Energetic Charge Carriers Research Articles

Atomic-scale strain engineering of atomically resolved Pt clusters transcending natural enzymes

Strain engineering plays an important role in tuning electronic structure and improving catalytic capability of biocatalyst, but it is still challenging to modify the atomic-scale strain for specific enzyme-like reactions. Here, we systematically design Pt single atom (Pt1), several Pt atoms (Ptn) and atomically-resolved Pt clusters (Ptc) on PdAu biocatalysts to investigate the correlation between atomic strain and enzyme-like catalytic activity by experimental technology and in-depth Density Functional Theory calculations. It is found that Ptc on PdAu (Ptc-PA) with reasonable atomic strain upshifts the d-band center and exposes high potential surface, indicating the sufficient active sites to achieve superior biocatalytic performances. Besides, the Pd shell and Au core serve as storage layers providing abundant energetic charge carriers. The Ptc-PA exhibits a prominent peroxidase (POD)-like activity with the catalytic efficiency (Kcat/Km) of 1.50 × 109 mM−1 min−1, about four orders of magnitude higher than natural horseradish peroxidase (HRP), while catalase (CAT)-like and superoxide dismutase (SOD)-like activities of Ptc-PA are also comparable to those of natural enzymes. Biological experiments demonstrate that the detection limit of the Ptc-PA-based catalytic detection system exceeds that of visual inspection by 132-fold in clinical cancer diagnosis. Besides, Ptc-PA can reduce multi-organ acute inflammatory damage and mitigate oxidative stress disorder.

Gadolinium modified g-C3N4 for S-Scheme heterojunction with monoclinic-WO3: Insights from DFT studies and related charge carrier dynamics

Modifying the surface structures of g-C3N4 through interfacial coupling with other semiconductors has been spotlighted as an efficient approach for improving photocatalytic efficiency. With the surge of S-scheme heterojunctions, the research is intensified towards designing this kind of composite for energy-environmental-related applications. In this context, a new approach involving surface modifications of g-C3N4 through Gd species and integrating with monoclinic-WO3 via a wet chemical approach to form S-scheme heterojunctions is investigated. The characterization results attested that the adopted protocol promotes the better dispersion of Gd species over the g-C3N4 surface and rigidly integrates with WO3. The optical response of the composite spanned a significant portion of the visible region in the solar spectrum. The computational studies and the findings of the Mott-Schottky plot collectively suggested that the position of band edges qualifies for the formation of S-scheme heterojunction. The results derived from photocurrent response measurements and photoluminescence technique attribute to the effective charge carrier separation in the heterostructure. The rate constant of Gd-g-C3N4/WO3 was 1.48 × 10−2 min−1 which was approximately 4.35 and 2.27 times greater than that of WO3 (0.34 × 10−2 min−1) and g-C3N4/WO3 (0.65 × 10−2 min−1) respectively. Furthermore, RhB degradation in the presence of scavengers validated the participation of superoxide and hydroxyl radicals in the degradation mechanisms. This was possible only when the conduction band electrons of WO3 recombined with the valence band holes of Gd-modified g-C3N4. The present work helps to understand the S-scheme heterojunction formation between surface-modified g-C3N4 and metal oxides and retain the involvement of energetic charge carriers in the desired redox reactions.

A semiconducting hybrid of RhOx/GaN@InGaN for simultaneous activation of methane and water toward syngas by photocatalysis.

Prior to the eventual arrival of carbon neutrality, solar-driven syngas production from methane steam reforming presents a promising approach to produce transportation fuels and chemicals. Simultaneous activation of the two reactants, i.e. methane and water, with notable geometric and polar discrepancy is at the crux of this important subject yet greatly challenging. This work explores an exceptional semiconducting hybrid of RhOx/GaN@InGaN nanowires for overcoming this critical challenge to achieve efficient syngas generation from methane steam reforming by photocatalysis. By coordinating density functional theoretical calculations and microscopic characterizations, with in situ spectroscopic measurements, it is found that the multifunctional RhOx/GaN interface is effective for simultaneously activating both CH4 and H2O by stretching the C-H and O-H bonds because of its unique Lewis acid/base attribute. With the aid of energetic charge carriers, the stretched C-H and O-H bonds of reactants are favorably cleaved, resulting in the key intermediates, i.e. *CH3, *OH, and *H, to sit on Rh sites, Rh sites, and N sites, respectively. Syngas is subsequently produced via energetically favored pathway without additional energy inputs except for light. As a result, a benchmarking syngas formation rate of 8.1 mol·gcat-1·h-1 is achieved with varied H2/CO ratios from 2.4 to 0.8 under concentrated light illumination of 6.3 W·cm-2, enabling the achievement of a superior turnover number of 10,493 mol syngas per mol Rh species over 300 min of long-term operation. This work presents a promising strategy for green syngas production from methane steam reforming by utilizing unlimited solar energy.

Plasmon driven super-high HER activity of electronic structure and lattice strain engineered single atomic layer Pd@Au nanorods

The development of efficient catalysts with low energy consumption has always been a key issue for sustainable hydrogen energy. Here, we report a catalyst comprising a single atomic Pd layer deposited on Au nanorods (ML-Pd@Au NRs) that shows a super-high HER activity and ultra-low overpotential under localized surface plasmon resonance condition. The Au NR plays triple determining roles in HER performance via adjusting the electronic structure and lattice strain of Pd that effectively reduces the adsorption energy of H-adatoms, eliminating the penetration of H adatoms in multilayer Pd crystal that decreases the H adatoms diffusion kinetics, and providing high energetic hot charge carriers under near-IR light irradiation that decreases the activation energy and onset potential of HER. The single atomic Pd layer on Au NRs ensures the hot electron transfer as the main dissipation pathway of the plasmonic hot charge carriers for HER. Thus, under near-IR light irradiation, HER on ML-Pd@Au NRs occurs with a high mass activity of 17.47 mA mg−1 at 100 mV and a very low overpotential of 13 mV at 10 mA cm−2, which are superior to the commercial Pd/C and commercial Pt/C catalysts under the same conditions.

D-Band Hole Dynamics in Gold Nanoparticles Measured with Time-Resolved Emission Upconversion Microscopy.

The performance of photocatalysts and photovoltaic devices can be enhanced by energetic charge carriers produced from plasmon decay, and the lifetime of these energetic carriers greatly affects overall efficiencies. Although hot electron lifetimes in plasmonic gold nanoparticles have been investigated, hot hole lifetimes have not been as thoroughly studied in plasmonic systems. Here, we demonstrate time-resolved emission upconversion microscopy and use it to resolve the lifetime and energy-dependent cooling of d-band holes formed in gold nanoparticles by plasmon excitation and by following plasmon decay into interband and then intraband electron-hole pairs.

Ligand-mediated electron transport channels enhance photocatalytic activity of plasmonic nanoparticles.

Photoexcitation of noble metal nanoparticles creates surface plasmons which further decay to form energetic charge carriers. These charge carriers can initiate and/or accelerate various chemical processes at nanoparticle surfaces, although the efficiency of such processes remains low as a large fraction of these carriers recombine before they can reach the reaction sites. Thus efficient utilization of these charge carriers requires designing nanostructures that promote the separation of charges and their transport toward the reaction sites. Here we demonstrate that covalently bound surface-coating ligands with suitable orbital alignment can provide electron transport channels boosting hot electron extraction from a gold nanostructure leading to a huge enhancement in the rate of hydrogen evolution reaction (HER) under NIR excitation. A (p)Br-Ph-SH substituted gold nanoprism (AuTP) substrate produced ∼4500 fold more hydrogen compared to a pristine AuTP substrate under 808 nm excitation. Further experimental and theoretical studies on a series of substituted benzene-thiol bound AuTP substrates showed that the extent of the ligand-mediated HER enhancement depends not only on the polarity of the ligand but on the interfacial orbitals interactions.

Piezotronic Effect Induced Schottky Barrier Decrease to Boost the Plasmonic Charge Separation of BaTiO3-Au Heterojunction for the Photocatalytic Selective Oxidation of Aminobenzyl Alcohol.

Charge carrier transfer efficiency as a crucial factor determines the performance of heterogeneous photocatalysis. Here, we demonstrate a simple nanohybrid structure of BaTiO3-Au (BTO-Au) for the efficient selective oxidization of benzyl alcohol to benzaldehyde upon piezotronic effect boosted plasmonic photocharge carrier transfer. With the aid of ultrasonic mechanical vibration, the reaction rate of the photocatalytic organic conversion would be considerably accelerated, which is about 4.2 and 6.2 times higher than those driven by sole visible light irradiation and sole ultrasonication, respectively. Photoelectrochemical tests under ultrasonic stimuli reveal the BTO-Au catalytic system is independent of the light intensity, showing a consistent photocurrent density, over a wide range of incident light brightness. The largely enhanced photocatalytic activity can be ascribed to the synergetic effect of surface plasmonic resonance (SPR)-piezotronic coupling by which a built-in electric field induced by the piezotronic effect significantly favors the oriented mobilization of energetic charge carriers generated by the SPR effect at the heterojunction. Notably, a decrease of the Schottky barrier height of ∼0.3 eV at the BTO-Au interface is verified experimentally, due to the band bending of BTO induced by the piezotronic effect, which can greatly augment the hot electron transfer efficiency. This work highlights the coupling of the piezotronic effect with SPR within the BTO-Au nanostructure as a versatile and promising route for efficient charge transfer in photocatalytic organic conversion.

Sunlight-active hierarchical Ag@insulator@ZnO core-shell array based on natural diatoms for environmental remediation

A nature inspired plasmonic core-shell architecture was proposed by incorporating a natural siliceous insulator shell (Navicula salinicola frustules) in Ag/diatomite/ZnO hierarchical nanostructures to overcome the recombination of energetic charge carriers (e−/h+), corrosion of bare metal, and to facilitate the composite separation after reaction. The photocatalytic performance of the as-prepared composites, monitored by decomposition of methylene blue (MB), was investigated under both UV and simulated sunlight irradiation. Ag/diatomite/ZnO exhibited efficient photocatalytic performance (near 100% degradation and 95% mineralization) under simulated sunlight irradiation with apparent rate constant of 0.0246 min−1, which was found to follow pseudo-first order kinetics. The enhanced photocatalysis action of metal/insulator/semiconductor as compared to metal/semiconductor and the semiconductor alone could be ascribed to the synergistic effects of the photonic structure of regular frustules, improved sunlight harvesting efficiency, suppressed back electron transfer, and prohibited oxidization of Ag. While the as-synthesized composite was easy to separate from the reaction, however, it was in the throes of losing the photocatalytic activity after three rounds of reuse. A possible mechanism of photocatalytic degradation of MB induced by Ag/diatomite/ZnO under sunlight irradiation was proposed based on dye degradation measurements and reactive species trapping experiments. While the reusability of as-prepared composite will doubtless be much scrutinized, our study may provide a new insight into the design and fabrication of plasmonic-based nanomaterials for use in industry applications under solar light illumination.

Structural measurement of electron-phonon coupling and electronic thermal transport across a metal-semiconductor interface

Scattering of energetic charge carriers and their coupling to lattice vibrations (phonons) in dielectric materials and semiconductors are crucial processes that determine the functional limits of optoelectronics, photovoltaics, and photocatalysts. The strength of these energy exchanges is often described by the electron-phonon coupling coefficient, which is difficult to measure due to the microscopic time- and length-scales involved. In the present study, we propose an alternate means to quantify the coupling parameter along with thermal boundary resistance and electron conductivity by performing a high angular-resolution time-resolved X-ray diffraction measurement of propagating lattice deformation following laser excitation of a nanoscale, polycrystalline metal film on a semiconductor substrate. Our data present direct experimental evidence for identifying the ballistic and diffusive transport components occurring at the interface, where only the latter participates in thermal diffusion. This approach provides a robust measurement that can be applied to investigate microscopic energy transport in various solid-state materials.

Plasmoelectric Potential in Plasmon-Mediated Electrochemistry.

Plasmon-mediated chemical reactions have attracted intensive research interest as a means of achieving desirable reaction yields and selectivity. The energetic charge carriers and elevated local temperature induced by the nonradiative decay of surface plasmons are thought to be responsible for improving reaction outcomes. This study reports that the plasmoelectric potential is another key contributor in plasmon-mediated electrochemistry. Additionally, we disclose a convenient and reliable method for quantifying the specific contributions of the plasmoelectric potential, hot electrons, and photothermal heating to the electroreduction of oxygen at the plasmonic Ag electrode, revealing that the plasmoelectric potential is the dominating nonthermal factor under short-wavelength illumination and moderate electrode bias. This work elucidates novel mechanistic understandings of plasmon-mediated electrochemistry, facilitating high-performance plasmonic electrocatalyst design optimization.

Effect of Material and Shape of Nanoparticles on Hot Carrier Generation

Nonradiative decay of photoexcited plasmons generates energetic nonthermal charge carriers. These hot charge carriers play a major role in plasmonic photocatalysis and photovoltaics. Therefore, establishing the relationship between the hot carrier generation efficiency and the structural and chemical parameters of nanoparticles is crucial for developing highly efficient plasmonic catalysts and photovoltaic materials. In this study, we compare the quantum efficiency of hot carrier generation between gold (AuNPs) and silver nanoparticles (AgNPs), and spherical (AuNSs) and cubic gold nanoparticles (AuNCs). We construct nanoparticle-on-mirror (NPoM) systems where reactant molecules are positioned in the nanogaps between the nanoparticles and gold films. Excitation of the NPoM at 785 nm, followed by the detection of products using surface-enhanced Raman spectroscopy allows us to measure the plasmon-driven reaction yields. Dividing the reaction yield by the calculated absorption cross section at the excitation laser wavelength provides the efficiency of hot carrier generation per absorbed photon. We reveal that AgNPs are more effective at generating hot carriers than AuNPs, which is consistent with the higher electron-surface scattering rate of AgNPs. The hot carrier generation of AuNCs is marginally better than that of AuNSs, which can be attributed to the enhanced electric fields inside the AuNCs in the nanogap region. This study contributes to a rational design of plasmonic catalysts or photovoltaic materials of higher efficiencies.

Investigation of SERS Frequency Fluctuations Relevant to Sensing and Catalysis.

The excitation of plasmon resonances on nanoparticles generates locally enhanced electric fields commonly used for sensing applications and energetic charge carriers can drive chemical transformations as photocatalysts. The surface-enhanced Raman scattering (SERS) spectra from mercaptobenzoic acid (MBA) adsorbed to gold nanoparticles (AuNP) and silica encapsulated gold nanoparticles (AuNP@silica) can be used to assess the impact of energetic charge carriers on the observed signal. Measurements were recorded using a traditional point focused Raman spectroscopy and a wide-field spectral imaging approach to assess changes in the spectra of the different particles at increasing power density. The wide-field approach provides an increase in sampling statistics and shows evidence of SERS frequency fluctuations from MBA at low power densities, where it is commonly difficult to record spectra from a point focused spot. The increased spectral resolution of the point spectroscopy measurement provides improved peak identification and the ability to correlate the frequency fluctuations to charged intermediate species. Interestingly, our work suggests that isolated nanoparticles may undergo frequency fluctuations more readily than aggregates.

Synergistic Combination of Charge Carriers and Energy-Transfer Processes in Plasmonic Photocatalysis.

Important efforts are currently under way in order to develop further the nascent field of plasmonic photocatalysis, striving for improved efficiencies and selectivities. A significant fraction of such efforts has been focused on distinguishing, understanding, and enhancing specific energy-transfer mechanisms from plasmonic nanostructures to their environment. Herein, we report a synthetic strategy that combines two of the main physical mechanisms driving plasmonic photocatalysis into an engineered system by rationally combining the photochemical features of energetic charge carriers and the electromagnetic field enhancement inherent to the plasmonic excitation. We do so by creating hybrid photocatalysts that integrate multiple plasmonic resonators in a single entity, controlling their joint contribution through spectral separation and differential surface functionalization. This strategy allows us to create complex hybrids with improved photosensitization capabilities, thanks to the synergistic combination of two photosensitization mechanisms. Our results show that the hot electron injection can be combined with an energy-transfer process mediated by the near-field interaction, leading to a significant increase in the final photocatalytic response of the material and moving the field of plasmonic photocatalysis closer to energy-efficient applications. Furthermore, our multimodal hybrids offer a test system to probe the properties of the two targeted mechanisms in energy-related applications such as the photocatalytic generation of hydrogen and open the door to wavelength-selective photocatalysis and novel tandem reactions.

Optical Metasurfaces for Energy Conversion.

Nanostructured surfaces with designed optical functionalities, such as metasurfaces, allow efficient harvesting of light at the nanoscale, enhancing light–matter interactions for a wide variety of material combinations. Exploiting light-driven matter excitations in these artificial materials opens up a new dimension in the conversion and management of energy at the nanoscale. In this review, we outline the impact, opportunities, applications, and challenges of optical metasurfaces in converting the energy of incoming photons into frequency-shifted photons, phonons, and energetic charge carriers. A myriad of opportunities await for the utilization of the converted energy. Here we cover the most pertinent aspects from a fundamental nanoscopic viewpoint all the way to applications.

Designing oxygen vacancy mediated bismuth molybdate (Bi2MoO6)/N-rich carbon nitride (C3N5) S-scheme heterojunctions for boosted photocatalytic removal of tetracycline antibiotic and Cr(VI): Intermediate toxicity and mechanism insight

Polymeric N-rich carbon nitride of C3N5 is being utilized as a new visible-light-driven catalyst due to its narrower bandgap (∼2.0 eV). Building step-scheme (S-scheme) heterojunction by coupling with other semiconductors especially those own oxygen vacancies (OVs) can further upgrade the photocatalytic performance of C3N5-based photocatalysts. Herein, a novel S-scheme heterojunction of OVs mediated Bi2MoO6/C3N5 was fabricated by in-situ growing Bi2MoO6 nanoparticles with OVs on C3N5 nanosheets. Benefiting from the efficient separation and transfer of high energetic charge carriers by S-scheme charge migration, enriched structural defects, as well as the close contact by the in-situ growth, the heterojunction exhibited superior visible-light photocatalytic performance toward the removal of tetracycline (TC) and Cr(VI) than C3N5, Bi2MoO6, and their mechanical mixture under visible light. The TC degradation routes and the bio-toxicity evolution of TC were explored. Moreover, the photocatalytic mechanism for TC decomposition and Cr(VI) reduction over Bi2MoO6/C3N5 with OVs were elucidated. This work presents a newfangled vision for designing promising C3N5-based S-scheme heterojunction photocatalysts for pollution control.

Unraveling the temperature dynamics and hot electron generation in tunable gap-plasmon metasurface absorbers

Abstract Localized plasmons formed in ultrathin metallic nanogaps can lead to robust absorption of incident light. Plasmonic metasurfaces based on this effect can efficiently generate energetic charge carriers, also known as hot electrons, owing to their ability to squeeze and enhance electromagnetic fields in confined subwavelength spaces. However, it is very challenging to accurately identify and quantify the dynamics of hot carriers, mainly due to their ultrafast time decay. Their nonequilibrium temperature response is one of the key factors missing to understand the short time decay and overall transient tunable absorption performance of gap-plasmon metasurfaces. Here, we systematically study the temperature dynamics of hot electrons and their transition into thermal carriers at various timescales from femto to nanoseconds by using the two-temperature model. Additionally, the hot electron temperature and generation rate threshold values are investigated by using a hydrodynamic nonlocal model approach that is more accurate when ultrathin gaps are considered. The derived temperature dependent material properties are used to study the ultrafast transient nonlinear modification in the absorption spectrum before plasmon-induced lattice heating is established leading to efficient tunable nanophotonic absorber designs. We also examine the damage threshold of these plasmonic absorbers under various pulsed laser illuminations, an important quantity to derive the ultimate input intensity limits that can be used in various emerging nonlinear optics and other tunable nanophotonic applications. The presented results elucidate the role of hot electrons in the response of gap-plasmon metasurface absorbers which can be used to design more efficient photocatalysis, photovoltaics, and photodetection devices.

Recent Progress and Challenges in Plasmon‐Mediated Reduction of CO2 to Chemicals and Fuels

AbstractThe realization of the strong interaction of plasmonic nanostructures with electromagnetic radiation, subdiffraction‐limit field localization, and unusually high field enhancement enables immense opportunities to harness visible light in the field of photocatalysis. Plasmon‐induced energetic charge carriers allow the metal nanostructures to catalyze surface reactions with selective pathways that are rather a holy grail of thermal catalysis. An intriguing application of plasmonic photocatalysis includes sequestration of atmospheric CO2 by its conversion into value‐added chemical fuels, thus mimicking the process of natural photosynthesis and addressing the problem of rising global warming and energy demands. In this regard, plasmonic photocatalysts circumvent the fallacy of conventional semiconductor photocatalysts to harvest visible light and modulate the CO2 reduction reaction pathways to attain selectivity. This review discusses the primary concepts of plasmonic catalysis, emphasizing the recent developments to tackle the obstacles present in achieving efficient and selective CO2 reduction by exploring various multicomponent plasmonic nanostructures that can extract maximum energy to perform a function. Some of the challenges that need more attention to optimize productivity are addressed and an outlook for future avenues in this field is provided.

Efficient Extraction of Energetic Charge Carriers from an Engineered Plasmonic Nanocomposite to Perform Cascade Reactions

AbstractThe realization of plasmon‐generated hot charge carriers presents tremendous opportunities for light‐harvesting in the field of photocatalysis. However, extracting the energetic charge carriers while competing with their recombination tendency is still a major bottleneck for efficient plasmonic photocatalysis. Therefore, strategic changes in the design principles of hybrid plasmonic nanocomposites to generate highly localized charge carriers at the catalytic site are imperative for hot electrons (holes) transfer to short‐lived reaction intermediates. Here, we engineered Au−Pt core‐shell nanostructures with only a few monolayers of epitaxially grown Pt onto Au nanocubes. The finite element method (FEM) simulations for optical properties of Au−Pt system support the design and hypothesis of selective funneling of plasmonic energy/charge carriers from Au core to Pt shell and their potential extraction for activating chemical bonds on Au−Pt nanocubes (Au−Pt NCs) surface. Further, investigating Au−Pt NCs as plasmonic catalysts, we show direct, visual evidence of plasmon‐assisted cascade reduction of nonfluorescent resazurin (Rz) dye to nonfluorescent dihydroresorufin (DHRf) via a highly fluorescent resorufin (Rf) intermediate form. In the excitation wavelength‐dependent study, the maximum apparent quantum efficiency of 48% (Rz to Rf conversion) and 8.4% (Rf to DHRf conversion) at 561 nm laser excitation demonstrates the plasmon assisted charge carrier driven cascade reduction on Au−Pt NCs surface. Control experiments carried out with only Au nanocubes (Au NCs) or Pt seed nanoparticles under the same reaction conditions show no significant cascade reduction of Rz, highlighting the synergistic effect of the plasmonic core and ultrathin catalytic shell.

Plasmon-mediated activation of persulfate for efficient photodegradation of ionic liquids over Ag@Pd core–shell nanocubes

In this study, we propose a novel photo-activation method to remove persistent organic pollutants through a SO4˙ˉ-based advanced oxidation process. Core–shell Ag@Pd nanocubes were prepared by a facile seed-mediated method and, afterward, explored for photodegradation of a representative ionic liquid (IL), [C4mim]Br. Electron paramagnetic resonance measurements and radical scavenging experiments demonstrated that the species mainly responsible for degrading [C4mim]Br were the radicals of SO4˙ˉ. The plasmon-mediated nature of the Ag@Pd catalysts was verified by their wavelength-dependent performance. Subsequent optical simulation indicated that, other than the plasmonic Ag core, the non-plasmonic Pd shell was the preferential site for dissipating the absorbed photons into energetic charge carriers to produce the radical species. Finally, based on the detected intermediates, we propose the degradation pathway of ILs in the plasmon-mediated process. The results of our method suggest favorable application in the treatment of wastewater.

Quantum Chemistry Treatment of Silicon-Hydrogen Bond Rupture by Nonequilibrium Carriers in Semiconductor Devices

Silicon-hydrogen bonds play a crucial role in modern microelectronics, especially regarding reliability. At the semiconductor-oxide interface these bonds are broken via interaction with energetic charge carriers, which spoils a MOSFET's performance, for example. This study develops a consistent physical picture of that phenomenon through a bottom-up approach based on quantum mechanical formulations, and also unravels the disparity of that effect in $n\ensuremath{-}$ and $p\ensuremath{-}$MOSFETs. The model is free of empirical parameters and can easily be extended to emerging material combinations.