Monodisperse nickel nanoparticles supported on SiO<Subscript>2</Subscript> as an effective catalyst for the hydrolysis of ammonia-borane

Monodisperse Ni nanoparticles (NPs) have been synthesized by the reduction of nickel(II) acetylacetonate with the borane-tributylamine complex in a mixture of oleylamine and oleic acid. These Ni NPs are an active catalyst for the hydrolysis of the ammonia-borane (AB, H₃N·BH₃) complex under ambient conditions and their activities are dependent on the chemical nature of the oxide support that they were deposited on. Among various oxides (SiO₂, Al₂O₃, and CeO₂) tested, SiO₂ was found to enhance Ni NP catalytic activity due to the etching of the 3.2 nm Ni NPs giving Ni(II) ions and the subsequent reduction of Ni(II) that led to the formation of 1.6 nm Ni NPs on the SiO₂ surface. The kinetics of the hydrolysis of AB catalyzed by Ni/SiO₂ was shown to be dependent on catalyst and substrate concentration as well as temperature. The Ni/SiO₂ catalyst has a turnover frequency (TOF) of 13.2 mol H₂·(mol Ni)⁻¹ · min⁻¹—the best ever reported for the hydrolysis of AB using a nickel catalyst, an activation energy of 34 kJ/mol ± 2 kJ/mol and a total turnover number of 15,400 in the hydrolysis of AB. It is a promising candidate to replace noble metals for catalyzing AB hydrolysis and for hydrogen generation under ambient conditions.     

Nickel Promoted Palladium Nanoparticles for Electrocatalysis of Carbohydrazide Oxidation Reaction

Carbohydrazide is a potential alternative to toxic hydrazine for fuel cell applications to overcome the challenges of storage and transportation of hydrogen. In this work, Ni‐alloyed Pd nanoparticles (NPs) with varied Pd–Ni ratios supported on carbon black (PdNi_x/C) are prepared and their catalytic performance for the carbohydrazide electro‐oxidation reaction is investigated. The catalytic performance of PdNi_x/C NPs is significantly improved in comparison to Pd/C NPs. The current density of PdNi_x/C NPs with optimized Pd–Ni atom ratio can reach 3.26 A mg^?1_metal at a potential of 0.4 V (vs reversible hydrogen electrode), which is an increase of 2.4 times compared to that of Pd/C. The density functional theory calculation indicates the enhanced catalytic activity is caused by the change of adsorption energy of carbohydrazide molecules on the metal surface. It exhibits a volcano relationship between the adsorption energy and the catalytic current density of PdNi_x/C with varied Pd–Ni atom ratios.     

Electrospun N‐Doped Porous Carbon Nanofibers Incorporated with NiO Nanoparticles as Free‐Standing Film Electrodes for High‐Performance Supercapacitors and CO2 Capture

Carbon nanofibers (CNF) with a 1D porous structure offer promising support to encapsulate transition‐metal oxides in energy storage/conversion relying on their high specific surface area and pore volume. Here, the preparation of NiO nanoparticle‐dispersed electrospun N‐doped porous CNF (NiO/PCNF) and as free‐standing film electrode for high‐performance electrochemical supercapacitors is reported. Polyacrylonitrile and nickel acetylacetone are selected as precursors of CNF and Ni sources, respectively. Dicyandiamide not only improves the specific surface area and pore volume, but also increases the N‐doping level of PCNF. Benefiting from the synergistic effect between NiO nanoparticles (NPs) and PCNF, the prepared free‐standing NiO/PCNF electrodes show a high specific capacitance of 850 F g^?1 at a current density of 1 A g^?1 in 6 m KOH aqueous solution, good rate capability, as well as excellent long‐term cycling stability. Moreover, NiO NPs dispersed in PCNF and large specific surface area provide many electroactive sites, leading to high CO₂ uptake, and high‐efficiency CO₂ electroreduction. The synthesis strategy in this study provides a new insight into the design and fabrication of promising multifunctional materials for high‐performance supercapacitors and CO₂ electroreduction.     

Hydrolytic dehydrogenation of ammonia borane catalyzed by poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets supported Ag0.3Co0.7 nanoparticles

Poly(amidoamine) dendrimers-modified reduced graphene oxide nanosheets (PAMAM/rGO) composite was selected as a carrier of heterogeneous Ag_0.3Co_0.7 nanoparticles in order to obtain an excellent catalyst for ammonia borane (AB) hydrolysis. During the synthetic processes, GO could easily assembled with PAMAM by the electrostatic and hydrogen-bonding interactions. Structural characterization revealed that Ag_0.3Co_0.7 bimetallic nanoparticles with uniform size distribution of 5 nm are well dispersed on PAMAM/rGO composite architecture. Ag_0.3Co_0.7@PAMAM/rGO was found to be a highly active and reusable catalyst in hydrogen generation from the hydrolysis of AB with a turnover frequency value (TOF) of 19.79 mol_H2 min^–1 mol_M^–1 at 25.0 ± 0.1 °C and retained 75.4% of their initial activity with a complete release of hydrogen in five runs. The relatively high TOF value and low apparent activation energy (34.21 kJ mol^–1) make these Ag_0.3Co_0.7@PAMAM/rGO NPs as a high-efficient catalyst for catalytic dehydrogenation of AB facilitating the development of practically applicable energy storage materials.     

From Single Atoms to Nanoparticles: Autocatalysis and Metal Aggregation in Atomic Layer Deposition of Pt on TiO2 Nanopowder

A fundamental understanding of the interplay between ligand‐removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO₂ nanopowder using trimethyl(methylcyclo‐pentadienyl)platinum(IV) as the precursor and O₂ as the coreactant is presented. The growth follows a pathway from single atoms to NPs as a function of the oxygen exposure (P_O2 × time). The growth kinetics is modeled by accounting for the autocatalytic combustion of the precursor ligands via a variant of the Finke–Watzky two‐step model. Even at relatively high oxygen exposures (<120 mbar s) little to no Pt is deposited after the first cycle and most of the Pt is atomically dispersed. Increasing the oxygen exposure above 120 mbar s results in a rapid increase in the Pt loading, which saturates at exposures >> 120 mbar s. The deposition of more Pt leads to the formation of NPs that can be as large as 6 nm. Crucially, high P_O2 (≥5 mbar) hinders metal aggregation, thus leading to narrow particle size distributions. The results show that ALD of Pt NPs is reproducible across small and large surface areas if the precursor ligands are removed at high P_O2.     

Tailoring N‐Terminated Defective Edges of Porous Boron Nitride for Enhanced Aerobic Catalysis

Tailoring terminated edge of hexagonal boron nitride (h‐BN) for enhancing catalysis has turned to be an imperative for the rational design of a highly active aerobic catalyst. Herein, a tailoring N‐terminated porous BN (P‐BN) strategy is reported with a zinc (Zn) salt as a dual‐functional template. The Zn salt acts as both an in situ template and an N‐terminated defective edges directing agent. The zinc salt template turns to Zn nanoparticles (Zn NPs) and functions as physical spacers, which are subsequently removed at a higher temperature, for producing P‐BN, whose high surface area is high to 1579 m² g^?1. Moreover, because of the lower electronegativity of Zn, boron (B) atoms are partly replaced by Zn atoms and ultimately preferred to N‐terminated edges with the volatilization of Zn NPs. Owing to the moderate dissociative energy of oxygen atoms on N‐terminated edges, the N‐terminated edges are proved to be the origin of an enhanced aerobic catalytic activity by density functional theory (DFT) calculations. Moreover, the DFT calculation result is experimentally verified.     

Biosynthesis and Characterization of Copper Nanoparticles Using Shewanella oneidensis: Application for Click Chemistry

Copper nanoparticles (Cu‐NPs) have a wide range of applications as heterogeneous catalysts. In this study, a novel green biosynthesis route for producing Cu‐NPs using the metal‐reducing bacterium, Shewanella oneidensis is demonstrated. Thin section transmission electron microscopy shows that the Cu‐NPs are predominantly intracellular and present in a typical size range of 20–40 nm. Serial block‐face scanning electron microscopy demonstrates the Cu‐NPs are well‐dispersed across the 3D structure of the cells. X‐ray absorption near‐edge spectroscopy and extended X‐ray absorption fine‐structure spectroscopy analysis show the nanoparticles are Cu(0), however, atomic resolution images and electron energy loss spectroscopy suggest partial oxidation of the surface layer to Cu₂O upon exposure to air. The catalytic activity of the Cu‐NPs is demonstrated in an archetypal “click chemistry” reaction, generating good yields during azide‐alkyne cycloadditions, most likely catalyzed by the Cu(I) surface layer of the nanoparticles. Furthermore, cytochrome deletion mutants suggest a novel metal reduction system is involved in enzymatic Cu(II) reduction and Cu‐NP synthesis, which is not dependent on the Mtr pathway commonly used to reduce other high oxidation state metals in this bacterium. This work demonstrates a novel, simple, green biosynthesis method for producing efficient copper nanoparticle catalysts.     

A Universal Strategy for Hollow Metal Oxide Nanoparticles Encapsulated into B/N Co‐Doped Graphitic Nanotubes as High‐Performance Lithium‐Ion Battery Anodes

Yolk–shell nanostructures have received great attention for boosting the performance of lithium‐ion batteries because of their obvious advantages in solving the problems associated with large volume change, low conductivity, and short diffusion path for Li⁺ ion transport. A universal strategy for making hollow transition metal oxide (TMO) nanoparticles (NPs) encapsulated into B, N co‐doped graphitic nanotubes (TMO@BNG (TMO = CoO, Ni₂O₃, Mn₃O₄) through combining pyrolysis with an oxidation method is reported herein. The as‐made TMO@BNG exhibits the TMO‐dependent lithium‐ion storage ability, in which CoO@BNG nanotubes exhibit highest lithium‐ion storage capacity of 1554 mA h g^?1 at the current density of 96 mA g^?1, good rate ability (410 mA h g^?1 at 1.75 A g^?1), and high stability (almost 96% storage capacity retention after 480 cycles). The present work highlights the importance of introducing hollow TMO NPs with thin wall into BNG with large surface area for boosting LIBs in the terms of storage capacity, rate capability, and cycling stability.     

From UV to Near‐Infrared Light‐Responsive Metal–Organic Framework Composites: Plasmon and Upconversion Enhanced Photocatalysis

The exploitation of photocatalysts that harvest solar spectrum as broad as possible remains a high‐priority target yet grand challenge. In this work, for the first time, metal–organic framework (MOF) composites are rationally fabricated to achieve broadband spectral response from UV to near‐infrared (NIR) region. In the core–shell structured upconversion nanoparticles (UCNPs)‐Pt@MOF/Au composites, the MOF is responsive to UV and a bit visible light, the plasmonic Au nanoparticles (NPs) accept visible light, whereas the UCNPs absorb NIR light to emit UV and visible light that are harvested by the MOF and Au once again. Moreover, the MOF not only facilitates the generation of “bare and clean” Au NPs on its surface and realizes the spatial separation for the Au and Pt NPs, but also provides necessary access for catalytic substrates/products to Pt active sites. As a result, the optimized composite exhibits excellent photocatalytic hydrogen production activity (280 µmol g^?1 h^?1) under simulated solar light, and the involved mechanism of photocatalytic H₂ production under UV, visible, and NIR irradiation is elucidated. Reportedly, this is an extremely rare study on photocatalytic H₂ production by light harvesting in all UV, visible, and NIR regions.     

Co@Co3O4@PPD Core@bishell Nanoparticle‐Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high‐performance primary zinc‐air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co₃O₄ core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co₃O₄@PPD core@bishell structure, obtained via a three‐step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co₃O₄ NPs encapsulated by ultrathin highly graphitized N‐doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N‐doped graphitic carbon outer shell and ultrathin nanocrystalline Co₃O₄ inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co₃O₄@PPD in air‐cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm^?2.     

Multifunctional Co0.85Se‐Fe3O4 Nanocomposites: Controlled Synthesis and Their Enhanced Performances for Efficient Hydrogenation of p‐Nitrophenol and Adsorbents

A new kind of multifunctional Co_0.85Se‐Fe₃O₄ nanocomposites is synthesized by loading Fe₃O₄ nanoparticles (NPs) with a size of about 5 nm on the surface of Co_0.85Se nanosheets under hydrothermal conditions without using any surfactant or structure‐directing agents. The Co_0.85Se‐Fe₃O₄ nanocomposite exhibits remarkable catalytic performance for hydrogenation of p‐nitrophenol (4‐NP) at room temperature and good adsorption behavior for methylene blue trihydrate in water. This nanocomposite also shows a high specific surface area and magnetic separation capability for recyclable utilization. The enhanced performances both in catalysis and adsorption are better than either individual component of Co_0.85Se nanosheets or Fe₃O₄ nanoparticles, demonstrating the possibility for designing new multifunctional nanocomposites with improved performances for catalysis, adsorbents, and other applications.     

Bioinspired Superhydrophobic Fe3O4@Polydopamine@Ag Hybrid Nanoparticles for Liquid Marble and Oil Spill

Fe₃O₄ nanoparticles (NPs) with Ag NPs evenly distributed on the surface are fabricated by using polydopamine (PDA) as the intermediate layer. Silanization and thiol chemistry are used to firmly combine the Fe₃O₄@ PDA core and outer surface Ag NPs. The spherical and hybrid nanoparticles are termed Fe₃O₄@PDA@Ag NPs, which possess a core–shell and hierarchical structure. After surface modification with 1H,1H,2H,2H‐perfluorodecanethiol, the hybrid Fe₃O₄@PDA@Ag NPs become highly hydrophobic. Slight rolling of a water droplet on the as‐prepared NPs causes the formation of a “liquid marble”, which is capable of performing remote actuation on various solid surfaces, such as glass sheet, paper, plastic, textile, and ceramic, and at the liquid–air interface using a permanent magnet. Liquid marbles with self‐assembled NPs on the liquid surface have potential to act as a miniaturized reactor for manipulation of inner liquid droplet with high positioning precision. In addition, the Fe₃O₄@PDA@Ag NPs are multifunctional and can be applied for oil/water separation and antibacterial purpose.     

Avalanche Carrier Multiplication in Multilayer Black Phosphorus and Avalanche Photodetector

A highly sensitive avalanche photodetector (APD) is fabricated by utilizing the avalanche multiplication mechanism in black phosphorus (BP), where a strong avalanche multiplication of electron–hole pairs is observed. Owing to the small bandgap (0.33 eV) of the multilayer BP, the carrier multiplication occurs at a significantly lower electric field than those of other 2D semiconductor materials. In order to further enhance the quantum efficiency and increase the signal‐to‐noise (S/N) ratio, Au nanoparticles (NPs) are integrated on the BP surface, which improves the light absorption by plasmonic effects. The BP–Au‐NPs structure effectively reduces both dark current (≈10 times lower) and onset of avalanche electric field, leading to higher carrier multiplication, photogain, quantum efficiency, and S/N ratio. For the BP–Au‐NPs APD, it is obtained that the external quantum efficiency (EQE) is 382 and the responsivity is 160 A W^‐1 at an electric field of 5 kV cm^‐1 (V_d ≈ 3.5 V, note that for the BP APD, EQE = 4.77 and responsivity = 2 A W^‐1 obtained at the same electric field). The significantly increased performance of the BP APD is promising for low‐power‐consumption, high‐sensitivity, and low‐noise photodevice applications, which can enable high‐performance optical communication and imaging systems.     

Atomic Carbon Layers Supported Pt Nanoparticles for Minimized CO Poisoning and Maximized Methanol Oxidation

Maximizing activity of Pt catalysts toward methanol oxidation reaction (MOR) together with minimized poisoning of adsorbed CO during MOR still remains a big challenge. In the present work, uniform and well‐distributed Pt nanoparticles (NPs) grown on an atomic carbon layer, that is in situ formed by means of dry‐etching of silicon carbide nanoparticles (SiC NPs) with CCl₄ gas, are explored as potential catalysts for MOR. Significantly, as‐synthesized catalysts exhibit remarkably higher MOR catalytic activity (e.g., 647.63 mA mg^?1 at a peak potential of 0.85 V vs RHE) and much improved anti‐CO poisoning ability than the commercial Pt/C catalysts, Pt/carbon nanotubes, and Pt/graphene catalysts. Moreover, the amount of expensive Pt is a few times lower than that of the commercial and reported catalyst systems. As confirmed from density functional theory (DFT) calculations and X‐ray absorption fine structure (XAFS) measurements, such high performance is due to reduced adsorption energy of CO on the Pt NPs and an increased amount of adsorbed energy OH species that remove adsorbed CO fast and efficiently. Therefore, these catalysts can be utilized for the development of large‐scale and industry‐orientated direct methanol fuel cells.     

Polyphenol‐Inspired Facile Construction of Smart Assemblies for ATP‐ and pH‐Responsive Tumor MR/Optical Imaging and Photothermal Therapy

Smart assemblies have attracted increased interest in various areas, especially in developing novel stimuli‐responsive theranostics. Herein, commercially available, natural tannic acid (TA) and iron oxide nanoparticles (Fe₃O₄ NPs) are utilized as models to construct smart magnetic assemblies based on polyphenol‐inspired NPs–phenolic self‐assembly between NPs and TA. Interestingly, the magnetic assemblies can be specially disassembled by adenosine triphosphate, which shows a stronger affinity to Fe₃O₄ NPs than that of TA and partly replaces the surface coordinated TA. The disassembly can further be facilitated by the acidic environment hence causing the remarkable change of the transverse relaxivity and potent “turn‐on” of fluorescence (FL) signals. Therefore, the assemblies for specific and sensitive tumor magnetic resonance and FL dual‐modal imaging and photothermal therapy after intravenous injection of the assemblies are successfully employed. This work not only provides understandings on the self‐assembly between NPs and polyphenols, but also will open new insights for facilely constructing versatile assemblies and extending their biomedical applications.     

Au Dotted Magnetic Network Nanostructure and Its Application for On‐Site Monitoring Femtomolar Level Pesticide

A novel magnetically responsive and surface‐enhanced Raman spectroscopy (SERS) active nanocomposite is designed and prepared by direct grafting of Au nanoparticles onto the surface of magnetic network nanostructure (MNN) with the help of a nontoxic and environmentally friendly reagent of inositol hexakisphosphate shortly named as IP₆. The presence of IP₆ as a stabilizer and a bridging agent could weave Fe₃O₄ nanoparticles (NPs) into magnetic network nanostructure, which is easily dotted with Au nanoparticles (Au NPs). It has been shown firstly that the huge Raman enhancement of Au‐MNN is reached by an external magnetic collection. Au‐MNN presenting the large surface and high detection sensitivity enables it to exhibit multifunctional applications involving sufficient adsorption of dissolved chemical species for enrichment, separation, as well as a Raman amplifier for the analysis of trace pesticide residues at femtomolar level by a portable Raman spectrometer. Therefore, such multifunctional nanocomposites can be developed as a smart and promising nanosystem that integrates SERS approach with an easy assay for concentration by an external magnet for the effective on‐site assessments of agricultural and environmental safety.     

Polyaniline/Pt Hybrid Nanofibers: High‐Efficiency Nanoelectrocatalysts for Electrochemical Devices

A simple and facile procedure to synthesize a novel hybrid nanoelectrocatalyst based on polyaniline (PANI) nanofiber‐supported supra‐high density Pt nanoparticles (NPs) or Pt/Pd hybrid NPs without prior PANI nanofiber functionalization at room temperature is demonstrated. This represents a new type of 1D hybrid nanoelectrocatalyst with several important benefits. First, the procedure is very simple and can be performed at room temperature using commercially available reagents without the need for templates and surfactants. Second, ultra‐high density small “bare” Pt NPs or Pt/Pd hybrid NPs are grown directly onto the surface of the PANI nanofiber, without using any additional linker. Most importantly, the present PANI nanofiber‐supported supra‐high density Pt NPs or Pt/Pd hybrid NPs can be used as a signal enhancement element for constructing electrochemical devices with high performance.     

WO3 Nanofiber‐Based Biomarker Detectors Enabled by Protein‐Encapsulated Catalyst Self‐Assembled on Polystyrene Colloid Templates

A novel catalyst functionalization method, based on protein‐encapsulated metallic nanoparticles (NPs) and their self‐assembly on polystyrene (PS) colloid templates, is used to form catalyst‐loaded porous WO₃ nanofibers (NFs). The metallic NPs, composed of Au, Pd, or Pt, are encapsulated within a protein cage, i.e., apoferritin, to form unagglomerated monodispersed particles with diameters of less than 5 nm. The catalytic NPs maintain their nanoscale size, even following high‐temperature heat‐treatment during synthesis, which is attributed to the discrete self‐assembly of NPs on PS colloid templates. In addition, the PS templates generate open pores on the electrospun WO₃ NFs, facilitating gas molecule transport into the sensing layers and promoting active surface reactions. As a result, the Au and Pd NP‐loaded porous WO₃ NFs show superior sensitivity toward hydrogen sulfide, as evidenced by responses (R_air/R_gas) of 11.1 and 43.5 at 350 °C, respectively. These responses represent 1.8‐ and 7.1‐fold improvements compared to that of dense WO₃ NFs (R_air/R_gas = 6.1). Moreover, Pt NP‐loaded porous WO₃ NFs exhibit high acetone sensitivity with response of 28.9. These results demonstrate a novel catalyst loading method, in which small NPs are well‐dispersed within the pores of WO₃ NFs, that is applicable to high sensitivity breath sensors.     

Nanoparticle‐Enhanced Silver‐Nanowire Plasmonic Electrodes for High‐Performance Organic Optoelectronic Devices

Improved performance in plasmonic organic solar cells (OSCs) and organic light‐emitting diodes (OLEDs) via strong plasmon‐coupling effects generated by aligned silver nanowire (AgNW) transparent electrodes decorated with core–shell silver–silica nanoparticles (Ag@SiO₂NPs) is demonstrated. NP‐enhanced plasmonic AgNW (Ag@SiO₂NP–AgNW) electrodes enable substantially enhanced radiative emission and light absorption efficiency due to strong hybridized plasmon coupling between localized surface plasmons (LSPs) and propagating surface plasmon polaritons (SPPs) modes, which leads to improved device performance in organic optoelectronic devices (OODs). The discrete dipole approximation (DDA) calculation of the electric field verifies a strongly enhanced plasmon‐coupling effect caused by decorating core–shell Ag@SiO₂NPs onto the AgNWs. Notably, an electroluminescence efficiency of 25.33 cd A^?1 (at 3.2 V) and a power efficiency of 25.14 lm W^?1 (3.0 V) in OLEDs, as well as a power conversion efficiency (PCE) value of 9.19% in OSCs are achieved using hybrid Ag@SiO₂NP–AgNW films. These are the highest values reported to date for optoelectronic devices based on AgNW electrodes. This work provides a new design platform to fabricate high‐performance OODs, which can be further explored in various plasmonic and optoelectronic devices.     

Electrochemical Characterization of a Porous Pt Nanoparticle ＂Nanocube-Mosaic＂ Prepared by a Modified Polyol Method with HCI Addition

Porous and single crystalline platinum (Pt) nanoparticles (NPs) have been successfully synthesized by reduction of H₂PtCl₆·6H₂O and then investigated by optical spectroscopy and transmission electron microscopy. H₂PtCl₆·6H₂O was reduced using ethylene glycol in the presence of polyvinylpyrrolidone under highly acidic conditions (pH < 1) to form single crystalline Pt particles about 5 nm in size. These particles were then stacked via {100} facets, forming 50-nm length porous nanocubes with a mosaic structure. The porous Pt NPs exhibited excellent catalytic properties for methanol oxidation. In particular, the electrochemical surface area was ∼63 m²/g, five times higher than that for non-porous Pt NPs prepared using a conventional method. We suggest that the high catalytic activity of porous Pt NPs is due to a combination of the crystalline structure having exposed {100} facets and a porous morphology.