Heterointerface engineering can be used to develop excellent catalysts through electronic coupling effects between different components or phases. As one kind of promising Pt‐free electrocatalysts for hydrogen evolution reaction (HER), pure‐phased metal phosphide exhibits the unfavorable factor of strong or weak H*‐adsorption performance. Here, 6 nm wall‐thick Ni2P–NiP2 hollow nanoparticle polymorphs combining metallic Ni2P and metalloid NiP2 with observable heterointerfaces are synthesized. It shows excellent catalytic performance toward the HER, requiring an overpotential of 59.7 mV to achieve 10 mA cm−2 with a Tafel slope of 58.8 mV dec−1. Density functional theory calculations verify electrons' transfer from P to Ni at the heterointerfaces, which decreases the absolute value of H* adsorption energy and simultaneously enhance electronic conductivity. That is, the heterojunctions balance the metallic Ni2P and the metalloid NiP2 to form an optimized phosphide polymorph catalyst for the HER. Furthermore, this polymorph combination is used with NiFe‐LDH nanosheets to form an alkaline electrolyzer. It shows highly desirable electrochemical properties, which can reach 10 mA cm−2 in 1 m KOH at 1.48 V and be driven by an AAA battery with a nominal voltage of 1.5 V. The work about interfacial charge transfer might provide an insight into designing excellent polymorph catalysts.

Photon‐coupling and electron dynamics are the key processes leading to the photocatalytic activity of plasmonic metal‐semiconductor nanohybrids. To better utilize and explore these effects, a facile large‐scale synthesis route to form Ag@AgCl cubic cages with well‐defined hollow interiors is carried out using a water‐soluble sacrificial salt‐crystal‐template process. Theoretical calculations and experimental probes of the electron transfer process are used in an effort to gain insight into the underlying plasmonic properties of the Ag@AgCl materials. Efficient utilization of solar energy to create electron‐hole pairs is attributed to the significant light confinement and enhancement around the Ag/AgCl interfacial plasmon hot spots and multilight‐reflection inside the cage structure. More importantly, an ultrafast electron transfer process (≤150 fs) from Ag nanoparticles to the AgCl surface is detected, which facilitates the charge separation efficiency in this system, contributing to high photocatalytic activity and stability of Ag@AgCl photocatalyst towards organic dye degradation.

Direct evidence of plasmon-enhanced H2 generation is observed in photocatalytic water reduction by using TiO2 electrospun nanofibers co-decorated with Au and Pt nanoparticles through dual-beam irradiation. The Au/Pt/TiO2 nanofibers exhibit certain activity for H2 generation under single irradiation at 420 nm that excites the defect/impurity states of TiO2. Significantly, when secondary irradiation at 550 nm is introduced to simultaneously excite Au SPR, we observed 2.5 times higher activity for H2 generation. Further investigation by finely controlling the irradiation wavelengths reveals that the enhancement factor on the photocatalytic activity for H2 generation is directly correlated with the plasmon absorption band of the Au nanoparticles in the Au/Pt/TiO2 nanofibers. The control experiments with different sacrificial agents suggest that the hot plasmonic electrons of Au are responsible for the enhanced photocatalytic activity that can be magnified when TiO2 is simultaneously excited.

Excitation of localized surface plasmons (LSPs) of metal nanoparticles (NPs)residing on a flat metal film has attracted great attentions recently due to the enhanced electromagnetic (EM) fields found to be higher than the case of NPs on a dielectric substrate. In the present work, it is shown that even much higher enhancement of EM fields is obtained by exciting the LSPs through extended surface plasmons (ESPs) generated at the metallic film surface using the Kretschmann-Raether configuration. We show that the largest EM field enhancement and the highest surface-enhanced fluorescence intensity are obtained when the incidence angle is the ESP resonance angle of the underlying metal film. The finite-difference time-domain simulations indicate that excitation of LSPs using ESPs can generate 1-3 orders higher EM field intensity than direct excitation of the LSPs using incidence from free space. The ultrahigh enhancement is attributed to the strong confinement of the ESP waves in the vertical direction. The drastically intensified EM fields are significant for highly-sensitive refractive index sensing, surface-enhanced spectroscopies, and enhancing the efficiency of optoelectronic devices.2 KEYWORDS: localized surface plasmon resonance, surface palsmon polariton, KretschmannRaether, metal nanoparticles, electromagnetic field enhancement, surface-enhanced spectroscopies 3

Spiky nanoparticles exhibit higher overall plasmonic excitation cross sections than their nonspiky peers. In this work, we demonstrate a two-step seed-mediated growth method to synthesize a new class of spiky Ag–Au octahedral nanoparticles with the aid of a high molecular weight poly(vinylpyrrolidone) polymer. The length of the nanospikes can be controlled from 10 to 130 nm with sharp tips by varying the amount of gold precursor added and the injection rates. Spatially resolved electron energy-loss spectroscopy (EELS) study and finite-difference time-domain (FDTD) simulations on individual spiky Ag–Au nanoparticles illustrate multipolar plasmonic responses. While the octahedral core retains its intrinsic plasmon response, the spike exhibits a hybridized dipolar surface plasmon resonance at lower energy. With increasing spike length from 50 to 130 nm, the surface plasmon of the spike can be tuned from 1.16 to 0.78 eV. The electric field at the spike region increases rapidly with increasing spike length, with a 104 field enhancement achieved at the tips of 130-nm spike. The results highlight that it is important to synthesize long spikes (>50 nm) on nanoparticles to achieve strong electric field enhancement. A hypothesis for the formation of sharp spikes is proposed based on our studies using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and high resolution transmission electron microscopy (TEM).