A Biphasic Strategy to Synergistically Accelerate Activation and CO Spillover in Formic Acid Oxidation Catalysis.

Developing highly efficient and carbon monoxide (CO)-tolerant platinum (Pt) catalysts for the formic acid oxidation reaction (FAOR) is vital for direct formic acid fuel cells (DFAFCs), yet it is challenging due to the high energy barrier of direct intermediates (HCOO* and COOH*) as well as the CO poisoning issues associated with Pt alloy catalysts. Here we present a versatile biphasic strategy by creating a hexagonal/cubic crystalline-phase-synergistic PtPb/C (h/c-PtPb/C) catalyst to tackle the aforementioned issues. Detailed investigations reveal that h/c-PtPb/C can simultaneously facilitate the adsorption of direct intermediates while inhibiting CO adsorption, thereby significantly improving the activation and CO spillover. As a result, h/c-PtPb/C showcases an outstanding FAOR activity of 8.1 A mgPt-1, which is 64.5 times higher than that of commercial Pt/C and significantly surpasses monophasic PtPb. Moreover, the h/c-PtPb/C-based membrane electrode assembly exhibits an exceptional peak power density of 258.7 mW cm-2 for practical DFAFC applications.

Scalable Molten Salt Synthesis of Platinum Alloys Planted in Metal-Nitrogen-Graphene for Efficient Oxygen Reduction.

Fuel cells are considered as a promising alternative to the existing traditional energy systems towards a sustainable future. Nevertheless, the synthesis of efficient and robust platinum (Pt) based catalysts remains a challenge for practical applications. In this work, we present a simple and scalable molten-salt synthesis method for producing a low-platinum (Pt) nanoalloy implanted in metal-nitrogen-graphene. The as-prepared low-Pt alloyed graphene exhibits a high oxygen reduction activity of 1.29 A mgPt -1 and excellent durability over 30 000 potential cycles. The catalyst nanoarchitecture of graphene encased Pt nanoalloy provides a robust capability against nanoparticle migration and corrosion due to a strong metal-support interaction. Similarly, advanced characterization and theoretical calculations show that the multiple active sites in platinum alloyed graphene synergistically account for the improved oxygen reduction. This work not only provides an efficient and robust low-Pt catalyst but also a facile design idea and scalable preparation technique for integrated catalysts to achieve more profound applications in fuel cells and beyond.

PtCuNi Tetrahedra Catalysts with Tailored Surfaces for Efficient Alcohol Oxidation.

Direct methanol/ethanol alkaline fuel cells (DMAFCs/DEAFCs) represent an attractive mobile power generation technology. The methanol/ethanol oxidation reaction (MOR/EOR) often requires high-performance yet expensive Pt-based catalysts that may be easily poisoned. Herein, we report the development of PtCuNi tetrahedra electrocatalysts with optimized specific activity and mass activity for MOR and EOR. Our synthetic and structural characterizations show that these PtCuNi tetrahedra have Cu-rich core and PtNi-rich shell with tunable surface composition. Electrocatalytic studies demonstrate that Pt56Cu28Ni16 exhibits exceptional MOR and EOR specific activities of 14.0 ± 1.0 mA/cm2 and 11.2 ± 1.0 mA/cm2, respectively and record high mass activity of 7.0 ± 0.5 A/mgPt and 5.6 ± 0.6 A/mgPt, comparing favorably with the best MOR or EOR Pt alloy-based catalysts reported to date. Furthermore, we show that the unique core-shell tetrahedra configuration can also lead to considerably improved durability.

Integration Construction of Hybrid Electrocatalysts for Oxygen Reduction.

There is notable progress in the development of efficient oxygen reduction electrocatalysts, which are crucial components of fuel cells. However, these superior activities are limited by imbalanced mass transport and cannot be fully reflected in actual fuel cell applications. Herein, the design concepts and development tracks of platinum (Pt)-nanocarbon hybrid catalysts, aiming to enhance the performance of both cathodic electrocatalysts and fuel cells, are presented. This review commences with an introduction to Pt/C catalysts, highlighting the diverse architectures developed to date, with particular emphasis on heteroatom modification and microstructure construction of functionalized nanocarbons based on integrated design concepts. This discussion encompasses the structural evolution, property enhancement, and catalytic mechanisms of Pt/C-based catalysts, including rational preparation recipes, superior activity, strong stability, robust metal-support interactions, adsorption regulation, synergistic pathways, confinement strategies, ionomer optimization, mass transport permission, multidimensional construction, and reactor upgrading. Furthermore, this review explores the low-barrier or barrier-free mass exchange interfaces and channels achieved through the impressive multidimensional construction of Pt-nanocarbon integrated catalysts, with the goal of optimizing fuel cell efficiency. In conclusion, this review outlines the challenges associated with Pt-nanocarbon integrated catalysts and provides perspectives on the future development trends of fuel cells and beyond.

Low-Platinum-Content Exchange-Coupled CoPt Nanoalloys with Enhanced Magnetic Properties.

Bimetallic colloidal CoPt nanoalloys with low platinum content were successfully synthesized following a modified polyol approach. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) studies were performed to estimate the crystal structure, morphology, and surface functionalization of the colloids, respectively, while the room-temperature magnetic properties were measured using a vibrating sample magnetometer (VSM). The particles exhibit excellent uniformity, with a narrow size distribution, and display strong room-temperature hysteretic ferromagnetic behavior even in the as-made form. Upon annealing at elevated temperatures, progressive formation and co-existence of exchange coupled, of both chemically ordered and disordered phases significantly enhanced the room-temperature coercivity.

CD44-hyaluronan mediating endocytosis of iron-platinum alloy nanoparticles induces ferroptotic cell death in mesenchymal-state lung cancer cells with tyrosine kinase inhibitor resistance.

While tyrosine kinase inhibitor resistance in cancer is a critical issue in the medical field, it is important for clinical testing as well, since it affects the ultimate outcome of cancer therapy. Yet, no effective solutions have been implemented till date. Clinical observations after tyrosine kinase inhibitor treatment reveal that acquired resistance inevitably limits the curative effects of non-small cell lung cancer treatment because of mutations in the epidermal growth factor receptor gene, which are accompanied by epithelial-mesenchymal transition. Here, for the first time, we report that the transmembrane glycoprotein CD44, which is associated with epithelial-mesenchymal transition, chemoresistance, and cancer progression, mediates enhanced endocytosis of iron-platinum alloy nanoparticles (FePt NPs) in the mesenchymal-state gefitinib-resistant (GR+ and M6) cells, via the binding of the CD44 ligand, hyaluronan, to the surface-absorbed hyaluronan-binding protein 2. Upon treatment with FePt NPs, there was higher cellular uptake in mesenchymal-state GR+ and M6 cells, resulting from cell death through ferroptosis and mitochondrial dysfunction, as compared to that observed in the epithelial-state cells. Mechanistically, inactivation of dihydroorotate dehydrogenase elevated the production of mitochondrial lipid peroxidation, and enhanced the cell death in the epithelial-state HCC827 cells, thereby indicating its role in defense against FePt NPs-induced ferroptosis. Furthermore, induction of ferroptosis has been shown to specifically promote the cell death of drug-tolerant "persister" cells and reverse their resistance as well. Therefore, we concluded that FePt NPs preferentially target mesenchymal drug-tolerant "persister" cells and promote ferroptosis, to overcome their resistance. STATEMENT OF SIGNIFICANCE: In the present study, we identified FePt NPs as an innovative agent for cancer treatment, particularly in mesenchymal-state cells that exhibit TKI resistance. Mesenchymal-state cancer cells showed enhanced uptake of FePt NPs via CD44-HA-mediated endocytosis, accompanied by severe cell death and mitochondrial morphology alterations, in comparison to epithelial-state cells. We further elucidated the mechanism underlying FePt NPs-induced ferroptotic cell death as via a burst of mitochondrial LPO and DHODH protein inactivation. In addition, we found that FePt NPs inhibit tumor growth in TKI-resistant mesenchymal GR+ cell-bearing mice with better efficacy than the ferroptotic inducer RSL3. Our current findings on using FePt NPs to overcome TKI resistance through ferroptosis activation may offer a alternative strategy for improved cancer treatment.

Exploring the Potential of Bimetallic PtPd/C Cathode Catalysts to Enhance the Performance of PEM Fuel Cells.

Bimetallic platinum-containing catalysts are deemed promising for electrolyzers and proton-exchange membrane fuel cells (PEMFCs). A significant number of laboratory studies and commercial offers are related to PtNi/C and PtCo/C electrocatalysts. The behavior of PtPd/C catalysts has been studied much less, although palladium itself is the metal closest to platinum in its properties. Using a series of characterization methods, this paper presents a comparative study of structural characteristics of the commercial PtPd/C catalysts containing 38% wt. of precious metals and the well-known HiSpec4000 Pt/C catalyst. The electrochemical behavior of the catalysts was studied both in a three-electrode electrochemical cell and in the membrane electrode assemblies (MEAs) of hydrogen-air PEMFCs. Both PtPd/C samples demonstrated higher values of the electrochemically active surface area, as well as greater specific and mass activity in the oxygen reduction reaction in comparison with conventional Pt/C, while not being inferior to the latter in durability. The MEA based on the best of the PtPd/C catalysts also exhibited higher performance in single tests and long-term durability testing. The results of this study conducted indicate the prospects of using bimetallic PtPd/C materials for cathode catalysts in PEMFCs.

Bacterial adhesion affinities of various implant abutment materials.

OBJECTIVES: To investigate bacterial adhesion to various abutment materials. MATERIAL AND METHODS: Thirty volunteers participated in this study. Resin splints were fabricated, and five types of disks were fabricated from pure titanium, gold-platinum alloy, zirconia, alumina, and hydroxyapatite with uniform surface roughness and attached to the buccal surface of each splint. After 4 days of use by the subjects, the plaque accumulated on the disk surfaces was analyzed. The bacterial community structure was evaluated using 16S rRNA gene profiling with terminal restriction fragment length polymorphism analysis. The total bacterial count on each disk was estimated using quantitative polymerase chain reaction. RESULTS: Terminal restriction fragment length polymorphism profiles were more similar between tested materials than between subjects, suggesting that the bacterial community structures on the abutment material were influenced more by the individuals than by the type of material. However, the total number of bacteria attached to a disk was significantly different among five materials (P < 0.001, Brunner-Langer test for longitudinal data). Fewer bacteria were attached to the gold-platinum alloy than to the other materials. CONCLUSIONS: Gold-platinum alloy appears to be useful material for abutments when considering the accumulation of plaque. However, alternative properties of the abutment material, such as effects on soft tissue healing, should also be taken into consideration when choosing an abutment material.

Nitrogen-Doped PtNi Catalysts on Polybenzimidazole-Functionalized Carbon Support for the Oxygen Reduction Reaction in Polymer Electrolyte Membrane Fuel Cells.

PtM (M = 3d transition metals) alloys are known as the promising oxygen reduction reaction catalysts and have been considered as the replacement of pure Pt catalysts for the commercialization of proton exchange membrane fuel cells. Although great progress has been made in the past three decades, the performance and durability of PtM catalysts still face stringent challenges from practical applications. Functionalization of a catalyst carbon support with nitrogen-contained groups can add charges onto its surface, which can be utilized to build a more complete ionomer/catalyst interface, to reduce the catalyst particle size, and to improve particle size distribution. Nitriding of PtNi catalysts can effectively improve the catalyst activity and stability by the modification of lattice strain. Hereby, we propose a synergistic approach of combining polybenzimidazole-grafted Vulcan XC72 carbon as the catalyst carbon support and the nitriding of PtNi to develop PtNiN/XC72-polybenzimidazole catalysts. Such PtNiN/XC72-PBI catalysts exhibit the excellent performance of fuel cell membrane electrode assembly (i.e., mass activity, 440 mA mgPt-1; electrochemical surface area, 51 m2 gPt-1; and rated power density, 836 mW cm-2) as well as promising catalyst stability. The developed PtNiN/XC72-PBI meets the US DOE 2020 targets of mass activity for the fuel cell catalysts. This work provides a novel approach and a promising pathway on the development of the catalyst using such a synergistic approach─modification of the catalyst structure by nitrogen doping and functionalization of carbon support by polybenzimidazole for both high performance and high durability.

Synergistic Hybrid Electrocatalysts of Platinum Alloy and Single-Atom Platinum for an Efficient and Durable Oxygen Reduction Reaction.

Pt single-atom materials possess an ideal atom economy but suffer from limited intrinsic activity and side reaction of producing H2O2 in catalyzing the oxygen reduction reaction (ORR); platinum alloys have higher intrinsic activity but weak stability. Here, we demonstrate that anchoring platinum alloys on single-atom Pt-decorated carbon (Pt-SAC) surmounts their inherent deficiencies, thereby enabling a complete four-electron ORR pathway catalysis with high efficiency and durability. Pt3Co@Pt-SAC demonstrates an exceptional mass and specific activities 1 order of magnitude higher than those of commercial Pt/C. They are durable throughout 50000 cycles, showing only a 10 mV decay in half-wave potential. An in situ Raman analysis and theoretical calculations reveal that Pt3Co core nanocrystals modulate electron structures of the adjacent Pt single atoms to facilitate the intermediate absorption for fast kinetics. The superior durability is attributed to the shielding effect of the Pt-SAC coating, which significantly mitigates the dissolution of Pt3Co cores. The hybridizing strategy might promote the development of highly active and durable ORR catalysts.

Toward a Comprehensive Understanding of Cation Effects in Proton Exchange Membrane Fuel Cells.

Metal alloy catalysts (e.g., Pt-Co) are widely used in fuel cells for improving the oxygen reduction reaction kinetics. Despite the promise, the leaching of the alloying element contaminates the ionomer/membrane, leading to poor durability. However, the underlying mechanisms by which cation contamination affects fuel cell performance remain poorly understood. Here, we provide a comprehensive understanding of cation contamination effects through the controlled doping of electrodes. We couple electrochemical testing results with membrane conductivity/water uptake measurements and impedance modeling to pinpoint where and how the losses in performance occur. We identify that (1) ∼44% of Co2+ exchange of the ionomer can be tolerated in the electrode, (2) loss in performance is predominantly induced by O2 and proton transport losses, and (3) Co2+ preferentially resides in the electrode under wet operating conditions. Our results provide a first-of-its-kind mechanistic explanation for cation effects and inform strategies for mitigating these undesired effects when using alloy catalysts.

Direct integration of ultralow-platinum alloy into nanocarbon architectures for efficient oxygen reduction in fuel cells.

Developing efficient platinum (Pt)-based electrocatalysts is enormously significant for fuel cells. Herein, we report an integrated electrocatalyst of ultralow-Pt alloy encapsulated into nitrogen-doped nanocarbon architecture for efficient oxygen reduction reaction. This hybrid Pt-based catalyst achieves a mass activity of 3.46 A mgpt-1 at the potential of 0.9 V vs. RHE with a negligible stability decay after 10,000 cycles. More importantly, this half-cell activity can be expressed at full cell level with a high Pt utilization of 10.22 W mgPt-1cathode and remarkable durability after 30,000 cycles in single-cell. Experimental and theoretical investigations reveal that a highly strained Pt structure with an optimal Pt-O binding energy is induced by the incorporation of Co/Ni into Pt lattice, which would account for the improved reaction kinetics. The synergistic catalysis due to nitrogen-doped nanocarbon architecture and active Pt component is responsible for the enhanced catalytic activity. Meanwhile, the strong metal-support interaction and optimized hydrophilic properties of nanocarbon matrix facilitate efficient mass transport and water management. This work may provide significant insights in designing the low-Pt integrated electrocatalysts for fuel cells and beyond.

3D CoPt nanostructures hybridized with iridium complexes for multimodal imaging and combined photothermal-chemotherapy.

Combined photothermal-chemotherapy has shown great potential in improving the efficiency of tumor treatment. In this article, we have designed a new type of nanocomposite Ir-CoPt-PVP composed of cobalt/platinum alloy nanoparticles (CoPt) and iridium(III) complex (Ir) for combined photothermal therapy (PTT) and chemotherapy. The obtained CoPt was synthesized by a simple solvothermal method and modified by polyvinyl pyrrolidone (PVP), which exhibited excellent photothermal efficiency and stability, and can also be a bimodal bioimaging contrast agent in photothermal imaging (PTI) and photoacoustic imaging (PAI). Furthermore, the combination therapy has shown obvious tumor cell-growth inhibition in vitro. Overall, the results revealed the great potential of Ir-CoPt-PVP nanocomposites in improving therapeutic efficiency by photothermal-chemotherapy and photothermal/photoacoustic imaging.

Au Nanoparticles Modified with Pt, Ru and SnO2 as Electrocatalysts for Ethanol Oxidation Reaction in Acids.

The anodic reaction in direct ethanol fuel cells (DEFCs), ethanol oxidation reaction (EOR) faces challenges, such as incomplete electrooxidation of ethanol and high cost of the most efficient electrocatalyst, Pt in acidic media at low temperature. In this study, core-shell electrocatalysts with an Au core and Pt-based shell (Au@Pt) are developed. The Au core size and Pt shell thickness play an important role in the EOR activity. The Au size of 2.8 nm and one layer of Pt provide the most optimized performance, having 6 times higher peak current density in contrast to commercial Pt/C. SnO2 as a support also enhances the EOR activity of Au@Pt by 1.73 times. Further modifying the Pt shell with Ru atoms achieve the highest EOR current density that is 15 and 2.5 times of Pt/C and Au@Pt. Our results suggest the importance of surface modification in rational design of advanced electrocatalysts.

NiPt Nanoparticles Anchored onto Hierarchical Nanoporous N-Doped Carbon as an Efficient Catalyst for Hydrogen Generation from Hydrazine Monohydrate.

Catalytic decomposition of the hydrogen-rich hydrazine monohydrate (N2H4·H2O) represents a promising hydrogen storage/production technology. A rational design of advanced N2H4·H2O decomposition catalysts requires an overall consideration of intrinsic activity, number, and accessibility of active sites. We herein report the synthesis of a hierarchically nanostructured NiPt/N-doped carbon catalyst using a three-step method that can simultaneously address these issues. The chelation of metal precursors with polydopamine and thermolysis of the resulting complexes under reductive atmosphere resulted in a concurrent formation of N-doped carbon substrate and catalytically active NiPt alloy nanoparticles. Thanks to the usage of a silica nanosphere template and dopamine precursor, the N-doped carbon substrate possesses a hierarchical macroporous-mesoporous architecture. This, together with the uniform dispersion of tiny NiPt nanoparticles on the carbon substrate, offers opportunity for creating abundant and accessible active sites. Benefiting from these favorable attributes, the NiPt/N-doped carbon catalyst enables a complete and rapid hydrogen production from alkaline N2H4·H2O solution with a rate of 1602 h-1 at 50 °C, which outperforms most existing catalysts for N2H4·H2O decomposition.

Icosahedral Pt-Ni Nanocrystalline Electrocatalyst: Growth Mechanism and Oxygen Reduction Activity.

Engineering the structure of Pt alloy offers an effective way to the design of high performance electrocatalysts. Herein, we synthesize a sandwich-structured, icosahedral Pt2.1 Ni catalyst through a hot injection method. Its growth involves three steps: 1) burst nucleation of Pt atoms to form a Pt-enriched core, 2) heterogeneous nucleation of Ni atoms onto the Pt core to form a Ni-enriched interlayer, and 3) kinetic controlled growth of a Pt-enriched shell. The Pt-enriched core protects the nanostructure from collapse and mitigates the strain change caused by lattice mismatch, and thus enhances the stability of the structure. The Ni-enriched interlayer induces the electronic modification of the outermost Pt shell, and in turn tunes the activity. The Pt-enriched shell provides more active sites through the exposure of (1 1 1) facets and retards the dissolution of Ni atoms. As a result, this sandwich-structure enables impressive electrocatalytic activity (0.91 mA cm-2 and 0.32 AmgPt-1 @ 0.9 V) and duability.

Oxide layer characteristics and interfacial analysis of porcelain fused to high-gold alloy using multitechnique analysis methods.

BACKGROUND/PURPOSE: In a previous fractural study, high-gold crowns possessed the second highest fracture force. The objective of this study is to analyze the interface of porcelain fused to high-gold alloy using different observation devices. MATERIALS AND METHODS: High-gold crowns specimens with the morphology of a maxillary second premolar were compressed vertically in the center of the occlusal surface until fracture using a universal testing machine. The fractured surfaces were examined using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM/EDX) to determine the failure mode. The ceramic-metal interface of the crown was examined with electron probe microanalysis (EPMA). In addition, sheet specimens with dimensions of 10 × 9 × 4 mm3 were prepared to examine the surface morphology and composition of high-gold alloy after oxidation using X-ray photoelectron spectrometer (XPS). RESULTS: The average fracture force was 1368 ± 312 N. Photograph of fractured crown and SEM/EDX analyses reveal that the crown initially suffered from cohesive failure in the upper and middle regions, with the fracture occurring mostly within the ceramic. XPS results and both EPMA color photomicrographs of crown and sheet specimens show that indium was observed along the porcelain-metal interface with a 1- to 2-µm disrupted zone of oxide layer. CONCLUSION: In2O3 and Au were found along the interface from the multitechnique analysis methods; the presence of this oxide at the boundary promotes ceramic-metal adhesion. In2O3 is suggested to be beneficial for the second highest fracture resistance in a previous fractural study of implant-supported crowns.