Ultralow-Loading Ruthenium-Iridium Fuel Cell Catalysts Dispersed on Zn-N Species-Doped Carbon.

Developing low-loading platinum-group-metal (PGM) catalysts is one of the key challenges in commercializing anion-exchange-membrane-fuel-cells (AEMFCs), especially for hydrogen oxidation reaction (HOR). Here, ruthenium-iridium nanoparticles being deposited on a Zn-N species-doped carbon carrier (Ru6Ir/Zn-N-C) are synthesized and used as an anodic catalyst for AEMFCs. Ru6Ir/Zn-N-C shows extremely high mass activity (5.87 A mgPGM -1) and exchange current density (0.92 mA cm-2), which is 15.1 and 3.9 times that of commercial Pt/C, respectively. Based on the Ru6Ir/Zn-N-C AEMFCs achieve a peak power density of 1.50 W cm-2, surpassing the state-of-the-art commercial PtRu catalysts and the power ratio of the normalized loading is 14.01 W mgPGM anode -1 or 5.89 W mgPGM -1 after decreasing the anode loading (87.49 µg cm-2) or the total PGM loading (0.111 mg cm-2), satisfying the US Department of Energy's PGM loading target. Moreover, the solvent and solute isotope separation method is used for the first time to reveal the kinetic process of HOR, which shows the reaction is influenced by the adsorption of H2O and OH-. The improvement of the hydrogen bond network connectivity of the electric double layer by adjusting the interfacial H2O structure together with the optimized HBE and OHBE is proposed to be responsible for the high HOR activity of Ru6Ir/Zn-N-C.

Self-Cascade Uricase/Catalase Mimics Alleviate Acute Gout.

Uricase-based therapies are limited for gout partially due to the accumulation of H2O2 in an arthrosis environment with slow metabolism. To tackle this limitation, previous studies adopted a cascade reaction between the degradation of uric acid (UA) and timely elimination of H2O2 using complicated composites of uricase and catalase (CAT)/CAT-like nanozyme. Herein, the self-cascade nanozyme Pt/CeO2 with high efficiency toward simultaneous UA degradation and H2O2 elimination is demonstrated on the basis of both uricase- and CAT-like activities in Pt, Ir, Rh, and Pd platinum-group metals. With an optimized molar ratio of Pt and CeO2, Pt/CeO2 (1/5) not only does better in degrading UA but also has excellent reactive oxygen species (ROS) and reactive nitrogen species (RNS) scavenging activities. In monosodium urate (MSU)-induced acute gout rats, Pt/CeO2 nanozyme markedly alleviates pain along with joint edema, thus improving gait claudication and tissue inflammation. These results provide novel insights into strategies of an efficient enzyme-mimetic treatment for gout.

Combination of Mn-Mo Oxide Nanoparticles on Carbon Nanotubes through Nitrogen Doping to Catalyze Oxygen Reduction.

An efficient and low-cost oxygen catalyst for the oxygen reduction reaction (ORR) was developed by in situ growth of Mn-Mo oxide nanoparticles on nitrogen-doped carbon nanotubes (NCNTs). Doped nitrogen effectively increases the electron conductivity of the MnMoO4@NCNT complex and the binding energy between the Mn-Mo oxide nanoparticles and carbon nanotubes (CNTs), leading to fast charge transfer and more catalytically active sites. Combining Mn and Mo with NCNTs improves the catalytic activity and promotes both electron and mass transfers, greatly enhancing the catalytic ability for ORR. As a result, MnMoO4@NCNT exhibited a comparable half-wave potential to commercial Pt/C and superior durability, demonstrating great potential for application in renewable energy conversion systems.

Suppressing Electron Back-Donation for a Highly CO-tolerant Fuel Cell Anode Catalyst via Cobalt Modulation.

Platinum on carbon (Pt/C) catalyst is commercially adopted in fuel cells but it undergoes formidable active-site poisoning by carbon monoxide (CO). In particular, given the sluggish kinetics of hydrogen oxidation reaction (HOR) in anion-exchange membrane fuel cell (AEMFC), the issues of Pt poisoning and slow rate would combine mutually, notably worsening the device performances. Here we overcome these challenges through incorporating cobalt (Co) into molybdenum-nickel alloy (MoNi4 ), termed Co-MoNi4 , which not only shows superior HOR activity over the Pt/C catalyst in alkali, but more intriguingly exhibits excellent CO tolerance with only small activity decay after 10 000 cycles in the presence of 500 parts per million (ppm) CO. When feeding with CO (250 ppm)/H2 , the AEMFC assembled by this catalyst yields a peak power density of 394 mW cm-2 , far exceeding the Pt/C catalyst. Experimental and computational studies reveal that weakened CO chemisorption originates from the electron-deficient Ni sites after Co incorporation that suppresses d→CO 2π* back-donation.

Extraction of platinum group metals from catalytic converters.

Platinum group metals (PGMs) assume an important role within the chemistry and chemical engineering due to their exceptional chemical stability in high temperatures and various environmental conditions. Their unique attributes make them highly demanded materials across an array of industries. Nevertheless, the gradual depletion of PGM reserves underscores necessitates of recycling PGM-containing waste as a means to ensure the reasonable utilization of resources. Recycling of catalytic waste, in particular, presents a more cost-effective and environmentally sustainable approach acquiring these metals, in contrast to the conventional practice of mining from natural ores. Of particular importance are spent automotive catalysts, which represent a valuable source of platinum group metals, featuring substantially higher PGM concentrations than their naturally occurring counterparts. Conventionally, the recovering of PGMs from waste materials predominantly employs hydrometallurgical and pyrometallurgical processes. Unfortunately, these established techniques entail the utilization of potent oxidizing acidic solutions, including aqua regia and hydrochloric acid with chlorine gas, which exert adverse ecological consequences. In recent years, there has been a growing focus on the development of alternative methodologies that are both environmentally friendly and economically viable for the recovery of PGMs from spent catalysts. Notable among these emerging techniques are solvometallurgy, molecular recognition technology, and magnetic separation. This comprehensive review endeavors to study and assess the latest advancements in the recovery of platinum group metals from spent catalysts, meticulously evaluating their respective advantages and disadvantages. Through an analysis, this review aspires to identify the most promising method - one that combines environmental friendliness and economic feasibility.

Recovery of Metals from Wastewater-State-of-the-Art Solutions with the Support of Membrane Technology.

This paper discusses the most important research trends in the recovery of metals from industrial wastewater using membrane techniques in recent years. Particular attention is paid to the preparation of new membranes with the required filtration and separation properties. At the same time, possible future applications are highlighted. The aspects discussed are divided into metals in order to clearly and comprehensibly list the most optimal solutions depending on the composition of the wastewater and the possibility of recovering valuable components (metalloids, heavy metals, and platinum group metals). It is shown that it is possible to effectively remove metals from industrial wastewater by appropriate membrane preparation (up to ~100%), including the incorporation of functional groups, nanoparticles on the membrane surface. However, it is also worth noting the development of hybrid techniques, in which membrane techniques are one of the elements of an effective purification procedure.

What is Next in Anion-Exchange Membrane Water Electrolyzers? Bottlenecks, Benefits, and Future.

As highlighted by the recent roadmaps from the European Union and the United States, water electrolysis is the most valuable high-intensity technology for producing green hydrogen. Currently, two commercial low-temperature water electrolyzer technologies exist: alkaline water electrolyzer (A-WE) and proton-exchange membrane water electrolyzer (PEM-WE). However, both have major drawbacks. A-WE shows low productivity and efficiency, while PEM-WE uses a significant amount of critical raw materials. Lately, the use of anion-exchange membrane water electrolyzers (AEM-WE) has been proposed to overcome the limitations of the current commercial systems. AEM-WE could become the cornerstone to achieve an intense, safe, and resilient green hydrogen production to fulfill the hydrogen targets to achieve the 2050 decarbonization goals. Here, the status of AEM-WE development is discussed, with a focus on the most critical aspects for research and highlighting the potential routes for overcoming the remaining issues. The Review closes with the future perspective on the AEM-WE research indicating the targets to be achieved.

Role of N in Transition-Metal-Nitrides for Anchoring Platinum-Group Metal Atoms toward Single-Atom Catalysis.

Single-atom catalysts (SACs) with a maximum atom utilization efficiency have received growing attention in heterogeneous catalysis. The supporting substrate that provides atomic-dispersed anchoring sites and the local electronic environment in these catalysts is crucial to their activity and stability. Here, inspired by N-doped graphene substrate, the role of N is explored in transition metal nitrides for anchoring single metal atoms toward single-atom catalysis. A pore-rich metallic vanadium nitride (VN) nanosheet is fabricated as one supporting-substrate example, whose surface features abundant unsaturated N sites with lower binding energy than that of widely used N-doped graphene. Impressively, it is found that this support can anchor nearly all platinum-group single atoms (e.g., platinum, palladium, iridium, and ruthenium), and even be extendable to multiple SACs, i.e., binary (Pt/Pd) and ternary (Pt/Pd/Ir). As a proof-of-concept application for hydrogen production, Pt-based SAC (Pt1 -VN) performs excellently, exhibiting a mass activity up to 22.55 A mg-1 Pt at 0.05 V and a high turnover frequency value close to 0.350 H2 s-1 , superior to commercial platinum/carbon catalyst. The catalyst's durability can be further improved by using binary (Pt1 Pd1 -VN) SAC. This work provides inexpensive and durable nitride-based support, giving a possible pathway for universally constructing platinum-group SACs.

Targeting Multiresistant Gram-Positive Bacteria by Ruthenium, Osmium, Iridium and Rhodium Half-Sandwich Type Complexes With Bidentate Monosaccharide Ligands.

Bacterial resistance to antibiotics is an ever-growing problem in heathcare. We have previously identified a set of osmium(II), ruthenium(II), iridium(III) and rhodium(III) half-sandwich type complexes with bidentate monosaccharide ligands possessing cytostatic properties against carcinoma, lymphoma and sarcoma cells with low micromolar or submicromolar IC50 values. Importantly, these complexes were not active on primary, non-transformed cells. These complexes have now been assessed as to their antimicrobial properties and found to be potent inhibitors of the growth of reference strains of Staphylococcus aureus and Enterococcus faecalis (Gram-positive species), though the compounds proved inactive on reference strains of Pseudomonas aerugonisa, Escherichia coli, Candida albicans, Candida auris and Acinetobacter baumannii (Gram-negative species and fungi). Furthermore, clinical isolates of Staphylococcus aureus and Enterococcus sp. (both multiresistant and susceptible strains) were also susceptible to the organometallic complexes in this study with similar MIC values as the reference strains. Taken together, we identified a set of osmium(II), ruthenium(II), iridium(III) and rhodium(III) half-sandwich type antineoplastic organometallic complexes which also have antimicrobial activity among Gram-positive bacteria. These compounds represent a novel class of antimicrobial agents that are not detoxified by multiresistant bacteria suggesting a potential to be used to combat multiresistant infections.

Anode Catalysts in Anion-Exchange-Membrane Electrolysis without Supporting Electrolyte: Conductivity, Dynamics, and Ionomer Degradation.

Anion-exchange-membrane water electrolyzers (AEMWEs) in principle operate without soluble electrolyte using earth-abundant catalysts and cell materials and thus lower the cost of green H2 . Current systems lack competitive performance and the durability needed for commercialization. One critical issue is a poor understanding of catalyst-specific degradation processes in the electrolyzer. While non-platinum-group-metal (non-PGM) oxygen-evolution catalysts show excellent performance and durability in strongly alkaline electrolyte, this has not transferred directly to pure-water AEMWEs. Here, AEMWEs with five non-PGM anode catalysts are built and the catalysts' structural stability and interactions with the alkaline ionomer are characterized during electrolyzer operation and post-mortem. The results show catalyst electrical conductivity is one key to obtaining high-performing systems and that many non-PGM catalysts restructure during operation. Dynamic Fe sites correlate with enhanced degradation rates, as does the addition of soluble Fe impurities. In contrast, electronically conductive Co3 O4 nanoparticles (without Fe in the crystal structure) yield AEMWEs from simple, standard preparation methods, with performance and stability comparable to IrO2 . These results reveal the fundamental dynamic catalytic processes resulting in AEMWE device failure under relevant conditions, demonstrate a viable non-PGM catalyst for AEMWE operation, and illustrate underlying design rules for engineering anode catalyst/ionomer layers with higher performance and durability.

Recent progress of electrocatalysts for oxygen reduction in fuel cells.

Oxygen reduction reaction (ORR) has gradually been in the limelight in recent years because of its great application potential for fuel cells and rechargeable metal-air batteries. Therefore, significant issues are increasingly focused on developing effective and economical ORR electrocatalysts. This review begins with the reaction mechanisms and theoretical calculations of ORR in acidic and alkaline media. The latest reports and challenges in ORR electrocatalysis are traced. Most importantly, the latest advances in the development of ORR electrocatalysts are presented in detail, including platinum group metal (PGM), transition metal, and carbon-based electrocatalysts with various nanostructures. Furthermore, the development prospects and challenges of ORR electrocatalysts are speculated and discussed. These insights would help to formulate the design guidelines for highly-active ORR electrocatalysts and affect future research to obtain new knowledge for ORR mechanisms.

Development of N,N,N',N'-tetra-2-ethylhexyl-thiodiglycolamide silica-based adsorbent to separate useful metals from simulated high-level liquid waste.

A novel silica-based adsorbent was synthesized by impregnating macroporous silica polymer composite (SiO2-P) particles with a mixture of N,N,N',N'-tetra-2-ethylhexyl-thiodiglycolamide (TEHTDGA) and tri-n-octylamine (TOA). Then, the possibility of separating Pd(II) and other metal ions from simulated high-level liquid waste (HLLW) using the newly synthesized adsorbent (TEHTDGA + TOA)/SiO2-P was evaluated based on various adsorption characteristics obtained via batch-adsorption experiments, such as the HNO3 concentration, contact time, reaction temperature, adsorption isotherm, and chemical stability of the adsorbent. Furthermore, column separation experiments were performed based on the characteristics obtained from the batch-adsorption experiment, and the possibility of simultaneous separation of multiple metal ions was examined. The experimental results revealed that (TEHTDGA + TOA)/SiO2-P performs well in the separation of multiple metal ions from simulated HLLW.

Modified tunicate nanocellulose liquid crystalline fiber as closed loop for recycling platinum-group metals.

Rising demand and elemental rarity requires the recycling of precious metals such as platinum group elements (PGMs). Recently, biosorption has been focused on the capability of recovering precious metals, but in practice, recycling is inefficient or far away from a closed-loop material system. Here we use a polyethylenimine (PEI)-grafted spun-fiber made of cellulose nanofibril (CNF) extracted from a tunicate as a biosorbent for PGMs. Liquid crystallinity (LC) of TCNF suspension appears to contribute the generation of well-developed open porous structure in the fiber. We show the fiber has the selectivity and high capacity of Pt (120.2 mg/g, 86%) and Pd (26.5 mg/g, 74.2%) adsorption under the presence of other metals in simulated automobile waste. The adsorbed Pt and Pd with nano-scale clusters were uniformly distributed on the porous surface, which were directly applied as a catalyst. These results propose an easy approach to recover precious metals and reuse them directly, thereby closing loops of metal recycling.

High Power Density Platinum Group Metal-free Cathodes for Polymer Electrolyte Fuel Cells.

Low cost and high-performing platinum group metal-free (PGM-free) cathodes have the potential to transform the economics of polymer electrolyte fuel cell (PEFC) commercialization. Significant advancements have been made recently in terms of PGM-free catalyst activity and stability. However, before PGM-free catalysts become viable in PEFCs, several technical challenges must be addressed including cathode's fabrication, ionomer integration, and transport losses. Here, we present an integrated optimization of cathode performance that was achieved by simultaneously optimizing the catalyst morphology and electrode structure for high power density. The chemically doped metal-organic framework derived Fe-N-C catalyst we used allows precise tuning of the particle size over a wide range, enabling this unique study. Our results demonstrate the careful interplay between the catalyst primary particle size and the polymer electrolyte ionomer integration. The primary particles must be sufficiently large to permit uniform ionomer thin films throughout the surrounding pores, but not so large as to impact intraparticle transport to the active sites. The content of ionomer must be carefully balanced between sufficient loading for the complete catalyst coverage and adequate proton conductivity, while not being excessive and inducing large oxygen transport losses and liquid water flooding. With the optimal 100 nm size catalyst and ionomer loading, we achieved a high power density of 410 mW/cm2 at a rated voltage and a peak power density of 610 mW/cm2 in an automotive-relevant operating condition.

Recovery of platinum from waste effluent using polyethyleneimine-modified nanocelluloses: Effects of the cellulose source and type.

Nanocellulose is a promising biosorbent for the recovery of precious metals from waste streams. A variety of nanocelluloses exhibit significant different properties that depend on the natural source and type. In this study, cellulose nanofibrils(P-CNF) and cellulose nanocrystals(P-CNC) obtained from hard wood pulp and CNF from tunicates(T-CNF) were evaluated for their ability to recover platinum(Pt) after modification with polyethyleneimine(PEI). The PEI grafting density on each nanocellulose was distinct, resulting in significant variations in the Pt adsorption performance. The Pt adsorption capacity of the PEI-modified nanocelluloses followed the order T-CNF>>P-CNC > P-CNF. The inherent characteristics of T-CNF, that is, the negative charge and high surface area caused by open porous structure, were found attributed to the grafting of ≈40% PEI and the excellent Pt adsorption capacity(≈600 mg/g). Also PEI-modified T-CNF exhibited high selectivity towards Pt in the presence of other metals. Finally, PEI modified T-CNF was applied for Pt recovery from simulated spent automobile catalyst leachate to prove feasibility in a real application.

PGM-Free Cathode Catalysts for PEM Fuel Cells: A Mini-Review on Stability Challenges.

In recent years, significant progress has been achieved in the development of platinum group metal-free (PGM-free) oxygen reduction reaction (ORR) catalysts for proton exchange membrane (PEM) fuel cells. At the same time the limited durability of these catalysts remains a great challenge that needs to be addressed. This mini-review summarizes the recent progress in understanding the main causes of instability of PGM-free ORR catalysts in acidic environments, focusing on transition metal/nitrogen codoped systems (M-N-C catalysts, M: Fe, Co, Mn), particularly MNx moiety active sites. Of several possible degradation mechanisms, demetalation and carbon oxidation are found to be the most likely reasons for M-N-C catalysts/cathodes degradation.

Progress in the Development of Fe-Based PGM-Free Electrocatalysts for the Oxygen Reduction Reaction.

Development of alternative energy sources is crucial to tackle challenges encountered by the growing global energy demand. Hydrogen fuel, a promising way to store energy produced from renewable power sources, can be converted into electrical energy at high efficiency via direct electrochemical conversion in fuel cells, releasing water as the sole byproduct. One important drawback to current fuel-cell technology is the high content of platinum-group-metal (PGM) electrocatalysts required to perform the sluggish oxygen reduction reaction (ORR). Addressing this challenge, remarkable progress has been made in the development of low-cost PGM-free electrocatalysts synthesized from inexpensive, earth-abundant, and easily sourced materials such as iron, nitrogen, and carbon (Fe-N-C). PGM-free Fe-N-C electrocatalysts now exhibit ORR activities approaching that of PGM electrocatalysts but at a fraction of the cost, promising to significantly reduce overall fuel-cell technology costs. Herein, recent developments in PGM-free electrocatalysis, demonstrating increased fuel-cell performance, as well as efforts aimed at understanding the key limiting factor, i.e., the nature of the PGM-free active site, are summarized. Further improvements will be accomplished through the controlled and/or rationally designed synthesis of materials with higher active-site densities, while at the same time establishing methods to mitigate catalyst degradation.

Integrating PGM-Free Catalysts into Catalyst Layers and Proton Exchange Membrane Fuel Cell Devices.

While proton exchange membrane fuel cells (PEMFCs) continue to expand into commercial markets, there is still pressure to decrease cost. One of the largest opportunities to reducing cost is to reduce the amount of platinum-group metal (PGM) catalysts used in the electrodes (particularly the cathode). Over the past decade, exciting advances in the Fe/N/C family of PGM-free oxygen reduction reaction (ORR) catalysts has provided great optimism that not only can PGMs at the cathode be reduced but possibly be completely eliminated. In fact, in September 2017, Ballard Power Systems announced the commercialization of the world's first PEMFC product to utilize a PGM-free catalyst at the cathode (FCgen-micro (non-precious-metal catalyst, NPMC)). However, for these catalysts to be used in more demanding applications, an improved understanding and new design approaches for PGM-free catalyst layers will be required. Herein, some of the latest research on both modeling and experimental studies in the field of PGM-free catalyst layer research are discussed. In addition, a short discussion on Ballard's new NPMC is provided.

Non-selective rapid electro-oxidation of persistent, refractory VOCs in industrial wastewater using a highly catalytic and dimensionally stable IrPd/Ti composite electrode.

Volatile organic compounds (VOCs) are highly toxic contaminants commonly dissolved in industrial wastewater. Therefore, treatment of VOC-containing wastewater requires a robust and rapid reaction because liquid VOCs can become volatile secondary pollutants. In this study, electro-oxidation with catalytic composite dimensionally stable anodes (DSAs)-a promising process for degrading organic pollutants-was applied to remove various VOCs (chloroform, benzene, toluene, and trichloroethylene). Excellent treatment efficiency of VOCs was demonstrated. To evaluate the VOC removal rate of each DSA, a titanium plate, a frequently used substratum, was coated with four different highly electrocatalytic composite materials (platinum group metals), Ir, IrPt, IrRu, and IrPd. Ir was used as a base catalyst to maintain the electrochemical stability of the anode. Current density and electrolyte concentration were evaluated over various ranges (20-45 mA/cm2 and 0.01-0.15 mol/L as NaCl, respectively) to determine the optimum operating condition. Results indicated that chloroform was the most refractory VOC tested due to its robust chemical bond strength. Moreover, the optimum current density and electrolyte concentration were 25 mA/cm2 and 0.05 M, respectively, representing the most cost-effective condition. Four DSAs were examined (Ir/Ti, IrPt/Ti, IrRu/Ti, and IrPd/Ti). The IrPd/Ti anode was the most suitable for treatment of VOCs presenting the highest chloroform removal performance of 78.8%, energy consumption of 0.38 kWh per unit mass (g) of oxidized chloroform, and the least volatilized fraction of 4.4%. IrPd/Ti was the most suitable anode material for VOC treatment because of its unique structure, high wettability, and high surface area.

Resolving Electrode Morphology's Impact on Platinum Group Metal-Free Cathode Performance Using Nano-CT of 3D Hierarchical Pore and Ionomer Distribution.

This article reports on the characterization of polymer electrolyte fuel cell (PEFC) cathodes featuring a platinum group metal-free (PGM-free) catalyst using nanoscale resolution X-ray computed tomography (nano-CT) and morphological analysis. PGM-free PEFC cathodes have gained significant interest in the past decade since they have the potential to dramatically reduce PEFC costs by eliminating the large platinum (Pt) raw material cost. However, several challenges remain before they are commercially viable. Since these catalysts have lower volumetric activity, the PGM-free cathodes are thicker and subject to increased gas and proton transport resistances that reduce the performance. To better understand the efficacy of the catalyst and improve electrode performance, a detailed understanding the correlation between electrode fabrication, morphology, and performance is crucial. In this work, the pore/solid structure and the ionomer distribution was resolved in three dimensions (3D) using nano-CT for three PGM-free electrodes of varying Nafion loading. The associated transport properties were evaluated from pore/particle-scale simulations within the nano-CT-imaged structure. These characterizations are then used to elucidate the microstructural origins of the dramatic changes in fuel cell performance with varying Nafion ionomer loading. We show that this is primarily a result of distinct changes in ionomer's spatial distribution. The significant impact of electrode morphology on performance highlights the importance of PGM-free electrode development in concert with efforts to improve catalyst activity and durability.