RESUMEN
Direct methanol fuel cells rely on the efficiency of their anode/cathode electrocatalysts to facilitate the methanol oxidation reaction and oxygen reduction reaction, respectively. Platinum-based nanocatalysts are at the forefront due to their superior catalytic properties. However, the high-cost, scarcity, and low CO tolerance of platinum pose challenges for the scalable application of DMFCs. Herein, we report novel ultrathin ternary PtNiRu alloy nanowires to improve Pt utilization and CO tolerance. These novel electrocatalysts incorporate the oxophilic metal Ru into ultrathin PtNi nanowires, aiming to enhance the intrinsic activity of platinum while leveraging the long-term durability and high utilization efficiency provided by the bimetallic synergistic effect. The PtNiRu NWs significantly enhance both mass activity and specific activity for ORR, performing about 6.9 times and 3.9 times better than commercial Pt/C, respectively. After a rigorous durability test of 10,000 cycles, the PtNiRu NWs only exhibited a 25.2 % loss in mass activity. Additionally, for MOR, the MA and SA of PtNiRu NWs exceed that of Pt/C catalyst by 4.30 and 2.72 times, respectively, and exhibit exceptional resistance to CO poisoning. Theoretical insights from density functional theory calculations suggest that the introduction of Ru modulates the d-band center of the surface Pt atoms, which contributes to decreased binding strength of oxygenated species and an elevated dissolution potential, substantiating the enhanced performance metrics, and the durability enhancement stems from the stronger PtM bonds than those in PtNiRu NWs resulted from PtRu covalent interactions. These findings not only provide a new perspective on platinum-based nanocatalysts but also significantly advance the quest for more efficient and durable electrocatalysts for DMFCs, representing a substantial stride in fuel cell technology.
RESUMEN
Breaking atomic monogeneity of catalyst surfaces is promising for constructing synergistic active centers to cope with complex multi-step catalytic reactions. Here, we report a defect-derived strategy for creating surface phosphorous vacancies (P-vacancies) on nanometric Rh2 P electrocatalysts toward drastically boosted electrocatalysis for alkaline hydrogen oxidation reaction (HOR). This strategy disrupts the monogeneity and atomic regularity of the thermodynamically stable P-terminated surfaces. Density functional theory calculations initially verify that the competitive adsorption behavior of Had and OHad on perfect P-terminated Rh2 P{200} facets (p-Rh2 P) can be bypassed on defective Rh2 P{200} surfaces (d-Rh2 P). The P-vacancies enable the exposure of sub-surface Rh atoms to act as exclusive H adsorption sites. Therein, the Had cooperates with the OHad on the peripheral P-sites to effectively accelerate the alkaline HOR. Defective Rh2 P nanowires (d-Rh2 P NWs) and perfect Rh2 P nanocubes (p-Rh2 P NCs) are then elaborately synthesized to experimentally represent the d-Rh2 P and p-Rh2 P catalytic surfaces. As expected, the P-vacancy-enriched d-Rh2 P NWs catalyst exhibits extremely high catalytic activity and outstanding CO tolerance for alkaline HOR electrocatalysis, attaining 5.7 and 14.3â times mass activity that of p-Rh2 P NCs and commercial Pt/C, respectively. This work sheds light on breaking the surface atomic monogeneity for the development of efficient heterogeneous catalysts.
RESUMEN
Due to the intrinsic layered structure, graphdiyne (GDY) strongly tends to form 2D materials, therefore, most of the current research are based on GDY 2D structures. Up to now, the synthesis of its ultrathin nanowires with a high aspect ratio has not been reported. Here, the ultrathin GDY nanowires with diameters below 3 nm are reported for the first time by a two-phase interface synthesis method, which has excellent crystallinity and an aspect ratio of more than 2500. Evidence shows that the GDY ultrathin nanowires are formed by the oriented-attachment mechanism of nanoparticles. The GDY ultrathin nanowires exhibit a significant quantum confinement effect, enhanced photoelectric effect, and promising applications in surface-enhanced Raman sensing.
RESUMEN
Rational design and controllable synthesis of catalysts with unique structure and composition are effective ways to promote electrocatalytic ethanol oxidation, thus contributing the direct ethanol fuel cells to gain ground. Herein, 2.5 nm-thin PtIrCu ternary alloy ultrathin nanowires (UNWs) with high-density planar defects are synthesized via oriented attachment with the assistance of H2. By adjusting the contents of Ir and Cu atoms, we find that the structure of the products changed from nanowires (NWs) to nanoparticles with the increase of Ir content. Density functional theory calculations show that when Cu atoms are replaced by Ir atoms, the vacancy formation energy of Pt atoms is increased, making the Pt atoms difficult to be activated by H2, which is not conducive to the formation of a one-dimensional structure. The optimal Pt43Ir32Cu25 UNWs achieve excellent ethanol electrooxidation reaction activity (1.05 A·mg-1Pt and 1.67 mA·cm-2), for it can significantly reduce the onset potential and improve the ability of CO anti-poisoning. The significant improvement in catalytic performance is attributed to the synergistic effect of the alloy and the NW structure with high-density planar defects.
RESUMEN
Hydrogen (H2), as a chemical energy carrier, is a cleaner alternative to conventional fossil fuels with zero carbon emission and high energy density. The development of fast, low-cost, and sensitive H2 detection systems is important for the widespread adoption of H2 technologies. Paper is an environment-friendly, porous, and flexible material with great potential for use in sustainable electronics. Here, we report a paper-based sensor for room-temperature H2 detection using ultrathin palladium nanowires (PdNWs). To elucidate the sensing mechanism, we compare the performance of polycrystalline and quasi-single-crystalline PdNWs. The polycrystalline PdNWs showed a response of 4.3% to 1 vol % H2 with response and recovery times of 4.9 and 10.6 s, while quasi-single-crystalline PdNWs showed a response of 8% to 1 vol % H2 with response and recovery times of 9.3 and 13.0 s, respectively. The polycrystalline PdNWs show excellent selectivity, stability, and sensitivity, with a limit of detection of 10 ppm H2 in air. The fast response of ultrathin polycrystalline PdNW paper-based sensors arises from the synergistic effects of their ultrasmall diameter, high-index surface facets, strain-coupled grain boundaries, and porous paper substrate. This paper-based sensor is one of the fastest chemiresistive H2 sensors reported and is potentially orders of magnitude less expensive than current state-of-the-art H2-sensing solutions. This brings low-cost, room-temperature chemiresistive H2 sensing closer to the performance of ultrafast optical sensors and high-temperature metal oxide-based sensors.
RESUMEN
Ultrathin nanowires (NWs) have always attracted the attention of researchers due to their unique properties, but their facile synthesis is still a great challenge. Herein we developed a general method for the synthesis of rare earth (RE) oxide ultrathin NWs at atmospheric pressure and low temperature (50 °C). The formation mechanism of ultrathin NWs lies in two aspects: thermodynamic advantage of one dimensional (1D) growth at low temperature, and supplement of effective monomers. As an extension, fifteen kinds of RE oxide ultrathin NWs were synthesized through this strategy, and they all exhibited polymer-like behaviors. Meanwhile, the high viscosity, organic gel, wet- and electro-spinning of Ce-Mo-O NWs were studied in detail, demonstrating the similarity of ultrathin inorganic NWs to polymers. In addition, the Ce-Mo-O ultrathin NWs were used as photocatalysts for toluene oxidation and showed excellent performance with toluene conversion ratio of 83.8 %, suggesting their potential application in organic photocatalysis.
RESUMEN
A crucial issue restricting the application of direct alcohol fuel cells (DAFCs) is the low activity of Pt-based electrocatalysts for alcohol oxidation reaction caused by the reaction intermediate (CO*) poisoning. Herein, a new strategy is demonstrated for making a class of sub-monolayer YOx /MoOx -surface co-decorated ultrathin platinum nanowires (YOx /MoOx -Pt NWs) to effectively eliminate the CO poisoning for enhancing methanol oxidation electrocatalysis. By adjusting the amounts of YOx and MoOx decorated on the surface of ultrathin Pt NWs, the optimized 22% YOx /MoOx -Pt NWs achieve a high specific activity of 3.35 mA cm-2 and a mass activity of 2.10 A mgPt -1 , as well as the enhanced stability. In situ Fourier transform infrared (FTIR) spectroscopy and CO stripping studies confirm the contribution of YOx and MoOx to anti-CO poisoning ability of the NWs. Density functional theory (DFT) calculations further reveal that the surface Y and Mo atoms with oxidation states allow COOH* to bind the surface through both the carbon and oxygen atoms, which can lower the free energy barriers for the oxidation of CO* into COOH*. The optimal NWs also show the superior activities toward the electro-oxidation of ethanol, ethylene glycol, and glycerol.
RESUMEN
Transition metal oxides (TMOs) have been under the spotlight as promising precatalysts for electrochemical oxygen evolution reaction (OER) in alkaline media. However, the slow and incomplete self-reconstruction from TMOs to (oxy)hydroxides as well as the formed (oxy)hydroxides with unmodified electronic structure gives rise to the inferior OER performance to the noble metal oxide ones. Herein, a unique dual metal oxides lattice coupling strategy is proposed to fabricate carbon cloth-supported ultrathin nanowires arrays, which are composed of pseudo-periodically welded NiO with CeO2 nanocrystals (NiO/CeO2 NW@CC). When served as an OER precatalyst in 1.0 m KOH, the NiO/CeO2 NW@CC shows an ultralow overpotential of 330 mV at 50 mA cm-2 , along with an impressive cycle durability of more than 3 days even at 50 mA cm-2 , surpassing CC-supported NiO and commercial IrO2 catalysts. The combined experimental and theoretical investigations unveil that the atomic coupling of CeO2 can not only appreciably trigger the generation of oxygen vacancies and expedite phase transformation of NiO into active NiOOH, but also in situ create a chemical bond with the formed NiOOH and enable the electron injection, thus effectively inhibiting the aggregation of the accessible NiOOH nanodomains and optimizing their reaction free energy towards oxygen-containing intermediates.
RESUMEN
Utilizing sustainable energy for chemical activation of small molecules, such as CO2 , to produce important chemical feedstocks is highly desirable. The simultaneous production of CO/H2 mixture (syngas) from photoreduction of CO2 and H2 O is highly promising. However, the relationships between structure, composition, crystallinity, and photocatalytic performance are still indistinct. Here, amorphous ultrathin CoO nanowires and polyoxometalate incorporated nanowires with even lower crystallinity were synthesized. The POM-incorporated ultrathin nanowires exhibit high photocatalytic syngas production activity, reaching H2 and CO evolution rates of 11555 and 4165â µmol g-1 h-1 respectively. Further experiments indicate that the ultrathin morphology and incorporation of POM both contribute to the superior performance. Multiple characterizations reveal the enhanced charge-hole separation efficiency of the catalyst would facilitate the photocatalysis.
RESUMEN
Synthesis of high-efficiency catalysts for alcohol oxidation reaction caused great interest in direct alcohol fuel cells (DAFCs). Ultrathin PdFePb nanowires (NWs) with an average diameter of 2.3â¯nm were synthesized by a simple and fast one-pot aqueous synthesis, using octylphenoxypolyethoxyethanol (NP-40) as the structure-directing agent. The as-prepared PdFePb NWs displayed an increscent electrochemically active surface area (ECSA, 121.18â¯m2â¯g-1â¯Pd). For ethylene glycol oxidation reaction (EGOR) and glycerol oxidation reaction (GOR), PdFePb NWs exhibited much higher activity and superior stability, outperforming those of homemade PdFe NWs, PdPb NWs, commercial Pd black and Pd/C (20â¯wt%). These results reveal dramatically high catalytic activity and durability of ultrathin PdFePb NWs in enhancing polyols electrooxidation.
RESUMEN
The development of new electrocatalysts with high activity and durability for alcohol oxidation is an emerging need of direct alcohol fuel cells. However, the commonly used Pt-based catalysts still exhibit drawbacks including limited catalytic activity, high overpotential, and severe CO poisoning. Here a general approach is reported for preparing ultrathin PtNiM (M = Rh, Os, and Ir) nanowires (NWs) with excellent anti-CO-poisoning ability and high activity. Owing to their superior nanostructure and optimal electronic interaction, the ultrathin PtNiM NWs show enhanced electrocatalytic performance for both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). The optimal PtNiRh NWs show mass activity of 1.72 A mg-1 and specific activity of 2.49 mA cm-2 for MOR, which are 3.17 and 2.79 times higher than those of Pt/C. In particular, the onset potentials of PtNiRh NWs for MOR and EOR shift down by about 65 and 85 mV compared with those of Pt/C. Density functional theory calculations further verify their high antipoison properties for MOR and EOR from both an electronic and energetic perspective. Facilitated by the introduction of Rh and Ni, the stable pinning of the Pt 5d band associated with electron-rich and depletion centers solves the dilemma between reactivity and anti-CO poisoning.
RESUMEN
Although all-inorganic CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) have been considered as a promising material for photoelectronic devices, their applications are still limited because of their poor stability and the lack of in-depth understanding. Here, we demonstrate a post-treatment method for the preparation of ultrathin CsPbX3 nanowires (NWs) by treating CsPbBr3 nanocubes with thiourea solution. A systematic study showed a consecutive interfacial transformation process, in which CsPbBr3 nanocubes were first converted to Cs4PbBr6 NCs in the presence of thiourea, followed by a further transformation to CsPbBr3 NCs through an interfacial CsX-stripping process. To reduce the surface energy, an oriented attachment process has been realized and CsPbBr3 NCs aggregated to form ultrathin NWs. The ultrathin CsPbBr3 NWs exhibited high photoluminescence quantum yield (up to 60%) and high resistance to water treatment, which can be attributed to the surface passivation by thiourea. In addition to thiourea, cysteine and thioacetamide that contain the thiol group can also be used to trigger this transformation. This work can not only offer a facile method for the synthesis of efficient and stable ultrathin CsPbBr3 NWs but also help to reveal the in-depth mechanisms which may be very useful in the field of metal halide perovskite NCs.
RESUMEN
The field of semiconductor nanowires (NWs) has become one of the most active and mature research areas. However, progress in this field has been limited, due to the difficulty in controlling the density, orientation, and placement of the individual NWs, parameters important for mass producing nanodevices. The work presented herein describes a novel nanosynthesis strategy for ultrathin self-aligned silicon carbide (SiC) NW arrays (≤ 20 nm width, 130 nm height and 200â»600 nm variable periodicity), with high quality (~2 Å surface roughness, ~2.4 eV optical bandgap) and reproducibility at predetermined locations, using fabrication protocols compatible with silicon microelectronics. Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopic ellipsometry, atomic force microscopy, X-ray diffractometry, and transmission electron microscopy studies show nanosynthesis of high-quality polycrystalline cubic 3C-SiC materials (average 5 nm grain size) with tailored properties. An extension of the nanofabrication process is presented for integrating technologically important erbium ions as emission centers at telecom C-band wavelengths. This integration allows for deterministic positioning of the ions and engineering of the ions' spontaneous emission properties through the resulting NW-based photonic structures, both of which are critical to practical device fabrication for quantum information applications. This holistic approach can enable the development of new scalable SiC nanostructured materials for use in a plethora of emerging applications, such as NW-based sensing, single-photon sources, quantum LEDs, and quantum photonics.
RESUMEN
Although aqueous synthesis of nanocrystals is advantageous in terms of the cost, convenience, environmental friendliness, and surface cleanness of the product, nanocrystals of Pt and non-noble metal alloys are difficult to obtain with controlled morphology and composition from this synthesis owing to a huge gap between the reduction potentials of respective metal salts. This huge gap could now be remedied by introducing a sulfite into the aqueous synthesis, which is believed to resemble an electroless plating mechanism, giving rise to a colloid of Pt-M (M=Ni, Co, Fe) alloy nanowires with an ultrasmall thickness (ca. 2.6â nm) in a high yield. The sulfite also leads to the formation of surface M-S bonds and thus atomic-level Pt/M-S(OH) interfaces for greatly boosted hydrogen evolution kinetics under alkaline conditions. An activity of 75.3â mA cm-2 has been achieved with 3â µg of Pt in 1 m KOH at an overpotential of 70â mV, which is superior to previously reported catalysts.
RESUMEN
Ultrathin nanostructures are attractive for diverse applications owing to their unique properties compared to their bulk materials. Transition-metal chalcogenides are promising electrocatalysts, yet it remains difficult to make ultrathin structures (sub-2â nm), and the realization of their chemical doping is even more challenging. Herein we describe a soft-template mediated colloidal synthesis of Fe-doped NiSe2 ultrathin nanowires (UNWs) with diameter down to 1.7â nm. The synergistic interplay between oleylamine and 1-dodecanethiol is crucial to yield these UNWs. The inâ situ formed amorphous hydroxide layers that is confined to the surface of the ultrathin scaffolds enable efficient oxygen evolution electrocatalysis. The UNWs exhibit a very low overpotential of 268â mV at 10â mA cm-2 in 0.1 m KOH, as well as remarkable long-term stability, representing one of the most efficient noble-metal-free catalysts.
RESUMEN
Ultrathin bimetallic nanowires are of importance and interest for applications in electronic devices such as sensors and heterogeneous catalysts. In this work, we have designed a new, highly reproducible and generalized wet chemical method to synthesize uniform and monodispersed Au-based alloy (AuCu, AuPd, and AuPt) nanowires with tunable composition using microwave-assisted reduction at the liquid-liquid interface. These ultrathin alloy nanowires are below 4 nm in diameter and about 2 µm long. Detailed microstructural characterization shows that the wires have an face centred cubic (FCC) crystal structure, and they have low-energy twin-boundary and stacking-fault defects along the growth direction. The wires exhibit remarkable thermal and mechanical stability that is critical for important applications. The alloy wires exhibit excellent electrocatalytic activity for methanol oxidation in an alkaline medium.
RESUMEN
Graphene-based composites have gained great attention in the field of gas sensor fabrication due to their higher surface area with additional functional groups. Decorating one-dimensional (1D) semiconductor nanomaterials on graphene also show potential benefits in gas sensing applications. Here we demonstrate the one-pot and low cost synthesis of W18O49 NWs/rGO composites with different amount of reduced graphene oxide (rGO) which show excellent gas-sensing properties towards toluene and strong dependence on their chemical composition. As compared to pure W18O49 NWs, an improved gas sensing response (2.8 times higher) was achieved in case of W18O49 NWs composite with 0.5 wt. % rGO. Promisingly, this strategy can be extended to prepare other nanowire based composites with excellent gas-sensing performance.
RESUMEN
Iridium (Ir) holds great promise for ethanol oxidation reaction (EOR), while its practical applications suffer from the limited shape-controlled synthesis due to its low-energy barrier for nucleation. To overcome this limitation, the preparation of a new class of ultrathin vein-like Ir-tin nanowires (IrSn NWs) with abundant oxidized Sn is reported. By tuning the ratio of Ir to Sn, the optimized Ir67 Sn33 /C exhibits the highest mass density of 95.6 mA mg-1 Ir for EOR at low potential (0.04 V), which is 4.1-fold and 20-fold higher than that of Ir/C and the commercial Pt/C, respectively. It also exhibits the smallest Tafel slope of 153 mV dec-1 and superior stability after 2 h chronoamperometric measurement. Electrochemical measurements and X-ray photoelectron spectra results confirm that the abundant oxidized Sn promotes a complete oxidization of ethanol into CO2 at low potential. This work highlights the importance of non-noble metal on enhancing the EOR performance.
RESUMEN
Well-designed hybrid materials based on noble metal-free elements have great potential to generate hydrogen (H2 ) and oxygen (O2 ) sustainably via overall water splitting for developing practical energy-related technologies. Herein, an accessible method is presented to synthesize nickel diselenide (NiSe2 ) ultrathin nanowires decorated with amorphous nickel oxide nanoparticles (NiOx NPs) as multifunctional electrocatalysts (NSWANs) for hydrogen and oxygen evolution reaction (HER and OER). The NSWANs exhibit quite low HER and OER overpotentials of 174 and 295 mV, respectively, holding the current density of 20 mA cm-2 for 24 h continuous operations in alkaline media. Meanwhile, a cell voltage of 1.547 V at the current density of 10 mA cm-2 for overall water splitting has been achieved by the NSWANs for the practical application, which could maintain fascinating activity of 20 mA cm-2 for 72 h without degradation. The decorated NiOx NPs not only prevent the NiSe2 from further oxidation but also expose requisite active sites for electrocatalytic process. It is believed that this study may provide a valuable strategy to design high-efficiency electrocatalysts and expand the applications of selenide-based materials.
RESUMEN
ZnO nanowires (NWs) are used as building blocks for a wide range of different devices, e.g. light emitters, resonators, and sensors. Integration of the NWs into such structures requires a high level of NWs' diameter control. Here, we present that the doping concentration of Zn x Al1-x O and Zn x Ga1-x O seed layers has a strong impact on the NW growth and allows to tune the diameter of the NWs by two orders of magnitude down to less than 7 nm. These ultrathin NWs exhibit a well-oriented vertical growth and thus are promising for the investigation of quantum effects. The doping of the ZnO seed layers has also an impact on the deposition temperature which can be reduced down to T≈400∘C. This temperature is much smaller than those typically used for the fabrication of NWs by pulsed laser deposition. A comparison of the NWs indicates a stronger impact of the Ga doping on the NW growth than for the Al doping which we attribute to an impact of the size of the dopants. The optical properties of the NWs were investigated by cathodoluminescence spectroscopy which revealed a high crystalline quality. For the thin nanowires, the emission characteristic is mainly determined by the properties of the surface near region.