Noble Metal Content Research Articles

(Invited) Organic Catalysis Promotor for Accelerating Oxygen Evolution Reaction Toward Advanced Water Electrolysis

As the concerns about energy and environmental issues rapidly increase, the requirements for developing renewable energy sources are highly demanded to achieve the carbon-neutrality by 2050. Among the suggested strategies for carbon neutrality, green hydrogen production via water electrolysis is treated as a promising breakthrough to alternate the currently used fossil fuel-based energy production since it utilizes clean and eco-friendly resources of water and electricity. However, there still remains a limitation of which mostly used noble metal-based catalyst materials such as iridium, and platinum result in severe carbon dioxide emission during production and recycling processes in addition to the extremely high cost and scarcity. Therefore, it is mandatory to minimize the noble metal contents in catalyst electrodes to ultimately reach carbon neutrality. Diverse approaches have been suggested to reduce the amount of noble metal contents such as developing non-noble metal catalysts and single-atom catalysts as well as designing electrode architecture for low loading on the support materials. Nonetheless, limited catalytic performances or increased process cost from suggested strategies still hinders the development of large-scale water electrolyzer. Herein, we suggest a novel concept of organic catalysis promotor as a strategy for minimizing noble metal contents in catalysts. Organic catalysis promotor as an additive in an electrolyte can enhance the hydrogen production efficiency with the spontaneous chemical interaction with the intermediate state of a catalyst during water electrolysis reaction, which can further result in reducing the required amount of noble metals for green hydrogen production. We developed the model organic catalysis promotor for oxygen evolution reaction in alkaline water electrolysis, and it successfully reduced overpotential of 70 mV at a current density of 100 mA cm-2 with only adding a slight amount of 1 mM organic catalysis promotor in KOH electrolyte. This catalysis promoting capability could be maintained even over a week, and the possibilities of further expansion of organic catalysis promotor material group and general applicability to representative oxygen evolution reaction catalysts were also proved. This novel concept of organic catalysis promotor has a great potential to be further expanded toward hydrogen evolution reaction promotion and acidic water electrolyzer. Furthermore, it can suggest a new breakthrough for the development of large-scale water electrolyzer with minimizing the noble metal contents in a sustainable and economical way.

Enhancing Electrochemical Seawater Oxidation with Noble Metal-Decorated Co3O4 Nanocubes

The pressing global challenge of overwhelming reliance on nonrenewable fossil fuels demands innovative solutions to decarbonize energy and industrial parts. Green hydrogen is produced through water electrolysis using renewable energy sources such as solar and wind and increasingly recognized as a promising alternative. This method leads to significant technological advancements and cost reductions in renewable electricity. Given that seawater accounts for 96.5% of Earth’s total water reserves, it presents a nearly inexhaustible resource for hydrogen production. However, the seawater electrolysis suffers from some challenges due to the complexity of seawater including various impurities that lead to corrosive and toxic byproducts. The experimental focus of seawater electrolysis encompasses the hydrogen evolution reaction (HER) at the cathode and the oxygen evolution reaction (OER) at the anode. Additionally, the anodic reaction is accompanied by competing with the chlorine evolution reaction (CER). The CER involving a two-electron reaction demonstrated faster kinetics than the OER (four-electron reaction) along with a decrease in the potential thermodynamic difference in acidic and neutral conditions. Though some research focuses on enhancing OER selectivity over CER, certain industries may prefer chlorine (Cl2) generation for wastewater treatment purposes. Noble metals for seawater electrolysis have been used with observed stability throughout overall pH values. However, they are a scarce element and quite expensive, so that lead to problems for industrial scale. Therefore, many transition metal-based catalysts have been introduced to reduce contents of noble metals for a long maintenance. Among these, cobalt is cost-effectiveness and showed better synergistic behavior on coupling with precious metals. In this regard, we synthesized spinel type of cobalt oxide, and then performed a simple deposition method with Ir and/or Pd precursor solution. The Co3O4 nanocubes (denoted as Co3O4NCs) was synthesized by hydrothermal reaction and they exhibited the size 145 ± 30 nm. The photodeposition of noble metals was subsequently conducted for enhancing catalytic activity. This approach aimed to reduce the usage of noble metals and significantly boost the electrochemical catalytic activity for both OER and the chloride oxidation reaction (COR). The 2wt% Ir decorated catalysts showed a considerable improvement in overall catalytic activity, while the catalysts with 6wt% Pd excelled the COR activity under simulated seawater conditions. Especially, metal palladium has been known as an excellent selectivity and activity for chlorine species, but it is too reactive to be a stable. However, the combined deposition of Pd onto Co3O4NCs@IrO2 surface not only demonstrated a synergistic effect, significantly outperforming other metal electrodes under 0.5 M NaCl conditions (FEHOCl ~100%), but also contributed to a notable improvement in catalyst stability at 40 mA/cm2 over 8 hours. This synergistic interaction between Ir and Pd on the Co3O4NCs surface, and the resultant enhanced stability, indicate the significance of our findings. Furthermore, the effective employment of noble metals would benefit from a design of catalysts based on precious metals. Our research paves the way for advancing hydrogen production technologies and propelling the hydrogen economy forward, illustrating the viability of seawater.

Flakes and Nanoparticles from Waste Ru-Plated Fashion Items through Food Waste by-Products.

Ruthenium is relevant for a broad range of applications, including catalysis and electronics. Like other metals of the platinum group, ruthenium stands out as one of the rarest elements in the Earth's crust. The demand for Ru from the industry is putting pressure on its availability. Hence, its recovery from secondary sources is imperative. Fashion solid residues of the plating industry are an important waste stream for Ru. Within this context, we propose a novel approach to Ru recovery for its safe, sustainable, and economically affordable upcycling. The approach is based on peeling from waste metal wires by a green oxidizing agent, H2O2, in an environment acidic by lactic acid, a by-product of the food industry. Peeled flakes were characterized by scanning electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy for their structure and (surface) chemical composition and bonding. Inductively Coupled Plasma Optical Emission Spectroscopy shows the ultra-low concentration of noble metals in the leachate, thereby suggesting their quantitative recovery in their metallic state. Further, we observed the colloidal nature of the washing water of the peeled flakes. Therefore, we hypothesized the presence of nanoparticles in the washing water and went for their characterization.

Reducing noble metal content in water electrolysis catalysts: A study on high-entropy oxides

This study presents the development of high-entropy oxide (HEO) catalysts based on Iridium-Ruthenium oxides (IrRuOx) for the oxygen evolution reaction (OER) in proton exchange membrane water electrolyzers (PEMWEs). By incorporating 3d transition metals such as Fe, Co, and Ni, we achieved catalysts with enhanced performance and stability. Using density functional theory (DFT) calculations, we predicted that HEOs possess a more favorable electronic structure for catalytic reactions. The synthesized rutile-type HEO catalyst (RuIrFeCoNi)O2, created via a molten salt oxidation method, exhibited a low overpotential of 261 mV and excellent cycling stability, maintaining a stable voltage of 1.73 V at 1 A cm−2 over 100 hours of electrolysis. This innovative approach not only reduces noble metal content but also leverages multimetallic synergistic effects to optimize the catalytic performance and stability, offering a promising avenue for the industrial application of acidic water electrolysis in PEMWEs.

Palladium-Functionalized Nanostructured Nickel-Cobalt Oxide as Alternative Catalyst for Hydrogen Sensing Using Pellistors.

To meet today's requirements, new active catalysts with reduced noble metal content are needed for hydrogen sensing. A palladium-functionalized nanostructured Ni0.5Co2.5O4 catalyst with a total Pd content of 4.2 wt% was synthesized by coprecipitation to obtain catalysts with an advantageous sheet-like morphology and surface defects. Due to the synthesis method and the reducible nature of Ni0.5Co2.5O4 enabling strong metal-metal oxide interactions, the palladium was highly distributed over the metal oxide surface, as determined using scanning transmission electron microscopy and energy-dispersive X-ray investigations. The catalyst tested in planar pellistor sensors showed high sensitivity to hydrogen in the concentration range below the lower flammability limit (LFL). At 400 °C and in dry air, a sensor response of 109 mV/10,000 ppm hydrogen (25% of LFL) was achieved. The sensor signal was 4.6-times higher than the signal of pristine Ni0.5Co2.5O4 (24.6 mV/10,000 ppm). Under humid conditions, the sensor responses were reduced by ~10% for Pd-functionalized Ni0.5Co2.5O4 and by ~27% for Ni0.5Co2.5O4. The different cross-sensitivities of both catalysts to water are attributed to different activation mechanisms of hydrogen. The combination of high sensor sensitivity to hydrogen and high signal stability over time, as well as low cross-sensitivity to humidity, make the catalyst promising for further development steps.

Electrodeposition of Non-Noble High-Entropy Alloys for Effective Hydrogen Evolution Electrocatalysts

As society works towards reducing its carbon footprint, various sectors such as energy, steelmaking and fertilizer production have begun to look increasingly towards decarbonization. Hydrogen production through electrolysis, when linked to renewables (solar, wind), provides a promising low-emission alternative as an energy carrier and chemical feedstock. With the decreasing cost of said renewables, greater focus is now on the capital cost of the electrolyser, and particularly the membrane/electrode structures. Conventional Proton Exchange Membrane (PEM) electrolysers rely on the use of electrocatalysts made with expensive noble metals such as platinum, ruthenium, and palladium [1]. Anion Exchange Membrane (AEM) electrolysers present an effective means of alkaline water splitting with low carbon emissions and can effectively utilize non-noble metal electrocatalysts for the Hydrogen Evolution Reaction (HER). A novel class of materials, High-Entropy Alloys (HEAs), made of non-noble metals or with reduced noble metal content have shown great promise as active electrocatalytic materials [2]. HEAs are typically defined as metal alloys made of five or more constituent elements each comprising at least 5% of the total material [3]. Having such a large number of principal alloying elements can lead to enhanced phase stability due to an increased configurational entropy, have unique chemical clustering, and can help prevent degradation of the material in harsh environments [2]. Additionally, the large lattice parameter mismatch between constituent elements can result in a high degree of strain which can help shift electronic states in a way that is favourable to hydrogen electrocatalysis [4]. These properties along with the so called “cocktail effect,” whereby combining multiple elements can result in unexpected synergistic interactions, makes HEAs uniquely suited to electrocatalytic applications [5].In this work, we investigate the electrocatalytic performance of electrodeposited FeNiCoMoW HEAs. The goal is to combine three hyper-d transition metals with two hypo-d transition metals to alter the electronic structure and improve electrocatalytic performance. Using chronoamperometric measurements, the Tafel slopes for FeNiCoMoW HEAs electrodeposited at pH 5, 6 and 7 were determined, with the pH 5 HEA demonstrating the smallest average Tafel slope of approximately 83 mV/dec. Compared to some electrodeposited binary alloys reported on in the literature, this marks an improvement and may be the result of unexpected interactions within the compositionally complex alloy. In the FeNiCoMoW HEA, the magnitude of the Tafel slope increased in tandem with the electrochemically active surface area (ECSA) as determined by Cyclic Voltammetry (CV) which suggests that the composition may be more important for improving performance. As the pH of the electrodeposition solution increased, the amount of cobalt in the as-deposited HEA decreased while the amounts of molybdenum and tungsten remained constant. The composition of nickel and iron appeared to vary inversely, reaching a maximum and minimum respectively at pH 6. From these results it seems that maximizing cobalt content and minimizing nickel content could potentially help to improve HER performance in the FeNiCoMoW system.

Electrochemical Conversion of Low-Cost Glycerol to Valuable Products

Over the last years, biodiesel production, a renewable fuel derived from biomass, has significantly increased, reaching an output of 40 million tons annually. This surge in production has resulted in excessive glycerol production, as a byproduct, accounting for 10 wt.% of biodiesel production. By 2025, it is predicted that glycerol production will amount to 6.3 million tons.1 However, the low demand for glycerol not only causes high disposal costs for this waste byproduct but also poses a threat to the ecosystem. Consequently, the valorization of glycerol is crucial for enhancing the biodiesel industry's economic viability and environmental sustainability.Among all the techniques for the valorization of glycerol, such as catalytic oxidation, dehydration, and hydrogenolysis, the electrochemical oxidation of glycerol stands out for its cost-effectiveness, simplicity, and eco-friendliness. The glycerol electrooxidation reaction (GOR) can yield a wide range of valuable chemicals, such as C3 products (glyceraldehyde, lactic acid, glyceric acid, tartronic acid), C2 products (glycolic acid, oxalic acid, acetic acid), and C1 products (formic acid). Among all the products, C3 products have notably higher economic value compared to others. In particular, glyceric acid stood out by having a price of over 200 folds of glycerol and having the highest worldwide demand among all the GOR products.2 However, a significant technical challenge lies in developing a highly selective catalyst for C3 products showing high activity, and stability. Thus far, most of the catalyst developed for GOR includes noble metals or their alloys, which limits their usage in realistic systems due to their high cost and scarcity.3 Therefore, developing a cost-effective catalyst with high selectivity, activity, and stability is necessary to make the valorization of glycerol economically viable.In this work, we demonstrate a bimetallic catalyst that, despite its low noble metal content, achieves high selectivity towards glyceric acid, along with notable catalytic activity and stability. Our analysis focuses on the impact of noble metal amount on activity and stability, and parametric analysis to improve the selectivity of C3 products. Furthermore, we outline the reasons for the discrepancies in the quantification of GOR products, especially in applying H-NMR analysis, and discuss the methods to improve the precision in GOR product analysis.

Room temperature thermocatalytic removal of formaldehyde in air using a copper manganite spinel-supported palladium catalyst with ultralow noble metal content

The room temperature (RT)-catalytic oxidation of gaseous formaldehyde (FA) in the dark is regarded as one of the most viable technical options for its removal from indoor air. Herein, the copper manganite spinel (CuMn2O4) supported palladium (Pd) catalysts are firstly synthesized for the thermocatalytic oxidation of FA in air. In particular, 0.05% Pd-CuMn2O4-R (‘R’ denotes high-temperature reduction pre-treatment using hydrogen) achieves 100% conversion (XFA) of 50 ppm FA at RT (gas hourly space velocity of 4342 h−1). The performance of 0.05% Pd-CuMn2O4-R against FA, if assessed in terms of the reaction kinetic rate (r at 10% XFA), is estimated as 3.01E−02 mmol g−1h−1. The lowering of XFA with the increases in FA concentration, flow rate, and relative humidity indicates the detrimental effects of such variables on the catalytic activity. FA oxidation kinetics predominantly follows the Mars van Krevelen mechanism. In-situ diffuse reflectance infrared Fourier transform spectroscopy shows that FA oxidation proceeds through multiple reaction intermediates (e.g., dioxymethylene and formate). The density functional theory simulations indicate that the catalytic oxidation efficacy of FA over CuMn2O4 increases by the synergy between Pd loading and surface reduction. The present study represents the first report on the synthesis of CuMn2O4-supported Pd catalysts and their application for the RT oxidative removal of FA in air under dark conditions. The findings of the present work offer valuable insights into the construction of efficient and cost-effective catalysts with ultra-low noble metal content for the RT oxidative removal of VOCs in indoor environment.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano‐Islands

AbstractCeO2‐supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2‐Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano-Islands.

CeO2-supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2-Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

Ratio design of bimetallic Pd‐Rh nanoparticles on MoS2 nanosheets: Excellent electrocatalysts for hydrogen evolution reaction

The decrease in noble metal content presents an efficient approach to attain commercial, effective, and durable electrocatalysts for the hydrogen evolution reaction (HER) at a low fabrication cost. Nonetheless, achieving a proper balance between bimetallic loading ratios and HER performance remains challenging. In this study, a simple and environmentally friendly sonochemical method is employed to successfully synthesize bimetallic palladium–rhodium nanoparticles (Pd‐Rh) with varying ratios, confined within molybdenum disulfide (MoS2) nanosheets. Bimetallic Pd‐Rh/MoS2 composite with different ratios of Pd:Rh is synthesized by adjusting the feed ratio of Pd and Rh precursors (1:4, 1:1, and 4:1). The HER electrocatalytic activity of the bimetallic Pd1‐Rh1/MoS2 composite exhibits the lowest overpotential and a superior Tafel slope, closely rivaling the electrocatalytic activity of the commercial 20 wt% Pt/C. Furthermore, the bimetallic Pd1‐Rh1/MoS2 composite exhibits remarkable stability and durability, with almost negligible performance decay after 2000 cycles. These outstanding HER electrocatalytic properties of the bimetallic composite result from a higher number of active sites, a significantly larger electrochemically active surface area, reduced charge‐transfer resistance, and a larger double‐layer capacitance. These factors collectively facilitate faster adsorption and desorption of hydron on the surface of electrocatalyst.

Metal-support interface engineering for stable and enhanced hydrogen evolution reaction

Hydrogen has emerged as a green and sustainable pathway towards achieving global decarbonization and net-zero emissions, intensely driving the need for efficient hydrogen production protocols. Electrocatalytic hydrogen evolution reaction (HER) holds great potential as a scalable, eco-friendly and safe avenue for efficient hydrogen production. However, the large-scale implementation of electrocatalytic HER is substantially challenged by the high-cost and unstable materials that are mainly fabricated from noble metals, e.g., Pt and Pd. Given this challenge, we adopted an interface engineering strategy to immobilize nanoscale Pt particles within the framework of nitrogen-doped CNTs, namely Pt@N-CNTs, where electronic metal-support interaction (EMSI) plays an important role in enabling orbital rehybridization and regulating the charge transfer through the metal-support interface, thereby considerably improving the electrocatalytic activity. With limited content of noble metals, our developed Pt@N-CNTs delivered superior HER performance with an ultralow overpotential of 5.8 mV at 10 mA cm−2 and demonstrated a high mass activity of 12.72 A mgPt−1 at an overpotential of 50 mV as well as excellent stability under harsh acidic conditions. At 500 mA cm−2, Pt@N-CNTs surprisingly exhibited an overpotential of 55.2 mV, outperforming that of commercial 20 wt% Pt/C catalysts (131.5 mV). Importantly, we established a straightforward, scalable, and time-saving microwave reduction strategy, alluding to its promising commercial viability. This work therefore sheds light on the development of high-performance electrocatalysts for hydrogen evolution and water electrolysis.

Investigation on the reaction mechanism and stability of Ruddlesden-Popper structure Srn+1BnO3n+1 (B=Ru, Ir, n=1, 2) as an oxygen evolution reaction electrocatalyst in acidic medium

R–P structured catalysts have attracted attention due to their low noble metal content and long-term stability. In this paper, we calculated the synthesis difficulty, Sr segregation, and OER catalytic activity of SrBO3, Srn+1BnO3n+1 (B = Ru, Ir, n = 1, 2), taking into account the effects of perovskite layer numbers and strain. The synthesis difficulty was calculated: SrBO3 < Sr2BO4 < Sr3B2O7. The perovskite layer numbers of R–P catalysts were also found to affect the OER process, from n = 1 to 2, the rate-controlling step changes from O*→OOH* to OOH*→O2. Sr2IrO4 was calculated to have the best catalytic activity but is very prone to Sr segregation. Due to the unique layered nature, Sr2IrO4 is still considered the most promising OER catalyst. Furthermore, we also concluded that applying strain impairs the OER catalytic performance of R–P oxides. Our work investigated the OER catalytic mechanisms of R–P oxides, which is significant for the development of water electrolysis.

Activating Ru in the pyramidal sites of Ru2P‐type structures with earth‐abundant transition metals for achieving extremely high HER activity while minimizing noble metal content

AbstractRational design of efficient pH‐universal hydrogen evolution reaction catalysts to enable large‐scale hydrogen production via electrochemical water splitting is of great significance, yet a challenging task. Herein, Ru atoms in the Ru2P structure were replaced with M = Co, Ni, or Mo to produce M2−xRuxP nanocrystals. The metals show strong site preference, with Co and Ni occupying the tetrahedral sites and Ru the square pyramidal sites of the CoRuP and NiRuP Ru2P‐type structures. The presence of Co or Ni in the tetrahedral sites leads to charge redistribution for Ru and, according to density functional theory calculations, a significant increase in the Ru d‐band centers. As a result, the intrinsic activity of CoRuP and NiRuP increases considerably compared to Ru2P in both acidic and alkaline media. The effect is not observed for MoRuP, in which Mo prefers to occupy the pyramidal sites. In particular, CoRuP shows state‐of‐the‐art activity, outperforming Ru2P with Pt‐like activity in 0.5 M H2SO4 (η10 = 12.3 mV; η100 = 52 mV; turnover frequency (TOF) = 4.7 s−1). It remains extraordinarily active in alkaline conditions (η10 = 12.9 mV; η100 = 43.5 mV) with a TOF of 4.5 s−1, which is 4x higher than that of Ru2P and 10x that of Pt/C. Further increase in the Co content does not lead to drastic loss of activity, especially in alkaline medium, where, for example, the TOF of Co1.9Ru0.1P remains comparable to that of Ru2P and higher than that of Pt/C, highlighting the viability of the adopted approach to prepare cost‐efficient catalysts.

Recent Advancements on Spin Engineering Strategies for Highly Efficient Electrocatalytic Oxygen Evolution Reactions.

Oxygen evolution reaction (OER) is a widely employed half-electrode reaction in oxygen electrochemistry, in applications such as hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. Unfortunately, its slow kinetics limits the commercialization of such applications. It is therefore highly imperative to develop highly robust electrocatalysts with high activity, long-term durability, and low noble-metal contents. Previously intensive efforts have been made to introduce the advancements on developing non-precious transition metal electrocatalysts and their OER mechanisms. Electronic structure tuning is one of the most effective and interesting ways to boost OER activity and spin angular momentum is an intrinsic property of the electron. Therefore, modulation on the spin states and the magnetic properties of the electrocatalyst enables the changes on energy associated with interacting electron clouds with radical absorbance, affecting the OER activity and stability. Given that few review efforts have been made on this topic, in this review, the-state-of-the-art research progress on spin-dependent effects in OER will be briefed. Spin engineering strategies, such as strain, crystal surface engineering, crystal doping, etc., will be introduced. The related mechanism for spin manipulation to boost OER activity will also be discussed. Finally, the challenges and prospects for the development of spin catalysis are presented. This review aims to highlight the significance of spin engineering in breaking the bottleneck of electrocatalysis and promoting the practical application of high-efficiency electrocatalysts.

A New Approach to Fuel Cell Electrodes: Lanthanum Aluminate Yielding Fine Pt Nanoparticle Exsolution for Oxygen Reduction Reaction

AbstractDesigning an electrocatalyst with low Pt content is an immediate need for essential reactions in low temperature fuel cell systems. In the present work, La0.9925Ba0.0075Al0.995Pt0.005O3 is aimed at using with low (only 0.5%) Pt doping as an electrocatalyst for oxygen reduction reaction (ORR). The low doping level renders exsolution of 1–2 nm nanoparticles with uniform dispersion upon reduction in H2/N2 at low temperatures. Pt exsolved perovskite oxides deliver significantly enhanced catalytic activity for ORR and improved stability in alkaline media. This study demonstrates that LaAlO3 with low noble metal content holds immense potential as an electrocatalyst in real fuel cell systems.

Solid-phase extractants based on carbon nanotubes for the concentration of noble metals from hydrochloric acid media

Effective solid-phase extractants (SPE) have been developed based on multi-walled carbon nanotubes (CNTs) of various structures modified with an organic reagent – 2-mercaptobenzothiazole. Using scanning and transmission electron microscopy, the morphological and structural features of SPE samples and their elemental composition were determined. It has been shown that the specific surface area of modified CNTs is approximately two times lower compared to the original CNTs. It was revealed that the modified materials are coils of CNTs coated with a uniform organic shell 10-15 nm thick. The sorption capacity of the original nanotubes in 1 M HCl and their modified forms (0.1-3.0 M HCl) at room temperature and at 80°C was determined. It was found that in strongly acidic media, SPE based on G-183 CNTs and 2-mercaptobenzothiazole is effective, which sorbs Pt, Pd and Au at room temperature, and also Ru and Rh at a temperature of 80°C. The possibility of selective extraction of platinum group metals and gold with this sorbent in the presence of macroquantities of Al, Fe, Cu, Ca and Mg was assessed.

Synthesis of low-cost multi-element Pt-based alloy nanoparticles as catalysts for the oxygen reduction reaction.

Due to their high catalytic activity, stability, and economic benefits, Pt-based multi-element alloyed nanoparticles (NPs) are considered promising electrodes for oxygen reduction reactions. However, a synthesis method capable of controlling the reduction reaction of elements with different redox potentials to synthesize multimetallic alloy NPs is yet to be developed. In this study, monodisperse NiPtPd alloy NPs with varying compositions were synthesized using 1-heptanol as a reducing solvent. The selection of low-reducing noble metal precursors and complexing agents is done strategically to adjust the reduction time of metal ions. The spectroscopic results confirmed that olelylamine (OAm) preferentially coordinates with Pt ions, while trioctylphosphine (TOP) preferentially coordinates with Pd ions. Consequently, control of the elemental distribution within the particle is successfully achieved by adjusting the OAm/Pt and TOP/Pd molar ratios. Subsequently, Ni78Pt11Pd11 alloy NPs were designed, and their catalytic properties as electrodes in the oxygen reduction reaction (ORR) were examined. Despite a low noble metal content of 22%, the catalytic performance and stability were superior to and comparable to those of commercial Pt NPs, respectively.

Lattice engineering of noble metal-based nanomaterials via metal-nonmetal interactions for catalytic applications.

Noble metal-based nanomaterials possess outstanding catalytic properties in various chemical reactions. However, the increasing cost of noble metals severely hinders their large-scale applications. A cost-effective strategy is incorporating noble metals with light nonmetal elements (e.g., H, B, C, N, P and S) to form noble metal-based nanocompounds, which can not only reduce the noble metal content, but also promote their catalytic performances by tuning their crystal lattices and introducing additional active sites. In this review, we present a concise overview of the recent advancements in the preparation and application of various kinds of noble metal-light nonmetal binary nanocompounds. Besides introducing synthetic strategies, we focus on the effects of introducing light nonmetal elements on the lattice structures of noble metals and highlight notable progress in the lattice strain engineering of representative core-shell nanostructures derived from these nanocompounds. In the meantime, the catalytic applications of the light element-incorporated noble metal-based nanomaterials are discussed. Finally, we discuss current challenges and future perspectives in the development of noble metal-nonmetal based nanomaterials.

Investigating the Effects on Replacing Platinum by Molybdenum as Cathode Electrocatalysts in Proton Exchange Membrane Water Electrolysis

Water electrolysis coupled to renewable energy sources has become in a crucial technique for the green hydrogen production. Hydrogen economy is currently in the spotlight to solve energy demands due to its advantages such as clean, sustainable, low footprint, as well as high-power density which is 3 times above gasoline and diesel. To produce large quantities of hydrogen, proton exchange membrane water electrolysis (PEMWE) has arisen as a promising system to solve hydrogen demands. The heart of the PEMWE consists in a membrane electrode assembly (MEA), where two gas diffusion layers (GDLs), hosting the respective catalysts, are sandwiched between an ionomer membrane. Commonly, noble metals are needed as catalyst in the anode (Ir, Ru) and cathode (Pt) to reach high current densities maintaining low cell voltages. The large content of noble metals, their high cost, and accelerated corrosion rates at high cell voltages are some drawbacks that limit the industrialization and commercialization of PEMWE technology. Replacing, decreasing, or simply extending the operational lifetime of these noble metals have a positive impact on the hydrogen economy. Molybdenum is an earth-abundant metal with low-cost which has been already used to produce highly active electrocatalysts, that can potentially replace Pt. However, most electrocatalytic studies are restricted to three-electrode cells with different operational conditions than those employed in PEM cells. The latter makes a complicated task to predict the performance of the catalyst and stability under relevant instrial applications. Here, we investigated the viability of using three selected Mo-based nanomaterials (1T’-MoS2, Co-MoS2, and ß-Mo2C) as potential electrocatalysts to replace Pt in PEMWE systems. We investigated the effects of replacing Pt in the catalyst loading, charge transfer resistance, kinetics, operational stability, and hydrogen production efficiency during PEMWE operation. Furthermore, we developed a methodology to identify the effects of tuning the cathode catalyst while keeping the anode catalyst in the overall kinetics of PEMWE system. Our results point that electrochemical performance in traditional open cell might not strictly predict the performance that could be seen in PEMWE cells due to differences in interfaces, contact between the components and porosity of the macroscopic catalyst layers. Among the catalyst studied, 1T’-MoS2 exhibited low overpotential associated to low charge transfer resistance while reaching 1 A cm-2 at 1.9 V. Our study highlights the importance to continue developing efficient electrocatalysts to replace noble metals suitable for PEMWE systems. Figure 1