Alloy Nanoparticles Research Articles

Highly Selective, Room-Temperature Triethylamine Sensor Using Humidity-Resistant Novel TiZn Alloy Nanoparticles-Decorated MoS₂ Nanosheets.

The future of environmental monitoring, medical diagnostics, and industrial safety depends on developing room-temperature, long-term operable, stable, miniaturized, ultrahigh-performance sensors integrated into the Internet of Things (IoT). While noble metals and high-entropy alloys (HEAs) lead in addressing the limitations of conventional transition-metal dichalcogenides (TMDs) like MoS₂, they face challenges such as high-cost, limited availability, and fabrication complexity. To address this, multifunctional, cost-effective, humidity-insensitive novel phase Ti₀.₅Zn₀.₅ (TiZn) alloy nanoparticle-decorated MoS₂ nanosheets (MoS₂_NP) is developed for ultra-selective and highly sensitive triethylamine (TEA) vapor detection at room temperature (RT). This exhibited a 24-fold increase in response compared to MoS₂, with a high signal-to-noise ratio, negligible humidity interference, sensitivity of 9.92×10⁻⁵ ppm⁻¹ at RT, and a detection limit of 48ppm. The enhanced catalytic activity and defect concentration, the reduction of the edge oxidation resulting in strong Fermi-level pinning, and the relatively high adsorption energy lead to a target gas-specific carrier-type response, demonstrating the potential of binary alloy nanoparticles (NPs) as decorative materials for enhanced sensing applications. The superior performance of the sensor led to the development of a TEA detection prototype interfaced with a mobile device via IoT for continuous monitoring, enhancing practicality and usability by offering immediate access to critical information.

Probing Active Sites on Pd/Pt Alloy Nanoparticles by CO Adsorption.

We studied the adsorption of CO on Pd/Pt nanoparticles (NPs) with varying compositions using polarization-dependent Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS) and theoretical calculations (DFT). We prepared PtPd alloy NPs via physical vapor codeposition on α-Al2O3(0001) supports. Our morphological and structural characterization by scanning electron microscopy and grazing incidence X-ray diffraction revealed well-defined, epitaxial NPs. We used CO as a probe molecule to identify the particles' surface active sites. Polarization-dependent FT-IRRAS enabled us to distinguish CO adsorption on top and side facets of the NPs. The role of the Pd/Pt alloy ratio on CO adsorption was investigated by comparing the experimental CO stretching band frequency for different alloy arrangements to the results for pure Pd and Pt NPs. Moreover, we studied the influence of hydrogen adsorption on the NP surface composition. We determined the dependence of the IR bands on the local atomic arrangement via DFT calculations, revealing that both bulk alloy composition and neighboring atoms influence the wavenumber of the bands.

Surface segregation on Ag@MNi (M = Pd, Pt, Rh, and Ru) core–shell nanocrystals for enhancing the oxygen reduction performance

Synthesis of cost-effective electrocatalysts for oxygen reduction reaction (ORR) has received wide attention due to their sluggish kinetics, which limits the development and application of fuel cell technique. In this work, we report a versatile synthetic approach to prepare a series of small-sized Ag@MNi (M = Pd, Pt, Rh, Ru) nanocrystals with core–shell structures by a simple solvothermal method. According to characterization analysis, surface segregation of Pd was proved in the outermost layer with the Pd-rich shell layer, which can regulate the adsorption energy of *OH. Electrochemical results show that the onset potential and half-wave potential of Ag@PdNi nanocrystals (Ag@PdNi NCs) are 1.005 and 0.913 V vs. RHE (reversible hydrogen electrode), respectively, with a Tafel slope of 55.31 mV dec-1 and strong ORR catalytic durability, which is similar to Ag@MNi (M = Pt, Rh, Ru) NCs and slightly higher than that of PdAg alloy nanoparticles (PdAg alloy NPs), PdNi alloy nanoparticles (PdNi alloy NPs), commercial Pd black and even commercial Pt/C, in alkaline medium. Density Functional (DFT) calculations show that the presence of Agcore effectively promotes the segregation of Pd atoms to the outer shell surface, where Ni provides better segregated substitution sites for Pd, which significantly improves the ORR activity and durability due to the electronic synergistic effect between Agcore nuclei and Pdshell can reduce the adsorption strength of OHads.

Synthesis of cotton-like FeCoNi-Nd(OH)3 nanoparticles via reactive mechanical milling: Investigating chemical properties for cellular signaling applications

In this study, FeCoNi alloy nanoparticles were combined with Nd(OH)3 nanostructures to create unique cotton-like nanoparticles (C-NPs). These C-NPs were synthesized through an accessible, two-step reactive chemical milling process. The nanoparticles originated from a blend of metal chlorides (FeCl2, CoCl2, and NiCl2) and sodium (Na), used as a precursor in the reaction, within a SPEX milling apparatus. The Fe, Co, and Ni were maintained at equal weight percentages (1:1:1). Subsequently, NdCl3 and Na were utilized to facilitate the attachment of Nd(OH)3 nanostructures onto the FeCoNi nanoparticles through a solid-state reaction in the same SPEX milling setup. The Nd content was varied to investigate its effect on the integration of Nd(OH)3 onto the surface of CoNiFe nanoparticles. Electron microscopy revealed the formation of cotton-like nanoparticles, and the distribution of elements was identified using secondary ion mass spectrometry. The CoNiFe alloy and Nd(OH)3 phases were verified by X-ray diffraction analysis. These nanoparticles were internalized into cells via endocytosis, as observed in transmission electron microscopy images after incubation with the BT20 cell line (triple-negative breast cancer), likely due to interactions between –OH groups and the cell membrane. Following this, the cells containing C-NPs underwent photoluminescence studies, revealing two distinct emission peaks at 400 nm, and 486 nm. X-ray photoelectron spectroscopy indicated the presence of various heterostructures within the FeCoNi-Nd(OH)3 complex, which may be responsible for these emission properties.

Microenvironment regulation to synthesize sub-3 nm Pt-based high-entropy alloy nanoparticles enabling compressed lattice to boost electrocatalysis

Microenvironment regulation to synthesize sub-3 nm Pt-based high-entropy alloy nanoparticles enabling compressed lattice to boost electrocatalysis

Multi-core–shell nanoboxes comprising polydopamine-derived C coated NiCo@C and FeCo@C nanohybrid for enhanced electrochemical quantification of nitrofurantoin

The development of a high-performance electrochemical sensing platform for monitoring nitrofurantoin (NFT) levels in various real samples plays an important role in the research community worldwide. To accomplish this objective, the crucial challenge is to construct sensing interfaces with outstanding electrocatalytic capabilities. In the present work, a highly efficient metal@carbon electrocatalyst with porous and multi-core–shell nanobox structure comprising polydopamine (PDA)-derived C coated NiCo@C and FeCo@C nanohybrid (named as NiCo@C/FeCo@C@C) was fabricated by simply pyrolyzing NiCo@FeCo Prussian blue analogues (PBA)@PDA. The carbonization of PDA into carbon shells protected the framework from collapsing during high-temperature pyrolysis process, thus enlarging the specific surface areas and porosity. The NiCo@C/FeCo@C@C composite attained an enhanced electrochemical capability, such as an outstanding electronic conductivity from the double carbon shell with porous structure, a large number of active sites and a high electrocatalytic activity from the metallic alloy nanoparticles, which exhibited a highly sensitive response to NFT. Under optimized experimental conditions, the established NiCo@C/FeCo@C@C electrochemical sensor displayed a wide linear range of 0.05–100 μM for NFT determination, coupled with a low detection limit of 14 nM. The practical feasibility of this sensor was also confirmed by the analysis of NFT in tablet and lake water samples with outstanding recovery rates. Moreover, the sustainability of the sensor was demonstrated through its prominent performance in high reproducibility, selectivity and long-term stability. This study thus introduces an innovative approach for the advance of highly efficient electrocatalysts in the area of electrochemical sensing.

Layered double hydroxides-derived CoNi alloy nanoparticles encapsulated by porous N-doped carbon nanofibers as efficient methanol electrocatalysts for alkaline direct methanol fuel cells

Layered double hydroxides-derived CoNi alloy nanoparticles encapsulated by porous N-doped carbon nanofibers as efficient methanol electrocatalysts for alkaline direct methanol fuel cells

Anchoring AuCu alloy nanoparticles on TiO2 nanosheets: exploiting synergistic effects and directed electron transfer for enhanced photocatalytic H2 evolution

Anchoring AuCu alloy nanoparticles on TiO2 nanosheets: exploiting synergistic effects and directed electron transfer for enhanced photocatalytic H2 evolution

Fabrication of Ultrafine L10-FePt-Based Magnetic Patterns Enabled by Single-Step Nanoimprint-Assisted Block Copolymer Self-Assembly.

The bit islands in magnetic patterns play a crucial role in advancing magnetic recording density, but the trade-off issues between miniaturization and scalable production are still challenging. Here we present a two-in-one technique of nanoimprint lithography (NIL)-assisted self-assembly using a specially engineered FePt-containing block copolymer (BCP), offering a simple one-step fabrication for L10-FePt bit-patterned media with high throughput. This method combines top-down NIL with bottom-up self-assembly to precisely control the ultrafine magnetic bits in the nanoscale patterns. The FePt-derived BCPs, designed with an equal atomic ratio of Fe and Pt, ensure the preparation of homogeneously dispersed L10-FePt nanoparticles (NPs). Subsequent BCP pyrolysis results in NPs with enhanced magnetic properties, significantly advancing high-density data storage devices. This strategy offers a novel approach to drive the innovative creation of ordered magnetic metal alloy NPs arrays for practical applications.

Dynamic Behavior of Pt Multimetallic Alloys for Active and Stable Propane Dehydrogenation Catalysts.

Improving the use of platinum in propane dehydrogenation catalysts is a crucial aspect to increasing the efficiency and sustainability of propylene production. A known and practiced strategy involves incorporating more abundant metals in supported platinum catalysts, increasing its activity and stability while decreasing the overall loading. Here, using colloidal techniques to control the size and composition of the active phase, we show that Pt/Cu alloy nanoparticles supported on alumina (Pt/Cu/Al2O3) displayed elevated rates for propane dehydrogenation at low temperature compared to a monometallic Pt/Al2O3 catalyst. We demonstrate that the enhanced catalytic activity is correlated with a higher surface Cu content and formation of a Pt-rich core and Cu-rich shell that isolates Pt sites and increases their intrinsic activity. However, rates declined on stream because of dynamic metal diffusion processes that led to a more uniform alloy structure. This transformation was only partially inhibited by adding excess hydrogen to the feed stream. Instead, cobalt was introduced to provide trimetallic Pt/Cu/Co catalysts with stabilized surface structure and stable activity and higher rates than the original Pt/Cu system. The structure-activity relationship insights in this work offer improved knowledge of propane dehydrogenation catalyst development featuring reduced Pt loadings and notable thermal stability for propylene production.

Focused Review on the Use of Bimetallic Alloy Nanoparticle Electrocatalysts in Water Splitting Reactions

Focused Review on the Use of Bimetallic Alloy Nanoparticle Electrocatalysts in Water Splitting Reactions

Photothermal Dry Reforming of Methane on Yolk‐Shell Co–Ni Alloy@SiO2 Catalyst

Photothermal dry reforming of methane (PT‐DRM) is an appealing pathway to convert carbon dioxide and methane into synthesis gas, a mixture of carbon monoxide and hydrogen, via photothermal heating induced by concentrated sunlight. Coke formation and sintering of active metal nanoparticles, however, are a key issue for catalyst stability. In the present study, we demonstrated Co–Ni alloy nanoparticles encapsulated with a porous SiO2 shell exhibited improved catalytic activity and stability for PT‐DRM using visible/near‐IR light irradiation without any other external heating. The addition of a trace amount of Co (1–5 mol% relative to total metal) and SiO2 encapsulation enhanced the stability by simultaneously suppressing coke formation and sintering of the metal nanoparticles. Furthermore, we revealed that the position of the light irradiation spot has a crucial role in the conversions of methane and carbon dioxide and product selectivity, presumably due to large temperature gradient under the light irradiation. These findings would contribute to designing for effective PT‐DRM catalysts with improved activity and enhanced resistance for both coke formation and sintering and emphasize the significant contribution of the temperature gradients to the performance in PT‐DRM.

Boosting Dry Reforming of Methane Over NiCo/CeO2 Catalysts Treated by Hydrogen Plasma

ABSTRACTNickel (Ni)‐based catalysts are prospective materials for dry reforming of methane (DRM) reaction, but suffer from coke formation and limited activity for CO2 conversion. To improve the reactivity of Ni‐based catalysts, a promising strategy is introducing cobalt (Co) metal. Here, we construct highly efficient NiCo sites on CeO2 support by H2 plasma, which enables the catalyst to obtain a remarkable increase in DRM reaction than the samples treated by conventional H2 reduction. H2 plasma treatment results in the formation of highly dispersed NiCo alloy nanoparticles and high‐concentration oxygen vacancy. These features create large numbers of highly active sites to boost the activation of CH4 and especially CO2 and their catalytic reactions, resulting in strong coke resistance in the DRM reaction.

“One‐Stone, Two‐Birds”: Zinc‐Rich Metal–Organic Frameworks as Precursors for High‐Entropy Zn‐Air Battery Electrocatalysts with Hierarchical Pore Structures

AbstractThe active sites of inexpensive transition metal electrocatalysts are sparse and singular, thus high‐entropy alloys composed of non‐precious metals have attracted considerable attention due to their multi‐component synergistic effects. However, the facile synthesis of high‐entropy alloy composites remains a challenge. Herein, we report a “one‐stone, two‐birds” method utilizing zinc (Zn)‐rich metal–organic frameworks as precursors, by virtue of the low boiling point of Zn (907 °C) and its high volatility in alloys, high‐entropy alloy carbon nanocomposite with a layered pore structure was ultimately synthesized. The experimental results demonstrate that the volatilization of zinc can prevent metal agglomeration and contribute to the formation of uniformly dispersed high‐entropy alloy nanoparticles at slower pyrolysis and cooling rates. Simultaneously, the volatilization of Zn plays a crucial role in creating the hierarchically porous structure. Compared to the zinc‐free HEA/NC‐1, the HEA/NC‐5 derived from the precursor containing 0.8 Zn exhibit massive micropores and mesopores. The resulting nanocomposites represent a synergistic effect between highly dispersed metal catalytic centers and hierarchical adsorption sites, thus achieving excellent electrocatalytic oxygen reduction performance with low catalyst loading compared to commercial Pt/C. This convenient zinc‐rich precursor method can be extended to the production of more high‐entropy alloys and various application fields.

"One-Stone, Two-Birds": Zinc-Rich Metal-Organic Frameworks as Precursors for High-Entropy Zn-Air Battery Electrocatalysts with Hierarchical Pore Structures.

The active sites of inexpensive transition metal electrocatalysts are sparse and singular, thus high-entropy alloys composed of non-precious metals have attracted considerable attention due to their multi-component synergistic effects. However, the facile synthesis of high-entropy alloy composites remains a challenge. Herein, we report a "one-stone, two-birds" method utilizing zinc (Zn)-rich metal-organic frameworks as precursors, by virtue of the low boiling point of Zn (907 °C) and its high volatility in alloys, high-entropy alloy carbon nanocomposite with a layered pore structure was ultimately synthesized. The experimental results demonstrate that the volatilization of zinc can prevent metal agglomeration and contribute to the formation of uniformly dispersed high-entropy alloy nanoparticles at slower pyrolysis and cooling rates. Simultaneously, the volatilization of Zn plays a crucial role in creating the hierarchically porous structure. Compared to the zinc-free HEA/NC-1, the HEA/NC-5 derived from the precursor containing 0.8 Zn exhibit massive micropores and mesopores. The resulting nanocomposites represent a synergistic effect between highly dispersed metal catalytic centers and hierarchical adsorption sites, thus achieving excellent electrocatalytic oxygen reduction performance with low catalyst loading compared to commercial Pt/C. This convenient zinc-rich precursor method can be extended to the production of more high-entropy alloys and various application fields.

FeCo Bimetallic ZIF Derivatives decorated with CoFe-LDH to Promote Bifunctional Oxygen Electrocatalysis Activation.

Reasonably screening the targeted oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) constituents and constructing high-efficiency and stabilized ORR/OER bifunctional electrocatalysts are pivotal for the advancement of rechargeable zinc-air batteries (ZABs). Here, CoFe layered double hydroxide (CoFe-LDH) nanosheets are deposited on nitrogen-doped graphite-carbon polyhedra with FeCo alloy nanoparticles (FeCo/LDH-NGCP). Due to the synergic effect between FeCo-NGCP, CoFe-LDH and FeCo/LDH-NGCP, the electrocatalyst with the abundant and accessible active sites can provide good charge/mass transfer, and thus shows wonderful ORR and OER bifunctional electrocatalytic performance. In ORR tests, FeCo/LDH-NGCP catalyst displays larger half-wave potential (E1/2, 0.89 V vs. 0.85 V), higher limiting current density (JL, 5.91 mA/cm2 vs. 5.14 mA/cm2) and better stability than commercial Pt/C. As for OER, FeCo/LDH-NGCP possesses a smaller overpotential (η) of 299.6 mV at a current density of 10 mA/cm2 and more durable stability than commercial RuO2 (330.6 mV). Furthermore, in ZAB tests, the cycling stability of ZAB-FeCo/LDH-NGCP (over 470 h) outperforms the ZAB-Pt/C+RuO2 (92 h) with commercial electrocatalyst (Pt/C+RuO2). Therefore, the FeCo/LDH-NGCP catalyst offers a new perspective to construct ZABs bifunctional catalysts and their commercial application in ZABs.

Decrypting Synergy of Alloy & Metal Nanoparticles Within Nitrogen-Doped Carbon Nanosheets for Zn-Air Batteries with Ultralong Cycling Stability.

The exploration of efficient, robust, and low-cost bifunctional electrocatalysts to drive the commercial application of Zn-air batteries (ZABs) is of great significance but still remains a challenge. Herein, a 1D coordination polymer (1D-CP) derived FeNi alloy & Co nanoparticles (NPs) co-implanted N-doped carbon nanosheets (FNC/NCS) is judiciously crafted and employed as a high-performance electrocatalyst for ultralong lifetime ZABs. The key to this strategy is the leveraging of metal-coordinated melamine to direct the pyrolysis of 1D-CP, enabling the in situ formation of well-dispersed FeNi alloy and Co NPs within the carbon matrix. The resulting FNC/NCS exhibits prominent oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity with a small overall oxygen potential difference (ΔE = 0.68V). Density functional theory (DFT) simulation demonstrates that the synergistic effect between FeNi alloy and Co NPs can reduce energy barriers, promote electron transfer, and optimize the formation of crucial intermediates, thereby largely boost ORR/OER activity of FNC/NCS. The FNC/NCS-assembled ZABs possess high specific capacity, large power density, and ultralong cycling life in both aqueous (> 3300h) and solid-state (150h) electrolytes. This work provides a viable strategy for 1D-CP-derived bifunctional electrocatalysts and dissects the synergistic effect between different metal species, affording significant guidance for the development of renewable energy materials.

Selective CO2 Reduction Electrocatalysis Using AgCu Nanoalloys Prepared by a "Host-Guest" Method.

Multimetallic nanoalloy catalysts have attracted considerable interest for enhancing the efficiency and selectivity of many electrochemically driven chemical processes. However, the preparation of homogeneous bimetallic alloy nanoparticles remains a challenge. Here, we present a room-temperature and scalable, host-guest approach for synthesis of dilute Cu in Ag alloy nanoparticles. In this approach, an ionic silver bromide precursor harboring exogenous Cu cations is reduced to yield ∼20 nm diameter AgCu alloy nanoparticles wherein the % Cu loading can be tuned precisely. AgCu nanoparticles with a 5% nominal loading of Cu exhibit peak activity (-0.23 mA/cm2 normalized partial current density) and selectivity (83.2% faradaic efficiency) for CO product formation from electrocatalytic reduction of CO2 at mild overpotentials. These AgCu nanoalloys exhibit a higher mass activity compared to Ag- and Cu-containing nanomaterials used for similar electrocatalytic transformations. Our host-guest synthesis platform holds promise for production of other nanoalloys with relevance in electrocatalysis and optics.

Impacting the Surface Chemistry of NiAu by Immobilizing on MgO/N-Rich Nanoporous Carbon Heterostructures for Boosting Catalytic Activities.

Tuning the physical and chemical interaction between metal-metal' (M-M') and metal-support is an ideal way to realize enhanced catalytic activity of metal nanoparticles (NPs). As a proof of concept, herein we report the fabrication of nickel-gold (Ni-Au) alloy nanoparticles attached to N-doped nanoporous carbon (NPC) intervened with MgO (Ni73Au27@MgO-NPC), achieved through the impregnation of metal precursors into Schiff-base network polymer (SNP) framework along with Mg(OH)2 and pyrolysis at 800 °C in N2 atmosphere. With high stability and heterogeneity, the nickel rich Ni73Au27@MgO-NPC exhibited higher catalytic activities with turnover frequencies of 29,272 h-1 (hydrogenation of p-nitrophenol), 93,843 h-1 (degradation of methyl orange), and 2,218 h-1 (epoxidation of stilbene), compared to commercial 10 wt % Pd/C. Enhanced catalytic activity is correlated to the synchronized electron density enhancement in Au, by Ni and MgO/N-rich nanoporous carbon heterostructures, as evident from detailed X-ray photoelectron spectroscopic studies.

Spatially Immobilized PtPdFeCoNi as an Excellent Bifunctional Oxygen Electrocatalyst for Zinc–Air Battery

AbstractDeveloping efficient oxygen electrocatalysts with low cost, high catalytic activity, and robust stability remains a formidable challenge for rechargeable zinc–air batteries (ZABs). Herein, highly dispersed ultrasmall PtPdFeCoNi high‐entropy alloy nanoparticles with a size of ≈ 2 nm and randomly distributed multimetallic single atoms spatially immobilized on the 3D hierarchically ordered porous nitrogen‐doped carbon skeleton (denoted as PtPdFeCoNi/HOPNC) are successfully synthesized via ultra‐rapid Joule heating process. The spatial immobilization on 3D HOPNC skeleton is the key to the high dispersion of multi‐active sites of oxygen electrocatalysts, and the formed hierarchical pore structure is conducive to the successful construction of the rapid mass transfer channel. As a result, the as‐prepared PtPdFeCoNi/HOPNC exhibits a positive half‐wave potential of 0.866 V versus RHE for oxygen reduction reaction (ORR), a low overpotential of 310 mV at 10 mA cm−2 for oxygen evolution reaction (OER), and low Tafel slopes for both ORR and OER. Furthermore, ZAB using PtPdFeCoNi/HOPNC as bifunctional oxygen catalysts exhibits excellent rate performances and superior cycling stability, surpassing that of a commercial Pt/C‐RuO2 mixture. The spatial immobilization strategy of HOPNC provides a new idea for the design and synthesis of efficient catalysts for various applications.