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1.
Among various platinum (Pt)‐based nanostructures, porous or hollow ones are of great importance because they exhibit fantastic oxygen reduction reaction (ORR) enhancements and maximize atomic utilization by exposing both exterior and interior surfaces. Here, a new class of porous Pt3Ni nanowires (NWs) with 1D architecture, an ultrathin Pt‐rich shell, high index facets, and a highly open structure is designed via a selective etching strategy by using the phase and composition segregated Pt‐Ni NWs as the starting material. The porous feature of Pt3Ni NWs can be readily fulfilled by changing the Pt/Ni atomic ratio of the starting Pt‐Ni NWs. Such porous Pt3Ni NWs show extraordinary activity and stability enhancements toward methanol oxidation reaction and ORR. The porous Pt3Ni NWs can deliver ORR mass activity of 5.60 A mg?1, which is 37.3‐fold higher than that of the Pt/C. They also show outstanding stability with negligible activity loss after 20 000 cycles. This study offers a unique approach for the design of complex nanostructures as efficient catalysts through precisely tailoring.  相似文献   

2.
Conductive nanowires (NWs) provide several advantages as a template and electrode material for solar cells due to their favorable light scattering properties. While the majority of NW solar cell architectures studied are based on semiconductor materials, metallic NWs could provide equivalent anti‐reflection properties, while acting as a low‐resistance back contact for charge transport, and facilitate light scattering in thin layers of semiconductors coated on the surface. However, fabrication of single‐crystalline highly anti‐reflective NWs on low‐cost, flexible substrates remains a challenge to drive down the cost of NW solar cells. In this study, metallic NixSi NW arrays are fabricated by a simple, bottom‐up, and low‐cost method based on the thermal decomposition of silane on the surface of flexible Ni foil substrates without the need for lithography, etching or catalysts. The optical properties of these NW arrays demonstrate broadband suppression of reflection to levels below 1% from 350 nm to 1100 nm, which is among the highest values reported for NWs. A simple route to control the diameter and density of the NWs is introduced based on variations in a carrier gas flow rate. A high‐resolution TEM, XRD and TEM‐EDS study of the NWs reveals that they are single crystalline, with the phase and composition varying between Ni2Si and NiSi. The nanowire resistivity is measured to be 10?4 Ω‐cm, suggesting their use as an efficient back electrode material for nanostructured solar cells with favorable light scattering properties.  相似文献   

3.
Developing nanostructured Ni and Co oxides with a small overpotential and fast kinetics of the oxygen evolution reaction (OER) have drawn considerable attention recently because their theoretically high efficiency, high abundance, low cost, and environmental benignity in comparison with precious metal oxides, such as RuO2 and IrO2. However, how to increase the specific activity area and improve their poor intrinsic conductivity is still challenging, which significantly limits the overall OER rate and largely prevent their utilization. Thus, developing effective OER electrocatalysts with abundant active sites and high electrical conductivity still remains urgent. In this work, a scrupulous design of OER electrode with a unique sandwich‐like coaxial structure of the three‐dimensional Ni@[Ni(2+/3+)Co2(OH)6–7]x nanotube arrays (3D NNCNTAs) is reported. A Ni nanotube array with open end is homogeneous coated with Ni and Co co‐hydroxide nanosheets ([Ni(2+/3+)Co2(OH)6–7]x) and is employed as multifunctional interlayer to provide a large surface area and fast electron transport and support the outermost [Ni(2+/3+)Co2(OH)6–7]x layer. The remarkable features of high surface area, enhanced electron transport, and synergistic effects have greatly assured excellent OER activity with a small overpotential of 0.46 V at the current density of 10 mA cm?2 and high stability.  相似文献   

4.
Silicon nanowires (Si NWs) have been identified as an excellent candidate material for the replacement of graphite in anodes, allowing for a significant boost in the capacity of lithium‐ion batteries (LIBs). Herein, high‐density Si NWs are grown on a novel 3D interconnected network of binary‐phase Cu‐silicide nanofoam (3D CuxSiy NF) substrate. The nanofoam facilitates the uniform distribution of well‐segregated and small‐sized catalyst seeds, leading to high‐density/single‐phase Si NW growth with an areal‐loading in excess of 1.0 mg cm?2 and a stable areal capacity of ≈2.0 mAh cm?2 after 550 cycles. The use of the 3D CuxSiy NF as a substrate is further extended for Al, Bi, Cu, In, Mn, Ni, Sb, Sn, and Zn mediated Si NW growth, demonstrating the general applicability of the anode architecture.  相似文献   

5.
Low-dimensional amorphous metallic nanomaterials provide great possibility for creating high-performance electrocatalysts owing to their conspicuous reacting merits derived from the flexible coordination structures, but remain extremely challenging in synthesis. Herein, this work reports a facile synthesis of carbon-loaded amorphous 1.5-nm-thick Pt–Ru nanowires (NWs) through a local oxidation induced amorphization process. During annealing premade crystalline Pt–Ru NWs/C in air, a local-oxidation of the oxyphilic Ru generates abundant random Ru–O bonds and disturbs the order bimetallic lattices. The as-prepared amorphous Pt53Ru47 (a-Pt53Ru47) NWs/C exhibits an extremely high activity (13.7 A mg−1 at 25 mV overpotential) and an excellent CO-tolerance for alkaline hydrogen oxidation reaction (HOR) electrocatalysis, drastically outperforming the crystalline counterpart and commercial benchmarks. Mechanism studies indicate the Pt–Ru bimetallic effects as well as the rich disordered “Pt–Ru–O” and/or “Pt–O–Ru” atomic heterojunctions can weaken the *H binding energy and inversely strengthen the *OH adsorption, thus promoting the alkaline HOR kinetics. More uniquely, the small interatomic spaces derived from the disordered bond nets present a H2/*H-selected permeability, which spatially obstruct the relatively larger CO molecules to poison the internal catalytic sites during HOR. The CO-shielded internal catalytic sites and the enriched surface *OH jointly upgrade the CO-tolerance of the a-Pt53Ru47 NWs/C catalysts.  相似文献   

6.
In this study, a general and effective phosphorization strategy is successfully demonstrated to enhance supercapacitor performance of various transition metals oxide or hydroxide, such as Ni(OH)2, Co(OH)2, MnO2, and Fe2O3. For example, a 3D networked Ni2P nanosheets array via a facile phosphorization reaction of Ni(OH)2 nanosheets is grown on the surface of a Ni foam. The Ni foam‐supported Ni2P nanosheet (Ni2P NS/NF) electrode shows a remarkable specific capacitance of 2141 F g?1 at a scan rate of 50 mV s?1 and remains as high as 1109 F g?1 even at the current density of 83.3 A g?1. The specific capacitance is much larger than those of Ni(OH)2 NS/NF (747 F g?1 at 50 mV s?1). Furthermore, the electrode retains a high specific capacitance of 1437 F g?1 even after 5000 cycles at a current density of 10 A g?1, in sharp contrast with only 403 F g?1 of Ni(OH)2 NS/NF at the same current density. The similar enhanced performance is observed for Ni2P powder, which eliminates the influence of nickel foam. The enhanced supercapacitor performances are attributed to the 3D porous nanosheets network, enhanced conductivity, and two active components of Ni2+ and Pδ? with rich valences of Ni2P.  相似文献   

7.
The visible‐light‐driven photocatalytic CO2 reduction is one appealing approach to simultaneously mitigate the energy crisis and environmental issues. It is highly desirable but challenging to selectively and efficiently convert CO2 into desirable products. Herein, a covalent organic framework hosting metalloporphyrin‐based carbon dots (M‐PCD@TD‐COF, M = Ni, Co, and Fe) is first presented, which serves as heterogeneous catalysts for CO2 photoreduction. M‐PCD@TD‐COF not only enriches available COF‐based catalytic materials, but also provides suitable environment for CO2 adsorption and activation on metalloporphyrin‐based carbon dots. The advantages of the host environment in COFs are highlighted by the satisfactory catalytic activity and remarkable selectivity of CO2‐to‐CO conversion over H2 generation up to 98%. The photocatalytic system is effective for both pure CO2 and the simulated flue gas. This work provides new protocols for the rational design of COF‐based heterogeneous catalysts for selective CO2 photoreduction.  相似文献   

8.
The formation of homojunctions and heterojunctions on two‐dimensional (2D) substrates plays a key role in the device performance of thin films. Accelerating the progress of device fabrication in nanowires (NWs) also necessitates a similar understanding in the one‐dimensional (1D) system. Nanohomojunction (GaN on GaN) and nanoheterojunction (InN on GaN) nanorods (NRs) were formed in a two‐step growth process by a vapor–liquid–solid (VLS) mechanism. Ga2O3 nanoribbons were formed using Ni as catalyst in a chemical vapor deposition (CVD) technique and then completely converted to GaN NWs with NH3 as reactant gas. An Au catalyst is used in the second step of the VLS process to grow GaN and InN NRs on GaN NWs using CVD techniques. A morphological study showed the formation of nanobrushes with different structural symmetries and sub‐symmetries in both homogeneous and heterogeneous systems. Structural characterizations showed nearly defect‐free growth of nanohomojunction (GaN) and nanoheterojunction (InN) NRs on 1D GaN NW substrates.  相似文献   

9.
High‐loading lithium–sulfur (Li–S) batteries suffer from poor electrochemical properties. Electrocatalysts can accelerate polysulfides conversion and suppress their migration to improve battery cyclability. However, catalysts for Li–S batteries usually lack a rational design. A d‐band tuning strategy is reported by alloying cobalt to metal sites of Ni2P to enhance the interaction between polysulfides and catalysts. A molecular or atomic level analysis reveals that Ni2Co4P3 is able to weaken the S? S bonds and lower the activation energy of polysulfides conversion, which is confirmed with temperature‐dependent experiments. Ni2Co4P3 nanowires are further fabricated on a porous nickel scaffold to unfold the catalytic activity by its large surface area. Using a simple ion‐selective filtration shell, a microreactor‐like S cathode (MLSC) is constructed to realize ultrahigh S loading (25 mg cm?2). As such, a microreactor design integrates reaction and separation in one cell and can effectively address the polysulfide issues, the MLSC cell demonstrates excellent properties of cyclability and high capacity (1223 mAh g?1 at 0.1 C). More importantly, the catalyst's designs and microreactor strategies provide new approaches for addressing the complicated issues of Li–S batteries.  相似文献   

10.
Nonmetallic plasmonic heterostructure TiO2‐mesocrystals/WO3?x‐nanowires (TiO2‐MCs/WO3?x‐NWs) are constructed by coupling mesoporous crystal TiO2 and plasmonic WO3?x through a solvothermal procedure. The continuous photoelectron injection from TiO2 stabilizes the free carrier density and leads to strong surface plasmon resonance (SPR) of WO3?x, resulting in strong light absorption in the visible and near‐infrared region. Photocatalytic hydrogen generation of TiO2‐MCs/WO3?x‐NWs is attributed to plasmonic hot electrons excited on WO3?x‐NWs under visible light irradiation. However, utilization of injected photoelectrons on WO3?x‐NWs has low efficiency for hydrogen generation and a co‐catalyst (Pt) is necessary. TiO2‐MCs/WO3?x‐NWs are used as co‐catalyst free plasmonic photocatalysts for CO2 reduction, which exhibit much higher activity (16.3 µmol g?1 h?1) and selectivity (83%) than TiO2‐MCs (3.5 µmol g?1 h?1, 42%) and WO3?x‐NWs (8.0 µmol g?1 h?1, 64%) for methane generation under UV–vis light irradiation. A photoluminescence study demonstrates the photoelectron injection from TiO2 to WO3?x, and the nonmetallic SPR of WO3?x plays a great role in the highly selective methane generation during CO2 photoreduction.  相似文献   

11.
This study provides a comparison of the influence of Pd(P) thickness on reactions during soldering with the Sn-3Ag-0.5Cu alloy. Soldering was carried out in an infrared-enhanced conventional reflow oven, and a multiple reflow test method (up to ten cycles) was performed. With increasing Pd(P) thickness, the (Cu,Ni)6Sn5 grew more slowly at the solder/Ni(P) interface, while the Ni2SnP/Ni3P bilayer became predominant after the first reflow. These three intermetallics, i.e., (Cu,Ni)6Sn5, Ni2SnP, and Ni3P, gradually coarsened as the number of reflow cycles increased. Furthermore, an additional (Ni,Cu)3Sn4 layer appeared between (Cu,Ni)6Sn5 and Ni2SnP, especially for the case of a thicker Pd(P) layer (0.2 μm). The attachment of the (Ni,Cu)3Sn4 to the Ni2SnP, however, was fairly poor, and a series of microcracks formed along the (Ni,Cu)3Sn4/Ni2SnP interface. To quantify the mechanical response of the interfacial microstructures, shear testing was conducted at two different shear speeds (0.0007 m/s and 2 m/s). The results indicated that the interfacial strength and the Pd(P) thickness were strongly correlated.  相似文献   

12.
Electrode surface wettability is critically important for heterogeneous electrochemical reactions taking place in aqueous and nonaqueous media. Herein, electrochemically inert g‐C3N4 (GCN) is successfully demonstrated to significantly enhance water oxidation by constructing a superhydrophilic catalyst surface and promoting substantial exposure of active sites. As a proof‐of‐concept application, superhydrophilic GCN/Ni(OH)2 (GCNN) hybrids with monodispersed Ni(OH)2 nanoplates strongly anchored on GCN are synthesized for enhanced water oxidation catalysis. Owing to the superhydrophilicity of functionalized GCN, the surface wettability of GCNN (contact angle 0°) is substantially improved as compared with bare Ni(OH)2 (contact angle 21°). Besides, GCN nanosheets can effectively suppress Ni(OH)2 aggregation to help expose more active sites. Benefiting from the well‐defined catalyst surface, the optimal GCNN hybrid shows significantly enhanced electrochemical performance over bare Ni(OH)2 nanosheets, although GCN is electrochemically inert. In addition, similar catalytic performance promotion resulting from wettability improvement induced by incorporation of hydrophilic GCN is also successfully demonstrated on Co(OH)2. The present results demonstrate that, in addition to developing new catalysts, building efficient surface chemistry is also vital to achieve extraordinary water oxidation performance.  相似文献   

13.
The effect of electromigration (EM) on the interfacial reaction in a line-type Cu/Sn/Ni-P/Al/Ni-P/Sn/Cu interconnect was investigated at 150°C under 5.0 × 103 A/cm2. When Cu atoms were under downwind diffusion, EM enhanced the cross-solder diffusion of Cu atoms to the opposite Ni-P/Sn (anode) interface compared with the aging case, resulting in the transformation of interfacial intermetallic compound (IMC) from Ni3Sn4 into (Cu,Ni)6Sn5. However, at the Sn/Cu (cathode) interface, the interfacial IMCs remained as Cu6Sn5 (containing less than 0.2 wt.% Ni) and Cu3Sn. When Ni atoms were under downwind diffusion, only a very small quantity of Ni atoms diffused to the opposite Cu/Sn (anode) interface and the interfacial IMCs remained as Cu6Sn5 (containing less than 0.6 wt.% Ni) and Cu3Sn. EM significantly accelerated the dissolution of Ni atoms from the Ni-P and the interfacial Ni3Sn4 compared with the aging case, resulting in fast growth of Ni3P and Ni2SnP, disappearance of interfacial Ni3Sn4, and congregation of large (Ni,Cu)3Sn4 particles in the Sn solder matrix. The growth kinetics of Ni3P and Ni2SnP were significantly accelerated after the interfacial Ni3Sn4 IMC completely dissolved into the solder, but still followed the t 1/2 law.  相似文献   

14.
Based on first-principles calculations, the effect of Cu solubility on the elastic moduli of Ni3Sn4-based intermetallic compound (IMC) is investigated. It is found that the stiffness tensor of a (Ni,Cu)3Sn4 single crystal is anisotropic, and the presence of Cu in the crystal compound reduces the moduli of (Ni,Cu)3Sn4 due to reduced hybridization between Ni and Sn states. Furthermore, our results show that higher Cu concentration in the (Ni,Cu)3Sn4-based IMCs leads to thermodynamically less stable compounds. Based on the single-crystal results, the elastic properties of polycrystalline (Ni,Cu)3Sn4 are also obtained.  相似文献   

15.
Replacement of precious metals with earth‐abundant electrocatalysts for oxygen evolution reaction (OER) holds great promise for realizing practically viable water‐splitting systems. It still remains a great challenge to develop low‐cost, highly efficient, and durable OER catalysts. Here, the composition and morphology of Ni–Co bimetal phosphide nanocages are engineered for a highly efficient and durable OER electrocatalyst. The nanocage structure enlarges the effective specific area and facilitates the contact between catalyst and electrolyte. The as‐prepared Ni–Co bimetal phosphide nanocages show superior OER performance compared with Ni2P and CoP nanocages. By controlling the molar ratio of Ni/Co atoms in Ni–Co bimetal hydroxides, the Ni0.6Co1.4P nanocages derived from Ni0.6Co1.4(OH)2 nanocages exhibit remarkable OER catalytic activity (η = 300 mV at 10 mA cm?2) and long‐term stability (10 h for continuous test). The density‐functional‐theory calculations suggest that the appropriate Co doping concentration increases density of states at the Fermi level and makes the d‐states more close to Fermi level, giving rise to high charge carrier density and low intermedia adsorption energy than those of Ni2P and CoP. This work also provides a general approach to optimize the catalysis performance of bimetal compounds.  相似文献   

16.
Cu‐nanowire‐doped graphene (Cu NWs/graphene) is successfully incorporated as the back contact in thin‐film CdTe solar cells. 1D, single‐crystal Cu nanowires (NWs) are prepared by a hydrothermal method at 160 °C and 3D, highly crystalline graphene is obtained by ambient‐pressure CVD at 1000 °C. The Cu NWs/graphene back contact is obtained from fully mixing the Cu nanowires and graphene with poly(vinylidene fluoride) (PVDF) and N‐methyl pyrrolidinone (NMP), and then annealing at 185 °C for solidification. The back contact possesses a high electrical conductivity of 16.7 S cm?1 and a carrier mobility of 16.2 cm2 V?1 s?1. The efficiency of solar cells with Cu NWs/graphene achieved is up to 12.1%, higher than that of cells with traditional back contacts using Cu‐particle‐doped graphite (10.5%) or Cu thin films (9.1%). This indicates that the Cu NWs/graphene back contact improves the hole collection ability of CdTe cells due to the percolating network, with the super‐high aspect ratio of the Cu nanowires offering enormous electrical transport routes to connect the individual graphene sheets. The cells with Cu NWs/graphene also exhibit an excellent thermal stability, because they can supply an active Cu diffusion source to form an stable intermediate layer of CuTe between the CdTe layer and the back contact.  相似文献   

17.
Synthesis of metal–organic frameworks (MOFs) is based on coordination‐driven self‐assembly of metal ions and organic ligands. However, to date, it remains difficult to adjust the coordination behaviors of MOFs and then control geometric shapes of nanostructures; especially their morphologies in 1D nanofibers or 2D nanosheets have seldom been explored. Here, a facile route at room temperature and ambient pressure is reported for the preparation of copper‐based MOFs with low‐dimensional shapes (i.e., nanofibers, nanorods, nanosheets, and nanocuboids), via thermodynamic and kinetic controls over the anisotropic growth. Importantly, the as‐prepared 2D MOF nanosheets with monocrystalline nature (100% exposed {010} facets) provide a material platform to the fabrication of 2D supported metal nanocatalysts. First, the MOF nanosheets can serve as a self‐templating solid precursor to prepare different CuO and CuO‐Cu2O nanocomposites, or even Cu metals via thermolysis or reduction under controlled atmospheres. Upon their formation, second, ultrafine noble metal nanoparticles (e.g., Au, Ag, Pt, Pd, Au0.4Pt0.6, Au0.4Pd0.6, and Au0.3Pt0.3Pd0.4) can be exclusively anchored on the external surfaces of the MOF nanosheets. To show their open accessibility, catalytic activities of the derived catalysts have been evaluated using CO2 hydrogenation and 4‐nitrophenol reduction in gas phase and liquid phase, respectively.  相似文献   

18.
The binary eutectic Sn-3.5wt.%Ag alloy was soldered on the Ni/Cu plate at 250°C, the thickness of the Ni layer changing from 0 through 2 and 4 μm to infinity, and soldering time changing from 30 to 120 s at intervals of 30 s. The infinite thickness was equivalent to the bare Ni plate. The morphology, composition and phase identification of the intermetallic compound (IMC, hereafter) formed at the interface were examined. Depending on the initial Ni thickness, different IMC phases were observed at 30 s: Cu6Sn5 on bare Cu, metastable NiSn3 + Ni3Sn4 on Ni(2 μm)/Cu, Ni3Sn4 on Ni(4 μm)/Cu, and Ni3Sn + Ni3Sn4 on bare Ni. With increased soldering time, a Cu-Sn-based η-(Cu6Sn5)1−xNix phase formed under the pre-formed Ni-Sn IMC layer both at 60 s in the Ni(2 μm)/Cu plate and at 90 s in the Ni(4 μm)/Cu plate. The two-layer IMC pattern remained thereafter. The wetting behavior of each joint was different and it may have resulted from the type of IMC formed on each plate. The thickness of the protective Ni layer over the Cu plate was found to be an important factor in determining the interfacial reaction and the wetting behavior.  相似文献   

19.
Seeking high‐capacity, high‐rate, and durable anode materials for lithium‐ion batteries (LIBs) has been a crucial aspect to promote the use of electric vehicles and other portable electronics. Here, a novel alloy‐forming approach to convert amorphous Si (a‐Si)‐coated copper oxide (CuO) core–shell nanowires (NWs) into hollow and highly interconnected Si–Cu alloy (mixture) nanotubes is reported. Upon a simple H2 annealing, the CuO cores are reduced and diffused out to alloy with the a‐Si shell, producing highly interconnected hollow Si–Cu alloy nanotubes, which can serve as high‐capacity and self‐conductive anode structures with robust mechanical support. A high specific capacity of 1010 mAh g?1 (or 780 mAh g?1) has been achieved after 1000 cycles at 3.4 A g?1 (or 20 A g?1), with a capacity retention rate of ≈84% (≈88%), without the use of any binder or conductive agent. Remarkably, they can survive an extremely fast charging rate at 70 A g?1 for 35 runs (corresponding to one full cycle in 30 s) and recover 88% capacity. This novel alloy‐nanotube structure could represent an ideal candidate to fulfill the true potential of Si‐loaded LIB applications.  相似文献   

20.
A transparent Schottky photodiode is constructed based on a SrTiO3 (STO) wafer, in which nickel‐coated silver nanowires (AgNi NWs) are proposed as the high‐work‐function transparent electrode. A selective photoresponse to harmful short‐wavelength blue (SWB) light is generated owing to the proper bandgap of STO, and the AgNi NWs effectively strengthen the photovoltaic behavior, resulting in an ultrafast response speed (trise/tfall = 7 µs/115 µs) and photocurrent of 16–38 nA under a 0 V bias. Meanwhile, the complete device maintains a transparency of ≈60% almost over the entire visible light region and blocks 96.7% UVA and >99.9% UVB. The combination of bias‐free SWB detection and transparent UV shielding is readily applicable to protect against light pollution. Furthermore, this work proposes a considerable method to modulate the work function of transparent Ag NW electrodes by surface coating, which provides inspiration for the development of transparent electrode materials with different work functions.  相似文献   

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