their proton-conductive behaviors were meticulously measured utilizing the AC impedance approach, and their best proton conductivities are 5.20 × 10-3, 2.31 × 10-3, and 1.72 × 10-4 S/cm at 100 °C/98% relative humidity (RH), respectively. Excitingly, MIL-53-FcDC-Al/Ga demonstrated an extraordinarily ultrahigh σ of above 10-4 S·cm-1 under 30 °C/98% RH. Using data from structural analysis, PXRD, SEM, thermogravimetry (TG), and activation energy, their proton transport mechanisms were thoroughly examined. The fact that these MOFs are notably easy to assemble, inexpensive, toxin-free, and stable will increase the range of practical uses for them.

Tandem supported, high metal-loading, non-PGM electrocatalysts for oxygen reduction reaction

Developing non-platinum group metal (non-PGM) electrocatalysts for the oxygen reduction reaction (ORR) is a critical effort toward low-cost fuel cells and metal–air batteries. Such catalysts require a uniform dispersion of metal atoms on a solid support, typically consisting of nitrogen doped carbon. However, the synthesis of non-PGM electrocatalysts is often complex, and metal loadings are typically below 10 wt. %, limiting the number of active sites and, therefore, the catalytic activity. In this work, we overcome these limits by synthesizing tandem supported, copper loaded electrocatalysts. Through one-pot pyrolysis, we make carbon black/Cu-doped graphitic carbon nitride (g-C3N4) core–shell structures to optimize the trade-off between conductivity and metal-loading capacity and achieve a Cu loading larger than 20 wt. %. By controlling the pyrolysis temperature, we systematically modulate the catalyst composition, structure, electrocatalytic activity, and stability. At a low pyrolysis temperature of only 600 °C, we achieve an onset potential of 0.90 V and a half-wave potential of 0.81 V vs RHE for alkaline ORR and negligible current loss after 10 000 potential cycles. These results demonstrate an effective approach to realize non-PGM electrocatalysts with optimum metal-loading, activity, and stability, thus unlocking their potential for real-world applications.

Surprising Route to a Monoazaporphyrin and Full Characterization of Its Complexes with Five Different 3d Metals.

In the search for mild agents for the oxidative cyclization of tetrapyrromethane to the corresponding corrole, we discovered a route that leads to a monoazaporphyrin with three meso-CF3 groups. Optimization studies that allowed access to appreciable amounts of this new macrocycle paved the way for the preparation of its cobalt, copper, nickel, zinc, and iron complexes. All complexes were fully characterized by various spectroscopic methods and X-ray crystallography. Their photophysical and electrochemical properties were determined and compared to those of analogous porphyrins in order to deduce the effect of the peripheral N atom. Considering the global efforts for designing efficient alternatives to platinum group metal (PGM) catalysts, they were also absorbed onto a porous carbon electrode material and studied as electrocatalysts for the oxygen reduction reaction (ORR). The cobalt complex was found to be operative at a quite positive catalytic onset potential and with good selectivity for the desirable 4-electrons/4-protons pathway.

Tailoring the Coordination Micro-Environment in Nanotraps for Efficient Platinum/Palladium Separation.

Recovering platinum group metals from secondary resources is crucial to meet the growing demand for high-tech applications. Various techniques are explored, and adsorption using porous materials has emerged as a promising technology due to its efficient performance and environmental beingness. However, the challenge lies in effectively recovering and separating individual platinum group metals (PGMs) given their similar chemical properties. Herein, a breakthrough approach is presented by sophisticatedly tailoring the coordination micro-environment in a series of aminopyridine-based porous organic polymers, which enables the creation of platinum-specific nanotraps for efficient separation of binary PGMs (platinum/palladium). The newly synthesized POP-o2NH2-Py demonstrates record uptakes and selectivity toward platinum over palladium, with the amino groups adjacent to the pyridine moieties being vital in improving platinum binding performance. Further breakthrough experiments underline its remarkable ability to separate platinum and palladium. Spectroscopic analysis reveals that POP-o2NH2-Py offers a more favorable coordination fashion to platinum ions compared to palladium ions owing to the greater interaction between N and Pt4+ and stronger intramolecular hydrogen bonding between the amino groups and four coordinating chlorines at platinum. These findings underscore the importance of fine-tuning the coordination micro-environment of nanotraps through subtle modifications that can greatly enhance the selectivity toward the desired metal ions.

Synthesis, characterisation, and catalytic application of a soluble molecular carrier of sodium hydride activated by a substituted 4-(dimethylamino)pyridine

Recently main group compounds have stepped into the territory of precious transition metal compounds with respect to utility in the homogeneous catalysis of fundamentally important organic transformations. Inspired by the need to promote more sustainability in chemistry because of their greater abundance in nature, this change of direction is surprising since main group metals generally do not possess the same breadth of reactivity as precious transition metals. Here, we introduce the dihydropyridylsodium compound, Na-1,2-tBu-DH(DMAP), and its monomeric variant [Na-1,2-tBu-DH(DMAP)]·Me6TREN, and demonstrate their effectiveness in transfer hydrogenation catalysis of the representative alkene 1,1-diphenylethylene to the alkane 1,1-diphenylethane using 1,4-cyclohexadiene as hydrogen source [DMAP = 4-dimethylaminopyridine; Me6TREN = tris(N,N-dimethyl-2-aminoethyl)amine]. Sodium is appealing because of its high abundance in the earth’s crust and oceans, but organosodium compounds have been rarely used in homogeneous catalysis. The success of the dihydropyridylsodium compounds can be attributed to their high solubility and reactivity in organic solvents.

Nanostructure Engineering of Cathode Layers in Proton Exchange Membrane Fuel Cells: From Catalysts to Membrane Electrode Assembly.

The membrane electrode assembly (MEA) is the core component of proton exchange membrane fuel cells (PEMFCs), which is the place where the reaction occurrence, the multiphase material transfer and the energy conversion, and the development of MEA with high activity and long stability are crucial for the practical application of PEMFCs. Currently, efforts are devoted to developing the regulation of MEA nanostructure engineering, which is believed to have advantages in improving catalyst utilization, maximizing three-phase boundaries, enhancing mass transport, and improving operational stability. This work reviews recent research progress on platinum group metal (PGM) and PGM-free catalysts with multidimensional nanostructures, catalyst layers (CLs), and nano-MEAs for PEMFCs, emphasizing the importance of structure-function relationships, aiming to guide the further development of the performance for PEMFCs. Then the design strategy of the MEA interface is summarized systematically. In addition, the application of in situ and operational characterization techniques to adequately identify current density distributions, hot spots, and water management visualization of MEAs is also discussed. Finally, the limitations of nanostructured MEA research are discussed and future promising research directions are proposed. This paper aims to provide valuable insights into the fundamental science and technical engineering of efficient MEA interfaces for PEMFCs.

Solution Structure and Dynamics of Hf-Al and Hf-Zn Heterobimetallic Adducts Mimicking Relevant Intermediates in Chain Transfer Reactions.

Cationic cyclometalated hafnocenes [CpPrCpCH2CH2CH2Hf][B(C6F5)4] (4Pr) and [CpiBuCpCH2CH(Me)CH2Hf][B(C6F5)4] (4aiBu and 4biBu) were synthesized from the corresponding [(CpPr)2HfMe][B(C6F5)4] (1Pr) and [(CpiBu)2HfMe][B(C6F5)4] (1iBu) complexes via C-H activation. 4aiBu, 4biBu, and 4Pr, mimicking a propagating M-polymeryl species (M = transition metal) with or without a β-methyl branch on the metalated chains, serve to investigate whether and how the nature of the last inserted olefin molecules changes the structure, stability, and reactivity of the corresponding heterobimetallic complexes, formed in the presence of aluminum- or zinc-alkyl chain transfer agents (CTAs), which are considered relevant intermediates in coordinative chain transfer polymerization (CCTP) and chain shuttling polymerization (CSP) technologies. NMR and DFT data indicate no major structural difference between the resulting heterobridged complexes, all characterized by the presence of multiple α-agostic interactions. On the contrary, thermodynamic and kinetic investigations, concerning the reversible formation and breaking of heterobimetallic adducts, demonstrate that isomer 4aiBu, in which the β-Me is oriented away from the reactive coordination site on Hf, but not 4biBu, having the β-Me pointing in the opposite direction, is capable of reacting with CTAs. Quantification of kinetic rate constants highlights that the formation process is rate limiting and that the nature of the last inserted α-olefin unit modulates transalkylation kinetics. The reaction of 4aiBu, 4biBu, and 4Pr with diisobutylaluminum hydride (DiBAlH) allows the interception and characterization of new heterobinuclear and heterotrinuclear species, featuring both hydride and alkyl bridging moieties, which represent structural models of elusive intermediates in CCTP and CSP processes, capturing the instant when an alkyl chain has just transferred from a transition metal to a main group metal, while the two metals remain engaged in a single heterobimetallic intermediate.

Solar-Powered AEM Electrolyzer via PGM-Free (Oxy)hydroxide Anode with Solar to Hydrogen Conversion Efficiency of 12.44.

Water electrolyzers powered by renewable energy are emerging as clean and sustainable technology for producing hydrogen without carbon emissions. Specifically, anion exchange membrane (AEM) electrolyzers utilizing non-platinum group metal (non-PGM) catalysts have garnered attention as a cost-effective method for hydrogen production, especially when integrated with solar cells. Nonetheless, the progress of such integrated systems is hindered by inadequate water electrolysis efficiency, primarily caused by poor oxygen evolution reaction (OER) electrodes. To address this issue, a NiFeCo─OOH has developed as an OER electrocatalyst and successfully demonstrated its efficacy in an AEM electrolyzer, which is powered by renewable electricity and integrated with a silicon solar cell.

Cathode Catalyst Layer Design in PEM Water Electrolysis toward Reduced Pt Loading and Hydrogen Crossover.

Reducing the use of platinum group metals is crucial for the large-scale deployment of proton exchange membrane (PEM) water electrolysis systems. The optimization of the cathode catalyst layer and decrease of the cathode Pt loading are usually overlooked due to the predominant focus of research on the anode. However, given the close relationship between the rate of hydrogen permeation through the membrane in an operating cell and the local hydrogen concentration near the membrane-cathode interface, the structural design of the cathode catalyst layer is considered to be of pivotal importance for reducing H2 crossover, particularly in combination with the use of thin (≲50 μm) membranes. In this study, we have conducted a detailed investigation on the cathode structural parameters, covering the Pt wt % of the Pt/C electrocatalyst, the type of carbon support (Vulcan and high surface area carbon, HSAC), and the ionomer content, with a goal to reduce Pt loading to 0.025 mgPt/cm2 while minimizing the rate of cell hydrogen crossover. We found that the electrochemical performance is mainly influenced by the changes in the interfacial contact resistance due to variations in the cathode thickness. Both the Pt wt % in Pt/C and the ionomer content showed a positive correlation with the measured H2 in O2% in the anode outlet, whereas the Pt loading exhibited an opposite trend. The rate of hydrogen crossover was analyzed in relation to the calculated local volumetric current density within the cathode catalyst layer. Based on the obtained hydrogen mass transfer coefficient, a cathode catalyst layer comprising 40 wt % Pt on HSAC support with an ionomer-to-carbon (I/C) ratio of 0.35 was found to be an optimum configuration for achieving a low Pt loading of 0.025 mgPt/cm2 and a reduced rate of hydrogen crossover.

Tau-borides (Mnx{Ru,Os,Ir}1-x)23B6: X-ray single crystal and TEM data, physical properties

Investigation (electron microprobe and X-ray powder and single crystal diffraction analyses) of the phase relations in the Mn-rich corner (> 45 at% Mn) of the systems Mn-{Ru,Os,Ir}-B, prompted in all three systems a ternary compound with formula (Mnx{Ru,Os,Ir}1-x)23B6. For the systems Mn-Ru-B, Mn-Ir-B phase equilibria have been determined at 950°C (Ru), 900°C (Ir) revealing in both cases a small homogeneity region at constant B-content (Mn1-xRux)23B6 (0.29 < x < 0.37); (Mn1-xOsx)23B6 (0.33 < x < 0.37), as well as (Mn1-xIrx)23B6 (0.29 < x < 0.34). The crystal structure of the three compounds was determined from single crystal and X-ray powder intensity data analyses to be isotypic with the Cr23B6-type (so-called tau-phase, space group Fm3¯m, No. 225). In all cases Mn atoms fully occupy the 4a site (0,0,0) at the origin of the unit cell. For the 8c site (¼,¼,¼) we observed a random distribution of Mn1-x(PM)x with decreasing PM content (PM stands for a platinum group metal atom) going from Ru to Os and Ir, where Mn atoms fully occupy 8c. Whereas the remaining sites (48h, 32f) show various ratios of the two metal species, boron atoms fully occupy the centers (24e site) of the Archimedean metal atom antiprisms. A transmission electron microscopic study confirms the absence of superstructures related to these metal atom disorder, thus Mn and PM atoms randomly share their sites. The latter is well reflected in the behavior of the electrical resistivity of these compounds, which is dominated by disorder scattering. For (Mn0.6{Ru,Os}0.4)23B6, temperature dependent dc magnetization studies reveal distinct antiferromagnetic-like anomalies at TN ≅ 72 K and 114 K, respectively. Low field dc and ac magnetic susceptibility data of (Mn0.7Ir0.3)23B6 display a distinct ferromagnetic-like transition at TC = 280 K, consistent with a pronounced specific heat anomaly and a rather continuous temperature dependent evolution of magnetic anisotropy effects. Mechanical properties (hardness) characterize the tau phases among rather hard and brittle intermetallics (about 5–6 GPa).

Regulating the Third Metal to Design and Engineer Multilayered NiFeM (M: Co, Mn, and Cu) Nanofoam Anode Catalysts for Anion‐Exchange Membrane Water Electrolyzers

AbstractAlkaline anion‐exchange membrane water electrolyzers (AEMWEs) for green hydrogen production have received intensive attention due to their feasibility of using earth‐abundant platinum group metal (PGM)‐free catalysts. Herein, the third metal is incorporated into NiFe‐based catalysts to regulate their electronic structures and morphologies, aiming to achieve sufficient oxygen evolution reaction (OER) activity and performance in AEMWEs. The ternary NiFeM (M: Cu, Co, or Mn) catalysts are featured with multiple layered structures and nanofoam network morphologies, consisting of highly OER‐active amorphous Ni‐rich oxide shells and electrically conductive metallic alloy cores. The physical and electronic perturbations to the NiFe induced by a third element lead to a fine‐tuning of the redox ability of the metal sites at the reaction centers, which breaks the scaling relationship between OH* and O* intermediates at the reaction centers. Thus, the unique structural configuration and electronic regulation simultaneously benefit catalytic activity and performance improvements. These NiFeM nanofoam catalysts demonstrated promising anode performance in actual AEMWEs, comparable to the IrO2 reference, especially at high current densities. Notably, using various electrolytes (e.g., KOH solution or pure water) for AEMWEs exhibited a different performance trend among studied NiFeM catalysts, likely due to dynamic changes of catalysts under various OER environments.

Insights into the Construction of Robust Pt Clusters with Satisfactory Stability on CeO2 for the Catalytic Oxidation of CO.

Improving the efficiency of platinum group metals (Pt, Pd, Rh, etc.) in catalytic oxidation reactions remains an urgent topic. The conflict between the low-temperature activity and high-temperature stability of noble metals can hardly reach a consensus. For instance, Pt cluster catalysts supported on CeO2 with high low-temperature activity will suffer from deactivation due to the redispersion under high-temperature lean-burn reaction conditions. Herein, two Pt1/CeO2 prepared by the incipient wetness impregnation method using different Pt precursors possessed varied Pt-O and Pt-O-Ce coordination numbers (CNs). They showed various priorities in CO oxidation versus NH3 selective catalytic oxidation, materials with higher CNPt-O-Ce selectively catalyzing NH3 oxidation to N2 more superior, conversely materials with lower CNPt-O-Ce performing better in CO oxidation. After activation by H2 reduction, both formed massive Pt clusters on the CeO2 surface but showed drastically distinct stability in lean-burn CO oxidation reactions. By summarizing the experimental results of high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, Raman spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it is beyond doubt that the difference in the initial states of Pt1 due to distinct precursors indeed determine the redispersion behavior of the reduced Pt clusters on CeO2. Materials with lower CNPt-O-Ce and higher CNPt-O are more likely to form robust Pt clusters, as they are not conducive to Pt anchoring, thus restricting the reversible structural evolution occurring under lean-burn CO oxidation and reductive conditions. This approach serves as a guide for the convenient and efficient construction and exploration of robust Pt cluster catalysts.

Transition Metal‐Free Catalytic C−H Zincation and Alumination

C−H metalation is the most efficient method to prepare aryl–zinc and –aluminium complexes that are ubiquitous nucleophiles. Virtually all C–H metalation routes to form Al/Zn organometallics require stoichiometric, strong Brønsted bases with no base‐catalyzed reactions reported. Herein we present a catalytic in amine/ammonium salt (Et3N/[(Et3N)H]+) C–H metalation process to form aryl‐zinc and aryl‐aluminium complexes. Key to this approach is coupling an endergonic C–H metalation step with a sufficiently exergonic dehydrocoupling step between the ammonium salt by‐product of C–H metalation ([(Et3N)H]+) and a Zn–H or Al–Me containing complex. This step, forming H2/MeH, makes the overall cycle exergonic while generating more of the reactive metal electrophile. Mechanistic studies supported by DFT calculations revealed metal‐specific dehydrocoupling pathways, with the divergent reactivity due to the different metal valency (which impacts the accessibility of amine‐free cationic metal complexes) and steric environment. Notably, dehydrocoupling in the zinc system proceeds through a ligand‐mediated pathway involving protonation of the b‐diketiminate Cg position. Given this process is applicable to two disparate metals (Zn and Al), other main group metals and ligand sets are expected to be amenable to this transition metal‐free, catalytic C−H metalation.

Transition Metal-Free Catalytic C-H Zincation and Alumination.

C-H metalation is the most efficient method to prepare aryl-zinc and -aluminium complexes that are ubiquitous nucleophiles. Virtually all C-H metalation routes to form Al/Zn organometallics require stoichiometric, strong Brønsted bases with no base-catalyzed reactions reported. Herein we present a catalytic in amine/ammonium salt (Et3N/[(Et3N)H]+) C-H metalation process to form aryl-zinc and aryl-aluminium complexes. Key to this approach is coupling an endergonic C-H metalation step with a sufficiently exergonic dehydrocoupling step between the ammonium salt by-product of C-H metalation ([(Et3N)H]+) and a Zn-H or Al-Me containing complex. This step, forming H2/MeH, makes the overall cycle exergonic while generating more of the reactive metal electrophile. Mechanistic studies supported by DFT calculations revealed metal-specific dehydrocoupling pathways, with the divergent reactivity due to the different metal valency (which impacts the accessibility of amine-free cationic metal complexes) and steric environment. Notably, dehydrocoupling in the zinc system proceeds through a ligand-mediated pathway involving protonation of the b-diketiminate Cg position. Given this process is applicable to two disparate metals (Zn and Al), other main group metals and ligand sets are expected to be amenable to this transition metal-free, catalytic C-H metalation.

Platinum Group Metals Extraction from Asteroids vs Earth: An Overview of the Industrial Ecosystems, Technologies and Risks

Platinum Group Metals Extraction from Asteroids vs Earth: An Overview of the Industrial Ecosystems, Technologies and Risks

Towards improved online dissolution evaluation of Pt-alloy PEMFC electrocatalysts via electrochemical flow cell - ICP-MS setup upgrades

Electrochemical flow cell coupled with an inductively coupled plasma mass spectrometer (EFC-ICP-MS) is a powerful electroanalytical technique to monitor in-situ dissolution of metallic electrocatalysts and to understand mechanism of degradation under operating conditions. Its utilisation has witnessed a notable increase in the electrocatalyst field in the last decade where it has been extensively used to study the stability of platinum group metals (PGMs) under oxygen reduction and oxygen evolution reaction conditions. Online ICP-MS has allowed the scientific and industrial community to optimise the activity and stability of PGMs thanks to a better understanding of the complex metal corrosion processes. Among the different setups, the electrochemical flow cell design is the most common as it is based on a commercially available design. Nonetheless, besides different materials and different electrochemical protocols, the impact of the geometry and various parameters of the setup on the recorded dissolution signal has not been studied until now. Such parameters can influence the results obtained with an EFC-ICP-MS and thus the interpretation of the dissolution mechanism and/or stability assessment. Hereby, we demonstrate that the length of the tubing between the outlet of the cell and the inlet of the ICP-MS impacts the resolution of the PtCo catalyst dissolution peaks. This, in turn, facilitates studies where the detection of extremely low concentrations is necessary, such as under a very narrow potential window. Similarly, a reduced internal volume of the cell restricts Pt redeposition, contributing to a more precise evaluation of stability. These claims were supported by dynamic continuum mechanics modelling of the ion concentration in a model EFC. Finally, we provide guidelines and advice to properly measure dissolution with an electrochemical cell coupled with ICP-MS.

Effect of metal doping on the microwave absorption performance of multi-element (metal, N, and Cl) doped carbon composites

Multi-element-doped carbons are actively being pursued as efficient lightweight microwave absorbers. In this work, metal, nitrogen and chlorine codoped carbons (metal,N,Cl–C, where metals = Ni, Co, Mn, or Zn) were synthesized through the high-temperature carbonization of polypyrrole doped with hydrochloric acid (PPy-HCl) and prepared in the presence of certain metal chloride salts (NiCl2, CoCl2, MnCl2, or ZnCl2). The dielectric parameters and microwave absorption properties of the metal,N,Cl–C composites could be regulated by simply altering the type of metal salt. Compared with N,Cl–C, it was discovered that Co,N,Cl–C and Ni,N,Cl–C possessed higher graphitization degrees, smaller particle sizes and more surface chemical functional groups (metal−N), which significantly improved the conduction loss and polarization loss effects including interfacial polarization and dipole polarization. At a filler ratio of 9.0 wt%, Ni,N,Cl–C displayed a wide effective absorption bandwidth (EAB, RL ≤ −10 dB) of 7.1 GHz at a thickness of 2.5 mm and a minimum reflection loss (RLmin) of −29.7 dB at 9.7 GHz and 3.5 mm thickness. Similarly, Co,N,Cl–C offered an RLmin value of −48.2 dB at 11.3 GHz and a thickness of 3.0 mm and an EAB of 6.0 GHz at a thickness of 2.5 mm. These results showcase the advantages of metal,N,Cl–C composites as microwave absorbers.

A facile high-efficiency preparation strategy for Al-containing multi-component boride microcrystals with superior comprehensive performance

Multi-component transition group metal borides (MMB2) have become a research hotspot due to their new composition design concepts and superior properties compared with conventional ceramics. Most of the current methods, however, are complicated and time-consuming, the mass production remains a challenge. Herein, we proposed a new high-efficiency strategy for synthesis of MMB2 using molten aluminum as the medium for the first time. The prepared Al-containing multi-component borides (TiZrHfNbTa)B2 microcrystals had a homogeneous composition with a hexagonal AlB2 structure and ultra-high hardness value of ∼35.3 GPa, which was much higher than data reported in the literature and the rule of mixture estimations. Furthermore, combined with the First-principles calculation results, we found that the Poisson's ratio (v) values exhibit a clearly ascending trend from 0.17 at VEC = 3.5 to 0.18 at VEC = 3.4, then to 0.201 at VEC = 3.2 with the increasing of Al content. This indicates that the intrinsic toughness of multi-component boride microcrystals is obviously enhanced by the trace-doped Al elements. Besides, the fabricated Al-containing multi-component boride microcrystals have superior oxidation activation energy and structural stability. The enhanced oxidation resistance is mainly attributed to the formation of a protective Al2O3 oxide layer and the lattice distortion, both of which lead to sluggish diffusion of O2. These findings propose a new unexplored avenue for the fabrication of MMB2 materials with superior comprehensive performance including ultra-hardness and intrinsically improved thermo-mechanical properties.

Solar-assisted selective separation and recovery of precious group metals from deactivated air purification catalysts

The mitigation of environmental and energy crises could be advanced by reclaiming platinum group precious metals (PGMs) from decommissioned air purification catalysts. However, the complexity of catalyst composition and the high chemical inertness of PGMs significantly impede this process. Consequently, recovering PGMs from used industrial catalysts is crucial and challenging. This study delves into an environmentally friendly approach to selectively recover PGMs from commercial air purifiers using photocatalytic redox technology. Our investigation focuses on devising a comprehensive strategy for treating three-way catalysts employed in automotive exhaust treatment. By meticulously pretreating and modifying reaction conditions, we achieved noteworthy results, completely dissolving and separating rhodium (Rh), palladium (Pd), and platinum (Pt) within a 12-h time frame. Importantly, the solubility selectivity persists despite the remarkably similar physicochemical properties of Rh, Pd, and Pt. To bolster the environmental sustainability of our method, we harness sunlight as the energy source to activate the photocatalysts, facilitating the complete dissolution of precious metals under natural light irradiation. This eco-friendly recovery approach demonstrated on commercial air purifiers, exhibits promise for broader application to a diverse range of deactivated air purification catalysts, potentially enabling implementation on a large scale.