Plasmonic photocatalysts were successfully synthesized by the modification of TiO2 mesocrystals with Au nanoparticles (NPs) by a simple impregnation method. The Au NP sensitizers show a strong photoelectrochemical response in the visible-light region (400-800 nm) due to their surface plasmon resonance (SPR). The diffuse reflectance spectroscopy measurements on a wide range of time scales (from picoseconds to minutes) demonstrate that a substantial part of electrons, injected from the Au NPs to the TiO2 mesocrystals through the SPR excitation, directionally migrate from the basal surfaces to the edges of the plate-like mesocrystals through the TiO2 nanocrystal networks and are temporally stored there for further reactions. This anisotropic electron flow significantly retarded the charge recombination of these electrons with the holes in the Au NPs, thereby improving the visible-light-photocatalytic activity (for organic-pollutant degradation) by more than an order of magnitude, as compared to that of conventional Au/TiO2 NP systems.
Nanomaterials-based biomimetic catalysts with multiple functions are necessary to address challenges in artificial enzymes mimicking physiological processes. Here we report a metal-free nanozyme of modified graphitic carbon nitride and demonstrate its bifunctional enzyme-mimicking roles. With oxidase mimicking, hydrogen peroxide is generated from the coupled photocatalysis of glucose oxidation and dioxygen reduction under visible-light irradiation with a near 100% apparent quantum efficiency. Then, the in situ generated hydrogen peroxide serves for the subsequent peroxidase-mimicking reaction that oxidises a chromogenic substrate on the same catalysts in dark to complete the bifunctional oxidase-peroxidase for biomimetic detection of glucose. The bifunctional cascade catalysis is successfully demonstrated in microfluidics for the real-time colorimetric detection of glucose with a low detection limit of 0.8 μM within 30 s. The artificial nanozymes with physiological functions provide the feasible strategies for mimicking the natural enzymes and realizing the biomedical diagnostics with a smart and miniature device.
The alignment of nanoparticle building blocks into ordered superstructures is one of the key topics in modern colloid and material chemistry. Metal oxide mesocrystals are superstructures of assembled nanoparticles of metal oxides and have potentially tunable electronic, optical and magnetic properties, which would be useful for applications ranging from catalysis to optoelectronics. Here we report a facile and general approach for synthesizing metal oxide mesocrystals and developing them into new nanocomposite materials containing two different metals. The surface and internal structures of the mesocrystals were fully characterized by electron microscopy techniques. Single-particle confocal fluorescence spectroscopy, electron paramagnetic resonance spectroscopy and time-resolved diffuse reflectance spectroscopy measurements revealed that efficient charge transfer occurred between n-type and p-type semiconductor nanoparticles in the composite mesocrystals. This behaviour is desirable for their applications ranging from catalysis, optoelectronics and sensing, to energy storage and conversion.
We show an effective experimental method to prepare hierarchically porous zinc oxide (ZnO) spherical nanoparticles through a self-assembly pathway using surface-modified colloidal ZnO nanocrystallites as the building blocks and P-123 copolymers as the template in aqueous solution. Copolymers are thoroughly removed by Soxhlet extraction with ethanol and calcination at 400 °C. The final products have been characterized by X-ray powder diffraction (XRD) pattern, scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and photoluminescence (PL) spectroscopy. On the basis of calorimetric measurements reported separately, the surface enthalpy (γ) of the hydrated porous ZnO is 1.42 ( 0.21 J/m 2 , in good agreement with that of ZnO nanoparticles. The calorimetric results support the presence of self-assembled ZnO nanocrystallites in the nanoporous ZnO. Photocatalytic activitiy of porous ZnO nanoparticles has been tested on the photodegradation of phenol under ambient condition, indicating that porous ZnO nanoparticles show superior activity to TiO 2 nanoparticles (PC-500).
Daytime passive radiative cooling is a promising electricity-free pathway for cooling terrestrial buildings. Current research interest in this cooling strategy mainly lies in tailoring the optical spectra of materials for strong thermal emission and high solar reflection. However, environmental heat gain poses a crucial challenge to building cooling at subambient temperatures. Herein, we devise a scalable thermal insulating cooler (TIC) consisting of hierarchically hollow microfibers as the building envelope that simultaneously achieves passive daytime radiative cooling and thermal insulation to reduce environmental heat gain. The TIC demonstrates efficient solar reflection (94%) and long-wave infrared emission (94%), yielding a temperature drop of about 9 °C under sunlight of 900 W/m 2 . Notably, the thermal conductivity of the TIC is lower than that of air, thus preventing heat flow from external environments to indoor space in the summer, an additional benefit that does not sacrifice the radiative cooling performance. A building energy simulation shows that 48.5% of cooling energy could be saved if the TIC is widely deployed in China.
Solar water splitting provides a promising path for sustainable hydrogen production and solar energy storage. In recent times, metal−organic frameworks (MOFs) have received considerable attention as promising materials for diverse solar energy conversion applications. However, their photocatalytic performance is poor and rarely explored due to rapid electron− hole recombination. Herein, we have developed a material MOF@rGO that exhibits highly enhanced visible-light photocatalytic activity. A real-time investigation reveals that a strong π−π interaction between MOF and rGO is responsible for efficient separation of electron−hole pairs, and thereby enhances the photocatalytic hydrogen production activity. Surprisingly, MOF@rGO showed ∼9.1-fold enhanced photocatalytic hydrogen production activity compared to that of pristine MOF. In addition, it is worth mentioning here that remarkable apparent quantum efficiency (0.66%) is achieved by π−π interaction mediated charge carrier separation.
Free-standing CeO(2) nanorods with different morphology grew directly on Ti substrates via an electrochemical assembly process, and their absorption edges show a remarkable red-shift to the visible region. Moreover, photoelectrochemical cell (PEC) measurements demonstrate these CeO(2) nanorods exhibit a photovoltaic response under visible light illumination (λ≥ 390 nm).
The higher-order structures of semiconductor-based photocatalysts play crucial roles in their physicochemical properties for efficient light-to-energy conversion. A novel perovskite SrTiO mesocrystal superstructure with well-defined orientation of assembled cubic nanocrystals was synthesized by topotactic epitaxy from TiO mesocrystals through a facile hydrothermal treatment. The SrTiO mesocrystal exhibits three times the efficiency for the hydrogen evolution of conventional disordered systems in alkaline aqueous solution. It also exhibits a high quantum yield of 6.7 % at 360 nm in overall water splitting and even good durability up to 1 day. Temporal and spatial spectroscopic observations revealed that the synergy of the efficient electron flow along the internal nanocube network and efficient collection at the larger external cubes produces remarkably long-lived charges for enhanced photocatalysis.
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