Bimetallic Platinum Research Articles

Luminescent Platinum(II) Complexes with Stimuli-Responsive Flexible Lewis Pair Ligands: Spectroscopic and Computational Studies.

A series of new luminescent bimetallic platinum(II) complexes with stimuli-responsive flexible Lewis pair (FlexLP) ligands are described. The FlexLP ligands consist of a dimesitylboron Lewis acid and diphenylphosphine oxide Lewis base which are in equilibrium between the unbound open form and the Lewis adduct, controlled by the hydrogen bond donating strength of the solvent. Spectroscopic techniques and density functional theory (DFT) calculations were used to interpret the photophysics of the platinum(II) complexes. All complexes exhibit tunable absorption in the region of 300-500 nm and green to orange photoluminescence, depending on the ratio of weak (THF) to strong (MeOH) hydrogen bond donating solvent employed. Spectroscopic and computational data shows that phosphine and peripheral acetylide ligands on the platinum(II) centers have limited influence on the emission energy, indicating the emission originates from the FlexLP-dominated fluorescence. Using time-resolved transient absorption spectroscopy it is shown that the complexes undergo intersystem crossing (ISC) to the triplet excited state upon photoexcitation, and the ISC efficiency is affected by the peripheral acetylide ligands. The triplet excited state lifetime can also be manipulated by the state of the FlexLP ligand, with the closed form complexes having longer lifetimes than the open form complexes.

Dinuclear platinum(ii) complexes with biphenyl-based bis-carbene ligands

New bimetallic platinum(ii) complexes with bis-NHC donor ligands featuring 4,4′-di-substitution pattern of the central biphenyl ring have been presented. The complex [2] has been tested as precatalyst in PtII-catalyzed cycloisomerization of enyne.

Bimetallic platinum rhenium catalyst for efficient low temperature dehydrogenation of perhydro benzyltoluene

H2 release from the liquid organic hydrogen carrier perhydro benzyltoluene (H12-BT) was accelerated using bimetallic Pt–Re/Al2O3 catalysts. An optimum Pt : Re ratio was identified and catalysts characterisation provided insight on Pt–Re interaction.

Highly sensitive electrochemical peptide-based biosensor for marine biotoxin detection using a bimetallic platinum and ruthenium nanoparticle-tethered metal-organic framework modified electrode.

Saxitoxin (STX) is a highly toxic small-molecule cyanotoxin that is water-soluble, stable in acidic media, and thermostable. STX is hazardous to human health and the environment in ocean, thus it is an important to detect it at very low concentrations. Herein, we developed an electrochemical peptide-based biosensor for the trace detection of STX in different sample matrix utilizing differential pulse voltammetry (DPV) signal. We synthesized the nanocomposite of zeolitic imidazolate framework-67 (ZIF-67) decorated bimetallic platinum (Pt) and ruthenium (Ru) nanoparticles (Pt-Ru@C/ZIF-67) using impregnation method. The nanocomposite modified with screen-printed electrode (SPE) was subsequently used to detect STX in the range of 1-1,000ngmL-1, with a detection limit (LOD) of 26.7pgmL-1. The developed peptide-based biosensor is highly selective and sensitive towards STX detection, thus it represents a promising strategy for the development of novel portable bioassay for monitoring various hazardous molecules in aquatic food chains.

Melamine Modification of the Carrier Regulating the Performance of PtBi/AC in Heptanol Oxidation

AbstractDifferent bimetallic platinum and bismuth catalysts supported on melamine‐modified activated carbon (AC) are designed by a co‐impregnation method. Through controlling the activation temperatures of the melamine−AC mixture, a series of N‐doped and C3N4‐modified AC (N−AC and C3N4−AC) are prepared. Combined powder X‐ray diffractions, X‐ray photoelectron spectroscopic, and high‐angle annual dark‐field scanning transmission electron microscopic studies demonstrate that the introduction of C3N4 favors the formation of PtBi alloy and leads to increased particle sizes in comparison to the pristine and N‐doped AC‐supported bimetallics. The catalytic performance of the developed catalysts is evaluated in the oxidation of n‐heptanol oxidation in a batch mode using O2 as the oxidant. PtBi/C3N4−AC exhibits significantly boosted activity as well as selectivity to heptanoic acid as compared with the other catalysts. A high yield of heptanoic acid of 69 % can be achieved under the optimized reaction conditions. Furthermore, our work points to the PtBi alloy as the most active sites for the alcohol oxidation. Catalyst deactivation occurs in the cycling tests, mainly due to the collapse of the alloy phase and likely the decrease in particle sizes.

Printed, Flexible, Ionic Liquid-Based Hydrogen Sensor via Aerosol Jet Printing of Nanomaterials

Low-cost, high-performance hydrogen sensors are highly demanded in hydrogen leakage detection. To increase the sensitivity and reliability of the hydrogen sensor, an ionic liquid (IL)-based electrochemical gas sensor is fabricated with bimetallic Platinum–Nickel (Pt-Ni) nanoparticles (NPs) with aerosol jet printing technology for continuous monitoring of hydrogen concentration. The Pt-Ni NPs covering the top surface of the metal electrodes can accelerate the catalysis and expand the sensing surface area. When hydrogen gas is sensed at room temperature, the uniquely reversible and rapid redox reactions of hydrogen at the IL/Pt electrode interface, thereby creating continuous measurement capability in a real-time manner with little signal drift. The full coverage of the sensor electrodes will increase the robustness and accuracy of the device. The fabricated sensors demonstrate excellent analytical sensing performance, reaching a limit of detection up to 19.3 ppm. The device takes advantage of an easy fabrication process, simple structure, high sensing response, and low cost, providing a promise for hydrogen sensing at room temperatures.

Anti-Cancer and Radio-Sensitizing Properties of New Bimetallic (N-Heterocyclic Carbene)-Amine-Pt(II) Complexes.

Bioactive NHC-transition metal complexes have shown promise as anti-cancer agents, but their potential use as radiosensitizers has been neglected so far. We disclose here a new series of bimetallic platinum(II) complexes displaying NHC-type bridging ligands, (bis-NHC)[trans-Pt(RNH2)I2]2, that have been synthesized via a simple, two-step procedure. They display cytotoxicity in the micromolar range on cancerous cell lines, accumulate in cells, and bind to genomic DNA, by inducing DNA damages. Notably, these bimetallic complexes demonstrate significant radiosensitizing effects on both ovarian cells A2780 and nonsmall lung carcinoma cells H1299. Further investigations revealed that bimetallic species make irradiation-induced DNA damages more persistent by inhibiting repair mechanisms. Indeed, a higher and persistent accumulation of both γ-H2AX and 53BP1 foci post-irradiation was detected, in the presence of the NHC-Pt complexes. Overall, we provide the first in vitro evidence for the radiosensitizing properties of NHC-platinum complexes, which suggests their potential use in combined chemo-radio therapy protocols.

Restructured zeolites anchoring singly dispersed bimetallic platinum and zinc catalysts for propane dehydrogenation

Restructuring of a heterogeneous catalyst under reaction conditions is a common phenomenon. Severe restructuring of a catalyst can result in deactivation in many catalytic systems—for example, the catalytic dehydrogenation of propane to propylene. Herein, we report the utilization of catalyst restructuring to improve activity and stability for the propane dehydrogenation reaction. A bimetallic platinum and zinc (Pt1Znm) catalyst protected by an in situ restructured silicalite-1 zeolite is prepared. The catalyst yields outstanding activity (initial conversion of ∼69.2%, initial selectivity of ∼91.1%) with high stability at 580°C, which is better than several commercial catalysts. Characterization shows the singly dispersed bimetallic sites of Pt1Znm serve as the catalytic sites during the reaction. Moreover, the less-stable silicalite-1 zeolite undergoes restructuring during the dehydrogenation reaction, forming a crucial protective layer on the Pt1Znm bimetallic nanocatalysts.

Controlling the Triplet Potential Energy Surface of Bimetallic Platinum(II) Complex by Constructing Structure-Property Relationship: A Theoretical Exploration.

For phosphorescent materials, managing the triplet potential energy surface stands for controlling the phosphorescence quantum yield. However, due to the complexity and variability, the triplet potential energy surface can be managed with difficulty. In this work, a series of bimetallic Pt(II) complexes, namely Pt-1, Pt-1-1, Pt-1-2, Pt-2, Pt-3-5, and Pt-6-7, are employed as models to construct a relationship between the structures and triplet potential energy surfaces, aiming to achieve meaningful information to manage the triplet potential energy surface. On the basis of the results, it is observed that the triplet potential energy surface has an intimate connection with the structures of bimetallic Pt(II) complexes. In the case of the primordial Pt(II) complex, the triplet potential energy surface consists of two minimal points, illustrating various properties, which can largely affect the phosphorescence quantum yield. Once the intramolecular steric hindrance, restriction effect, and metallophilic interaction (Pt-Pd/Pd-Pd) are employed by tailoring the structures of primordial Pt(II) complexes, the triplet potential energy surface can be reconstructed via one minimal point-charactered short metal-metal distance, resulting in different photophysical properties. The relationship between the triplet potential energy surface and structure is essentially unveiled from the structural and electronic viewpoints. The conclusions originated from the structural and electronic investigations can be regarded as indicators to accurately and expediently predict the triplet potential energy surfaces of bimetallic Pt(II) complexes. The results presented here are helpful in addressing the designed strategies as they show that the triplet potential energy surfaces of bimetallic Pt(II) complexes can be properly tuned.

Lignin-derived bimetallic platinum group metal-free oxygen reduction reaction electrocatalysts for acid and alkaline fuel cells

Metal-nitrogen-carbons (M-N-Cs) as a reliable substitution for platinum-group-metals (PGMs) for oxygen reduction reaction (ORR) are emerging candidates to rationalize the technology of fuel cells. The development of M-N-Cs can further be economized by consuming waste biomass as an inexpensive carbon source for the electrocatalyst support. Herein, we report the simple fabrication and in-depth characterization of electrocatalysts using lignin-derived activated char. The activated char (LAC) was functionalized with metal phthalocyanine (FePc and MnPc) via atmosphere-controlled pyrolysis to produce monometallic M-N-Cs (L_Mn and L_Fe) and bimetallic M1-M2-N-Cs (L_FeMn) electrocatalysts. Raman spectroscopy and transmission electron microscopy (TEM) revealed a defect-rich architecture. XPS confirmed the coexistence of various nitrogen-containing active moieties. L_Fe and L_FeMn demonstrated appreciable ORR in both acidic and alkaline conditions whereas L_FeMn helped in restricting the peroxide yield, particularly in alkaline media. L_Fe and L_FeMn demonstrated remarkable onset potential (Eonset) of ∼0.942 V (vs RHE) with an E1/2 of 0.874 V (vs RHE) in 0.1 M KOH. In acid, L_FeMn had an Eonset of 0.817 V (vs RHE) and an E1/2 of ∼0.76 V (vs RHE). Finally, the L_FeMn as a cathode electrocatalyst was integrated and tested in PEMFC and AEMFC. AEMFC demonstrated optimistic performance with a peak power density of 261 mW cm−2 at the current density of ∼577 mA cm−2.

Phosphorescent Bimetallic C^C* Platinum(ii) Complexes with Bridging Substituted Diphenylformamidinates.

A series of phosphorescent bimetallic platinum(II) complexes is presented, which were synthesized by the combination of bidentate cyclometalated N-heterocyclic carbene ligands and different bridging diphenylformamidinates. The complexes were characterized by standard techniques and additionally two solid-state structures could be obtained. Photoluminescence measurements revealed the strong emissive behavior of the compounds with quantum yields of up to 90 % and emission lifetimes of approx. 2 μs. The effect of the substitution pattern in the bridging ligands on the structural and photophysical properties of the complexes was examined in detail and rationalized by density functional theory calculations (PBE0/6-311G*).

Bimetallic platinum–ruthenium nanoparticles immobilized on reduced graphene oxide-TiO2 (RGO-TiO2) support for ethanol electro oxidation in acidic media

The present work addresses the potentialities of Pt–Ru nanoparticles deposited on a graphene oxide (RGO) and TiO2 composite support towards electrochemical oxidation of ethanol in acidic media relevant for fuel cell applications. To immobilize platinum–ruthenium bimetallic nanoparticles on to an RGO-TiO2 nanohybrid support a simple solution-phase chemical reduction method is utilized. An examination using electron microscopy and energy dispersive X-ray spectroscopy (EDS) indicated that Pt–Ru particles of 4–8 nm in diameter are dispersed on RGO-TiO2 composite support. The corresponding Pt–Ru/RGO-TiO2 nanocomposite electrocatalyst was studied for the electrochemical oxidation of ethanol in acidic media. Compared to the commercial Pt–Ru/C and Pt/C catalysts, Pt–Ru/RGO-TiO2 nanocomposite yields higher mass-specific activity of about 1.4 and 3.2 times, respectively towards ethanol oxidation reaction (EOR). The synergistic boosting provided by RGO-TiO2 composite support and Pt–Ru ensemble together contributed to the observed higher EOR activity and stability to Pt–Ru/RGO-TiO2 nanocomposite compared with other in-house synthesized Pt–Ru/RGO, Pt/RGO and commercial Pt–Ru/C and Pt/C electrocatalysts. Further optimization of RGO-TiO2 composite support provides opportunity to deposit many other types of metallic nanoparticles onto it for fuel cell electrocatalysis applications.

Effects of second metals (M = Fe, Cu, Ga, In, Sn) on the geometric and electronic properties of platinum for the direct dehydrogenation of propane

Supported Pt-based bimetallic catalysts are representative types of dehydrogenation catalysts used for alkanes to olefins conversion. The platinum in these catalysts exhibits unique structural features accompanied with changes in electronic states due to the addition of the second metal. To investigate the impact of each effect on the activity for propane dehydrogenation, a series of Pt-M/SiO 2 (M= Fe, Cu, Ga, In and Sn) catalysts were prepared and used for propane dehydrogenation. Utilizing various characterization techniques, the geometric and electronic properties of these catalysts were studied. The relationships between the specific activity of bimetallic platinum catalysts in propane dehydrogenation and atomic sizes of alloys (i) and the total density of unoccupied d bands in platinum (ii) were considered. Via alloy formation, it was found that dilution of the active metal Pt occurred in these SiO 2 supported bimetallic catalysts, and the lattice parameter of Pt-M alloys decreased on Pt-Fe, Pt-Cu and Pt-Ga alloys, but increased on Pt-In and Pt-Sn alloys when compared with that of Pt foil. Catalytic activity was evidently shown to not be a function of the lattice parameters of Pt-M alloys, but appears closely related with the d -holes of Pt in Pt-M bimetallic catalysts. More d holes show favorably high activity. Among the studied Pt-M/SiO 2 (M= Fe, Cu, Ga, In and Sn) catalysts, the prominent and primary role of the electronic effect was demonstrated. • Mansour’method was used to quantitatively determine the electronic state of Pt. • Pt-Ga/SiO 2 catalyst exhibits biggest d -holes and highest initial conversion of propane. • The electronic effect plays a crucial role in studied systems.

DNA Conformational Changes Induced by Its Interaction with Binuclear Platinum Complexes in Solution Indicate the Molecular Mechanism of Platinum Binding.

Platinum anticancer drugs inhibit the division of cancer cells through a DNA binding mechanism. The bimetallic platinum compounds have a possibility for blocking DNA replication via the cross-linking of DNA functional groups at different distances. Many compounds with metals of the platinum group have been tested for possible antitumor activity. The main target of their biological action is a DNA molecule. A combined approach to the study of the interaction of DNA with biologically active compounds of this type is proposed. The capabilities of various methods (hydrodynamic, spectral, microscopy) in obtaining information on the type of binding of coordination compounds to DNA are compared. The analysis of DNA binding with platinum binuclear compounds containing pyrazine, tetrazole, 5- methyltetrazole, 3-propanediamine as bridging ligands in a solution was carried out with the methods of circular dichroism (CD), luminescent spectroscopy (LS), low gradient viscometry (LGV), flow birefringence (FB) and atomic force microscopy (AFM). The competitive binding of different platinum compounds to DNA and the analysis of platinum attachment to DNA after protonation of its nitrogen bases simply indicates the involvement of N7 guanine in binding. Fluorescent dye DAPI was also used to recognize the location of platinum compounds in DNA grooves. DNA conformational changes recorded by variations in persistent length, polyelectrolyte swelling, DNA secondary structure, and its stability clarify the molecular mechanism of the biological activity of platinum compounds.

Electrocatalysts for the Oxygen Reduction Reaction: From Bimetallic Platinum Alloys to Complex Solid Solutions

The oxygen reduction reaction has been the object of intensive research in an attempt to improve the sluggish kinetics that limit the performance of renewable energy storage and utilization systems. Platinum or platinum bimetallic alloys are common choices as the electrode material, but prohibitive costs hamper their use. Complex alloy materials, such as high-entropy alloys (HEAs), or more generally, multiple principal component alloys (MPCAs), have emerged as a material capable of overcoming the limitations of platinum and platinum-based materials. Theoretically, due to the large variety of active sites, this new kind of material offers the opportunity to identify experimentally the optimal binding site on the catalyst surface. This review discusses recent advances in the application of such alloys for the oxygen reduction reaction and existing experimental challenges in the benchmarking of the electrocatalytic properties of these materials.

Homo and heterobimetallic palladium and platinum complexes bearing μ-diphosphane bridges involved in biological studies.

Given the increasing reports of well-defined bimetallic molecular complexes as potential anticancer agents in the last decades, along with the prevalence of platinum in anticancer therapy, we report here a detailed survey of bimetallic platinum and palladium complexes investigated as potential anticancer agents. Specifically, we will concentrate on the synthesis, characterisation and biological (anticancer) studies of a sub-class of these agents, namely homo and heterobimetallic complexes bearing a bridging phosphane ligand of the type: [LnM1(μ-R2P(CH2)nPR2)M2Lm] (where M1 is platinum or palladium, M2 is any other transition metal, R=alkyl or aryl substituents, Ln or Lm are co-ligands, n=1-6). We will review the invitro and invivo activities and any mechanistic anticancer studies of these complexes with a view of trying to delineate patterns in biological activity and structure-activity relationships (SAR). We do not include the review of bimetallic complexes in this class that have not undergone any anticancer testing, nor those that have been involved in other biological investigations unrelated to cancer studies.

General Design Rules for Bimetallic Platinum(II) Complexes.

A series of platinum(II) bimetallic complexes were studied to investigate the effects of ligands on both the geometric and electronic structure. Modulating the Pt-Pt distance through the bridging ligand architecture was found to dictate the nature of the lowest energy electronic transitions, localized in one-half of the molecule or delocalized across the entire molecule. By reducing the separation between the platinum atoms, the lowest energy electronic transitions will be dominated by the metal-metal-to-ligand charge transfer transition. Conversely, by increasing the distance between the platinum atoms, the lowest electronic transition will be largely localized metal-to-ligand charge transfer or ligand centered in nature. Additionally, the cyclometalating ligands were observed to have a noticeable stabilizing effect on the triplet excited states as the conjugation increased, arising from geometric reorientation and increased electron delocalization of the ligands. Such stabilization of the triplet state energy has been shown to alter the excited state potential energy landscape as well as the excited state trajectory.

Hydrodeoxygenation of Isoeugenol over Carbon-Supported Pt and Pt–Re Catalysts for Production of Renewable Jet Fuel

A series of monometallic platinum and bimetallic platinum–rhenium catalysts supported on mesoporous carbon Sibunit, which is a type of mesoporous, microcrystalline carbon, were investigated for hydrodeoxygenation (HDO) of isoeugenol (IE) at 200–300 °C and 30 bar of H2, using dodecane as a solvent. Catalytic activity was tested in a batch reactor to screen the catalysts and, for comparison, also in the continuous mode. For batch experiments, complete conversion, and a high yield of the desired product, propylcyclohexane (PCH), were obtained for all bimetallic PtRe/Sibunit in 240 min, with the highest yield of PCH when Pt:Re ratio was 1:1 or 1:3. The results for Pt–Re (1:1) were reproducible, in terms of catalytic activity and reusability of catalysts, which showed no deactivation. Monometallic Pt catalysts displayed low activity. Continuous experiments were performed with PtRe(1:1)/Sibunit at 30 bar H2, 0.5 mL/min of the liquid flow, and temperatures between 75 °C and 200 °C. The distribution of products showed deoxygenation at higher temperatures, while at lower temperatures, mainly oxygenated products were formed. XPS results confirmed the presence of ReOx species, where an increase in the platinum loading resulted in a decrease in the fraction of ReOx species and subsequently lower PCH yield.

Theoretical and Experimental Study of Optical Response of Bimetallic Platinum and Gold Nanoparticles: Nanoalloys and Core/Shell Configurations

Theoretical and Experimental Study of Optical Response of Bimetallic Platinum and Gold Nanoparticles: Nanoalloys and Core/Shell Configurations

Platinum–Nickel Bimetallic Nanosphere–Ionic Liquid Interface for Electrochemical Oxygen and Hydrogen Sensing

By exploiting the benefits of bimetallic platinum–nickel (Pt–Ni) alloy nanosphere and an ionic liquid (IL) (i.e., 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BmpyNTf2), an organic–inorganic hybrid interface of IL/Pt–Ni was designed and characterized for electrochemical sensing of oxygen and hydrogen gases for miniaturized electrochemical gas sensor development. The spherical Pt–Ni alloy nanoparticles (NPs) were synthesized through template-free, one-pot solvothermal method. The morphology, crystal structure, and chemical composition of Pt–Ni alloy NPs were thoroughly characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The obtained Pt–Ni alloy NPs were used to fabricate the planar sensor devices and tested for oxygen and hydrogen sensing. The oxygen-sensing performance of the resulting planar electrochemical sensor was investigated over a low concentration range of 500–5000 ppm of O2 at room temperature by using constant potential amperometry. The planar electrochemical sensor device exhibited a high sensitivity to O2 ((3.04 ± 0.18) × 10–5 mA cm–2 ppm–1) compared to commercial Pt/C-based sensor ((2.57 ± 0.22) × 10–5 mA cm–2 ppm–1). The planar electrochemical sensor device also showed good reproducibility and selectivity for oxygen detection during sensing tests. Moreover, the sensor device based on the obtained Pt–Ni alloy NPs was investigated for hydrogen detection with excellent analytical performance in hydrogen sensing. The outstanding gas sensing properties were attributed to unique interface properties and highly efficient catalytic reaction of gas species of oxygen and hydrogen at the interface of IL/Pt–Ni alloy NPs. This work demonstrated that the integration of Pt–Ni alloy NPs with ILs enabled beneficial electrode interface for O2 and H2 gases sensing with high sensitivity, rapid gas response, and superior reproducibility based on a novel planar electrochemical sensor platform.