DataSheet1_The applicability of sunshine-based global solar radiation models modified with meteorological factors for different climate zones of China.docx

With the development of renewable energy, the exploitation and utilization of solar energy resources also need continuous progress, but solar radiation data shortage has become a serious concern. A method for estimating global solar radiation has been developed to address this issue. The sunshine-based model is currently the most widely used model due to its high calculation accuracy and few input parameters. This paper will first review 13 subcategories (8 categories in total) of the global solar radiation prediction model based on sunshine. Subsequently, the astronomical factors were introduced to modify empirical coefficients, and 8 new categories of models based on sunshine rate were introduced. The radiation data from 83 meteorological stations in China was used to train and validate the model, and the performance of the model was evaluated by using evaluation indicators, such as coefficient of determination (R2), root mean square error (RMSE), mean absolute bias error (MABE), mean bias error (MBE), and global performance index (GPI). The results show that the R2 value of the unmodified empirical model is in a range of 0.82–0.99, and the RMSE value is in a range of 0.018–3.09. In contrast, with the introduction of the astronomical factor, the model accuracy improves significantly, and the modified power function model (N3) gains its best performance. The R2 of model N3 is in a range of 0.86–0.99, and the RMSE value is in a range of 0.018–2.62. The R2 increases by 0.49%, while the RMSE value 6.44%. Above all, it does not require the input of other meteorological parameters for predicting the value of global solar radiation.</p

Precisely Designed Mesoscopic Titania for High-Volumetric-Density Pseudocapacitance

Surface redox pseudocapacitance, which enables short charging times and high power delivery, is very attractive in a wide range of sites. To achieve maximized specific capacity, nanostructuring of active materials with high surface area is indispensable. However, one key limitation for capacitive materials is their low volumetric capacity due to the low tap density of nanomaterials. Here, we present a promising mesoscale TiO2 structure with precisely controlled mesoporous frameworks as a high-density pseudocapacitive model system. The dense-packed mesoscopic TiO2 in micrometer size offers a high accessible surface area (124 m2 g–1) and radially aligned mesopore channels, but high tap density (1.7 g cm–3) that is much higher than TiO2 nanoparticles (0.47 g cm–3). As a pseudocapacitive sodium-ion storage anode, the precisely designed mesoscopic TiO2 model achieved maximized gravimetric capacity (240 mAh g–1) and volumetric capacity (350 mAh cm–3) at 0.025 A g–1. Such a designed pseudocapacitive mesostructure further realized a commercially comparable areal capacity (2.1 mAh cm–2) at a high mass loading of 9.47 mg cm–2. This mesostructured electrode that enables fast sodiation in dense nanostructures has implications for high-power applications, fast-charging devices, and pseudocapacitive electrode design

Stepwise Monomicelle Assembly for Highly Ordered Mesoporous TiO₂ Membranes with Precisely Tailored Mesophase and Porosity

Mesoporous materials with crystalline frameworks have been acknowledged as very attractive materials in various applications. Nevertheless, due to the cracking issue during crystallization and incompatible hydrolysis and assembly, the precise control for crystalline mesoscale membranes is quite infertile. Herein, we presented an ingenious stepwise monomicelle assembly route for the syntheses of highly ordered mesoporous crystalline TiO2 membranes with delicately controlled mesophase, mesoporosity, and thickness. Such a process involves the preparation of monomicelle hydrogels and follows self-assembly by stepwise solvent evaporation, which enables the sensitive hydrolysis of TiO2 oligomers and dilatory micelle assembly to be united. In consequence, the fabricated mesoporous TiO2 membranes exhibit a broad flexibility, including tunable ordered mesophases (worm-like, hexagonal p6mm to body-centered cubic Im3̅m), controlled mesopore sizes (3.0–8.0 nm), and anatase grain sizes (2.3–8.4 nm). Besides, such mesostructured crystalline TiO2 membranes can be extended to diverse substrates (Ti, Ag, Si, FTO) with tailored thickness. The great mesoporosity of the in situ fabricated mesoscopic membranes also affords excellent pseudocapacitive behavior for sodium ion storage. This study underscores a novel pathway for balancing the interaction of precursors and micelles, which could have implications for synthesizing crystalline mesostructures in higher controllability

Two-Dimensional Mesoporous Heterostructure Delivering Superior Pseudocapacitive Sodium Storage via Bottom-Up Monomicelle Assembly

Two-dimensional (2D) heterostructures endowed with mesoporosities offer exciting opportunities in electrocatalysis, photocatalysis, energy storage, and conversion technologies due to their integrated functionalities, abundant active sites and shortened diffusion distance. However, layered mesostructures have not been combined due to the immense difficulties by conventional chemical, mechanical exfoliation or self-assembly approaches. Herein, we explore a bottom-up strategy, carried out under mild conditions, for the facile synthesis of monolayered mesoporous-titania–mesoporous-carbon vertical heterostructure with uniform mesopore size, which enables ultrahigh rate capability and cycling longevity for pseudocapacitive sodium-ion storage in nonaqueous electrolyte. Such a brand-new type of heterostructure consists of well-ordered monolayered mesoporous titania nanosheets and surrounding two mesoporous carbon monolayers assembled at both sides. Remarkably, the combination of interconnected large mesoporosity and heterointerface leads to highly promoted reversible pseudocapacitance (96.4% of total charge storage at a sweep rate of 1 mV s–1), and it enables the material to retain strong mechanical stability during the rapid sodiation and desodiation processes. This study reveals the importance of incorporating mesopores into heterointerface as a strategy for enhancing charge storage kinetics of electroactive materials

Mesoporous TiO₂ Single-Crystal Particles from Controlled Crystallization-Driven Mono-Micelle Assembly as an Efficient Photocatalyst

Mesoporous materials with crystalline frameworks have been widely explored in many fields due to their unique structure and crystalline feature, but accurate manipulations over crystalline scaffolds, mainly composed of uncontrolled polymorphs, are still lacking. Herein, we explored a controlled crystallization-driven monomicelle assembly approach to construct a type of uniform mesoporous TiO2 particles with atomically aligned single-crystal frameworks. The resultant mesoporous TiO2 single-crystal particles possess an angular shape ∼80 nm in diameter, good mesoporosity (a high surface area of 112 m2 g–1 and a mean pore size at 8.3 nm), and highly oriented anatase frameworks. By adjusting the evaporation rate during assembly, such a facile solution-processed strategy further enables the regulation of the particle size and mesopore size without the destruction of the oriented crystallites. Such a combination of ordered mesoporosity and crystalline orientation provides both effective mass and charge transportation, leading to a significant increase in the hydrogen generation rate. A maximum hydrogen evolution rate of 12.5 mmol g–1 h–1 can be realized, along with great stability under solar light. Our study is envisaged to extend the possibility of mesoporous single crystal growth to a range of functional ceramics and semiconductors toward advanced applications

Uniform Ordered Two-Dimensional Mesoporous TiO₂ Nanosheets from Hydrothermal-Induced Solvent-Confined Monomicelle Assembly

Two-dimensional (2D) nanomaterials have been the focus of substantial research interest recently owing to their fascinating and excellent properties. However, 2D porous materials have remained quite rare due to the difficulty of creating pores in 2D nanostructures. Here, we have synthesized a novel type of single-layered 2D mesoporous TiO₂ nanosheets with very uniform size and thickness as well as ordered mesostructure from an unprecedented hydrothermal-induced solvent-confined assembly approach. The F127/TiO₂ spherical monomicelles are first formed and redispersed in ethanol and glycerol, followed by a hydrothermal treatment to assemble these subunits into single-layered 2D mesostructure owing to the confinement effect of highly adhered glycerol solvent. The obtained 2D mesoporous TiO₂ nanosheets have a relative mean size at around 500 × 500 nm and can be randomly stacked into a bulk. The TiO₂ nanosheets possess only one layer of ordered mesopores with a pore size of 4.0 nm, a very high surface area of 210 m² g^–1 and a uniform thickness of 5.5 nm. The thickness can be further manipulated from 5.5 to 27.6 nm via simply tuning precursor concentration or solvent ratio. Due to the well-defined 2D morphology and large mesoporosity as well as crystalline anatase mesopore walls, these uniform TiO₂ nanosheets are capable of providing large accessible voids for sodium ion adsorption and intercalation as well as preventing volume expansion. As expected, these mesoporous TiO₂ nanosheets have exhibited an excellent reversible capacity of 220 mAh g^–1 at 100 mA g^–1 as sodium-ion battery anodes, and they can retain at 199 mAh g^–1 after numerous cycles at different current densities. The capacity is retained at 44 mAh g^–1 even at a large current density of 10 A g^–1 after 10 000 cycles, demonstrating a remarkable performance for energy storage

Constructing Three-Dimensional Mesoporous Bouquet-Posy-like TiO₂ Superstructures with Radially Oriented Mesochannels and Single-Crystal Walls

Constructing three-dimensional (3-D) hierarchical mesostructures with unique morphology, pore orientation, single-crystal nature, and functionality remains a great challenge in materials science. Here, we report a confined microemulsion self-assembly approach to synthesize an unprecedented type of 3-D highly ordered mesoporous TiO₂ superstructure (Level-1), which consists of 1 spherical core and 12 symmetric satellite hemispheres epitaxially growing out of the core vertices. A more complex and asymmetric TiO₂ superstructure (Level-2) with 13 spherical cores and up to 44 symmetric satellite hemispheres can also be well manipulated by increasing the size or content of impregnated TiO₂ precursor emulsion droplets. The obtained 3-D mesoporous TiO₂ superstructures have well-defined bouquet-posy-like topologies, oriented hexagonal mesochannels, high accessible surface area (134–148 m²/g), large pore volume (0.48–0.51 cm³/g), and well single-crystalline anatase walls with dominant (001) active facets. More interestingly, all cylindrical mesopore channels are highly interconnected and radially distributed within the whole superstructures, and all TiO₂ nanocrystal building blocks are oriented grown into a single-crystal anatase wall, making them ideal candidates for various applications ranging from catalysis to optoelectronics. As expected, the bouquet-posy-like mesoporous TiO₂ superstructure supported catalysts show excellent catalytic activity (≥99.7%) and selectivity (≥96%) in <i>cis</i>-semihydrogenation of various alkynes, exceeding that of commercial TiO₂ (P25) supported catalyst by a factor of 10. No decay in the activity was observed for 25 cycles, revealing a high stability of the mesoporous TiO₂ superstructure supported catalyst

Constructing Unique Mesoporous Carbon Superstructures via Monomicelle Interface Confined Assembly

Constructing hierarchical three-dimensional (3D) mesostructures with unique pore structure, controllable morphology, highly accessible surface area, and appealing functionality remains a great challenge in materials science. Here, we report a monomicelle interface confined assembly approach to fabricate an unprecedented type of 3D mesoporous N-doped carbon superstructure for the first time. In this hierarchical structure, a large hollow locates in the center (∼300 nm in diameter), and an ultrathin monolayer of spherical mesopores (∼22 nm) uniformly distributes on the hollow shells. Meanwhile, a small hole (4.0–4.5 nm) is also created on the interior surface of each small spherical mesopore, enabling the superstructure to be totally interconnected. Vitally, such interconnected porous supraparticles exhibit ultrahigh accessible surface area (685 m2 g–1) and good underwater aerophilicity due to the abundant spherical mesopores. Additionally, the number (70–150) of spherical mesopores, particle size (22 and 42 nm), and shell thickness (4.0–26 nm) of the supraparticles can all be accurately manipulated. Besides this spherical morphology, other configurations involving 3D hollow nanovesicles and 2D nanosheets were also obtained. Finally, we manifest the mesoporous carbon superstructure as an advanced electrocatalytic material with a half-wave potential of 0.82 V (vs RHE), equivalent to the value of the commercial Pt/C electrode, and notable durability for oxygen reduction reaction (ORR)

Mesoporous TiO₂ Mesocrystals: Remarkable Defects-Induced Crystallite-Interface Reactivity and Their in Situ Conversion to Single Crystals

Oriented self-assembly between inorganic nanocrystals and surfactants is emerging as a route for obtaining new mesocrystalline semiconductors. However, the actual synthesis of mesoporous semiconductor mesocrystals with abundant surface sites is extremely difficult, and the corresponding new physical and chemical properties arising from such an intrinsic porous mesocrystalline nature, which is of fundamental importance for designing high-efficiency nanostructured devices, have been rarely explored and poorly understood. Herein, we report a simple evaporation-driven oriented assembly method to grow unprecedented olive-shaped mesoporous TiO₂ mesocrystals (FDU-19) self-organized by ultrathin flake-like anatase nanocrystals (∼8 nm in thickness). The mesoporous mesocrystals FDU-19 exhibit an ultrahigh surface area (∼189 m²/g), large internal pore volume (0.56 cm³/g), and abundant defects (oxygen vacancies or unsaturated Ti³⁺ sites), inducing remarkable crystallite-interface reactivity. It is found that the mesocrystals FDU-19 can be easily fused in situ into mesoporous anatase single crystals (SC-FDU-19) by annealing in air. More significantly, by annealing in a vacuum (∼4.0 × 10^–5 Pa), the mesocrystals experience an abrupt three-dimensional to two-dimensional structural transformation to form ultrathin anatase single-crystal nanosheets (NS-FDU-19, ∼8 nm in thickness) dominated by nearly 90% exposed reactive (001) facets. The balance between attraction and electrostatic repulsion is proposed to determine the resulting geometry and dimensionality. Dye-sensitized solar cells based on FDU-19 and SC-FDU-19 samples show ultrahigh photoconversion efficiencies of up to 11.6% and 11.3%, respectively, which are largely attributed to their intrinsic single-crystal nature as well as high porosity. This work gives new understanding of physical and chemical properties of mesoporous semiconductor mesocrystals and opens up a new pathway for designing various single-crystal semiconductors with desired mesostructures for applications in catalysis, sensors, drug delivery, optical devices, etc

Mesoporous TiO₂ Mesocrystals: Remarkable Defects-Induced Crystallite-Interface Reactivity and Their in Situ Conversion to Single Crystals

Oriented self-assembly between inorganic nanocrystals and surfactants is emerging as a route for obtaining new mesocrystalline semiconductors. However, the actual synthesis of mesoporous semiconductor mesocrystals with abundant surface sites is extremely difficult, and the corresponding new physical and chemical properties arising from such an intrinsic porous mesocrystalline nature, which is of fundamental importance for designing high-efficiency nanostructured devices, have been rarely explored and poorly understood. Herein, we report a simple evaporation-driven oriented assembly method to grow unprecedented olive-shaped mesoporous TiO₂ mesocrystals (FDU-19) self-organized by ultrathin flake-like anatase nanocrystals (∼8 nm in thickness). The mesoporous mesocrystals FDU-19 exhibit an ultrahigh surface area (∼189 m²/g), large internal pore volume (0.56 cm³/g), and abundant defects (oxygen vacancies or unsaturated Ti³⁺ sites), inducing remarkable crystallite-interface reactivity. It is found that the mesocrystals FDU-19 can be easily fused in situ into mesoporous anatase single crystals (SC-FDU-19) by annealing in air. More significantly, by annealing in a vacuum (∼4.0 × 10^–5 Pa), the mesocrystals experience an abrupt three-dimensional to two-dimensional structural transformation to form ultrathin anatase single-crystal nanosheets (NS-FDU-19, ∼8 nm in thickness) dominated by nearly 90% exposed reactive (001) facets. The balance between attraction and electrostatic repulsion is proposed to determine the resulting geometry and dimensionality. Dye-sensitized solar cells based on FDU-19 and SC-FDU-19 samples show ultrahigh photoconversion efficiencies of up to 11.6% and 11.3%, respectively, which are largely attributed to their intrinsic single-crystal nature as well as high porosity. This work gives new understanding of physical and chemical properties of mesoporous semiconductor mesocrystals and opens up a new pathway for designing various single-crystal semiconductors with desired mesostructures for applications in catalysis, sensors, drug delivery, optical devices, etc