CONSPECTUS:As a new class of photocatalysts, plasmonic noble metal nanoparticles with the unique ability to harvest solar energy across the entire visible spectrum and produce effective energy conversion have been explored as a promising pathway for the energy crisis. The resonant excitation of surface plasmon resonance allows the nanoparticles to collect the energy of photons to form a highly enhanced electromagnetic field, and the energy stored in the plasmonic field can induce hot carriers in the metal. The hot electron−hole pairs ultimately dissipate by coupling to phonon modes of the metal nanoparticles, resulting in a higher lattice temperature. The plasmonic electromagnetic field, hot electrons, and heat can catalyze chemical reactions of reactants near the surface of the plasmonic metal nanoparticles. This Account summarizes recent theoretical and experimental advances on the excitation mechanisms and energy transfer pathways in the plasmonic catalysis on molecules. Especially, current advances on plasmon-driven crystal growth and transformation of nanomaterials are introduced. The efficiency of the chemical reaction can be dramatically increased by the plasmonic electromagnetic field because of its higher density of photons. Similar to traditional photocatalysis, energy overlap between the plasmonic field and the HOMO− LUMO gap of the reactant is needed to realize resonant energy transfer. For hot-carrier-driven catalysis, hot electrons generated by plasmon decay can be transferred to the reactant through the indirect electron transfer or direct electron excitation process. For this mechanism, the energy of hot electrons needs to overlap with the unoccupied orbitals of the reactant, and the particular chemical channel can be selectively enhanced by controlling the energy distribution of hot electrons. In addition, the local thermal effect following plasmon decay offers an opportunity to facilitate chemical reactions at room temperature. Importantly, surface plasmons can not only catalyze chemical reactions of molecules but also induce crystal growth and transformation of nanomaterials. As a new development in plasmonic catalysis, plasmon-driven crystal transformation reveals a more powerful aspect of the catalysis effect, which opens the new field of plasmonic catalysis. We believe that this Account will promote clear understanding of plasmonic catalysis on both molecules and materials and contribute to the design of highly tunable catalytic systems to realize crystal transformations that are essential to achieve efficient solar-to-chemical energy conversion.

As one of the most important semiconductors, silicon has been used to fabricate electronic devices, waveguides, detectors, solar cells, etc. However, the indirect bandgap and low quantum efficiency (10−7) hinder the use of silicon for making good emitters. For integrated photonic circuits, silicon-based emitters with sizes in the range of 100−300 nm are highly desirable. Here, we show the use of the electric and magnetic resonances in silicon nanoparticles to enhance the quantum efficiency and demonstrate the white-light emission from silicon nanoparticles with feature sizes of ~200 nm. The magnetic and electric dipole resonances are employed to dramatically increase the relaxation time of hot carriers, while the magnetic and electric quadrupole resonances are utilized to reduce the radiative recombination lifetime of hot carriers. This strategy leads to an enhancement in the quantum efficiency of silicon nanoparticles by nearly five orders of magnitude as compared with bulk silicon, taking the three-photon-induced absorption into account.

The high spatial frequency periodic structures induced on metal surface by femtosecond laser pulses was investigated experimentally and numerically. It is suggested that the redistribution of the electric field on metal surface caused by the initially formed low spatial frequency periodic structures plays a crucial role in the creation of high spatial frequency periodic structures. The field intensity which is initially localized in the grooves becomes concentrated on the ridges in between the grooves when the depth of the grooves exceeds a critical value, leading to the ablation of the ridges in between the grooves and the formation of high spatial frequency periodic structures. The proposed formation process is supported by both the numerical simulations based on the finite-difference time-domain technique and the experimental results obtained on some metals such as stainless steel and nickel.

A task-specific ionic liquid strategy was proposed for designing oxygen vacancy-rich α-Fe2O3 nanocubes toward excellently electrocatalytic N2 fixation to NH3.

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Periodic surface structures with periods as small as about one-tenth of the irradiating femtosecond (fs) laser light wavelength were created on the surface of a titanium (Ti) foil by exploiting laser-induced oxidation and third harmonic generation (THG). They were achieved by using 100-fs laser pulses with a repetition rate of 1 kHz and a wavelength ranging from 1.4 to 2.2 μm. It was revealed that an extremely thin TixOy layer was formed on the surface of the Ti foil after irradiating fs laser light with a fluence smaller than the ablation threshold of Ti, leading to a significant enhancement in THG which may exceed the ablation threshold of TixOy. As compared with Ti, the maximum efficacy factor for TixOy appears at a larger normalized wavevector in the direction perpendicular to the polarization of the fs laser light. As a result, the THG-dominated laser ablation of TixOy induces 100-nm periodic structures parallel to the polarization of the fs laser light. The depth of the periodic structures was found to be ~10 nm by atomic force microscopy and the formation of the thin TixOy layer was verified by energy dispersive X-ray spectroscopy.

Employing phosphonium-based ionic liquid, tetrabutylphosphonium chloride [P 4444 ]Cl as novel phosphorus source and reaction medium, a facile approach for fabricating nanostructured Ni 2 P and Ni 12 P 5 was developed upon microwave heating in 1−2 min or conventional heating at 350 °C for 3 h. In a microwave-driven approach, controlling counteranions of various nickel salts could conveniently tune the phase of as-synthesized nickel phosphides. Ni(acac) 2 and Ni(OAc) 2 •4H 2 O as Ni source could yield Ni 2 P nanoparticles, while NiCl 2 •6H 2 O and NiSO 4 •7H 2 O offered Ni 12 P 5 nanocrystals. The synthesized products were characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Their electrocatalytic behavior toward hydrogen evolution reaction in acidic medium was investigated. The assynthesized Ni 2 P nanoparticles presented more excellent catalytic efficiency than Ni 12 P 5 . Ni 2 P nanoparticles from Ni(acac) 2 require overpotentials of only 102 mV to reach 10 mA cm −2 with a small Tafel slope of 46 mV dec −1 , showing its best activity among those tested catalysts. The present novel ionic liquid-mediated strategy for the synthesis of nickel phosphide provides the remarkable advantage of operating in very short time by microwave heating, which is of particular interest from the viewpoint of energysaving, fast synthesis, and easy operation.

We report on the formation of one- and two-dimensional (1D and 2D) nanohole arrays on the surface of a silicon wafer by scanning with a femtosecond laser with appropriate power and speed. The underlying physical mechanism is revealed by numerical simulation based on the finite-difference time-domain technique. It is found that the length and depth of the initially formed gratings (or ripples) plays a crucial role in the generation of 1D or 2D nanohole arrays. The silicon surface decorated with such nanohole arrays can exhibit vivid structural colors through efficiently diffracting white light.