Surface Of Pt Nanoparticles Research Articles

Enhanced light harvesting ability in hollow Pt/TiO2 nanoreactor for boosting tetracycline photodegradation

Utilizing solar energy to decompose tetracycline (TC) is a green strategy to treat wastewater. Herein, a heterogeneous hollow structured TiO2 decorated Pt nanoparticles were successfully designed and synthesized via hard-template approach and photo-deposition process toward TC photodegradation. The Pt nanoparticles loaded on the surface of hollow structured TiO2 can increase the visible light absorption due to the local surface plasmon resonance (LSPR) effect. Furthermore, owing to the tough electron oscillation of the LSPR excitation, the plasmonic hot holes on the surface of Pt nanoparticles can capture the electrons of TiO2, effectively facilitating the separation of photo-excited charge carriers because of the formation of Schottky junction constructed between Pt and TiO2. Combined the natural merits of shorten conveying path of charge carriers and physical structural stability for hollow structure, the optimal Pt/TiO2 hetero-junction hybrid showed superior photocatalytic activity and durability for TC photodegradation with the degradation efficiency of 93.8 ​% after 30 ​min and the rate constant of 0.09196 min−1 under 300 ​W Xe lamp irradiation. This work displays a heterogeneous hybrids catalyst based on eco-friendly metal and semiconductor materials which can be used in the fields including without limitation TC photodegradation.

Role of polyvinylpyrrolidone in the polyol synthesis of platinum nanoparticles.

In this work, platinum (Pt) nanoparticles (NPs) were prepared via the reduction of Pt salts in an ethylene glycol induced polyol process with an altered polyvinylpyrrolidone (PVP)/Pt molar ratio. With the systematic elucidation of the hydrodynamic size in a liquid; the solid-state size and morphology, crystal structure, surface chemical state and thermal decomposition behavior of the synthesized Pt NPs; as well as the reducing dynamic of Pt cations, the role of PVP in the polyol synthesis of Pt NPs is clarified for the first time. It was found that the amount of PVP does not affect the reducing dynamic of Pt cations, but the chemical state of PVP capped on Pt NPs and the resultant particle size significantly depend on the initial PVP/Pt molar ratio in the precursor solution. Dense-packed PVP via the chemisorption of carbonyl oxygen on the surface of Pt NPs occurs in the case of a higher PVP/Pt ratio, suppressing particle growth and resulting in smaller Pt NPs. On the contrary, the chemical structure of PVP is tuned by the cleavage of the N-C bond and results in the chemisorption of the N atom on the surface of Pt NPs, which promotes the production of larger Pt NPs when a lower PVP/Pt ratio is applied.

Interfacial Structures of Heterogeneous Systems Determined by Using in-Situ XAFS

During chemical reactions and catalysis, the surface and interfacial structural properties of materials are considerably important to understand and control the reactions. However, in-situ measurements have many limits during reactions. We used in-situ X-ray absorption fine structure (XAFS) to understand the local structural properties at the surface and the interface of metal catalysts on transition−metal−oxide supports. Pt nanoparticles (NPs) with a mean size of ~1 nm on TiO2 supports are synthesized using an incipient wetness method. In-situ XAFS measurements are performed from the Pt NPs/TiO2 at Pt L3 and Ti K edges during heating from room temperature to 500 ℃ in an H2 environment. Fourier−transformed extended X-ray absorption fine structure (FT−EXAFS), which is a unique tool to quantitatively determine the local structural properties of materials around a selected species element, shows a lack of oxygen atoms as the nearest neighbors of Pt atoms at T = 250 ℃; meanwhile, the wavelet-transformed EXAFS (WT-EXAFS) with enhanced resolution shows a weak but distinguishable oxygen signal around Pt atoms. Pt−O bonds likely exist at the interface of Pt/TiO2, although oxygens on the outer surfaces of Pt NPs are mostly dissociated at T > 250 ℃ in an H2 environment. This finding strongly suggests that the combination of FT−EAXFS and WT−EXAFS can more accurately describe small amounts of light elements bonding with heavy elements than FT−EXAFS can alone. DFT calculations confirm that the presence of extra oxygen atoms at the interfaces of Pt NPs/TiO2, playing a critical role in the stability and the dispersion of Pt NPs.

In-Situ Observation of Adsorption Species on Platinum Catalyst in Oxygen Reduction Reaction Using High Energy Resolution XAFS

The oxygen reduction reaction (ORR) on Pt surfaces, for examples, Pt single crystals, polycrystalline Pt electrodes, Pt nanoparticles (NPs), Pt-based alloys, and core–shell Pt nanostructures, has been discussed in the last few decades.In polymer electrolyte fuel cells (PEFCs), hydrogen peroxide and its radicals are known to be fatal attacking species not only for electrode catalysts but also for carbon materials and polymer membranes.A thorough understanding of ORR schemes has led to the development of seamless four-electron reduction cathodes, contributing to improved endurance reliability of both anion-exchange membrane (AEM) and proton-exchange membrane (PEM) fuel cells.In this study, the reaction pathway, and intermediate species such as molecular oxygen, in the ORR were investigated in alkaline and acidic environments, respectively.In this work, High Energy Resolution Fluorescence Detection X-ray Absorption Spectroscopy (HERFD-XAS) at the Pt L III-edge, which enhances resolution by partially collecting fluorescent X-ray was employed.X-ray absorption fine structure (XAFS) can detect the electronic structure of Pt, and its high energy resolution makes it possible to distinguish between different adsorption species on the surface of Pt nanoparticles.In addition, photon-in photon-out experiments using hard X-ray with high penetrating ability make it relatively easy to perform in-situ/operando measurements in potential controlled solutions.Carbon-supported Pt nanoparticles as powder catalysts were used for measurement as more realistic conditions, and the species adsorbed on the Pt nanoparticles were analyzed while controlling under the potentials both in acidic and basic electrolyte solutions with N2 or O2 gas bubbling.In N2-saturated solutions, the XANES spectra of the Pt LIII-edge reflected the presence of the adsorption species such as Pt-O (*O), Pt-OH (*OH), Pt-H (*H), as well as PtO2 oxide and Pt metallic states without any adsorption, during the ORR with the potential change.In O2-saturated solutions, one additional adsorption species of molecular oxygen was observed in both acidic and basic electrolyte solutions. It was analyzed that the intermediate species adsorbed to platinum in a side-on configuration as a superoxide anion in an alkaline environment.This intermediate species is identified as hydrogen superoxide, also known as hydroperoxyl radical, with the chemical formula HO2 by being protonated in an acidic environment.The results of research on adsorption species using HERFD-XAS have provided important knowledge for designing catalysts that enable seamless four-electron reduction.The preferred cathode catalyst design will be discussed in detail in an oral presentation at the 244th ECS Meeting. Acknowledgments: The synchrotron radiation experiments were performed at the BL11XU in the SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal Numbers of 2012B3506, 2013A3506, 2014A3506, 2014B3506, 2015B3506, 2016A3556 2019A3508, 2019B3508, 2020A3508, 2021A3508, 2021B3508, 2022A3508 and 2022B3597 at BL11XU). This work was supported by JSPS KAKENHI Grant Number JP22H02188). Figure 1

Interfacial structures of Pt nanoparticles and transition-metal-oxide supports

Local structural properties at the interface of Pt nanoparticles (NPs) and transition−metal−oxide supports are examined using wavelet−transformed extended X−ray absorption fine structure (WT−EXAFS) with an enhanced resolution at Pt L3 edge. The Pt NPs with a mean size of ∼1 nm on TiO2 supports are synthesized using an incipient wetness method. EXAFS measurements are performed from the Pt NPs/TiO2 during heating from room temperature to 250 °C in an H2 environment. Fourier−transformed EXAFS (FT−EXAFS) shows an absence of oxygen atoms around Pt atoms at T = 250 °C; meanwhile, the WT−EXAFS reveals a weak but distinguishable oxygen signal around Pt atoms. Pt–O bonds likely exist at the interface of Pt/TiO2 because oxygens on the outer surfaces of Pt NPs should be dissociated at T = 250 °C under an H2 environment. This finding indicates that the combination of FT−EAXFS and WT−EXAFS can more accurately describe the heterogeneous interfaces of nanostructures.

Multiplex Assays of MicroRNAs by Using Single Particle Electrochemical Collision in a Single Run.

It is important to quantify multiple biomarkers in a single run due to the advantages of precious samples and diagnostic accuracy. Based on the distinguishability of two types of current signals from single particle electrochemical collision (SPEC), step-type current transients produced by Pt nanoparticles (PtNPs) catalyzed hydrazine oxidation and peak-type current transients produced by Ag nanoparticles (AgNPs) oxidation, a kind of multiplex immunoassay of target microRNAs (miRNA-21 and Let-7a) have been established during SPEC in a single run. When the single-stranded DNA (ssDNA1) that was perfectly complementary to miRNA-21 was coupled to the surface of PtNPs, the SPEC of PtNPs electrocatalysis was inhibited and the step-type current transients disappeared, while the single-stranded DNA (ssDNA2) that was perfectly complementary to Let-7a was coupled to the surface of AgNPs, the SPEC of AgNPs oxidation was inhibited, and the peak-type current transients disappeared, thus the signals were in the "off" state at this time. After that, miRNA-21 and Let-7a were added into solution, complementary base pairing disrupted the weak DNA-NP interaction and restored the electrocatalysis of PtNPs and the electrooxidation of AgNPs, and the step-type current signals and peak-type current signals were in the "on" state. Moreover, the frequencies from two different recovered signals (PtNPs catalysis and AgNPs oxidation) corresponded to the amount of added miRNA-21 and Let-7a, thus a multiplex immunoassay method for dual quantification of miRNA-21 and Let-7a in a single run was established.

High-pressure steam treatment with Pt/TiO2 enhances the low temperature formaldehyde oxidation performance

A facile high-pressure steam treatment is developed to improve the formaldehyde oxidation performance of the typical Pt/TiO2 catalyst at low temperatures. The formaldehyde oxidation rate of the treated Pt/TiO2 catalyst can be increased by 4.8 times compared with that of the pristine one. Simultaneously, the treated Pt/TiO2 catalyst possesses the good catalytic stability and catalytic resistance to dry environment. The kinetic study shows that formaldehyde molecules are more liable to be oxidized on the treated Pt/TiO2. A series of characterization results display that the structural parameters of Pt and TiO2 treated with high-pressure steam are not altered. It is found that a layer of bound water is formed on the surface of Pt nanoparticles, which can modify some surface properties of treated Pt/TiO2 catalyst. The interaction strength of intermediates (e.g. CO) with Pt is significantly weakened. Moreover, the amounts of oxygen species and surface hydroxyl for HCHO oxidation are dramatically increased on the treated Pt/TiO2. Based on these characteristics, two reaction steps of formate and CO can be accelerated to enhance the low temperature HCHO oxidation performance of treated Pt/TiO2 catalyst according to the HCHO-DRIFTS studies.

Mechanistic and kinetic insights into size-dependent activity in ultra-small Pt/CNTs nanozymes during antibacterial process

In enzyme-like catalytic reactions, the size effect of nanoparticles has been an essential yet unclear factor for the catalytic activity of nanozymes. Moreover, the synthesis of nanozymes with controllable size and electronic structures represents a grand challenge, which limits the systemic exploration the underlying nature of their structure–property relations and practical application. In this work, we proposed a novel strategy to regulate the size of Pt (0.55 ∼ 2.81 nm) by atomic layer deposition for precisely tailoring Pt-based nanozymes. The size-dependent electronic and kinetic effects have been observed for the peroxidase-like reaction and antibacterial process, revealing a volcano-type dependence of intrinsic activity on Pt nanoparticle sizes, and the optimum Pt nanoparticle size was found to be ca. 1.69 nm. A combination of kinetic study and XPS analyses, as well as multiple nanozyme characterizations, demonstrates that Pt nanoparticles with an appropriate size contribute to proper affinity to the substrates, relating to a high ratio of Pt0/Pt2+ on the surface of Pt nanoparticles, which is beneficial to obtain the excellent catalytic performance and antibacterial activity. Our work provides insights for an in-depth understanding size-dependent catalytic mechanism of nanozymes during antibacterial processes.

Adsorption selectivity of TiCl4 precursor on Pt surfaces for atomic layer deposition via density functional theory

There is an interest in atomic layer deposition as a tool for precise catalyst design and synthesis, due to advantages such as uniform coating, excellent step coverage, and control of thin-film thickness at the atomic level. Using selective atomic layer deposition on platinum-based nanoparticle catalysts improves or maintains catalytic performance, and also improves sintering resistance under high-temperature and -pressure conditions through fine control of the surface. In this study, we used density functional theory to elucidate the mechanism of the initial TiCl4 half-cycle reaction for TiO2 formation on the surface of Pt nanoparticles, and the deposition characteristics according to the crystal properties. In the surface reaction, TiCl4 is adsorbed on Pt (111), (100), and (211) surfaces containing an –OH functional group, and the reaction proceeds through formation of a Pt−O−TiCl3 complex followed by HCl. The chemical adsorption of TiCl4 to the Pt−OH surface has an energy between −2.44 and −2.76 eV, thus providing a highly stable chemical bond. The activation energy of the TiCl4 half-cycle reaction on the surface of Pt nanoparticles is 1.15 – 1.24 eV, in the order Pt (211) > (100) > (111). Via electronic structure analysis of TiCl4-adsorbed Pt nanoparticles, we confirmed that the Pt (111) surface is a favorable pathway for the release of HCl, enhancing its response to the surface reaction. This study provides a quantitative understanding of the selective atomic layer deposition reaction of the precursor TiCl4 on Pt catalyst surfaces. As theoretical understanding of the deposition process improves, we expect that it will become possible to design precursor materials and process conditions applicable to the specifications required by various industries.

Electrochemically-Assisted Synthesis of Platinum Nanoparticles Using Gas-Diffusion Electrocrystallization (GDEx) and Their Electrocatalytic Activity for Methanol Oxidation

In recent years, interest in using unsupported catalysts, especially Pt-based nanomaterials, has resurged in direct methanol fuel cells (DMFC). Unsupported catalysts eliminate the problems related to the corrosion of carbon catalyst supports, thus improving the long-term stability of DMFC. In addition, the design of catalyst synthesis protocols to tailor nanostructured materials with high surface area and catalytic activity improves catalyst performance.1 Consequently, we recently reported a method for the synthesis of platinum group metal (PGM, i.e., Pt, Pd, Rh) nanoparticles (NPs), using a process called Gas Diffusion Electrocrystallization (GDEx) (Fig. 1a).2 The simultaneous electrochemical reduction of CO2 and water occurs at the triple-phase boundary of uncatalyzed gas-diffusion electrodes, producing H2 and CO. Both gases, but especially H2, are reducing agents for water-soluble noble metal ions leading to the formation of small metal nanoclusters. CO can also act as a capping agent. Furthermore, the presence of CO2 stabilizes the pH, avoiding the formation of metal (hydr)oxides.In this work, we used the GDEx process to synthesize unsupported Pt NPs using polyvinyl pyrrolidone (PVP, 55000 Mw) as a stabilizer and evaluated their electrocatalytic activity for methanol oxidation. The synthesis was performed at -30 mA cm-2, using 3.0 mM Pt4+ (as H2PtCl4) as metal precursor and different concentrations of PVP (i.e., 0.0, 0.01, 0.1 and 1.0 g L-1). We chose low concentrations of stabilizer to facilitate its removal after synthesis, as clean surface catalysts are required for electrocatalytic applications. The size distribution of the Pt NPs, measured using Scanning Electron Microscopy (SEM), was 64 ± 22, 60 ± 22, 42 ± 18, and 38 ± 12 nm for PVP 0.0, PVP 0.01, PVP 0.1, and PVP 1.0, respectively. For comparison, the reduction of 3.0 mM Pt4+ using 1.0 g L-1 PVP with only H2 (either electrogenerated or bubbled) produced bigger and much more polydisperse particles (100 nm–1000 nm), highlighting the importance of the GDEx process and the presence of CO to synthesize small NPs using low concentrations of stabilizer. Furthermore, Transmission Electron Microscopy (TEM) images (Fig. 1b) revealed that the NPs are nanoclusters of single crystals of 2 nm–4 nm in diameter.The synthesized Pt NPs were cleaned using NaOH,3 and their electrocatalytic activity was evaluated in acidic media. The CV curves of Pt NPs in 0.5 M H2SO4 are shown in Fig. 1c. All catalysts showed hydrogen adsorption-desorption peaks from -0.2 to 0.1 VAg/AgCl. The calculated electrochemical surface area (ECSA), obtained by integrating the charge in the hydrogen adsorption-desorption region, was 7.6 ± 0.7, 14.1 ± 1.2, 33.6 ± 1.2, and 30.3 ± 1.0 m2 g-1 Pt for PVP 0.0, PVP 0.01, PVP 0.1 and PVP 1.0 respectively. The MeOH electro-oxidation experiments were performed in 0.5 M H2SO4 containing 1.0 M MeOH, and the CV curves are shown in Fig. 1d. The forward anodic peak (If) at about 0.7 VAg/AgCl corresponds to MeOH oxidation, while the backward anodic peak (Ib) at about 0.5 VAg/AgCl corresponds to the oxidation of the incompletely oxidized carbonaceous species formed in the forward sweep. The mass activity (MA), defined by the forward peak current density per unit of catalyst loading, was 71 ± 2, 136 ± 7, 463 ± 28, and 341 ± 25 mA mg-1 Pt for PVP 0.0, PVP 0.01, PVP 0.1, and PVP 1.0 g L-1, respectively. Hence, the MA scale with the ECSA . Besides, ECSA (and hence MA) increases when the PVP concentration during synthesis increases. However, this trend is not followed for a PVP concentration of 1.0 g L-1. Even though all catalysts were cleaned using the same protocol, residual PVP might still be left on the surface of Pt NPs synthesized using 1.0 g L-1 PVP, lowering their electrocatalytic activity.Overall, the GDEx process was a useful tool for synthesizing unsupported Pt NPs using low concentrations of stabilizer and with high electrocatalytic activity. This project has received funding from the European Union's Horizon 2020 Research and Innovation program under Grant Agreements n° 730224 (PLATIRUS) and n° 958302 (PEACOC) 1. E. Antolini, J. Perez, J. Mat. Sci, 2011, 46, 4435–4457.2. X. Dominguez-Benetton, O. Martinez-Mora, J. Fransaer, EP21165681, 2021.3. A. Zalineeva, S. Baranton, C. Coutanceau, G. Jerkiewicz, Langmuir, 2015, 31, 1605–1609. Figure 1

In situ Re‐construction of Pt Nanoparticles Interface for Highly Selective Synthesis of Primary Amines

AbstractRegulation of the catalyst interface by adsorbates has been demonstrated as an efficacious methodology to enhance the catalytic selectivity. Herein, we demonstrated an in situ modifications induced by reactants to re‐construct the local interface of Pt nanoparticles anchored on the CoFe layered double hydroxides (CoFe‐LDH) supports for a highly selective synthesis of primary amines from reductive amination of aldehydes and ammonia. The strong metal‐support interaction between Pt metals and CoFe‐LDH supports results in the highly electron‐enriched surface of Pt and thereby makes the surface of Pt nanoparticles favor the enrichment of NH4+ species and adsorption of NH3. Such a tailored interface can create an interfacial stereo‐hindrance effect and effectively slug the reaction kinetics of side‐reactions, further preventing the formation of side‐products. We anticipate that such an in situ re‐construction of metal interface by reactants and afterwards the constructed local environment of active sites may provide a new approach for the optimization of metal catalysts.

Sulphonated melamine polymer for enhancing the oxygen reduction reaction activity and stability of a Pt catalyst

• Poly(melamine) sulphonate enhances the oxygen reduction activity of Pt catalysts. • The enhancement of the activity persists even after a deterioration test at 79 °C. • The melamine polymer suppresses the degradation of Pt nanoparticles. Poly(melamine) sulphonate (Poly-MS) adsorbed on the surface of Pt nanoparticles enhanced the activity of Pt/C in the oxygen reduction reaction (ORR). This enhancement persisted even after an accelerated deterioration test (ADT) at 79 °C. Analysis of the particle size distribution using transmission electron microscopy (TEM) clearly showed that Poly-MS enhanced the stability of the Pt nanoparticles, enabling them to withstand the conditions of the ADT. These findings were supported by CO stripping voltammetry analysis.

Fe3O4@Pt nanoparticles to enable combinational electrodynamic/chemodynamic therapy

Electrodynamic therapy (EDT) has recently emerged as a potential external field responsive approach for tumor treatment. While it presents a number of clear superiorities, EDT inherits the intrinsic challenges of current reactive oxygen species (ROS) based therapeutic treatments owing to the complex tumor microenvironment, including glutathione (GSH) overexpression, acidity and others. Herein for the first time, iron oxide nanoparticles are decorated using platinum nanocrystals (Fe3O4@Pt NPs) to integrate the current EDT with chemodynamic phenomenon and GSH depletion. Fe3O4@Pt NPs can effectively induce ROS generation based on the catalytic reaction on the surface of Pt nanoparticles triggered by electric field (E), and meanwhile it may catalyze intracellular H2O2 into ROS via Fenton reaction. In addition, Fe3+ ions released from Fe3O4@Pt NPs under the acidic condition in tumor cells consume GSH in a rapid fashion, inhibiting ROS clearance to enhance its antitumor efficacy. As a result, considerable in vitro and in vivo tumor inhibition phenomena are observed. This study has demonstrated an alternative concept of combinational therapeutic modality with superior efficacy.

Isolating the contributions of surface Sn atoms in the bifunctional behaviour of PtSn CO oxidation electrocatalysts

The bifunctional mechanism is well-acknowledged for the promoted CO oxidation on Pt-based bimetallic electrocatalysts. However, the direct identification of the active oxygenated species and the nature and electrochemistry of the second component are still a matter of debate. Herein, Snad-Pt/C catalysts, where Sn ad-atoms are exclusively on the surface of Pt nanoparticles at low coverages ranging from 0.0033 to 0.2 monolayers to avoid sub-surface Sn and alloy formation, were prepared as a model system to resolve these issues using a surface organometallic chemistry approach. Effects of the Sn ad-atoms on CO oxidation were studied by CO stripping voltammograms as a function of Sn coverage. Using in situ XAS measurements, the Sn average oxidation state is estimated to increase from +0.2 to +3.1 as the potential increases from 0 to 0.8 VRHE, with the number of the oxygen neighbours increasing stepwise. Pt4.5-Sn-(OH)1.5 is revealed as the active species responsible for the bifunctional mechanism at low overpotentials and is generated via a redox couple corresponding to Pt4.5-Sn*/Pt4.5-Sn-(OH)1.5.

Copper Single-Atom-Covered Pt Nanoparticles for Selective Hydrogenation of Phenylacetylene

The selective hydrogenation of alkynes to alkenes is very important for both industry and scientific investigation, and overhydrogenation of alkynes to alkanes is the biggest problem to be solved. Suppressing the catalytic hydrogenation of alkenes to alkanes and keeping the efficient conversion from alkynes to alkenes at the same time is a viable solution, but the slight difference in structure between alkynes and the corresponding alkenes causes great difficulty in realizing such a target. The Pt/C–Cu bimetallic catalysts are used to catalyze the selective hydrogenation of phenylacetylene (PA) to styrene (ST). High-resolution STEM and EXAFS results show that the prepared Pt/C–Cu catalysts are composed of copper single atoms and Pt nanoparticles. In particular, Pt/C–Cu is a catalyst in which copper single atoms cover the surface of Pt nanoparticles. The experimental results reveal that the selectivity of ST strongly depends on the coverage of Cu single atoms over Pt nanoparticles in Pt/C–Cu, so selective hydrogenation of PA is a structure-sensitive reaction. The selectivity of ST can reach 94.4% at a PA conversion of 100% in the selective hydrogenation of PA over Pt/C–0.5Cu, an optimized Pt–Cu bimetallic catalyst; after selective removal of PA in ST from 100 to 30 ppm over the same catalyst, the yield of ST reaches 99.97%. The chemisorption results of H2 and probe molecule ethene (C2H4) over the Pt–Cu/C catalysts reveal that Cu single atoms covering on the surface of Pt nanoparticles weaken the Pt–H and Pt–C2H4 interactions, so the catalytic hydrogenation of the carbon–carbon double bond over Pt/C–0.5Cu can be tremendously suppressed. The added Cu single atoms over Pt nanoparticles are not poisonous sites because they can also act as the active centers to activate hydrogen and the carbon–carbon double bond.

Platinum Nanoparticle Based Dip‐Catalyst for Facile Hydrogenation of Quinoline, Unfunctionalized Olefins, and Imines

AbstractDeveloping a bio‐inspired catalyst with the efficiency of homogeneous catalysts and recyclability similar to heterogeneous catalysts is quite desirable but challenging. Incorporation of metal nanoparticles (<10 nm) on abundant, low‐cost supports from agricultural waste can yield highly active and product‐selective pseudo‐homogeneous catalysts, with attributes such as ease of retrieval for next use, reusability, etc. In this work, the fabrication of an efficient and reusable ‘dip‐catalyst’ by anchoring platinum nanoparticles on white jute plant (Corchorus capsularis) stems (JPS) and its use for the hydrogenation of N‐heteroarenes, unfunctionalized olefins, and imines are described. The catalyst was characterized using XRD, SEM, EDS, TEM, HRTEM, FTIR, and XPS, and TEM shows spherical (average diameter 4–5 nm) non‐agglomerated metal nanoparticles. Catalyst was used for the chemoselective (>99 % selectivity) hydrogenation of quinoline with a quantitative (>99 %) conversion to 1,2,3,4‐tetrahydroquinoline (py‐THQ) under hydrogen at a pressure <30 bar. Also, functional group tolerance is indicated by the quantitative hydrogenation of 6‐chloroquinoline to 6‐chloro‐1,2,3,4‐tetrahydroquinoline, which is a longstanding challenge owing to C−Cl bond cleavage. In the hydrogenation of structurally‐challenging trisubstituted trans‐2‐methyl‐3‐phenyl‐2‐propen‐1‐ol olefins, 64 % conversion and >99 % selectivity was achieved. A series of imines with different chain lengths was also hydrogenated selectively in methanol with >99 % conversion. Density functional theory (DFT) calculations reveal the efficient adsorption of 6‐chloroquinoline on the surface of Pt nanoparticles on Pt@JPS strips in a tilted orientation placing the C−Cl bond away from the metal and allowing facile desorption of 6‐chloro‐1,2,3,4‐tetrahydroquinoline leading to higher chemoselectivity. The spent catalyst can be reused for 12 consecutive cycles without significant damage to the cellulosic surface.

Develepment of Catalystic Systems for Electroreduction of Highly Inert Reactants Such As Arsenate, Nitrite and Oxohalogenates

Noble metal nanoparticles (Pt, Rh, Ir Pd), when deposited on an inert electrode substrates, exhibit electrocatalytic properties during both oxidation of As(III) and reduction of As(V) in acid medium (e.g. 0.5 mol dm-3 H2SO4). For example, upon application of the appropriate potential, both As(III) and As(V) are preconcentrated on surfaces of Pt nanoparticles. Consequently, their presence can monitored under voltammetric conditions. Population of protons does affect the systems’ electrochemical characteristics. The nature of arsenic voltammetric peaks is strongly dependent on the preconcentration potential. While the reduction and deposition of As(III) is induced by adsorbed hydrogen on Pt formed at potentials lower than 0.25 V (vs. RHE), the adsorption and preconcentration of As(V) can be readily achieved at Pt oxides generated at Pt nanoparticles at potentials higher than 0.85 V (vs. RHE). From mechanistic point of view, voltammetric oxidation of bulk As(III) is catalyzed by Pt oxo species but electrocatalytic reduction of As(V) requires its prior adsorption. Electroreduction of the resulting As(V) adsorbates is catalyzed by both metallic platinum and by platinum on which hydrogen atoms are adsorbed; the resulting voltammetric peak current densities are dependent on concentration of As(V) in solution. A unique feature of the adsorbed As(III) and As(V) oxo species is the ability to agglomerate and form stable polynuclear electroactive films on Pt nanoparticles. Their performance resembles behavior of redox conducting polymers, and their redox transitions are fast and reversible. Electrochemical experiments are supported by the data from scanning and transmission electron microscopies and Raman spectroscopy.In conclusion, the present observations demonstrate the utility of Pt nanoparticles as the catalytic system for inducing of (otherwise highly inert) electrode processes of As(III) and As(V) in acid medium. While the electrocatalytic activity of platinum (particularly PtO) toward electrooxidation of As(III) was previously postulated, we clearly show here that arsenates(V) can be adsorbed, preconcentrated, and electrocatalytically reduced (without prior chemical treatment) and, thus, detected on surfaces of Pt nanostructures. On mechanistic grounds, As(V) must be first adsorbed on bare (metallic) Pt surface before the actual electron transfer can take place. In addition to the structural importance, ivolvement of protons is crucial to effective electrocatalysis. It is also noteworthy that the current signals can be correlated to concentration of As(V) in bulk solution. The present study also provides evidence of obtaining a stable redox-polymer-like As(III,V) oxo film capable of fast charge propagation (electron-self exchange rate on the level 8*106 dm3 mol-1 s-1) within the adsorbed layer existing on surfaces of platinum nanoparticles. The latter observation is of both fundamental and analytical significance. Observations made during electrocatalytic and photoelectrochemical reductions of bromates, nitrites and carbon dioxide with use of various metal nanoparticles and nanostructured metal oxides can serve as guides for such research.

Pyrolysis of Iron(III) porphyrin coated Pt/C toward oxygen reduction reaction in acidic medium

Design and synthesis of highly active and durable electrocatalysts toward oxygen reduction reaction (ORR) is of particular importance for proton exchange membrane fuel cells (PEMFCs), yet remains a grand challenge. Herein, we report the deposition of iron (III) porphyrin (FeP) on house-made Pt/C by rotary evaporation of the mixture of FeP and house-made Pt/C dispersed in chloroform, followed by pyrolysis at 650 °C in argon atmosphere. This approach led to the synthesis of new non-precious metal electrocatalyst (NPME)-Pt/C composites (Pt/C–FeP) with an average nanoparticle diameter of 3.1 ± 1.5 nm without aggregation. According to X-ray photoelectron spectroscopy (XPS), the binding energy of Pt 4f7/2 became larger due to the presence of pyrolyzed FeP. In addition, the electrochemically active surface area (ECSA) of Pt/C–FeP-650 is 65 m2/g less than that of house-made Pt/C (80.2 m2/g). This implies that the pyrolyzed FeP may have partially covered the surface of Pt nanoparticles and thus lowering the ECSA. Interestingly, the mass activity (MA) of Pt/C–FeP turns out to be 349.0 mA/mgPt @0.9 V vs. RHE, which is 2.6 times and 1.5 times of house-made Pt/C and commercial Pt/C, respectively. It is speculated that the electronic interaction and possible synergy between Pt and pyrolyzed FeP as NPME might have contributed to the ORR activity improvement despite of partial loss of ECSA. During accelerated durability tests (ADTs), the MA of Pt/C–FeP-650 degrades 64.3% inferior to commercial Pt/C (52.2%). The main reason likely arises from the degradation of pyrolyzed FeP, which is a bottleneck problem confronting NPMEs.

Pt Nanoparticles with High Oxidase-Like Activity and Reusability for Detection of Ascorbic Acid.

Noble metal nanoenzymes such as Pt, Au, Pd, etc. exhibit magnificent activity. However, due to the scarce reserves and expensive prices of precious metals, it is essential to investigate their enzyme-like activity and explore the possibility of their reuse. In this work, the oxidase-like activity and reusability of several Pt nanoparticles with different morphologies were detected. We compared the Pt nanoparticles (NPs) with a size of about 30 nm self-assembled by 5 nm Pt nanoparticles and Pt nanoparticles (Pt-0 HCl) with a diameter of about 5 nm, and found that their Michaelis−Menten constants (Km) were close and their initial performance similar, but the Pt NPs had better reusability. This was probably attributed to the stacked structure of Pt NPs, which was conducive to the substance transport and sufficient contact. At the same time, it was found that the size, dispersion, and organic substances adsorbed on the surface of Pt nanoparticles would have a significant impact on their reusability. A colorimetric detection method was designed using the oxidase-like activity of Pt NPs to detect ascorbic acid in triplicate. The limits of detection were 131 ± 15, 144 ± 14, and 152 ± 9 nM, with little difference. This research not only showed that the morphology of the catalyst could be changed and its catalytic performance could be controlled by a simple liquid phase synthesis method, but also that it had great significance for the reuse of Pt nanoenzymes in the field of bioanalysis.

(Invited) Develepment of Electrocatalystic Systems for Highly Inert Reactants: Reduction of Arsenic(V), Nitrite, Oxohalogenates and CO2 in Acid Medium

Noble metal nanoparticles (Pt, Rh, Ir Pd), when deposited on an inert electrode substrates, exhibit electrocatalytic properties during both oxidation of As(III) and reduction of As(V) in acid medium (e.g. 0.5 mol dm-3 H2SO4). For example, upon application of the appropriate potential, both As(III) and As(V) are preconcentrated on surfaces of Pt nanoparticles. Consequently, their presence can monitored under voltammetric conditions. Population of protons does affect the systems’ electrochemical characteristics. The nature of arsenic voltammetric peaks is strongly dependent on the preconcentration potential. While the reduction and deposition of As(III) is induced by adsorbed hydrogen on Pt formed at potentials lower than 0.25 V (vs. RHE), the adsorption and preconcentration of As(V) can be readily achieved at Pt oxides generated at Pt nanoparticles at potentials higher than 0.85 V (vs. RHE). From mechanistic point of view, voltammetric oxidation of bulk As(III) is catalyzed by Pt oxo species but electrocatalytic reduction of As(V) requires its prior adsorption. Electroreduction of the resulting As(V) adsorbates is catalyzed by both metallic platinum and by platinum on which hydrogen atoms are adsorbed; the resulting voltammetric peak current densities are dependent on concentration of As(V) in solution. A unique feature of the adsorbed As(III) and As(V) oxo species is the ability to agglomerate and form stable polynuclear electroactive films on Pt nanoparticles. Their performance resembles behavior of redox conducting polymers, and their redox transitions are fast and reversible. Electrochemical experiments are supported by the data from scanning and transmission electron microscopies and Raman spectroscopy.In conclusion, the present observations demonstrate the utility of Pt nanoparticles as the catalytic system for inducing of (otherwise highly inert) electrode processes of As(III) and As(V) in acid medium. While the electrocatalytic activity of platinum (particularly PtO) toward electrooxidation of As(III) was previously postulated, we clearly show here that arsenates(V) can be adsorbed, preconcentrated, and electrocatalytically reduced (without prior chemical treatment) and, thus, detected on surfaces of Pt nanostructures. On mechanistic grounds, As(V) must be first adsorbed on bare (metallic) Pt surface before the actual electron transfer can take place. In addition to the structural importance, ivolvement of protons is crucial to effective electrocatalysis. It is also noteworthy that the current signals can be correlated to concentration of As(V) in bulk solution. The present study also provides evidence of obtaining a stable redox-polymer-like As(III,V) oxo film capable of fast charge propagation (electron-self exchange rate on the level 8*106 dm3 mol-1 s-1) within the adsorbed layer existing on surfaces of platinum nanoparticles. The latter observation is of both fundamental and analytical significance. Observations made during electrocatalytic and photoelectrochemical reductions of bromates, nitrites and carbon dioxide with use of various metal nanoparticles and nanostructured metal oxides can serve as guides for such research.