Photocatalyst Interface Engineering: Spatially Confined Growth of ZnFe2O4 within Graphene Networks as Excellent Visible‐Light‐Driven Photocatalysts

High‐performance photocatalysts should have highly crystallized nanocrystals (NCs) with small sizes, high separation efficiency of photogenerated electron–hole pairs, fast transport and consumption of photon‐excited electrons from the surface of catalyst, high adsorption of organic pollutant, and suitable band gap for maximally utilizing sunlight energy. However, the design and synthesis of these versatile structures still remain a big challenge. Here, we report a novel strategy for the synthesis of ultrasmall and highly crystallized graphene–ZnFe₂O₄ photocatalyst through interface engineering by using interconnected graphene network as barrier for spatially confined growth of ZnFe₂O₄, as transport channels for photon‐excited electron from the surface of catalyst, as well as the electron reservoir for suppressing the recombination of photogenerated electron–hole pairs. As a result, about 20 nm ZnFe₂O₄ NCs with highly crystallized (311) plane confined in the graphene network exhibit an excellent visible‐light‐driven photocatalytic activity with an ultrafast degradation rate of 1.924 × 10^?7 mol g^?1 s^?1 for methylene blue, much higher than those of previously reported photocatalysts such as spinel‐based photocatalysts (20 times), TiO₂‐based photocatalysts (4 times), and other photocatalysts (4 times). Our strategy can be further extended to fabricate other catalysts and electrode materials for supercapacitors and Li‐ion batteries.     

Zinc Ferrite Photoanode Nanomorphologies with Favorable Kinetics for Water‐Splitting

The n‐type semiconducting spinel zinc ferrite (ZnFe₂O₄) is used as a photoabsorber material for light‐driven water‐splitting. It is prepared for the first time by atomic layer deposition. Using the resulting well‐defined thin films as a model system, the performance of ZnFe₂O₄ in photoelectrochemical water oxidation is characterized. Compared to benchmark α‐Fe₂O₃ (hematite) films, ZnFe₂O₄ thin films achieve a lower photocurrent at the reversible potential. However, the oxidation onset potential of ZnFe₂O₄ is 200 mV more cathodic, allowing the water‐splitting reaction to proceed at a lower external bias and resulting in a maximum applied‐bias power efficiency (ABPE) similar to that of Fe₂O₃. The kinetics of the water oxidation reaction are examined by intensity‐modulated photocurrent spectroscopy. The data indicate a considerably higher charge transfer efficiency of ZnFe₂O₄ at potentials between 0.8 and 1.3 V versus the reversible hydrogen electrode, attributable to significantly slower surface charge recombination. Finally, nanostructured ZnFe₂O₄ photoanodes employing a macroporous antimony‐doped tin oxide current collector reach a five times higher photocurrent than the flat films. The maximum ABPE of these host–guest photoanodes is similarly increased.     

Compositionally Modulated Magnetic Epitaxial Spinel/Perovskite Nanocomposite Thin Films

There is great interest in self‐assembled oxide vertical nanocomposite films consisting of epitaxial spinel pillars in a single crystal perovskite matrix, due to their tunable electronic, magnetic, and multiferroic properties. Varying the composition or geometry of the pillars in the out‐of‐plane direction has not been previously reported but can provide new routes to tailoring their properties in three dimensions. In this work, ferrimagnetic epitaxial CoFe₂O₄, MgFe₂O₄, or NiFe₂O₄ spinel nanopillars with an out‐of‐plane modulation in their composition and shape are grown in a BiFeO₃ matrix on a (001) SrTiO₃ substrate using pulsed laser deposition. Changing the pillar composition during growth produces a homogeneous pillar composition due to cation interdiffusion, but this can be suppressed using a sufficiently thick blocking layer of BiFeO₃ to produce bi‐pillar films containing for example a layer of magnetically hard CoFe₂O₄ pillars and a layer of magnetically soft MgFe₂O₄ pillars, which form in different locations. A thinner blocking layer enables contact between the top of the CoFe₂O₄ and the bottom of the MgFe₂O₄ which leads to correlated growth of the MgFe₂O₄ pillars directly above the CoFe₂O₄ pillars and provides a path for interdiffusion. The magnetic hysteresis of the nanocomposites is related to the pillar structure.     

Surface functional composition and sensor properties of ZnO, Fe2O3, and ZnFe2O4

Zinc and iron oxide (ZnO, Fe₂O₃) and zinc ferrite (ZnFe₂O₄) nanopowders are obtained by chemical co-precipitation. The gas-sensitive properties of materials upon exposure to acetone and ethanol vapors are analyzed. It is found that the sensitivity of ZnFe₂O₄ to ethanol and acetone is better than the sensitivity of simple oxides by one and two orders of magnitude, respectively. Analysis of the surface of the materials under study shows that the observed differences in their gas sensitivity are caused by a high concentration of Brönsted acid centers on the ZnFe₂O₄ surface, which can be involved in redox reactions and facilitate the selective adsorption of ethanol.     

A Three Component Self‐Assembled Epitaxial Nanocomposite Thin Film

A self‐assembled three phase epitaxial nanocomposite film is grown consisting of ≈3 nm diameter fcc metallic Cu nanorods within square prismatic SrO rocksalt nanopillars in a Sr(Ti,Cu)O_3‐δ perovskite matrix. Each phase has an epitaxial relation to the others. The core–shell‐matrix structures are grown on SrTiO₃ substrates and can also be integrated onto Si using a thin SrTiO₃ buffer. The structure is made by pulsed laser deposition in vacuum from a SrTi_0.75Cu_0.25O₃ target, and formed as a result of the limited solubility of Cu in the perovskite matrix. Wet etching removes the 3 nm diameter Cu nanowires leaving porous SrO pillars. The three‐phase nanocomposite film is used as a substrate for growing a second epitaxial nanocomposite consisting of CoFe₂O₄ spinel pillars in a BiFeO₃ perovskite matrix, producing dramatic effects on the structure and magnetic properties of the CoFe₂O₄. This three‐phase vertical nanocomposite provides a complement to the well‐known two‐phase nanocomposites, and may offer a combination of properties of three different materials as well as additional avenues for strain‐mediated coupling within a single film.     

Synthesis of micro-nano Ag3PO4/ZnFe2O4 with different organic additives and its enhanced photocatalytic activity under visible light irradiation

Several novel micro-nano Ag₃PO₄/ZnFe₂O₄ with excellent magnetic separation property and photocatalytic performance were successfully synthesized using different organic additives for the first time. In the composite, Ag₃PO₄ with flower-like, quadrangular prism and flake structures were obtained when the organic additive is hexadecyl trimethyl ammonium bromide (CTAB), sodium diethyldithiocarbamate (DDTC), or DL-malic acid (DLMA), respectively, while the ZnFe₂O₄ showed uniform spherical structure. From the results of the photocatalytic activity analysis, the Ag₃PO₄/ZnFe₂O₄ gained with the organic additive of DDTC showed the highest photocatalytic capability for 2, 4-dichlorophenol (2, 4-DCP) degradation under visible light irradiation compared with those of CTAB and DLMA as the additives. Moreover, the composition of the composite seriously influences the photocatalytic activity, and when the mass ratio of Ag₃PO₄ and ZnFe₂O₄ in the Ag₃PO₄/ZnFe₂O₄ (DITCH) is 9:1, the apparent photo degradation rate constant of 2, 4-DC is 0.0155 min⁻¹, which is 5.74 times of ZnFe₂O₄ (0.0027 min⁻¹) and 1.89 times of Ag₃PO₄ (0.0082 min⁻¹). Finally, the photocatalytic mechanism of Ag₃PO₄/ZnFe₂O₄ was discussed based on the heterojunction energy-band theory and Z-Scheme theory in detail.     

Enhanced Sensitivity of ZnFe2O4 Based on Ordered Magnetic Moment Induced by Magnetic Field: A New Insight into Mechanism

Semiconductor gas sensor mainly relies on the interaction between sensitive materials and gas to obtain gas information. Deep insight into the interaction mechanism is increasingly important for designing high performance gas sensors. Here, ZnFe₂O₄ microspheres (MSs) are utilized with tunable magnetism through the assistance of magnetic field to study the essential elements of sensitive processes. The gas sensing properties of ZnFe₂O₄ MS under different applied magnetic field intensities and various gaseous environments are systematically investigated. The results suggest that ordered magnetic moment induced by magnetic field promotes the probability of contact and reaction between gases and sensitive materials, thus significantly improving the sensitivity. Especially, ZnFe₂O₄ annealed at 500 °C sensor under the action of 54.6 mT magnetic field exhibits excellent ethanol detection performance (S = 67.8), which is ≈4 times higher than that without magnetic field. By carefully analyzing the experimental results, this research proposes a new physical model called “port docking” to re-explain the sensitivity mechanism. This work systematically studies the role of the magnetic moment in the sensing process, and provides a new idea for designing high-performance gas sensors.     

Electrochemical Method for Synthesis of a ZnFe2O4/TiO2 Composite Nanotube Array Modified Electrode with Enhanced Photoelectrochemical Activity

An electrode with intimate and well‐aligned ZnFe₂O₄/TiO₂ composite nanotube arrays is prepared via electrochemical anodization of pure titanium foil in fluorine‐containing ethylene glycol, followed by a novel cathodic electrodeposition method. The deposition of ZnFe₂O₄ is promoted in the self‐aligned, vertically oriented TiO₂ nanotube arrays but minimized at the tube entrances. Thus, pore clogging is prevented. Environmental scanning electron microscopy, energy‐dispersive X‐ray spectra, high‐resolution transmission electron microscopy, X‐ray diffraction patterns, and X‐ray photoelectron spectroscopy indicate that the as‐prepared samples are highly ordered and vertically aligned TiO₂ nanotube arrays with ZnFe₂O₄ nanoparticles loading. The TiO₂ nanotubes are anatase with the preferential orientation of <101> plane. Enhanced absorption in both UV and visible light regions is observed for the composite nanotube arrays. The current–voltage curve of ZnFe₂O₄‐loaded TiO₂ nanotube arrays reveals a rectifying behavior. The enhanced separation of photoinduced electrons and holes is demonstrated by surface photovoltage and photocurrent measurements. Meanwhile, the photoelectrochemical investigations verify that the ZnFe₂O₄/TiO₂ composite nanotube array modified electrode has a more effective photoconversion capability than the aligned TiO₂ nanotube arrays alone. In addition, the photoelectrocatalytic ability of the novel electrode is found enhanced in the degradation of 4‐chlorophenol.     

Confinement of Thermoresponsive Hydrogels in Nanostructured Porous Silicon Dioxide Templates

A thermoresponsive hydrogel, poly(N‐isopropylacrylamide) (poly(NIPAM)), is synthesized in situ within an oxidized porous Si template, and the nanocomposite material is characterized. Infiltration of the hydrogel into the interconnecting nanoscale pores of the porous SiO₂ host is confirmed by scanning electron microscopy. The optical reflectivity spectrum of the nanocomposite hybrid displays Fabry–Pérot fringes characteristic of thin film interference, enabling direct, real‐time observation of the volume phase transition of the confined poly(NIPAM) hydrogel. Reversible optical reflectivity changes are observed to correlate with the temperature‐dependent volume phase transition of the hydrogel, providing a new means of studying nanoscale confinement of responsive hydrogels. The confined hydrogel displays a swelling and shrinking response to changes in temperature that is significantly faster than that of the bulk hydrogel. The porosity and pore size of the SiO₂ template, which are precisely controlled by the electrochemical synthesis parameters, strongly influence the extent and rate of changes in the reflectivity spectrum of the nanocomposite. The observed optical response is ascribed to changes in both the mechanical and the dielectric properties of the nanocomposite.     

Toward On‐and‐Off Magnetism: Reversible Electrochemistry to Control Magnetic Phase Transitions in Spinel Ferrites

The magnetoelectric effect, i.e., electric‐field control of magnetism in artificial heterostructures is usually limited to surface/interface atoms of the magnetic materials. In order to attain electrical control of magnetism in bulk ferromagnets, this study proposes to extend the definition of magnetoelectric phenomena to include reversible, chemistry‐controlled magnetization switching. A large and reversible change in the room temperature magnetization in strong ferromagnets is reported, with electrochemistry‐driven Li‐ion exchange; carefully chosen spinel ferrites demonstrate a reversible magnetization variation up to 50% for CuFe₂O₄ and 70% for ZnFe₂O₄. In case of CuFe₂O₄, the magnetization variation is predominantly associated with the preferential reduction of Cu²⁺ to Cu⁺ ions, and, hence, abides a nearly one‐to‐one relationship with the amount of injected Li‐ions. In addition, the reduction of Cu²⁺ also annihilates the Fe³⁺? O? Cu²⁺ magnetic interaction, resulting in a marked decrease in the Neél temperature of CuFe₂O₄. In contrast, the electrical tuning of superexchange interactions is found to play the decisive role in ZnFe₂O₄, where the simple electrochemical reduction model of magnetic cations can only explain a nominal fraction of the total magnetization variation, and indeed an electrochemically controlled reversible change in transition temperature is found necessary to account for the large magnetization variation observed.     

Band Diagram and Rate Analysis of Thin Film Spinel LiMn2O4 Formed by Electrochemical Conversion of ALD‐Grown MnO

Nanoscale spinel lithium manganese oxide is of interest as a high‐rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn₂O₄) between 20 and 200 nm in thickness by room‐temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn₂O₄ thin films in electrolytes containing Li⁺, Na⁺, K⁺, and Mg²⁺ are investigated. A unified electrochemical band‐diagram (UEB) analysis of LiMn₂O₄ informed by screened hybrid density functional theory calculations is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn₂O₄. It is shown that the incorporation of Li⁺ or other cations into the host manganese dioxide spinel structure (λ‐MnO₂) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn₂O₄. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn₂O₄ arises from bulk electronic charge‐switching which does not require compensating cation mass transport. The hybrid ALD‐electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion‐incorporation charge storage.     

Integration of Self‐Assembled Epitaxial BiFeO3–CoFe2O4 Multiferroic Nanocomposites on Silicon Substrates

Perovskite‐spinel epitaxial nanocomposite thin films are commonly grown on single crystal perovskite substrates, but integration onto a Si substrate can greatly increase their usefulness in devices. Epitaxial BiFeO₃–CoFe₂O₄ nanocomposites consisting of CoFe₂O₄ pillars in a BiFeO₃ matrix are grown on (001) Si with two types of buffer layers: molecular beam epitaxy (MBE)‐grown SrTiO₃‐coated Si and pulsed‐laser‐deposited (PLD) Sr(Ti_0.65Fe_0.35)O₃/CeO₂/yttria‐stabilized ZrO₂/Si. The nanocomposite grows with the same crystallographic orientation and morphology as that observed on single crystal SrTiO₃ when the buffered Si substrates are smooth, but roughness of the Sr(Ti_0.65Fe_0.35)O₃ promoted additional CoFe₂O₄ pillar orientations with 45° rotation. The nanocomposites on MBE‐buffered Si show very high magnetic anisotropy resulting from magnetoelastic effects, whereas the hysteresis of nanocomposites on PLD‐buffered Si can be understood as a combination of the hysteresis of the Sr(Ti_0.65Fe_0.35)O₃ film and the CoFe₂O₄ pillars.     

Self‐Sacrifice Template Fabrication of Hierarchical Mesoporous Bi‐Component‐Active ZnO/ZnFe2O4 Sub‐Microcubes as Superior Anode Towards High‐Performance Lithium‐Ion Battery

In the work, a facile yet efficient self‐sacrifice strategy is smartly developed to scalably fabricate hierarchical mesoporous bi‐component‐active ZnO/ZnFe₂O₄ (ZZFO) sub‐microcubes (SMCs) by calcination of single‐resource Prussian blue analogue of Zn₃[Fe(CN)₆]₂ cubes. The hybrid ZZFO SCMs are homogeneously constructed from well‐dispersed nanocrstalline ZnO and ZnFe₂O₄ (ZFO) subunites at the nanoscale. After selectively etching of ZnO nanodomains from the hybrid, porously assembled ZFO SMCs with integrate architecture are obtained accordingly. When evaluated as anodes for LIBs, both hybrid ZZFO and ZFO samples exhibit appealing electrochemical performance. However, the as‐synthesized ZZFO SMCs demonstrate even better electrochemical Li‐storage performance, including even larger initial discharge capacity and reversible capacity, higher rate behavior and better cycling performance, particularly at high rates, compared with the single ZFO, which should be attributed to its unique microstructure characteristics and striking synergistic effect between the bi‐component‐active, well‐dispersed ZnO and ZFO nanophases. Of great significance, light is shed upon the insights into the correlation between the electrochemical Li‐storage property and the structure/component of the hybrid ZZFO SMCs, thus, it is strongly envisioned that the elegant design concept of the hybrid holds great promise for the efficient synthesis of advanced yet low‐cost anodes for next‐generation rechargeable Li‐ion batteries.     

Polaron Transport and Thermoelectric Behavior in La‐Doped SrTiO3 Thin Films with Elemental Vacancies

The electrodynamic properties of La‐doped SrTiO₃ thin films with controlled elemental vacancies are investigated using optical spectroscopy and thermopower measurement. In particular, a correlation between the polaron formation and thermoelectric properties of the transition metal oxide (TMO) thin films is observed. With decreasing oxygen partial pressure during the film growth (P(O₂)), a systematic lattice expansion is observed along with the increased elemental vacancy and carrier density, experimentally determined using optical spectroscopy. Moreover, an absorption in the mid‐infrared photon energy range is found, which is attributed to the polaron formation in the doped SrTiO₃ system. Thermopower of the La‐doped SrTiO₃ thin films can be largely modulated from –120 to –260 μV K^?1, reflecting an enhanced polaronic mass of ≈3 < m _polron/m < ≈4. The elemental vacancies generated in the TMO films grown at various P(O₂) influences the global polaronic transport, which governs the charge transport behavior, including the thermoelectric properties.     

Bulk Embedding of Ferroelectric Nanodomains in CuBi2O4 Photocathodes Enables Boosted Photoelectrochemical Hydrogen Generation

It is widely accepted that metal oxide-based photoelectrodes (MOPs) hold great promise for future solar hydrogen generation but are facing awkward challenge arising from their low intrinsic carrier mobility. The highly polarized nature of the predominantly ionic metal-oxygen bond always leads to the formation of small polarons that are responsible for the localized trapping of photo-generated carriers. Present study explores the reduction of carriers transport barrier via bulk embedding of ferroelectric nanodomains (FNDs) in MOPs that results in a new performance benchmark for the CuBi₂O₄ photocathode. By embedding laser-generated sub-10 nm BaTiO₃ nanocrystals in the bulk of CuBi₂O₄ photocathode, numerous FNDs are created that can lead to two times enhancement of the carrier mobility, which is proposed to originate from the overlaying of the internal electric fields and effective electrons transport channel at the heterointerfaces of BaTiO₃/CuBi₂O₄. Such strategy leads to the CuBi₂O₄ photocathode with the photocurrent density of up to 3.21 mA cm⁻² at 0.6 V_RHE, as well as a pronounced absorbed photon-to-current efficiency up to 80% at 400 nm. The universal feature of present technology is further verified by laser embedding of SrTiO₃ FNDs, providing an effective route for addressing the charge transport limitations in MOPs.     

Enhanced Photocatalytic Activity of Two-Pot-Synthesized BiFeO<Subscript>3</Subscript>–ZnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Heterojunction Nanocomposite

BiFeO₃–ZnFe₂O₄ heterojunction nanocomposites have been produced by a chemical synthesis method using one- and two-pot approaches. X-ray diffraction patterns of as-calcined samples indicated formation of pure zinc ferrite (ZnFe₂O₄) and bismuth ferrite (BiFeO₃) phases, each retaining its crystal structure. Diffuse reflectance spectrometry was applied to calculate the optical bandgap of the photocatalysts, revealing values in the range from 2.03 eV to 2.17 eV, respectively. The maximum photodegradation of methylene blue of about 97% was achieved using two-pot-synthesized photocatalyst after 120 min of visible-light irradiation due to the higher probability of charge separation of photogenerated electron–hole pairs in the heterojunction structure. Photoluminescence spectra showed lower emission intensity of two-pot-synthesized photocatalyst, due to its lower recombination rate originating from greater charge separation.     

Low Temperature Stabilization of Nanoscale Epitaxial Spinel Ferrite Thin Films by Atomic Layer Deposition

In this work heteroepitaxial stabilization with nanoscale control of the magnetic Co₂FeO₄ phase at 250 °C is reported. Ultrasmooth and pure Co₂FeO₄ thin films (5–25 nm) with no phase segregation are obtained on perovskite SrTiO₃ single crystal (100) and (110) oriented substrates by atomic layer deposition (ALD). High resolution structural and chemical analyses confirm the formation of the Co‐rich spinel metastable phase. The magneto‐crystalline anisotropy of the Co₂FeO₄ phase is not modified by stress anisotropy because the films are fully relaxed. Additionally, high coervice fields, 15 kOe, and high saturation of magnetization, 3.3 μ_B per formula unit (at 10 K), are preserved down to 10 nm. Therefore, the properties of the ALD‐Co₂FeO₄ films offer many possibilities for future applications in sensors, actuators, microelectronics, and spintronics. In addition, these results are promising for the use of ALD compared to the existing thin‐film deposition techniques to stabilize epitaxial multicomponent materials with nanoscale control on a wide variety of substrates for which the processing temperature is a major drawback.     

Fabrication and properties of ZnFe<Subscript>2</Subscript>S<Subscript>4</Subscript> single crystals and structures based on them

A new class of ternary semiconductor compounds has been proposed and synthesized. ZnFe₂S₄ single crystals, which belong to this class, have been grown for the first time; and their structural, electrical, and optical properties have been investigated. The first photosensitive structures have been fabricated, and their photoelectric characteristics have been studied. A conclusion was made that heterostructures and surface-barrier structures based on ZnFe₂S₄ single crystals are promising for practical applications.     

Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries

A critical challenge in the commercialization of layer‐structured Ni‐rich materials is the fast capacity drop and voltage fading due to the interfacial instability and bulk structural degradation of the cathodes during battery operation. Herein, with the guidance of theoretical calculations of migration energy difference between La and Ti from the surface to the inside of LiNi_0.8Co_0.1Mn_0.1O₂, for the first time, Ti‐doped and La₄NiLiO₈‐coated LiNi_0.8Co_0.1Mn_0.1O₂ cathodes are rationally designed and prepared, via a simple and convenient dual‐modification strategy of synchronous synthesis and in situ modification. Impressively, the dual modified materials show remarkably improved electrochemical performance and largely suppressed voltage fading, even under exertive operational conditions at elevated temperature and under extended cutoff voltage. Further studies reveal that the nanoscale structural degradation on material surfaces and the appearance of intergranular cracks associated with the inconsistent evolution of structural degradation at the particle level can be effectively suppressed by the synergetic effect of the conductive La₄NiLiO₈ coating layer and the strong Ti? O bond. The present work demonstrates that our strategy can simultaneously address the two issues with respect to interfacial instability and bulk structural degradation, and it represents a significant progress in the development of advanced cathode materials for high‐performance lithium‐ion batteries.     

The syntheses and microstructures of tabular SrTiO3 crystal

In the present paper, the microstructures of SrTiO₃ particles obtained in two different methods were examined by scanning electron microscopy (SEM) and X-ray diffraction pattern (XRD). The two synthesis techniques included a conventional mixed solid method and a molten salt synthesis method (MSS), which proceeded through two steps. In the first, precursor Sr₃Ti₂O₇ particles were synthesized. Tabular SrTiO₃ crystals were synthesized via the superposition of the SrTiO₃ basic cell on the interface of Sr₃Ti₂O₇ particles. The microstructures of SrTiO₃ particles synthesis in those two ways were quite different. The microstructures of SrTiO₃ obtained by MSS method were high purity and obviously tabular in structure. Oriented growth faces included typical (0 0 1), (1 0 0), (1 1 0), etc. The mechanism of the oriented growth of tabular SrTiO₃ could be considered as the superposition of coordination polyhedron Ti–O₆ octahedron basic cell on the interface of Sr₃Ti₂O₇ particles.