Understanding the Enhancement Mechanisms of Surface Plasmon‐Mediated Photoelectrochemical Electrodes: A Case Study on Au Nanoparticle Decorated TiO2 Nanotubes

Surface plasmon resonance (SPR) enhancement in photocatalyst and photovoltaics has been widely studied and different enhancement mechanisms have been established based on different heterostructure interface configurations. This work is intended to unveil the mechanisms behind charge or energy transfer in different plasmonic configurations of metal particle–semiconductor interfaces, especially with a dielectric layer. For this purpose, a series of composite photoelectrodes based on anodic TiO₂ nanotube (TONT) backbones coated with Au, Al₂O_3, or both are designed and characterized systematically. In conjunction with both experimental measurements and numerical simulations, it is revealed that in the TONT‐Al₂O₃‐Au electrode system (i.e., a thin nonconductive spacer between semiconductor and metal), the enhancement is dominantly governed by SPR‐mediated hot‐electron injection rather than conventional‐thought near‐field electromagnetic enhancement. Among all configurations, the TONT‐Au‐Al₂O₃ electrode shows the best photoresponse in both UV and visible regions. The superior visible light response of the TONT‐Au‐Al₂O₃ electrode is ascribed to the Al₂O₃ intensified local electromagnetic field that enhances the hot‐electron injection through the TiO₂‐Au interface, and an effective surface passivation by the Al₂O₃ coating.     

A Nonmetal Plasmonic Z‐Scheme Photocatalyst with UV‐ to NIR‐Driven Photocatalytic Protons Reduction

Ultrabroad‐spectrum absorption and highly efficient generation of available charge carriers are two essential requirements for promising semiconductor‐based photocatalysts, towards achieving the ultimate goal of solar‐to‐fuel conversion. Here, a fascinating nonmetal plasmonic Z‐scheme photocatalyst with the W₁₈O₄₉/g‐C₃N₄ heterostructure is reported, which can effectively harvest photon energies spanning from the UV to the nearinfrared region and simultaneously possesses improved charge‐carrier dynamics to boost the generation of long‐lived active electrons for the photocatalytic reduction of protons into H₂. By combining with theoretical simulations, a unique synergistic photocatalysis effect between the semiconductive Z‐scheme charge‐carrier separation and metal‐like localized‐surface‐plasmon‐resonance‐induced “hot electrons” injection process is demonstrated within this binary heterostructure.     

Light-induced ultrafast proton-coupled electron transfer responsible for H2 evolution on silver plasmonics

Light-driven proton-coupled electron transfer (PCET) reactions on nanoplasmonics would bring temporal control of their reactive pathways, in particular, prolong their charge separation state. Using a silver nano-hybrid plasmonic structure, we observed that optical excitation of Ag-localized surface plasmon instigated electron injection into TiO₂ conduction band and oxidation of isopropanol alcoholic functionality. Femtosecond transient infrared absorption studies show that electron transfer from Ag to TiO₂ occurs in ca. 650?fs, while IPA molecules near the Ag surface undergo an ultrafast bidirectional PCET step within 400?fs. Our work demonstrates that ultrafast PCET reaction plays a determinant role in prolonging charge separation state, providing an innovative strategy for visible-light photocatalysis with plasmonic nanostructures.     

Controlled synthesis and structure characterization of nanostructured MnWO4

Using Mn to partly substitute the W in W₁₈O₄₉ nanowires, the synthesis of MnWO₄ hubnerite nano-cocoons is described in this paper, by using mixed MnCl₂ and WCl₆ as the precursors and cyclohexanol as the solvent, in a simple solvothermal process. Detailed characterization of the resulting products, using electron microscopy and spectroscopy, has shown that the gradual increase of MnCl₂ concentration changes the long W₁₈O₄₉ nanowires to cocoon-like nanomaterials of stable MnWO₄ phase. The driving force for such transformations is attributed to the Mn²⁺ inclusion within the W₁₈O₄₉. At low Mn²⁺ concentration, internal stresses would be introduced to the W₁₈O₄₉ nanowires; whilst at high Mn²⁺ concentration close to the stoichiometric composition of MnWO₄, the formation of the nano-cocoons is triggered by the intrinsic crystalline feature of the hubnerite. It is believed that a combination of the initial nanowire nucleation and competing growth, and of self-assembly of neighboring parallel nanowires, leads to the final structure.     

Aluminum‐Ion‐Intercalation Supercapacitors with Ultrahigh Areal Capacitance and Highly Enhanced Cycling Stability: Power Supply for Flexible Electrochromic Devices

Electrochemical capacitor systems based on Al ions can offer the possibilities of low cost and high safety, together with a three‐electron redox‐mechanism‐based high capacity, and thus are expected to provide a feasible solution to meet ever‐increasing energy demands. Here, highly efficient Al‐ion intercalation into W₁₈O₄₉ nanowires (W₁₈O₄₉NWs) with wide lattice spacing and layered single‐crystal structure for electrochemical storage is demonstrated. Moreover, a freestanding composite film with a hierarchical porous structure is prepared through vacuum‐assisted filtration of a mixed dispersion containing W₁₈O₄₉NWs and single‐walled carbon nanotubes. The as‐prepared composite electrode exhibits extremely high areal capacitances of 1.11–2.92 F cm^?2 and 459 F cm^?3 at 2 mA cm^?2, enhanced electrochemical stability in the Al³⁺ electrolyte, as well as excellent mechanical properties. An Al‐ion‐based, flexible, asymmetric electrochemical capacitor is assembled that displays a high volumetric energy density of 19.0 mWh cm^?3 at a high power density of 295 mW cm^?3. Finally, the Al‐ion‐based asymmetric supercapacitor is used as the power source for poly(3‐hexylthiophene)‐based electrochromic devices, demonstrating their promising capability in flexible electronic devices.     

Probing Bidirectional Plasmon-Plasmon Coupling-Induced Hot Charge Carriers in Dual Plasmonic Au/CuS Nanocrystals

Heterostructured Au/CuS nanocrystals (NCs) exhibit localized surface plasmon resonance (LSPR) centered at two different wavelengths (551 and 1051 nm) with a slight broadening compared to respective homostructured Au and CuS NC spectra. By applying ultrafast transient absorption spectroscopy we show that a resonant excitation at the respective LSPR maxima of the heterostructured Au/CuS NCs leads to the characteristic hot charge carrier relaxation associated with both LSPRs in both cases. A comparison of the dual plasmonic heterostructure with a colloidal mixture of homostructured Au and CuS NCs shows that the coupled dual plasmonic interaction is only active in the heterostructured Au/CuS NCs. By investigating the charge carrier dynamics of the process, we find that the observed interaction is faster than phononic or thermal processes (< 100 fs). The relaxation of the generated hot charge carriers is faster for heterostructured nanocrystals and indicates that the interaction occurs as an energy transfer (we propose Landau damping or interaction via LSPR beat oscillations as possible mechanisms) or charge carrier transfer between both materials. Our results strengthen the understanding of multiplasmonic interactions in heterostructured Au/CuS NCs and will significantly advance applications where these interactions are essential, such as catalytic reactions.     

MXenes for Plasmonic Photodetection

MXenes have recently shown impressive optical and plasmonic properties associated with their ultrathin‐atomic‐layer structure. However, their potential use in photonic and plasmonic devices has been only marginally explored. Photodetectors made of five different MXenes are fabricated, among which molybdenum carbide MXene (Mo₂CT_x) exhibits the best performance. Mo₂CT_x MXene thin films deposited on paper substrates exhibit broad photoresponse in the range of 400–800 nm with high responsivity (up to 9 A W^?1), detectivity (≈5 × 10¹¹ Jones), and reliable photoswitching characteristics at a wavelength of 660 nm. Spatially resolved electron energy‐loss spectroscopy and ultrafast femtosecond transient absorption spectroscopy of the MXene nanosheets reveal that the photoresponse of Mo₂CT_x is strongly dependent on its surface plasmon‐assisted hot carriers. Additionally, Mo₂CT_x thin‐film devices are shown to be relatively stable under ambient conditions, continuous illumination and mechanical stresses, illustrating their durable photodetection operation in the visible spectral range. Micro‐Raman spectroscopy conducted on bare Mo₂CT_x film and on gold electrodes allowing for surface‐enhanced Raman scattering demonstrates surface chemistry and a specific low‐frequency band that is related to the vibrational modes of the single nanosheets. The specific ability to detect and excite individual surface plasmon modes provides a viable platform for various MXene‐based optoelectronic applications.     

Efficient All-Optical Plasmonic Modulators with Atomically Thin Van Der Waals Heterostructures

All-optical modulators are attracting significant attention due to their intrinsic perspective on high-speed, low-loss, and broadband performance, which are promising to replace their electrical counterparts for future information communication technology. However, high-power consumption and large footprint remain obstacles for the prevailing nonlinear optical methods due to the weak photon–photon interaction. Here, efficient all-optical mid-infrared plasmonic waveguide and free-space modulators in atomically thin graphene-MoS₂ heterostructures based on the ultrafast and efficient doping of graphene with the photogenerated carrier in the monolayer MoS₂ are reported. Plasmonic modulation of 44 cm⁻¹ is demonstrated by an LED with light intensity down to 0.15 mW cm⁻², which is four orders of magnitude smaller than the prevailing graphene nonlinear all-optical modulators (≈10³ mW cm⁻²). The ultrafast carrier transfer and recombination time of photogenerated carriers in the heterostructure may achieve ultrafast modulation of the graphene plasmon. The demonstration of the efficient all-optical mid-infrared plasmonic modulators, with chip-scale integrability and deep-sub wavelength light field confinement derived from the van der Waals heterostructures, may be an important step toward on-chip all-optical devices.     

PABA-assisted hydrothermal fabrication of W18O49 nanowire networks and its transition to WO3 for photocatalytic degradation of methylene blue

W₁₈O₄₉ nanowire networks have been fabricated by a facile hydrothermal method. In this method, p-aminobenzoic acid (PABA) was used as an assistant agent to control the morphology transformation. W₁₈O₄₉ and its products annealed at different temperature were characterized by XRD, SEM, TEM, UV–vis absorption spectroscopy, XPS, TGA, and FTIR. Formation mechanism and thermal stability of W₁₈O₄₉ nanowire networks were studied in detail. The experiment data showed that PABA played an important role in the induced crystal growth of W₁₈O₄₉ nanowires along [0?1?0] axis. In transformation, the structure of samples was controlled: from irregular particles to nanowire networks. W₁₈O₄₉ nanowire networks were annealed at different temperature. The nanowire networks collapsed at 450?°C, while WO₃ nanocrystals were obtained. The W₁₈O₄₉ nanowire networks annealed at 400?°C have a superior photocatalytic performance to degrade methylene blue and its specific surface area was up to 147?m²?g^?1.     

Rutile Nanorod/Anatase Nanowire Junction Array as Both Sensor and Power Supplier for High‐Performance,Self‐Powered,Wireless UV Photodetector

Self‐powered UV photodetectors based on TiO₂ nanotree arrays have captured much attention in recent years because of their many advantages. In this work, rutile/anatase TiO₂ (R/A‐TiO₂) heterostructured nanotree arrays are fabricated by assembling anatase nanowires as branches on rutile nanorods. External quantum efficiencies as high as 90% are reached at 325 nm. These high quantum efficiencies are related to the higher amount of light harvesting due to the larger surface area, the better separation ability of the photogenerated carriers by the rutile/anatase heterostructure, and the faster electron transport, related to the 1D nanostructure and lattice connection at the interface of the two kinds of TiO₂. Furthermore, a self‐powered wireless UV photodetector is shown with excellent wireless detection performance. Such devices will enable significant advances for next‐generation photodetection and photosensing applications.     

Hot‐Electron‐Assisted Femtosecond All‐Optical Modulation in Plasmonics

The optical Kerr nonlinearity of plasmonic metals provides enticing prospects for developing reconfigurable and ultracompact all‐optical modulators. In nanostructured metals, the coherent coupling of light energy to plasmon resonances creates a nonequilibrium electron distribution at an elevated electron temperature that gives rise to significant Kerr optical nonlinearities. Although enhanced nonlinear responses of metals facilitate the realization of efficient modulation devices, the intrinsically slow relaxation dynamics of the photoexcited carriers, primarily governed by electron–phonon interactions, impedes ultrafast all‐optical modulation. Here, femtosecond (≈190 fs) all‐optical modulation in plasmonic systems via the activation of relaxation pathways for hot electrons at the interface of metals and electron acceptor materials, following an on‐resonance excitation of subradiant lattice plasmon modes, is demonstrated. Both the relaxation kinetics and the optical nonlinearity can be actively tuned by leveraging the spectral response of the plasmonic design in the linear regime. The findings offer an opportunity to exploit hot‐electron‐induced nonlinearities for design of self‐contained, ultrafast, and low‐power all‐optical modulators based on plasmonic platforms.     

Au Nanowires Decorated Ultrathin Co3O4 Nanosheets toward Light-Enhanced Nitrate Electroreduction

Nitrate is a reasonable alternative instead of nitrogen for ammonia production due to the low bond energy, large water-solubility, and high chemical polarity for good absorption. Nitrate electroreduction reaction (NO₃RR) is an effective and green strategy for both nitrate treatment and ammonia production. As an electrochemical reaction, the NO₃RR requires an efficient electrocatalyst for achieving high activity and selectivity. Inspired by the enhancement effect of heterostructure on electrocatalysis, Au nanowires decorated ultrathin Co₃O₄ nanosheets (Co₃O₄-NS/Au-NWs) nanohybrids are proposed for improving the efficiency of nitrate-to-ammonia electroreduction. Theoretical calculation reveals that Au heteroatoms can effectively adjust the electron structure of Co active centers and reduce the energy barrier of the determining step (*NO → *NOH) during NO₃RR. As the result, the Co₃O₄-NS/Au-NWs nanohybrids achieve an outstanding catalytic performance with high yield rate (2.661 mg h⁻¹ mg_cat⁻¹) toward nitrate-to-ammonia. Importantly, the Co₃O₄-NS/Au-NWs nanohybrids show an obviously plasmon-promoted activity for NO₃RR due to the localized surface plasmon resonance (LSPR) property of Au-NWs, which can achieve an enhanced NH₃ yield rate of 4.045 mg h⁻¹ mg_cat⁻¹. This study reveals the structure–activity relationship of heterostructure and LSPR-promotion effect toward NO₃RR, which provide an efficient nitrate-to-ammonia reduction with high efficiency.     

A Dopant Replacement‐Driven Molten Salt Method toward the Synthesis of Sub‐5‐nm‐Sized Ultrathin Nanowires

The high‐temperature molten‐salt method is an important inorganic synthetic route to a wide variety of morphological phenotypes. However, its utility is limited by the fact that it is typically incapable of producing ultrathin (<5 nm diameter) nanowires, which have a crucial role in novel nanotechnology applications. Herein, a rapid molten salt‐based synthesis of sub‐5‐nm‐sized nanowires of hexagonal tungsten oxide (h‐WO₃) that is critically dependent on a substantial proportion of molybdenum (Mo) dopant is described. This dopant‐driven morphological transition in tungsten oxide (WO₃) may be attributable to the collapse of layered structure, followed by nanocluster aggregation, coalescence, and recrystallization to form ultrathin nanowires. Interestingly, due to the structural properties of h‐WO₃, the thus‐formed ultrathin nanowires are demonstrated to be excellent photocatalysts for the production of ammonia (NH₃) from nitrogen (N₂) and water. The ultrathin nanowires exhibit a high photocatalytic NH₃‐production activity with a rate of 370 µmol g^?1 h^?1 and an apparent quantum efficiency of 0.84% at 420 nm, which is more than twice that obtained from the best‐performing Mo‐doped W₁₈O₄₉ nanowire catalysts. It is envisaged that the dopant replacement‐driven synthetic protocol will allow for rapid access to a series of ultrathin nanostructures with intriguing properties and increase potential applications.     

Improving All‐Inorganic Perovskite Photodetectors by Preferred Orientation and Plasmonic Effect

All‐inorganic perovskites have high carrier mobility, long carrier diffusion length, excellent visible light absorption, and well overlapping with localized surface plasmon resonance (LSPR) of noble metal nanocrystals (NCs). The high‐performance photodetectors can be constructed by means of the intrinsic outstanding photoelectric properties, especially plasma coupling. Here, for the first time, inorganic perovskite photodetectors are demonstrated with synergetic effect of preferred‐orientation film and plasmonic with both high performance and solution process virtues, evidenced by 238% plasmonic enhancement factor and 10⁶ on/off ratio. The CsPbBr₃ and Au NC inks are assembled into high‐quality films by centrifugal‐casting and spin‐coating, respectively, which lead to the low cost and solution‐processed photodetectors. The remarkable near‐field enhancement effect induced by the coupling between Au LSPR and CsPbBr₃ photogenerated carriers is revealed by finite‐difference time‐domain simulations. The photodetector exhibits a light on/off ratio of more than 10⁶ under 532 nm laser illumination of 4.65 mW cm^?2. The photocurrent increases from 0.67 to 2.77 μA with centrifugal‐casting. Moreover, the photocurrent rises from 245.6 to 831.1 μA with Au NCs plasma enhancement, leading to an enhancement factor of 238%, which is the most optimal report among the LSPR‐enhanced photodetectors, to the best of our knowledge. The results of this study suggest that all‐inorganic perovskites are promising semiconductors for high‐performance solution‐processed photodetectors, which can be further enhanced by Au plasmonic effect, and hence have huge potentials in optical communication, safety monitoring, and biological sensing.     

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.     

Plasmon Modes Induced by Anisotropic Gap Opening in Au@Cu2O Nanorods

Integration of semiconductors with noble metals to form heteronanostructures can give rise to many interesting plasmonic and electronic properties. A number of such heteronanostructures have been demonstrated comprising noble metals and n‐type semiconductors, such as TiO₂, ZnO, SnO₂, Fe₃O₄, and CuO. In contrast, reports on heteronanostructures made of noble metals and p‐type semiconductors are scarce. Cu₂O is an unintentional p‐type semiconductor with unique properties. Here, the uniform coating of Cu₂O on two types of Au nanorods and systematic studies of the plasmonic properties of the resultant core–shell heteronanostructures are reported. One type of Au nanorods is prepared by seed‐mediated growth, and the other is obtained by oxidation of the as‐prepared Au nanorods. The (Au nanorod)@Cu₂O nanostructures produced from the as‐prepared nanorods exhibit two transverse plasmon peaks, whereas those derived from the oxidized nanorods display only one transverse plasmon peak. Through electrodynamic simulations the additional transverse plasmon peak is found to originate from a discontinuous gap formed at the side of the as‐prepared nanorods. The existence of the gap is verified and its formation mechanism is unraveled with additional experiments. The results will be useful for designing metal–semiconductor heteronanostructures with desired plasmonic properties and therefore also for exploring plasmon‐enhanced applications in photocatalysis, solar‐energy harvesting, and biotechnologies.     

Short‐Wave Infrared Sensor by the Photothermal Effect of Colloidal Gold Nanorods

Photodetection in the short‐wave infrared (SWIR) spectrum is a challenging task achieved often by costly low bandgap compound semiconductors involving highly toxic elements. In this work, an alternative low‐cost approach is reported for SWIR sensors that rely on the plasmonic‐induced photothermal effect of solution‐processed colloidal gold nanorods (Au NRs). A series of uniform solution‐processed Au NRs of various aspect ratios are prepared exhibiting a strong and well‐defined longitudinal localized surface plasmon resonance (L‐LSPR) maximum from 900 nm to 1.3 µm. A hybrid device structure is fabricated by applying Au NRs on the surface of a thermistor. Under a monochromatic illumination, hybrid Au‐NR/thermistor devices exhibit a clear photoresponse in the form of photoinduced resistance drop in the wavelength window from 1.0 to 1.8 µm. The photoresponsivity of such hybrid devices reaches a maximum value of 4.44 × 10⁷ Ω W^?1 at λ = 1.4 µm (intensity = 0.28 mW cm^?2), a wavelength in agreement with the L‐LSPR of the Au NRs applied. Colloidal Au NRs, capable to perform fast conversion between photon absorption and thermal energy, thus open an interesting avenue for alternative low‐cost SWIR photodetection.     

Fabrication of Hollow CoP/TiOx Heterostructures for Enhanced Oxygen Evolution Reaction

Transition‐metal phosphides have flourished as promising candidates for oxygen evolution reaction (OER) electrocatalysts. Herein, it is demonstrated that the electrocatalytic OER performance of CoP can be greatly improved by constructing a hybrid CoP/TiO_x heterostructure. The CoP/TiO_x heterostructure is fabricated using metal–organic framework nanocrystals as templates, which leads to unique hollow structures and uniformly distributed CoP nanoparticles on TiO_x. The strong interactions between CoP and TiO_x in the CoP/TiO_x heterostructure and the conductive nature of TiO_x with Ti³⁺ sites endow the CoP–TiO_x hybrid material with high OER activity comparable to the state‐of‐the‐art IrO₂ or RuO₂ OER electrocatalysts. In combination with theoretical calculations, this work reveals that the formation of CoP/TiO_x heterostructure can generate a pathway for facile electron transport and optimize the water adsorption energy, thus promoting the OER electrocatalysis.     

Multichannel Charge Transfer and Mechanistic Insight in Metal Decorated 2D–2D Bi2WO6–TiO2 Cascade with Enhanced Photocatalytic Performance

Promising semiconductor‐based photocatalysis toward achieving efficient solar‐to‐chemical energy conversion is an ideal strategy in response to the growing worldwide energy crisis, which however is often practically limited by the insufficient photoinduced charge‐carrier separation. Here, a rational cascade engineering of Au nanoparticles (NPs) decorated 2D/2D Bi₂WO₆–TiO₂ (B–T) binanosheets to foster the photocatalytic efficiency through the manipulated flow of multichannel‐enhanced charge‐carrier separation and transfer is reported. Mechanistic characterizations and control experiments, in combination with comparative studies over plasmonic Au/Ag NPs and nonplasmonic Pt NPs decorated 2D/2D B–T composites, together demonstrate the cooperative synergy effect of multiple charge‐carrier transfer channels in such binanosheets‐based ternary composites, including Z‐scheme charge transfer, “electron sink,” and surface plasmon resonance effect, which integratively leads to the boosted photocatalytic performance.