Constructing Patch‐Ni‐Shelled Pt@Ni Nanoparticles within Confined Nanoreactors for Catalytic Oxidation of Insoluble Polysulfides in Li‐S Batteries

Reducing the deposit of discharge products and suppressing the polysulfide shuttle are critical to enhancing reaction kinetics in Li‐S batteries. Herein, a Pt@Ni core–shell bimetallic catalyst with a patch‐like or complete Ni shell based on a confined catalysis reaction in porous carbon spheres is reported. The Pt nanodots can effectively direct and catalyze in situ reduction of Ni²⁺ ions to form core–shell catalysts with a seamless interface that facilitates the charge transfer between the two metals. Thus, the bimetallic catalysts offer a synergic effect on catalyzing reactions, which shows dual functions for catalytic oxidation of insoluble polysulfides to soluble polysulfides by effectively reducing the energy barrier with simultaneous strong adsorption, ensuring a high reversible capacity and cycling stability. A novel process based on the Pt@Ni core–shell bimetallic catalyst with a patch‐like Ni shell is proposed: electronic migration from Ni to Pt forces Ni to activate Li₂S₂/Li₂S molecules by promoting the transformation of Li‐S‐Li to Ni‐S‐Li, consequently releasing Li⁺ and free electrons, simultaneously enhancing protonic/electronic conductivity. The presence of the intermediate state Ni‐S‐Li is more active to oxidize Li₂S to polysulfides. The Li₂S bound to adjacent Pt sites reacts with abundant ‐S‐Li species and then releases the Pt sites for the next round of reactions.     

A General Strategy Assisted with Dual Reductants and Dual Protecting Agents for Preparing Pt‐Based Alloys with High‐Index Facets and Excellent Electrocatalytic Performance

Synthesizing noble metallic nanoparticles (NPs) enclosed by high‐index facets (HIFs) is challenged as it involves the tuning of growth kinetics, the selective adsorption of certain chemical species, and the epitaxial growth from HIF enclosed seeds. Herein, a simple and general strategy is reported by using dual reduction agents and dual capping agents to prepare Pt‐based alloy NPs with HIFs, in which both glycine and poly(vinylpyrrolidone) serve as the reductants and capping agents. Due to the facilely tunable growth/nucleation rates and protecting abilities of the reductants and capping agents, Pt concave nanocube (CNC), binary Pt–Ni CNC, ternary Pt–Mn–Cu CNC, and Pt–Mn–Cu ramiform polyhedron alloy NPs terminated by HIFs as well as other NPs with well‐defined morphologies such as Pt–Mn–Cu nanocube and Pt–Mn–Cu nanoflower are obtained with this approach. Owing to the high density of low‐coordinated Pt sites (HIF structure) and the unique electronic effect of Pt–Mn–Cu ternary alloys, the as‐prepared Pt–Mn–Cu NPs show enhanced catalytic activity toward methanol and formic acid electro‐oxidation reactions with excellent stability. This work provides a promising methodology for designing and fabricating Pt‐based alloy NPs as efficient fuel cell catalyst.     

Size‐Controlled Synthesis of Sub‐10 nm PtNi3 Alloy Nanoparticles and their Unusual Volcano‐Shaped Size Effect on ORR Electrocatalysis

Dealloyed Pt bimetallic core–shell catalysts derived from low‐Pt bimetallic alloy nanoparticles (e.g, PtNi₃) have recently shown unprecedented activity and stability on the cathodic oxygen reduction reaction (ORR) under realistic fuel cell conditions and become today's catalyst of choice for commercialization of automobile fuel cells. A critical step toward this breakthrough is to control their particle size below a critical value (≈10 nm) to suppress nanoporosity formation and hence reduce significant base metal (e.g., Ni) leaching under the corrosive ORR condition. Fine size control of the sub‐10 nm PtNi₃ nanoparticles and understanding their size dependent ORR electrocatalysis are crucial to further improve their ORR activity and stability yet still remain unexplored. A robust synthetic approach is presented here for size‐controlled PtNi₃ nanoparticles between 3 and 10 nm while keeping a constant particle composition and their size‐selected growth mechanism is studied comprehensively. This enables us to address their size‐dependent ORR activities and stabilities for the first time. Contrary to the previously established monotonic increase of ORR specific activity and stability with increasing particle size on Pt and Pt‐rich bimetallic nanoparticles, the Pt‐poor PtNi₃ nanoparticles exhibit an unusual “volcano‐shaped” size dependence, showing the highest ORR activity and stability at the particle sizes between 6 and 8 nm due to their highest Ni retention during long‐term catalyst aging. The results of this study provide important practical guidelines for the size selection of the low Pt bimetallic ORR electrocatalysts with further improved durably high activity.     

Double core---shell nanostructured Sn---Cu alloy as enhanced anode materials for lithium and sodium storage

Sn-based alloy materials are considered as a promising anode candidate for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs), whereas they suffer from severe volume change during the discharge/charge process. To address the issue, double core–shell structured Sn–Cu@SnO₂@C nanocomposites have been prepared by a simple co-precipitation method combined with carbon coating approach. The double core–shell structure consists of Sn–Cu multiphase alloy nanoparticles as the inner core, intermediate SnO₂ layer anchored on the surface of Sn–Cu nanoparticle and outer carbon layer. The Sn–Cu@SnO₂@C electrode exhibits outstanding electrochemical performances, delivering a reversible capacity of 396 mA·h·g⁻¹ at 100 mA·g⁻¹ after 100 cycles for LIBs and a high initial reversible capacity of 463 mA·h·g⁻¹ at 50 mA·g⁻¹ and a capacity retention of 86% after 100 cycles, along with a remarkable rate capability (193 mA·h·g⁻¹ at 5000 mA·g⁻¹) for SIBs. This work provides a viable strategy to fabricate double core–shell structured Sn-based alloy anodes for high energy density LIBs and SIBs.     

Gradient-Concentration Design of Stable Core–Shell Nanostructure for Acidic Oxygen Reduction Electrocatalysis

Manipulating the surface structure of electrocatalysts at the atomic level is of primary importance to simultaneously achieve the activity and stability dual-criteria in oxygen reduction reaction (ORR) for proton exchange membrane fuel cells. Here, a durable acidic ORR electrocatalyst with the “defective-armored” structure of Pt shell and Pt–Ni core nanoparticle decorated on graphene (Pt–Ni@Pt_D/G) using a facile and controllable galvanic replacement reaction to generate gradient distribution of Pt–Ni composition from surface to interior, followed by a partial dealloying approach, leaching the minor nickel atoms on the surface to generate defective Pt skeleton shell, is reported. The Pt–Ni@Pt_D/G catalyst shows impressive performance for ORR in acidic (0.1 m HClO₄) electrolyte, with a high mass activity of threefold higher than that of Pt/C catalyst owing to the tuned electronic structure of locally concave Pt surface sites through synergetic contributions of Pt–Ni core and defective Pt shell. More importantly, the electrochemically active surface areas still retain 96% after 20 000 potential cycles, attributing to the Pt atomic shell acting as the protective “armor” to prevent interior Ni atoms from further dissolution during the long-term operation.     

纳米多孔Pd-Cu/Pd-Ag催化剂的制备及其电催化性能EI北大核心CSCD

针对直接甲醇燃料电池(direct methanol fuel cell,DMFE)对高效阳极催化剂的需求,设计研发Ca-Mg-Pd-M(M=Cu,Ag)非晶合金前躯体体系,并采用去合金化制备系带-孔道双连续结构的纳米多孔Pd-Cu/Pd-Ag合金。通过设计前驱体合金比例可调节多孔结构的元素比例和尺寸,Pd元素可与Cu,Ag元素形成连续固溶体,在去合金化过程中可以降低Cu,Ag元素的扩散,进而细化纳米多孔的系带尺寸(由100 nm减小到10 nm)。相较于纳米多孔Pd,纳米多孔Pd-Cu/Pd-Ag合金表现出更优异的甲醇催化活性(催化电流强度:45 mA/mg)和抗毒化能力(J f/J b值为1.56),还具有低成本的优点,在直接甲醇燃料电池阳极催化剂方面有着良好的应用前景。     

Structure and properties of nanoporous FePt fabricated by dealloying a melt-spun Fe_(60)Pt_(20)B_(20) alloy and subsequent annealing

A nanoporous FePt alloy has been fabricated by dealloying a melt-spun Fe(60)Pt(20)B(20)alloy composed of nanoscale amorphous and face-centered-cubic FePt(fcc-FePt)phases in H2 SO4 aqueous solution.The nanoporous alloy consists of single fcc-FePt phase with an Fe/Pt atomic ratio of about 55.3/44.7,and possesses a uniform interpenetrating ligament-channel structure with average ligament and pore sizes of 27 nm and 12 nm,respectively.The nanoporous fcc-FePt alloy shows soft magnetic characteristics with a saturation magnetization of 37.9 emu/g and better electrocatalytic activity for methanol oxidation than commercial Pt/C in acidic environment.The phase transformation from disordered fcc-Fe Pt into ordered face-centered-tetragonal FePt(L10-FePt)in the nanoporous alloy has been realized after annealing at823-943 K for 600 s.The volume fraction of the L10-FePt phase in the alloy increases with the rise of annealing temperature,which results in the enhancements of coercivity and saturation magnetization from 0.14 kOe and 38.5 emu/g to 8.42 kOe and 51.4 emu/g,respectively.The ligament size of the samples is increased after annealing.     

Synthesis and characteristics of Ag/Pt bimetallic nanocomposites by arc-discharge solution plasma processing

Arc discharge in solution, generated by applying a high voltage of unipolar pulsed dc to electrodes of Ag and Pt, was used as a method to form Ag/Pt bimetallic nanocomposites via electrode erosion by the effects of the electric arc at the cathode (Ag rod) and the sputtering at the anode (Pt rod). Ag/Pt bimetallic nanocomposites were formed as colloidal particles dispersed in solution via the reduction of hydrogen radicals generated during discharge without the addition of chemical precursor or reducing agent. At a discharge time of 30?s, the fine bimetallic nanoparticles with a mean particle size of approximately 5?nm were observed by transmission electron microscopy (TEM). With increasing discharge time, the bimetallic nanoparticle size tended to increase by forming an agglomeration. The presence of the relatively small amount of Pt dispersed in the Ag matrix could be observed by the analytical mapping mode of energy-dispersive x-ray spectroscopy and high-resolution TEM. This demonstrated that the synthesized particle was in the form of a nanocomposite. No contamination of other chemical substances was detected by x-ray photoelectron spectroscopy. Hence, solution plasma could be a clean and simple process to effectively synthesize Ag/Pt bimetallic nanocomposites and it is expected to be widely applicable in the preparation of several types of nanoparticle.     

Morphology and surface plasma changes of Au-Pt bimetallic nanoparticles

In this study, we examined the amount-dependent change in morphology in a series of Au-Pt bimetallic nanoparticles synthesized using chemical reduction. The amount of Au precursor was kept constant throughout the experiment. The Au/Pt molar ratio was varied from 1/1 to 1/4 to synthesize Pt shell layers with different thicknesses. We observed a remarkable shift of the surface plasmon band at around 410 nm. By high-resolution transmission electron microscopy (HRTEM) and energy-dispersive spectrometry (EDS), the composition of the shell layer was found to be Pt-enriched Au-Pt alloy. As the concentration of Pt increases, Pt clusters (ca. 1.8 nm in diameter) form a string-like shape on the surface of nanoparticles.     

New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method

In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE.     

添加Al对燃料电池阴极催化剂(Pt-Fe)/Pt合金微观组织及氧还原催化性能的影响

为提高燃料电池阴极催化剂(Pt-Fe)/Pt合金的氧还原催化活性和稳定性,在Pt-Fe合金体系中引入元素Al,熔炼得到中间合金(Pt-Fe)Al,再经过NaOH溶液定向腐蚀得到(Pt1-xFex)₃Al/Pt合金,用其作为燃料电池氧还原反应的催化剂,并对其结构、催化活性和稳定性进行了研究。结果表明,所制备的催化剂材料(Pt1-xFex)₃Al/Pt合金具有由几个原子层厚的纯Pt外壳和成分为(Pt1-xFex)₃Al的内核构成的双模孔隙且内部互通的包覆式结构。相比于传统燃料电池的氧还原反应催化剂Pt/C材料以及由Pt-Fe体系制备的Pt₄₆Fe₅₄/Pt合金,(Pt1-xFex)₃Al/Pt合金的比活性分别是Pt₄₆Fe₅₄/Pt合金、Pt/C比活性的 1.21倍和2.69倍,其质量活性分别是Pt₄₆Fe₅₄/Pt和Pt/C的1.17倍和5.3倍。在催化稳定性方面,(Pt1-xFex)₃Al/Pt的电化学活性面积在10 000圈伏安循环后衰减到89%,然后趋于稳定,且循环40 000圈后其仍保留80%的电化学活性面积。由此可见,所制备的催化剂材料(Pt1-xFex)₃Al/Pt合金具有较高的催化活性及催化稳定性。     

Core–shell nanostructure supported Pt catalyst with improved electrocatalytic stability in oxygen reduction reaction

Core–shell nanostructure electrode (TiO₂@C) for oxygen reduction reaction is prepared with TiO₂ nanoparticles at 900 °C in a methane atmosphere. The TiO₂@C supported Pt catalyst (Pt/TiO₂@C) contains Pt nanoparticles on TiO₂@C nanostructure electrodes consisting of TiO₂ as a core and carbon as a shell. In the accelerated stability test, the Pt/TiO₂@C exhibits a superior ORR stability to conventional carbon supported Pt catalyst. It is likely that the enhanced catalytic properties of the nanostructure supported Pt catalyst may be due to graphite-like carbon and an improved electronic conductivity of the core–shell nanostructure.     

Facile synthesis of metal and alloy nanoparticles by ultrasound-assisted dealloying of metallic glasses

Metal and alloy nanoparticles synthesized by chemical reduction have attracted increasing attention due to their superior physical,chemical,and biological properties.However,most chemical synthesis processes rely on the use of harsh reducing agents and complicated chemical ingredients.Herein,we report a novel reduction-agent-free and surfactant(stabilizer)-free strategy to synthesize Cu,Ag,Au,Cu-Pt,Cu-Au,Cu-Au-Pt-Pd,and Au-Pt-Pd-Cu nanoparticles by ultrasound-assisted dealloying of Mg-based metallic glasses.The formation mechanism of the metal and alloy nanoparticles is revealed by a detailed investigation of sequential intermediate products.We demonstrate that the glass-liquid phase transition of the initially dealloying metallic glasses,together with the synergistic effect of dealloying and ultrasound-driven ligament-breakage of small enough nanoporous intermediates,play key roles in preparing the uniformly dispersed metal and alloy nanoparticles.This approach greatly simplifies the up-scaling synthesis of monometallic and bimetallic nanoparticles,and also provides a general strategy for synthesizing unprecedented multimetallic nanoparticles.     

Synthesis of a thermoresponsive platinum nanocomposite using a three-layer onion-like polymer as template

Using a well-designed three-layer onion-like polymer as template, a one-pot procedure that led to stable, narrow-sized and thermoresponsive Pt nanocomposites is described. The polymer consists of an outer shell of thermoresponsive poly(N-isopropylacrylamide), an inner shell of crosslinked poly(N,N-dimethylaminoethyl acrylate) and a hyperbranched polyglycerol core. The core is physically trapped by the shell, with a few thiol groups located on the interface between the core and the shell. The polymer is used as a template for the synthesis of platinum nanoparticles, ¹H NMR and TEM analyses suggest that the in-situ produced, narrow-sized Pt nanoparticle is loaded in the core part of the polymer so that the nanocomposite retains thermoresponsive activity.     

A facile synthesis of Cu(2)O/SiO(2) and Cu/SiO(2) core-shell octahedral nanocomposites

We report here a simple approach to the synthesis of Cu(2)O/SiO(2) core-shell nanocomposites in water solution. The Cu(2)O cores have a perfect octahedral structure with uniform size of about 200-300?nm. A compact SiO(2) shell 9?nm in thickness is located at the surfaces of Cu(2)O octahedra, and it is composed of fine SiO(2) nanoparticles. During the depositing of the SiO(2) particles, as we presumed, dynamic absorbing and disengaging of Na(+) at the interface of Cu(2)O octahedra and the solution made it possible for the formation of Cu-O-Si bonds between core and shell in the composites. The existence of Cu-O-Si bonds in our core-shell composite can be substantiated by peak changes at?1236 and 1080?cm(-1) in the FT-IR spectra. This is the reason why the SiO(2) shell is so compact and uniform. Moreover, these Cu(2)O/SiO(2) core-shell octahedra were further used as precursors, depending on a simple disproportionation reaction of Cu(2)O in acid, to easily achieve Cu/SiO(2) movable multicore-shell octahedral nanocomposites. In the final Cu/SiO(2) core-shell composite, the thin SiO(2) octahedral shell was held, inside of which formed several free Cu nanoparticles 50-80?nm in size. Studies on the Cu(2)O/SiO(2) core-shell octahedral composites and Cu/SiO(2) movable multicore-shell octahedral nanocomposites would be a good thing not only for fundamental research but also for applications.     

Convenient immobilization of Pt-Sn bimetallic catalysts on nitrogen-doped carbon nanotubes for direct alcohol electrocatalytic oxidation

Pt-Sn alloy nanoparticles were conveniently immobilized on nitrogen-doped carbon nanotubes (NCNTs) through microwave-assisted ethylene glycol reduction. The nanoparticles have a narrow particle size distribution with the average particle size around 3 nm as measured by transmission electron microscopy and x-ray diffraction. The binding energy of metallic Sn passively shifts due to the charge transfer from Sn to Pt, as revealed by x-ray photoelectron spectroscopy. In comparison with the commercial Pt/C catalyst, Pt/NCNT presents a clear increase in activity for alcohol electro-oxidation due to the improved support, while the bimetallic Pt-Sn/NCNT has even higher activity owing to the alloying of Pt with Sn. Both Pt-Sn/NCNT and Pt/NCNT catalysts exhibit competitive long-term stability to Pt/C catalyst. The low cost, simple preparation and superior electrocatalytic performance indicate the great potential of Pt-Sn/NCNT in direct alcohol fuel cells.     

Topotactic Transformations in an Icosahedral Nanocrystal to Form Efficient Water‐Splitting Catalysts

Designing high‐performance, precious‐metal‐based, and economic electrocatalysts remains an important challenge in proton exchange membrane (PEM) electrolyzers. Here, a highly active and durable bifunctional electrocatalyst for PEM electrolyzers based on a rattle‐like catalyst comprising a Ni/Ru‐doped Pt core and a Pt/Ni‐doped RuO₂ frame shell, which is topotactically transformed from an icosahedral Pt/Ni/Ru nanocrystal, is reported. The RuO₂‐based frame shell with its highly reactive surfaces leads to a very high activity for the oxygen evolution reaction (OER) in acidic media, reaching a current density of 10 mA cm^?2 at an overpotential of 239 mV, which surpasses those of previously reported catalysts. The Pt dopant in the RuO₂ shell enables a sustained OER activity even after a 2000 cycles of an accelerated durability test. The Pt‐based core catalyzes the hydrogen evolution reaction with an excellent mass activity. A two‐electrode cell employing Pt/RuO₂ as the electrode catalyst demonstrates very high activity and durability, outperforming the previously reported cell performances.     

Structure determination of chitosan-stabilized Pt and Pd based bimetallic nanoparticles by X-ray photoelectron spectroscopy and transmission electron microscopy

Chitosan (CTS)-stabilized bimetallic nanoparticles were prepared at room temperature (rt.) in aqueous solution. Palladium (Pd) and platinum (Pt) were selected as the first metals while iron (Fe) and nickel (Ni) functioned as the second metals. In order to obtain the noble metal core-transition metal shell structures, bimetallic nanoparticles were prepared in a two-step process: the preparation of mono noble metallic (Pd or Pt) nanoparticles and the deposition of transition metals (Fe or Ni) on the surface of the monometallic nanoparticles. The structures of the nanoparticles were studied using X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The XPS results show that Pd and Pt exist mainly in zero valences. The presence of Fe and Ni in the bimetallic nanoparticles affects the binding energy of Pd and Pt. Moreover, the studies of O 1s spectra indicate the presence of Fe or Ni shells. The analyses of TEM micrographs give the particle size and size distributions while the high-resolution TEM (HRTEM) micrographs show the existence of noble metal core lattices. The results confirm the formation of noble metal core-transition metal shell structures.     

High‐Indexed PtNi Alloy Skin Spiraled on Pd Nanowires for Highly Efficient Oxygen Reduction Reaction Catalysis

The catalytic performance of Pt‐based catalysts for oxygen reduction reactions (ORR) can generally be enhanced by constructing high‐index exposed facets (HIFs). However, the synthesis of Pt alloyed high‐index skins on 1D non‐Pt surfaces to further improve Pt utilization and stability remains a fundamental challenge for practical nanocrystals. In this work, Pd nanowires (NWs) are selected as a rational medium to facilitate the epitaxial growth of Pt and Ni. Based on the different nucleation and growth habits of Pt and Ni, a continuous PtNi alloy skin bounded with HIFs spiraled on a Pd core can be obtained. Here, the as‐prepared helical Pd@PtNi NWs possess high HIF densities, low Pt contents, and optimized oxygen adsorption energies, demonstrating an enhanced ORR mass activity of 1.75 A mg_Pt^?1 and a specific activity of 3.18 mA cm^?2, which are 10 times and 12 times higher than commercial Pt/C catalysts, respectively. In addition, the 1D nanostructure enables the catalyst to be highly stable after 30 000 potential sweeping cycles. This work successfully extends bulky high‐indexed Pt alloys to core–shell nanostructures with the design of a new, highly efficient and stable Pt‐based catalyst for fuel cells.     

Multi-walled carbon nanotubes-supported Fe(naph)3 nanoparticles to prepare polyacetylene/multi-walled carbon nanotubes nanocomposites

Carbon nanotubes (CNTs) are a promising candidate for preparing conductive polymer/CNT nanocomposites. CNTs are also an alternative to conventional catalyst support. This report studies multi-walled carbon nanotubes (MWNTs) supported-Fe(naph)₃ nanoparticles to prepare polyacetylene (PA)/MWNT nanocomposites with core–shell structure. The XPS spectra and HRTEM images demonstrate the Fe(naph)₃ nanoparticles successfully deposited on the walls of MWNTs and partially transformed to γ-Fe₂O₃ nanoparticles after heated at 100 °C for 2 h. XRD analysis indicates the formation of PA on the walls of MWNTs. Structural analysis using HRTEM shows that PA/MWNT nanocomposites exhibit core–shell structure. TGA data reveals the stability of PA grown on the exterior walls of MWNTs has been improved. The growth mechanism of PA/MWNT nanocomposites can be explained by a heterogeneous process. The conductivity of the nanocomposites was studied by a four-probe approach and a relatively high conductivity was observed.