PtNi Alloy Research Articles

Diastereoselective Hydrogenation of Tetrasubstituted Olefins using a Heterogeneous Pt-Ni Alloy Catalyst.

Stereoselective hydrogenation of tetrasubstituted olefins is an attractive method to access compounds with two contiguous stereocenters. However, homogeneous catalysts for enantio- and diastereoselective hydrogenation exhibit low reactivity toward tetrasubstituted olefins due to steric crowding between the ligand scaffold and the substrate. Monometallic heterogeneous catalysts, on the other hand, provide accessible surface active sites for hindered olefins but exhibit unpredictable and inconsistent stereoinduction. In this work, we develop a Pt-Ni bimetallic alloy catalyst that can diastereoselectively hydrogenate unactivated, sterically-bulky tetrasubstituted olefins, utilizing the more oxophilic Ni atoms to adsorb a hydroxyl directing group and direct facially-selective hydrogen addition to the olefin via the Pt atoms. Structure-activity studies on several Pt-Ni compositions underscore the importance of exposing a uniform PtNi alloy surface to achieve high diastereoselectivity and minimize side reactions. The optimized Pt-Ni/SiO2 catalyst exhibits good functional group tolerance and broad scope for tetrasubstituted olefins in a cyclopentene scaffold, generating cyclopentanol products with three contiguous stereocenters. The synthetic utility of the method is demonstrated in a four-step synthesis of (1R,2S)-(+)-cis-methyldihydrojasmonate with high yield and enantiopurity.

Effects of Zr dopants on properties of PtNi nanoparticles for ORR catalysis: A DFT modeling.

Pt-based alloys, such as Pt3Ni, are among the best electrocatalysts for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells. Doping of PtNi alloys with Zr was shown to enhance the durability of the operating ORR catalysts. Rationalizing these observations is hindered by the absence of atomic-level data for these tri-metallic materials, even when not exposed to the fuel cell operation conditions. This study aims at understanding structure-property relations in Zr-doped PtNi nanoparticles as a key to their ORR function. In particular, we calculated, using a method based on density functional theory, the most stable chemical orderings of pristine and Zr-doped Pt3Ni particles containing over 400 atoms. We thus clarify (i) preferential location and charge states of Zr atoms in the Pt3Ni NPs; (ii) effect of doping Zr atoms on the stability of the Pt skin of the Pt3Ni NPs; (iii) charge redistribution induced by Zr dopants; (iv) layer-by-layer atomic ordering in the Pt3Ni/Zr NPs with the increasing Zr content; and (v) effect of Zr atoms on the adsorption energies of O and OH species as indicators of the ORR activity.

Diastereoselective Hydrogenation of Tetrasubstituted Olefins using a Heterogeneous Pt‐Ni Alloy Catalyst

AbstractStereoselective hydrogenation of tetrasubstituted olefins is an attractive method to access compounds with two contiguous stereocenters. However, homogeneous catalysts for enantio‐ and diastereoselective hydrogenation exhibit low reactivity toward tetrasubstituted olefins due to steric crowding between the ligand scaffold and the substrate. Monometallic heterogeneous catalysts, on the other hand, provide accessible surface active sites for hindered olefins but exhibit unpredictable and inconsistent stereoinduction. In this work, we develop a Pt−Ni bimetallic alloy catalyst that can diastereoselectively hydrogenate unactivated, sterically‐bulky tetrasubstituted olefins, utilizing the more oxophilic Ni atoms to adsorb a hydroxyl directing group and direct facially‐selective hydrogen addition to the olefin via the Pt atoms. Structure‐activity studies on several Pt−Ni compositions underscore the importance of exposing a uniform PtNi alloy surface to achieve high diastereoselectivity and minimize side reactions. The optimized Pt−Ni/SiO2 catalyst exhibits good functional group tolerance and broad scope for tetrasubstituted olefins in a cyclopentene scaffold, generating cyclopentanol products with three contiguous stereocenters. The synthetic utility of the method is demonstrated in a four‐step synthesis of (1R,2S)‐(+)‐cis‐methyldihydrojasmonate with high yield and enantiopurity.

Integrating theory with the nanoreactor concept to synthesize hollow carbon sphere‐encapsulated PtNi alloys for enhanced H2 generation

AbstractThe rational design of efficient bimetallic nanoparticle (NP) catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction. Here, we report the rational design of nanoreactors comprising hollow carbon sphere‐confined PtNi bimetallic NPs (PtNi@HCS) as highly efficient catalysts for hydrogen generation via ammonia borane hydrolysis in water. Using both density functional theory calculations and molecular dynamics simulations, the effects of an active PtNi combination and the critical synergistic role of a hollow carbon shell on the molecule diffusion adsorption behaviors are explored. Kinetic isotope effects and theoretical calculations allow the clarification of the mechanism, with oxidative addition of an O–H bond of water to the catalyst surface being the rate‐determining step. The remarkable catalytic activity of the PtNi@HCS nanoreactor was also utilized for successful tandem catalytic hydrogenation reactions, using in situ‐generated H2 from ammonia borane with high efficiency. The concerted design, theoretical calculations, and experimental work presented here shed light on the rational elaboration of efficient nanocatalysts and contribute to the establishment of a circular carbon economy using green hydrogen.

Edge dislocation-induced strains break the limit of PtNi alloys in boosting Pt mass activity for efficient alkaline hydrogen evolution

Edge dislocation-induced strains break the limit of PtNi alloys in boosting Pt mass activity for efficient alkaline hydrogen evolution

Synthesis of bimetallic Ni-Pt/SAPO-11 composite and the catalytic application in n-heptane hydroisomerization

The monometallic Pt/SAPO-11 and bimetallic Ni-Pt/SAPO-11 catalysts were synthesized with Instant Exactness Synthesis (IES) method and characterized by XRD, nitrogen adsorption–desorption, SEM, TEM, FT-IR, Py-IR, NH3-TPD and XPS, and their properties were evaluated for the n-heptane hydroisomerization. The catalysts had spherical structure and moderate acid strength, and exhibited good n-heptane conversion and catalytic selectivity toward n-heptane isomers. Typically, Ni-Pt/SAPO-11 exhibited an isomer selectivity of 80.9% with a conversion of 69.9% at 310 °C, which was obviously better than Pt/SAPO-11 (isomer selectivity of 75.1% with a conversion of 60.6% at 310 °C). Moreover, the Ni-Pt/SAPO-11 catalyst displayed higher percentage of i-heptane (79%) and lower percentage of n-heptane (6%) than Pt/SAPO-11. The continuous test of 360 min indicated Ni-Pt/SAPO-11 catalyst had good catalytic stability. Bimetallic Ni-Pt alloy loaded on SAPO-11 had significantly effect on catalytic properties of n-heptane hydroisomerization.

Highly Active and Stable Bimetallic Ordered Catalysts for Oxygen Reduction Reaction Improvement in Polymer Exchange Membrane Fuel Cells

Demand for replacing the Pt catalyst in proton exchange membrane fuel cells (PEMFCs) has increased because Pt metal is rare and high cost. The most reasonable way is synthesizing Pt-base alloy using transition metals such as Co, Ni, Fe, and Mo. The Pt-based alloy catalysts exhibit excellent catalytic activity by creating a synergistic effect through the interaction between Pt and the transition metals. Here we present the best PtNi alloy composition and maximize the performance of the oxygen reduction reaction (ORR) activity in fuel cells by annealing the alloy under a hydrogen atmosphere. The Pt7Ni3/C catalyst indicated a higher ORR activity than other compositions due to different structural changes, and the annealing catalysts at 700 °C under an H2 atmosphere improved the electrochemical activity and stability. The heat treatment increased the conductivity by reducing oxygen bonding as well as changing the structure into an ordered face-centered tetragonal (FCT) structure with good activity. The result of these studies provides a new way to develop high-performance and low-cost catalyst materials for fuel cells.

The ultra-high oxygen evolution activity of Fe modified NiPt alloy assisted by Pt pre-oxidation in alkaline electrolyte

Constructing ultra-high activity, highly efficient and robust oxygen evolution reaction (OER) electrocatalysts, especially at large current density, plays a key role in the development of the electrolytic water industry but remains challenging. Highly dispersed alloy compound with large electrolyte contact area and excellent internal conductivity is considered as a kind of ideal candidate. Here, we have rationally designed and synthesized a nickel-platinum alloy with octahedral structure loaded on the surface of the carbon layer (NiPt/C). Under the in-situ modulation of the iron-containing electrolyte, the Fe modified NiPt/C catalyst displays an amazing OER activity in 1 M KOH, and only requires low overpotentials of 183 and 242 mV to reach 100 and 1000 mA cm−2, respectively. The comprehensive characterization analysis and property measurements reveal that the pre-oxidation of Pt at OER potential contribute to the rapid production of nickel hydroxide, thus promoting the deposition of more iron active sites on its surface. Moreover, the Pt/C/CP(−)//NiPt/C/CP(+) couple embedded in anion-exchange membrane water electrolyser also displays a low cell voltage of 2.03 V at 1000 mA cm−2 with significant electrochemical stability, which endows it a great potential in the field of hydrogen production and electrochemical energy storage.

Development of PtNi/C and PtSnNi/C Nanocatalysts for Energy Convertion from Ethanol Electrooxidation

Literature describes the importance in studying morphological and structural electrocatalysts features since they influence catalytic activity toward ethanol electrooxidation. Thus, this work consists in studying the relation between structural/composition features and catalytic activity toward ethanol electrooxidation from Pt, PtSn, PtNi and PtSnNi alloys nanoparticles supported on Vulcan Carbon XC72R. These nanoparticles were obtained by the impregnation reduction method at 130 ºC, employing a mixture of water/ethylene glycol (75/25 v/v) with different amounts of Pt, Sn and Ni. The nanostructured catalysts obtained were characterized by Rutherford Backscattering Spectroscopy (RBS), X-Ray Diffraction (XRD), High Resolution Transmission Electronic Microscopy (HRTEM) and Cyclic Voltammetry (CV). Preliminary results showed that the impregnation reduction is a reasonable method to obtain Pt-based nanoparticles with a composition control. XRD analysis showed that tin and nickel addition promoted a crystal lattice dilation and contraction, respectively. Besides, the simultaneous addition of Sn and Ni to Pt did not significantly affect the reticular lattice value. Moreover, crystallite size is diminished with Ni or Ni and Sn addition. PtSn, PtNi and PtSnNi/C nanoparticles have higher catalytic activity than Pt/C toward ethanol electrooxidation, which was verified by a significant current density values increase and an onset potential decrease. The best catalytic activity was observed to PtNi/C electrocatalyst.

Surface Redox Reaction for the Synthesis of NiPt Catalysts for the Upgrading of Renewable Ethanol/Methanol Mixtures

Mixtures of ethanol and methanol being synthesized from CO2 and green H2 can serve as sustainable base chemicals for a number of chemical processes. Amongst these processes, the catalytically supported synthesis of CO2-neutral C4 to C10 alcohols is of increasing importance as, e.g., iso-butanol can be used as a drop-in fuel or after dehydration to produce iso-butene as a feedstock for the synthesis of plastics. 2-ethyl-hexanol can be further refined into solvents, tensides, or monomers. In this respect, NiPt alloys on an activated carbon support were found to be active and stable catalysts for the synthesis of iso-butanol following the Guerbet reaction scheme. In this study, two different routes are applied to the synthesis of these NiPt catalysts: a more conventional one based on the impregnation of Ni and Pt salts and an advanced path with a surface redox reaction between elemental Ni on the support and Pt ions in a polar solution. The experimental evaluation shows that the Pt particles from the surface redox reaction being exposed on the Ni particles are more active than those on the impregnated catalysts due to their high surface energy. Their specific space-time yields are 10–20 times higher.

Identifying the distinct roles of dual dopants in stabilizing the platinum-nickel nanowire catalyst for durable fuel cell

Stabilizing active PtNi alloy catalyst toward oxygen reduction reaction is essential for fuel cell. Doping of specific metals is an empirical strategy, however, the atomistic insight into how dopant boosts the stability of PtNi catalyst still remains elusive. Here, with typical examples of Mo and Au dopants, we identify the distinct roles of Mo and Au in stabilizing PtNi nanowires catalysts. Specifically, due to the stronger interaction between atomic orbital for Ni-Mo and Pt-Au, the Mo dopant mainly suppresses the outward diffusion of Ni atoms while the Au dopant contributes to the stabilization of surface Pt overlayer. Inspired by this atomistic understanding, we rationally construct the PtNiMoAu nanowires by integrating the different functions of Mo and Au into one entity. Such catalyst assembled in fuel cell cathode thus presents both remarkable activity and durability, even surpassing the United States Department of Energy technical targets for 2025.

Low‐Electronegativity Mn‐Contraction of PtMn Nanodendrites Boosts Oxygen Reduction Durability

AbstractPlatinum metal (PtM, M=Ni, Fe, Co) alloys catalysts show high oxygen reduction reaction (ORR) activity due to their well‐known strain and ligand effects. However, these PtM alloys usually suffer from a deficient ORR durability in acidic environment as the alloyed metal is prone to be dissolved due to its high electronegativity. Herein, we report a new class of PtMn alloy nanodendrite catalyst with low‐electronegativity Mn‐contraction for boosting the oxygen reduction durability of fuel cells. The moderate strain in PtMn, induced by Mn contraction, yields optimal oxygen reduction activity at 0.53 A mg−1 at 0.9 V versus reversible hydrogen electrode (RHE). Most importantly, we show that relative to well‐known high‐electronegativity Ni‐based Pt alloy counterpart, the PtMn nanodendrite catalyst experiences less transition metals’ dissolution in acidic solution and achieves an outstanding mass activity retention of 96 % after 10,000 degradation cycles. Density functional theory calculation reveals that PtMn alloys are thermodynamically more stable than PtNi alloys in terms of formation enthalpy and cohesive energy. The PtMn nanodendrite‐based membrane electrode assembly delivers an outstanding peak power density of 1.36 W cm−2 at a low Pt loading and high‐performance retention over 50 h operations at 0.6 V in H2‐O2 hydrogen fuel cells.

Low-Electronegativity Mn-Contraction of PtMn Nanodendrites Boosts Oxygen Reduction Durability.

Platinum metal (PtM, M=Ni, Fe, Co) alloys catalysts show high oxygen reduction reaction (ORR) activity due to their well-known strain and ligand effects. However, these PtM alloys usually suffer from a deficient ORR durability in acidic environment as the alloyed metal is prone to be dissolved due to its high electronegativity. Herein, we report a new class of PtMn alloy nanodendrite catalyst with low-electronegativity Mn-contraction for boosting the oxygen reduction durability of fuel cells. The moderate strain in PtMn, induced by Mn contraction, yields optimal oxygen reduction activity at 0.53 A mg-1 at 0.9 V versus reversible hydrogen electrode (RHE). Most importantly, we show that relative to well-known high-electronegativity Ni-based Pt alloy counterpart, the PtMn nanodendrite catalyst experiences less transition metals' dissolution in acidic solution and achieves an outstanding mass activity retention of 96 % after 10,000 degradation cycles. Density functional theory calculation reveals that PtMn alloys are thermodynamically more stable than PtNi alloys in terms of formation enthalpy and cohesive energy. The PtMn nanodendrite-based membrane electrode assembly delivers an outstanding peak power density of 1.36 W cm-2 at a low Pt loading and high-performance retention over 50 h operations at 0.6 V in H2 -O2 hydrogen fuel cells.

Enhanced Sensitivity of Electrochemical Sensors for Ammonia-Nitrogen via In-Situ Synthesis PtNi Nanoleaves on Carbon Cloth.

Pt-based electrochemical ammonia-nitrogen sensors played a significance role in real-time monitoring the ammonia-nitrogen concentration. The alloying of Pt and transition metals was one of the effective ways to increase the detectability of the sensitive electrode. In this paper, a self-supported electrochemical electrode for the detection of ammonia nitrogen was obtained by the electrodeposition of PtNi alloy nanoleaves on a carbon cloth (PtNi-CC). Experimental results showed that the PtNi-CC electrode exhibited enhanced detection performance with a wide linear range from 0.5 to 500 µM, high sensitivity (7.83 µA µM-1 cm-2 from 0.5 to 150 μM and 0.945 µA µM-1 cm-2 from 150 to 500 μM) and lower detection limit (24 nM). The synergistic effect between Pt and Ni and the smaller lattice spacing of the PtNi alloy were the main reasons for the excellent performance of the electrode. This work showed the great potential of Pt-based alloy electrodes for the detection of ammonia-nitrogen.

Enhanced electrocatalytic performance of PtNi bimetallic alloys on carbon nanotube for ethanol oxidation reaction

In this paper, Ni-Pt bimetallic alloy nanoparticles were loaded on carbon nanotubes to prepare Ni-Pt nanoparticles/carbon nanotubes composites (Ni-Pt NPs/CNTs) as excellent catalytic materials for ethanol electro-oxidation reaction (EOR). X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and special aberration corrected transmission electron microscope (STEM) were used to characterize its morphology and structure. The activity and stability of the composite were measured by cyclic voltammetry (CV) and chronoamperometry (CA). The catalytic performance was explored by adjusting the ratio of Ni to Pt. Performance test results showed that the Ni-Pt alloy formed 10–15 nm spherical particles and dispersed uniformly on the surface of carbon nanotubes. The Ni1Pt1 NPs/CNTs composite showed excellent performance for EOR. Its mass activity of ethanol electro-oxidation was 620 mA·mg−1Pt, which was 5.08, 18.2 times higher than that of commercial Pt/C and Pt black catalyst, respectively.

Solution-plasma interaction for synthesizing highly active Pt-Ni alloy oxygen reduction nanocatalysts for PEMFCs.

A highly active PtNi-alloy catalyst (p-PtNi/KB) is synthesized using solution-plasma interaction. The plasma effect results in a substantial increase of active sites on the support surface. This facilitates the alloying and functionalization of supports, enabling achievement of enhanced catalytic activity and effective resolution of cost-related challenges in fuel cells.

A novel core-shell nanostructure of Ti-Au nanocrystal with PtNi alloy skin: Enhancing the durability for oxygen reduction reaction

The sluggish oxygen reduction reaction (ORR) at the cathode largely hinders the practical application of the proton-exchange membrane fuel cells (PEMFCs). Pt-based nanocrystals are the most effective electrocatalysts for the oxygen reduction reaction, however, suffer high cost, scarcity and unsatisfied durability. Herein, we report a new category of annealed multimetallic core-shell catalyst of gold core doped with titanium and platinum-nickel (PtNi) shell with Pt-rich surface as a highly active and robust electrocatalyst for ORR. The introduction of titanium can effectively stabilize the gold core, avoiding the outward migration of Au atoms and ensuring the exposure of Pt-Ni active sites. The experimental findings revealed that the annealed Ti-Au@PtNi NPs catalyst provides 19.26 and 9.84 times higher mass and specific activities than commercial Pt/C catalysts for the oxygen reduction reaction. Moreover, durability tests of annealed Ti-Au@PtNi NPs show no noticeable activity loss even after 20000 potential cycles between 0.6 and 1.0 V vs. RHE, demonstrating a promising catalyst for the oxygen reduction reaction.

Hydrodeoxygenation of anisole over SBA-15-supported Ni, Pd, and Pt mono- and bimetallic catalysts: effect of the metal's nature on catalytic activity and selectivity.

Monometallic Ni, Pd and Pt and bimetallic catalysts formed by combinations of the above metals supported on SBA-15 silica were synthesized, characterized and tested in the hydrodeoxygenation reaction of anisole. The objective of the work was to detect the effect of the nature of metals on the activity of the catalysts at different steps of anisole hydrodeoxygenation: hydrogenation of the aromatic ring of anisole and C-O bond cleavage in the intermediate cyclohexyl methyl ether. The support and the catalysts were characterized by N2 physisorption, X-ray diffraction, UV-vis diffuse reflectance spectroscopy, temperature-programmed reduction, scanning electron microscopy-energy dispersive X-ray spectroscopy, transmission electron microscopy and HAADF-STEM. The catalytic activity tests were carried out in a batch reactor at 280 °C and 7.3 MPa pressure. The activity results show that the NiPd/SBA-15 catalyst had the greatest ability for hydrogenation of the aromatic ring of anisole, while its NiPt/SBA-15 analog resulted in better activity for C-O bond hydrogenolysis. The bimetallic NiPt/SBA-15 catalyst showed the best catalytic performance in the HDO of anisole ascribed to the formation of a Ni-Pt alloy. On the other hand, the combination of Pd and Pt metals in the PdPt/SBA-15 catalyst resulted in the formation of bimetallic particles with Pd-rich and Pt-rich domains, showing high selectivity for the formation of the cyclohexyl methyl ether, which can be useful for the hydrogenation of aromatic rings in O-containing reactants with the formation of saturated O-containing products. According to the characterization results (HAADF-STEM), the different catalytic behavior of NiPd/SBA-15, NiPt/SBA-15, and PdPt/SBA-15 catalysts could be attributed to different characteristics of the bimetallic active phases in them.

Comprehensive investigation of Ni-rich PtNi alloy nanoparticles: structural, magnetic, and catalytic properties for efficient alkaline water electrolysis

Comprehensive investigation of Ni-rich PtNi alloy nanoparticles: structural, magnetic, and catalytic properties for efficient alkaline water electrolysis

(Invited) Current Status and Progress in Anion Exchange Membrane Electrolysis

Anion exchange membrane (AEM) electrolysis is a promising solution for large-scale hydrogen production from renewable energy resources. However, the performance of AEM electrolysis is still lower than what can be achieved with conventional technologies. Materials chemistry, MEA designs, and optimal operation conditions have driven recent advancements. Majority of the AEM research has focused on improving ionic conductivity and alkaline stability. Many AEMs exceed 0.1 S/cm (at 60–80 °C), however stability at temperatures above 60 °C needs improvement. Oxygen evolution reaction OER remains a bottleneck. The active-site mechanism of NiFe catalysts is disputed, and their long-term stability is unknown. Co boosts NiFe catalyst conductivity. Carbon-supported Pt dominates the hydrogen evolution process (HER), whereas PtNi alloys and clusters of Ni(OH)2 on Pt compete. Well-dispersed Ru nanoparticles on functionalized high-surface-area carbon substrates show promising HER actions. New in situ methods, AEMWE evaluation processes, and catalyst-structure designs could help the field advance faster. Nonetheless, single AEM water electrolyzer cells have operated for several thousand hours at 60 °C and 1 A/cm2.