Enhanced Charge Separation for Efficient Photocatalytic H2 Production by Long-Lived Trap-State-Induced Interfacial Charge Transfer.

Photogeneration of charge carriers in semiconductors provides the scientific fundamental for photocatalytic water splitting. However, an ongoing challenge is the development of a new mechanism promoting charge carrier separation. Here we propose a trap-state-induced interfacial charge-transfer transition mechanism (TSICTT), in which electrons in long-lived trap states recombine with holes on the valence band (VB) of the semiconductor, thus prolonging the electron lifetime. We demonstrate this concept in the Sr4Al14O25:Eu2+, Dy3+/CdS (SAO/CdS) heterostructure, where trapped electrons with a lifetime of up to several hours in the SAO persistent luminescence phosphor (PLP) can continuously consume holes on the VB of CdS nanoparticles (NPs). We discover that the interfacial interaction and the work function difference between SAO and CdS are crucial for the TSICTT, which finally contributes to the improved H2 production from 34.4 to 1212.9 µmol gCdS-1 h-1 under visible-light irradiation. This model introduces a new strategy to manipulate charge carrier transport for the effective utilization of solar energy.

π-d Electron-Coupled PBDIT/CdS Heterostructure Enables Hole Extraction for Efficient Photocatalytic Hydrogen Production.

Construction of heterostructures is one of the most promising strategies for designing photocatalysts for highly efficient solar hydrogen (H2) production because the introduction of an electron-donating counterpart contributes to more effective photon absorption, while the heterostructures benefit spatial carrier separation. However, the hole-transfer rate is usually 2-3 orders of magnitude slower than that of the electron-transfer rate within the heterostructures, ensuing serious charge recombination. Here, we find the energy band offset-driven charge-transfer behavior in a donor-acceptor (D-A)-conjugated polymer/CdS organic/inorganic heterostructure and realize hole-transfer improvement in cooperation with a further hole removal motif of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. The photocatalytic H2 production activity is increased by nearly 2 orders of magnitude with the apparent quantum yield hitting ca. 80% at 450 nm without co-catalysts. Ultrafast transient absorption together with surface photovoltage characterizations consolidates the hole extraction mechanism. The intimate bond formed at the interface between the polymer and the inorganic semiconductor acts as an interpenetrating network at the nanoscale level, thus providing a charge-transfer freeway for boosting charge separation.

A 25 micron-thin microscope for imaging upconverting nanoparticles with NIR-I and NIR-II illumination.

Rationale: Intraoperative visualization in small surgical cavities and hard-to-access areas are essential requirements for modern, minimally invasive surgeries and demand significant miniaturization. However, current optical imagers require multiple hard-to-miniaturize components including lenses, filters and optical fibers. These components restrict both the form-factor and maneuverability of these imagers, and imagers largely remain stand-alone devices with centimeter-scale dimensions. Methods: We have engineered INSITE (Immunotargeted Nanoparticle Single-Chip Imaging Technology), which integrates the unique optical properties of lanthanide-based alloyed upconverting nanoparticles (aUCNPs) with the time-resolved imaging of a 25-micron thin CMOS-based (complementary metal oxide semiconductor) imager. We have synthesized core/shell aUCNPs of different compositions and imaged their visible emission with INSITE under either NIR-I and NIR-II photoexcitation. We characterized aUCNP imaging with INSITE across both varying aUCNP composition and 980 nm and 1550 nm excitation wavelengths. To demonstrate clinical experimental validity, we also conducted an intratumoral injection into LNCaP prostate tumors in a male nude mouse that was subsequently excised and imaged with INSITE. Results: Under the low illumination fluences compatible with live animal imaging, we measure aUCNP radiative lifetimes of 600 µs - 1.3 ms, which provides strong signal for time-resolved INSITE imaging. Core/shell NaEr0.6Yb0.4F4 aUCNPs show the highest INSITE signal when illuminated at either 980 nm or 1550 nm, with signal from NIR-I excitation about an order of magnitude brighter than from NIR-II excitation. The 55 µm spatial resolution achievable with this approach is demonstrated through imaging of aUCNPs in PDMS (polydimethylsiloxane) micro-wells, showing resolution of micrometer-scale targets with single-pixel precision. INSITE imaging of intratumoral NaEr0.8Yb0.2F4 aUCNPs shows a signal-to-background ratio of 9, limited only by photodiode dark current and electronic noise. Conclusion: This work demonstrates INSITE imaging of aUCNPs in tumors, achieving an imaging platform that is thinned to just a 25 µm-thin, planar form-factor, with both NIR-I and NIR-II excitation. Based on a highly paralleled array structure INSITE is scalable, enabling direct coupling with a wide array of surgical and robotic tools for seamless integration with tissue actuation, resection or ablation.

Bright sub-20-nm cathodoluminescent nanoprobes for electron microscopy.

Electron microscopy has been instrumental in our understanding of complex biological systems. Although electron microscopy reveals cellular morphology with nanoscale resolution, it does not provide information on the location of different types of proteins. An electron-microscopy-based bioimaging technology capable of localizing individual proteins and resolving protein-protein interactions with respect to cellular ultrastructure would provide important insights into the molecular biology of a cell. Here, we synthesize small lanthanide-doped nanoparticles and measure the absolute photon emission rate of individual nanoparticles resulting from a given electron excitation flux (cathodoluminescence). Our results suggest that the optimization of nanoparticle composition, synthesis protocols and electron imaging conditions can lead to sub-20-nm nanolabels that would enable high signal-to-noise localization of individual biomolecules within a cellular context. In ensemble measurements, these labels exhibit narrow spectra of nine distinct colours, so the imaging of biomolecules in a multicolour electron microscopy modality may be possible.

Low irradiance multiphoton imaging with alloyed lanthanide nanocrystals.

Multiphoton imaging techniques that convert low-energy excitation to higher energy emission are widely used to improve signal over background, reduce scatter, and limit photodamage. Lanthanide-doped upconverting nanoparticles (UCNPs) are among the most efficient multiphoton probes, but even UCNPs with optimized lanthanide dopant levels require laser intensities that may be problematic. Here, we develop protein-sized, alloyed UCNPs (aUCNPs) that can be imaged individually at laser intensities >300-fold lower than needed for comparably sized doped UCNPs. Using single UCNP characterization and kinetic modeling, we find that addition of inert shells changes optimal lanthanide content from Yb3+, Er3+-doped NaYF4 nanocrystals to fully alloyed compositions. At high levels, emitter Er3+ ions can adopt a second role to enhance aUCNP absorption cross-section by desaturating sensitizer Yb3+ or by absorbing photons directly. Core/shell aUCNPs 12 nm in total diameter can be imaged through deep tissue in live mice using a laser intensity of 0.1 W cm-2.

Continuous-wave upconverting nanoparticle microlasers.

Reducing the size of lasers to microscale dimensions enables new technologies1 that are specifically tailored for operation in confined spaces ranging from ultra-high-speed microprocessors2 to live brain tissue3. However, reduced cavity sizes increase optical losses and require greater input powers to reach lasing thresholds. Multiphoton-pumped lasers4-7 that have been miniaturized using nanomaterials such as lanthanide-doped upconverting nanoparticles (UCNPs)8 as lasing media require high pump intensities to achieve ultraviolet and visible emission and therefore operate under pulsed excitation schemes. Here, we make use of the recently described energy-looping excitation mechanism in Tm3+-doped UCNPs9 to achieve continuous-wave upconverted lasing action in stand-alone microcavities at excitation fluences as low as 14 kW cm-2. Continuous-wave lasing is uninterrupted, maximizing signal and enabling modulation of optical interactions10. By coupling energy-looping nanoparticles to whispering-gallery modes of polystyrene microspheres, we induce stable lasing for more than 5 h at blue and near-infrared wavelengths simultaneously. These microcavities are excited in the biologically transmissive second near-infrared (NIR-II) window and are small enough to be embedded in organisms, tissues or devices. The ability to produce continuous-wave lasing in microcavities immersed in blood serum highlights practical applications of these microscale lasers for sensing and illumination in complex biological environments.

Supported black phosphorus nanosheets as hydrogen-evolving photocatalyst achieving 5.4% energy conversion efficiency at 353 K.

Solar-driven water splitting using powdered catalysts is considered as the most economical means for hydrogen generation. However, four-electron-driven oxidation half-reaction showing slow kinetics, accompanying with insufficient light absorption and rapid carrier combination in photocatalysts leads to low solar-to-hydrogen energy conversion efficiency. Here, we report amorphous cobalt phosphide (Co-P)-supported black phosphorus nanosheets employed as photocatalysts can simultaneously address these issues. The nanosheets exhibit robust hydrogen evolution from pure water (pH = 6.8) without bias and hole scavengers, achieving an apparent quantum efficiency of 42.55% at 430 nm and energy conversion efficiency of over 5.4% at 353 K. This photocatalytic activity is attributed to extremely efficient utilization of solar energy (~75% of solar energy) by black phosphorus nanosheets and high-carrier separation efficiency by amorphous Co-P. The hybrid material design realizes efficient solar-to-chemical energy conversion in suspension, demonstrating the potential of black phosphorus-based materials as catalysts for solar hydrogen production.

Facile bottom-up synthesis of partially oxidized black phosphorus nanosheets as metal-free photocatalyst for hydrogen evolution.

Few-layer black phosphorus (BP) nanosheets were first reported as a 2D material for the application of field-effect transistors in 2014 and have stimulated intense activity among physicists, chemists, and material and biomedical scientists, driving research into novel synthetic techniques to produce BP nanosheets. At present, exfoliation is the main route toward few-layer BP nanosheets via employing bulk BP as raw material. However, this is a complicated and time-consuming process, which is difficult for the large-scale synthesis of BP nanosheets. Moreover, BP degrades rapidly when exfoliated to nanoscale dimensions, resulting in the rapid loss of semiconducting properties. Here, we report the direct wet-chemical synthesis of few-layer BP nanosheets in gram-scale quantities in a bottom-up approach based on common laboratory reagents at low temperature, showing excellent stability due to partial oxidation of surface. Solvent and temperature are two critical factors, controlling not only the formation of BP nanosheets but also the thickness. The as-prepared BP nanosheets can extract hydrogen from pure water (pH = 6.8), exhibiting more than 24-fold higher activity than the well-known C3N4 nanosheets. Our results reporting the ability to prepare few-layer BP nanosheets with a facile, scalable, low-cost approach take us a step closer to real-world applications of phosphorene including next-generation metal-free photocatalysts for photosynthesis.

UV-driven overall water splitting using unsupported gold nanoparticles as photocatalysts.

We confirmed that Au nanoparticles (>10 nm) exhibit photocatalytic overall water splitting into H2 and O2 simultaneously with a ratio close to 2 : 1 without the assistance of sacrificial electron donors and cocatalysts under UV illumination for the first time. The hydrogen production rate of 5.7 µmol g-1 h-1 in pure water was achieved, which is higher than that of TiO2 nanoparticles (P25, 1.2 µmol g-1 h-1). The interband transitions from 5d (valence band) to 6sp (conduction band) are responsible for this photocatalytic activity over Au nanoparticles.

Photostable and efficient upconverting nanocrystal-based chemical sensors.

Chemical sensing in living systems demands optical sensors that are bright, stable, and sensitive to the rapid dynamics of chemical signaling. Lanthanide-doped upconverting nanoparticles (UCNPs) efficiently convert near infrared (NIR) light to higher energy emission and allow biological systems to be imaged with no measurable background or photobleaching, and with reduced scatter for subsurface experiments. Despite their advantages as imaging probes, UCNPs have little innate chemical sensing ability and require pairing with organic fluorophores to act as biosensors, although the design of stable UCNP-fluorophore hybrids with efficient upconverted energy transfer (UET) has remained a challenge. Here, we report Yb3+- and Er3+-doped UCNP-fluorophore conjugates with UET efficiencies up to 88%, and photostabilities 100-fold greater by UET excitation than those of the free fluorophores under direct excitation. Despite adding distance between Er3+ donors and organic acceptors, thin inert shells significantly enhance overall emission without compromising UET efficiency. This can be explained by the large increase in quantum yield of Er3+ donors at the core/shell interface and the large number of fluorophore acceptors at the surface. Sensors excited by UET show increases in photostability well beyond those reported for other methods for increasing the longevity of organic fluorophores, and those covalently attached to UCNP surface polymers show greater chemical stability than those directly coordinated to the nanocrystal surface. By conjugating other fluorescent chemosensors to UCNPs, these hybrids may be extended to a series of NIR-responsive biosensors for quantifying the dynamic chemical populations critical for cell signaling.

Concentration Quenching and Energy Transfer in Tm3+ and Dy3+ Single- and Double-Doped Nano-Sized GdVO4 Phosphors.

In this paper, Tm3+ and Dy3+ single- and double-doped nano-sized GdVO4 phosphors were prepared via a co-precipitation reaction. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and photoluminescence (PL) were utilized to characterize the as-prepared samples. The XRD and FE-SEM results reveal that the samples are single phase and that the average size is about 30 nm, respectively. Under 280 nm ultraviolet excitation, Dy3+ and Tm3+ single-doped nano-sized GdVO4 phosphors show the characteristic emissions of Dy3+ (4F9/2 --> 6H15/2 and 4F9/2 -*6H13/2 transitions) and Tm3+ (1G4 --> 3H6 transition), respectively. All the luminescence results from efficient energy transfer from the GdVO4 host to the doped Dy3+ and Tm3+ ions. Moreover, the interaction types for Dy3+ and Tm3+ ions in nano-sized GdVO4 host are confirmed as exchange and electrical dipole-dipole interaction by theoretical calculation. In Tm3+ and Dy3+ co-doped nanosized GdVO4 phosphors, the luminescence intensities of Dy3+ ions increase with increasing Tm3+ ion doping concentration, which suggests that energy transfer from Tm3+ to Dy3+ ions occurs. The responding luminescence mechanisms have been proposed in this paper. Finally, in order to evaluate the luminescence of Tm3+ and Dy3+ co-doped nano-sized GdVO4 phosphors, the color coordinates were calculated.

Excellent optical thermometry based on single-color fluorescence in spherical NaEuF4 phosphor.

Temperature-dependent luminescence of spherical NaEuF4 phosphors with different particle sizes was studied. The thermally coupled 5D0 and 5D1 level of Eu³âº was observed. The linear dependence of emission intensities of 5D0 level of NaEuF4 phosphor on temperature confirmed the excellent temperature sensing performance. Sensitivity up to 0.43% is achieved via decreasing the particle size, which is higher than that of reported thermometry based on upconversion of lanthanide ions. Moreover, the original luminescent intensity of 90% was recovered after 10 temperature-changed cycles, indicating good sensing stability. Therefore, spherical NaEuF4 phosphor might be a promising candidate for optical temperature sensors.

Microwave-assisted hydrothermal synthesis and temperature sensing application of Er3+/Yb3+ doped NaY(WO4)2 microstructures.

Laurustinus shaped NaY(WO4)2 micro-particles assembled by nanosheets were synthesized via a microwave-assisted hydrothermal (MH) route. The growing mechanisms for the obtained resultants with various morphologies were proposed based on the observation of scanning electron microscopic (SEM) images. It was found that Na3Cit added into the reaction solution greatly influenced the formation and size dimension of the nano-sheets, furthermore determined assembling of the laurustinus shaped micro-particles. The temperature sensing performance of NaY(WO4)2:Er(3+)/Yb(3+) was evaluated. Thermal effect induced by the 980nm laser irradiation in laurustinus-shaped NaY(WO4)2:Er(3+)/Yb(3+) phosphor was studied. It was found that the green upconversion luminescence intensity increased in the first stage of laser irradiation, and then decreased after reaching a maximum. Based on the thermal sensing technology the laurustinus NaY(WO4)2:Er(3+)/Yb(3+) microparticles were used as thermal probe to discover thermal effect of upconversion luminescence in laurustinus NaY(WO4)2:Tm(3+)/Yb(3+) micro-particles.

Hydrothermal synthesis and tunable luminescence of persimmon-like sodium lanthanum tungstate:Tb3+, Eu3+ hierarchical microarchitectures.

Persimmon-like NaLa(WO(4))(2) microarchitectures were prepared via hydrothermal process with using trisodium citrate (Na(3)Cit) as chelated reagent and characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), photoluminescence (PL), and fluorescent dynamics. The influences of Na(3)Cit concentration, organic additivities, and reaction time on the morphologies of NaLa(WO(4))(2) phosphor were studied. The results revealed that Na(3)Cit species had double functions of strong ligand and structure-directing reagent that could efficiently control the formation of persimmon-like NaLa(WO(4))(2) microarchitectures. The possible mechanism for the growth of persimmon-like NaLa(WO(4))(2) microarchitectures was attributed to the Ostwald ripening mechanism. The energy transfer from Tb(3+) to Eu(3+) in the persimmon-like NaLa(WO(4))(2) phosphors was observed. The energy transfer efficiencies and emission colors can be tuned by changing the concentration of Eu(3+). Finally, it was deduced that the electric dipole-dipole interaction (D-D) is the main mechanism for energy transfer between Tb(3+) and Eu(3+) in the persimmon-like NaLa(WO(4))(2) phosphor.